CN111848990A - Preparation method of bidirectional shape memory elastomer constructed based on self-nucleation effect - Google Patents
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Abstract
The invention relates to a shape memory elastomer technology, and aims to provide a preparation method of a bidirectional shape memory elastomer constructed based on a self-nucleation effect. The method comprises the following steps: dissolving double-bond-terminated polyester or polyether, a cross-linking agent and a catalyst in dimethylformamide to form a prepolymer; the reaction is finished and the crosslinking is finished; demolding and vacuum drying to obtain semi-crystalline cross-linked polymer; heating the elastomer to be isothermally molten; and then applying constant strain, and repeating the operations of cooling, isothermy, heating and isothermy to crystallize the molten crystallizable segment part to form original platelets, thereby finally obtaining the two-way shape memory elastomer. The present invention is based on a self-nucleation heat treatment procedure to prepare elastomers with excellent two-way shape memory behavior. The two-way shape memory elastomer is suitable for all semi-crystalline elastomers, is realized only through a heat treatment process, and has strong applicability; the preparation is simple and is beneficial to large-scale preparation.
Description
Technical Field
The invention relates to a shape memory elastomer technology, in particular to a method for preparing a semi-crystalline two-way shape memory elastomer based on self-nucleation heat treatment.
Background
Shape memory polymers refer to a class of polymeric materials that are capable of returning from a temporary shape to a permanent shape in response to an external specified stimulus, such as heat, light, electricity, magnetism, pH, solvent, or the like. Conventional shape memory polymers exhibit a one-way shape memory effect and therefore require reprogramming during each shape memory cycle. Recent research has focused on the two-way shape memory effect, which allows reversible switching of deformation under opposing external stimuli without additional programming. Therefore, the two-way shape memory polymer has wide application prospect in the fields of intelligent instruments, biomedicine, sensors, drivers, soft robots, aerospace and the like. In general, the two-way shape memory polymers under the condition of no external force can be classified into four types according to the preparation method: (1) thermoplastic polymer, (2) chemically crosslinked semicrystalline polymer, (3) liquid crystal polymer, (4) layered polymer composite. Among them, chemically crosslinked crystalline polymers are attracting attention because of their easy availability of raw materials, simple preparation, and excellent two-way shape memory effect.
The general chemically crosslinked semicrystalline two-way shape memory polymer is required to have a multiple or wider melting transition temperature. The Lendlein group achieved a two-way shape memory effect without external force in 2013 through a wide melt transition range of a chemically crosslinked poly (ethylene-vinyl acetate) copolymer, and was applied to a reversible driving switch (Lendlein et al, proc.natl.acad.sci., 2013, 110, 12555). The subject group also realized reversible deformation without external force by using a double-crystalline phase network prepared by chemically crosslinking poly (-caprolactone) and poly (omega-pentadecanolide) in 2013, and was applied to underwater gripper drivers (Lendlein et al, adv. However, all of the above works are required for the amount and distribution of crystalline phases in the polymer.
The Hu group achieved reversible stretching of the splines by storing constant internal stress in the poly (-caprolactone) network by distributed cross-linking in 2010 (Hu et al, compound.sci.technol., 2010, 70, 1437). Although this work achieved the two-way shape memory behavior of conventional semicrystalline polymers using step-wise crosslinking, certain limitations still exist. On one hand, the distribution crosslinking puts higher requirements on the preparation process of the material; on the other hand, the polymer can only change in length in macroscopic deformation, and because the internal stress is determined in the preparation process, the reversible strain amount is also determined, and cannot be changed.
From the above, the construction of the two-way shape memory elastomer based on the common semicrystalline polymer still has great challenges, and the design of a simple and easy way to prepare the semicrystalline two-way shape memory elastomer has very important significance.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a preparation method of a bidirectional shape memory elastomer constructed based on a self-nucleation effect. The method realizes differentiation of polymer crystal forms through a self-nucleation heat treatment procedure, induces the formation of thickened platelets and original platelets with different melting points, and enables the chemically crosslinked semi-crystalline polymer to show excellent two-way shape memory behavior under the condition of no external force.
In order to solve the technical problem, the solution of the invention is as follows:
the preparation method of the two-way shape memory elastomer constructed based on the self-nucleation effect is provided, the two-way shape memory elastomer is prepared by self-nucleation heat treatment of a semi-crystalline cross-linked polymer, and the preparation method specifically comprises the following steps:
(1) dissolving double-bond terminated polyester or polyether, a cross-linking agent and a catalyst in dimethylformamide, and forming a prepolymer by the polyester or polyether, the cross-linking agent and the catalyst; in the mixed solution, the concentration of polyester or polyether is 0.5g/ml, the molar ratio of double bonds in the polyester or polyether to sulfydryl in the crosslinking agent is 1: 1, and the catalyst accounts for 10 wt% of the total mass of the prepolymer;
(2) transferring the mixed solution into a mold, and reacting at 80 ℃ for 8h to complete crosslinking; demoulding and vacuum drying at 40 ℃ for 24h to obtain semi-crystalline cross-linked polymer, namely elastomer;
(3) heating the elastomer to 70 ℃, and keeping the temperature constant for 3 minutes to completely melt the elastomer; then applying constant strain of 10-97% relative to the original length, cooling to the temperature below the crystallization temperature, and keeping the temperature constant for 20 minutes to enable the elastomer to form a crystal phase;
(4) heating the elastomer to a self-nucleation temperature of 40-45 ℃ under the condition of keeping constant strain; then isothermal annealing treatment is carried out for 5 minutes, so that part of the platelets in the crystalline phase is melted, and the unmelted platelets are thickened to form thickened platelets; then cooling to the temperature below the crystallization temperature again, and keeping the temperature constant for 20 minutes to ensure that the melted crystallizable chain segment is partially crystallized to form original platelets, thereby finally obtaining the two-way shape memory elastomer.
In the present invention, the double bond-terminated polyester is poly (-caprolactone) diacrylate and the polyether is polyethylene glycol diacrylate.
In the invention, the crosslinking agent is at least one of pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate) or pentaerythritol tetrakis (2-mercaptoacetate).
In the invention, the catalyst is triethylamine.
Description of the inventive principles:
in the invention, the bidirectional shape memory elastomer is prepared from a semicrystalline polymer through a chemical crosslinking reaction. The elastomer undergoes a self-nucleating heat treatment process during the shape fixing: the elastomer is heated to be completely melted, then the temperature is reduced to be lower than the crystallization temperature to form a crystal phase, then the crystal phase is heated to be the self-nucleation temperature, most of the lamella in the elastomer crystal phase is melted, the unmelted lamella is annealed at the temperature, the thickness of the wafer is increased, the crystallization is more complete, the melting point is improved, and an anisotropic structure is formed in the network. The elastomer is then cooled below the crystallization temperature, and the molten molecular chains can rapidly crystallize to form the original platelets because of the presence of the self-seeding crystals. And finally, circularly heating and cooling the bidirectional shape memory elastomer under the condition of no external force to realize bidirectional reversible deformation. The thickened platelets are not melted all the time in the subsequent heating process, so that the differentiation of the internal crystal structure of the two-way shape memory elastomer is kept, the two types of platelets (the thickened platelets and the original platelets) coexist, and the two-way shape memory effect of the two-way shape memory elastomer is ensured.
In the invention, the bidirectional shape memory elastomer prepared based on the self-nucleation effect has the following bidirectional shape memory process:
(1) subjecting the elastomer having a permanent shape of shape a to a self-nucleation thermal procedure while being pre-stretched to deform into shape B; (2) placing the two-way shape memory elastomer fixed in the shape B in ThighIn the environment of (a), thermal shrinkage is achieved, and the shape is converted into a shape C; (3) placing a two-way shape memory elastomer having a shape C at TlowIn the environment of (a), cold elongation is achieved, transforming into shape D. (4) At ThighAnd TlowThe two-way shape memory elastic body realizes the reversible switching between the shape C and the shape D by the cyclic temperature change process.
Compared with the prior art, the invention has the following technical advantages:
(1) the present invention is based on a self-nucleation heat treatment procedure to prepare elastomers with excellent two-way shape memory behavior.
(2) The two-way shape memory elastomer is suitable for all semi-crystalline elastomers, is realized only through a heat treatment process, and has strong applicability.
(3) The bidirectional shape memory elastomer is simple to prepare and is beneficial to large-scale preparation.
Drawings
FIG. 1 is a plot of the melting behavior of examples 2, 4, 5 after a self-nucleation heat treatment.
FIG. 2 is a small angle X-ray scatter plot of examples 2, 4, 5.
FIG. 3 is a shape memory cycle test curve of example 2.
Detailed Description
The invention is described in further detail below with reference to the drawings and the detailed description, but the scope of the invention as claimed is not limited to the scope of the embodiments.
Examples 1 to 8
Raw materials:
poly (-caprolactone) diacrylate (M)n4000g/mol, Alfa Aesar); pentaerythritol tetrakis (3-mercaptopropionate) (TCI corporation); triethylamine (national medicine reagent)
(1) The preparation method of the elastomer comprises the following steps:
dissolving poly (-caprolactone) diacrylate, pentaerythritol tetrakis (3-mercaptopropionate) and triethylamine in dimethylformamide to form a prepolymer; in the mixed solution, the concentration of the poly (-caprolactone) diacrylate is 0.5g/ml, and the molar ratio of double bonds in the poly (-caprolactone) diacrylate to mercapto groups in pentaerythritol tetrakis (3-mercaptopropionate) is 1: 1; triethylamine accounts for 10 wt% of the total mass of the prepolymer;
transferring the mixed solution into a mold, reacting at 80 ℃ for 8h to complete crosslinking, demolding, and vacuum drying at 40 ℃ for 24h to obtain a semi-crystalline crosslinked polymer, namely an elastomer, wherein the crystallization temperature of the elastomer is 20 ℃.
(2) Self-nucleation heat treatment procedure:
heating the elastomer to 70 ℃, and keeping the temperature constant for 3 minutes to completely melt the elastomer; applying a constant strain of 10% to 97% to the elastomer relative to its original length while cooling to 10 ℃; keeping the temperature constant for 20 minutes to enable the elastomer to form a crystal phase; keeping constant strain, heating to a self-nucleation temperature (40-45 ℃), carrying out isothermal annealing treatment for 5 minutes to melt part of platelets in a crystal phase, and thickening unmelted platelets to form thickened platelets; then cooling to 10 ℃ again, keeping the temperature constant for 20 minutes, and enabling the melted crystallizable chain segment to partially crystallize to form original lamella, thereby finally obtaining the two-way shape memory elastomer.
(3) Bidirectional memory behavior characterization:
placing a two-way shape memory elastomer at ThighAnd TlowAnd the cyclic temperature changing process is carried out to realize reversible thermal shrinkage and cold elongation deformation.
(1) Subjecting the elastomer having a permanent shape of shape a to a self-nucleation thermal procedure while being pre-stretched to deform into shape B; (2) placing the two-way shape memory elastomer fixed in the shape B in ThighIn the environment of (a), thermal shrinkage is achieved, and the shape is converted into a shape C; (3) placing a two-way shape memory elastomer having a shape C at TlowIn the environment of (a), cold elongation is achieved, transforming into shape D. (4) At T highAnd TlowThe two-way shape memory elastic body realizes the reversible switching between the shape C and the shape D by the cyclic temperature change process.
The temperature range of the self-nucleation temperature is controlled to be 40-45 ℃, and ThighThe temperature ranges of the two are respectively controlled to be 39-49 ℃, and TlowThe temperature range of (2) is controlled at 10 ℃.
Example 9
Raw materials:
polyethylene glycol diacrylate (M)n2000g/mol, Alfa Aesar corporation); pentaerythritol tetrakis (3-mercaptopropionate) (TCI corporation); triethylamine (national medicine reagent)
(1) The preparation method of the elastomer comprises the following steps:
dissolving polyethylene glycol diacrylate, pentaerythritol tetra (3-mercaptopropionate) and triethylamine in dimethylformamide to form a prepolymer; in the mixed solution, the concentration of the polyethylene glycol diacrylate is 0.5g/ml, and the molar ratio of double bonds in the polyethylene glycol diacrylate to sulfydryl in the pentaerythritol tetra (3-mercaptopropionate) is 1: 1; triethylamine accounts for 10 wt% of the total mass of the prepolymer;
transferring the mixed solution into a mold, reacting at 80 ℃ for 8h to complete crosslinking, and performing vacuum drying at 40 ℃ for 24h after demolding; a semicrystalline crosslinked polymer, i.e.an elastomer, is obtained, the crystallization temperature of which is 20 ℃.
(2) Self-nucleation heat treatment procedure:
heating the elastomer to 70 ℃, and keeping the temperature constant for 3 minutes to completely melt the elastomer; applying a constant strain of 10% to 97% to the elastomer relative to its original length while cooling to 10 ℃; keeping the temperature constant for 20 minutes to enable the elastomer to form a crystal phase; keeping constant strain, heating to a self-nucleation temperature (40-45 ℃), carrying out isothermal annealing treatment for 5 minutes to melt part of platelets in a crystal phase, and thickening unmelted platelets to form thickened platelets; then cooling to 10 ℃ again, keeping the temperature constant for 20 minutes, and enabling the melted crystallizable chain segment to partially crystallize to form original lamella, thereby finally obtaining the two-way shape memory elastomer.
(3) Bidirectional memory behavior characterization:
placing a two-way shape memory elastomer at ThighAnd TlowAnd the cyclic temperature changing process is carried out to realize reversible thermal shrinkage and cold elongation deformation. The specific procedures are as in examples 1-8, and the data for the implementation are shown in Table 1.
Example 10
Raw materials:
poly (-caprolactone) diacrylate (M)n4000g/mol, Alfa Aesar); pentaerythritol tetrakis (2-mercaptoacetate) (TCI corporation); triethylamine (national medicine reagent)
(1) The preparation method of the elastomer comprises the following steps:
dissolving poly (-caprolactone) diacrylate, tetra (2-thioglycolic acid) pentaerythritol ester and triethylamine in dimethylformamide to form a prepolymer; in the mixed solution, the concentration of the poly (-caprolactone) diacrylate is 0.5g/ml, and the molar ratio of double bonds in the poly (-caprolactone) diacrylate to sulfydryl in the pentaerythritol tetra (2-mercaptoacetate) is 1: 1; triethylamine accounts for 10 wt% of the total mass of the prepolymer;
transferring the mixed solution into a mold, reacting at 80 ℃ for 8h to complete crosslinking, demolding, and vacuum drying at 40 ℃ for 24h to obtain a semi-crystalline crosslinked polymer, namely an elastomer, wherein the crystallization temperature of the elastomer is 20 ℃.
(2) Self-nucleation heat treatment procedure:
heating the elastomer to 70 ℃, and keeping the temperature constant for 3 minutes to completely melt the elastomer; applying a constant strain of 10% to 97% to the elastomer relative to its original length while cooling to 10 ℃; keeping the temperature constant for 20 minutes to enable the elastomer to form a crystal phase; keeping constant strain, heating to a self-nucleation temperature (40-45 ℃), carrying out isothermal annealing treatment for 5 minutes to melt part of platelets in a crystal phase, and thickening unmelted platelets to form thickened platelets; then cooling to 10 ℃ again, keeping the temperature constant for 20 minutes, and enabling the melted crystallizable chain segment to partially crystallize to form original lamella, thereby finally obtaining the two-way shape memory elastomer.
(3) Bidirectional memory behavior characterization:
placing a two-way shape memory elastomer at ThighAnd TlowAnd the cyclic temperature changing process is carried out to realize reversible thermal shrinkage and cold elongation deformation. The specific procedures are as in examples 1-8, and the data for the implementation are shown in Table 1.
Table 1: pre-strain, self-nucleation temperature, T applied by two-way shape memory elastomers of examples 1-10highAnd Tlow
| Elastic body | Prestrain (%) | Self nucleation temperature (. degree.C.) | Thigh(℃) | Tlow(℃) |
| Example 1 | 10 | 43 | 43 | 10 |
| Example 2 | 24 | 43 | 43 | 10 |
| Example 3 | 97 | 43 | 43 | 10 |
| Example 4 | 25 | 41 | 43 | 10 |
| Example 5 | 24 | 45 | 43 | 10 |
| Example 6 | 26 | 43 | 39 | 10 |
| Example 7 | 25 | 43 | 44 | 10 |
| Example 8 | 25 | 43 | 49 | 10 |
| Example 9 | 24 | 40 | 40 | 10 |
| Example 10 | 26 | 43 | 43 | 10 |
In the present invention, the two-way shape memory elastomer constructed based on the self-nucleation effect can be characterized by the following analytical instruments, which specifically include:
differential Scanning Calorimetry (DSC): the melting behavior of the elastomer after the self-nucleation thermal program was analyzed with NETZSCH214Polyma DSC (NETZSCH, Germany) with a heating rate of 10 ℃/min; and calculating the degree of crystallinity (χ) from the enthalpy of fusionc)：
Small angle X-ray scattering test (SAXS): analyzing the crystal structure of the polymer by using a light source BL16B1 line station of Shanghai synchrotron radiation device, scanning a sample film by using X-rays with the wavelength lambda of 0.124nm, and calculating the thickness (L) of a wafer according to a one-dimensional electron density correlation function K (z) c)：
Two-way shape memory cycle test (DMA): the two-way shape memory behavior of the two-way shape memory elastomer was quantitatively characterized using DMA Q850(TA instruments). Clamping the sample strip in a stretching clamp, and heating to a deformation temperature of 70 ℃; then, cooling to 10 ℃ under constant strain, and keeping the temperature constant for 20 min; then heating to the self-nucleation temperature, and keeping for 5 min; then cooling to 10 ℃ again to define the strain of the sample strip at the momentload(ii) a Then removing external force, heating to ThighThe resulting strain of the sample is defined ashigh(ii) a Cooling to TlowThe resulting strain of the sample is defined aslow. All heating and cooling rates were 10 ℃/min.The reversible deformation amount (Δ) of the sample can be quantitatively calculated using the following formula.
Δ＝1ow-high；
And (3) analyzing experimental data:
from the DSC analysis results (fig. 1 and table 2), the chemically crosslinked poly (-caprolactone) network had different melting points and melting range after undergoing self-nucleation heat treatment at different self-nucleation temperatures. In example 2, the highest melting point and the widest melting range were exhibited, and two melting peaks were exhibited. This is due to the fact that at a self-nucleation temperature of 43 ℃, most of the platelets in the elastomer crystalline phase melt. The unmelted platelets were annealed at 43 ℃ to form high melting point thickened platelets. When the temperature is reduced to 10 ℃ again, the melted molecular chains are rapidly crystallized to form original platelets with low melting point under the induction of the self-crystal seeds. Therefore, the melting range of the elastomer shifts to a higher and wider range. In examples 4 and 5, the self-nucleation temperatures were 41 ℃ and 45 ℃, respectively, and the melting range and melting point were reduced compared to those of example 2.
From the SAXS analysis results (fig. 2 and table 2), the crystalline phases of the chemically cross-linked poly (-caprolactone) network have different platelet thicknesses after undergoing a self-nucleation thermal program at different self-nucleation temperatures. In example 2, the scattering vector q exhibits a minimum value, and therefore its platelet thickness is a maximum of 6.2 nm. This is due to the annealing of the unmelted platelets above the self-nucleation temperature to form thicker platelets. In examples 4 and 5, a reduction in wafer thickness was observed compared to example 2.
As can be seen from the DMA results (fig. 3 and table 2), example 2 exhibited an excellent two-way shape memory effect under no external force conditions with a reversible deformation amount of 16.8% after undergoing the self-nucleation heat treatment procedure.
On the other hand, the two-way shape memory elastomers of examples 1-3 applied pre-strain of 10%, 24%, and 97%, respectively, and the results show that the amount of reversible deformation increases with increasing pre-strain, since a greater external force increases the anisotropy and internal stress of the polymer network. The results of examples 2, 4 and 5 using different self-nucleation temperatures of 43 deg.C, 41 deg.C and 45 deg.C, respectively, show the two-way shape memory of example 2The memoelastomers exhibit the most pronounced two-way shape memory behavior because at this temperature the two-way shape memory elastomers have the widest melting transition range and the greatest platelet thickness; examples 2, 6 to 8 use different T highThe results were 43 deg.C, 39 deg.C, 44 deg.C and 49 deg.C, respectively, and showed that the two-way shape memory elastomer of example 2 had the most excellent two-way memory property because of having the most suitable distribution of the skeleton phase and the reversible phase at that temperature.
Table 2: examples 1-10 gel content, self-nucleated melting point, crystallinity, wafer thickness and reversible deformation of two-way shape memory elastomers
As can be seen from the above table, the examples have different melting points, wafer thicknesses and reversible deformation amounts after undergoing different self-nucleation heat treatment procedures. Therefore, it can be concluded that the construction of two-way shape memory elastomers based on self-nucleation is a simple and feasible approach.
Finally, it should be noted that the above-listed embodiments are specific embodiments of the present invention. It is obvious that the present invention is not limited to the above embodiments, but many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (4)
1. A preparation method of a two-way shape memory elastomer constructed based on a self-nucleation effect is characterized in that the two-way shape memory elastomer is prepared by self-nucleation heat treatment of a semi-crystalline cross-linked polymer, and specifically comprises the following steps:
(1) Dissolving double-bond terminated polyester or polyether, a cross-linking agent and a catalyst in dimethylformamide, and forming a prepolymer by the polyester or polyether, the cross-linking agent and the catalyst; in the mixed solution, the concentration of polyester or polyether is 0.5g/ml, the molar ratio of double bonds in the polyester or polyether to sulfydryl in the crosslinking agent is 1: 1, and the catalyst accounts for 10 wt% of the total mass of the prepolymer;
(2) transferring the mixed solution into a mold, and reacting at 80 ℃ for 8h to complete crosslinking; demoulding and vacuum drying at 40 ℃ for 24h to obtain semi-crystalline cross-linked polymer, namely elastomer;
(3) heating the elastomer to 70 ℃, and keeping the temperature constant for 3 minutes to completely melt the elastomer; then applying constant strain of 10-97% relative to the original length, cooling to the temperature below the crystallization temperature, and keeping the temperature constant for 20 minutes to enable the elastomer to form a crystal phase;
(4) heating the elastomer to a self-nucleation temperature of 40-45 ℃ under the condition of keeping constant strain; then isothermal annealing treatment is carried out for 5 minutes, so that part of the platelets in the crystalline phase is melted, and the unmelted platelets are thickened to form thickened platelets; then cooling to the temperature below the crystallization temperature again, and keeping the temperature constant for 20 minutes to ensure that the melted crystallizable chain segment is partially crystallized to form original platelets, thereby finally obtaining the two-way shape memory elastomer.
2. The method of claim 1, wherein the double bond-terminated polyester is poly (-caprolactone) diacrylate and the polyether is polyethylene glycol diacrylate.
3. The method of claim 1, wherein the crosslinking agent is at least one of pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), or pentaerythritol tetrakis (2-mercaptoacetate).
4. The process of claim 1, wherein the catalyst is triethylamine.
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| CN113480798A (en) * | 2021-07-26 | 2021-10-08 | 中国兵器科学研究院 | Preparation of photoinduced deformation supporting arm and method for regulating and controlling unfolding state of space reflector by utilizing photoinduced deformation supporting arm |
| CN113480798B (en) * | 2021-07-26 | 2022-05-13 | 中国兵器科学研究院 | Preparation of photoinduced deformation supporting arm and method for regulating and controlling unfolding state of space reflector by utilizing photoinduced deformation supporting arm |
| CN114656604A (en) * | 2022-03-26 | 2022-06-24 | 哈尔滨工业大学 | Preparation and application of bidirectional shape memory polymer |
| CN116063799A (en) * | 2023-01-06 | 2023-05-05 | 华南理工大学 | Ultra-wide melting range two-way shape memory polymer composite material without external force and preparation method thereof |
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