CN115536814A - Shape memory epoxy resin and preparation method and application thereof - Google Patents
Shape memory epoxy resin and preparation method and application thereof Download PDFInfo
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- CN115536814A CN115536814A CN202211185146.9A CN202211185146A CN115536814A CN 115536814 A CN115536814 A CN 115536814A CN 202211185146 A CN202211185146 A CN 202211185146A CN 115536814 A CN115536814 A CN 115536814A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 70
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 34
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000004593 Epoxy Substances 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 229920000768 polyamine Polymers 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 43
- 238000002156 mixing Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- CYCBPQPFMHUATH-UHFFFAOYSA-N 4-(oxiran-2-ylmethoxy)butan-1-ol Chemical compound OCCCCOCC1CO1 CYCBPQPFMHUATH-UHFFFAOYSA-N 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 12
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 5
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 3
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 3
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 3
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims 2
- 230000007334 memory performance Effects 0.000 abstract description 7
- -1 benzene ring amine Chemical class 0.000 abstract description 5
- 239000000463 material Substances 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 238000007142 ring opening reaction Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 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 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- ITWBWJFEJCHKSN-UHFFFAOYSA-N 1,4,7-triazonane Chemical compound C1CNCCNCCN1 ITWBWJFEJCHKSN-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012781 shape memory material Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000002076 thermal analysis method 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
-
- 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/226—Mixtures of di-epoxy compounds
-
- 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/308—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing halogen atoms
-
- 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
-
- 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 provides a shape memory epoxy resin and a preparation method and application thereof, wherein the shape memory epoxy resin comprises the following components in parts by weight: 40-60 parts of glycerol ether containing two epoxy monomers, 1-10 parts of glycidyl ether containing two or more aliphatic groups, 4-8 parts of benzene ring amine-containing curing agent and 1-3 parts of aliphatic polyamine. The shape memory epoxy resin provided by the invention has a flexible chain segment and a rigid group, forms a three-dimensional cross-linked network structure with higher strength and higher toughness through hydrogen bonds, has good variable stiffness property and shape memory performance, has the elongation at break of 1000% or more, and can be applied to the fields of aerospace and the like.
Description
Technical Field
The invention relates to the technical field of shape memory materials, in particular to shape memory epoxy resin and a preparation method and application thereof.
Background
With the development of industries such as aviation, aerospace, electronics and the like to high speed and high integration, people have higher and higher requirements on materials, and the materials are required to have high toughness and ultrahigh tensile property in addition to the requirements on high temperature resistance, chemical corrosion resistance and the like, so that the requirement on large deformation is met.
At present, due to the defects of poor high temperature resistance, poor brittleness after curing and the like, the shape memory epoxy resin has high internal stress, and the thermosetting shape memory epoxy resin has small deformation caused by a cured three-dimensional network structure, so that the application of the thermosetting shape memory epoxy resin in the aerospace industry is limited. Generally, if the deformation amount of the material is large, the rigidity is small, the toughness is poor, and the overstretching is difficult. That is, toughness and strength of a material are often conflicting issues. How to make the material have high toughness and high strength is a problem of performance contradiction which is difficult to solve at present. Therefore, it is necessary to explore how the shape memory epoxy resin has both rigidity and toughness, and improves comprehensive performance, so that the shape memory epoxy resin can be applied to the fields of aerospace and the like.
Disclosure of Invention
The invention aims to provide the shape memory epoxy resin, the preparation method and the application thereof, which can give consideration to both rigidity and toughness and have good comprehensive performance, so that the shape memory epoxy resin can be applied to the fields of aerospace and the like.
In order to solve the problems, the invention provides shape memory epoxy resin which comprises the following components in parts by weight: 40-60 parts of glycerol ether containing two epoxy monomers, 1-10 parts of glycidyl ether containing two or more aliphatic groups, 4-8 parts of benzene ring amine-containing curing agent and 1-3 parts of aliphatic polyamine.
Preferably, the glycidyl ether containing two epoxy monomers comprises one or more of bisphenol a diglycidyl ether, bisphenol S diglycidyl ether, and bisphenol F diglycidyl ether.
Preferably, the glycidyl ether of two or more aliphatic groups includes one of ethylene glycol diglycidyl ether, 1, 4-butanediol glycidyl ether, and 1, 6-hexanediol diglycidyl ether.
Preferably, the benzene ring-containing amine curing agent includes one of m-xylylenediamine, m-phenylenediamine, and diaminodiphenylmethane.
Preferably, the aliphatic polyamine comprises one of diethylenetriamine, triethylenetetramine and tetramethylenediamine.
Preferably, the shape memory epoxy resin is a three-dimensional cross-linked network structure, and the three-dimensional cross-linked network structure comprises a flexible chain structure, a rigid group and a hydrogen bond.
Preferably, the shape memory epoxy resin has an elongation at break of greater than or equal to 1000%.
The shape memory epoxy resin is obtained through the glycidyl ether containing two epoxy monomers, the glycidyl ether containing two or more aliphatic groups, the phenylcyclo amine curing agent and the aliphatic polyamine, the glycidyl ether containing two epoxy monomers is beneficial to forming a three-dimensional network structure, the glycidyl ether containing two or more aliphatic groups can improve the crosslinking density and can be used as a chain extender, the phenylcyclo amine curing agent has a rigid group, can improve the rigidity of a polymer chain and improve the shape memory performance, the ring opening of the aliphatic polyamine can form a three-dimensional network structure, and contains multi-active hydrogen, so that the crosslinking density can be improved through chain extension, in addition, the glycidyl ether containing two or more aliphatic groups can provide a flexible chain segment for the epoxy resin, the phenylcyclo amine curing agent can provide a rigid group, and ether bonds in the glycidyl ether containing two or more aliphatic groups can form hydrogen bonds with hydroxyl groups formed after the ring opening of the glycidyl ether containing two or more epoxy monomers; namely, the shape memory epoxy resin provided by the invention has a flexible chain segment and a rigid group, forms a three-dimensional cross-linked network structure with higher strength and higher toughness through hydrogen bonds, has good variable stiffness characteristic and shape memory performance, has the elongation at break of 1000% or more, and can be applied to the fields of aerospace and the like.
In another aspect, the present invention also provides a method for preparing the shape memory epoxy resin, which is used for preparing the shape memory epoxy resin, and comprises the following steps:
s1, mixing a benzene ring-containing amine curing agent and aliphatic polyamine to obtain a first mixture;
s2, mixing glycerol ether containing two epoxy monomers and glycidyl ether containing two or more aliphatic groups to obtain a second mixture;
and S3, mixing the first mixture and the second mixture, and heating and curing to obtain the shape memory epoxy resin.
Preferably, the step S3 includes:
and mixing the first mixture and the second mixture, keeping the mixture at 80 ℃ for 3h, then heating to 120 ℃ for 3h, and then heating to 150 ℃ for 8h to obtain the shape memory epoxy resin.
The shape memory epoxy resin can be prepared by a solvent-free system, the production cost can be reduced, the product quality is improved, the safety and the stability are better, and the prepared shape memory epoxy resin has good shape memory performance and simultaneously has rigidity and toughness.
In a further aspect, the present invention provides the use of a shape memory epoxy resin as described above in the aerospace industry.
The shape memory epoxy resin provided by the invention has rigidity and toughness, has good shape memory performance, can have the characteristic of changing the shape under the excitation of external conditions, has multi-dimensional designability, and can adapt to complex environments in aerospace environments.
Drawings
FIG. 1 is a schematic structural diagram of a shape memory epoxy in an embodiment of the present invention;
FIG. 2 is a schematic flow chart of a method for preparing a shape memory epoxy resin according to an embodiment of the present invention;
FIG. 3 is a static tensile stress-strain plot of a shape memory epoxy in accordance with an embodiment of the present invention;
FIG. 4 is a graph of dynamic thermomechanical analysis of a shape memory epoxy in an embodiment of the present disclosure.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, specific embodiments thereof are described in detail below.
It should be noted that the features in the embodiments of the present invention may be combined with each other without conflict. The terms "comprising," "including," "containing," and "having" are intended to be inclusive, i.e., that additional steps and other ingredients may be added without affecting the result. The above terms encompass the terms "consisting of (8230); 8230; composition" and "consisting essentially of (8230); 8230; composition". Materials, equipment and reagents are commercially available unless otherwise specified.
The embodiment of the invention provides shape memory epoxy resin which comprises the following components in parts by weight: 40-60 parts of glycerol ether containing two epoxy monomers, 1-10 parts of glycidyl ether containing two or more aliphatic groups, 4-8 parts of benzene ring amine-containing curing agent and 1-3 parts of aliphatic polyamine.
The glycidyl ether containing two epoxy monomers is beneficial to forming a three-dimensional network structure, the glycidyl ether containing two or more aliphatic groups can improve the crosslinking density and can be used as a chain extender, the benzene ring-containing amine curing agent has a rigid group and can improve the rigidity of a molecular chain and improve the shape memory performance, the aliphatic polyamine open ring can form the three-dimensional network structure and contains multiple active hydrogens, the chain extension can be carried out, so that the crosslinking density is improved, in addition, the glycidyl ether containing two or more aliphatic groups can provide a flexible chain segment for the epoxy resin, the benzene ring-containing amine curing agent can provide the rigid group, and ether bonds in the glycidyl ether containing two or more aliphatic groups can form hydrogen bonds with hydroxyl groups formed after the glycidyl ether containing two epoxy monomers open ring.
Specifically, the glycidyl ether containing two epoxy monomers comprises one or more of bisphenol a diglycidyl ether, bisphenol S diglycidyl ether, and bisphenol F diglycidyl ether;
the glycidyl ether of two or more aliphatic groups comprises one of ethylene glycol diglycidyl ether, 1, 4-butanediol glycidyl ether and 1, 6-hexanediol diglycidyl ether;
the curing agent containing benzene ring amines comprises one of m-xylylenediamine, m-phenylenediamine and diaminodiphenylmethane;
the aliphatic polyamine comprises one of diethylenetriamine, triethylenetetramine and tetramethylenediamine.
It should be noted that the components and the mixture ratio of the components provided by the embodiment of the present invention can obtain the desired shape memory epoxy resin, and the ratio of the components is different, and when different components are selected, the properties of the obtained shape memory epoxy resin also have a certain difference, for example, 1, 4-butanediol glycidyl ether can provide more hydroxyl content, when 1, 4-butanediol glycidyl ether is used, the hydrogen bonds between the main chains in the obtained shape memory epoxy resin are more, thereby showing better strength and toughness, when 1, 6-hexanediol diglycidyl ether is used, because it has longer flexible chain, the resistance between molecules is smaller, the molecules are easy to move, the obtained shape memory epoxy resin can show more tensile property, but the strength is reduced.
The structure of the shape memory epoxy resin provided by the embodiment of the invention is shown in fig. 1, and a good three-dimensional cross-linked network structure is formed by curing four components, wherein the three-dimensional cross-linked network structure comprises a flexible chain structure, a rigid group and a hydrogen bond, the flexible chain structure is provided by glycidyl ether containing two or more aliphatic groups, the rigid group is provided by a benzene ring amine curing agent, hydroxyl formed by ring opening of epoxy monomers in the glycidyl ether containing two epoxy monomers can form a hydrogen bond with ether bonds in the glycidyl ether containing two or more aliphatic groups, and thus the toughness of the three-dimensional cross-linked network structure is improved.
In the shape memory epoxy resin provided by the embodiment of the invention, the ether bond and the hydroxyl group formed by ring opening of the epoxy monomer are both located on the main chain, and the hydrogen bond formed between the ether bond and the hydroxyl group is also located between the main chains, so that the toughness of the material can be improved through the hydrogen bond between the main chains, and the material has both high rigidity and high toughness.
The shape memory epoxy resin provided by the embodiment of the invention has the elongation at break of more than or equal to 1000%, and has the performances of super-tension and high toughness, so that the shape memory epoxy resin can be suitable for complex environments such as aerospace and the like.
As shown in fig. 2, another embodiment of the present invention provides a method for preparing a shape memory epoxy resin, for preparing the shape memory epoxy resin, comprising the steps of:
s1, mixing a benzene ring-containing amine curing agent and aliphatic polyamine to obtain a first mixture;
s2, mixing glycerol ether containing two epoxy monomers and glycidyl ether containing two or more aliphatic groups to obtain a second mixture;
and S3, mixing the first mixture and the second mixture, and heating and curing to obtain the shape memory epoxy resin.
Specifically, in the step S1, benzene-ring-containing amine curing agent and aliphatic polyamine are mixed according to a proportion, stirred and ultrasonically oscillated for 10-20min until the solution is transparent and uniform to obtain a first mixture;
in the step S2, mixing glycerol ether containing two epoxy monomers and glycidyl ether containing two or more aliphatic groups according to a ratio, heating to 80 ℃, stirring for 20min, and then vacuumizing to remove bubbles until the solution is transparent and uniform to obtain a second mixture;
in the step S3, the first mixture and the second mixture are mixed and poured into a mould, and heating and curing procedures of 80 ℃/3h, 120 ℃/3h and 150 ℃/8h are set, namely heating is carried out for 3h at 80 ℃, then heating is carried out for 3h at 120 ℃, then heating is carried out for 8h at 150 ℃, and the heating rate is controlled to be 5 ℃/min in the heating process.
The preparation method of the shape memory epoxy resin provided by the invention can prepare the shape memory epoxy resin through a solvent-free system, can reduce the production cost, improves the product quality, and has better safety and stability.
A further embodiment of the present invention provides the use of a shape memory epoxy resin as described above in the aerospace industry.
The shape memory epoxy resin provided by the embodiment of the invention has rigidity and toughness, has good shape memory performance, can have the characteristic of changing the shape under the excitation of external conditions, has multi-dimensional designability, and can adapt to the complex environment in the aerospace environment.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are examples of experimental procedures not specified under specific conditions, generally according to the conditions recommended by the manufacturer.
Example 1
1.1, stirring 2.3g of diaminodiphenylmethane and 0.7g of diethylenetriamine, and uniformly mixing by ultrasonic oscillation to obtain a first mixture;
1.2, pouring 20g of bisphenol F diglycidyl ether and 4.2g of 1, 4-butanediol glycidyl ether into a beaker, and melting at 80 ℃ and fully and uniformly mixing to obtain a second mixture;
1.3, pouring the first mixture and the second mixture into a beaker, uniformly stirring and mixing, and then putting into a vacuum box to remove bubbles to obtain a composition;
and 1.4, transferring the composition into a mold, feeding the mold into a high-temperature curing furnace, and setting heating and curing programs of 80 ℃/3h, 120 ℃/3h and 150 ℃/8h, wherein the heating rate is controlled at 5 ℃/min, so as to obtain the shape memory epoxy resin.
Example 2
2.1, stirring 2.9g of diaminodiphenylmethane and 0.83g of diethylenetriamine, and uniformly mixing by ultrasonic oscillation to obtain a first mixture;
2.2, pouring 20g of bisphenol F diglycidyl ether and 4.8g of 1, 4-butanediol glycidyl ether into a beaker, and melting at 80 ℃ and fully and uniformly mixing to obtain a second mixture;
2.3, pouring the first mixture and the second mixture into a beaker, uniformly stirring and mixing, and then putting into a vacuum box to remove bubbles to obtain a composition;
2.4, transferring the composition into a mold, feeding the mold into a high-temperature curing furnace, and setting heating curing procedures of 80 ℃/3h, 120 ℃/3h and 150 ℃/8h, wherein the heating rate is controlled at 5 ℃/min, so as to obtain the shape memory epoxy resin.
Example 3
3.1, stirring 3.6g of m-xylylenediamine and 0.4g of triethylene triamine, and uniformly mixing by ultrasonic oscillation to obtain a first mixture;
3.2, pouring 20g of bisphenol F diglycidyl ether and 4.9g of 1, 6-hexanediol diglycidyl ether into a beaker, and melting at 80 ℃ and fully and uniformly mixing to obtain a second mixture;
3.3, pouring the first mixture and the second mixture into a beaker, uniformly stirring and mixing, and then putting into a vacuum box to remove bubbles to obtain the composition;
3.4, transferring the composition into a mold, feeding the mold into a high-temperature curing furnace, and setting heating curing procedures of 80 ℃/3h, 120 ℃/3h and 150 ℃/8h, wherein the heating rate is controlled at 5 ℃/min, so as to obtain the shape memory epoxy resin.
Experimental example 1
The mechanical properties of the shape memory epoxy resin samples obtained in examples 1, 2 and 3 were measured using a static universal tensile machine, the samples in the three examples all being dumbbell-shaped, having a thickness of 2-3mm and a width of 8mm, and a tensile speed of 2mm/min at the time of the test.
The test results are shown in fig. 3, in which the abscissa in fig. 3 represents the elongation at break (the ratio of the elongation after stretching to the length before stretching when the sample is pulled apart by an external force is referred to as the elongation at break) in units, and the ordinate represents the tensile strength (in the tensile test, the maximum tensile stress applied to the sample until breakage is referred to as the tensile strength) in units of MPa.
As can be seen from fig. 3, the shape-memory epoxy resins obtained in examples 1, 2 and 3 all had an elongation at break of 1000% or more and a tensile strength of 20MPa or more, and had good strength and tensile properties. Wherein, because the main chain of the 1, 4-butanediol glycidyl ether is relatively short, and the 1, 6-hexanediol diglycidyl ether is relatively long, when the 1, 4-butanediol glycidyl ether is adopted, the hydroxyl content between the main chains with the same length is higher, so that more hydrogen bonds can be generated, and the obtained shape memory epoxy resin also has the effect of strengthening and toughening along with the increase of the adding amount of the 1, 4-butanediol glycidyl ether, compared with the example 1, the example 2 adds more 1, 4-butanediol glycidyl ether, so that the breaking elongation is larger; when 1, 6-hexanediol diglycidyl ether is used, the elongation at break of the shape memory epoxy resin in example 3 is maximized because the flexible chain in the formed shape memory epoxy resin is longer due to the longer main chain, the intermolecular resistance is small, and the molecules are easily moved, thereby exhibiting greater tensile properties.
Experimental example 2
The thermomechanical properties of the shape memory epoxy resins obtained in example 1, example 2 and example 3 were investigated using dynamic mechanical thermal analysis (DMA). The size of the shape memory epoxy resin samples obtained in example 1, example 2 and example 3 was 40mm × 4mm × 2mm. The temperature range was set to 25-150 ℃.
The results are shown in fig. 4, in which the abscissa in fig. 4 represents the temperature in deg.c, the temperature range is 25-150 deg.c, the left ordinate in fig. 4 represents the storage modulus in MPa, and the right ordinate in the figure represents the loss factor, the three upper curves in fig. 4 correspond to the variation of the storage modulus, and the three lower curves correspond to the variation of the loss factor. It should be noted that the peak value of the dissipation factor is the Tg (glass transition temperature) of the corresponding sample.
As can be seen from fig. 4, the shape-memory epoxy resins obtained in example 1, example 2 and example 3 gradually decreased in Tg and also gradually decreased in storage modulus. This is mainly due to the fact that the amount of 1, 4-butanediol glycidyl ether added in example 1 is less than that added in example 2, and the Tg decreases as the number of flexible chains in the shape-memory epoxy resin increases; in addition, 1, 6-hexanediol diglycidyl ether, which was added in example 3, had a longer main chain, so that the length of the flexible chain in the resulting shape-memory epoxy resin was increased, and also showed a tendency to decrease the Tg. The storage modulus decreases with decreasing Tg, and as can be seen from fig. 4, the trend of storage modulus is the same as the trend of loss factor.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be effected therein by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present disclosure, and these changes and modifications are intended to be within the scope of the present disclosure.
Claims (10)
1. The shape memory epoxy resin is characterized by comprising the following components in parts by weight: 40-60 parts of glycerol ether containing two epoxy monomers, 1-10 parts of glycidyl ether containing two or more aliphatic groups, 4-8 parts of benzene ring-containing amine curing agent and 1-3 parts of aliphatic polyamine.
2. The shape memory epoxy resin of claim 1, wherein the glycidyl ether of two epoxy monomers comprises one or more of diglycidyl ether of bisphenol a, diglycidyl ether of bisphenol S, and diglycidyl ether of bisphenol F.
3. The shape memory epoxy resin according to claim 1, wherein the glycidyl ether of two or more aliphatic groups comprises one of ethylene glycol diglycidyl ether, 1, 4-butanediol glycidyl ether, and 1, 6-hexanediol diglycidyl ether.
4. The shape memory epoxy resin according to claim 1, wherein the benzene ring-containing amine-based curing agent comprises one of m-xylylenediamine, m-phenylenediamine, and diaminodiphenylmethane.
5. The shape memory epoxy of claim 1, wherein the aliphatic polyamine comprises one of diethylenetriamine, triethylenetetramine, and tetramethylenediamine.
6. The shape memory epoxy resin according to claim 1, wherein the shape memory epoxy resin is a three-dimensional cross-linked network structure including a flexible chain structure, a rigid group, and a hydrogen bond.
7. The shape memory epoxy of claim 1, wherein the shape memory epoxy has an elongation at break of greater than or equal to 1000%.
8. A method for preparing a shape memory epoxy resin for use in preparing a shape memory epoxy resin according to any one of claims 1 to 7, comprising the steps of:
step S1, mixing a benzene-ring-containing amine curing agent and aliphatic polyamine to obtain a first mixture;
s2, mixing glycerol ether containing two epoxy monomers and glycidyl ether containing two or more aliphatic groups to obtain a second mixture;
and S3, mixing the first mixture and the second mixture, and heating and curing to obtain the shape memory epoxy resin.
9. The method of preparing a shape memory epoxy resin according to claim 8, wherein the step S3 comprises:
and mixing the first mixture and the second mixture, keeping the mixture at 80 ℃ for 3h, heating to 120 ℃ for 3h, and heating to 150 ℃ for 8h to obtain the shape memory epoxy resin.
10. Use of a shape memory epoxy resin according to claim 8 or 9 in the field of the aerospace industry.
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| CN101100545A (en) * | 2007-06-29 | 2008-01-09 | 哈尔滨工业大学 | Shape memory epoxy resin system |
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| CN114773782A (en) * | 2022-04-07 | 2022-07-22 | 深圳大学 | Preparation method and application of thermoplastic shape memory epoxy resin |
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| CN111961190A (en) * | 2020-08-27 | 2020-11-20 | 哈尔滨工业大学 | Shape memory epoxy resin with narrow temperature transition range and preparation method thereof |
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