CN112094397A - Preparation method of sisal hemp based shape memory polyurethane foam - Google Patents
Preparation method of sisal hemp based shape memory polyurethane foam Download PDFInfo
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Abstract
The invention provides a preparation method of sisal hemp-based shape memory polyurethane foam, which comprises the following steps: (1) respectively weighing polycaprolactone and modified sisal hemp, placing in a reactor, and mixing uniformly; (2) adding liquid diphenylmethane diisocyanate into the reactor, placing the reactor in an oil bath kettle at the temperature of 80 ℃, stirring, and then adding tween-80, a catalyst, triethanolamine, cyclohexane, n-pentane and a stabilizer for reaction; (3) and finally adding half of water drop serving as a foaming agent into the reactor, stirring at 70-85 ℃, standing for foaming, and finishing foaming after 2-3min to obtain the shape memory polyurethane foam SMPU-PSF. The invention takes the sisal fiber as the cross-linking point, and the prepared shape memory polyurethane foam not only can broaden the functionality of the shape memory polyurethane foam, but also provides a new way for the research and development of the shape memory polyurethane foam.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of sisal hemp based shape memory polyurethane foam.
Background
As is known, shape memory polyurethane foam has the advantages of high compression ratio, high specific modulus, good energy storage effect, high porosity, high elasticity and the like, and is not possessed by common shape memory polyurethane materials. The shape memory polyurethane foam material mainly takes shape memory polyurethane as a matrix, and based on the matrix, the preparation processes such as molecular structure and foaming are designed, so that the SMPU with a single structure is converted into a multilayer random network structure.
The preparation method of the shape memory polyurethane foam mainly comprises the following steps: the first is a gas foaming process, which means that during the curing reaction, upon heating or pressure change, the gas generated by the chemical reaction or blowing agent remains in the polymer network and creates pores therein, curing into a foamed polyurethane. The second is composite foam, which means that the liquid shape memory polymer and the hollow glass microsphere are mixed and then undergo a curing reaction to prepare the closed-cell composite foam containing the glass hollow microsphere. The third is a particle leaching process, which refers to wetting and drying the salt particles in a container to form a template, pouring the shape memory polymer into a container to solidify the shape memory polymer, and removing the salt particles by water dissolution to form an open-cell foam. The fourth method is a solid foaming method, which means that no foaming agent or liquid treatment is needed in the preparation process, and the density of the synthesized foam is higher.
In the aerospace field, Loredana Santo is prepared by carrying experiments, and the shape-memory epoxy type foam is prepared by Loredana Santo through a solid foaming method. The shape memory epoxy foam was tested in the aerospace mission of International Space Station, ISS-International Space Station, BION-M. So that there is a difference in the behavior characteristics of the shape memory epoxy-type foam as compared to gravity. The system is composed of three systems of batteries, control and heating, data recording and the like. They also investigated the case of indentation recovery, recovery of material shape at different temperatures.
The Amirahmad Mohammad-Belgium Luwen university professor proposes that the shape discipline foam is used for a recyclable environment-friendly mold in the molding process under a low-pressure environment according to the shape memory performance of the shape memory foam and the advantage of the larger compression ratio of the shape memory foam. And respectively compare the accumulation of single points of material in the formation at room temperature in a high temperature environment, and they also discuss the possibility of using shape memory polyurethane foam in a custom made insole.
Sisal hemp is used as a renewable resource, caprolactone is used as a raw material, and PCL (polycaprolactone) is synthesized by ring-opening polymerization, wherein the PCL consists of ester groups (1) and methylene groups (5). PCL has good flexibility, good viscoelasticity, relatively good crystallization property and low glass transition temperature. This is several of the great features of PCL. On the basis of biological materials, the PCL (polycaprolactone) has good biocompatibility and degradability, good chemical stability, and good mechanical properties (especially the elongation or high elastic modulus) and thermal properties. On the other hand, polycaprolactone has a larger development platform in the fields of biology and medicine as the U.S. food and drug administration allows for use in the human body. However, polycaprolactone lacks surface functional groups and is hydrophobic, so that cells are difficult to adsorb on the scaffold, and therefore certain limitation is placed on tissue engineering construction. Therefore, the method has very important significance for the research of the mechanism.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of sisal hemp based shape memory polyurethane foam, which has higher compression ratio and controllability and obvious shape memory effect.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of sisal hemp based shape memory polyurethane foam comprises the following steps:
(1) respectively weighing 8.010-8.026 g of polycaprolactone and 0.102-0.300 g of modified sisal hemp, placing in a reactor, and uniformly mixing;
(2) adding 2.313-2.383 g of liquid diphenylmethane diisocyanate into the reactor, placing the reactor in an oil bath kettle at 80 ℃, stirring for 4min, and then adding 0.327-0.335 g of Tween-80, 3 drops of catalyst, 2 drops of triethanolamine, 3.010-3.178 g of cyclohexane, 1.520-1.600 g of n-pentane and 1.256-1.278 g of stabilizer for reaction;
(3) and finally adding half of water drop serving as a foaming agent into the reactor, stirring for 10-20s at the temperature of 70-85 ℃, standing for foaming, and finishing foaming after 2-3min to obtain the shape memory polyurethane foam SMPU-PSF.
Further, the synthetic method of the modified sisal hemp comprises the following steps:
(a) firstly, pretreating sisal hemp to remove pectin and lignin on the surface of the sisal hemp, cutting the sisal hemp into pieces with the length of less than 2cm, and then cleaning the sisal hemp by using deionized water;
(b) putting the cleaned sisal hemp into a high-pressure reaction kettle, and adding NaOH and Na into the high-pressure reaction kettle2SO4·10H2O and distilled water react for 2-3h at the temperature of 170-180 ℃;
(c) reacting the product with 40mL of sulfuric acid with the volume fraction of 65% for 30min, pouring the product into ice water, diluting the product to be neutral, centrifuging and drying the product to obtain sisal fibers;
(d) dispersing the sisal fibers obtained in the step (3) in caprolactone, heating and stirring at 140 ℃, stirring for 20-30min, and adding 0.1-0.2g of stannous octoate with the mass fraction of 1% to obtain a mixture;
(e) and (3) reacting the mixture for 12-14h at the temperature of 140-150 ℃ under the protection of nitrogen, dissolving the product in hot DMF for 10h after the reaction, and then filtering and drying in vacuum to constant weight to obtain the modified sisal PSF.
Further, in step (b), the NaOH: na (Na)2SO4·10H2O: the mass ratio of the distilled water added is 1:1: 30.
Further, in the step (d), the weight ratio of the sisal fibers to the caprolactone is 4: 1.
further, the molecular weight of the polycaprolactone was 2000, and it was dried before use.
Further, the catalyst is dibutyltin dilaurate.
Further, the stabilizer is silicone oil.
Compared with the prior art, the invention has the following beneficial effects:
the invention takes the sisal fiber as the cross-linking point, and the prepared shape memory polyurethane foam not only can broaden the functionality of the shape memory polyurethane foam, but also provides a new way for the research and development of the shape memory polyurethane foam. The foam has high compressibility and controllability, and the shape memory effect is obvious.
Drawings
FIG. 1 is a diagram of the synthesis process of a sisal-based shape-memory polyurethane foam of the present invention;
FIG. 2 is an infrared spectrum of a sisal-based shape memory polyurethane foam of the present invention;
FIG. 3 is a thermogravimetric plot of a sisal-based shape memory polyurethane foam of the present invention;
FIG. 4 is a DSC plot of a sisal-based shape-memory polyurethane foam of the present invention;
FIG. 5 is a photograph of the shape memory-recovery process of the sisal-based shape memory polyurethane foam of the present invention.
Detailed Description
The process of the present invention will be described in detail with reference to specific examples. The sisal hemp-based shape memory polyurethane foam can be abbreviated as SMPU-PSF, the modified sisal hemp can be abbreviated as PSF, and the final product of the invention is characterized by a series of characters such as infrared, TG and DSC. In the invention, the PCL is named as polycaprolactone in the Chinese language, diphenylmethane diisocyanate is abbreviated as MDI, and dibutyltin dilaurate is abbreviated as DBTDL.
Firstly, the preparation of the sisal hemp based shape memory polyurethane foam
Example 1
A preparation method of sisal hemp-based shape memory polyurethane foam comprises the following steps:
(1) respectively weighing 8.022g of polycaprolactone and 0.102g of modified sisal hemp, placing the polycaprolactone and the modified sisal hemp in a reactor, and uniformly mixing;
(2) adding 2.323g of liquid diphenylmethane diisocyanate (MDI) into the reactor, placing the reactor in an oil bath kettle at 80 ℃, stirring for 4min, and then adding 0.334g of Tween-80, 3 drops of dibutyltin dilaurate (DBTDL), 2 drops of triethanolamine, 3.178g of cyclohexane, 1.520g of n-pentane and 1.265g of silicone oil for reaction;
(3) and finally adding half of water drop serving as a foaming agent into the reactor, stirring for 10s at 70 ℃, standing for foaming, and finishing foaming after 2min to obtain the shape memory polyurethane foam SMPU-PSF, which is recorded as P1.
Example 2
A preparation method of sisal hemp-based shape memory polyurethane foam comprises the following steps:
(1) respectively weighing 8.010g of polycaprolactone and 0.150g of modified sisal hemp, placing the weighed materials in a reactor, and uniformly mixing;
(2) 2.383g of liquid diphenylmethane diisocyanate (MDI) is added into the reactor, the reactor is placed in an oil bath kettle at the temperature of 80 ℃, after stirring for 4min, 0.328g of Tween-80, 3 drops of dibutyltin dilaurate (DBTDL), 2 drops of triethanolamine, 3.010g of cyclohexane, 1.523g of n-pentane and 1.278g of silicone oil are added for reaction;
(3) and finally adding half of water drop serving as a foaming agent into the reactor, stirring for 20s at 85 ℃, standing for foaming, and finishing foaming after 3min to obtain the shape memory polyurethane foam SMPU-PSF, which is recorded as P2.
Example 3
A preparation method of sisal hemp-based shape memory polyurethane foam comprises the following steps:
(1) respectively weighing 8.015g of polycaprolactone and 0.180g of modified sisal hemp, placing the polycaprolactone and the modified sisal hemp in a reactor, and uniformly mixing;
(2) 2.321g of liquid diphenylmethane diisocyanate (MDI) is added into the reactor, the reactor is placed in an oil bath kettle at the temperature of 80 ℃, after stirring for 4min, 0.326g of Tween-80, 3 drops of dibutyltin dilaurate (DBTDL), 2 drops of triethanolamine, 3.050g of cyclohexane, 1.600g of n-pentane and 1.256g of silicone oil are added for reaction;
(3) and finally adding half of water drop serving as a foaming agent into the reactor, stirring for 15s at 75 ℃, standing for foaming, and finishing foaming after 2.5min to obtain the shape memory polyurethane foam SMPU-PSF, which is recorded as P3.
Example 4
A preparation method of sisal hemp-based shape memory polyurethane foam comprises the following steps:
(1) respectively weighing 8.020g of polycaprolactone and 0.200g of modified sisal hemp, placing the weighed materials in a reactor, and uniformly mixing;
(2) adding 2.313g of liquid diphenylmethane diisocyanate (MDI) into the reactor, putting the reactor into an oil bath kettle at 80 ℃, stirring for 4min, and then adding 0.335g of Tween-80, 3 drops of dibutyltin dilaurate (DBTDL), 2 drops of triethanolamine, 3.084g of cyclohexane, 1.540g of n-pentane and 1.262g of silicone oil for reaction;
(3) and finally adding half of water drop serving as a foaming agent into the reactor, stirring for 12s at the temperature of 80 ℃, standing for foaming, and finishing foaming after 2min to obtain the shape memory polyurethane foam SMPU-PSF, which is recorded as P4.
Example 5
A preparation method of sisal hemp-based shape memory polyurethane foam comprises the following steps:
(1) respectively weighing 8.026g of polycaprolactone and 0.300g of modified sisal hemp, placing in a reactor, and mixing uniformly;
(2) 2.332g of liquid diphenylmethane diisocyanate (MDI) is added into the reactor, the reactor is placed in an oil bath kettle at the temperature of 80 ℃, after stirring for 4min, 0.327g of Tween-80, 3 drops of dibutyltin dilaurate (DBTDL), 2 drops of triethanolamine, 3.104g of cyclohexane, 1.534g of n-pentane and 1.265g of silicone oil are added for reaction;
(3) and finally adding half of water drop serving as a foaming agent into the reactor, stirring for 18s at 85 ℃, standing for foaming, and finishing foaming after 3min to obtain the shape memory polyurethane foam SMPU-PSF, which is recorded as P5.
In examples 1 to 5, the molecular weight of the polycaprolactone was 2000, and the drying treatment was required before use.
The preparation method of the modified sisal in the above examples 1-5 is as follows:
(a) firstly, pretreating sisal hemp to remove pectin and lignin on the surface of the sisal hemp, cutting the sisal hemp into pieces with the length of less than 2cm, and then cleaning the sisal hemp by using deionized water;
(b) putting the cleaned sisal hemp into a high-pressure reaction kettle, and adding NaOH and Na into the high-pressure reaction kettle2SO4·10H2O and distilled water react for 2-3h at the temperature of 170-180 ℃; the NaOH: na (Na)2SO4·10H2O: adding distilled water in a mass ratio of 1:1: 30;
(c) reacting the product with 40mL of sulfuric acid with the volume fraction of 65% for 30min, pouring the product into ice water, diluting the product to be neutral, centrifuging and drying the product to obtain sisal fibers;
(d) dispersing the sisal fibers obtained in the step (3) in caprolactone, heating and stirring at 140 ℃, stirring for 20-30min, and adding 0.1-0.2g of stannous octoate with the mass fraction of 1% to obtain a mixture; the mass ratio of the sisal fibers to the caprolactone is 4: 1.
(e) and (3) reacting the mixture for 12-14h at the temperature of 140-150 ℃ under the protection of nitrogen, dissolving the product in hot DMF for 10h after the reaction, and then filtering and drying in vacuum to constant weight to obtain the modified sisal PSF.
Secondly, performance test of the sisal hemp-based shape memory polyurethane foam prepared by the invention
1. Infrared test (FT-IR)
The results of infrared spectroscopy on PSF and SMPU-PSF are shown in FIG. 2. As can be seen from the figure, the SMPU-PSF is 3398cm-1Stretching vibration absorption peak of hydroxyl groupIs significantly reduced in intensity and is at 3506cm-1Is treated as the stretching vibration peak of N-H in amide and is at 1733cm-1Has a stretching vibration absorption peak of-CONHR at 1222cm-1The absorption peak of the C-O-C stretching vibration of the soft segment is at 2275cm-1～2250cm-1There is no absorption peak of N ═ C ═ O, indicating complete reaction of MDI in the prepolymerization stage.
2. Thermal Property analysis (TG-DSC)
2.1) TGA test analysis
FIG. 3 is a TGA graph of polyurethane foams of P1, P2, P3, P4 and P5 synthesized in examples 1-5, wherein it can be seen that the initial decomposition temperature shows a tendency of increasing and then decreasing with increasing PSF content, and the thermal stability of SMPU-PSF is better.
2.2) DSC test analysis
FIG. 4 shows the thermal effect of the reaction of the shape-memory polyurethane foams with different PSF contents at different temperatures, and it can be seen that all the samples only have a glass transition temperature (Tg) during the temperature rising and lowering processes, the crystal melting peak does not appear here, and the glass transition temperature is slightly increased due to the increase of the PSF content, which indicates that the prepared shape-memory polyurethane foams have good shape-memory recovery performance.
3. Heat drive recovery Performance test
The recovery and shape retention of shape memory foams is an important criterion for evaluating the performance of shape memory foams, which corresponds to the recovery and fixation of shape memory foams. FIG. 5 is a view showing a recovery process of the shape-memory polyurethane foam prepared in the present invention, in which the foam is cut into a shape of a trapezoid having a height of about 1cm, softened by heating at a high temperature of 100 ℃ and compressed into a 2mm trapezoid by an external force of 1N, and then cooled to room temperature to obtain a temporary shape. The shape recovery process is that the foam gradually recovers to the original shape along with the temperature rise when the temperature is 60 ℃ and 100 ℃, which shows that the sisal hemp based shape memory foaming polyurethane has good shape fixing and shape recovery performance.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (7)
1. A preparation method of sisal hemp based shape memory polyurethane foam is characterized by comprising the following steps:
(1) respectively weighing 8.010-8.026 g of polycaprolactone and 0.102-0.300 g of modified sisal hemp, placing in a reactor, and uniformly mixing;
(2) adding 2.313-2.383 g of liquid diphenylmethane diisocyanate into the reactor, placing the reactor in an oil bath kettle at 80 ℃, stirring for 4min, and then adding 0.327-0.335 g of Tween-80, 3 drops of catalyst, 2 drops of triethanolamine, 3.010-3.178 g of cyclohexane, 1.520-1.600 g of n-pentane and 1.256-1.278 g of stabilizer for reaction;
(3) and finally adding half of water drop serving as a foaming agent into the reactor, stirring for 10-20s at the temperature of 70-85 ℃, standing for foaming, and finishing foaming after 2-3min to obtain the shape memory polyurethane foam SMPU-PSF.
2. The method of claim 1, wherein the method of synthesizing the modified sisal comprises the steps of:
(a) firstly, pretreating sisal hemp to remove pectin and lignin on the surface of the sisal hemp, cutting the sisal hemp into pieces with the length of less than 2cm, and then cleaning the sisal hemp by using deionized water;
(b) putting the cleaned sisal hemp into a high-pressure reaction kettle, and adding NaOH and Na into the high-pressure reaction kettle2SO4·10H2O and distilled water react for 2-3h at the temperature of 170-180 ℃;
(c) reacting the product with 40mL of sulfuric acid with the volume fraction of 65% for 30min, pouring the product into ice water, diluting the product to be neutral, centrifuging and drying the product to obtain sisal fibers;
(d) dispersing the sisal fibers obtained in the step (3) in caprolactone, heating and stirring at 140 ℃, stirring for 20-30min, and adding 0.1-0.2g of stannous octoate with the mass fraction of 1% to obtain a mixture;
(e) and (3) reacting the mixture for 12-14h at the temperature of 140-150 ℃ under the protection of nitrogen, dissolving the product in hot DMF for 10h after the reaction, and then filtering and drying in vacuum to constant weight to obtain the modified sisal PSF.
3. The method of preparing a sisal-based shape-memory polyurethane foam of claim 2, wherein in step (b), the NaOH: na (Na)2SO4·10H2O: the mass ratio of the distilled water added is 1:1: 30.
4. The method of claim 2, wherein in step (d), the sisal fibers and caprolactone are added in a mass ratio of 4: 1.
5. the method of claim 1, wherein the polycaprolactone has a molecular weight of 2000 and is dried before use.
6. The method of claim 1 wherein the catalyst is dibutyltin dilaurate.
7. The method of preparing a sisal-based shape-memory polyurethane foam of claim 1, wherein said stabilizer is silicone oil.
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