CN109049880B - Preparation method of gutta-percha and polycaprolactone multilayer composite film - Google Patents
Preparation method of gutta-percha and polycaprolactone multilayer composite film Download PDFInfo
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- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
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Abstract
The invention discloses a preparation method of a eucommia ulmoides gum base composite film, which comprises the following steps: (1) dissolving gutta-percha and polycaprolactone in chloroform respectively to obtain a gutta-percha solution and a polycaprolactone solution; (2) pouring the gutta-percha solution into a mold, and drying to obtain a gutta-percha film layer; (3) pouring a polycaprolactone solution on the eucommia ulmoides rubber film layer obtained in the step (2), and drying to obtain a polycaprolactone film layer; (4) repeating the step (2) to obtain a sandwich type gutta-percha/polycaprolactone/gutta-percha composite membrane layer; (5) and stripping and drying the composite film layer. The raw materials used by the invention are green and degradable, the cost is low, and the process is simple. The composite membrane is formed on a mould by casting the gutta percha and the polycaprolactone solution layer by layer, and the composite membrane with different performances can be obtained by changing the concentration and the proportion of reactants. The obtained gutta-percha/polycaprolactone/gutta-percha composite membrane material has good elasticity, hydrophobicity and toughness.
Description
Technical Field
The invention relates to the field of composite membranes synthesized by using renewable high polymer materials, in particular to a preparation method of a composite membrane of gutta percha and polycaprolactone with good hydrophobicity and toughness.
Background
With the rapid increase of the consumption of fossil resources, it becomes more and more important to promote forest biomass resources to replace petroleum to prepare products such as chemicals. More than 99% of eucommia resources in the world have great advantages in China and China in the aspects of development and application of gutta-percha. Compared with natural rubber, the gutta-percha has rubber-plastic duality and extremely high cohesiveness, has good thermoplastic processability, and shows more excellent processability compared with plastics. The gutta-percha has potential application value in the fields of navigation, aviation, green tires, medical instruments, damping materials and the like by modifying or blending with high polymer materials such as rubber, plastics and the like. In recent years, studies on gutta percha have been increasing, but much attention has been focused on methods and apparatuses for extracting gutta percha.
The gutta percha has the advantages of easy crystallization, lower melting point, strong insulativity, water resistance, cold resistance, acid and alkali resistance, good thermoplasticity, excellent shape memory, excellent fatigue resistance, wear resistance, shock resistance, tear resistance and the like. The gutta-percha as a functional material has great development potential and expansion space. Polycaprolactone is a high molecular material which has good toughness, good thermal stability and low strength and can be biologically degraded. Polycaprolactone and many high polymers have good compatibility, and the flexibility, dyeability and adhesiveness of the material can be improved by blending the polycaprolactone with the high polymers. The blending research on the gutta percha and the synthetic polymer material is less, and the gutta percha and the filler can be blended to prepare the film material with excellent performance based on the thought of complementary performance advantages. In the currently granted patent, for example, chinese patent application CN107383443 discloses a composite film of gutta percha and nanocellulose and a preparation method thereof, and the composite film which is degradable and reproducible, has a contact angle of 90.5-76.9 degrees and an elongation at break of 200-365 percent is obtained. However, as the demands on the materials increase, there is still a need to improve the processes of the prior art in order to obtain products with better properties.
Disclosure of Invention
Aiming at the problems in the prior art, the invention firstly extracts eucommia ulmoides gum from eucommia ulmoides seeds, and forms a composite membrane by casting the eucommia ulmoides gum and polycaprolactone solution layer by layer in a simple membrane forming mode, so that the composite membrane with good performance is obtained, and the composite membrane has stronger hydrophobicity and higher elongation at break and tensile strength.
The invention aims to provide a preparation method of a eucommia ulmoides gum base composite film, which is characterized by comprising the following steps of:
(1) dissolving gutta-percha and polycaprolactone in chloroform respectively to obtain a gutta-percha solution with the mass percent concentration of 0.4-0.6 wt% and a polycaprolactone solution with the mass percent concentration of 0.17-1.30 wt%;
(2) pouring the gutta-percha solution into a flat polytetrafluoroethylene mold, and drying for 1-6h under ventilation conditions to obtain a gutta-percha film layer;
(3) pouring a polycaprolactone solution on the eucommia ulmoides gum film layer obtained in the step (2), and drying for 1-6h under a ventilation condition to obtain a polycaprolactone film layer;
(4) pouring the gutta-percha solution on the polycaprolactone film layer obtained in the step (3) to obtain a sandwich type operation gutta-percha/polycaprolactone/gutta-percha composite film layer;
(5) and (3) drying the composite film layer obtained in the step (4) for more than 24 hours under the condition of room temperature ventilation to obtain a composite film, stripping the composite film from the mold, and drying the composite film in a vacuum drying oven.
Wherein the gutta-percha in the step (1) is obtained by extracting eucommia seeds with petroleum ether.
Preferably, the steps (2) and (3) can be alternately performed for a plurality of times to form a composite film with the eucommia ulmoides gum and the polycaprolactone alternately in a multi-layer mode.
Preferably, the multilayer alternating composite film of gutta percha and polycaprolactone can be 3-7 layers, preferably 3-5 layers, and most preferably 3 layers, and the outermost layer of the multilayer alternating composite film is a gutta percha layer.
Preferably, the weight ratio of the eucommia ulmoides gum to the polycaprolactone in each eucommia ulmoides gum layer and each polycaprolactone layer is controlled by the pouring amount of each layer.
Preferably, the drying time of the individual layers is 2-3h, more preferably 1-2 h.
The invention also aims to provide the eucommia ulmoides gum and polycaprolactone-based composite film, which is prepared by the method.
Preferably, the composite film is a composite film formed by alternately stacking 3-7 layers of gutta-percha and polycaprolactone, preferably 3-5 layers, most preferably 3 layers, and the outermost layer of the composite film is a gutta-percha layer.
Preferably, the weight ratio of the eucommia ulmoides gum in each eucommia ulmoides gum layer to the polycaprolactone in each polycaprolactone layer in the composite film is 10:1 to 1:1, and 8:1 to 1:1 is preferred.
Preferably, when the composite film is of a three-layer structure, namely the gutta-percha/polycaprolactone/gutta-percha composite film layer, the weight ratio of the gutta-percha to the polycaprolactone to the gutta-percha is 8:1:8 to 1:1: 1.
Has the advantages that:
the raw materials used in the invention are green and degradable, and the method used is low in cost and simple in process. The composite membrane is formed on a mould by casting the gutta percha and the polycaprolactone solution layer by layer, and the composite membrane with different performances can be obtained by changing the concentration and the proportion of reactants. The obtained gutta-percha/polycaprolactone/gutta-percha composite membrane material has good elasticity, hydrophobicity and toughness.
Drawings
FIG. 1 is a schematic diagram showing the process of the present invention;
FIG. 2 is an infrared spectrum of a gutta percha/polycaprolactone/gutta percha composite film prepared according to an embodiment;
fig. 3 is a tensile stress-tensile strain diagram of the gutta percha/polycaprolactone/gutta percha composite film prepared according to the example.
Fig. 4 is a water contact angle diagram of the gutta percha/polycaprolactone/gutta percha composite membrane prepared according to the example.
Detailed Description
Hereinafter, the present invention will be described in detail. Before the description is made, it should be understood that the terms used in the present specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description proposed herein is just a preferable example for the purpose of illustrations only, not intended to limit the scope of the invention, so it should be understood that other equivalents and modifications could be made thereto without departing from the spirit and scope of the invention.
In the preparation method according to the present invention, the gutta-percha in the step (1) is obtained by extracting eucommia seeds with petroleum ether, and the extraction and separation can be performed according to the extraction method of gutta-percha disclosed in chinese patent application CN104231281, for example.
In addition, in the preparation method according to the present invention, the reaction conditions for dissolving gutta percha in chloroform in the step (1) are as follows: the reaction temperature is 50 ℃, the rotating speed of a magnetic stirrer is 700rpm, and the reaction time is 3 h. The reaction conditions for dissolving polycaprolactone in chloroform are as follows: the reaction temperature is 40 ℃, the rotating speed of the magnetic stirrer is 600rpm, and the reaction time is 3 h.
Preferably, in the preparation method according to the present invention, the casting interval time between the second polyhexamethylene lactone layer and the first gutta-percha layer is 2-3h, that is, the drying time of the first gutta-percha layer, and by controlling the casting interval time (drying time), the casting can be performed before the first layer of film is not completely dried, which is beneficial to mutual diffusion, permeation and entanglement of two polymer chains. Similarly, the casting interval time between the third eucommia ulmoides gum layer and the second polyhexamethylene lactone layer is 1-2 h.
Preferably, when the gutta percha layer is a lower layer, and the polycaprolactone layer is cast thereon, the casting interval time is preferably 2-3h because the diffusion speed of polycaprolactone is slow. When the polycaprolactone layer is a lower layer on which the gutta percha layer is cast, the casting interval time is preferably 1-2 hours, because the gutta percha layer diffuses relatively faster. Preferably, the degree of interdiffusion between the gutta percha layer and the polycaprolactone layer can be controlled by controlling the casting interval time, so as to obtain a multilayer structure with proper performance according to needs.
Preferably, the drying time of the individual layers is 2-3h, more preferably 1-2 h.
The following examples are given by way of illustration of embodiments of the invention and are not to be construed as limiting the invention, and it will be understood by those skilled in the art that modifications may be made without departing from the spirit and scope of the invention. Unless otherwise specified, reagents and equipment used in the following examples are commercially available products.
The schematic diagram of the compounding method of gutta-percha and polycaprolactone is shown in fig. 1, wherein the thick line represents gutta-percha (EUG) molecules, the thin line represents Polycaprolactone (PCL) molecules, and the composite membrane is formed in a layer-by-layer casting mode. From the FT-IR spectrum (figure 2), it can be seen that no new chemical bonds are formed between the composite membranes, which means that the composite membranes are physically mixed and have physical molecular chain diffusion, penetration and entanglement.
In the research on the mixed membrane of gutta-percha and high polymer materials in the prior art, the elongation at break is 43.2-365%; the breaking elongation of the gutta-percha and polycaprolactone composite membrane can reach 514 percent at most, the highest water contact angle value is 106.5 degrees, and the hydrophobicity is good.
Comparative example 1
The method comprises the following steps: (1) taking 70g of crushed eucommia seeds, adding the crushed eucommia seeds into a heating container according to the material-liquid ratio l:20, cooking the mixture by using 2% NaOH at 80 ℃ for 180min, and filtering the mixture to obtain filtrate and residues. Filtering, washing the obtained filter residue with water to neutrality, and drying or freeze drying in a 50 deg.C oven for use.
(2) Extracting the dried residue with petroleum ether (boiling range of 60-90 deg.C) under reflux in 80-85 deg.C water bath for 6-7h, cooling to room temperature, freezing the filtrate in-18 deg.C refrigerator for 3h, taking out, and filtering to obtain residue which is crude gutta Percha. The crude gum is decolorized by acetone in a Soxhlet extractor to obtain white eucommia ulmoides gum extract. Finally, wrapping the paper with tinfoil paper, and storing the paper in a vacuum drying box for later use.
Step two: mixing 0.08g gutta Percha with 10ml chloroform, stirring at 50 deg.C for 3 hr, and rotating at 700 rpm. The obtained gutta-percha solution was placed in a vacuum drying oven for 1 hour to be degassed. The gutta percha solution was then cast in a teflon mold for 2h in a fume hood at room temperature as a first layer of film.
Step three: mixing 0.08g gutta Percha with 10ml chloroform, stirring at 50 deg.C for 3 hr, and rotating at 700 rpm. The obtained gutta-percha solution was placed in a vacuum drying oven for 1 hour to be degassed. The gutta percha solution was then cast onto the first membrane as a second membrane in a fume hood at room temperature. After 24h the composite film was peeled from the mold and placed in a vacuum oven for 3 days and labeled P0.
The elongation at break of the composite film was determined to be 389%. The water contact angle was 84.15 °.
Example 1
The method comprises the following steps: gutta-percha was extracted in the same manner as in comparative example 1.
Step two: mixing 0.08g gutta Percha with 10ml chloroform, stirring at 50 deg.C for 3 hr, and rotating at 700 rpm. The obtained gutta-percha solution was placed in a vacuum drying oven for 1 hour to be degassed. The gutta percha solution was then cast in a teflon mold for 2h in a fume hood at room temperature as a first layer of film.
Step three: mixing 0.01g of polycaprolactone with 4ml of chloroform, stirring for 3h under the heating condition of 40 ℃, rotating at 600rpm to obtain a polycaprolactone solution with the mass concentration of 0.17 wt%. The polycaprolactone solution obtained was placed in a vacuum oven for 30min for degassing. The polycaprolactone solution was then cast on the first film as a second film in a fume hood at room temperature for 1 h.
Step four: mixing 0.08g gutta Percha with 10ml chloroform, stirring at 50 deg.C for 3 hr, and rotating at 700 rpm. The obtained gutta-percha solution was placed in a vacuum drying oven for 1 hour to be degassed. The gutta percha solution was then cast onto the second membrane as a third membrane in a fume hood at room temperature. After 24h the composite film was peeled from the mold and placed in a vacuum oven for 3 days and labeled P0.17wt%.
The elongation at break of the composite film was found to be 459%. The water contact angle was 101.85 °.
Example 2
The method comprises the following steps: gutta-percha was extracted in the same manner as in comparative example 1.
Step two: the first film was prepared in the same manner as in example 1.
Step three: mixing 0.03g of polycaprolactone with 4ml of chloroform, stirring for 3 hours under the heating condition of 40 ℃, and rotating at 600rpm to obtain a polycaprolactone solution with the mass concentration of 0.51 wt%. The polycaprolactone solution obtained was placed in a vacuum oven for 30min for degassing. The polycaprolactone solution was then cast on the first film as a second film in a fume hood at room temperature for 1 h.
Step four: mixing 0.08g gutta Percha with 10ml chloroform, stirring at 50 deg.C for 3 hr, and rotating at 700 rpm. The obtained gutta-percha solution was placed in a vacuum drying oven for 1 hour to be degassed. The gutta percha solution was then cast onto the second membrane as a third membrane in a fume hood at room temperature. After 24h the composite film was peeled from the mould and placed in a vacuum oven at 30 ℃ for 3 days and labelled P0.51wt%.
The elongation at break of the composite film was found to be 442%. The water contact angle was 99.65 °.
Example 3
The method comprises the following steps: gutta-percha was extracted in the same manner as in comparative example 1.
Step two: the first film was prepared in the same manner as in example 1.
Step three: mixing 0.05g of polycaprolactone with 4ml of chloroform, stirring for 3h under the heating condition of 40 ℃, rotating at 600rpm to obtain a polycaprolactone solution with the mass concentration of 0.84 wt%. The polycaprolactone solution obtained was placed in a vacuum oven for 30min for degassing. The polycaprolactone solution was then cast on the first film as a second film in a fume hood at room temperature for 1 h.
Step four: mixing 0.08g gutta Percha with 10ml chloroform, stirring at 50 deg.C for 3 hr, and rotating at 700 rpm. The obtained gutta-percha solution was placed in a vacuum drying oven for 1 hour to be degassed. The gutta percha solution was then cast onto the second membrane as a third membrane in a fume hood at room temperature. After 24h the composite film was peeled from the mold and placed in a vacuum oven for 3 days and labeled P0.84wt%.
The elongation at break of the composite film was determined to be 514%. The water contact angle is 106.5 °
Example 4
The method comprises the following steps: gutta-percha was extracted in the same manner as in comparative example 1.
Step two: the first film was prepared in the same manner as in example 1.
Step three: mixing 0.08g polycaprolactone with 4ml chloroform, stirring at 600rpm under heating at 40 deg.C for 3 hr. The polycaprolactone solution obtained was placed in a vacuum oven for 30min for degassing. The polycaprolactone solution was then cast on the first film as a second film in a fume hood at room temperature for 1 h.
Step four: mixing 0.08g gutta Percha with 10ml chloroform, stirring at 50 deg.C for 3 hr, and rotating at 700 rpm. The obtained gutta-percha solution was placed in a vacuum drying oven for 1 hour to be degassed. The gutta percha solution was then cast onto the second membrane as a third membrane in a fume hood at room temperature. After 24h the composite film was peeled from the mold and placed in a vacuum oven for 3 days and labeled P1.30wt%.
The elongation at break of the composite film was determined to be 398%. The water contact angle was 92.6 °.
Example 5
The method comprises the following steps: gutta-percha was extracted in the same manner as in comparative example 1.
Step two: the first film was prepared in the same manner as in example 1.
Step three: 0.08g of polycaprolactone is mixed with 4ml of trichloromethane, and the mixture is stirred for 3 hours under the heating condition of 40 ℃ and the rotating speed is 600 rpm. The polycaprolactone solution obtained was placed in a vacuum oven for 30min for degassing. The polycaprolactone solution was then cast on the first film as a second film in a fume hood at room temperature for 1 h.
Step four: mixing 0.08g gutta Percha with 10ml chloroform, stirring at 50 deg.C for 3 hr, and rotating at 700 rpm. The obtained gutta-percha solution was placed in a vacuum drying oven for 1 hour to be degassed. The gutta percha solution was then cast onto the second membrane as a third membrane in a fume hood at room temperature.
Step five: and (4) preparing a polycaprolactone solution according to the method in the third step, and casting the polycaprolactone solution on the third layer of film for 1h to serve as a fourth layer of film.
Step six: and C, preparing the gutta-percha solution according to the method in the step four, and casting the gutta-percha solution on the fourth membrane in the ventilation cabinet to serve as a fifth membrane. After 24h, the composite film was peeled off from the mold and placed in a vacuum oven for 3 days.
The elongation at break of the composite film was determined to be 137%. The water contact angle was 110.5 °.
The eucommia ulmoides gum base composite film material is prepared in a green, simple and rapid mode, the film material is good in hydrophobicity and has certain toughness, and the series of composite film materials can be considered to be used in the field of packaging.
Claims (16)
1. A preparation method of a eucommia ulmoides gum base composite film is characterized by comprising the following steps:
(1) dissolving gutta-percha and polycaprolactone in chloroform respectively to obtain a gutta-percha solution with the mass percent concentration of 0.4-0.6 wt% and a polycaprolactone solution with the mass percent concentration of 0.17-1.30 wt%;
(2) pouring the gutta-percha solution into a flat polytetrafluoroethylene mold, and drying for 1-6h under ventilation conditions to obtain a gutta-percha film layer;
(3) pouring a polycaprolactone solution on the eucommia ulmoides gum film layer obtained in the step (2), and drying for 1-6h under a ventilation condition to obtain a polycaprolactone film layer;
(4) pouring the gutta-percha solution on the polycaprolactone film layer obtained in the step (3) to obtain a sandwich type gutta-percha/polycaprolactone/gutta-percha composite film layer;
(5) and (3) drying the composite film layer obtained in the step (4) for more than 24 hours under the condition of room temperature ventilation to obtain a composite film, stripping the composite film from the mold, and drying the composite film in a vacuum drying oven.
2. The method according to claim 1, wherein the gutta percha in the step (1) is obtained by extracting eucommia seed with petroleum ether.
3. The preparation method according to claim 1, wherein the steps (2) and (3) are alternately performed a plurality of times to form a composite film in which gutta percha and polycaprolactone are alternately layered.
4. The preparation method according to claim 3, wherein the multilayer alternating composite film of gutta percha and polycaprolactone is 3-7 layers, and the outermost layer of the multilayer alternating composite film is a gutta percha layer.
5. The preparation method according to claim 4, wherein the multilayer alternating composite film of gutta percha and polycaprolactone is 3-5 layers, and the outermost layer of the multilayer alternating composite film is a gutta percha layer.
6. The preparation method according to claim 4, wherein the multilayer alternating composite film of gutta percha and polycaprolactone is 3 layers, and the outermost layer of the multilayer alternating composite film is a gutta percha layer.
7. The method according to claim 3, wherein the weight ratio of gutta percha to polycaprolactone in each gutta percha layer and each polycaprolactone layer is controlled by the casting amount of each layer.
8. The method of claim 1, wherein the drying time of each layer is 2 to 3 hours.
9. The method of claim 8, wherein the drying time of each layer is 1 to 2 hours.
10. An gutta-percha and polycaprolactone-based composite membrane prepared according to the preparation method of any one of claims 1 to 9.
11. The gutta-percha and polycaprolactone-based composite film according to claim 10, wherein the composite film is a composite film in which 3 to 7 layers of gutta-percha and polycaprolactone are alternately stacked, and the outermost layer of the composite film is a gutta-percha layer.
12. The gutta-percha and polycaprolactone-based composite film according to claim 11, wherein the composite film is a composite film in which 3 to 5 layers of gutta-percha and polycaprolactone are alternately stacked, and the outermost layer of the composite film is a gutta-percha layer.
13. The gutta-percha and polycaprolactone-based composite film according to claim 11, wherein the composite film is a composite film in which 3 layers of gutta-percha and polycaprolactone are alternately stacked, and the outermost layer of the composite film is a gutta-percha layer.
14. The gutta-percha and polycaprolactone-based composite film according to claim 10, wherein a weight ratio of the gutta-percha in each gutta-percha layer to the polycaprolactone in each polycaprolactone layer in the composite film is 10:1 to 1: 1.
15. The gutta-percha and polycaprolactone-based composite film according to claim 14, wherein a weight ratio of the gutta-percha in each gutta-percha layer to the polycaprolactone in each polycaprolactone layer in the composite film is 8:1 to 1: 1.
16. The gutta-percha and polycaprolactone-based composite film according to claim 10, wherein when the composite film is a three-layer structure, namely the gutta-percha/polycaprolactone/gutta-percha composite film layer, the weight ratio of the gutta-percha to the polycaprolactone to the gutta-percha is 8:1:8 to 1:1: 1.
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