CN108276738B - Flexible shape memory polymer network forming system for thermal and optical two-stage reaction and preparation method thereof - Google Patents
Flexible shape memory polymer network forming system for thermal and optical two-stage reaction and preparation method thereof Download PDFInfo
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- CN108276738B CN108276738B CN201810085880.5A CN201810085880A CN108276738B CN 108276738 B CN108276738 B CN 108276738B CN 201810085880 A CN201810085880 A CN 201810085880A CN 108276738 B CN108276738 B CN 108276738B
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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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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Abstract
A flexible shape memory polymer network forming system of heat and light two-stage reaction and a preparation method thereof belong to the field of shape memory materials. The flexible shape memory polymer network forming system is composed of polyether amine, epoxy resin, acrylic resin and a photoinitiator. The method comprises the following steps: mixing and reacting polyether amine, epoxy resin and a photoinitiator; reacting to obtain a prepolymer; adding acrylic resin into the prepolymer to obtain a first-stage polymer; the final polymer was obtained by further irradiation with an ultraviolet lamp. The invention prepares the first-stage polymer with good shape memory performance through the first stage; through further photocrosslinking, a polymer with higher crosslinking density can be obtained, the mechanical property of the material can be improved, and the service life of the material can be prolonged; the method has important prospect in the advanced manufacturing field, and solves the problems of undefined structure of the raw materials of the shape memory polymer system at the next stage, poor flexibility of the intermediate state polymer, environmental pollution and the like.
Description
Technical Field
The invention belongs to the field of shape memory materials, and particularly relates to a novel flexible shape memory polymer network forming system based on green chemistry thermal and optical two-stage reaction and a preparation method thereof, wherein the system is simple in process and easy to control reaction conditions and is based on polyether amine, epoxy resin and acrylic resin.
Background
The shape memory polymer network formation system of the two-stage reaction was first reported in 2012 by Devatha p. Nair et al (adv. funct. mater.2012221502-10) of the university of colorado. They reported a shape memory polymer network forming system of thermal/optical two-stage reaction using thiol and acrylic resin as raw materials, and made a preliminary study on the shape memory property of the material and the application of the material in the aspect of optical devices. However, this method also has many problems, and first, the commercial structurally sound acrylic resin Ebecryl 1290 is used as a raw material, thus increasing the difficulty of preparing a novel two-stage reaction shape memory polymer network-forming system using these raw materials. Second, the mechanical properties of the material in terms of its flexibility are not studied. Thirdly, the reaction mechanism is not green enough, the used micromolecular catalyst triethylamine does not meet the requirements of green chemistry, and the environment is polluted to a certain extent. Until now, there has been no report on the simultaneous solution of the above problems, and it is therefore very significant to develop a flexible shape memory polymer network forming system based on the thermal and photo two-stage reaction of green chemistry.
Disclosure of Invention
The invention aims to solve the problems of environmental pollution, uncertain structure and undefined performance of the traditional shape memory polymer network forming system related to two-stage reaction, and provides a novel shape memory polymer network forming system based on green chemical heat and light two-stage reaction and a preparation method thereof, wherein the system is simple in process, easy to control environment-friendly reaction conditions, definite in reaction raw material structure and good in flexibility, and the first-stage polymer is based on polyetheramine, epoxy resin and acrylic resin.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a flexible shape memory polymer network forming system for a heat and light two-stage reaction comprises, by mass, 10-30% of polyetheramine, 20-50% of epoxy resin, 30-60% of acrylic resin and 0.5-3% of a photoinitiator.
A method for preparing the above-mentioned flexible shape memory polymer network forming system for the thermal and optical two-stage reaction, comprising the steps of:
the method comprises the following steps: fully and uniformly mixing polyether amine, epoxy resin and a photoinitiator, and reacting at the temperature of 0-180 ℃ for 0.2-20 h to obtain a prepolymer;
step two: adding acrylic resin into the prepolymer obtained in the first step, uniformly stirring, and reacting at the temperature of 0-150 ℃ for 1-120 h to obtain a first-stage polymer;
step three: and (3) carrying out shape memory research on the first-stage polymer obtained in the second step: first the glass transition temperature of the first stage polymer was determined by DMATg 1 ，Tg 1 The shape memory fixation rate of the polymer in the first stage is tested at-30 to 50 DEG CR f1 And shape memory recoveryR r1 ，R f1 AndR r1 the tensile strength is more than 90%, the elongation at break is recorded as S1, and the elongation at break is recorded as 5-200% in S1;
step four: using 0.1-100 mW/cm of the first-stage polymer obtained in the step two2Irradiating for 1-100 min by using an ultraviolet lamp to obtain a final state polymer, and determining the glass transition temperature of the final state polymer by using DMA (direct memory access)Tg 2 ，Tg 2 Performing tensile test at 55-150 ℃, and recording the elongation at break as S2 and the S2 as 0.1-180%;
step five: after the test is finished, the following corresponding relations exist:Tg 1 < Tg 2 ，S1>S2。
compared with the prior art, the invention has the beneficial effects that: the first-stage polymer with good shape memory performance can be prepared through the first stage; through further photocrosslinking, a polymer with higher crosslinking density can be obtained, the mechanical property of the material can be improved, and the service life of the material can be prolonged; the method has important prospect in the advanced manufacturing field, and solves the problems that the structure of the shape memory polymer raw material at the current two stages is not clear, the prepared polymer has poor flexibility, the environment pollution exists and the like.
Drawings
FIG. 1 is a schematic view of the structure of the raw material used in example 1.
FIG. 2 is a schematic diagram of the process of preparing polymers of different structures by using the system.
Detailed Description
The technical solution of the present invention is further described below with reference to the drawings and the embodiments, but the present invention is not limited thereto, and modifications or equivalent substitutions may be made to the technical solution of the present invention without departing from the spirit of the technical solution of the present invention, and the technical solution of the present invention is covered by the protection scope of the present invention.
The first embodiment is as follows: the embodiment describes a flexible shape memory polymer network forming system for two-stage reaction of heat and light, which comprises 10-30% of polyether amine, 20-50% of epoxy resin, 30-60% of acrylic resin and 0.5-3% of photoinitiator according to mass percentage.
The second embodiment is as follows: the flexible shape memory polymer network forming system comprises 30 mass percent of polyether amine, 30 mass percent of epoxy resin, 39.5 mass percent of acrylic resin and 0.5 mass percent of photoinitiator.
The third concrete implementation mode: a method for preparing a flexible shape memory polymer network forming system for thermal and optical two-stage reaction according to one or two embodiments, the method comprising the steps of:
the method comprises the following steps: fully and uniformly mixing polyether amine, epoxy resin and a photoinitiator, and reacting at the temperature of 0-180 ℃ for 0.2-20 h to obtain a prepolymer;
step two: adding acrylic resin into the prepolymer obtained in the first step, uniformly stirring, and reacting at the temperature of 0-150 ℃ for 1-120 h to obtain a first-stage polymer;
step three: polymerization of the first stage obtained in step twoShape memory study of the material: first the glass transition temperature of the first stage polymer was determined by DMATg 1 ，Tg 1 The shape memory fixation rate of the polymer in the first stage is tested at-30 to 50 DEG CR f1 And shape memory recoveryR r1 ，R f1 AndR r1 are all more than 90 percent. Performing a tensile test, wherein the elongation at break is recorded as S1, and S1 is 5-200%;
step four: using 0.1-100 mW/cm of the first-stage polymer obtained in the step two2Irradiating for 1-100 min by using an ultraviolet lamp to obtain a final state polymer, and determining the glass transition temperature of the final state polymer by using DMA (direct memory access)Tg 2 ，Tg 2 Performing tensile test at 55-150 ℃, and recording the elongation at break as S2 and the S2 as 0.1-180%;
step five: after the test is finished, the following corresponding relations exist:Tg 1 < Tg 2 ，S1>S2。
the fourth concrete implementation mode: in the first step, the polyetheramine is one of polyetheramine D230, polyetheramine D400, polyetheramine D2000, polyetheramine T403, and polyetheramine T5000; the epoxy resin is epoxy resin E44 or epoxy resin E51; the photoinitiator is 2, 2-dimethoxy-phenyl acetophenone or 2, 4, 6-trimethyl benzoyl phenyl ethyl phosphonate.
The fifth concrete implementation mode: in the second step, the acrylate is trimethylolpropane triacrylate or pentaerythritol tetraacrylate.
The sixth specific implementation mode: in the fifth step, the light irradiation is either complete irradiation or selective irradiation.
Example 1:
a, 101 g of polyetheramine D230, 200 g of epoxy resin E44 and 13.73 g of 2, 2-dimethoxy-phenylacetophenone are weighed and uniformly mixed, and reacted for 60min at 60 ℃ to obtain a prepolymer, as shown in FIG. 1, which is a structural schematic diagram of the raw materials used in the example.
And b, adding 157 g of trimethylolpropane triacrylate into the prepolymer, uniformly mixing, and reacting at 40 ℃ for 48 hours to obtain the first-stage polymer.
c performing shape memory study on the obtained first-stage polymer: first the glass transition temperature of the first stage polymer was determined by DMATg 1 ，Tg 1 The shape memory fixation rate of the first stage polymer was measured at 42 ℃R f1 And shape memory recoveryR r1 ，R f1 AndR r1 91% and 93%, respectively. And performing a tensile test, wherein the elongation at break is recorded as S1, and S1 is 151%;
d using 8 mW/cm of the first-stage polymer obtained in the step b2And (5) irradiating for 20 min by using an ultraviolet lamp to obtain the final state polymer. The glass transition temperature of the final polymer was then determined by DMATg 2 ，Tg 2 At 68 ℃, and performing a tensile test, wherein the elongation at break is recorded as S2, and S2 is 42%;
after the test, the following relationships apply:Tg 1 < Tg 2 ，S1>S2。
the first-stage reaction of the embodiment obtains the first-stage polymer, and then combines the shape memory property of the first-stage polymer with photocrosslinking, namely, the first-stage polymer is endowed with different shapes and structures through the shape memory property, and the crosslinking density of the first-stage polymer is improved after selective photocuring, so that the structure can be fixed, and the functional structural material with the blank selective property is prepared.
Example 2:
a, weighing 101 g of polyetheramine D230, 200 g of epoxy resin E44 and 16.86 g of 2, 2-dimethoxy-phenylacetophenone, uniformly mixing, and reacting at 60 ℃ for 60min to obtain a prepolymer.
And b, adding 261 g of trimethylolpropane triacrylate into the prepolymer, uniformly mixing, and reacting at 40 ℃ for 48 hours to obtain the first-stage polymer.
c performing shape memory study on the obtained first-stage polymer: first the glass transition temperature of the first stage polymer was determined by DMATg 1 ，Tg 1 The shape memory fixation rate of the first stage polymer was measured at 26 deg.CR f1 And shape memory recoveryR r1 ，R f1 AndR r1 92% and 94%, respectively. And performing a tensile test, wherein the elongation at break is recorded as S1, and S1 is 112%;
d using 8 mW/cm of the first-stage polymer obtained in the step b2And (5) irradiating for 20 min by using an ultraviolet lamp to obtain the final state polymer. The glass transition temperature of the final polymer was then determined by DMATg 2 ，Tg 2 At 85 ℃, performing a tensile test, and recording the elongation at break as S2 and the elongation at break of S2 as 32%;
after the test, the following relationships apply:Tg 1 < Tg 2 ，S1>S2。
the first-stage reaction of the embodiment obtains the first-stage polymer, and then combines the shape memory property of the first-stage polymer with photocrosslinking, namely, the first-stage polymer is endowed with different shapes and structures through the shape memory property, and the crosslinking density of the first-stage polymer is improved after selective photocuring, so that the structure can be fixed, and the functional structural material with the blank selective property is prepared.
Example 3:
a, weighing 101 g of polyetheramine D230, 200 g of epoxy resin E44 and 20.7 g of 2, 2-dimethoxy-phenylacetophenone, uniformly mixing, and reacting at 60 ℃ for 60min to obtain a prepolymer.
b, adding 391 g of trimethylolpropane triacrylate into the prepolymer, uniformly mixing, and reacting at 40 ℃ for 48 hours to obtain the first-stage polymer.
c performing shape memory study on the obtained first-stage polymer: first the glass transition temperature of the first stage polymer was determined by DMATg 1 ，Tg 1 The shape memory fixation rate of the first stage polymer was measured at 12 DEG CR f1 And shape memory recoveryR r1 ，R f1 AndR r1 92% and 93%, respectively. And performing a tensile test, wherein the elongation at break is recorded as S1, and S1 is 86%;
d using 8 mW/cm of the first-stage polymer obtained in the step b2And (5) irradiating for 20 min by using an ultraviolet lamp to obtain the final state polymer. The glass transition temperature of the final polymer was then determined by DMATg 2 ，Tg 2 At 99 ℃, performing a tensile test, and recording the breaking elongation as S2 and the breaking elongation as S2 being 21%;
after the test, the following relationships apply:Tg 1 < Tg 2 ，S1>S2。
the first-stage reaction of the embodiment obtains the first-stage polymer, and then combines the shape memory property of the first-stage polymer with photocrosslinking, namely, the first-stage polymer is endowed with different shapes and structures through the shape memory property, and the crosslinking density of the first-stage polymer is improved after selective photocuring, so that the structure can be fixed, and the functional structural material with the blank selective property is prepared.
Claims (5)
1. A preparation method of a flexible shape memory polymer network forming system for a heat and light two-stage reaction comprises the following steps of 10-30% of polyether amine, 20-50% of epoxy resin, 30-60% of acrylic resin and 0.5-3% of photoinitiator by mass percent; the method is characterized in that: the method comprises the following steps:
the method comprises the following steps: fully and uniformly mixing polyether amine, epoxy resin and a photoinitiator, and reacting at the temperature of 0-180 ℃ for 0.2-20 h to obtain a prepolymer;
step two: adding acrylic resin into the prepolymer obtained in the first step, uniformly stirring, and reacting at the temperature of 0-150 ℃ for 1-120 h to obtain a first-stage polymer;
step three: and (3) carrying out shape memory research on the first-stage polymer obtained in the second step: first the glass transition temperature of the first stage polymer was determined by DMATg 1 ，Tg 1 The shape memory fixation rate of the polymer in the first stage is tested at-30 to 50 DEG CR f1 And shape memory recoveryR r1 ，R f1 AndR r1 are all more than 90 percent; performing a tensile test, wherein the elongation at break is recorded as S1, and S1 is 5-200%;
step four: using 0.1-100 mW/cm of the first-stage polymer obtained in the step two2Irradiating for 1-100 min by using an ultraviolet lamp to obtain a final state polymer, and determining the glass transition temperature of the final state polymer by using DMA (direct memory access)Tg 2 ，Tg 2 Performing tensile test at 55-150 ℃, and recording the elongation at break as S2 and the S2 as 0.1-180%;
step five: after the test is completed, the following relationships exist:Tg 1 <Tg 2 ，S1>S2。
2. the method for preparing a system for forming a flexible shape memory polymer network for a thermal and optical two-stage reaction according to claim 1, wherein: the flexible shape memory polymer network forming system is composed of 30% of polyether amine, 30% of epoxy resin, 39.5% of acrylic resin and 0.5% of photoinitiator according to mass percentage.
3. The method for preparing a system for forming a flexible shape memory polymer network for a thermal and optical two-stage reaction according to claim 1, wherein: in the first step, the polyetheramine is one of polyetheramine D230, polyetheramine D400, polyetheramine D2000, polyetheramine T403 and polyetheramine T5000; the epoxy resin is epoxy resin E44 or epoxy resin E51; the photoinitiator is 2, 2-dimethoxy-phenyl acetophenone or 2, 4, 6-trimethyl benzoyl phenyl ethyl phosphonate.
4. The method for preparing a system for forming a flexible shape memory polymer network for a thermal and optical two-stage reaction according to claim 1, wherein: in the second step, the acrylic resin is trimethylolpropane triacrylate or pentaerythritol tetraacrylate.
5. The method for preparing a system for forming a flexible shape memory polymer network for a thermal and optical two-stage reaction according to claim 1, wherein: in the fifth step, the illumination is complete illumination or selective illumination.
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| 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 |
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| 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 |
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