CN109758930A - A kind of preparation method of hollow-fibre membrane that treating hyperlipemia - Google Patents
A kind of preparation method of hollow-fibre membrane that treating hyperlipemia Download PDFInfo
- Publication number
- CN109758930A CN109758930A CN201910071140.0A CN201910071140A CN109758930A CN 109758930 A CN109758930 A CN 109758930A CN 201910071140 A CN201910071140 A CN 201910071140A CN 109758930 A CN109758930 A CN 109758930A
- Authority
- CN
- China
- Prior art keywords
- hollow
- fibre membrane
- sulfone
- preparation
- polyether sulfone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 89
- 239000012528 membrane Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 54
- 201000005577 familial hyperlipidemia Diseases 0.000 title claims abstract description 15
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 79
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 78
- 238000005266 casting Methods 0.000 claims abstract description 71
- 150000003457 sulfones Chemical class 0.000 claims abstract description 56
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 230000021523 carboxylation Effects 0.000 claims abstract description 5
- 238000006473 carboxylation reaction Methods 0.000 claims abstract description 5
- 238000012545 processing Methods 0.000 claims abstract description 5
- 238000002166 wet spinning Methods 0.000 claims abstract description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 248
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 62
- 238000006640 acetylation reaction Methods 0.000 claims description 41
- 230000021736 acetylation Effects 0.000 claims description 40
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 30
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 30
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 30
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 23
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 22
- 229940113088 dimethylacetamide Drugs 0.000 claims description 22
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 14
- 238000009987 spinning Methods 0.000 claims description 14
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004088 foaming agent Substances 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 230000001112 coagulating effect Effects 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- FXXACINHVKSMDR-UHFFFAOYSA-N acetyl bromide Chemical compound CC(Br)=O FXXACINHVKSMDR-UHFFFAOYSA-N 0.000 claims description 2
- LEKJTGQWLAUGQA-UHFFFAOYSA-N acetyl iodide Chemical compound CC(I)=O LEKJTGQWLAUGQA-UHFFFAOYSA-N 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical group 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000004040 pyrrolidinones Chemical class 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims 1
- -1 Ether sulfone Chemical class 0.000 claims 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 210000004369 blood Anatomy 0.000 abstract description 43
- 239000008280 blood Substances 0.000 abstract description 43
- 150000002632 lipids Chemical class 0.000 abstract description 28
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 23
- 229920000570 polyether Polymers 0.000 abstract description 23
- 125000001174 sulfone group Chemical group 0.000 abstract description 23
- 238000002844 melting Methods 0.000 abstract description 20
- 230000008018 melting Effects 0.000 abstract description 20
- 235000012489 doughnuts Nutrition 0.000 abstract description 8
- 238000001631 haemodialysis Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 63
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 23
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 20
- 238000004090 dissolution Methods 0.000 description 20
- 239000012153 distilled water Substances 0.000 description 20
- 238000011010 flushing procedure Methods 0.000 description 20
- 238000002791 soaking Methods 0.000 description 14
- 238000005406 washing Methods 0.000 description 13
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 12
- 230000015271 coagulation Effects 0.000 description 12
- 238000005345 coagulation Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000012286 potassium permanganate Substances 0.000 description 11
- 235000012000 cholesterol Nutrition 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 108010007622 LDL Lipoproteins Proteins 0.000 description 7
- 102000007330 LDL Lipoproteins Human genes 0.000 description 7
- 230000036541 health Effects 0.000 description 7
- 229920001661 Chitosan Polymers 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 108010010234 HDL Lipoproteins Proteins 0.000 description 5
- 102000015779 HDL Lipoproteins Human genes 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000003610 charcoal Substances 0.000 description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 150000003626 triacylglycerols Chemical class 0.000 description 4
- 208000024172 Cardiovascular disease Diseases 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 201000010099 disease Diseases 0.000 description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000012510 hollow fiber Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 210000002966 serum Anatomy 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 102000014914 Carrier Proteins Human genes 0.000 description 2
- 108010078791 Carrier Proteins Proteins 0.000 description 2
- 208000032928 Dyslipidaemia Diseases 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 208000031226 Hyperlipidaemia Diseases 0.000 description 2
- 208000017170 Lipid metabolism disease Diseases 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008081 blood perfusion Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 208000026106 cerebrovascular disease Diseases 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002526 effect on cardiovascular system Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 108010022197 lipoprotein cholesterol Proteins 0.000 description 2
- 239000011806 microball Substances 0.000 description 2
- 208000001889 Acid-Base Imbalance Diseases 0.000 description 1
- 201000001320 Atherosclerosis Diseases 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 208000017667 Chronic Disease Diseases 0.000 description 1
- 208000035150 Hypercholesterolemia Diseases 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 238000009098 adjuvant therapy Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003146 anticoagulant agent Substances 0.000 description 1
- 229940127219 anticoagulant drug Drugs 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 239000000385 dialysis solution Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 235000006694 eating habits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000000322 hemodialysis Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 208000019423 liver disease Diseases 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a kind of preparation methods of hollow-fibre membrane for treating hyperlipemia.The preparation method of this hollow-fibre membrane is the following steps are included: 1) the carboxylation processing of polyether sulfone；2) ectonexine casting solution is prepared；3) dry-jet wet spinning prepares hollow-fibre membrane.Obtained active carbon/carboxylated poiyether sulfone/polyether sulphone hollow fibre film is a kind of hollow-fibre membrane for treating hyperlipemia.The advantages that hollow-fibre membrane that the present invention is prepared is with high security, preparation manipulation is simple, at low cost, it can be applied to the haemodialysis of blood lipid fat melting.The open porous structure for the doughnut film inner layer that the present invention is prepared can selectively be such that blood lipid fat melting passes through, and the structure, charge recognition site in extexine then optionally combine blood lipid fat melting, to effectively remove blood lipid fat melting.
Description
Technical field
The present invention relates to a kind of tunica fibrosa, in particular to a kind of preparation side for the hollow-fibre membrane for treating hyperlipemia
Method.
Background technique
Hyperlipemia is a kind of common disease, is caused by human body lipid metaboli is not normal, refers mainly to total cholesterol in serum, sweet
Oily three esters and low-density lipoprotein white level is excessively high or hdl level is too low.Hyperlipidemia can accelerate atherosclerosis,
Once artery occlusion will cause many diseases, such as cardiovascular and cerebrovascular disease, kidney trouble, liver diseases.
Cardiovascular and cerebrovascular disease is the main reason for middle-aged and the old is lethal, is the number one killer for threatening human health.According to the world
Health organization statistics, about 17,000,000 people die of this chronic disease every year, account for 30% or so of global total death toll.According to
Asia cardiovascular disease joint study shows that age-standardized serum cholesterol raising accounts for about in Chinese 35~74 years old crowd in 2016
23.8% (1.125 hundred million people), and 9.0% (ten thousand people more than 4000) serum cholesterol has built up.Serum low-density LP increases
Account for about 17.0% (80,000,000 people), raised to account for about 5.1% (24,000,000 people), superelevation accounts for about 2.7% (12,820,000 people), high
Density lipoprotein it is relatively low account for about 19.2% (90,000,000 people).According to ministry of Health of China, the Department of Science and Technology and statistics bureau in October, 2016
" Chinese residents nutrition and the Health Situation " of joint publication claims, and China's dyslipidemia illness rate is 18.6%, that is, estimates national blood
Rouge is extremely existing to suffer from number about 1.6 hundred million.Different types of dyslipidemia illness rate is respectively hypercholesterolemia 2.9%, high glycerine
Three ester diseases 11.9%, low-density lipoprotein mass formed by blood stasis 7.4% separately have 3.9% crowd's cholesterol to increase.
Hyperlipemia seriously threatens human health, with the continuous improvement of our people's living standard, urbanization and work
The development of industry changes the eating habit of people, and physical exertion gradually decreases, and China's people with hyperlipidemia will further expansion.
Also, with economic and science and technology development, requirement of the people to quality of life is also higher and higher, reaches preceding institute to the attention of health
The degree not having.The related blood purification method with adjuvant treatment hyperlipemia of exploitation, there is the huge market demand, prospect ten
Divide wide.
The blood purification therapy of current existing document report hyperlipemia, the curative effects for paying close attention to blood perfusion more.Though with tradition
The blood purifications modes such as dialysis are compared, and the mode of Blood index increases to the Scavenging activity of blood lipid fat melting.But Blood index
Agent can not solve electrolyte, acid-base balance.So blood perfusion will be generally combined with haemodialysis at this stage.Meanwhile blood
Adsorbent is mostly wide spectrum adsorbent, lacks selectivity to the removing of blood lipid fat melting, is easy the excessive beneficiating ingredient removed in blood.
In existing disclosed document, CN107827105A discloses a kind of active carbon for treating hyperlipemia；Huang Xunming etc.
(preparation of polyvinyl alcohol modification medical chitosan microballoon and its blood lipid adsorption experiment, Chinese Sea pharmacy, 2003,3,25-27)
Blood lipid absorption research is carried out to the PVA modification of chitosan microballoon of preparation；(synthesis of blood lipid adsorbent and the absorption property such as Mo Jiankun
Research, No.1 Military Medical Univ.'s journal, 2005,25,1161-1163) blood has been carried out to polyethylene glycol/Nano composite material of montmorillonite
Rouge Study on adsorption properties；The rich grade in field (chitosan microball preparation and its research to blood lipid absorption property, health care equipment,
1998,4,7-9) the blood lipid absorption property of the chitosan microball of preparation is studied；(the external blood of chitosan such as Zhang Shuqin
Rouge adsorption capacity and Regulation serum lipids observation, 2004,21,4224-4225) it blood lipid absorption has been carried out to chitosan derivatives has ground
Study carefully.But the above blood purification method is Blood index mode, is unfavorable for being easy to cause blood samples of patients acid-base imbalance, electrolyte lacks
It loses.The still rare dialyzing method removed for blood lipid at present.
Summary of the invention
It is of the existing technology in order to overcome the problems, such as, it is treated in hyperlipemia the purpose of the present invention is to provide a kind of
The preparation method of empty fiber membrane.
The preparation method is that first carrying out carboxylation processing to polyether sulfone, the macromolecule with negative electricity is obtained, simultaneously will
Active carbon is scattered in formation outer layer casting solution in its Polymer Solution；Unmodified polyether sulfone is as internal layer casting solution, by dry
Method spining technology is squirted, a kind of active carbon for having adsorption function/carboxylated poiyether sulfone/polyether sulphone hollow fibre film is prepared.
In order to achieve the above purpose, the technical solution used in the present invention is:
A kind of preparation method of hollow-fibre membrane, comprising the following steps:
1) the carboxylation processing of polyether sulfone: polyether sulfone is first subjected to acetylization reaction, obtains acetylation polyether sulfone；Again by acetyl
Change polyether sulfone and carry out oxidation reaction, obtains carboxylated poiyether sulfone；
2) it prepares ectonexine casting solution: polyether sulfone and pore-foaming agent being dissolved in solvent, deaeration, obtain internal layer casting solution；It will
Carboxylated poiyether sulfone, active carbon, pore-foaming agent and solvent mixing, deaeration obtain outer layer casting solution；
3) dry-jet wet spinning prepares hollow-fibre membrane: by internal layer casting solution and outer layer casting solution simultaneously through diplopore spinning head
Spray, under certain core flow velocity and air section distance condition enter coagulating bath shape, obtain active carbon/carboxylated poiyether sulfone/
Polyether sulphone hollow fibre film.
Preferably, in the preparation method step 1) of this hollow-fibre membrane, acetylization reaction is specifically: polyether sulfone is dissolved in
In organic solvent, acetylation reagent and acetylization reaction catalyst, hybrid reaction is added, obtains acetylation polyether sulfone.
Preferably, in the acetylization reaction of the preparation method step 1) of this hollow-fibre membrane, polyether sulfone, acetylation reagent
Mass ratio with acetylization reaction catalyst is 1:(1.15~1.25): (0.3~0.6)；The dosage of polyether sulfone and organic solvent
Than for 1g:(5~8) mL.
Preferably, in the acetylization reaction of the preparation method step 1) of this hollow-fibre membrane, organic solvent is dimethyl
At least one of sulfoxide, N-Methyl pyrrolidone, DMAC N,N' dimethyl acetamide；It is further preferred that organic solvent is N- first
Base pyrrolidones.
Preferably, in the acetylization reaction of the preparation method step 1) of this hollow-fibre membrane, acetylation reagent is acetyl
At least one of chlorine, acetyl bromide, acetyl iodide；It is further preferred that acetylation reagent is chloroacetic chloride.
Preferably, in the acetylization reaction of the preparation method step 1) of this hollow-fibre membrane, acetylization reaction catalyst
For at least one of aluminium chloride, frerrous chloride, stannous chloride；It is further preferred that acetylization reaction catalyst is aluminium chloride；
In some preferred embodiments of the present invention, aluminium chloride used is anhydrous aluminum chloride.
Preferably, in the acetylization reaction of the preparation method step 1) of this hollow-fibre membrane, the temperature of reaction is 80 DEG C
~100 DEG C；The time of reaction is 1h~3h.
Preferably, in the acetylization reaction of the preparation method step 1) of this hollow-fibre membrane, by product water after reaction
It is washed till neutrality, it is dry, obtain acetylation polyether sulfone；Dry temperature is 60 DEG C~80 DEG C, and the dry time is 8h~12h.
Preferably, in the preparation method step 1) of this hollow-fibre membrane, oxidation reaction is specifically: by acetylation polyether sulfone
It is dissolved in organic solvent, oxidant and oxidation reaction catalyst, hybrid reaction is added, obtains carboxylated poiyether sulfone.
Preferably, in the oxidation reaction of the preparation method step 1) of this hollow-fibre membrane, acetylation polyether sulfone, oxidant
Mass ratio with oxidation reaction catalyst is 1g:(0.05~0.1) g:(0.015~0.02) g；Acetylation polyether sulfone with it is organic molten
The amount ratio of agent is 1g:(6~9) mL.
Preferably, in the oxidation reaction of the preparation method step 1) of this hollow-fibre membrane, organic solvent is that dimethyl is sub-
At least one of sulfone, N-Methyl pyrrolidone, DMAC N,N' dimethyl acetamide.
Preferably, in the oxidation reaction of the preparation method step 1) of this hollow-fibre membrane, oxidant is permanganate；Into
One step is preferred, and oxidant is potassium permanganate.
Preferably, in the oxidation reaction of the preparation method step 1) of this hollow-fibre membrane, oxidation reaction catalyst is alkali
Metal hydroxides；It is further preferred that oxidation reaction catalyst is at least one of sodium hydroxide, potassium hydroxide.
Preferably, in the oxidation reaction of the preparation method step 1) of this hollow-fibre membrane, the temperature of reaction is 80 DEG C~
100℃；The time of reaction is 4h~8h.
Preferably, in the oxidation reaction of the preparation method step 1) of this hollow-fibre membrane, by product centrifugation point after reaction
From, it is dry, obtain carboxylated poiyether sulfone；Dry temperature is 60 DEG C~80 DEG C, and the dry time is for 24 hours~48h.
Preferably, in internal layer casting solution described in the preparation method step 2) of this hollow-fibre membrane, polyether sulfone, pore-foaming agent
Amount ratio with solvent is 1g:(0.04~0.08) g:(0.5~1.5) mL.
Preferably, in outer layer casting solution described in the preparation method step 2) of this hollow-fibre membrane, carboxylated poiyether sulfone, work
Property charcoal, pore-foaming agent and solvent amount ratio be 1g:(0.01~0.1) g:(0.04~0.08) g:(0.5~2.5) mL.
Preferably, in the preparation method step 2) of this hollow-fibre membrane, pore-foaming agent is polyvinylpyrrolidone, poly- second two
Alcohol, polyvinyl alcohol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, ethylene glycol, glycerine, at least one in diethylene glycol (DEG)
Kind；It is further preferred that pore-foaming agent is at least one of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol；Further
Preferably, pore-foaming agent is polyvinylpyrrolidone；In some preferred embodiments of the present invention, used in internal layer casting solution
Polyvinylpyrrolidone model K30；Polyvinylpyrrolidone model K90 used in outer layer casting solution.
Preferably, in the preparation method step 2) of this hollow-fibre membrane, solvent is dimethyl acetamide, dimethyl formyl
At least one of amine, dimethyl sulfoxide, N-Methyl pyrrolidone, DMAC N,N' dimethyl acetamide；It is further preferred that solvent is
Dimethyl acetamide or dimethylformamide.
Preferably, in the preparation method step 2) of this hollow-fibre membrane, the mode of deaeration is negative pressure leaching or standing；It takes out
Filtering filter membrane material used is nylon66 fiber, average pore size 220nm；The time of standing is 8h~12h, the temperature of standing is 10 DEG C~
35℃。
Preferably, in the preparation method step 3) of this hollow-fibre membrane, the driving pressure that internal layer casting solution sprays is
0.1MPa~0.4MPa；The driving pressure that outer layer casting solution sprays is 0.05MPa~0.1MPa.
Preferably, in the preparation method step 3) of this hollow-fibre membrane, core flow velocity is 10mL/min~50mL/min.
Preferably, in the preparation method step 3) of this hollow-fibre membrane, air section distance is 0~20cm.
Preferably, in the preparation method step 3) of this hollow-fibre membrane, core liquid is water.
Preferably, in the preparation method step 3) of this hollow-fibre membrane, solidification liquid used in coagulating bath is water.
Preferably, the obtained membrane material of forming is soaking, dry place in the preparation method step 3) of this hollow-fibre membrane
Reason, obtains finished product.
Preferably, in the preparation method step 3) of this hollow-fibre membrane, impregnate for by membrane material through 20 DEG C~30 DEG C
Water soaking and washing for 24 hours~72h.
Preferably, it in the preparation method step 3) of this hollow-fibre membrane, dries to dry in air.
A kind of hollow-fibre membrane for treating hyperlipemia is made by above-mentioned preparation method.
The beneficial effects of the present invention are:
It the advantages that hollow-fibre membrane that the present invention is prepared is with high security, preparation manipulation is simple, at low cost, can answer
Haemodialysis for blood lipid fat melting.The open porous structure for the doughnut film inner layer that the present invention is prepared can be selective
Ground passes through blood lipid fat melting, and the structure, charge recognition site in extexine then optionally combine blood lipid fat melting, thus effectively
Remove blood lipid fat melting in ground.
Specifically, advantages of the present invention is as follows:
1) active carbon/carboxylated poiyether sulfone/polyether sulphone hollow fibre film for being prepared of the present invention while there is the macro of internal layer
The microstructure of structure and outer layer is seen, permeability is strong, and mass transfer dynamics are fast.
2) active charcoal in active carbon/carboxylated poiyether sulfone/polyether sulphone hollow fibre film outer layer that the present invention is prepared, can
Timely and effectively adsorption and diffusion improves the clearance rate to blood lipid fat melting to the blood lipid fat melting of dialysis fluid side.
3) active carbon/carboxylated poiyether sulfone/polyether sulphone hollow fibre film that the present invention is prepared, the carboxylic acid group of outer layer can
The fat melting of reference state under " taking by force " from the carrier protein of blood lipid fat melting improve carrier protein can continuing with fat melting to blood lipid
The clearance rate of fat melting.
4) active carbon/carboxylated poiyether sulfone/polyether sulphone hollow fibre film that the present invention is prepared, the surface structure of outer layer
Carboxylic acid group can be cooperateed with to adsorb blood lipid fat melting, improve the clearance rate to blood lipid fat melting.
5) active carbon/carboxylated poiyether sulfone/polyether sulphone hollow fibre film that the present invention is prepared, internal layer are polyether sulfone,
Outer layer is carboxylated poiyether sulfone, and blood compatibility is good.
6) active carbon/carboxylated poiyether sulfone/polyether sulphone hollow fibre film that the present invention is prepared has well blood lipid fat melting
Cleaning performance, to the clearance rate of total cholesterol up to 30.19%.
Specific embodiment
The contents of the present invention are described in further detail below by way of specific embodiment.Original used in embodiment
Material unless otherwise specified, can be obtained from routine business approach.
Embodiment 1
40g polyether sulfone is weighed, is placed in 500mL three-necked bottle with the dissolution of 200mL N- N-methyl 2-pyrrolidone N.It is to be dissolved uniformly after,
At 90 DEG C, it is slowly added to 46g chloroacetic chloride and 12g anhydrous aluminum chloride, reacts 2h, is done with after distilled water flushing to neutrality at 60 DEG C
Dry 12h obtains acetylation polyether sulfone.
40g acetylation polyether sulfone is weighed, is placed in 500mL three-necked bottle with the dissolution of 280mL N- N-methyl 2-pyrrolidone N.It is to be dissolved
After uniformly, at 80 DEG C, it is slowly added to 2.0g potassium permanganate, 0.6g sodium hydroxide reacts 6h, after distilled water flushing to neutrality
Dry 36h, obtains carboxylated poiyether sulfone at 60 DEG C.
40g polyether sulfone and 1.6g K30- polyvinylpyrrolidone are dissolved in 20mL dimethyl acetamide, filters, then exists
10h is stood at 10 DEG C, obtains internal layer casting solution.
30g carboxylated poiyether sulfone 1.0g active carbon and 1.2g K90- polyvinylpyrrolidone are dissolved in/are dispersed in 30mL diformazan
Yl acetamide filters, then stands 10h at 10 DEG C, obtain outer layer casting solution.
Outer layer casting solution is sprayed through diplopore spinning head under 0.2MPa driving simultaneously in 0.06MPa, internal layer casting solution,
Enter coagulation bath (water) under the core liquid (water) and 10cm air section distance condition of 50mL/min to shape.By solid hollow-fibre membrane
It after 20 DEG C of water soaking and washing 36h, dries in air, obtains active carbon/carboxylated poiyether sulfone/polyether sulphone hollow fibre film.
Embodiment 2
40g polyether sulfone is weighed, is placed in 500mL three-necked bottle with the dissolution of 240mL N- N-methyl 2-pyrrolidone N.It is to be dissolved uniformly after,
At 80 DEG C, be slowly added to 50g chloroacetic chloride and 20g anhydrous aluminum chloride, react 3h, with after distilled water flushing to neutrality at 80 DEG C
Dry 8h, obtains acetylation polyether sulfone.
40g acetylation polyether sulfone is weighed, is placed in 500mL three-necked bottle with the dissolution of 360mL N- N-methyl 2-pyrrolidone N.It is to be dissolved
After uniformly, at 100 DEG C, it is slowly added to 4.0g potassium permanganate, 0.8g sodium hydroxide reacts 8h, with distilled water flushing to neutrality
The dry 48h at 70 DEG C afterwards, obtains carboxylated poiyether sulfone.
40g polyether sulfone and 2.1g K30- polyvinylpyrrolidone are dissolved in 70mL dimethyl acetamide, filters, then exists
11h is stood at 15 DEG C, obtains internal layer casting solution.
40g carboxylated poiyether sulfone 1.0g active carbon and 1.6g K90- polyvinylpyrrolidone are dissolved in/are dispersed in 40mL diformazan
Base formamide filters, then stands 11h at 15 DEG C, obtain outer layer casting solution.
Outer layer casting solution is sprayed through diplopore spinning head under 0.1MPa driving simultaneously in 0.05MPa, internal layer casting solution,
Enter coagulation bath (water) under the core liquid (water) and 0cm air section distance condition of 45mL/min to shape.By solid hollow-fibre membrane
It after 25 DEG C of water soaking and washing 42h, dries in air, obtains active carbon/carboxylated poiyether sulfone/polyether sulphone hollow fibre film.
Embodiment 3
20g polyether sulfone is weighed, is placed in 500mL three-necked bottle with the dissolution of 100mL N- N-methyl 2-pyrrolidone N.It is to be dissolved uniformly after,
At 80 DEG C, be slowly added to 23g chloroacetic chloride and 6g anhydrous aluminum chloride, react 3h, with after distilled water flushing to neutrality at 70 DEG C
Dry 10h, obtains acetylation polyether sulfone.
20g acetylation polyether sulfone is weighed, is placed in 500mL three-necked bottle with the dissolution of 120mL N- N-methyl 2-pyrrolidone N.It is to be dissolved
After uniformly, at 80 DEG C, it is slowly added to 2.0g potassium permanganate, 0.38g sodium hydroxide reacts 6h, with distilled water flushing to neutrality
The dry 36h at 80 DEG C afterwards, obtains carboxylated poiyether sulfone.
20g polyether sulfone and 1.2g K30- polyvinylpyrrolidone are dissolved in 10mL dimethyl acetamide, filters, then exists
8h is stood at 10 DEG C, obtains internal layer casting solution.
20g carboxylated poiyether sulfone 2.0g active carbon and 0.8g K90- polyvinylpyrrolidone are dissolved in/are dispersed in 40mL diformazan
Yl acetamide filters, then stands 8h at 10 DEG C, obtain outer layer casting solution.
Outer layer casting solution is sprayed through diplopore spinning head under 0.1MPa driving simultaneously in 0.06MPa, internal layer casting solution,
Enter coagulation bath (water) under the core liquid (water) and 11cm air section distance condition of 20mL/min to shape.By solid hollow-fibre membrane
It after 20 DEG C of water soaking and washing 48h, dries in air, obtains active carbon/carboxylated poiyether sulfone/polyether sulphone hollow fibre film.
Embodiment 4
40g polyether sulfone is weighed, is placed in 500mL three-necked bottle with the dissolution of 280mL N- N-methyl 2-pyrrolidone N.It is to be dissolved uniformly after,
At 90 DEG C, be slowly added to 50g chloroacetic chloride and 16g anhydrous aluminum chloride, react 2h, with after distilled water flushing to neutrality at 60 DEG C
Dry 10h, obtains acetylation polyether sulfone.
40g acetylation polyether sulfone is weighed, is placed in 500mL three-necked bottle with the dissolution of 240mL N- N-methyl 2-pyrrolidone N.It is to be dissolved
After uniformly, at 100 DEG C, it is slowly added to 2.8g potassium permanganate, 0.6g sodium hydroxide reacts 8h, with distilled water flushing to neutrality
The dry 48h at 60 DEG C afterwards, obtains carboxylated poiyether sulfone.
40g polyether sulfone and 0.8g K30- polyvinylpyrrolidone are dissolved in 40mL dimethyl acetamide, filters, then exists
12h is stood at 30 DEG C, obtains internal layer casting solution.
35g carboxylated poiyether sulfone 1.8g active carbon and 2.1g K90- polyvinylpyrrolidone are dissolved in/are dispersed in 35mL diformazan
Yl acetamide filters, then stands 12h at 30 DEG C, obtain outer layer casting solution.
Outer layer casting solution is sprayed through diplopore spinning head under 0.15MPa driving simultaneously in 0.07MPa, internal layer casting solution,
Enter coagulation bath (water) under the core liquid (water) and 15cm air section distance condition of 30mL/min to shape.By solid doughnut
Film through 30 DEG C water soaking and washing for 24 hours after, dry in air, obtain active carbon/carboxylated poiyether sulfone/Polyethersulfone Hollow Fiber Plasma
Film.
Embodiment 5
30g polyether sulfone is weighed, is placed in 500mL three-necked bottle with the dissolution of 150mL N- N-methyl 2-pyrrolidone N.It is to be dissolved uniformly after,
At 100 DEG C, be slowly added to 34.5g chloroacetic chloride and 18g anhydrous aluminum chloride, react 1h, with after distilled water flushing to neutrality 60
Dry 12h, obtains acetylation polyether sulfone at DEG C.
30g acetylation polyether sulfone is weighed, is placed in 500mL three-necked bottle with the dissolution of 240mL N- N-methyl 2-pyrrolidone N.It is to be dissolved
After uniformly, at 90 DEG C, it is slowly added to 3.0g potassium permanganate, 0.54g sodium hydroxide reacts 4h, with distilled water flushing to neutrality
Drying for 24 hours, obtains carboxylated poiyether sulfone at 70 DEG C afterwards.
30g polyether sulfone and 2.4g K30- polyvinylpyrrolidone are dissolved in 15mL dimethyl acetamide, filters, then exists
12h is stood at 20 DEG C, obtains internal layer casting solution.
35g carboxylated poiyether sulfone 0.67g active carbon and 1.6g K90- polyvinylpyrrolidone are dissolved in/are dispersed in 20mL bis-
Methylformamide filters, then stands 12h at 20 DEG C, obtain outer layer casting solution.
Outer layer casting solution is sprayed through diplopore spinning head under 0.3MPa driving simultaneously in 0.08MPa, internal layer casting solution,
Enter coagulation bath (water) under the core liquid (water) and 20cm air section distance condition of 40mL/min to shape.By solid hollow-fibre membrane
It after 28 DEG C of water soaking and washing 54h, dries in air, obtains active carbon/carboxylated poiyether sulfone/polyether sulphone hollow fibre film.
Embodiment 6
35g polyether sulfone is weighed, is placed in 500mL three-necked bottle with the dissolution of 280mL N- N-methyl 2-pyrrolidone N.It is to be dissolved uniformly after,
At 80 DEG C, be slowly added to 42g chloroacetic chloride and 14g anhydrous aluminum chloride, react 2h, with after distilled water flushing to neutrality at 70 DEG C
Dry 8h, obtains acetylation polyether sulfone.
35g acetylation polyether sulfone is weighed, is placed in 500mL three-necked bottle with the dissolution of 210mL N- N-methyl 2-pyrrolidone N.It is to be dissolved
After uniformly, at 80 DEG C, it is slowly added to 2.8g potassium permanganate, 0.7g sodium hydroxide reacts 6h, after distilled water flushing to neutrality
Drying for 24 hours, obtains carboxylated poiyether sulfone at 80 DEG C.
35g polyether sulfone and 2.1g K30- polyvinylpyrrolidone are dissolved in 35mL dimethyl acetamide, filters, then exists
8h is stood at 35 DEG C, obtains internal layer casting solution.
35g carboxylated poiyether sulfone 1.75g active carbon and 2.1g K90- polyvinylpyrrolidone are dissolved in/are dispersed in 35mL bis-
Methylformamide filters, then stands 8h at 35 DEG C, obtain outer layer casting solution.
Outer layer casting solution is sprayed through diplopore spinning head under 0.4MPa driving simultaneously in 0.1MPa, internal layer casting solution,
Enter coagulation bath (water) under the core liquid (water) and 13cm air section distance condition of 35mL/min to shape.By solid hollow-fibre membrane
It after 22 DEG C of water soaking and washing 72h, dries in air, obtains active carbon/carboxylated poiyether sulfone/polyether sulphone hollow fibre film.
Embodiment 7
25g polyether sulfone is weighed, is placed in 500mL three-necked bottle with the dissolution of 200mL N- N-methyl 2-pyrrolidone N.It is to be dissolved uniformly after,
At 100 DEG C, be slowly added to 30g chloroacetic chloride and 15g anhydrous aluminum chloride, react 1h, with after distilled water flushing to neutrality at 80 DEG C
Lower dry 12h, obtains acetylation polyether sulfone.
25g acetylation polyether sulfone is weighed, is placed in 500mL three-necked bottle with the dissolution of 200mL N- N-methyl 2-pyrrolidone N.It is to be dissolved
After uniformly, at 90 DEG C, it is slowly added to 2.0g potassium permanganate, 0.375g sodium hydroxide reacts 4h, with distilled water flushing to neutrality
The dry 42h at 80 DEG C afterwards, obtains carboxylated poiyether sulfone.
25g polyether sulfone and 2.0g K30- polyvinylpyrrolidone are dissolved in 25mL dimethylformamide, filters, then exists
10h is stood at 20 DEG C, obtains internal layer casting solution.
20g carboxylated poiyether sulfone 1.0g active carbon and 1.6g K90- polyvinylpyrrolidone are dissolved in/are dispersed in 20mL diformazan
Yl acetamide filters, then stands 10h at 20 DEG C, obtain outer layer casting solution.
Outer layer casting solution is sprayed through diplopore spinning head under 0.25MPa driving simultaneously in 0.1MPa, internal layer casting solution,
Enter coagulation bath (water) under the core liquid (water) and 5cm air section distance condition of 25mL/min to shape.By solid hollow-fibre membrane
It after 21 DEG C of water soaking and washing 30h, dries in air, obtains active carbon/carboxylated poiyether sulfone/polyether sulphone hollow fibre film.
Embodiment 8
30g polyether sulfone is weighed, is placed in 500mL three-necked bottle with the dissolution of 210mL N- N-methyl 2-pyrrolidone N.It is to be dissolved uniformly after,
At 100 DEG C, be slowly added to 36g chloroacetic chloride and 9g anhydrous aluminum chloride, react 3h, with after distilled water flushing to neutrality at 70 DEG C
Dry 10h, obtains acetylation polyether sulfone.
30g acetylation polyether sulfone is weighed, is placed in 500mL three-necked bottle with the dissolution of 240mL N- N-methyl 2-pyrrolidone N.It is to be dissolved
After uniformly, at 100 DEG C, it is slowly added to 1.5g potassium permanganate, 0.57g sodium hydroxide reacts 8h, with distilled water flushing to neutrality
The dry 36h at 70 DEG C afterwards, obtains carboxylated poiyether sulfone.
30g polyether sulfone and 1.2g K30- polyvinylpyrrolidone are dissolved in 60mL dimethyl acetamide, filters, then exists
9h is stood at 35 DEG C, obtains internal layer casting solution.
25g carboxylated poiyether sulfone 2.5g active carbon and 1.5g K90- polyvinylpyrrolidone are dissolved in/are dispersed in 50mL diformazan
Yl acetamide filters, then stands 9h at 35 DEG C, obtain outer layer casting solution.
Outer layer casting solution is sprayed through diplopore spinning head under 0.3MPa driving simultaneously in 0.08MPa, internal layer casting solution,
Enter coagulation bath (water) under the core liquid (water) and 19cm air section distance condition of 10mL/min to shape.By solid hollow-fibre membrane
It after 24 DEG C of water soaking and washing 66h, dries in air, obtains active carbon/carboxylated poiyether sulfone/polyether sulphone hollow fibre film.
Embodiment 9
20g polyether sulfone is weighed, is placed in 500mL three-necked bottle with the dissolution of 160mL N- N-methyl 2-pyrrolidone N.It is to be dissolved uniformly after,
At 90 DEG C, be slowly added to 25g chloroacetic chloride and 12g anhydrous aluminum chloride, react 1h, with after distilled water flushing to neutrality at 80 DEG C
Dry 8h, obtains acetylation polyether sulfone.
20g acetylation polyether sulfone is weighed, is placed in 500mL three-necked bottle with the dissolution of 180mL N- N-methyl 2-pyrrolidone N.It is to be dissolved
After uniformly, at 90 DEG C, it is slowly added to 1.0g potassium permanganate, 0.4g sodium hydroxide reacts 4h, after distilled water flushing to neutrality
Dry 30h, obtains carboxylated poiyether sulfone at 60 DEG C.
20g polyether sulfone and 1.6g K30- polyvinylpyrrolidone are dissolved in 20mL dimethyl acetamide, filters, then exists
8h is stood at 20 DEG C, obtains internal layer casting solution.
30g carboxylated poiyether sulfone 2.0g active carbon and 2.4g K90- polyvinylpyrrolidone are dissolved in/are dispersed in 60mL diformazan
Yl acetamide filters, then stands 8h at 20 DEG C, obtain outer layer casting solution.
Outer layer casting solution is sprayed through diplopore spinning head under 0.35MPa driving simultaneously in 0.09MPa, internal layer casting solution,
Enter coagulation bath (water) under the core liquid (water) and 7cm air section distance condition of 25mL/min to shape.By solid doughnut
Film dries in air after 26 DEG C of water soaking and washing 60h, obtains active carbon/carboxylated poiyether sulfone/Polyethersulfone Hollow Fiber Plasma
Film.
Comparative example 1
20g polyether sulfone is weighed, is placed in 500mL three-necked bottle with the dissolution of 160mL N- N-methyl 2-pyrrolidone N.It is to be dissolved uniformly after,
At 90 DEG C, be slowly added to 25g chloroacetic chloride and 12g anhydrous aluminum chloride, react 1h, with after distilled water flushing to neutrality at 80 DEG C
Dry 8h, obtains acetylation polyether sulfone.
20g acetylation polyether sulfone is weighed, is placed in 500mL three-necked bottle with the dissolution of 180mL N- N-methyl 2-pyrrolidone N.It is to be dissolved
After uniformly, at 90 DEG C, it is slowly added to 1.0g potassium permanganate, 0.4g sodium hydroxide reacts 4h, after distilled water flushing to neutrality
Dry 30h, obtains carboxylated poiyether sulfone at 60 DEG C.
20g polyether sulfone and 1.6g K30- polyvinylpyrrolidone are dissolved in 20mL dimethyl acetamide, filters, then exists
8h is stood at 20 DEG C, obtains internal layer casting solution.
30g carboxylated poiyether sulfone and 2.4g K90- polyvinylpyrrolidone are dissolved in/are dispersed in 60mL dimethyl acetamide,
It filters, then stands 8h at 20 DEG C, obtain outer layer casting solution.
Outer layer casting solution is sprayed through diplopore spinning head under 0.35MPa driving simultaneously in 0.09MPa, internal layer casting solution,
Enter coagulation bath (water) under the core liquid (water) and 7cm air section distance condition of 25mL/min to shape.By solid doughnut
Film dries in air after 26 DEG C of water soaking and washing 60h, obtains carboxylated poiyether sulfone/polyether sulphone hollow fibre film.
Comparative example 2
20g polyether sulfone and 1.6g K30- polyvinylpyrrolidone are dissolved in 20mL dimethyl acetamide, filters, then exists
8h is stood at 20 DEG C, obtains internal layer casting solution.
30g polyether sulfone 2.0g active carbon and 2.4g K90- polyvinylpyrrolidone are dissolved in/are dispersed in 60mL dimethyl second
Amide filters, then stands 8h at 20 DEG C, obtain outer layer casting solution.
Outer layer casting solution is sprayed through diplopore spinning head under 0.35MPa driving simultaneously in 0.09MPa, internal layer casting solution,
Enter coagulation bath (water) under the core liquid (water) and 7cm air section distance condition of 25mL/min to shape.By solid doughnut
Film dries in air after 26 DEG C of water soaking and washing 60h, obtains active carbon/polyether sulphone hollow fibre film.
Comparative example 3
20g polyether sulfone and 1.6g K30- polyvinylpyrrolidone are dissolved in 20mL dimethyl acetamide, filters, then exists
8h is stood at 20 DEG C, obtains internal layer casting solution.
30g polyether sulfone and 2.4g K90- polyvinylpyrrolidone are dissolved in/are dispersed in 60mL dimethyl acetamide, is filtered,
8h then is stood at 20 DEG C, obtains outer layer casting solution.
Outer layer casting solution is sprayed through diplopore spinning head under 0.35MPa driving simultaneously in 0.09MPa, internal layer casting solution,
Enter coagulation bath (water) under the core liquid (water) and 7cm air section distance condition of 25mL/min to shape.By solid doughnut
Film dries in air after 26 DEG C of water soaking and washing 60h, obtains polyether sulphone hollow fibre film.
Using test
The above-mentioned hollow-fibre membrane being prepared is applied to treatment hyperlipemia, the specific method is as follows:
The active carbon that embodiment 1-9 is prepared/carboxylated poiyether sulfone/polyether sulphone hollow fibre film and comparative example 1-3 system
Standby obtained hollow-fibre membrane working process, is made hollow-fibre membrane haemodialyser, and every dialyzer includes in about 4200
Empty fiber membrane, effective length 190mm, effective area 0.6m2.Blood is the anticoagulant pig blood of sodium citrate, passes through outer addition
Total cholesterol, triglycerides, low-density lipoprotein and make its total cholesterol concentration be about 4.0mmol/L, triglyceride concentration is about
For 6.0mmol/L, ldl concn is about 200ppm, and high-density lipoprotein concentration is about 1.0mmol/L.Each implementation
Example three Duplicate Samples of setting.Inflow control is 200mL/min, medium after dialyzer filters without any processing, again
It returns in medium bottle, forms a circulating system, periodically sampling is detected.To after time point, each sample, sample preparation simultaneously make
It is detected with kit, calculates the concentration and clearance rate of total cholesterol, triglycerides, low-density lipoprotein and high-density lipoprotein.
Test result is as follows shown in table 1.
Clearance rate of 1 hollow-fibre membrane of table to solute and albumen
| Triglycerides (%) | Total cholesterol (%) | Low-density lipoprotein (%) | High-density lipoprotein (%) | |
| Embodiment 1 | 78.38 | 68.38 | 78.21 | 12.42 |
| Embodiment 2 | 79.38 | 64.31 | 79.47 | 12.25 |
| Embodiment 3 | 80.39 | 69.21 | 78.19 | 12.48 |
| Embodiment 4 | 79.38 | 67.39 | 77.49 | 11.93 |
| Embodiment 5 | 79.32 | 67.49 | 79.28 | 12.05 |
| Embodiment 6 | 77.49 | 66.34 | 77.10 | 12.15 |
| Embodiment 7 | 81.24 | 65.59 | 80.28 | 12.54 |
| Embodiment 8 | 80.13 | 67.49 | 82.48 | 11.94 |
| Embodiment 9 | 77.38 | 70.19 | 80.28 | 11.84 |
| Comparative example 1 | 50.49 | 43.98 | 48.71 | 11.51 |
| Comparative example 2 | 43.16 | 40.75 | 37.49 | 13.09 |
| Comparative example 3 | 32.19 | 30.45 | 27.96 | 12.84 |
Test result shows active carbon/carboxylated poiyether sulfone/polyether sulphone hollow fibre film pair that embodiment 1-9 is prepared
Triglycerides, total cholesterol and low-density lipoprotein etc. have good clearance rate, and with comparative example 1 (inactive charcoal), comparison
Example 2 (no carboxylated poiyether sulfone) is compared with the hollow-fibre membrane of comparative example 3 (inactive charcoal and carboxylated poiyether sulfone), to glycerol three
The cleaning performance of ester, total cholesterol and low-density lipoprotein is more excellent.And active carbon/carboxylated poiyether sulfone/polyether sulphone hollow fibre film
It is relatively low to the clearance rate of high-density lipoprotein, there is good safety.
A kind of double-layer hollow fiber film of the outer layer with open nano-micrometre hierarchical porous structure is prepared in the present invention,
The preparation method is easy to operate.Gained active carbon/carboxylated poiyether sulfone/polyether sulphone hollow fibre film can adsorb removing free state in time
It is high to blood lipid clearance rate with the blood lipid fat melting of reference state, it is particularly suitable for the hemodialysis of hyperlipemia.And doughnut
The basis material of film is polyether sulfone, has biological safety.
Finally, it should be noted that the above is only a preferred embodiment of the present invention, it is not intended to restrict the invention.For this
For the technical staff in field, the present invention can have various change and change, all within the spirits and principles of the present invention, done
Any modification, equivalent substitution, improvement and etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of hollow-fibre membrane, it is characterised in that: the following steps are included:
1) the carboxylation processing of polyether sulfone: polyether sulfone is first subjected to acetylization reaction, obtains acetylation polyether sulfone；Acetylation is gathered again
Ether sulfone carries out oxidation reaction, obtains carboxylated poiyether sulfone；
2) it prepares ectonexine casting solution: polyether sulfone and pore-foaming agent being dissolved in solvent, deaeration, obtain internal layer casting solution；By carboxylation
Polyether sulfone, active carbon, pore-foaming agent and solvent mixing, deaeration obtain outer layer casting solution；
3) dry-jet wet spinning prepares hollow-fibre membrane: internal layer casting solution and outer layer casting solution are sprayed through diplopore spinning head simultaneously
Out, coagulating bath is entered under certain core flow velocity and air section distance condition to shape, obtains active carbon/carboxylated poiyether sulfone/poly-
Ether sulfone hollow-fibre membrane.
2. a kind of preparation method of hollow-fibre membrane according to claim 1, it is characterised in that: in step 1), acetylation
Reaction is specifically: polyether sulfone is dissolved in organic solvent, addition acetylation reagent and acetylization reaction catalyst, hybrid reaction,
Obtain acetylation polyether sulfone.
3. a kind of preparation method of hollow-fibre membrane according to claim 2, it is characterised in that: the acetylation of step 1) is anti-
Ying Zhong, the mass ratio of polyether sulfone, acetylation reagent and acetylization reaction catalyst are 1:(1.15~1.25): (0.3~0.6)；
The amount ratio of polyether sulfone and organic solvent is 1g:(5~8) mL；The organic solvent is dimethyl sulfoxide, N- crassitude
At least one of ketone, DMAC N,N' dimethyl acetamide；The acetylation reagent be chloroacetic chloride, acetyl bromide, in acetyl iodide extremely
Few one kind；The acetylization reaction catalyst is at least one of aluminium chloride, frerrous chloride, stannous chloride；The temperature of reaction
Degree is 80 DEG C~100 DEG C；The time of reaction is 1h~3h.
4. a kind of preparation method of hollow-fibre membrane according to claim 1, it is characterised in that: in step 1), oxidation is anti-
It should be specifically: acetylation polyether sulfone is dissolved in organic solvent, oxidant is added and oxidation reaction catalyst, hybrid reaction obtain
To carboxylated poiyether sulfone.
5. a kind of preparation method of hollow-fibre membrane according to claim 4, it is characterised in that: the oxidation reaction of step 1)
In, the mass ratio of acetylation polyether sulfone, oxidant and oxidation reaction catalyst is 1g:(0.05~0.1) g:(0.015~0.02)
g；The amount ratio of acetylation polyether sulfone and organic solvent is 1g:(6~9) mL；The organic solvent is dimethyl sulfoxide, N- first
At least one of base pyrrolidones, DMAC N,N' dimethyl acetamide；The oxidant is permanganate；The oxidation reaction
Catalyst is alkali metal hydroxide；The temperature of reaction is 80 DEG C~100 DEG C；The time of reaction is 4h~8h.
6. a kind of preparation method of hollow-fibre membrane according to claim 1, it is characterised in that: internal layer described in step 2)
In casting solution, the amount ratio of polyether sulfone, pore-foaming agent and solvent is 1g:(0.04~0.08) g:(0.5~1.5) mL；Described is outer
In layer casting solution, carboxylated poiyether sulfone, active carbon, pore-foaming agent and solvent amount ratio be 1g:(0.01~0.1) g:(0.04~
0.08) g:(0.5~2.5) mL.
7. a kind of preparation method of hollow-fibre membrane according to claim 6, it is characterised in that: in step 2), pore-foaming agent
For polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, ethylene glycol, third
At least one of triol, diethylene glycol (DEG)；Solvent is dimethyl acetamide, dimethylformamide, dimethyl sulfoxide, N- methylpyrrole
At least one of alkanone, DMAC N,N' dimethyl acetamide.
8. a kind of preparation method of hollow-fibre membrane according to claim 1, it is characterised in that: in step 3), internal layer casting
The driving pressure that film liquid sprays is 0.1MPa~0.4MPa；The driving pressure that outer layer casting solution sprays is 0.05MPa~0.1MPa；
Core flow velocity is 10mL/min~50mL/min, and air section distance is 0~20cm.
9. a kind of preparation method of hollow-fibre membrane according to claim 8, it is characterised in that: in step 3), core liquid is
Water；Solidification liquid used in coagulating bath is water.
10. a kind of hollow-fibre membrane for treating hyperlipemia, it is characterised in that: be by according to any one of claims 1 to 9
Preparation method is made.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910071140.0A CN109758930B (en) | 2019-01-25 | 2019-01-25 | Preparation method of hollow fiber membrane for treating hyperlipidemia |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910071140.0A CN109758930B (en) | 2019-01-25 | 2019-01-25 | Preparation method of hollow fiber membrane for treating hyperlipidemia |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109758930A true CN109758930A (en) | 2019-05-17 |
| CN109758930B CN109758930B (en) | 2021-08-24 |
Family
ID=66455350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910071140.0A Active CN109758930B (en) | 2019-01-25 | 2019-01-25 | Preparation method of hollow fiber membrane for treating hyperlipidemia |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109758930B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114011389A (en) * | 2021-12-08 | 2022-02-08 | 广州康盛生物科技股份有限公司 | Blood purification material for sepsis and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101791521A (en) * | 2010-04-06 | 2010-08-04 | 东华大学 | Polyether sulfone/active carbon composite membrane and preparation method and application thereof |
| EP2487278A2 (en) * | 2009-10-07 | 2012-08-15 | Sion Tech Co., Ltd | Ion-selective capacitive deionization composite electrode, and method for manufacturing a module |
| CN108126528A (en) * | 2017-08-30 | 2018-06-08 | 江苏向阳科技有限公司 | A kind of preparation method of double-layer hollow fiber NF membrane |
| CN108939957A (en) * | 2018-08-01 | 2018-12-07 | 中南大学湘雅医院 | A kind of preparation method of the modified dialysis membrane of Avacopan |
-
2019
- 2019-01-25 CN CN201910071140.0A patent/CN109758930B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2487278A2 (en) * | 2009-10-07 | 2012-08-15 | Sion Tech Co., Ltd | Ion-selective capacitive deionization composite electrode, and method for manufacturing a module |
| CN101791521A (en) * | 2010-04-06 | 2010-08-04 | 东华大学 | Polyether sulfone/active carbon composite membrane and preparation method and application thereof |
| CN108126528A (en) * | 2017-08-30 | 2018-06-08 | 江苏向阳科技有限公司 | A kind of preparation method of double-layer hollow fiber NF membrane |
| CN108939957A (en) * | 2018-08-01 | 2018-12-07 | 中南大学湘雅医院 | A kind of preparation method of the modified dialysis membrane of Avacopan |
Non-Patent Citations (2)
| Title |
|---|
| 金明兰等: "《高血脂健康百事通》", 31 July 2013, 浙江科学技术出版社 * |
| 麻开旺: "一种低密度脂蛋白选择性吸附剂的制备及其性能研究", 《中国博士学位论文全文数据库（工程科技Ⅰ辑）》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114011389A (en) * | 2021-12-08 | 2022-02-08 | 广州康盛生物科技股份有限公司 | Blood purification material for sepsis and preparation method thereof |
| CN114011389B (en) * | 2021-12-08 | 2023-10-31 | 广州康盛生物科技股份有限公司 | Blood purification material for sepsis and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109758930B (en) | 2021-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101703893B (en) | Hollow fiber ultrafiltration composite membrane, preparation method and application thereof | |
| CN101817519B (en) | Preparation method and use of millimetre-sized mesoporous carbon spheres | |
| CN103301759B (en) | A kind of hollow polysulfone fiber dialysis membrane and manufacture method thereof | |
| CN109758930A (en) | A kind of preparation method of hollow-fibre membrane that treating hyperlipemia | |
| CN109794172B (en) | Preparation method of antibacterial hollow fiber membrane for blood purification | |
| CN101810892B (en) | Method for filtering liquid medicine and application of composite membrane in filtering liquid medicine | |
| CN116966756A (en) | Blood purifying membrane for removing proinflammatory cytokines and preparation method thereof | |
| CN210844570U (en) | Dual plasma exchange device | |
| CN109647227A (en) | A kind of filter membrane and preparation method thereof removing low-density lipoprotein | |
| CN114392655A (en) | Preparation method of hemodialysis filtration membrane | |
| CN112426801B (en) | Preparation method of filter medium material | |
| CN109745868A (en) | It is a kind of for treating the preparation method of uremic antibacterial hollow-fibre membrane | |
| CN107381970A (en) | One kind dialysis effluent purifying device | |
| CN101422460B (en) | Preparation method of FK506 slow-release film for repairing nerve damage | |
| Liu et al. | The facile method developed for preparing polyvinylidene fluoride plasma separation membrane via macromolecular interaction | |
| CN200994952Y (en) | Blood filter | |
| WO2010082064A3 (en) | Extracorporeal blood filtration | |
| JP2011000145A (en) | Hollow fiber blood purification membrane and method of manufacturing the same | |
| CN207537303U (en) | A kind of dialysis effluent purifying device | |
| CN206026804U (en) | Infusion utensil is with automatic bubble device that removes | |
| CN101590110A (en) | The extracting method of biology total flavones in the Fructus Mori | |
| CN108714416A (en) | A kind of broad spectrum activity depth blood purification sorbing material and preparation method for medical treatment | |
| JP2004339165A (en) | Coating material for medical tool and leukocyte-removing filter using the same | |
| US11224686B2 (en) | Filter material and manufacturing method thereof | |
| CN213554278U (en) | Autologous blood recovery, cleaning and purification device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: No. 1307, Guangzhou Avenue middle, Tianhe District, Guangzhou, Guangdong 510500 Patentee after: Institute of health medicine, Guangdong Academy of Sciences Country or region after: China Address before: No. 1307, Guangzhou Avenue middle, Tianhe District, Guangzhou, Guangdong 510500 Patentee before: GUANGDONG INSTITUTE OF MEDICAL INSTRUMENTS Country or region before: China |
|
| CP03 | Change of name, title or address | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240202 Address after: No.10, shiliugang Road, Haizhu District, Guangzhou City, Guangdong Province 510000 Patentee after: Institute of biological and medical engineering, Guangdong Academy of Sciences Country or region after: China Address before: No. 1307, Guangzhou Avenue middle, Tianhe District, Guangzhou, Guangdong 510500 Patentee before: Institute of health medicine, Guangdong Academy of Sciences Country or region before: China |
|
| TR01 | Transfer of patent right |