CN109467929B - Shape memory cyanate resin material resistant to gamma ray irradiation and preparation method thereof - Google Patents
Shape memory cyanate resin material resistant to gamma ray irradiation and preparation method thereofDownload PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/0644—Poly(1,3,5)triazines
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/12—Shape memory
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
Translated fromChinese
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a shape memory cyanate ester resin material resistant to gamma ray irradiation and a preparation method thereof.
Background
With the rapid development of aerospace science and technology, human beings have more and more frequent exploration actions on outer space, and the flight distance of a spacecraft is further and further, so that the requirement on the spacecraft is more and more severe. The spacecraft is inevitably subjected to various space severe environments such as vacuum, high and low temperature, atomic oxygen, ultraviolet rays, gamma ray irradiation and the like during the service period of the space. In order to reduce the damage of the systems of the spacecraft in the severe environment of the space, the research and development of space irradiation resistant, high transition temperature and high mechanical strength materials which can be used for the spacecraft are urgent.
The polymer resin material has low cost, high hardness, high toughness, high corrosion resistance, high wear resistance, excellent thermodynamic performance and high chemical stability, and thus has excellent application foreground in aeronautics and astronautics. Cyanate ester resins are thermosetting polymers having a glass transition temperature of up to 400 ℃ and generally contain two or more-O-C.ident.N, cyanate ester functional groups in their molecular structure. At a certain temperature, a cyanate ester functional group (-O-C.ident.N) undergoes trimerization to form a triazine ring. The triazine ring is a six-membered ring consisting of carbon-nitrogen single bonds and carbon-nitrogen double bonds alternately, and has highly symmetrical structure and excellent thermal stability and chemical stability. However, the material has large brittleness, poor deformation and high glass transition temperature, and even if the material is above the glass transition temperature, the material is difficult to deform, so that the application of the cyanate ester resin in an engineering structure is greatly limited, and meanwhile, the research on the space irradiation resistance of the cyanate ester resin material as a spacecraft is urgent.
In view of the above-mentioned drawbacks, the present inventors have made the present invention through long-term research and practice.
Disclosure of Invention
In order to solve the technical defects, the invention adopts the technical scheme that the preparation method of the shape memory cyanate ester resin material resisting the gamma ray irradiation comprises the following steps:
the first step is as follows: placing 50-80% of cyanate ester monomer in an oil bath pot, adding 10-20% of plasticizer and 10-30% of cross-linking agent after the cyanate ester monomer is completely dissolved, and performing magnetic stirring to obtain uniform cyanate ester precursor solution;
the second step is that: and injecting the cyanate precursor solution prepared in the first step into a preheated mold, and placing the preheated mold in an oven for heating and curing to prepare the shape memory cyanate resin material resistant to gamma ray irradiation.
Further, the cyanate ester monomer in the first step is bisphenol a cyanate ester.
Further, the plasticizer is characterized by comprising one or more of epoxy resin, polycaprolactone and polyol ester.
Further, the crosslinking agent comprises one or more of polyethylene oxide, diethylene glycol divinyl ether and polyethylene glycol.
Further, the preheating temperature of the die in the first step is 90-120 ℃.
Furthermore, the conditions of the heating and curing in the second step are that the temperature is 150-.
The shape memory cyanate resin material which can resist the gamma ray irradiation is prepared according to the method.
Furthermore, gamma ray irradiation has no influence on the shape memory performance of the material.
Further, the material achieves shape recovery at the heating temperature of 160-220 ℃ before and after gamma ray irradiation, and the time for recovering the material to the original shape is 30-90 s.
Further, the maximum heat-resisting temperature of the material is 350-360 ℃ before and after the gamma ray irradiation.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation process of the shape memory cyanate ester resin material resisting the gamma ray irradiation is simple, the operation is easy, and the cost is low;
(2) the shape memory cyanate ester resin material has the gamma ray irradiation resistance, can be used for preparing shape memory locking, driving and other members, can effectively reduce the damage of gamma rays to main components of the spacecraft in on-orbit service, and improves the on-orbit safety of the spacecraft.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below.
FIG. 1 is a simplified flow chart of a method for preparing a shape memory cyanate ester resin material resistant to gamma ray irradiation in example 1 of the present invention
Fig. 2 is a thermal weight loss curve of a shape memory cyanate resin material and cyanate resin materials irradiated by different doses of gamma rays inembodiment 2 of the present invention;
fig. 3 is a stress-strain curve of the shape memory cyanate ester resin material and the cyanate ester resin material irradiated by different doses of gamma rays, which is stretched at room temperature inembodiment 2 of the present invention;
FIG. 4 is a photograph showing the shape memory recovery process of a shape memory cyanate resin material before being irradiated with gamma rays inembodiment 2 of the present invention;
fig. 5 is a photograph showing the shape memory recovery process of the shape memory cyanate ester resin material after being irradiated by gamma rays inembodiment 2 of the present invention.
Detailed Description
The above and further features and advantages of the present invention are described in more detail below with reference to the accompanying drawings.
Example 1
Referring to fig. 1, this embodiment provides a method for preparing a shape memory cyanate ester resin material resistant to gamma ray irradiation, which includes the following steps:
the first step is as follows: placing 50-80% of cyanate ester monomer in an oil bath pan at the temperature of 100-120 ℃, after the cyanate ester monomer is completely dissolved, adding 10-20% of plasticizer and 10-30% of cross-linking agent by mass, and performing magnetic stirring for 30-60min to prepare a uniform cyanate ester precursor solution, wherein the cyanate ester is bisphenol A cyanate ester; the plasticizer is one or more of epoxy resin, polycaprolactone and polyol ester; the crosslinking agent is one or more of polyethylene oxide, diethylene glycol divinyl ether and polyethylene glycol;
the second step is that: and injecting the cyanate ester precursor solution prepared in the first step into a preheated mold, wherein the preheating temperature is 90-120 ℃, and placing the preheated mold in a blast oven to perform heating and curing under the conditions that the temperature is 150-230 ℃ and the heating rate is 0.5-1.0 ℃/min, so as to prepare the shape memory cyanate ester resin material resistant to gamma ray irradiation. The shape memory performance of the gamma ray irradiation resistant shape memory cyanate resin material is not obviously changed before and after the gamma ray irradiation, and the highest heat-resisting temperature is 350-360 ℃, wherein the dose of the gamma ray irradiation is 0-1000KGy, and the amplification rate of the dose is 4.0-6.0 Gy/s.
Therefore, the preparation process of the shape memory cyanate resin material resistant to gamma ray irradiation is simple, easy to operate and low in cost; and because of the gamma ray irradiation resistance, the shape memory locking and driving components can be prepared, the damage of the gamma ray to the main components of the spacecraft in on-orbit service can be effectively reduced, and the on-orbit safety of the spacecraft is improved.
Example 2
The embodiment provides a preparation method of a shape memory cyanate ester resin material resistant to gamma ray irradiation, which comprises the following steps:
the first step is as follows: placing 60% by mass of bisphenol A type cyanate ester monomer in an oil bath pan at the temperature of 110 ℃, adding 20% by mass of epoxy resin and 20% by mass of polyethylene glycol after the cyanate ester monomer is completely dissolved, and performing magnetic stirring for 45min to obtain a uniform cyanate ester precursor solution;
the second step is that: and injecting the cyanate ester precursor solution prepared in the first step into a preheated mould, wherein the preheating temperature is 100 ℃, and placing the mould into a forced air oven for heating and curing, wherein the curing process comprises the steps of heating at 150 ℃ for 2h, curing at 180 ℃ for 2h, curing at 210 ℃ for 3h, and heating up at a rate of 0.8 ℃/min, so as to prepare the shape memory cyanate ester resin material resistant to gamma ray irradiation.
Example 3
The embodiment provides a preparation method of a shape memory cyanate ester resin material resistant to gamma ray irradiation, which comprises the following steps:
the first step is as follows: putting 60% by mass of bisphenol A type cyanate ester monomer into an oil bath pan at the temperature of 100 ℃, after the cyanate ester monomer is completely dissolved, adding 20% by mass of polycaprolactone, 10% by mass of polyethylene oxide and 10% by mass of polyethylene glycol, and performing magnetic stirring for 30min to obtain a uniform cyanate ester precursor solution;
the second step is that: and injecting the cyanate ester precursor solution prepared in the first step into a preheated mould, wherein the preheating temperature is 90 ℃, and placing the mould into a forced air oven for heating and curing, wherein the curing process comprises the steps of heating at 150 ℃ for 2 hours, curing at 190 ℃ for 3 hours, curing at 220 ℃ for 3 hours, and heating up at a rate of 0.5 ℃/min, so as to prepare the shape memory cyanate ester resin material resistant to gamma ray irradiation.
Example 4
The embodiment provides a preparation method of a shape memory cyanate ester resin material resistant to gamma ray irradiation, which comprises the following steps:
the first step is as follows: putting 70% by mass of bisphenol A type cyanate ester monomer into an oil bath pan at the temperature of 120 ℃, after the cyanate ester monomer is completely dissolved, adding 15% by mass of polycaprolactone and 25% by mass of polyethylene oxide, and magnetically stirring for 50min to obtain a uniform cyanate ester precursor solution;
the second step is that: and injecting the cyanate ester precursor solution prepared in the first step into a preheated mould, wherein the preheating temperature is 120 ℃, and placing the mould into a blast oven for heating and curing, wherein the curing process comprises the steps of heating at 150 ℃ for 2 hours, curing at 180 ℃ for 2 hours, curing at 210 ℃ for 3 hours, and heating up at a rate of 0.6 ℃/min, so as to prepare the shape memory cyanate ester resin material resistant to gamma ray irradiation.
Example 5
The embodiment provides a preparation method of a shape memory cyanate ester resin material resistant to gamma ray irradiation, which comprises the following steps:
the first step is as follows: placing bisphenol A type cyanate ester monomer with the mass fraction of 80% in an oil bath pan with the temperature of 115 ℃, adding epoxy resin with the mass fraction of 10% and polyethylene oxide with the mass fraction of 10% after the cyanate ester monomer is completely dissolved, and carrying out magnetic stirring for 60min to prepare uniform cyanate ester precursor solution;
the second step is that: and injecting the cyanate ester precursor solution prepared in the first step into a preheated mould, wherein the preheating temperature is 110 ℃, and placing the mould into a forced air oven for heating and curing, wherein the curing process comprises the steps of heating at 160 ℃ for 2 hours, curing at 190 ℃ for 2 hours, curing at 230 ℃ for 2 hours, and heating up at a rate of 1.0 ℃/min, so as to prepare the shape memory cyanate ester resin material resistant to gamma ray irradiation.
Example 6
In order to more clearly illustrate the changes of the thermodynamic properties and the shape memory properties of the shape memory cyanate ester resin material prepared by the present invention before and after the gamma ray irradiation, the present example briefly describes the changes of the properties of the shape memory cyanate ester resin material prepared in example 2 before and after the gamma ray irradiation.
In this embodiment, the gamma irradiation doses are 10KGy, 100KGy and 1000KGy, the amplification rate of the dose is 4.0 to 6.0Gy/s, and before and after the gamma irradiation, the color change exists in the appearance of the shape memory cyanate ester resin material, and the dark brown color before the irradiation gradually changes into light brown color after the irradiation.
As shown in fig. 2, the weight of the cyanate ester resin material after being irradiated by three doses of gamma rays has no change at a high temperature of 360 ℃, and the weight of the cyanate ester resin material has a slight decrease at a temperature of more than 420 ℃, and the change is more obvious when the dose of gamma rays is larger. This shows that after the cyanate resin material is irradiated by gamma ray with high energy, molecular chains are cracked to generate small molecules, and these small molecular chains are decomposed at high temperature to generate gas, which escapes to reduce weight. The cracking reaction mainly comes from the cracking of hydroxyl, alkyl and other branched chains in materials such as cyanate ester, epoxy resin, polyol ester, polyethylene glycol and the like, and the synthesized shape memory cyanate ester resin is subjected to gamma ray high-energy irradiation to cause the cracking of the branched chains.
As shown in fig. 3, the tensile strain of the cyanate ester resin material at room temperature is 5.0-7.0%, and after 1000KGy gamma ray irradiation, the tensile strain of the cyanate ester resin material is 8.0-9.0%, so that the strain of the cyanate ester resin material after three doses of gamma ray irradiation is increased at room temperature, and the change is more obvious when the gamma ray dose is larger, which indicates that the crosslinking degree in the system is increased after the cyanate ester resin material is irradiated with high energy of gamma ray, because the reactive functional groups in each component undergo a polymerization reaction when the cyanate ester precursor solution is heated and cured, mainly the cyano group in the cyanate ester monomer and the reactive groups in the plasticizer, epoxy group, hydroxyl group and the like in the crosslinking agent undergo a polymerization reaction to generate a macromolecular crosslinked network. In the curing reaction, the resin cannot reach 100% of curing degree due to factors such as curing temperature, curing time, system viscosity, steric hindrance and the like, and a part of the component monomers remain in the resin. When the resin is irradiated with high-energy gamma rays, the above-mentioned polymerization reaction proceeds further, resulting in an increase in the degree of crosslinking of the system.
As shown in fig. 4 and 5, in the same 180 ℃ temperature environment, the shape recovery rate of the cyanate resin material before and after gamma ray irradiation is 100%, and the shape recovery time is 50-70s, which is not obviously different. This is because the superiority and inferiority of the shape memory property of the resin are generally determined by the shape recovery rate, the shape fixation rate and the shape recovery time. The shape memory performance is mainly related to a cross-linked network structure in a resin system, and the cracking of a molecular chain is to destroy the network structure, is not beneficial to the shape memory performance and belongs to negative influence; the polymerization reaction of the monomers generates a network structure, which is beneficial to the shape memory performance of the monomers and belongs to positive influence. After the irradiation of gamma rays, the change of the shape memory property of the cyanate resin material is the comprehensive reflection of the cracking reaction and the polymerization reaction, the influence of the cracking reaction and the polymerization reaction on the shape memory effect of the resin is enhanced along with the increase of the dosage of the gamma rays, and the two influences can be mutually counteracted, so the change of the shape memory property of the cyanate resin before and after the irradiation of the gamma rays is not large.
Therefore, the shape memory cyanate resin material in the embodiment has the gamma ray irradiation resistance, which is specifically shown in that the cyanate resin material can realize the shape recovery at the heating temperature of 160-220 ℃ before and after the gamma ray irradiation, and the time for recovering to the initial shape is 30-90 s. The highest heat-resisting temperature is 350-360 ℃, and the strain of the cyanate resin material after gamma ray irradiation is increased at room temperature, so that the shape memory cyanate resin material in the embodiment can be used for preparing shape memory locking, driving and other members, the damage of the gamma ray to the main components of the in-orbit spacecraft can be effectively reduced, and the in-orbit safety of the spacecraft can be improved.
The foregoing is merely a preferred embodiment of the invention, which is intended to be illustrative and not limiting. It will be understood by those skilled in the art that various changes, modifications and equivalents may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (6)
1. A preparation method of a shape memory cyanate ester resin material resistant to gamma ray irradiation is characterized by comprising the following steps:
the first step is as follows: placing 50-80% of cyanate ester monomer in an oil bath pot, adding 10-20% of plasticizer and 10-30% of cross-linking agent after the cyanate ester monomer is completely dissolved, and performing magnetic stirring to obtain uniform cyanate ester precursor solution;
the cyanate monomer is bisphenol A cyanate, the plasticizer is epoxy resin, and the crosslinking agent is polyethylene glycol;
the second step is that: injecting the cyanate ester precursor solution prepared in the first step into a preheated mold, and placing the preheated mold in an oven for heating and curing to prepare the shape memory cyanate ester resin material resistant to gamma ray irradiation;
the material can realize shape recovery at the heating temperature of 160-220 ℃ before and after gamma ray irradiation, and the time for recovering to the original shape is 30-90 s.
2. The method of claim 1, wherein the preheating temperature of the mold in the second step is 90 to 120 ℃.
3. The method as claimed in claim 1, wherein the conditions for the second step of heating and curing are 150 ℃ and 230 ℃ and the heating rate is 0.5-1.0 ℃/min.
4. A shape memory cyanate ester resin material which can resist gamma ray irradiation and prepared by the preparation method according to any one of claims 1 to 3.
5. The gamma ray irradiation resistant shape memory cyanate ester resin material according to claim 4, wherein gamma ray irradiation has no influence on the shape memory property of the material.
6. The shape memory cyanate ester resin material resistant to gamma ray irradiation as claimed in claim 4, wherein the maximum heat resistant temperature of said material is 350-360 ℃ before and after gamma ray irradiation.
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| 《Effect of Phenol End Functional Switching Segments on the Shape Memory Properties of Epoxy-Cyanate Ester System》;R. Biju等;《Journal or Applied Polymer Scienc》;20141231;第131卷;第41196-41203页* |
| 《High transition temperature shape memory polymers (SMPs) by telechelic oligomer approach》;K.S. Santhosh Kumar等;《Reactive & Functional Polymers》;20140228;第78卷;第7-13页* |
| 《Shape memory polymers based on cyanate ester-epoxy-poly (tetramethyleneoxide) co-reacted system》;R. Biju等;《European Polymer Journal》;20111207;第48卷;第499-511页* |
| 《Shape memory polymers: Past, present and future developments》;Martin D. Hager等;《Progress in Polymer Science》;20150414;第49-50卷;第3-33页* |
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| CN109467929A (en) | 2019-03-15 |
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