CN114984768A - Surface modification method of hollow fiber membrane for artificial membrane lung - Google Patents
Surface modification method of hollow fiber membrane for artificial membrane lung Download PDFInfo
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- CN114984768A CN114984768A CN202210741361.6A CN202210741361A CN114984768A CN 114984768 A CN114984768 A CN 114984768A CN 202210741361 A CN202210741361 A CN 202210741361A CN 114984768 A CN114984768 A CN 114984768A
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- 239000012528 membrane Substances 0.000 title claims abstract description 181
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 146
- 210000004072 lung Anatomy 0.000 title claims abstract description 32
- 239000000823 artificial membrane Substances 0.000 title claims abstract description 28
- 238000002715 modification method Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 26
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000005251 gamma ray Effects 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims description 16
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 7
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 claims description 7
- GVEUEBXMTMZVSD-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C GVEUEBXMTMZVSD-UHFFFAOYSA-N 0.000 claims description 6
- NKAMGQZDVMQEJL-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodec-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C NKAMGQZDVMQEJL-UHFFFAOYSA-N 0.000 claims description 6
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- 238000010521 absorption reaction Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
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- FYQFWFHDPNXORA-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooct-1-ene Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C FYQFWFHDPNXORA-UHFFFAOYSA-N 0.000 claims description 4
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- 230000035699 permeability Effects 0.000 abstract description 3
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- -1 polypropylene Polymers 0.000 description 64
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- 102000004506 Blood Proteins Human genes 0.000 description 3
- 108010017384 Blood Proteins Proteins 0.000 description 3
- HTTJABKRGRZYRN-UHFFFAOYSA-N Heparin Chemical compound OC1C(NC(=O)C)C(O)OC(COS(O)(=O)=O)C1OC1C(OS(O)(=O)=O)C(O)C(OC2C(C(OS(O)(=O)=O)C(OC3C(C(O)C(O)C(O3)C(O)=O)OS(O)(=O)=O)C(CO)O2)NS(O)(=O)=O)C(C(O)=O)O1 HTTJABKRGRZYRN-UHFFFAOYSA-N 0.000 description 3
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- YHHSONZFOIEMCP-UHFFFAOYSA-O phosphocholine Chemical compound C[N+](C)(C)CCOP(O)(O)=O YHHSONZFOIEMCP-UHFFFAOYSA-O 0.000 description 3
- 229950004354 phosphorylcholine Drugs 0.000 description 3
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 238000012512 characterization method Methods 0.000 description 2
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- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
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- 230000004083 survival effect Effects 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
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- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 238000006385 ozonation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
-
- 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
- A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
- A61M1/14—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis
- A61M1/16—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis with membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/38—Graft polymerization
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Heart & Thoracic Surgery (AREA)
- Urology & Nephrology (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Biomedical Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Vascular Medicine (AREA)
- Anesthesiology (AREA)
- Plasma & Fusion (AREA)
- Hematology (AREA)
- Emergency Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- External Artificial Organs (AREA)
Abstract
The application provides a surface modification method of a hollow fiber membrane for an artificial membrane lung, which adopts low-temperature ozone or gamma ray irradiation to introduce peroxide groups on the surface of the hollow fiber membrane, and grafts low-surface functional molecules on the surface of the hollow fiber membrane through polymerization reaction of the peroxide groups on the surface of the hollow fiber membrane and the low-surface functional molecules containing double bonds, thereby realizing the surface modification of the hollow fiber membrane. The hollow fiber membrane with the surface modified with low surface energy functional molecules prepared by the method has improved gas permeability and blood pollution resistance; in addition, in the application, the low surface energy functional molecules are grafted on the surface of the hollow fiber membrane in a chemical bond mode, so that the stability of the structure of the hollow fiber membrane is ensured, and the lasting stability of various performances of the hollow fiber membrane is ensured.
Description
Technical Field
The application relates to the technical field of biological materials, in particular to a surface modification method of a hollow fiber membrane for an artificial membrane lung.
Background
The membrane type external oxygenator is a device for exchanging oxygen and carbon dioxide by utilizing a membrane type artificial lung. The membrane type artificial lung is an important component of the membrane type external oxygenator, and the structure and the performance of the membrane type external oxygenator directly influence the using effect of the membrane type external oxygenator.
Currently, membrane-type artificial lungs are generally made of hollow fiber membranes, such as polypropylene hollow fiber membranes. When the membrane type extracorporeal oxygenator is actually used, the membrane type artificial lung prepared by the polypropylene hollow fiber membrane is used as a place for exchanging blood and gas, and the microporous structure on the polypropylene hollow fiber membrane is utilized to exchange blood and oxygen in a specific pore channel, so that the exchange of gas on the membrane is realized.
In order to improve the usability of the membrane type extracorporeal oxygenator, the surface of the hollow fiber membrane is usually modified, and the commonly used surface modification method includes a surface chemical grafting method, i.e., functional molecules are grafted on the surface of the membrane through a chemical bond form, for example, phosphorylcholine, heparin and other substances are grafted on the surface of the hollow fiber membrane. However, this surface modification method is not suitable for surface modification of a polypropylene hollow fiber membrane because: molecules such as heparin and phosphorylcholine can change the surface performance of the membrane, so that originally hydrophobic micropores become hydrophilic, namely the hydrophobicity is reduced, and the risk of plasma leakage is increased; meanwhile, molecules such as heparin and phosphorylcholine can reduce the blood pollution resistance of the membrane surface, and substances such as proteins, red blood cells and platelets in plasma can be non-specifically combined with the membrane surface, so that thrombus is formed.
Disclosure of Invention
The application provides a surface modification method of a hollow fiber membrane for an artificial membrane lung, which aims to solve the problem that the hydrophobicity and the blood pollution resistance of the existing membrane type extracorporeal oxygenator need to be improved.
The application provides a surface modification method of a hollow fiber membrane for an artificial membrane lung, which comprises the following steps:
introducing peroxy groups on the surface of the hollow fiber membrane by adopting low-temperature ozone or gamma ray irradiation;
the hollow fiber membrane with surface carried with peroxy group is soaked in the low surface energy functional molecule solution containing double bond, under the action of catalyst, the peroxy bond in the peroxy group is heated and broken, and is polymerized with the low surface energy functional molecule containing double bond in the solution, namely graft reaction, to generate the hollow fiber membrane with surface modified with low surface energy functional molecule.
In some embodiments, the method for modifying the surface of a hollow fiber membrane used for an artificial membrane lung further comprises washing the generated hollow fiber membrane with a functional molecule with a low surface energy modified on the surface in a volatile non-polar solvent.
In some embodiments, the introducing of the peroxy group on the surface of the hollow fiber membrane by using low-temperature ozone specifically comprises introducing ozone into a low-temperature constant-temperature tank, and activating the surface of the hollow fiber membrane by using the ozone, wherein the concentration of the ozone is 3-20g/m 3 The setting temperature of the low-temperature constant-temperature tank is-10 ℃ to 5 ℃, and the ventilation time is 5min to 30 min.
In some embodiments, the introducing peroxy groups to the surface of the hollow fiber membrane by low-temperature gamma ray irradiation specifically comprises,
the surface of the hollow fiber membrane in the low-temperature constant-temperature tank is irradiated by low-temperature gamma rays to activate the surface of the hollow fiber membrane, wherein the irradiation atmosphere is air, the temperature of the low-temperature constant-temperature tank is set to be-10-5 ℃, the absorption dose is 50-200kGy, and the irradiation time is 5-20 h.
In some embodiments, the double bond-containing low surface energy functional molecule comprises any one or a combination of two of a long chain alkane molecule containing a double bond and a polyfluoride containing a double bond.
In some embodiments, the long-chain alkane molecule containing a double bond comprises any one or a combination of two or more of vinyl laurate and vinyl stearate.
In some embodiments, the double bond-containing polyfluoride includes any one or a combination of two or more of 1H, 2H-perfluoro-1-hexene, perfluorohexylethylene, and 1H, 2H-perfluoro-1-decene.
In some embodiments, the reaction time for the grafting reaction is 6 to 24 hours and the reaction temperature is 30 to 80 ℃.
The application provides a surface modification method of a hollow fiber membrane for an artificial membrane lung, which is characterized in that a functional molecule with low surface energy is modified on the surface of the hollow fiber membrane by a chemical grafting method initiated by a peroxide group, so that the hydrophobicity of the membrane surface is improved, and the adsorbability to protein, red blood cells and platelets is reduced. And low surface energy functional molecules are connected on the surface of the hollow fiber membrane in a chemical bond mode, so that the surface modification effect and the stability and durability of the modified surface performance are further improved. In addition, the surface chemical grafting method does not influence the original pore structure and reduce the original gas flux, so that the hollow fiber membrane modified by the low-surface-energy functional molecules has a wide application prospect in an in-vitro oxygenator.
According to the surface modification method of the hollow fiber membrane for the artificial membrane lung, low-temperature ozone or gamma ray irradiation is adopted, peroxide groups are introduced to the surface of the hollow fiber membrane, and the low-surface functional molecules are grafted to the surface of the hollow fiber membrane through polymerization reaction of the peroxide groups on the surface of the hollow fiber membrane and the low-surface-energy functional molecules containing double bonds, so that the surface modification of the hollow fiber membrane is realized. The hollow fiber membrane with the surface modified with the low-surface-energy functional molecules, which is prepared by the method, has improved gas permeability and blood pollution resistance; in addition, in the application, the low surface energy functional molecules are grafted on the surface of the hollow fiber membrane in a chemical bond mode, so that the stability of the structure of the hollow fiber membrane is ensured, and the lasting stability of various performances of the hollow fiber membrane is ensured.
Drawings
In order to more clearly explain the technical solution of the present application, the drawings needed to be used in the embodiments are briefly described below, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a flow chart of a method for modifying the surface of a hollow fiber membrane useful in an artificial membrane lung according to the present application;
FIG. 2 is a flow chart of the present application for irradiation treatment with low temperature gamma rays;
FIG. 3 is a flow chart of the present application employing low temperature ozone treatment;
FIG. 4 is a representation of the infrared spectra of the surface of the polypropylene hollow fiber membrane before and after modification;
FIG. 5 is a scanning electron microscope image of an unmodified polypropylene hollow fiber membrane after being soaked in bovine blood;
FIG. 6 is a scanning electron microscope image of the modified polypropylene hollow fiber membrane after being soaked in bovine blood.
Detailed Description
In order to solve the problems of lasting hydrophobicity and blood pollution resistance of the surface of a polypropylene hollow fiber membrane of a membrane type extracorporeal oxygenator, the application provides a surface modification method of the hollow fiber membrane for an artificial membrane lung.
Fig. 1 is a flowchart of a surface modification method of a hollow fiber membrane that can be used in an artificial membrane lung according to the present application, and as shown in fig. 1, the surface modification method of a hollow fiber membrane that can be used in an artificial membrane lung specifically includes the following steps:
firstly, a low-temperature ozone or gamma ray irradiation treatment method is adopted to introduce peroxy groups on the surface of the hollow fiber membrane. In order to prolong the service life of peroxy groups, a treatment method under a low-temperature condition is adopted in the application, and the set temperature of a low-temperature thermostatic bath is-10 ℃ to 5 ℃. Under the low temperature environment of-10 ℃ to 5 ℃, the survival time of the peroxide radical can be prolonged, and further the surface grafting density is higher. Of course, the skilled person can adjust the set temperature of the cryostat tank as desired, all falling within the scope of the present application.
In the application, low-temperature ozone is adopted to introduce peroxy groups on the surface of the hollow fiber membrane, and the method specifically comprises the steps of introducing ozone into a low-temperature thermostatic bath, and activating the surface of the hollow fiber membrane by using the ozone, wherein the concentration of the ozone is 3-20g/m 3 The low-temperature constant-temperature tank is providedThe temperature is kept between minus 10 ℃ and 5 ℃, and the ventilation time is 5 to 30 min. Or, irradiating by using low-temperature gamma rays, and introducing peroxy groups on the surface of the hollow fiber membrane, specifically, irradiating the surface of the hollow fiber membrane in a low-temperature thermostatic bath by using the low-temperature gamma rays, and activating the surface of the hollow fiber membrane, wherein the irradiation atmosphere is air, the setting temperature of the low-temperature thermostatic bath is-10 ℃ to 5 ℃, the absorption dose is 50 kGy to 200kGy, and the irradiation time is 5 to 20 hours. In the application, the peroxide group is introduced to the surface of the material by an ozonization method or a gamma ray irradiation method, and the peroxide group is introduced to the surface of the hollow fiber membrane, so that the uniformity is better.
Then, soaking the hollow fiber membrane with peroxy groups on the surface in a low surface energy functional molecule solution containing double bonds, and under the action of a catalyst, allowing the peroxy groups (-O-O-R, wherein R is H or CH) 3 ) The peroxide bond (-O-O-) is broken after being heated, is decomposed to generate two corresponding free radicals, and is subjected to polymerization reaction with the double-bond-containing low-surface-energy functional molecule solution, so that the functional monomer is initiated to perform grafting reaction on the surface of the membrane by heating. In the present application, the low surface energy functional molecules and the hollow fiber membranes are linked in the form of carbon-oxygen chemical bonds, thereby ensuring the long-lasting stability of the modification.
In the present application, the double bond-containing low surface energy functional molecule includes any one or a combination of two of a long chain alkane molecule containing a double bond and a polyfluoride containing a double bond. In the application, the long-chain alkane molecule containing double bonds comprises any one or combination of more than two of vinyl laurate and vinyl stearate; the double bond-containing polyfluoride includes any one or a combination of more than two of 1H,1H, 2H-perfluoro-1-hexene, perfluorohexylethylene and 1H,1H, 2H-perfluoro-1-decene. In addition, other double bond-containing polyfluorides or double bond-containing polyfluorides may be selected by those skilled in the art as desired and are within the scope of the present application.
And finally, taking the hollow fiber membrane subjected to grafting treatment out of the reaction solution, putting the hollow fiber membrane into a volatile non-volatile solvent for cleaning, and drying to obtain the hollow fiber membrane subjected to surface grafting, namely the hollow fiber membrane modified with low-surface-energy functional molecules on the surface.
It should be noted that the surface modification method of the present application can be applied to hollow fiber membranes of various materials, not only polypropylene hollow fiber membranes, but also hollow fiber membranes of corresponding materials, such as poly (4-methyl-1-pentene) hollow fiber membranes, which are suitable for the protection scope of the present application, and can be selected by those skilled in the art according to the implementation requirements.
In order to facilitate the technical solution of the present application to be better understood by those skilled in the art, the following will further describe a polypropylene hollow fiber membrane as an example.
Example 1
Fig. 2 is a flow chart of the low-temperature gamma ray irradiation treatment according to the present application, and as shown in fig. 2, the surface modification method of the hollow fiber membrane applicable to the artificial membrane lung of the present embodiment specifically includes the following steps:
firstly, placing a reaction container filled with a polypropylene hollow fiber membrane to be treated in a low-temperature constant-temperature tank at 0 ℃, introducing air into the reaction container, and then irradiating the polypropylene hollow fiber membrane for 12 hours by adopting gamma rays with the absorption dosage of 100 kGy.
Then, soaking the polypropylene hollow fiber membrane after irradiation treatment in isooctane solution containing 1H,1H, 2H-perfluoro-1-hexene with the concentration of 100mg/mL, and heating and reacting for 6 hours under the catalysis of ferrocene and the condition of 80 ℃, so as to initiate the grafting reaction of the functional monomer on the surface of the polypropylene membrane.
And finally, taking the grafted polypropylene hollow fiber membrane out of the reaction solution, putting the grafted polypropylene hollow fiber membrane into a normal hexane solvent for cleaning, and drying in an oven at 40 ℃ to obtain the polypropylene hollow fiber membrane with the surface functionalized modification.
The surfaces of the polypropylene hollow fiber membrane before modification (before PP modification) and the modified polypropylene hollow fiber membrane after modification (after PP modification) are subjected to infrared spectrum characterization, as shown in figure 4, the infrared spectrum results show that the surface grafting modification is carried out at 1200 cm and 1140cm -1 Nearby and in the fingerprint region (660, 550, 525 cm) -1 ) The characteristic absorption peak of the fluorocarbon bond appears, which indicates that 1H,1H, 2H-perfluoro-1-hexaneAlkenes have been successfully modified to the membrane surface.
Example 2
FIG. 3 is a flow chart of the present application of low-temperature ozone treatment, and as shown in FIG. 3, the method for modifying the surface of a hollow fiber membrane for an artificial membrane lung specifically comprises the following steps:
firstly, a reaction vessel filled with a polypropylene hollow fiber membrane to be treated is placed in a low-temperature constant-temperature tank at 0 ℃, and the reaction vessel is filled with a solution with the concentration of 10g/m 3 Treating for 15 min.
Then, soaking the polypropylene hollow fiber membrane treated by ozone in tetradecane solution containing vinyl laurate with the concentration of 100mg/mL, and heating and reacting at 60 ℃ for 5 hours under the catalytic action of cuprous naphthoate to initiate the grafting reaction of the vinyl laurate on the surface of the polypropylene membrane.
And finally, taking the grafted polypropylene hollow fiber membrane out of the reaction solution, putting the grafted polypropylene hollow fiber membrane into a normal hexane solvent for cleaning, and drying in an oven at 40 ℃ to obtain the polypropylene hollow fiber membrane with the functionalized and modified surface.
Example 3:
the surface modification method of the hollow fiber membrane applicable to the artificial membrane lung specifically comprises the following steps:
firstly, a reaction vessel filled with a polypropylene hollow fiber membrane to be treated is placed in a low-temperature constant-temperature tank at 0 ℃, and the reaction vessel is filled with a solution with the concentration of 30g/m 3 Treating with ozone for 5 min.
Then, soaking the polypropylene hollow fiber membrane treated by ozone in tetradecane solution containing 1H,1H, 2H-perfluoro-1-decene with the concentration of 100mg/mL, and heating and reacting for 6H at 60 ℃ under the catalytic action of triethylaluminum to initiate the grafting reaction of the 1H,1H, 2H-perfluoro-1-decene on the surface of the polypropylene membrane.
And finally, taking the grafted polypropylene hollow fiber membrane out of the reaction solution, putting the grafted polypropylene hollow fiber membrane into a normal hexane solvent for cleaning, and drying in an oven at 40 ℃ to obtain the polypropylene hollow fiber membrane with the surface functionalized modification.
In order to show that the polypropylene hollow fiber membrane prepared by the surface modification method for the hollow fiber membrane for the artificial membrane lung has lasting hydrophobicity and blood pollution resistance, the polypropylene hollow fiber membrane is subjected to performance characterization such as a membrane material water contact angle test, a membrane material static blood adsorption test, a gas flux test and the like.
In the water contact angle test of the membrane material, an unmodified polypropylene hollow fiber membrane and samples 1, 2 and 3 in the embodiment are fixed on a test bench, a contact angle tester is used for measuring the static water contact angle, each sample selects 3 different point positions for testing, the volume of water drop of each test is 1 mu L, the average value of the test results is obtained, and the results are shown in table 1.
TABLE 1 Water contact Angle data before and after graft modification of Polypropylene hollow fiber membranes
| Unmodified polypropylene hollow fiber membrane | Example 1 | Example 2 | Example 3 | |
| Water contact Angle (°) | 122 | 136 | 132 | 138 |
The experimental result shows that the water contact angle of the unmodified polypropylene hollow fiber membrane is 122 degrees, the water contact angles of the polypropylene hollow fiber membrane after the surface of the membrane is grafted and modified by 1H,1H, 2H-perfluoro-1-hexene, vinyl laurate and 1H,1H, 2H-perfluoro-1-decene in the examples 1 to 3 are respectively increased to 136 degrees, 132 degrees and 138 degrees, and the experimental result shows that the hydrophobicity of the polypropylene hollow fiber membrane after the surface grafting modification is further increased. Among them, the water contact angle of the modified fluorine group-containing polypropylene hollow fiber membranes of examples 1 and 3 was increased more in magnitude because the grafted fluorine-containing molecules had lower surface free energy.
In the gas flux test of the membrane material, the unmodified polypropylene hollow fiber membrane and the samples 1, 2 and 3 in the examples are assembled in a gas test system, the pressure of a gas inlet is set to be 2.0 atmospheric pressure (bar), the pressure of a gas outlet is set to be 1.8bar, a gas flowmeter is adopted to test the gas flux of a permeation side, and the test gas is nitrogen. Three groups of samples were tested for each batch, and the average value of the tests was taken. The experimental results are shown in table 2, and the flux of the modified polypropylene hollow fiber membrane is not obviously reduced, which indicates that the pore structure of the polypropylene hollow fiber membrane cannot be changed by adopting the modification method of surface grafting initiated by peroxide, and the gas transmission in the use process cannot be influenced.
TABLE 2 gas flux data before and after graft modification of polypropylene hollow fiber membranes
| Unmodified polypropylene hollow fiber membrane | Example 1 | Example 2 | Example 3 | |
| Gas flux (mL/min cm) 2 bar) | 18.5 | 18.3 | 18.4 | 18.0 |
In the static blood adsorption test of the membrane material, an unmodified polypropylene hollow fiber membrane and samples 1, 2 and 3 in the example are respectively put into 5mL of bovine blood containing an anticoagulant and are kept still for 7 days in a 37 ℃ incubator; then taking out, putting into phosphate buffer solution with pH of 7.4, soaking for 2h, taking out, and naturally airing to remove surface moisture; and finally, detecting the protein adsorption amount on the surfaces of the polypropylene hollow fiber membranes before and after modification by using a BCA protein quantitative kit, wherein the experimental results are shown in a table 3.
TABLE 3 adsorption amount data of protein on membrane surface in static blood adsorption experiment before and after graft modification of polypropylene hollow fiber membrane
| Unmodified polypropylene hollow fiber membrane | Example 1 | Example 2 | Example 3 | |
| Protein adsorption capacity (μ g/g) | 6.2 | 1.3 | 1.4 | 0.9 |
According to the data in Table 3, the unmodified polypropylene hollow fiber membrane has a protein adsorption capacity of 6.2 mug/g after being soaked in the bovine blood for 7 days; after the modifications of examples 1, 2 and 3, the protein adsorption amount was reduced to 1.3, 1.4 and 0.9. mu.g/g.
In the static blood adsorption test of the membrane material, the unmodified and modified polypropylene hollow fiber membrane of example 1 after being soaked in the bovine blood is selected, the surface morphology of the membrane is observed by a scanning electron microscope, and the test result of the surface scanning electron microscope is shown in fig. 5 and fig. 6. After 7 days of static blood adsorption experiments, the unmodified polypropylene hollow fiber membrane is observed to adsorb a layer of substances on the surface of the membrane, wherein the adsorbed substances are serum protein, platelets, red blood cells and the like in bovine blood. After 7 days of static adsorption experiment of blood, the polypropylene hollow fiber membrane modified by 1H,1H, 2H-perfluoro-1-hexene in the example 1 still maintains the original shape of the membrane surface, and no phenomenon of bovine blood pollution is found. As can be seen from comparison between fig. 5 and fig. 6, the adsorption of the modified polypropylene hollow fiber membrane in example 1 to substances such as serum proteins, platelets, erythrocytes, and the like in bovine blood is significantly reduced, and thus it is understood that the blood contamination resistance of the modified polypropylene hollow fiber membrane is significantly improved.
In summary, the unmodified polypropylene hollow fiber membrane is used as a reference to test parameters such as surface morphology, pore structure, water contact angle of membrane material, gas flux and the like, and the test result is as follows: the modified polypropylene hollow fiber membrane keeps the original gas transmission performance; the surface of the modified polypropylene hollow fiber membrane has certain superhydrophobicity, and the water contact angle of the surface of the modified polypropylene hollow fiber membrane is increased compared with that of an unmodified polypropylene hollow fiber membrane; the modified polypropylene hollow fiber membrane has reduced adsorption amount of substances such as serum protein, platelet, erythrocyte, etc. in blood.
The application provides a surface modification method of a hollow fiber membrane for an artificial membrane lung, which comprises the following specific implementation processes:
activating the surface of the polypropylene hollow fiber membrane by using a low-temperature ozone treatment technology, wherein the concentration of ozone introduced into a reaction container in a low-temperature constant-temperature tank is 3-20g/m3, and the treatment time is 5-30 min. Or, activating the surface of the polypropylene hollow fiber membrane in a low-temperature constant-temperature tank by adopting a low-temperature gamma ray irradiation method, wherein the absorbed dose is 50-200kGy, the irradiation atmosphere is air, and the irradiation time is 5-20 h;
then, in the process of peroxide radical initiated surface grafting, the selectable double-bond-containing low-surface-energy functional molecules comprise double-bond-containing long-chain alkane molecules, such as vinyl laurate and vinyl stearate, or double-bond-containing polyfluoride, such as one of 1H,1H, 2H-perfluoro-1-hexene, perfluorohexylethylene and 1H,1H, 2H-perfluoro-1-decene, the grafting reaction time is 6-24H, and the grafting temperature is 30-80 ℃.
Finally, in the process of initiating surface grafting by peroxide radicals, the selected catalyst is an oil-soluble reducing agent, such as one of tertiary amine, ferrocene, triethyl aluminum, cuprous naphthoate and the like, and the catalyst has the function of promoting peroxide radicals to be decomposed into free radicals to initiate double bond polymerization.
According to the surface modification method of the hollow fiber membrane for the artificial membrane lung, the peroxide groups are uniformly introduced to the surface of the polypropylene hollow fiber membrane by adopting a low-temperature ozone or gamma ray irradiation treatment method, and the survival time of the peroxide groups is prolonged under a low-temperature environment, so that the surface grafting density is increased. The surface modification method of the hollow fiber membrane for the artificial membrane lung, disclosed by the application, grafts the low-surface-energy functional molecules containing double bonds on the surface of the membrane in the form of chemical bonds, so that the lasting stability is ensured. The hollow fiber membrane modified by the method keeps good gas permeability, and simultaneously, the blood pollution resistance is improved.
The foregoing is illustrative of the best mode contemplated for carrying out the present application and all those parts not specifically mentioned are within the common general knowledge of a person of ordinary skill in the art. The protection scope of the present application is subject to the content of the claims, and any equivalent transformation based on the technical teaching of the present application is also within the protection scope of the present application.
Claims (8)
1. A surface modification method of a hollow fiber membrane applicable to an artificial membrane lung, comprising:
introducing peroxy groups on the surface of the hollow fiber membrane by adopting low-temperature ozone or gamma ray irradiation;
the hollow fiber membrane with surface carried with peroxy group is soaked in the low surface energy functional molecule solution containing double bond, under the action of catalyst, the peroxy bond in the peroxy group is heated and broken, and is polymerized with the low surface energy functional molecule containing double bond in the solution, namely graft reaction, to generate the hollow fiber membrane with surface modified with low surface energy functional molecule.
2. The method for modifying the surface of a hollow-fiber membrane for an artificial membrane lung according to claim 1, further comprising washing the resulting hollow-fiber membrane with a functional molecule having a low surface energy modified thereon in a volatile non-volatile solvent.
3. The method for modifying the surface of a hollow fiber membrane applicable to an artificial membrane lung according to claim 1, wherein the introduction of peroxy groups onto the surface of the hollow fiber membrane using low-temperature ozone comprises introducing ozone into a low-temperature thermostat tank, and activating the surface of the hollow fiber membrane using ozone, wherein the ozone concentration is 3 to 20g/m 3 The setting temperature of the low-temperature constant-temperature bath is-10 ℃ to 5 ℃, and the ventilation time is 5min to 30 min.
4. The surface modification method of the hollow fiber membrane applicable to the artificial membrane lung according to claim 1, wherein the surface of the hollow fiber membrane is irradiated by low-temperature gamma rays to introduce peroxy groups, and specifically comprises,
the surface of the hollow fiber membrane in the low-temperature constant-temperature tank is irradiated by low-temperature gamma rays to activate the surface of the hollow fiber membrane, wherein the irradiation atmosphere is air, the temperature of the low-temperature constant-temperature tank is set to be-10-5 ℃, the absorption dose is 50-200kGy, and the irradiation time is 5-20 h.
5. The method for modifying the surface of a hollow fiber membrane applicable to an artificial membrane lung according to claim 1, wherein the double bond-containing low surface energy functional molecule comprises any one or a combination of two of a double bond-containing long-chain alkane molecule and a double bond-containing polyfluoride.
6. The method for modifying the surface of a hollow fiber membrane that can be used for an artificial membrane lung according to claim 5, wherein the long-chain alkane molecule having a double bond comprises any one of vinyl laurate and vinyl stearate or a combination of two or more thereof.
7. The method for modifying the surface of a hollow-fiber membrane usable for an artificial membrane lung according to claim 5, wherein the double-bond-containing polyfluoride includes any one or a combination of two or more of 1H,1H, 2H-perfluoro-1-hexene, perfluorohexylethylene, and 1H,1H, 2H-perfluoro-1-decene.
8. The method for modifying the surface of a hollow fiber membrane applicable to an artificial membrane lung according to claim 1, wherein the reaction time of the grafting reaction is 6 to 24 hours and the reaction temperature is 30 to 80 ℃.
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Application publication date: 20220902 |