CN108276738A - A kind of flexible shape memory polymer networks formation system and preparation method thereof of light and heat two-stage reaction - Google Patents
A kind of flexible shape memory polymer networks formation system and preparation method thereof of light and heat two-stage reaction Download PDFInfo
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- CN108276738A CN108276738A CN201810085880.5A CN201810085880A CN108276738A CN 108276738 A CN108276738 A CN 108276738A CN 201810085880 A CN201810085880 A CN 201810085880A CN 108276738 A CN108276738 A CN 108276738A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/02—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/12—Shape memory
Abstract
A kind of flexible shape memory polymer networks formation system and preparation method thereof of light and heat two-stage reaction, belongs to shape-memory material field.The flexible shape memory polymer networks form system and are made of polyetheramine, epoxy resin, acrylic resin and photoinitiator.The method is as follows：By polyetheramine, epoxy resin, photoinitiator hybrid reaction；React to obtain prepolymer；Acrylic resin is added in prepolymer and obtains first stage polymer；Further most final state polymer is obtained with UV illumination.The present invention prepares the first stage polymer with excellent in shape memory performance by the first stage；Again by further photo-crosslinking, the polymer with bigger crosslink density can be obtained, the mechanical property and service life of material can be improved；The problems such as such method has important foreground in advanced manufacturing field, and the structure for solving two-stage shape-memory polymer system raw material instantly is indefinite, and intermediate state polymer flexibility is poor and existing environmental pollution.
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 flexible shape of the novel light and heat two-stage reaction based on Green Chemistry of polyetheramine, epoxy resin, acrylic resin
Memory polymer networks formation system and preparation method thereof.
Background technology
It is big by Colorade USA in 2012 earliest that the shape memory polymer networks of two-stage reaction, which form system,
Devatha P. Nair etc.（Adv. Funct. Mater.2012 22 1502-10）Report.They report it is a kind of with
The shape memory polymer networks that mercaptan and heat/light two-stage that acrylic resin is raw material react form system, to the material
Shape-memory properties, the application in terms of optical device, which has been done, tentatively to be probed into.However, there is also much ask simultaneously for this method
It inscribes, first, the Eudragit E becryl 1290 of commercial structure secrecy has been used in raw material, therefore increase and utilize these
Raw material prepare the difficulty of the shape memory polymer networks formation system of novel two-stage reaction.Second, the related side of material
The mechanical property in face, it is such as flexible not study.Third, reaction mechanism is not environmentally protective enough, used micromolecule catalyst three
Ethamine and the requirement for not meeting Green Chemistry, have environment certain pollution.Up to now, there is not relevant report yet
It can solve the above problems simultaneously, therefore develop a kind of flexible shape memory of the light and heat two-stage reaction based on Green Chemistry
Polymer network, which forms system, just seems very significant.
Invention content
The purpose of the present invention is to solve traditional shape memory polymer networks about two-stage reaction to form body
There are environmental pollution, structures not to know for system, the indefinite problem of performance, provides a kind of reaction item simple for process, environmental-friendly
Part is easy to control, reaction raw materials structure determination, have preferably flexible first stage polymer based on polyetheramine, epoxy resin,
The shape memory polymer networks of the novel light and heat two-stage reaction based on Green Chemistry of acrylic resin form system
And preparation method thereof.
To achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of flexible shape memory polymer networks formation system of light and heat two-stage reaction, flexible shape memory are poly-
Polymeric network forms system according to mass percent by polyetheramine 10-30%, epoxy resin 20-50%, acrylic resin 30-
60% and photoinitiator 0.5-3% is formed.
A kind of flexible shape memory polymer networks of above-mentioned light and heat two-stage reaction form the preparation method of system,
Described method includes following steps：
Step 1：Polyetheramine, epoxy resin, photoinitiator are sufficiently mixed uniformly, 0.2 ~ 20 is reacted at a temperature of 0 ~ 180 DEG C
H obtains prepolymer；
Step 2：In the prepolymer that acrylic resin addition step 1 is obtained, stirs evenly, react 1 at a temperature of 0 ~ 150 DEG C
~ 120 h obtain first stage polymer；
Step 3：Shape memory research is carried out to the first stage polymer that step 2 obtains：The first rank is determined by DMA first
The glass transition temperature of section polymerTg 1 ,Tg 1 It is -30 ~ 50 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%, and carries out extension test, elongation at break is denoted as S1, and S1 is 5 ~
200%；
Step 4：0.1 ~ 100 mW/cm of the first stage polymer that step 2 is obtained21 ~ 100min of UV illumination, obtains
To most final state polymer, then pass through the glass transition temperature of DMA determinations most final state polymerTg 2 ,Tg 2 It goes forward side by side for 55 ~ 150 DEG C
Row extension test, elongation at break are denoted as S2, and S2 is 0.1 ~ 180%；
Step 5：After being completed, there is following correspondence：Tg 1 < Tg 2 , S1>S2.
The advantageous effect of the present invention compared with the existing technology is：The present invention can prepare one kind by the first stage to be had
The first stage polymer of excellent in shape memory performance；Again by further photo-crosslinking, can obtain being crosslinked with bigger close
The polymer of degree can improve the mechanical property and service life of material；By by the shape-memory properties of first stage polymer
It is combined with photo-crosslinking, i.e., by shape-memory properties, assigns first stage polymer different shape and structure first, then lead to
After crossing photocuring, the crosslink density of first stage polymer is improved, thus this structure can be fixed, further, it is also possible to select
The different location of the irradiation first stage polymer of selecting property, prepares the functional structure material with empty selection performance, such method
There is important foreground in advanced manufacturing field, and the structure for solving two-stage shape-memory polymer raw material instantly is indefinite,
The problems such as polymer flexibility of preparation is poor and there are environmental pollutions.
Description of the drawings
Fig. 1 is structural schematic diagram raw materials used in embodiment 1.
Fig. 2 is the process schematic that this system prepares different structure polymer.
Specific implementation mode
Technical scheme of the present invention is further described with reference to the accompanying drawings and examples, however, it is not limited to this,
Every to be modified to technical solution of the present invention or equivalent replacement, range without departing from the spirit of the technical scheme of the invention should all
Cover among protection scope of the present invention.
Specific implementation mode one：What present embodiment was recorded is that a kind of flexible shape memory of light and heat two-stage reaction is poly-
Polymeric network forms system, and the flexible shape memory polymer networks form system according to mass percent by polyetheramine
10-30%, epoxy resin 20-50%, acrylic resin 30-60% and photoinitiator 0.5-3% compositions.
Specific implementation mode two：A kind of flexible shape memory of reaction of light and heat two-stage described in specific implementation mode one
Polymer network forms system, and the flexible shape memory polymer networks form system according to mass percent by polyetheramine
30%, epoxy resin 30%, acrylic resin 39.5% and photoinitiator 0.5% form.
Specific implementation mode three：A kind of flexible shape of light and heat two-stage reaction described in specific implementation mode one or two
Memory polymer networks form the preparation method of system, and described method includes following steps, as shown in Figure 2：
Step 1：Polyetheramine, epoxy resin, photoinitiator are sufficiently mixed uniformly, 0.2 ~ 20 is reacted at a temperature of 0 ~ 180 DEG C
H obtains prepolymer；
Step 2：In the prepolymer that acrylic resin addition step 1 is obtained, stirs evenly, react 1 at a temperature of 0 ~ 150 DEG C
~ 120 h obtain first stage polymer；
Step 3：Shape memory research is carried out to the first stage polymer that step 2 obtains：The first rank is determined by DMA first
The glass transition temperature of section polymerTg 1 ,Tg 1 It is -30 ~ 50 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%.And extension test is carried out, and elongation at break is denoted as S1, and S1 is 5 ~
200%；
Step 4：0.1 ~ 100 mW/cm of the first stage polymer that step 2 is obtained21 ~ 100min of UV illumination, obtains
To most final state polymer, then pass through the glass transition temperature of DMA determinations most final state polymerTg 2 ,Tg 2 It goes forward side by side for 55 ~ 150 DEG C
Row extension test, elongation at break are denoted as S2, and S2 is 0.1 ~ 180%；
Step 5：After being completed, there is following correspondence：Tg 1 < Tg 2 , S1>S2.
Specific implementation mode four：A kind of flexible shape memory of reaction of light and heat two-stage described in specific implementation mode three
Polymer network forms the preparation method of system, and in step 1, the polyetheramine is polyetheramine D230, polyetheramine D400, poly-
One kind in ether amines D2000, polyetheramine T403, polyetheramine T5000；The epoxy resin is epoxy resin E44 or asphalt mixtures modified by epoxy resin
Fat E51；The photoinitiator is 2,2- dimethoxy-phenylfs acetophenone or 2,4,6- trimethylbenzoyl phenyl phosphonic acids second
Ester.
Specific implementation mode five：A kind of flexible shape memory of reaction of light and heat two-stage described in specific implementation mode three
Polymer network forms the preparation method of system, and in step 2, the acroleic acid resin is trimethylolpropane tris acrylic acid
Ester or pentaerythritol tetraacrylate.
Specific implementation mode six：A kind of flexible shape memory of reaction of light and heat two-stage described in specific implementation mode three
Polymer network forms the preparation method of system, and in step 5, the illumination is irradiation or elective irradiation completely.
Embodiment 1：
A weighs 101 g polyetheramines D230,200 g epoxy resin E44,13.73 g 2, the mixing of 2- dimethoxy-phenylf acetophenones
Uniformly, 60min is reacted at 60 DEG C, obtains prepolymer, as shown in Figure 1, for the raw materials used structural schematic diagram of the present embodiment.
157 g trimethylolpropane trimethacrylates are added in prepolymer b, are uniformly mixed, react 48h at 40 DEG C,
Obtain first stage polymer.
C 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 42 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 93%.And extension test is carried out, elongation at break is denoted as S1, S1 151%；
8 mW/cm of the first stage polymer that d obtains step b220 min of UV illumination obtains most final state polymer.
The glass transition temperature of most final state polymer is determined by DMA againTg 2 ,Tg 2 It is 68 DEG C, and carries out extension test, extension at break
Rate is denoted as S2, S2 42%；
After e is completed, have below for relationship：Tg 1 < Tg 2 , S1>S2.
First stage polymer is obtained by the reaction in the present embodiment first stage, then again remembers the shape of first stage polymer
Recall performance to be combined with photo-crosslinking, that is, assigns first stage polymer different shapes by shape-memory properties first
And structure, then after curing by selective light, the crosslink density of first stage polymer is improved, thus this structure can be consolidated
It is fixed, the functional structure material with empty selection performance is prepared, it is former that such method solves two-stage shape-memory polymer instantly
The problems such as structure of material is indefinite, and the intermediate state polymer flexibility of preparation is poor and there are environmental pollutions, in advanced manufacturing field
With important foreground.
Embodiment 2：
A weighs 101 g polyetheramines D230,200 g epoxy resin E44,16.86 g 2, the mixing of 2- dimethoxy-phenylf acetophenones
Uniformly, 60min is reacted at 60 DEG C, obtains prepolymer.
261 g trimethylolpropane trimethacrylates are added in prepolymer b, are uniformly mixed, react 48h at 40 DEG C,
Obtain first stage polymer.
C 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 26 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 94%.And extension test is carried out, elongation at break is denoted as S1, S1 112%；
8 mW/cm of the first stage polymer that d obtains step b220 min of UV illumination obtains most final state polymer.
The glass transition temperature of most final state polymer is determined by DMA againTg 2 ,Tg 2 It is 85 DEG C, and carries out extension test, extension at break
Rate is denoted as S2, S2 32%；
After e is completed, have below for relationship：Tg 1 < Tg 2 , S1>S2.
First stage polymer is obtained by the reaction in the present embodiment first stage, then again remembers the shape of first stage polymer
Recall performance to be combined with photo-crosslinking, that is, assigns first stage polymer different shapes by shape-memory properties first
And structure, then after curing by selective light, the crosslink density of first stage polymer is improved, thus this structure can be consolidated
It is fixed, the functional structure material with empty selection performance is prepared, it is former that such method solves two-stage shape-memory polymer instantly
The problems such as structure of material is indefinite, and the intermediate state polymer flexibility of preparation is poor and there are environmental pollutions, in advanced manufacturing field
With important foreground.
Embodiment 3：
A weighs 101 g polyetheramines D230,200 g epoxy resin E44,20.7 g 2, the mixing of 2- dimethoxy-phenylf acetophenones
Uniformly, 60min is reacted at 60 DEG C, obtains prepolymer.
391 g trimethylolpropane trimethacrylates are added in prepolymer b, are uniformly mixed, react 48h at 40 DEG C,
Obtain first stage polymer.
C 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 12 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%.And extension test is carried out, elongation at break is denoted as S1, S1 86%；
8 mW/cm of the first stage polymer that d obtains step b220 min of UV illumination obtains most final state polymer.
The glass transition temperature of most final state polymer is determined by DMA againTg 2 ,Tg 2 It is 99 DEG C, and carries out extension test, extension at break
Rate is denoted as S2, S2 21%；
After e is completed, have below for relationship：Tg 1 < Tg 2 , S1>S2.
First stage polymer is obtained by the reaction in the present embodiment first stage, then again remembers the shape of first stage polymer
Recall performance to be combined with photo-crosslinking, that is, assigns first stage polymer different shapes by shape-memory properties first
And structure, then after curing by selective light, the crosslink density of first stage polymer is improved, thus this structure can be consolidated
It is fixed, the functional structure material with empty selection performance is prepared, it is former that such method solves two-stage shape-memory polymer instantly
The problems such as structure of material is indefinite, and the intermediate state polymer flexibility of preparation is poor and there are environmental pollutions, in advanced manufacturing field
With important foreground.
Claims (6)
1. a kind of flexible shape memory polymer networks of light and heat two-stage reaction form system, it is characterised in that：Described
Flexible shape memory polymer networks formed system according to mass percent by polyetheramine 10-30%, epoxy resin 20-50%,
Acrylic resin 30-60% and photoinitiator 0.5-3% compositions.
2. a kind of flexible shape memory polymer networks of light and heat two-stage reaction according to claim 1 form body
System, it is characterised in that：The flexible shape memory polymer networks formed system according to mass percent by polyetheramine 30%,
Epoxy resin 30%, acrylic resin 39.5% and photoinitiator 0.5% form.
3. a kind of flexible shape memory polymer networks of light and heat two-stage reaction as claimed in claim 1 or 2 form system
Preparation method, it is characterised in that：Described method includes following steps：
Step 1：Polyetheramine, epoxy resin, photoinitiator are sufficiently mixed uniformly, 0.2 ~ 20 is reacted at a temperature of 0 ~ 180 DEG C
H obtains prepolymer；
Step 2：In the prepolymer that acrylic resin addition step 1 is obtained, stirs evenly, react 1 at a temperature of 0 ~ 150 DEG C
~ 120 h obtain first stage polymer；
Step 3：Shape memory research is carried out to the first stage polymer that step 2 obtains：The first rank is determined by DMA first
The glass transition temperature of section polymerTg 1 ,Tg 1 It is -30 ~ 50 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%；And extension test is carried out, and elongation at break is denoted as S1, and S1 is 5 ~
200%；
Step 4：0.1 ~ 100 mW/cm of the first stage polymer that step 2 is obtained21 ~ 100min of UV illumination, obtains
Most final state polymer, then the glass transition temperature by DMA determinations most final state polymerTg 2 ,Tg 2 For 55 ~ 150 DEG C and carry out
Extension test, elongation at break are denoted as S2, and S2 is 0.1 ~ 180%；
Step 5：After being completed, have below for relationship：Tg 1 < Tg 2 , S1>S2.
4. a kind of flexible shape memory polymer networks of light and heat two-stage reaction according to claim 3 form system
Preparation method, it is characterised in that：In step 1, the polyetheramine is polyetheramine D230, polyetheramine D400, polyetheramine
One kind in D2000, polyetheramine T403, polyetheramine T5000；The epoxy resin is epoxy resin E44 or epoxy resin
E51；The photoinitiator is 2,2- dimethoxy-phenylfs acetophenone or 2,4,6- trimethylbenzoyl phenyl phosphonic acids second
Ester.
5. a kind of flexible shape memory polymer networks of light and heat two-stage reaction according to claim 3 form system
Preparation method, it is characterised in that：In step 2, the acroleic acid resin is trimethylolpropane trimethacrylate or season penta
Tetra-acrylate.
6. a kind of flexible shape memory polymer networks of light and heat two-stage reaction according to claim 3 form system
Preparation method, it is characterised in that：In step 5, the illumination is complete irradiation or elective irradiation.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114752019A (en) * | 2022-04-08 | 2022-07-15 | 哈尔滨工业大学 | Two-stage preparation method and glass transition temperature in-situ regulation and control method of double-network shape memory polymer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104559813A (en) * | 2015-01-30 | 2015-04-29 | 中国工程物理研究院化工材料研究所 | Double cured adhesive suitable for ultralow-temperature environment and preparation method of double cured adhesive |
| CN105860889A (en) * | 2016-04-20 | 2016-08-17 | 黑龙江省科学院石油化学研究院 | Water-based strippable gasket adhesive and preparation method thereof |
| CN106471421A (en) * | 2014-07-03 | 2017-03-01 | 3M创新有限公司 | There is the edge intrusion of reduction and the quantum dot product of the colour stability improved |
| CN106947213A (en) * | 2016-01-07 | 2017-07-14 | 湖南师范大学 | A kind of epoxy resin of polyetheramides toughness reinforcing |
-
2018
- 2018-01-29 CN CN201810085880.5A patent/CN108276738B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106471421A (en) * | 2014-07-03 | 2017-03-01 | 3M创新有限公司 | There is the edge intrusion of reduction and the quantum dot product of the colour stability improved |
| CN104559813A (en) * | 2015-01-30 | 2015-04-29 | 中国工程物理研究院化工材料研究所 | Double cured adhesive suitable for ultralow-temperature environment and preparation method of double cured adhesive |
| CN106947213A (en) * | 2016-01-07 | 2017-07-14 | 湖南师范大学 | A kind of epoxy resin of polyetheramides toughness reinforcing |
| CN105860889A (en) * | 2016-04-20 | 2016-08-17 | 黑龙江省科学院石油化学研究院 | Water-based strippable gasket adhesive and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114752019A (en) * | 2022-04-08 | 2022-07-15 | 哈尔滨工业大学 | Two-stage preparation method and glass transition temperature in-situ regulation and control method of double-network shape memory polymer |
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