CN108250412A - A kind of shape memory polymer networks formation system of reversible curing lock based on disulfide bond and preparation method thereof - Google Patents
A kind of shape memory polymer networks formation system of reversible curing lock based on disulfide bond and preparation method thereof Download PDFInfo
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- CN108250412A CN108250412A CN201810085882.4A CN201810085882A CN108250412A CN 108250412 A CN108250412 A CN 108250412A CN 201810085882 A CN201810085882 A CN 201810085882A CN 108250412 A CN108250412 A CN 108250412A
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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
- C08G59/66—Mercaptans
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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
- C08G59/68—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 catalysts used
- C08G59/686—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 catalysts used containing nitrogen
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Abstract
A kind of shape memory polymer networks formation system of reversible curing lock based on disulfide bond and preparation method thereof, belongs to shape-memory material field.The method is as follows：Mercaptan, epoxy resin, catalyst are sufficiently mixed reaction, obtain first stage polymer；Shape memory and tension failure research are carried out to first stage polymer；First stage polymer is placed in oxidant and is reacted；Shape memory and tension failure research are carried out to the polymer of disulfide bond crosslinking after oxidation；The polymer of disulfide bond crosslinking after oxidation is washed, vacuum drying；It will be reacted in dried polymer merging reducing agent, washes clean, vacuum drying；Shape memory and tension failure research are carried out to dried polymer.The present invention can prepare a kind of polymer with excellent in shape memory performance；Utilization can be continued cycling through, the contradiction sex chromosome mosaicism between the mechanics of materials, heat resistance and shape-memory properties and cycling and reutilization can be efficiently solved.
Description
Technical field
The invention belongs to shape-memory material fields, and in particular to a kind of simple for process, base of easy control of reaction conditions
In the oxidizing sulfydryl of the utilization of mercaptan, epoxy resin, the lock of the reversible curing based on disulfide bond of reducing agent Reduction of Disulfide
Shape memory polymer networks formation system and preparation method thereof.
Background technology
In general shape-memory polymer is by certain stimulation form, polymer can be made to be changed by original-shape
For temporary shapes, temporary shapes can be returned to original-shape by certain stimulation again.The two-stage shape memory of reaction gathers
Polymeric network forms system, and mainly obtained is in second-stage solidification reaction, can cure what be prepared by the first stage
Intermediate state polymer with shape-memory properties.By using the shape-memory properties of intermediate state polymer, then pass through second
The reaction in stage further improves the crosslink density and mechanical property of polymer, obtains stable most final state polymer.Such shape
It is by Devatha P. Nair of Univ Colorado-Boulder USA etc. earliest in 2012 that shape memory polymer, which forms system,（Adv.
Funct. Mater.2012 22 1502-10）Report.They report a kind of be based on by using mercaptan and acrylic resin
The shape memory polymer networks of heat/light two-stage reaction for raw material form system, to the shape-memory properties of the material,
Application in terms of optical device, which has been done, tentatively to be probed into.Although their report is very significant, still there are some aspects to have
It is to be hoisted, as material circulating resources the problems such as.Other reports（Advanced Materials. 2014,26 (48):
8114-8119）Although it is contemplated that the above problem, it is based on commercial nafion film systems, although such material performance
It is a kind of commercial product that the shortcomings that excellent, but maximum, which is exactly it, and production technology is rested in fewer companies hand, and price is relatively
It is expensive.
Invention content
It is deposited the purpose of the present invention is to solve traditional about second order solidification shape memory polymer networks formation system
Resources circulation, develop and utilize the problem of, provide it is a kind of based on disulfide bond reversible curing lock shape-memory polymer
Network former system and preparation method thereof.
To achieve the above object, the technical solution that the present invention takes is as follows：
A kind of shape memory polymer networks of the reversible curing lock based on disulfide bond form system, the shape memory polymers
Object Network former system is according to mass percent by mercaptan 15-35%, epoxy resin 60-80%, catalyst 0.1-4%, oxidant
0.1-4%, reducing agent 0.01-2% are formed.
A kind of shape memory polymer networks of the above-mentioned reversible curing lock based on disulfide bond form the preparation side of system
Method, described method includes following steps：
Step 1：Mercaptan, epoxy resin, catalyst are sufficiently mixed uniformly, 0.1 ~ 20h is reacted at a temperature of 0 ~ 200 DEG C, is obtained
First stage polymer；
Step 2：Shape memory research is carried out to the first stage polymer that step 1 obtains：The first rank is determined by DMA first
The glass transition temperature of section polymerTg 1 ,Tg 1 It is 10 ~ 70 DEG C, tests the shape memory fixed rate of first stage polymerR f1
With shape memory response rateR r1 ,R f1 WithR r1 It is all higher than 90%；
Step 3：The test of tension failure performance is carried out to the first stage polymer that step 1 obtains, tension failure rate is denoted as
S1, S1 are 0.1 ~ 90%；
Step 4：First stage polymer is placed in oxidant, the two 1 ~ 120h of reaction is made at a temperature of 0 ~ 100 DEG C, is obtained
The polymer of disulfide bond crosslinking after oxidation with methanol by the polymer washes clean of disulfide bond crosslinking after oxidation, removes impurity,
1 ~ 96h is dried in vacuo at a temperature of 25 ~ 150 DEG C；
Step 5：DMA tests are carried out to the polymer of disulfide bond crosslinking after oxidation, determine polymerTg 2 ,Tg 2 It is 20 ~ 130
DEG C, and its tensile property is tested, tension failure rate is denoted as S2, and S2 is 0.1 ~ 70%；
Step 6：By in the polymer of disulfide bond crosslinking merging reducing agent, 1 ~ 120h is reacted at a temperature of 0 ~ 100 DEG C, obtain by
Disulfide bond reduction is the polymer of sulfydryl, then by polymer methanol washes clean, it is dried in vacuo 1 under the conditions of 25 ~ 150 DEG C ~
96h；
Step 7：Polymer after being restored to step 6 carries out DMA tests, determines polymerTg 3 ,Tg 3 It is 10 ~ 70 DEG C, surveys
The shape memory fixed rate of polymer after examination reductionR f3 With shape memory response rateR r3 ,R f3 WithR r3 It is all higher than 90%；
And tensile property test is carried out to it, tension failure rate is denoted as S3, and S3 is 0.1 ~ 90%；
Step 8：After being completed, following correspondence is obtained：Tg 1 ≈Tg 3 < Tg 2 , S1≈S3>S2, R f1 ≈ R f3 , R r1 ≈ R r3 。
The present invention is relative to the advantageous effect of the prior art：A kind of reversible curing lock based on disulfide bond of the present invention
Shape memory polymer networks form system can prepare a kind of gathering with excellent in shape memory performance by the first stage
Close object；The disulfide bond of chemical crosslinking is formed by aoxidizing sulfydryl, the polymer with bigger crosslink density can be obtained, improves material
The mechanical property and service life of material；Disulfide bond can be reduced into sulfydryl by reducing agent again, reach the crosslinked effect of solution, finally
The polymer being reduced still has preferable shape-memory properties, can continue cycling through utilization.Such method can be solved effectively
The certainly contradiction sex chromosome mosaicism between the mechanics of materials, heat resistance and shape-memory properties and cycling and reutilization.
Description of the drawings
Fig. 1 is raw materials used structure chart in embodiment 1.
Fig. 2 is redox mechanism schematic diagram in embodiment 1.
Fig. 3 is reversible crosslink process schematic of the present invention.
Specific embodiment
Technical scheme of the present invention is further described with reference to the accompanying drawings and examples, however, it is not limited to this,
It is every technical solution of the present invention to be modified or equivalent replacement, it, should all without departing from the scope of technical solution of the present invention
Cover among protection scope of the present invention.
Specific embodiment one：What present embodiment was recorded is a kind of shape memory of the reversible curing lock based on disulfide bond
Polymer network forms system, and the shape memory polymer networks form system according to mass percent by by mercaptan 15-
35%th, epoxy resin 60-80%, catalyst 0.1-4%, oxidant 0.1-4%, reducing agent 0.01-2% compositions.
Specific embodiment two：A kind of shape note of the lock of the reversible curing based on disulfide bond described in specific embodiment one
Recall the preparation method that polymer network forms system, described method includes following steps, as shown in Figure 3：
Step 1：Mercaptan, epoxy resin, catalyst are sufficiently mixed uniformly, 0.1 ~ 20h is reacted at a temperature of 0 ~ 200 DEG C, is obtained
First stage polymer；
Step 2：Shape memory research is carried out to the first stage polymer that step 1 obtains：The first rank is determined by DMA first
The glass transition temperature of section polymerTg 1 ,Tg 1 It is 10 ~ 70 DEG C, tests the shape memory fixed rate of first stage polymerR f1
With shape memory response rateR r1 ,R f1 WithR r1 It is all higher than 90%；
Step 3：The test of tension failure performance is carried out to the first stage polymer that step 1 obtains, tension failure rate is denoted as
S1, S1 are 0.1 ~ 90%；
Step 4：First stage polymer is placed in oxidant, the two 1 ~ 120h of reaction is made at a temperature of 0 ~ 100 DEG C, is obtained
The polymer of disulfide bond crosslinking after oxidation with methanol by the polymer washes clean of disulfide bond crosslinking after oxidation, removes impurity,
1 ~ 96h is dried in vacuo at a temperature of 25 ~ 150 DEG C；
Step 5：DMA tests are carried out to the polymer of disulfide bond crosslinking after oxidation, determine polymerTg 2 , and to its draftability
It can be tested, tension failure rate is denoted as S2, and S2 is 0.1 ~ 70%；
Step 6：By in the polymer of disulfide bond crosslinking merging reducing agent, 1 ~ 120h is reacted at a temperature of 0 ~ 100 DEG C, obtain by
Disulfide bond reduction is the polymer of sulfydryl, then by polymer methanol washes clean, it is dried in vacuo 1 under the conditions of 25 ~ 150 DEG C ~
96h；
Step 7：Polymer after being restored to step 6 carries out DMA tests, determines polymerTg 3 ,Tg 3 It is 10 ~ 70 DEG C, surveys
The shape memory fixed rate of polymer after examination reductionR f3 With shape memory response rateR r3 ,R f3 WithR r3 It is all higher than 90%；
And tensile property test is carried out to it, tension failure rate is denoted as S3, and S3 is 0.1 ~ 90%；
Step 8：After being completed, following correspondence is obtained：Tg 1 ≈Tg 3 < Tg 2 , S1≈S3>S2, R f1 = R f3 , R r1 = R r3 。
Specific embodiment three：A kind of shape note of reversible curing lock based on disulfide bond described in specific embodiment two
Recall the preparation method that polymer network forms system, in step 1, the mercaptan is four（3- mercaptopropionic acids）Pentaerythritol ester
Or propane -1,2, tri- mercaptan of 3-, the epoxy resin are epoxy resin E44 or epoxy resin E51, the catalyst is three
Ethamine.
Specific embodiment four：A kind of shape note of reversible curing lock based on disulfide bond described in specific embodiment two
Recall the preparation method that polymer network forms system, in step 3, the oxidant is ferric trichloride or iodine.
Specific embodiment five：A kind of shape note of reversible curing lock based on disulfide bond described in specific embodiment two
Recall the preparation method that polymer network forms system, in step 6, the reducing agent is tributylphosphine, triphenylphosphine or boron hydrogen
Change sodium.
Embodiment 1：
A weighs 65.1 g tetra-（3- mercaptopropionic acids）Pentaerythritol ester, 200 g epoxy resin E44,8 g triethylamines are uniformly mixed,
60min is reacted at 60 DEG C, then 4h is reacted at 130 DEG C, obtains first stage polymer, as shown in Figure 1, used for the present embodiment
Raw material mix schematic diagram, Fig. 2 are the redox mechanism figure of the present embodiment.
B carries out shape memory research to obtained first stage polymer：First stage polymer is determined by DMA first
Glass transition temperatureTg 1 ,Tg 1 It is 56 DEG C, tests the shape memory fixed rate of first stage polymerR f1 And shape memory
Response rateR r1 ,R f1 WithR r1 Respectively 92% and 93%；The test of tension failure performance is carried out to obtained first stage polymer,
Tension failure rate is denoted as 8%；
Polymer is placed in the dichloromethane and tetrahydrofuran of the ferric trichloride of 5mmol/L by c（The body of dichloromethane and tetrahydrofuran
Product ratio 80：20）Mixed solution in, temperature be 25 DEG C, for 24 hours, the polymer of disulfide bond crosslinking after being aoxidized.
The polymer of disulfide bond crosslinking after oxidation methanol solvate washes clean is removed impurity by d, true under the conditions of 60 DEG C
The dry 48h of sky.
E carries out DMA tests to the polymer of disulfide bond crosslinking after oxidation, determines polymerTg 2 ,Tg 2 It it is 75 DEG C, and right
Its tensile property is tested, and tension failure rate is denoted as S2, S2 4%；
F is by the tetrahydrofuran solution of dried polymer merging tributylphosphine, and 25 DEG C of temperature, 15h is obtained disulfide bond also
Originally it was the polymer of sulfydryl, then by polymer methanol washes clean, 48h is dried in vacuo under the conditions of 60 DEG C.
G carries out DMA tests to the polymer after being restored in step f, determines polymerTg 3 ,Tg 3 It it is 55 DEG C, according to step
Method test shape-memory properties in b, the shape memory fixed rate of polymerR f3 With shape memory response rateR r3 ,R f3 WithR r3
Respectively 91.8% and 93.1%, its tensile property is tested, tension failure rate is denoted as S3, S3 7.8%.
After h is completed, have below for relationship： Tg 1 ≈Tg 3 < Tg 2 , S1≈S3>S2, R f1 ≈ R f3 , R r1 ≈R r3 。
As can be seen from the above data, the present invention is based on the shape memory polymer networks shapes of the reversible curing of disulfide bond lock
The first stage polymer of architectonical has good shape-memory properties, and two sulphur of chemical crosslinking are formed by aoxidizing sulfydryl
Key can obtain the polymer with bigger crosslink density, improve the mechanical property and service life of material；Disulfide bond again can be with
Sulfydryl is reduced by reducing agent, reaches the crosslinked effect of solution, the polymer being finally reduced still has preferable shape memory
Performance can continue cycling through utilization.Such method can efficiently solve the mechanics of materials, heat resistance and shape-memory properties,
And the contradiction sex chromosome mosaicism between cycling and reutilization.
Embodiment 2：
A weighs 81.3 g tetra-（3- mercaptopropionic acids）Pentaerythritol ester, 200 g epoxy resin E44,8.4 g triethylamines are uniformly mixed,
60min is reacted at 60 DEG C, then 4h is reacted at 130 DEG C, obtains first stage polymer.
B carries out shape memory research to obtained first stage polymer：First stage polymer is determined by DMA first
Glass transition temperatureTg 1 , Tg 1 It is 47 DEG C, tests the shape memory fixed rate of first stage polymerR f1 And shape memory
Response rateR r1 ,R f1 WithR r1 Respectively 91% and 92%.The test of tension failure performance is carried out to obtained first stage polymer,
Tension failure rate is denoted as 10%；
Polymer is placed in the dichloromethane and tetrahydrofuran of the ferric trichloride of 5mmol/L by c（The body of dichloromethane and tetrahydrofuran
Product ratio 80：20）Mixed solution in, temperature be 25 DEG C, for 24 hours, the polymer of disulfide bond crosslinking after being aoxidized.
The polymer of disulfide bond crosslinking after oxidation methanol solvate washes clean is removed impurity by d, true under the conditions of 60 DEG C
The dry 48h of sky.
E carries out DMA tests to the polymer of disulfide bond crosslinking after oxidation, determines polymerTg 2 ,Tg 2 For 78 DEG C and to it
Tensile property is tested, and tension failure rate is denoted as S2, S2 3%；
F is by the tetrahydrofuran solution of dried polymer merging tributylphosphine, and 25 DEG C of temperature, 15h is obtained disulfide bond also
Originally it was the polymer of sulfydryl, then by polymer methanol washes clean, 48h is dried in vacuo under the conditions of 60 DEG C.
G carries out DMA tests to the polymer after being restored in step f, determines polymerTg 3 ,Tg 3 It it is 47 DEG C, according to step
Method test shape-memory properties in b, the shape memory fixed rate of polymerR f3 With shape memory response rateR r3 ,R f3 WithR r3
Respectively 91.1% and 92.1%, its tensile property is tested, tension failure rate is denoted as S3, S3 10.2%.
After h is completed, have below for relationship： Tg 1 ≈Tg 3 < Tg 2 , S1≈S3>S2, R f1 ≈ R f3 , R r1 ≈ R r3 。
As can be seen from the above data, the present invention is based on the shape memory polymer networks shapes of the reversible curing of disulfide bond lock
The first stage polymer of architectonical has good shape-memory properties, and two sulphur of chemical crosslinking are formed by aoxidizing sulfydryl
Key can obtain the polymer with bigger crosslink density, improve the mechanical property and service life of material；Disulfide bond again can be with
Sulfydryl is reduced by reducing agent, reaches the crosslinked effect of solution, the polymer being finally reduced still has preferable shape memory
Performance can continue cycling through utilization.Such method can efficiently solve the mechanics of materials, heat resistance and shape-memory properties,
And the contradiction sex chromosome mosaicism between cycling and reutilization.
Embodiment 3：
A weighs 97.6 g tetra-（3- mercaptopropionic acids）Pentaerythritol ester, 200 g epoxy resin E44,8.9 g triethylamines are uniformly mixed,
60min is reacted at 60 DEG C, then 4h is reacted at 130 DEG C, obtains first stage polymer.
B carries out shape memory research to obtained first stage polymer：First stage polymer is determined by DMA first
Glass transition temperatureTg 1 , Tg 1 It is 39 DEG C, tests the shape memory fixed rate of first stage polymerR f1 And shape memory
Response rateR r1 ,R f1 WithR r1 Respectively 92.5% and 93.4%.The survey of tension failure performance is carried out to obtained first stage polymer
Examination, tension failure rate are denoted as 12%；
Polymer is placed in the dichloromethane and tetrahydrofuran of the ferric trichloride of 5mmol/L by c（The body of dichloromethane and tetrahydrofuran
Product ratio 80：20）Mixed solution in, temperature be 25 DEG C, for 24 hours, the polymer of disulfide bond crosslinking after being aoxidized.
The polymer of disulfide bond crosslinking after oxidation methanol solvate washes clean is removed impurity by d, true under the conditions of 60 DEG C
The dry 48h of sky.
E carries out DMA tests to the polymer of disulfide bond crosslinking after oxidation, determines polymerTg 2 ,Tg 2 It it is 75 DEG C, and right
Its tensile property is tested, and tension failure rate is denoted as S2, S2 2.5%；
F is by the tetrahydrofuran solution of dried polymer merging tributylphosphine, and 25 DEG C of temperature, 15h is obtained disulfide bond also
Originally it was the polymer of sulfydryl, then by polymer methanol washes clean, 48h is dried in vacuo under the conditions of 60 DEG C.
G carries out DMA tests to the polymer after being restored in step f, determines polymerTg 3 ,Tg 3 It it is 40 DEG C, according to step
Method test shape-memory properties in b, the shape memory fixed rate of polymerR f3 With shape memory response rateR r3 ,R f3 WithR r3
Respectively 92.8% and 93.5%, its tensile property is tested, tension failure rate is denoted as S3, S3 11.8%.
After h is completed, have below for relationship： Tg 1 ≈Tg 3 < Tg 2 , S1≈S3>S2, R f1 ≈ R f3 , R r1 ≈R r3 。
As can be seen from the above data, the present invention is based on the shape memory polymer networks shapes of the reversible curing of disulfide bond lock
The first stage polymer of architectonical has good shape-memory properties, and two sulphur of chemical crosslinking are formed by aoxidizing sulfydryl
Key can obtain the polymer with bigger crosslink density, improve the mechanical property and service life of material；Disulfide bond again can be with
Sulfydryl is reduced by reducing agent, reaches the crosslinked effect of solution, the polymer being finally reduced still has preferable shape memory
Performance can continue cycling through utilization.Such method can efficiently solve the mechanics of materials, heat resistance and shape-memory properties,
And the contradiction sex chromosome mosaicism between cycling and reutilization.
Claims (5)
1. a kind of shape memory polymer networks of the reversible curing lock based on disulfide bond form system, it is characterised in that：It is described
Shape memory polymer networks formed system according to mass percent by mercaptan 15-35%, epoxy resin 60-80%, catalysis
Agent 0.1-4%, oxidant 0.1-4%, reducing agent 0.01-2% compositions.
2. a kind of shape memory polymer networks of the reversible curing lock described in claim 1 based on disulfide bond form system
Preparation method, it is characterised in that：Described method includes following steps：
Step 1：Mercaptan, epoxy resin, catalyst are sufficiently mixed uniformly, 0.1 ~ 20h is reacted at a temperature of 0 ~ 200 DEG C, is obtained
First stage polymer；
Step 2：Shape memory research is carried out to the first stage polymer that step 1 obtains：The first rank is determined by DMA first
The glass transition temperature of section polymerTg 1 ,Tg 1 It is 10 ~ 70 DEG C, tests the shape memory fixed rate of first stage polymerR f1
With shape memory response rateR r1 ,R f1 WithR r1 It is all higher than 90%；
Step 3：The test of tension failure performance is carried out to the first stage polymer that step 1 obtains, tension failure rate is denoted as
S1, S1 are 0.1 ~ 90%；
Step 4：First stage polymer is placed in oxidant, the two 1 ~ 120h of reaction is made at a temperature of 0 ~ 100 DEG C, is obtained
The polymer of disulfide bond crosslinking after oxidation with methanol by the polymer washes clean of disulfide bond crosslinking after oxidation, removes impurity,
1 ~ 96h is dried in vacuo at a temperature of 25 ~ 150 DEG C；
Step 5：DMA tests are carried out to the polymer of disulfide bond crosslinking after oxidation, determine polymerTg 2 ,Tg 2 It is 20 ~ 130
DEG C, and its tensile property is tested, tension failure rate is denoted as S2, and S2 is 0.1 ~ 70%；
Step 6：By in the polymer of disulfide bond crosslinking merging reducing agent, 1 ~ 120h is reacted at a temperature of 0 ~ 100 DEG C, obtain by
Disulfide bond reduction is the polymer of sulfydryl, then by polymer methanol washes clean, it is dried in vacuo 1 under the conditions of 25 ~ 150 DEG C ~
96h；
Step 7：Polymer after being restored to step 6 carries out DMA tests, determines polymerTg 3 ,Tg 3 It is 10 ~ 70 DEG C, test
The shape memory fixed rate of polymer after reductionR f3 With shape memory response rateR r3 ,R f3 WithR r3 It is all higher than 90%,
And its tensile property is tested, tension failure rate is denoted as S3, and S3 is 0.1 ~ 90%；
Step 8：After being completed, following correspondence is obtained：Tg 1 ≈Tg 3 < Tg 2 , S1≈S3>S2, R f1 ≈ R f3 ,R r1 ≈ R r3 。
3. a kind of shape memory polymer networks of reversible curing lock based on disulfide bond according to claim 2 form body
The preparation method of system, it is characterised in that：In step 1, the mercaptan is four（3- mercaptopropionic acids）Pentaerythritol ester or propane-
1,2,3- tri- mercaptan, the epoxy resin are epoxy resin E44 or epoxy resin E51, and the catalyst is triethylamine.
4. a kind of shape memory polymer networks of reversible curing lock based on disulfide bond according to claim 2 form body
The preparation method of system, it is characterised in that：In step 3, the oxidant is ferric trichloride or iodine.
5. a kind of shape memory polymer networks of reversible curing lock based on disulfide bond according to claim 2 form body
The preparation method of system, it is characterised in that：In step 6, the reducing agent is tributylphosphine, triphenylphosphine or sodium borohydride.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942873A (en) * | 2019-03-04 | 2019-06-28 | 山东大学 | A kind of preparation method of Silicone foam |
| CN114905588A (en) * | 2022-05-13 | 2022-08-16 | 南京林业大学 | Transparent wood with editable shape and preparation method thereof |
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| US20080085946A1 (en) * | 2006-08-14 | 2008-04-10 | Mather Patrick T | Photo-tailored shape memory article, method, and composition |
| US20160137778A1 (en) * | 2014-10-29 | 2016-05-19 | The University Of Rochester | Shape memory polymers and methods of making and use thereof |
| CN105802196A (en) * | 2016-02-19 | 2016-07-27 | 中山大学 | High polymer material with two-way shape memory effect and preparation method thereof |
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- 2018-01-29 CN CN201810085882.4A patent/CN108250412B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080085946A1 (en) * | 2006-08-14 | 2008-04-10 | Mather Patrick T | Photo-tailored shape memory article, method, and composition |
| US20160137778A1 (en) * | 2014-10-29 | 2016-05-19 | The University Of Rochester | Shape memory polymers and methods of making and use thereof |
| CN105802196A (en) * | 2016-02-19 | 2016-07-27 | 中山大学 | High polymer material with two-way shape memory effect and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942873A (en) * | 2019-03-04 | 2019-06-28 | 山东大学 | A kind of preparation method of Silicone foam |
| CN109942873B (en) * | 2019-03-04 | 2020-03-13 | 山东大学 | Preparation method of organic silicon foam material |
| CN114905588A (en) * | 2022-05-13 | 2022-08-16 | 南京林业大学 | Transparent wood with editable shape and preparation method thereof |
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