CN114989546B - FEP film for producing cell therapy liquid storage bag - Google Patents
FEP film for producing cell therapy liquid storage bag Download PDFInfo
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- CN114989546B CN114989546B CN202210272169.7A CN202210272169A CN114989546B CN 114989546 B CN114989546 B CN 114989546B CN 202210272169 A CN202210272169 A CN 202210272169A CN 114989546 B CN114989546 B CN 114989546B
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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
- A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
- A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
- A61J1/05—Containers specially adapted for medical or pharmaceutical purposes for collecting, storing or administering blood, plasma or medical fluids ; Infusion or perfusion containers
- A61J1/10—Bag-type containers
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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
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
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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
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
The invention discloses an FEP film for producing a cell therapy liquid storage bag, which relates to the technical field of composite materials, is a composite film material and at least comprises FEP resin and modified polyimide; the modified polyimide comprises a polyimide activation reaction and an amidation reaction product; the activation reaction raw materials comprise spermine or polyethyleneimine; the amidation reaction raw material comprises perfluoro caprylic acid; the polyimide is a transparent polyimide material. The FEP film provided by the invention has excellent light transmittance and oxygen permeability, and meanwhile, the mechanical property of the FEP film is obviously improved, and the tensile strength of the FEP film is obviously enhanced; the friction and abrasion resistance of the membrane material is effectively improved, the application field of the membrane material is expanded, and the membrane material has a huge application prospect in the field of cell therapy liquid storage bag production.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to an FEP film for producing a cell therapy liquid storage bag.
Background
Cell therapy is a method of treating diseases using autologous or allogeneic adult cells or stem cells. The healthy cells or stem cells are transplanted into a patient, the diseased cells are supplemented and replaced, the organ functions are activated, the organ activity is improved, the organ quality is improved, the organ lesions are delayed, and the normal physiological functions of the organs are recovered, so that the purposes of treating diseases or resisting aging are achieved, and the cell treatment has been widely used for serious diseases such as advanced liver cirrhosis, bone marrow transplantation, osteonecrosis, myocardial infarction, tumors and the like in the disease treatment field. Cell therapy has been used in the health care field to delay aging, enhance physical fitness, etc. In the cell treatment process, the externally cultured cell fluid is required to be input into a medical target body, and then, a higher requirement is put on a liquid storage bag for bearing the cell fluid.
FEP materials (perfluoroethylene propylene copolymers) are free of plasticizers and the like that might penetrate and alter delicate cellular tissues, are non-cytotoxic and tissue toxic, and are also suitable for storage of antibodies, cytokines and other genetic materials; the air permeability is good, and high oxygen can be transmitted to cells in culture; the water permeability is extremely low, water loss can be neglected and a moist incubator is not required to be provided for the water permeability; the light transmittance is higher than 95%, and the risk of pollution to cells and tissues can be avoided by directly observing the light transmittance through a microscope; and is also suitable for low-temperature preservation. Therefore, the FEP material has wide application prospect in the field of cell therapy liquid storage bag production. However, FEP materials, while having a range of excellent properties, also have significant weaknesses, especially poor mechanical properties and susceptibility to breakage, which severely affects their use.
Disclosure of Invention
The invention aims to provide an FEP film for producing a cell therapy liquid storage bag, which has excellent light transmittance and oxygen permeability, and simultaneously has remarkably improved mechanical properties and obviously enhanced tensile strength; and the friction and abrasion resistance of the film material is effectively improved, and the application field of the film material is expanded.
The technical scheme adopted by the invention for achieving the purpose is as follows:
an FEP film is a composite film material, and at least comprises FEP resin and,
modifying polyimide; the modified polyimide comprises a polyimide activation reaction and an amidation reaction product; the activation reaction raw materials comprise spermine or polyethyleneimine; the amidation reaction raw material comprises perfluoro caprylic acid;
the polyimide is a transparent polyimide material. The FEP film provided by the invention is a composite film material, polyimide and FEP resin are well compounded through chemical design, so that the film material with excellent comprehensive performance is obtained, and the FEP film can be better applied to production of cell therapy liquid storage bags. According to the invention, spermine is adopted to carry out ring opening activation on polyimide, and then a compound containing carboxyl functional groups is utilized to carry out chemical modification, so that the polyimide can be well compounded with FEP resin; the modified polyimide has more excellent dispersion capability in the FEP resin matrix, the two are mixed more uniformly, the mechanical property of the composite film material is obviously improved, and the tensile strength of the composite film material is obviously enhanced; the formed film has more uniform structure and higher network stability, so that the composite film material has better friction and wear resistance; meanwhile, the oxygen permeability of the membrane material is further improved, the high-level delivery of oxygen is better realized, and the requirement of the cell culture process for oxygen is met. The FEP film prepared by the invention has reduced visible light transmittance, but still maintains a higher light transmittance level, and the visible light transmittance is more than 91 percent, so that the FEP film can meet the observation of morphological characteristics and the like in the cell treatment process.
In a specific embodiment, the mass ratio of the modified polyimide to the FEP resin is 0.01-0.02: 1.
in particular embodiments, the FEP film has a tensile strength of > 24MPa; more preferably, the FEP film has a tensile strength of > 27MPa.
The preparation method of the FEP film comprises the following steps:
polyimide is activated, polyimide materials are soaked in spermine or polyethyleneimine aqueous solution, and activated polyimide is obtained through an activation reaction;
polyimide is modified, and perfluoro caprylic acid is adopted to carry out chemical modification on the activated polyimide through amidation reaction to obtain modified polyimide;
preparation of FEP composite film, wherein modified polyimide is compounded with FEP resin, and the FEP film is prepared by adopting a tape casting method.
Further, the preparation method of the FEP film comprises the following specific steps:
activating polyimide, namely cutting a CPI film, immersing the cut CPI film into a spermine or polyethyleneimine aqueous solution for 5-8 hours or 20-24 hours, washing the cut CPI film with deionized water for multiple times, and drying the cut CPI film at 50-60 ℃ for 10-12 hours to obtain activated polyimide;
modifying polyimide, adding a methanol solution of perfluoro caprylic acid into the activated polyimide, stirring and reacting for 20-24 hours, then washing with methanol for 3-5 times, washing with deionized water for many times, and drying for 10-12 hours at 50-60 ℃ to obtain modified polyimide;
preparation of FEP composite film, wherein modified polyimide is compounded with FEP resin, and an extrusion casting method is adopted to prepare the FEP film.
In a specific embodiment, the concentration of the aqueous solution of spermine or polyethylenimine is 9 to 12wt%.
In a specific embodiment, the concentration of the methanolic perfluorooctanoic acid solution is 4-7 wt%.
In a specific embodiment, the mass ratio of the activated polyimide to the perfluorooctanoic acid is 1:0.2 to 0.4.
The process steps of the extrusion casting method are all the prior art and are conventionally understood by those skilled in the art.
In a specific embodiment, the FEP film thickness is 0.1 to 0.3mm.
More preferably, 5-methyl-1- (3-trifluoromethylphenyl) -1H-pyrazole-3-carboxylic acid is used instead of perfluorooctanoic acid in the preparation of FEP film. According to the invention, in the polyimide modification process, 5-methyl-1- (3-trifluoromethyl phenyl) -1H-pyrazole-3-carboxylic acid is grafted on the activated polyimide through amidation reaction, so that the uniformity of mixing the modified polyimide with FEP resin is further enhanced, the overall network structure of the composite material is beneficially influenced, the mechanical property of the film material is remarkably improved, and the tensile strength is further enhanced; the water vapor permeability of the membrane material is obviously reduced, and the water loss is reduced; under the condition that the polyimide is activated by the polyethyleneimine, the formed film structure is more stable, and the friction and abrasion resistance is obviously enhanced; meanwhile, the two materials are compounded cooperatively, so that the oxygen permeability of the film material is improved, and the level of the pure FEP resin film is basically reached.
It is a further object of the present invention to provide the use of the modified polyimide described above for enhancing the mechanical properties of FEP films.
The invention also discloses application of the FEP film in preparation of a liquid storage bag for cell therapy.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the polyimide is modified by adopting the compound such as spermine and the like, so that the aim of more uniform compounding with the FEP resin is fulfilled, the mechanical property of the composite film material is obviously improved, and the tensile strength of the composite film material is obviously enhanced; the composite membrane material has better friction and wear resistance; meanwhile, the oxygen permeability of the membrane material is further improved, and the high-level transportation of oxygen is better realized. In addition, the invention adopts 5-methyl-1- (3-trifluoromethyl phenyl) -1H-pyrazole-3-carboxylic acid to further modify the activated polyimide, thus obviously improving the mechanical property of the film material and further enhancing the tensile strength; the water vapor permeability of the membrane material is reduced, and the water loss is reduced; meanwhile, under the condition that the polyimide is activated by the polyethyleneimine, the abrasion resistance of the film material is improved more obviously; and the effect of improving the oxygen permeability of the membrane material is better. Compared with the pure FEP film, the FEP film prepared by the invention has reduced oxygen permeability, water vapor permeability and visible light transmittance, but still maintains a higher light transmittance level, thereby meeting the basic requirements of the cell treatment process on the liquid storage bag; on the basis, the mechanical property of the film material is greatly improved, the film material has more excellent processing property, and the application field is expanded.
Therefore, the invention provides the FEP film for producing the cell therapy liquid storage bag, which has excellent light transmittance and oxygen permeability, and simultaneously has obviously improved mechanical properties and obviously enhanced tensile strength; and the friction and abrasion resistance of the film material is effectively improved, and the application field of the film material is expanded.
Drawings
FIG. 1 shows the IR spectra of the polyimide, the activated polyimide and the modified polyimide according to test example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to the specific embodiments and the attached drawings:
CPI membranes used in the examples of the present invention were purchased from Huizhou Dugaku New Material Co., ltd; the FEP resin used was purchased from Irelli plastics materials Inc. of Suzhou.
Example 1:
preparation of FEP film:
activating polyimide, namely cutting a CPI film, immersing the cut CPI film in a spermine aqueous solution with the concentration of 10.5wt percent for 7 hours, washing the cut CPI film with deionized water for multiple times, and drying the cut CPI film at the temperature of 60 ℃ for 12 hours to obtain activated polyimide;
modifying polyimide, namely adding 5.6wt% of methanol solution of perfluoro caprylic acid into the activated polyimide, stirring and reacting for 22 hours, washing with methanol for 4 times, washing with deionized water for multiple times, and drying at 60 ℃ for 12 hours to obtain modified polyimide; specifically, the mass ratio of the activated polyimide to the perfluorooctanoic acid is 1:0.32;
preparation of FEP composite film, wherein modified polyimide and FEP resin (the mass ratio of the modified polyimide to the FEP resin is 0.014:1) are compounded, and an extrusion casting method is adopted to prepare the FEP composite film, wherein the thickness of the FEP composite film is 0.18mm. Wherein the extrusion casting process comprises: extruding by an extruder, casting by a T-shaped die, cooling by a cooling roller, cutting waste edges, and coiling; the extruder extrusion process, the melting temperature is 280 ℃, and the extrusion temperature is 310 ℃.
Example 2:
the FEP film was prepared differently from example 1:
the concentration of the aqueous spermine solution was 9.4wt%;
the concentration of the methanol solution of perfluorooctanoic acid was 4.6wt%;
the mass ratio of the activated polyimide to the perfluorooctanoic acid is 1:0.23;
the mass ratio of the modified polyimide to the FEP resin is 0.01:1.
example 3:
the FEP film was prepared differently from example 1:
the concentration of the aqueous spermine solution was 11.2wt%;
the concentration of the methanol solution of perfluorooctanoic acid was 6.3wt%;
the mass ratio of the activated polyimide to the perfluorooctanoic acid is 1:0.34;
the mass ratio of the modified polyimide to the FEP resin is 0.016:1.
example 4:
preparation of FEP film:
activating polyimide, namely cutting a CPI film, immersing the cut CPI film into a 10.5wt% concentration polyethyleneimine aqueous solution, immersing for 24 hours, washing the cut CPI film with deionized water for multiple times, and drying the washed CPI film at 60 ℃ for 12 hours to obtain activated polyimide;
modifying polyimide, namely adding 5.6wt% of methanol solution of perfluoro caprylic acid into the activated polyimide, stirring and reacting for 22 hours, washing with methanol for 4 times, washing with deionized water for multiple times, and drying at 60 ℃ for 12 hours to obtain modified polyimide; specifically, the mass ratio of the activated polyimide to the perfluorooctanoic acid is 1:0.32;
preparation of FEP composite film, wherein modified polyimide and FEP resin (the mass ratio of the modified polyimide to the FEP resin is 0.014:1) are compounded, and an extrusion casting method is adopted to prepare the FEP composite film, wherein the thickness of the FEP composite film is 0.18mm. Wherein the extrusion casting process comprises: extruding by an extruder, casting by a T-shaped die, cooling by a cooling roller, cutting waste edges, and coiling; the extruder extrusion process, the melting temperature is 280 ℃, and the extrusion temperature is 310 ℃.
Example 5:
preparation of FEP film:
activating polyimide, namely cutting a CPI film, immersing the cut CPI film in a spermine aqueous solution with the concentration of 10.5wt percent for 7 hours, washing the cut CPI film with deionized water for multiple times, and drying the cut CPI film at the temperature of 60 ℃ for 12 hours to obtain activated polyimide;
modifying polyimide, namely adding 5.6wt% of methanol solution of 5-methyl-1- (3-trifluoromethyl phenyl) -1H-pyrazole-3-carboxylic acid into the activated polyimide, stirring and reacting for 22 hours, washing with methanol for 4 times, washing with deionized water for multiple times, and drying at 60 ℃ for 12 hours to obtain modified polyimide; specifically, the mass ratio of the activated polyimide to the perfluorooctanoic acid is 1:0.32;
preparation of FEP composite film, wherein modified polyimide and FEP resin (the mass ratio of the modified polyimide to the FEP resin is 0.014:1) are compounded, and an extrusion casting method is adopted to prepare the FEP composite film, wherein the thickness of the FEP composite film is 0.18mm. Wherein the extrusion casting process comprises: extruding by an extruder, casting by a T-shaped die, cooling by a cooling roller, cutting waste edges, and coiling; the extruder extrusion process, the melting temperature is 280 ℃, and the extrusion temperature is 310 ℃.
Example 6:
the FEP film was prepared differently from example 5:
the concentration of the aqueous spermine solution was 11.2wt%;
the concentration of the methanol solution of 5-methyl-1- (3-trifluoromethylphenyl) -1H-pyrazole-3-carboxylic acid was 6% by weight;
the mass ratio of the activated polyimide to the 5-methyl-1- (3-trifluoromethyl phenyl) -1H-pyrazole-3-carboxylic acid is 1:0.28;
the mass ratio of the modified polyimide to the FEP resin is 0.017:1.
example 7:
the FEP film was prepared differently from example 5:
the concentration of the aqueous spermine solution was 9.8wt%;
the concentration of the methanol solution of 5-methyl-1- (3-trifluoromethylphenyl) -1H-pyrazole-3-carboxylic acid was 5% by weight;
the mass ratio of the activated polyimide to the 5-methyl-1- (3-trifluoromethyl phenyl) -1H-pyrazole-3-carboxylic acid is 1:0.22;
the mass ratio of the modified polyimide to the FEP resin is 0.015:1.
example 8:
the FEP film was prepared differently from example 5: and (3) adopting polyethyleneimine to replace spermine, and soaking for 24 hours.
Example 9:
the FEP film was prepared differently from example 8:
the concentration of the aqueous polyethyleneimine solution was 11.5wt%;
the concentration of the methanol solution of 5-methyl-1- (3-trifluoromethylphenyl) -1H-pyrazole-3-carboxylic acid was 7% by weight;
the mass ratio of the activated polyimide to the 5-methyl-1- (3-trifluoromethyl phenyl) -1H-pyrazole-3-carboxylic acid is 1:0.3;
the mass ratio of the modified polyimide to the FEP resin is 0.019:1.
comparative example 1:
the FEP film was prepared differently from example 1: and adopting ethylenediamine methanol solution to replace spermine aqueous solution.
Test example 1:
1. infrared test
And measuring the sample structure by adopting a Fourier infrared spectrometer. Wherein the wave number ranges from 4000 cm to 500cm -1 Resolution of 4cm -1 。
The above test was performed on the polyimide, the activated polyimide prepared in example 1, and the modified polyimide prepared in examples 1 and 5, and the results are shown in fig. 1. As can be seen from the analysis in the figure, 1773cm in the infrared spectrum of polyimide after spermine activation compared with the infrared spectrum test result of polyimide -1 And 1358cm -1 The intensity of the characteristic absorption peak of the symmetrical vibration of the carbonyl and the vibration of the carbon-nitrogen bond in the adjacent imide ring is obviously reduced, and the intensity is 1645cm -1 And 1540cm -1 Characteristic absorption peaks of carbonyl stretching vibration and N-H bending vibration in CONH group appear nearby, 3321cm -1 And 3040cm -1 The characteristic absorption peak of primary ammonia appears nearby, which indicates that imide in the polyimide structure is successfully opened after spermine activation treatment. In the infrared spectrum of the modified polyimide prepared in example 1, 3321cm -1 And 3040cm -1 The characteristic absorption peak of nearby primary ammonia is basically disappeared, 1322cm -1 Characteristic absorption peaks of C-F bonds appear nearby, which indicate that the perfluoro caprylic acid and the polyimide after activation successfully undergo amidation reaction. Also, in the infrared spectrum of the modified polyimide prepared in example 5, 3321cm -1 And 3040cm -1 The characteristic absorption peak of the nearby primary ammonia also substantially disappears, 1252cm -1 Characteristic absorption peaks of C-F bonds appear nearby, which indicate that the amidation reaction of the 5-methyl-1- (3-trifluoromethyl phenyl) -1H-pyrazole-3-carboxylic acid and the polyimide after activation is successful.
2. Testing of tensile Strength
The test method is performed with reference to the standard specified in ASTM-D638.
The above test was performed on the pure FEP resin film, the FEP films prepared in comparative example 1, examples 1 to 9, and the results are shown in table 1:
TABLE 1 tensile Strength test results
From the analysis in table 1, the tensile strength of the FEP film compounded with the modified polyimide was significantly higher than that of the pure FEP resin film. The FEP film prepared in the example 1 has obviously higher tensile strength than that of the FEP film prepared in the comparative example 1, which shows that the polyimide is activated by using spermine and then subjected to chemical modification, and the FEP film can effectively improve the tensile strength of the film material and enhance the mechanical property of the film material when being applied to the preparation of the FEP film material. The effect of example 5 is obviously better than that of example 1, and the effect of example 8 is obviously better than that of example 4, which shows that the mechanical property of the film material can be further enhanced by adopting the polyimide after the modification and activation of 5-methyl-1- (3-trifluoromethyl phenyl) -1H-pyrazole-3-carboxylic acid and then compounding with FEP resin.
3. Friction performance test
The test method is performed with reference to the standard specified in ASTM F735.
The above test was performed on the pure FEP resin film, the FEP films prepared in comparative example 1, examples 1 to 9, and the results are shown in table 2:
TABLE 2 Friction Performance test results
| Sample of | Wear Rate (. Times.10) -5 mm 3 ·N -1 ·m -1 ) |
| Pure FEP resin film | 2.93 |
| Comparative example 1 | 2.82 |
| Example 1 | 2.75 |
| Example 2 | 2.76 |
| Example 3 | 2.74 |
| Example 4 | 2.68 |
| Example 5 | 2.73 |
| Example 6 | 2.74 |
| Example 7 | 2.73 |
| Example 8 | 2.55 |
| Example 9 | 2.53 |
From the analysis in table 2, the abrasion rate of the FEP film compounded with the modified polyimide was significantly lower than that of the pure FEP resin film. The abrasion rate of the FEP film prepared in the example 1 is obviously lower than that of the FEP film prepared in the comparative example 1, which shows that the polyimide is activated by using spermine and then subjected to chemical modification, and the FEP film can effectively improve the abrasion rate of the film material and enhance the abrasion performance of the film material when being applied to the preparation of the FEP film material. The effect of example 5 is equivalent to that of example 1, and the effect of example 8 is obviously better than that of example 4, which shows that the polyimide after being modified by 5-methyl-1- (3-trifluoromethyl phenyl) -1H-pyrazole-3-carboxylic acid and being activated by spermine is compounded with FEP resin to prepare the film material, and the friction performance of the film material is not negatively influenced. And polyimide after the polyethyleneimine is modified by 5-methyl-1- (3-trifluoromethyl phenyl) -1H-pyrazole-3-carboxylic acid and activated is compounded with FEP resin to prepare the film material, and the two materials play a role in compounding and synergism, so that the friction performance of the film material can be further enhanced.
Test example 2:
1. oxygen permeability test
The test is performed with reference to the standard specified in ASTM D3985. The test instrument measures the oxygen transmission rate using an OTR analyzer at 37 ℃.
The above test was performed on the pure FEP resin film, the FEP films prepared in comparative example 1, examples 1 to 9, and the results are shown in table 3:
TABLE 3 oxygen permeation Performance test results
| Sample of | OTR(cc/(m 2 ·day·atm)) |
| Pure FEP resin film | 2900 |
| Comparative example 1 | 2680 |
| Example 1 | 2750 |
| Example 2 | 2742 |
| Example 3 | 2760 |
| Example 4 | 2820 |
| Example 5 | 2800 |
| Example 6 | 2809 |
| Example 7 | 2796 |
| Example 8 | 2890 |
| Example 9 | 2895 |
From the analysis in table 3, the oxygen permeability of the FEP film compounded with the modified polyimide was slightly reduced compared to the pure FEP resin film. The FEP film prepared in example 1 has higher oxygen permeability than that of comparative example 1, which shows that the polyimide is activated by spermine and then subjected to chemical modification, and the oxygen permeability of the film material can be slightly improved when the FEP film is applied to the preparation of the FEP film material. Example 5 has better effect than example 1, and example 8 has better effect than example 4, which shows that polyimide after being modified by 5-methyl-1- (3-trifluoromethyl phenyl) -1H-pyrazole-3-carboxylic acid and refined amine is used for preparing the membrane material by compounding with FEP resin, and has certain regulation effect on oxygen permeability of the membrane material. And polyimide after the activation of the polyethyleneimine is modified by 5-methyl-1- (3-trifluoromethyl phenyl) -1H-pyrazole-3-carboxylic acid, and the polyimide is compounded with FEP resin to prepare the film material, so that the oxygen permeability of the film material can be obviously improved, and the oxygen permeability of the pure FEP resin film can be basically achieved.
2. Water vapor permeability test
The test is performed with reference to the standard specified in ASTM F1249. The experiment uses the U.S. MOCON company Permatran W700 water vapor analyzer to sample membrane water vapor transmittance measurement. The temperature was measured at 40℃and the average water loss in 14 d.
The above test was performed on the pure FEP resin film, the FEP films prepared in comparative example 1, examples 1 to 9, and the results are shown in table 4:
TABLE 4 results of Water vapor permeability test
| Sample of | Average moisture loss/% |
| Pure FEP resin film | 0.23 |
| Comparative example 1 | 1.02 |
| Example 1 | 0.98 |
| Example 2 | 1.00 |
| Example 3 | 0.97 |
| Example 4 | 0.74 |
| Example 5 | 0.86 |
| Example 6 | 0.84 |
| Example 7 | 0.87 |
| Example 8 | 0.48 |
| Example 9 | 0.46 |
From the analysis in table 4, it is seen that the average moisture loss of the FEP film compounded with the modified polyimide was increased as compared with the pure FEP resin film. The average moisture loss of the FEP film prepared in example 1 is equivalent to that of comparative example 1, which shows that the polyimide is activated by spermine and then subjected to chemical modification, and the FEP film is applied to the preparation of the FEP film material, so that the water vapor permeability of the film material is not negatively affected. Example 5 is better than example 1, and example 8 is significantly better than example 4, indicating that the use of the polyimide modified and activated by 5-methyl-1- (3-trifluoromethylphenyl) -1H-pyrazole-3-carboxylic acid, and the composition of the polyimide and FEP resin, can significantly reduce the water vapor permeability of the film material and reduce the loss of water.
Test example 3:
light transmittance test
The light transmittance of the sample film was measured using a UV-Vis-NIR spectrophotometer.
The above test was performed on the pure FEP resin film, the FEP films prepared in comparative example 1, examples 1 to 9, and the results are shown in table 5:
TABLE 5 light transmittance test results
| Sample of | Visible light transmittance/% |
| Pure FEP resin film | 95.8 |
| Comparative example 1 | 91.3 |
| Example 1 | 92.0 |
| Example 2 | 91.8 |
| Example 3 | 92.2 |
| Example 4 | 92.5 |
| Example 5 | 92.3 |
| Example 6 | 92.1 |
| Example 7 | 92.2 |
| Example 8 | 92.7 |
| Example 9 | 93.0 |
From the analysis in table 5, the visible light transmittance of the FEP film compounded with the modified polyimide was reduced as compared with that of the pure FEP resin film. The light transmittance of the FEP film prepared in example 1 is equivalent to that of comparative example 1, which shows that polyimide is activated by spermine and then subjected to chemical modification, and the FEP film is applied to the preparation of an FEP film material, so that the light transmittance of the film material is not negatively affected. The effect of example 5 is equivalent to that of example 1, and the effect of example 8 is equivalent to that of example 4, which shows that the polyimide after modification and activation by using 5-methyl-1- (3-trifluoromethylphenyl) -1H-pyrazole-3-carboxylic acid is compounded with FEP resin to prepare the film material, and the light transmittance of the film material is not negatively affected. The visible light transmittance of the FEP film prepared by the method is reduced, but the visible light transmittance is still maintained at a higher light transmittance level, so that the observation of morphological characteristics and the like in the cell treatment process can be satisfied.
The conventional technology in the above embodiments is known to those skilled in the art, and thus is not described in detail herein.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (7)
1. An FEP film is a composite film material, and at least comprises FEP resin and,
modifying polyimide; the modified polyimide comprises a product of a polyimide activation reaction and an amidation reaction; the activation reaction raw material comprises spermine or polyethyleneimine; the amidation reaction raw material comprises 5-methyl-1- (3-trifluoromethyl phenyl) -1H-pyrazole-3-carboxylic acid;
the polyimide is a transparent polyimide material;
the mass ratio of the modified polyimide to the FEP resin is 0.01-0.02:1.
2. The FEP film of claim 1, wherein: the FEP film has a tensile strength of > 27MPa.
3. The method of producing an FEP film of claim 1, comprising:
polyimide is activated, polyimide materials are soaked in spermine or polyethyleneimine aqueous solution, and activated polyimide is obtained through an activation reaction;
polyimide is modified, and the activated polyimide is subjected to chemical modification by adopting 5-methyl-1- (3-trifluoromethyl phenyl) -1H-pyrazole-3-carboxylic acid through amidation reaction to obtain modified polyimide;
and (3) preparing an FEP composite film, namely compounding the modified polyimide with FEP resin, and preparing the FEP composite film by adopting a tape casting method.
4. The method of producing an FEP film according to claim 3, wherein: the concentration of the spermine or polyethyleneimine water solution is 9-12 wt%.
5. The method of producing an FEP film according to claim 3, wherein: the mass ratio of the activated polyimide to the 5-methyl-1- (3-trifluoromethyl phenyl) -1H-pyrazole-3-carboxylic acid is 1:0.2 to 0.4.
6. Use of the modified polyimide as claimed in claim 1 for enhancing the mechanical properties of FEP films.
7. Use of the FEP film of claim 1 in the manufacture of a pouch for cell therapy.
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Citations (4)
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|---|---|---|---|---|
| US3770566A (en) * | 1971-06-08 | 1973-11-06 | Du Pont | Interdiffusionally bonded structures of polyimide and fluoropolymer |
| TW200831089A (en) * | 2006-11-17 | 2008-08-01 | Pfizer | Substituted bicyclocarboxyamide compounds |
| CN107208014A (en) * | 2014-12-22 | 2017-09-26 | 美国圣戈班性能塑料公司 | cell capture system and method |
| CN109337108A (en) * | 2018-10-26 | 2019-02-15 | 镇江龙成绝缘材料有限公司 | A kind of polyimides-perfluoroethylene-propylene preparation method of composite film |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SG108269A1 (en) * | 2001-08-15 | 2005-01-28 | Inst Materials Research & Eng | Chemical modification of polyimides |
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- 2022-07-05 CN CN202210272169.7A patent/CN114989546B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3770566A (en) * | 1971-06-08 | 1973-11-06 | Du Pont | Interdiffusionally bonded structures of polyimide and fluoropolymer |
| TW200831089A (en) * | 2006-11-17 | 2008-08-01 | Pfizer | Substituted bicyclocarboxyamide compounds |
| CN107208014A (en) * | 2014-12-22 | 2017-09-26 | 美国圣戈班性能塑料公司 | cell capture system and method |
| CN109337108A (en) * | 2018-10-26 | 2019-02-15 | 镇江龙成绝缘材料有限公司 | A kind of polyimides-perfluoroethylene-propylene preparation method of composite film |
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| Title |
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| Synthesis and characterization of novel polyimides containing fluorine and phosphine oxide moieties;K.U.Jeong et al;《polymer》;第6019-6030页 * |
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