CN112724366A - Reworkable shape memory epoxy resin and preparation method and application thereof - Google Patents
Reworkable shape memory epoxy resin and preparation method and application thereof Download PDFInfo
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 55
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 25
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 6
- 239000004305 biphenyl Substances 0.000 claims abstract description 5
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000007860 aryl ester derivatives Chemical class 0.000 claims abstract description 3
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 58
- 239000002904 solvent Substances 0.000 claims description 31
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 23
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical group C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 7
- 150000004820 halides Chemical class 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 4
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 4
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 230000007334 memory performance Effects 0.000 abstract description 9
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 8
- 229920000431 shape-memory polymer Polymers 0.000 abstract description 8
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 238000011084 recovery Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- KXAUPESBGZWKML-UHFFFAOYSA-N 1-(3,5-dimethylphenyl)-3,5-dimethylbenzene phenol Chemical compound C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.CC=1C=C(C=C(C1)C)C1=CC(=CC(=C1)C)C KXAUPESBGZWKML-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 8
- -1 3, 5' -di-tert-butyl-5, 3' -dimethyl biphenyl diglycidyl ether Chemical compound 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical group CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- RMIBXGXWMDCYEK-UHFFFAOYSA-N oxonane-2,9-dione Chemical compound O=C1CCCCCCC(=O)O1 RMIBXGXWMDCYEK-UHFFFAOYSA-N 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- DIBHLCJAJIKHGB-UHFFFAOYSA-N dec-5-ene Chemical compound [CH2]CCCC=CCCCC DIBHLCJAJIKHGB-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000002520 smart material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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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
- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
-
- 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
- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/022—Polycondensates containing more than one epoxy group per molecule characterised by the preparation process or apparatus used
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The invention belongs to the field of preparation of shape memory polymer materials, and provides a reworkable shape memory epoxy resin, which comprises an orientable liquid crystal element and a dynamically exchangeable ester bond; the orientable mesogen includes any one or more of biphenyl, azo, aryl ester and alpha-methyl styrene. The shape memory epoxy resin has excellent shape memory performance and excellent reworkability. The application also provides a preparation method and application of the reworkable shape memory epoxy resin, and the preparation method is simple and feasible, and can be used for preparing the reworkable shape memory epoxy resin with high efficiency and high quality.
Description
Technical Field
The invention relates to the field of preparation of shape memory polymer materials, in particular to a reworkable shape memory epoxy resin, and a preparation method and application thereof.
Background
Shape Memory Polymers (SMPs), an emerging class of smart materials, are a class of polymeric materials designed to program an initial shape, then obtain a temporary shape by fixing the programmed shape, and return to the initial shape under an external stimulus. Common external stimuli are heat, electric current, light, magnetic field, moisture, pH, enzymes, etc. When the SMP is subjected to an external stimulus, programmable motion, such as shape, position, strain, etc., can occur. Because of the flexible nature and programming, high recovery strain, ease of processing, light weight, and low cost, SMPs have received much attention over the past few decades.
As an important SMPs, the epoxy resin has the advantages of high mechanical property, good chemical resistance and thermal stability, good processability and the like, has wide development prospect in the field of space expandable structures and structural materials, and is one of the hot spots of research in recent years.
Chinese patent with application number CN201410798270.1 discloses a lateral group substituted biphenyl type shape memory liquid crystal epoxy resin and a preparation method and application thereof, the liquid crystal epoxy resin with excellent shape memory performance is prepared by reacting 3, 5' -di-tert-butyl-5, 3' -dimethyl biphenyl diglycidyl ether and 3,3',5,5' -tetramethyl-4, 4 ' -biphenyl diglycidyl ether with different proportions and different curing agent systems of amines and acid anhydrides, the liquid crystal epoxy resin contains ester bonds, and the liquid crystal epoxy resin can not be reprocessed because the system does not contain catalysts and the ester bonds can not be exchanged. M.krajnc topic group (R).
A. 
M.krajnc, express.polym.lett.2020,14,808) prepared an epoxy-benzoxazine copolymer with a strong shape memory capacity and enhanced rigidity, however, the epoxy resin consisted of covalent bonds and also did not have reworkability.
The epoxy resins all have excellent shape memory properties, but the epoxy resins are extremely difficult to rework due to the presence of irreversible covalent crosslinking structures. Considering the importance of epoxy resins in practical applications, the lack of reworkability hinders their development. Combining epoxy resins with dynamic covalent bonds provides a feasible solution for the study of reworkable SMPs, and many researchers have studied to prepare reworkable shape memory epoxy resins by designing a reasonable route.
The existing shape memory epoxy resin is difficult to meet the requirements of excellent reworkability and shape memory performance. Reworkable epoxy resins are often limited by problems of low shape recovery accuracy, poor repeatability, small tensile strain, etc. Therefore, the development of SMPs having good shape-recovering ability and repetitive performance is a technical problem that the prior art has failed to solve.
Disclosure of Invention
A first object of the present invention is to provide a reworkable shape memory epoxy resin having not only excellent shape memory properties but also excellent reworkability.
The second object of the present invention is to provide a method for producing the reworkable shape memory epoxy resin, which is simple and feasible and can produce the reworkable shape memory epoxy resin with high efficiency and high quality.
In order to achieve the purpose, the invention adopts the technical scheme that:
a reworkable shape memory epoxy resin comprising orientable mesogens and dynamically exchangeable ester linkages; the orientable mesogen includes any one or more of biphenyl, azo, aryl ester and alpha-methyl styrene.
Based on the research of the prior art, the invention introduces orientable liquid crystal elements into the epoxy resin to improve the shape memory performance of the epoxy resin, introduces ester bonds capable of being dynamically exchanged to improve the reworkability of the epoxy resin, and combines the two groups into the same epoxy resin to obtain the epoxy resin with excellent shape memory performance and excellent reworkability.
Specifically, the shape memory epoxy resin which can be reprocessed in the present invention may be represented by the formula (I-1) or (I-2), and is preferably a compound represented by the formula (I-1):
in the formula (I-2), R is selected from-N ═ N-, -COO- (C)6H4) -OOC-or- (CH)3)CH＝CH2-； R1Is selected from CH3Or H. N in the above formula (I-1) and the formula (I-2) is not less than 0, and is correlated with the crosslinking density, and in the present application, the compounds represented by the above formula (I-1) and the formula (I-2) have the crosslinking density of 10 to 50mol/m3。
The shape memory epoxy resin shown in the formula (I-1) is a preferable one in the shape memory epoxy resin designed by the invention, and has the advantages of simple synthesis, easy manufacture and the like besides excellent shape memory performance and excellent reworkability.
The mechanism that the introduction of ester bonds capable of being dynamically exchanged can improve the reworkability of the ester bonds is as follows:
R1，R2，R3and R4Are molecular segments of various portions of the polymer network. First, TBD (1,5, 7-triazabicyclo [4.4.0]]Dec-5-ene) reacts with esters through nucleophilic attack, i.e., the disubstituted nitrogen atom in TBD attacks the carbonyl group on the ester linkage, then forms nitrogen cations, oxygen anions, carbon nitrogen bonds and hydrogen bonds, thereby forming a betaine-like intermediate a. Secondly, proton transfer readily occurs on the nitrogen ion, forming an intermediate B, i.e. a TBD containing a carbonyl group, with alcohol production. Then, the intermediate product B reacts with the alcohol in the system to form a new ester and TBD, thereby completing the transesterification reaction. The newly formed ester and the dissociated TBD continue to participate in the transesterification reaction. In addition, cleavage of ester bonds in the epoxy network is facilitated by consumption of TBD, thereby generating more alcohol and allowing the epoxy resin to be rapidly depolymerized. Thus, the transesterification will be carried out at TBD regardless of the presence of other alcohols in the systemThe following takes place.
The above-mentioned reworkable shape memory epoxy resin of the present invention can be prepared by polymerizing a compound represented by the formula (II-1) or (II-2) with a compound represented by the formula (III) in the presence of a catalyst, specifically, a compound represented by the formula (I-1) can be prepared by reacting a compound represented by the formula (II-1) with a compound represented by the formula (III), a compound represented by the formula (I-2) can be prepared by reacting a compound represented by the formula (II-2) with a compound represented by the formula (III),
wherein R in the formula (II-2) is selected from-N ═ N-, -COO- (C)6H4) -OOC-or- (CH)3)CH＝CH2-；
The compound shown in the formula (III) is a mixture consisting of one or more of suberic acid, suberoyl halide and suberic dianhydride.
By adopting the reaction monomer, not only can orientable liquid crystal elements be well introduced, but also reprocessable ester bonds capable of being dynamically exchanged can be introduced, and the preparation method has the advantage of simplicity and feasibility. The preparation of the various substances of the invention is conveniently achieved by the selection of specific monomers.
The polymerization reaction is preferably a solution polymerization, and the reaction specifically comprises the following steps:
adding a compound shown as a formula (II-1) or a formula (II-2) into a solvent, stirring and dissolving, adding a compound shown as a formula (III), finally adding a catalyst, stirring and dissolving at room temperature to obtain a mixed solution;
vacuumizing to remove air, slowly pouring the mixed solution into a mold, curing at high temperature for a period of time, and demolding.
The invention adopts solution polymerization reaction, the reaction can be smoothly carried out, and the polymer of the invention can be prepared with high efficiency and high quality.
Specifically, in the above reaction: the molar ratio of the compound shown in the formula (II-1) or the formula (II-2) to the compound shown in the formula (III) is 1: 0.8-1.2.
The solvent is N, N-dimethylacetamide, and the adding amount of the solvent is 50-75% of the total mass of the reaction system by mass. The N, N-dimethylacetamide is selected to be capable of dissolving the monomer, and the boiling point of the N, N-dimethylacetamide is 166 ℃, so that the curing reaction at high temperature is facilitated.
The catalyst is selected from 1,5, 7-triazabicyclo [4.4.0] dec-5-ene or zinc acetylacetonate, and is preferably 1,5, 7-triazabicyclo [4.4.0] dec-5-ene.
The addition amount of the catalyst is recorded as 0.5-5.0% of the molar amount of M, and M is the molar amount of-OM in the compound shown in the formula (III).
The reaction curing temperature is controlled to be 145-160 ℃, and the optimized temperature is 145 ℃; the curing time is controlled to be 10 h-14 h, preferably 12 h.
It should be noted that, when the compound represented by formula (iii) is selected from suberoyl halide and/or suberic anhydride during the reaction of the present application, a curing accelerator needs to be added, and the curing accelerator is preferably benzyldimethylamine; the amount of the curing accelerator added is preferably 3% by mole of the compound represented by the formula (III).
The invention selects the catalyst and the solvent to be matched with the monomer, and prepares the target product of the invention by reasonably designing the monomer ratio, the reaction temperature, the polymerization method, the catalyst dosage and the like, so that the liquid crystal elements (such as biphenyl) and the exchangeable esters exist together with the epoxy resin of the invention, and the epoxy resin with excellent shape memory performance and reworkability is further prepared.
The invention also provides application of the reworkable shape memory epoxy resin. In particular, the method can be applied to the fields of biomedicine and aerospace.
The invention has the beneficial effects that:
1. the introduction of alignable mesogens such as biphenyls into the epoxy resin improves the shape memory properties by replacing the alignable mesogens for alignment under the action of high temperature and external force.
2. Ester bonds are introduced into the polymer network, and shape memory epoxy resin has good reworkability through ester bond exchange, so that the reworkable shape memory epoxy resin is prepared. The epoxy resin material is cut into small pieces, put into a mould, and then subjected to ester bond exchange at high temperature and high pressure to form a new polymer network, so that the reworking can be realized.
3. The epoxy resin can realize repair to a certain extent through molecular bond segment diffusion and winding above the glass transition temperature, and is favorable for realizing the heavy processing performance.
4. The preparation method can conveniently prepare the target product of the application, and the obtained epoxy resin has good shape memory performance, reworking performance, solid plastic reshaping and the like, and is an effective method for obtaining excellent shape memory performance and reworking performance.
Drawings
FIG. 1 is an IR spectrum of a reworkable shape memory epoxy resin prepared in accordance with example 4.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the present invention is further described with reference to specific embodiments below.
Example 1
Preparing raw materials:
solvent: 4.1760g of N, N-diethylacetamide;
a compound represented by the formula (II-1): 1.2000g of 3,3', 5' -tetramethylbiphenyl bisphenol diglycidyl ether;
a compound represented by the formula (III): suberic acid 0.5697 g;
catalyst: 0.0047g of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene.
The preparation method comprises the following steps:
first, 1.200g of 3,3',5,5' -tetramethylbiphenyl bisphenol diglycidyl ether was weighed using an analytical balance, and 4.1760g of N, N-dimethylacetamide was weighed in a round-bottomed flask. 3,3',5,5' -tetramethyl biphenyl bisphenol diglycidyl ether and a stirring bar are added into a round-bottom flask filled with a solvent, and the mixture is placed on a magnetic stirrer to be stirred for 10 min. In addition, 0.5897g of suberic acid, 0.0047g of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene was weighed out by an analytical balance. Suberic acid and 1,5, 7-triazabicyclo [4.4.0] dec-5-ene were then added to a round-bottomed flask containing solvent and monomers, and stirred on a magnetic stirrer for several minutes until the reagents were sufficiently dissolved. Next, a vacuum was pulled until there were no air bubbles in the solution. Finally, the solution was slowly poured into the mold, covered with a lid, and placed in an oven to cure at 145 ℃ for 12 h. After the reaction is finished, demoulding, preparing a sample according to the requirement, and fully drying the sample for use.
The performance index of the product is as follows:
after being reprocessed for 6min at 210 ℃ and 12MPa, the shape fixing rate is 96.22 percent, 97.12 percent, 97.04 percent and 97.11 percent after four shape memory cycles are carried out; the shape recovery rates were 100.65%, 99.52%, 99.97%, and 100.26%.
Example 2
Preparing raw materials:
solvent: 4.1800g of N, N-diethylacetamide;
a compound represented by the formula (II-1): 1.2000g of 3,3', 5' -tetramethylbiphenyl bisphenol diglycidyl ether;
a compound represented by the formula (III): suberic acid 0.5697 g;
catalyst: 0.0189g of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene.
The preparation method comprises the following steps:
first, 1.200g of 3,3',5,5' -tetramethylbiphenyl bisphenol diglycidyl ether was weighed using an analytical balance, and 4.1760g of N, N-dimethylacetamide was weighed in a round-bottomed flask. 3,3',5,5' -tetramethyl biphenyl bisphenol diglycidyl ether and a stirring bar are added into a round-bottom flask filled with a solvent, and the mixture is placed on a magnetic stirrer to be stirred for 10 min. In addition, 0.5897g of suberic acid, 0.0189g of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene was weighed out by an analytical balance. Suberic acid and 1,5, 7-triazabicyclo [4.4.0] dec-5-ene were then added to a round-bottomed flask containing solvent and monomers, and stirred on a magnetic stirrer for several minutes until the reagents were sufficiently dissolved. Next, a vacuum was pulled until there were no air bubbles in the solution. Finally, the solution was slowly poured into the mold, covered with a lid, and placed in an oven to cure at 145 ℃ for 12 h. After the reaction is finished, demoulding, preparing a sample according to the requirement, and fully drying the sample for use.
The performance index of the product is as follows:
after being reprocessed for 6min at the temperature of 210 ℃ and the pressure of 12MPa, four shape memory cycles are carried out, and the shape fixing rates are 96.69%, 97.12%, 97.55% and 97.69%; the shape recovery was 100.00%, 99.40%, 99.66%, 99.22%.
Example 3
Preparing raw materials:
solvent: 4.1800g of N, N-diethylacetamide;
a compound represented by the formula (II-1): 1.2000g of 3,3', 5' -tetramethylbiphenyl bisphenol diglycidyl ether;
a compound represented by the formula (III): suberic acid 0.5697 g;
catalyst: 0.0330g of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene.
The preparation method comprises the following steps:
first, 1.200g of 3,3',5,5' -tetramethylbiphenyl bisphenol diglycidyl ether was weighed using an analytical balance, and 4.1760g of N, N-dimethylacetamide was weighed in a round-bottomed flask. 3,3',5,5' -tetramethyl biphenyl bisphenol diglycidyl ether and a stirring bar are added into a round-bottom flask filled with a solvent, and the mixture is placed on a magnetic stirrer to be stirred for 10 min. In addition, 0.5897g of suberic acid, 0.0330g of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene was weighed out by an analytical balance. Suberic acid and 1,5, 7-triazabicyclo [4.4.0] dec-5-ene were then added to a round-bottomed flask containing solvent and monomers, and stirred on a magnetic stirrer for several minutes until the reagents were sufficiently dissolved. Next, a vacuum was pulled until there were no air bubbles in the solution. Finally, the solution was slowly poured into the mold, covered with a lid, and placed in an oven to cure at 145 ℃ for 12 h. After the reaction is finished, demoulding, preparing a sample according to the requirement, and fully drying the sample for use.
The performance index of the product is as follows:
after being reprocessed for 6min at 210 ℃ and 12MPa, the shape fixing rate is 96.76%, 96.94%, 96.91% and 96.98% after four shape memory cycles; the shape recovery was 99.99%, 99.90%, 100.28%, 99.80%.
Example 4
Preparing raw materials:
solvent: 4.1800g of N, N-diethylacetamide;
a compound represented by the formula (II-1): 1.2000g of 3,3', 5' -tetramethylbiphenyl bisphenol diglycidyl ether;
a compound represented by the formula (III): suberic acid 0.5697 g;
catalyst: 0.0471g of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene.
The preparation method comprises the following steps:
first, 1.200g of 3,3',5,5' -tetramethylbiphenyl bisphenol diglycidyl ether was weighed using an analytical balance, and 4.1760g of N, N-dimethylacetamide was weighed in a round-bottomed flask. 3,3',5,5' -tetramethyl biphenyl bisphenol diglycidyl ether and a stirring bar are added into a round-bottom flask filled with a solvent, and the mixture is placed on a magnetic stirrer to be stirred for 10 min. In addition, 0.0471g of octanedioic acid, 0.5897g, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene were weighed out using an analytical balance. Suberic acid and 1,5, 7-triazabicyclo [4.4.0] dec-5-ene were then added to a round-bottomed flask containing solvent and monomers, and stirred on a magnetic stirrer for several minutes until the reagents were sufficiently dissolved. Next, a vacuum was pulled until there were no air bubbles in the solution. Finally, the solution was slowly poured into the mold, covered with a lid, and placed in an oven to cure at 145 ℃ for 12 h. After the reaction is finished, demoulding, preparing a sample according to the requirement, and fully drying the sample for use.
The performance index of the product is as follows:
after being reprocessed for 6min at 210 ℃ and 12MPa, the shape fixing rate is 96.26%, 96.57%, 96.99% and 96.97% after four shape memory cycles are carried out; the shape recovery rates were 100.02%, 99.66%, 99.88%, and 99.78%.
Example 5
Preparing raw materials:
solvent: n, N-diethylacetamide; a compound represented by the formula (II-1): 3,3', 5' -tetramethylbiphenol diglycidyl ether; a compound represented by the formula (III): phthalic anhydride; catalyst: zinc acetylacetonate; curing accelerator: benzyl dimethylamine.
Wherein the molar ratio of the compound shown in the formula (II-1) to the compound shown in the formula (III) is 1: 0.8; the adding amount of the solvent is 50 percent of the total mass of the reaction system by mass; the amount of the catalyst added was expressed in terms of molar amount as 3% of the molar amount of M in the compound represented by formula (III); the amount of the curing accelerator added was 3% by mole of the compound represented by formula (III).
The preparation method comprises the following steps:
the differences from example 1 are: (1) the reaction monomers, the solvent, the catalyst and the curing accelerator are selected and used according to the preparation raw materials of the embodiment; (2) the curing accelerator and the suberic anhydride are added simultaneously; (3) placing the mixture into an oven to be cured for 10 hours at 150 ℃.
The performance index of the product is as follows:
after being reprocessed for 6min at 210 ℃ and 12MPa, the shape fixing rate is 93.13%, 93.23%, 93.10% and 93.15% after four shape memory cycles; the shape recovery was 97.01%, 97.03%, 97.05%, 97.10%.
Example 6
Preparing raw materials:
solvent: n, N-diethylacetamide; a compound represented by the formula (II-2): r is-N-; a compound represented by the formula (III): suberic acid; catalyst: and (3) zinc acetylacetonate.
Wherein the molar ratio of the compound shown in the formula (II-2) to the compound shown in the formula (III) is 1: 1.2; the addition amount of the solvent is 75% of the total mass of the reaction system by mass; the amount of the catalyst added was represented by a molar amount of 5% of the molar amount of-OM in the compound represented by the formula (III).
The preparation method comprises the following steps:
the differences from example 1 are: (1) the selection and the amount of the reaction monomer, the solvent and the catalyst are used according to the preparation raw materials of the embodiment; (2) placing into an oven to be cured for 8h at 150 ℃.
The performance index of the product is as follows:
after being reprocessed for 6min at 210 ℃ and 12MPa, the shape fixing rate is 92.26%, 92.21%, 92.35% and 92.42% after four shape memory cycles are carried out; the shape recovery was 96.99%, 96.03%, 96.08%, 96.01%.
Example 7
Preparing raw materials:
solvent: n, N-diethylacetamide; a compound represented by the formula (II-2): r is-COO-; a compound represented by the formula (III): phthalic anhydride; catalyst: 1,5, 7-triazabicyclo [4.4.0] dec-5-ene; curing accelerator: benzyl dimethylamine.
Wherein the molar ratio of the compound shown in the formula (II-2) to the compound shown in the formula (III) is 1: 1.0; the addition amount of the solvent was 65% by mass of the total mass of the reaction system; the addition amount of the catalyst is recorded as 1.2 percent of the molar amount of-OM in the compound shown in the formula (III); the amount of the curing accelerator added was 3% by mole of the compound represented by formula (III).
The preparation method comprises the following steps:
the differences from example 1 are: (1) the selection and the amount of the reaction monomer, the solvent and the catalyst are used according to the preparation raw materials of the embodiment; (2) the curing accelerator and the suberic anhydride are added simultaneously; (3) placing the mixture into an oven to be cured for 14h at 145 ℃.
The performance index of the product is as follows:
after being reprocessed for 6min at 210 ℃ and 12MPa, the shape fixing rate is 91.98%, 92.02%, 91.99% and 91.97% after four shape memory cycles; the shape recovery was 94.98%, 94.92%, 95.08%, 94.94%.
Example 8
Preparing raw materials:
solvent: n, N-diethylacetamide; a compound represented by the formula (II-2): r is selected from- (CH)3)CH＝CH2-; a compound represented by the formula (III): suberoyl halide; catalyst: 1,5, 7-triazabicyclo [4.4.0]Dec-5-ene; curing accelerator: benzyl dimethylamine.
Wherein the molar ratio of the compound shown in the formula (II-2) to the compound shown in the formula (III) is 1: 1.0; the addition amount of the solvent was 65% by mass of the total mass of the reaction system; the addition amount of the catalyst was recorded as a molar amount which was 2.6% of the molar amount of-OM in the compound represented by the formula (III); the amount of the curing accelerator added was 3% by mole of the compound represented by formula (III).
The preparation method comprises the following steps:
the differences from example 1 are: (1) the reaction monomers, the solvent, the catalyst and the curing accelerator are selected and used according to the preparation raw materials of the embodiment; (2) simultaneously adding a curing accelerator and suberoyl halide; (3) placing the mixture into an oven to be cured for 12 hours at 145 ℃.
The performance index of the product is as follows:
after being reprocessed for 6min at 210 ℃ and 12MPa, the shape fixing rate is 91.13%, 91.21%, 91.18% and 91.15% after four shape memory cycles; the shape recovery rates were 95.81%, 95.83%, 95.90%, 95.91%.
Examples of the experiments
The reprocessable shape memory epoxy resin prepared in example 4 was subjected to infrared spectroscopic measurements, the results of which are shown in FIG. 1, and it can be seen from FIG. 1 that the compound represented by formula (I) was prepared by the preparation method of the present invention.
The results of the above examples show that: the reworkable shape memory epoxy resin of the present invention has good shape memory properties and good reworking properties. And the preparation process is simple and is convenient for realizing industrialization.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A reworkable shape memory epoxy resin comprising orientable mesogens and dynamically exchangeable ester linkages; the orientable mesogen includes any one or more of biphenyl, azo, aryl ester and alpha-methyl styrene.
2. The reworkable shape memory epoxy resin of claim 1, wherein the epoxy resin has the formula (I-1) or (I-2):
wherein R is selected from the group consisting of-N-, -COO- (C)6H4) -OOC-or- (CH)3)CH＝CH2-；R1Is selected from CH3Or H.
3. The method for preparing a reprocessable shape memory epoxy resin according to claim 2, which is characterized in that the shape memory epoxy resin is prepared by polymerizing a compound represented by the formula (II-1) or (II-2) with a compound represented by the formula (III) in the presence of a catalyst,
wherein R in the formula (II-2) is selected from-N ═ N-, -COO- (C)6H4) -OOC-or- (CH)3)CH＝CH2-；
The compound shown in the formula (III) is selected from one or a mixture of more of suberic acid, suberoyl halide or suberic dianhydride.
4. The method of preparing a reworkable shape memory epoxy resin of claim 3 comprising the steps of:
adding a compound shown as a formula (II-1) or a formula (II-2) into a solvent, stirring and dissolving, adding a compound shown as a formula (III), finally adding a catalyst, stirring and dissolving at room temperature to obtain a mixed solution;
vacuumizing to remove air, slowly pouring the mixed solution into a mold, curing at high temperature for a period of time, and demolding.
5. The method for preparing a reprocessable shape memory epoxy resin according to claim 3 or 4, wherein the molar ratio of the compound of formula (II-1) or (II-2) to the compound of formula (III) is 1:0.8 to 1.2.
6. The method of claim 4, wherein the solvent is N, N-dimethylacetamide.
7. The method for preparing a reworkable shape memory epoxy resin according to claim 4, wherein the solvent is added in an amount by mass of 50 to 75% based on the total mass of the reaction system.
8. The method of claim 3 or 4, wherein the catalyst is selected from 1,5, 7-triazabicyclo [4.4.0] dec-5-ene or zinc acetylacetonate.
9. The method of claim 3 or 4, wherein the catalyst is added in an amount of 0.5 to 5.0 mol% based on-OM in the compound of formula (III).
10. Use of a reworkable shape memory epoxy resin according to any one of claims 1 to 2.
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