CN111849112B - Super-hydrophobic styrene thermoplastic elastomer material, preparation method thereof, infusion medical device and application - Google Patents
Super-hydrophobic styrene thermoplastic elastomer material, preparation method thereof, infusion medical device and application Download PDFInfo
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- CN111849112B CN111849112B CN202010788499.2A CN202010788499A CN111849112B CN 111849112 B CN111849112 B CN 111849112B CN 202010788499 A CN202010788499 A CN 202010788499A CN 111849112 B CN111849112 B CN 111849112B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M5/00—Devices for bringing media into the body in a subcutaneous, intra-vascular or intramuscular way; Accessories therefor, e.g. filling or cleaning devices, arm-rests
- A61M5/14—Infusion devices, e.g. infusing by gravity; Blood infusion; Accessories therefor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/08—Heat treatment
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M2205/00—General characteristics of the apparatus
- A61M2205/02—General characteristics of the apparatus characterised by a particular materials
- A61M2205/0216—Materials providing elastic properties, e.g. for facilitating deformation and avoid breaking
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
- C08J2491/06—Waxes
Abstract
The invention provides a preparation method of a super-hydrophobic styrene thermoplastic elastomer material, which utilizes plastic SEBS as a substrate, induces SEBS phase separation by means of a good solvent/poor solvent, introduces low-surface-energy palm wax and performs annealing treatment to prepare a super-hydrophobic SEBS surface, fully utilizes the super-hydrophobic surface prepared by low surface energy and a rough structure to achieve a hydrophobic effect, and further resists the adsorption of butylphthalide drugs dissolved in an aqueous solution so as to be used for resisting the adsorption of the butylphthalide drugs. The good solvent/poor solvent induced phase separation method does not need expensive equipment, and has simple process and convenient production; the super-hydrophobic SEBS surface is constructed, the rough surface structure is utilized, the low surface energy performance of the palm wax is fully utilized, and the butylphthalide resistance effect is more excellent. The invention also provides a super-hydrophobic styrene thermoplastic elastomer material, an infusion medical device and application.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a super-hydrophobic styrene thermoplastic elastomer material, a preparation method thereof, an infusion medical device and an application thereof.
Background
With the rapid development of economy and society, the living conditions and medical conditions of people are continuously improved, however, the morbidity and mortality of some diseases are obviously improved due to improper living modes, rapid working rhythm and accelerated population aging, and the health of people is seriously threatened. For example, stroke, called stroke, is brain tissue damage (including hemorrhagic stroke and ischemic stroke) caused by blood failing to flow through the brain due to rupture of cerebral blood vessels or blockage of blood vessels, the stroke morbidity in China is 250 tens of thousands, wherein 200 tens of deaths are encountered, about 75% of survivors have disabilities of different degrees, wherein the number of serious disabilities is 40%, and the disease has the characteristics of high morbidity, high mortality and high disability rate, and has become the first cause of death in China.
Fortunately, our country independently develops new butylphthalide which has better therapeutic effect on ischemic stroke, however, during the process of infusion, the wall-hanging phenomenon appears on the surface of the infusion device, i.e. the drug has higher adsorption rate on the surface of the infusion device, which not only causes drug loss, but also seriously threatens the life safety of patients, thus arousing extensive attention of people. Hydrogenated polystyrene-b-butadiene-b-polystyrene (SEBS) has the characteristics of excellent thermal stability, thermoplasticity, high transparency and the like, and is an ideal material for replacing PVC medical materials, so that the SEBS material capable of efficiently resisting adsorption of the butylphthalide drug is designed and prepared and has important significance.
However, the research on the anti-butylphthalide drug adsorbing material and even on the common drug adsorbing material is less. For example, in patent CN109517206B, a vitamin E-like layer is constructed by biomimetic adhesion of dopamine on the surface of SEBS, so that adsorption of butylphthalide on the surface of SEBS can be effectively inhibited; the patent CN 101537216 prepares a polyurethane/polyvinyl chloride double-layer infusion apparatus by a co-extrusion blow molding method, thereby reducing the adsorption amount of drug molecules on the surface of a single polyvinyl chloride infusion apparatus. CN108329440A prepares low drug adsorbing material by melt grafting vinyl fluorosilicone oil to styrene thermoplastic elastomer.
The preparation method involves chemical reaction and large-scale equipment in the preparation process, and has high cost and relatively complex process.
Disclosure of Invention
The invention aims to provide a super-hydrophobic styrene thermoplastic elastomer material, a preparation method thereof, an infusion medical device and application.
The invention provides a preparation method of a super-hydrophobic styrene thermoplastic elastomer material, which comprises the following steps:
A) preparing a good solvent solution of SEBS;
B) adding a low-surface-energy substance and a poor solvent into the good solvent solution of the SEBS in the step A) to obtain a mixed solution;
the boiling point of the good solvent is 120-155 ℃, and the boiling point of the poor solvent is 200-280 ℃;
the low surface energy substance is one or more of palm wax, beeswax, sliced paraffin wax, liquid paraffin and fluorine silicon compounds;
C) volatilizing the mixed solution in the step B) in a container to form a film, and annealing the obtained film to obtain the super-hydrophobic styrene thermoplastic elastomer material.
Preferably, the mass concentration of the SEBS in the good solvent solution of the SEBS is 0.05-50 wt%;
preferably, the good solvent is one or more of xylene, octane, chlorobenzene and N, N dimethylformamide, and the poor solvent is one or more of n-decanol, diethylene glycol, ethylene carbonate and benzyl alcohol.
Preferably, the volume ratio of the good solvent to the poor solvent is 10: 1-1: 10.
preferably, the ratio of the mass of the low surface energy substance to the total mass of the good solvent and the poor solvent is (0.01 to 25): 100.
preferably, the temperature for volatilization in the step C) is 20-30 ℃; and C), volatilizing for 1-48 hours.
Preferably, the annealing temperature in the step C) is 30-150 ℃, and the annealing time in the step C) is 0.1-48 hours.
The invention provides a super-hydrophobic styrene thermoplastic elastomer material prepared by the preparation method.
The invention provides an infusion medical device which is prepared from the super-hydrophobic styrene thermoplastic elastomer material.
Use of a superhydrophobic styrenic thermoplastic elastomer material as described above or an infusion-type medical device as described above for the infusion of an easily adsorbable drug.
The invention provides a preparation method of a super-hydrophobic styrene thermoplastic elastomer material, which comprises the following steps: A) preparing a good solvent solution of SEBS; B) adding a low-surface-energy substance and a poor solvent into the good solvent solution of the SEBS in the step A) to obtain a mixed solution; the boiling point of the good solvent is 100-150 ℃, and the boiling point of the poor solvent is 200-280 ℃; the low surface energy substance is one or more of palm wax, beeswax, sliced paraffin wax, liquid paraffin and fluorine silicon compounds; C) volatilizing the mixed solution in the step B) in a container to form a film, and annealing the obtained film to obtain the super-hydrophobic styrene thermoplastic elastomer material. The invention aims to utilize the plastic SEBS as a substrate, induce SEBS phase separation by means of a good solvent/poor solvent, introduce low-surface-energy carnauba wax and perform annealing treatment to prepare the super-hydrophobic SEBS surface, fully utilize the super-hydrophobic surface prepared by the low surface energy and the rough structure to achieve a hydrophobic effect, and further resist the adsorption of butylphthalide drugs dissolved in an aqueous solution so as to be used for anti-butylphthalide drug adsorption. The SEBS material has strong plasticity, and can be made into medical products with various shapes in the later processing process; the good solvent/poor solvent induced phase separation method does not need expensive equipment, and has simple process and convenient production; the super-hydrophobic SEBS surface is constructed, the rough surface structure is utilized, the low surface energy performance of the palm wax is fully utilized, and the butylphthalide resistance effect is more excellent.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 shows the test results of an ultraviolet spectrophotometer in which butylphthalide stock solution is adsorbed for 1 hour at room temperature inside the bag-shaped samples of example 1 and comparative examples 1-2 of the present invention;
FIG. 2 shows the concentration of butylphthalide stock solution after adsorbing the inside of the bag-shaped samples of example 1 and comparative examples 1 to 2 of the present invention at room temperature for 1 hour, relative to the stock solution.
Detailed Description
The invention provides a preparation method of a super-hydrophobic styrene thermoplastic elastomer material, which comprises the following steps:
A) preparing a good solvent solution of SEBS;
B) adding a low-surface-energy substance and a poor solvent into the good solvent solution of the SEBS in the step A) to obtain a mixed solution;
the boiling point of the good solvent is 120-155 ℃, and the boiling point of the poor solvent is 200-280 ℃;
the low surface energy substance is one or more of palm wax, beeswax, sliced paraffin wax, liquid paraffin and fluorine silicon compounds;
C) volatilizing the mixed solution in the step B) in a container to form a film, and annealing the obtained film to obtain the super-hydrophobic styrene thermoplastic elastomer material.
Firstly, SEBS (hydrogenated polystyrene-b-butadiene-b-polystyrene) is dissolved in a good solvent, and is uniformly stirred at room temperature to prepare a good solvent solution of the SEBS.
In the invention, the boiling point of the good solvent is preferably one or more of xylene (the boiling point is 138 ℃), octane (the boiling point is 125-127 ℃), chlorobenzene (132.2 ℃) and N, N dimethylformamide (the boiling point is 152.8 ℃), and the good solvent is more preferably xylene; in the good solvent solution of the SEBS, the mass concentration of the SEBS is preferably 0.05 to 50wt%, more preferably 1 to 40 wt%, and most preferably 5 to 30 wt%, and specifically, in the embodiment of the present invention, may be 5 to 15 wt%.
The source of the SEBS used in the present invention is not particularly limited, and the method of the present invention is applicable to various types of SEBS, and preferably, the SEBS having a number average molecular weight Mn of 74800 and a styrene repeating unit content of 29 wt% is selected in the examples of the present invention, and its commercial product type is G1652.
After a good solvent solution of SEBS is obtained, a low-surface-energy substance and a poor solvent are added into the good solvent solution of SEBS, and stirring is carried out under a heating condition to obtain a mixed solution of SEBS.
The poor solvent in the invention is preferably one or more of n-decanol (233 ℃), diethylene glycol (245 ℃), ethylene glycol carbonate (270 ℃) and benzyl alcohol (205.7 ℃), and more preferably n-decanol.
In the invention, the low surface energy substance is preferably a low surface energy substance, and is preferably one or more of palm wax, beeswax, sliced paraffin wax, liquid paraffin and fluorine silicon compounds.
The SEBS is induced to separate by using a good solvent/poor solvent, the SEBS is firstly dissolved into a mixed solvent of the good solvent and the poor solvent by heating, then at room temperature, the SEBS solubility is reduced and gradually precipitated as the good solvent is volatilized because the good solvent has a low boiling point such as xylene (138 ℃) and is easy to volatilize, and the poor solvent has a high boiling point such as n-decanol (233 ℃) and has a slow volatilization speed, and the SEBS film precipitated is further used as a liquid template and has a similar action with a pore-forming agent because the poor solvent has a slow volatilization speed of the n-decanol. So that the SEBS surface can build a rough structure, and when the surface rough structure is rough enough, the super-hydrophobic effect can be achieved.
In the present invention, the volume ratio of the good solvent to the poor solvent is preferably 10: 1-1: 10, more preferably 8: 1 to 1:8, most preferably 5:1 to 1:5, and specifically, in the embodiment of the present invention, may be 3: 1.
In the embodiment of the invention, the good solvent is preferably xylene, the poor solvent is preferably n-decanol, firstly, the xylene is used as the good solvent and can dissolve SEBS, the xylene volatilization speed is slower than that of chloroform and the like, the surface can form a complete spherical structure, and the solvent with the higher volatilization speed such as chloroform and the like can cause the microsphere structures to be adhered and can not form a super-hydrophobic structure surface; the n-decanol not only serves as a precipitator of the SEBS polymer to induce SEBS phase separation, but also serves as a liquid template to stabilize a microsphere structure formed on the surface of the SEBS. Similarly, both good and poor solvents that can achieve the above process can be used to perform the above process, such as several of the good and poor solvents listed in the present invention.
Because most of the prior medicaments such as butylphthalide and the like are coated by cyclodextrin and other compounds capable of forming cavities or pore channels, such as crown ether, calixarene, cucurbituril and other crystalline inclusion compounds, molecular inclusion compounds, macromolecular inclusion compounds and the like, the invention introduces low-surface-energy substances, and the low-surface-energy substances mainly have the effect of further reducing the interaction between high-molecular materials such as SEBS and easily-absorbable medicaments such as cyclodextrin butylphthalide inclusion compounds, so that the adsorption of the cyclodextrin butylphthalide inclusion compounds is reduced, when the addition amount of the low-surface-energy substances is higher, the occurrence of phase separation is influenced, and the surfaces cannot form rough surfaces with microsphere structures. Therefore, the ratio of the low surface energy substance to the total mass of the good solvent and the poor solvent in the present invention is preferably (0.01 to 25): 100, more preferably (0.1 to 20): 100, most preferably (1-15): 100, and in particular, in embodiments of the present invention, may be 2: 100.
In the invention, the heating temperature of the SEBS in the good solvent/poor solvent is preferably 30-150 ℃, more preferably 40-120 ℃, and most preferably 50-100 ℃; in the invention, the solution is preferably stirred at the heating temperature for 1 to 24 hours, more preferably 3 to 20 hours, and most preferably 5 to 15 hours.
After the mixed solution of SEBS is obtained, the mixed solution is preferably poured into a container and volatilized at room temperature to form a film. In the present invention, the container may be an aluminum container, a stainless steel container, a polytetrafluoroethylene container, or the like.
After film formation, the prepared film is ultrasonically cleaned by ethanol and dried for later use.
According to the invention, the dried film is preferably annealed to obtain the super-hydrophobic styrene thermoplastic elastomer material.
The annealing treatment in the invention can cause the low surface energy substance with low surface energy to generate surface migration, but the annealing temperature is too high, so that the microsphere structure is collapsed, condensed and adhered, and the rough surface of the microsphere structure can be damaged. In the invention, the annealing temperature is preferably 30-150 ℃, more preferably 40-120 ℃, and most preferably 50-100 ℃, specifically, in the embodiment of the invention, 60 ℃; the annealing time is preferably 0.1 to 48 hours, more preferably 3 to 36 hours, and most preferably 8 to 24 hours.
The invention also provides a super-hydrophobic styrene thermoplastic elastomer material prepared by the preparation method.
The invention also provides an infusion medical device which is obtained by processing the super-hydrophobic styrene-based thermoplastic elastomer material, wherein the processing refers to the processing of the shape and the size of the super-hydrophobic styrene-based thermoplastic elastomer material, or the addition, the modification, even the addition of the preparation steps and the like of the conventional raw materials which are well known by the technical personnel on the basis of not departing from the preparation principle of the super-hydrophobic styrene-based thermoplastic elastomer material.
The invention also provides an application of the super-hydrophobic styrene thermoplastic elastomer material or the infusion medical device in the infusion of the easily-absorbed medicine.
In the invention, the easily-adsorbed drug refers to a drug which is easily adsorbed on the surface of an infusion apparatus and is easily hung on the wall on the surface of the infusion apparatus. Such as butylphthalide, vitamin D2, etc., in the art, compounds with pore or cavity, such as cyclodextrin, crown ether, calixarene, cucurbituril, etc., crystalline inclusion compounds, molecular inclusion compounds, macromolecular inclusion compounds, etc., are usually used to carry and include the insoluble drugs.
The invention provides a preparation method of a super-hydrophobic styrene thermoplastic elastomer material, which comprises the following steps: A) preparing a good solvent solution of SEBS; B) adding a low-surface-energy substance and a poor solvent into the good solvent solution of the SEBS in the step A) to obtain a mixed solution; the boiling point of the good solvent is 100-150 ℃, and the boiling point of the poor solvent is 200-280 ℃; the low surface energy substance is one or more of palm wax, beeswax, sliced paraffin wax, liquid paraffin and fluorine silicon compounds; C) volatilizing the mixed solution in the step B) in a container to form a film, and annealing the obtained film to obtain the super-hydrophobic styrene thermoplastic elastomer material. The invention aims to utilize the plastic SEBS as a substrate, induce SEBS phase separation by means of a good solvent/poor solvent, introduce low-surface-energy carnauba wax and perform annealing treatment to prepare the super-hydrophobic SEBS surface, fully utilize the super-hydrophobic surface prepared by the low surface energy and the rough structure to achieve a hydrophobic effect, and further resist the adsorption of butylphthalide drugs dissolved in an aqueous solution so as to be used for anti-butylphthalide drug adsorption. The SEBS material has strong plasticity, and can be made into medical products with various shapes in the later processing process; the good solvent/poor solvent induced phase separation method does not need expensive equipment, and has simple process and convenient production; the super-hydrophobic SEBS surface is constructed, the rough surface structure is utilized, the low surface energy performance of the palm wax is fully utilized, and the butylphthalide resistance effect is more excellent.
Compared with the prior art, the method has the following advantages:
1) the method is characterized in that the plastic SEBS is used as a substrate, a good solvent/poor solvent is used for inducing SEBS phase separation, low-surface-energy carnauba wax is introduced, and annealing treatment is carried out to prepare the super-hydrophobic SEBS surface, so that the super-hydrophobic surface prepared by the low surface energy and the rough structure is fully utilized to achieve a hydrophobic effect, and then adsorption of the butylphthalide drug dissolved in the water solution is resisted, and the super-hydrophobic SEBS surface is used for resisting adsorption of the butylphthalide drug. The SEBS material has strong plasticity, and can be made into medical products with various shapes in the later processing process; the good solvent/poor solvent induced phase separation method does not need expensive equipment, and has simple process and convenient production;
2) by introducing the low-surface-energy carnauba wax and annealing treatment, the super-hydrophobic SEBS surface without introducing the carnauba wax and annealing treatment has more excellent anti-butylphthalide adsorption effect.
3) There is no report on any relevant patent and literature about the anti-adsorption of butylphthalide drug by using xylene/n-decanol to induce SEBS phase separation, introducing low-surface-energy carnauba wax and preparing super-hydrophobic SEBS through annealing treatment.
In order to further illustrate the present invention, the following examples are provided to describe the super-hydrophobic styrene-based thermoplastic elastomer material, the preparation method thereof, the infusion medical device and the application thereof in detail, but the invention should not be construed as limiting the scope of the present invention.
Example 1
Firstly, 10g of SEBS powder is dissolved in 100mL of dimethylbenzene, the mixture is stirred for 3h at room temperature, 75mL of n-decanol and certain mass (1%) of palm wax are added, the mixture is stirred vigorously for 3h at 100 ℃, the mixed solution is poured into an aluminum alloy mold, and the mixture is volatilized overnight at room temperature. Taking out the membrane, placing the membrane in ethanol for ultrasonic treatment for a certain time, drying the membrane, and then annealing the membrane at 60 ℃ for later use, wherein the membrane is named SEBS-SHB-1-60 ℃.
The super-hydrophobic SEBS membrane (SEBS-SHB-1-60 ℃) prepared by the method is made into a blood bag shape by a heat sealing instrument, then 1mLNBP stock solution is added, standing and adsorption are carried out for 1h at room temperature, then an ultraviolet visible spectrophotometer is used for testing the concentration of the butylphthalide solution in the bag, and the result is shown in figures 1-2, wherein the concentration of the internal solution is 89.85% of the concentration of the original solution, compared with the concentration of the unmodified SEBS internal solution (35.8% of the concentration of the original solution), the content of the internal butylphthalide is improved by about 151%, and the adsorption amount is reduced by 84.2%.
Example 2
Firstly, 10g of SEBS powder is dissolved in 100mL of dimethylbenzene, the mixture is stirred for 3h at room temperature, 75mL of n-decanol and a certain mass of palm wax are added, the mixture is stirred vigorously for 3h at 100 ℃, the mixed solution is poured into a polytetrafluoroethylene mold, and the mixture is volatilized overnight at room temperature. And taking out the film, placing the film in ethanol for ultrasonic treatment for a certain time, drying the film, and then carrying out annealing treatment for later use.
The super-hydrophobic SEBS membrane prepared by the method is made into a blood bag shape by a heat sealing instrument, 1mLNBP stock solution is added, standing and adsorption are carried out for 1h at room temperature, then an ultraviolet visible spectrophotometer is used for testing the concentration of the butylphthalide solution in the bag, and the result is shown in figure 1, wherein the concentration of the internal solution is 85% of the concentration of the original solution, the content of the internal butylphthalide is improved by about 137% compared with the concentration of the internal solution of the unmodified SEBS (35.8% of the concentration of the original solution), and the adsorption amount is reduced by 76.6%.
Example 3
Firstly, 10g of SEBS powder is dissolved in 100mL of dimethylbenzene, the mixture is stirred for 3h at room temperature, 75mL of n-decanol and a certain mass of palm wax are added, the mixture is stirred vigorously for 3h at 100 ℃, the mixed solution is coated on the surface of aluminum foil paper, and the mixture is volatilized overnight at room temperature. And taking out the film, placing the film in ethanol for ultrasonic treatment for a certain time, drying the film, and then carrying out annealing treatment for later use.
The super-hydrophobic SEBS membrane prepared by the method is made into a blood bag shape by a heat sealing instrument, 1mLNBP stock solution is added, standing and adsorption are carried out for 1h at room temperature, then an ultraviolet visible spectrophotometer is used for testing the concentration of the butylphthalide solution in the bag, and the result is shown in figure 1, wherein the concentration of the internal solution is 83% of the concentration of the original solution, the content of the internal butylphthalide is improved by about 131% compared with the concentration of the internal solution of the unmodified SEBS (35.8% of the concentration of the original solution), and the adsorption amount is reduced by 73.5%.
Comparative example 1
Firstly, 10g of SEBS powder is dissolved in 100mL of dimethylbenzene, the mixture is stirred for 3h at room temperature, 75mL of n-decanol is added, the mixture is stirred vigorously for 3h at 100 ℃, the mixed solution is poured into a polytetrafluoroethylene mold, and the mixture is volatilized overnight at room temperature. And taking out the membrane, placing the membrane in ethanol, performing ultrasonic treatment for a certain time, and drying the membrane for later use to be named SEBS-SHB.
The super-hydrophobic SEBS membrane (SEBS-SHB) prepared by the method is made into a blood bag shape by using a heat sealing instrument, then 1mLNBP stock solution is added, standing and adsorption are carried out for 1h at room temperature, then an ultraviolet-visible spectrophotometer is used for testing the concentration of the butylphthalide solution in the bag, and the result is shown in figures 1-2, and the result shows that the concentration of the internal solution is 63.7% of the concentration of the original solution, the content of the internal butylphthalide is improved by about 77.9% and the adsorption amount is reduced by 43.5% compared with the concentration of the unmodified SEBS internal solution (35.8% of the concentration of the original solution).
Comparative example 2
Firstly, 10g of SEBS powder is dissolved in 100mL of dimethylbenzene, the mixture is stirred for 3h at room temperature, 75mL of n-decanol and certain mass (1%) of palm wax are added, the mixture is stirred vigorously for 3h at 100 ℃, the mixed solution is poured into an aluminum alloy mold, and the mixture is volatilized overnight at room temperature. And taking out the membrane, placing the membrane in ethanol for ultrasonic treatment for a certain time, and drying the membrane for later use, wherein the membrane is named as SEBS-SHB-1%.
The super-hydrophobic SEBS membrane (SEBS-SHB-1%) prepared by the method is made into a blood bag shape by using a heat sealing instrument, then 1mLNBP stock solution is added, standing is carried out at room temperature for adsorption for 1h, then an ultraviolet-visible spectrophotometer is used for testing the concentration of the butylphthalide solution in the bag, and the result is shown in figures 1-2, wherein the concentration of the internal solution is 65.1% of that of the original solution, compared with the concentration of the unmodified SEBS internal solution (35.8% of that of the original solution), the content of the internal butylphthalide is improved by about 81.8%, and the adsorption amount is reduced by 45.6%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A preparation method of a super-hydrophobic styrene thermoplastic elastomer material comprises the following steps:
A) preparing a good solvent solution of SEBS;
B) adding a low-surface-energy substance and a poor solvent into the good solvent solution of the SEBS in the step A) to obtain a mixed solution;
the boiling point of the good solvent is 120-155 ℃, and the boiling point of the poor solvent is 200-280 ℃;
the ratio of the mass of the low surface energy substance to the total mass of the good solvent and the poor solvent is 1: 100, respectively;
the low surface energy substance is one or more of palm wax, beeswax, sliced paraffin wax and liquid paraffin;
C) volatilizing the mixed solution in the step B) in a container to form a film, and annealing the obtained film to obtain a super-hydrophobic styrene thermoplastic elastomer material;
the annealing temperature in the step C) is 60 ℃, and the annealing time in the step C) is 0.1-48 hours.
2. The preparation method according to claim 1, wherein the mass concentration of the SEBS in the good solvent solution of the SEBS is 0.05-50 wt%.
3. The method according to claim 1, wherein the good solvent is one or more selected from xylene, octane, chlorobenzene and N, N dimethylformamide, and the poor solvent is one or more selected from n-decanol, diethylene glycol, ethylene glycol carbonate and benzyl alcohol.
4. The production method according to claim 1, wherein the volume ratio of the good solvent to the poor solvent is 10: 1-1: 10.
5. the preparation method according to claim 1, wherein the temperature for volatilization in the step C) is 20-30 ℃; and C), volatilizing for 1-48 hours.
6. A super-hydrophobic styrene thermoplastic elastomer material prepared by the preparation method of any one of claims 1 to 5.
7. An infusion-type medical device prepared from the superhydrophobic styrene-based thermoplastic elastomer material of claim 6.
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| CN202010788499.2A CN111849112B (en) | 2020-08-07 | 2020-08-07 | Super-hydrophobic styrene thermoplastic elastomer material, preparation method thereof, infusion medical device and application |
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