CN115677998A - Functionalized polycarbonate and preparation method and application thereof - Google Patents
Functionalized polycarbonate and preparation method and application thereof Download PDFInfo
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- CN115677998A CN115677998A CN202211437816.1A CN202211437816A CN115677998A CN 115677998 A CN115677998 A CN 115677998A CN 202211437816 A CN202211437816 A CN 202211437816A CN 115677998 A CN115677998 A CN 115677998A
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- Prior art keywords
- bisphenol
- water
- sodium
- polycarbonate
- prepolymer
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 75
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 210000004369 blood Anatomy 0.000 claims abstract description 25
- 239000008280 blood Substances 0.000 claims abstract description 25
- 238000000746 purification Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 27
- -1 diallyl bisphenol compound Chemical class 0.000 claims description 26
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- 229930185605 Bisphenol Natural products 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 17
- 229940047670 sodium acrylate Drugs 0.000 claims description 17
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims description 17
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 239000003146 anticoagulant agent Substances 0.000 claims description 11
- 229940127219 anticoagulant drug Drugs 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 11
- 239000012498 ultrapure water Substances 0.000 claims description 11
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N Bisphenol F Natural products C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- YQUQWHNMBPIWGK-UHFFFAOYSA-N 4-isopropylphenol Chemical compound CC(C)C1=CC=C(O)C=C1 YQUQWHNMBPIWGK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001631 haemodialysis Methods 0.000 claims description 4
- 230000000322 hemodialysis Effects 0.000 claims description 4
- 230000001951 hemoperfusion Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000004005 microsphere Substances 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 2
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 claims description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- UMPGNGRIGSEMTC-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexyl]phenol Chemical compound C1C(C)CC(C)(C)CC1(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 UMPGNGRIGSEMTC-UHFFFAOYSA-N 0.000 claims description 2
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 206010018910 Haemolysis Diseases 0.000 abstract description 8
- 230000008588 hemolysis Effects 0.000 abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 6
- 230000010118 platelet activation Effects 0.000 abstract description 4
- 230000005764 inhibitory process Effects 0.000 abstract description 3
- 230000010100 anticoagulation Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 24
- 238000005227 gel permeation chromatography Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 108090000190 Thrombin Proteins 0.000 description 4
- 230000002411 adverse Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 210000001772 blood platelet Anatomy 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229960004072 thrombin Drugs 0.000 description 4
- 206010019663 Hepatic failure Diseases 0.000 description 3
- 208000001647 Renal Insufficiency Diseases 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000005102 attenuated total reflection Methods 0.000 description 3
- 201000006370 kidney failure Diseases 0.000 description 3
- 208000007903 liver failure Diseases 0.000 description 3
- 231100000835 liver failure Toxicity 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- LSEBTZWHCPGKEF-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C=C1 LSEBTZWHCPGKEF-UHFFFAOYSA-N 0.000 description 2
- 238000002965 ELISA Methods 0.000 description 2
- 108010022355 Fibroins Proteins 0.000 description 2
- 206010062713 Haemorrhagic diathesis Diseases 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 102100030304 Platelet factor 4 Human genes 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 208000007536 Thrombosis Diseases 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 208000031169 hemorrhagic disease Diseases 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 210000004185 liver Anatomy 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- NIONDZDPPYHYKY-SNAWJCMRSA-N (2E)-hexenoic acid Chemical compound CCC\C=C\C(O)=O NIONDZDPPYHYKY-SNAWJCMRSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 238000008157 ELISA kit Methods 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 208000032843 Hemorrhage Diseases 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- 229920000057 Mannan Polymers 0.000 description 1
- 108090000778 Platelet factor 4 Proteins 0.000 description 1
- 108010094028 Prothrombin Proteins 0.000 description 1
- 102100027378 Prothrombin Human genes 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NIONDZDPPYHYKY-UHFFFAOYSA-N Z-hexenoic acid Natural products CCCC=CC(O)=O NIONDZDPPYHYKY-UHFFFAOYSA-N 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000001785 acacia senegal l. willd gum Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- WWMWAMFHUSTZTA-KQYNXXCUSA-N adenosine 5'-(pentahydrogen tetraphosphate) Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(O)=O)[C@@H](O)[C@H]1O WWMWAMFHUSTZTA-KQYNXXCUSA-N 0.000 description 1
- 230000002429 anti-coagulating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 208000034158 bleeding Diseases 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 210000000601 blood cell Anatomy 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UJTPZISIAWDGFF-UHFFFAOYSA-N ethenylsulfonylbenzene Chemical compound C=CS(=O)(=O)C1=CC=CC=C1 UJTPZISIAWDGFF-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000034217 membrane fusion Effects 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010412 perfusion Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 229940039716 prothrombin Drugs 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000013878 renal filtration Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 208000010110 spontaneous platelet aggregation Diseases 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Abstract
The invention relates to a functionalized polycarbonate and a preparation method and application thereof. The functionalized polycarbonate simultaneously comprises carboxyl and sulfonic group-containing groups on the molecular side chain, and has the structure shown in the formula (1):
Description
Technical Field
The invention belongs to the technical field of biomedical high polymer materials, and relates to functionalized polycarbonate and a preparation method thereof, which can be used as a blood contact product.
Background
With the further development of medical technology, the demand for medical devices has further increased. Medical instruments applied in special fields require materials with some special properties. In the course of blood treatment such as extracorporeal hemodialysis, hemoperfusion, and in vivo stent graft, the material is required to have good blood compatibility
Polycarbonate (PC) is widely applied to the fields of automobiles, electronic equipment, buildings, office supplies, optical disks, sports equipment, medical care, computers, aerospace and the like due to good mechanical properties, heat resistance, optical properties and chemical resistance of the PC as an engineering plastic. However, polycarbonate is less applicable in the field of blood contact materials, and due to its poor blood compatibility, direct contact with blood may cause a series of adverse effects such as platelet aggregation activation, thrombus formation, and blood cell destruction.
It has been shown that the biocompatibility of polycarbonate is improved by blending with biologically active substances. For example, in patent CN105062029B, polycarbonate, chitin and hydroxypropyl methyl cellulose are blended to prepare a polycarbonate biological purification material. The patent CN108815590A blends corn starch, arabic gum, mannan, silk fibroin and other components with polyvinyl carbonate and polycarbonate to prepare the polysaccharide-silk fibroin composite anticoagulant biomaterial. However, the method of blending is used to improve the biocompatibility of the polycarbonate, and a small molecule plasticizer is usually added to improve the compatibility among the components. There is a risk of migration and leakage of the small molecule plasticizer, which may have an adverse effect on the human body. In addition, the biocompatibility of the polycarbonate is improved by blending with natural macromolecules such as cellulose, starch, polysaccharide, protein and the like, and adverse effects such as modulus reduction, poor impact strength, thermal property reduction and the like can be caused on the performance of the polycarbonate.
The method for improving the blood compatibility of the polycarbonate by the copolymerization method is a safer and more effective method. CN113402704A provides a method for preparing carboxyl functionalized polycarbonate, which improves the blood compatibility of polycarbonate and does not cause adverse effect when the polycarbonate is contacted with blood. However, since it has no self-anticoagulation property, it is still necessary to add an additional anticoagulant to prevent thrombus formation when it is prepared into, for example, a hemodialysis membrane or hemoperfusion microspheres for extracorporeal treatment of renal failure or hepatic failure. The traditional anticoagulant is directly injected, so that the traditional anticoagulant still plays an anticoagulant effect after the treatment is finished because the traditional anticoagulant returns to the body along with blood circulation, and a patient has bleeding tendency. Moreover, most anticoagulants need to be metabolized by the kidney or liver, however, most patients receiving blood purification are renal failure or liver failure patients, the renal filtration rate or the liver metabolic capacity is reduced, and the bleeding tendency is further aggravated by the prolonged clearance time of the anticoagulants in the body. In addition, clinicians often have difficulty determining anticoagulant biases due to individual patient variability.
Disclosure of Invention
In view of the above problems in the prior art, the present invention is directed to a functionalized polycarbonate and a preparation method thereof, which has good blood compatibility, particularly, self-anticoagulation, low hemolysis rate, and platelet activation inhibition, while maintaining the original properties of polycarbonate, and has good mechanical properties and processability, and can be used as a blood contact product, for example, as a purification material for extracorporeal treatment of renal failure and liver failure blood.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the invention provides a functionalized polycarbonate, the molecular side chain of which simultaneously comprises carboxyl and sulfonic group, and the functionalized polycarbonate has a structure shown in a formula (1):
wherein m is 1-10, preferably 4-7; n is 1-10, preferably 3-6.
The functionalized polycarbonates according to the invention have a weight-average molecular weight of 23000 to 36000g/mol, preferably 25000 to 28000g/mol.
The invention also provides a preparation method of the functionalized polycarbonate, which is carried out in two steps, relates to two polymerization methods of free radical and polycondensation, and has the advantages of mild reaction conditions, low energy consumption and stable product quality.
The preparation method of the functionalized polycarbonate specifically comprises the following steps:
(1) Mixing sodium acrylate, sodium p-styrene sulfonate, a diallyl bisphenol compound, an initiator and water, and carrying out prepolymerization reaction for 2-24h, preferably 6-12h at 60-80 ℃, preferably 70-75 ℃ under the protection of nitrogen to obtain a prepolymer;
(2) Mixing the prepolymer in the step (1), a bisphenol compound, an alkali metal hydroxide, a capping agent and water in a nitrogen environment, stirring to obtain a clear solution, adding an inert organic solvent, and stirring to obtain a water-oil mixed system;
(3) And (3) introducing phosgene into the water-oil mixed system in the step (2) under the protection of nitrogen, adding a catalyst, and carrying out polymerization reaction at the temperature of 25-35 ℃, preferably 30-32 ℃ for 0.5-4h, preferably 2-3h to obtain the functionalized polycarbonate.
In step (1) of the present invention, the diallylbisphenol compound is at least one selected from the group consisting of diallylbiphenol, diallylbisphenol a, diallylbisphenol Z, diallylbisphenol F, diallylbisphenol S and the like, preferably diallylbisphenol a;
the initiator is selected from at least one of ammonium persulfate, potassium persulfate and sodium persulfate, and preferably ammonium persulfate.
In the step (1) of the invention, the molar ratio of the sodium acrylate to the sodium p-styrene sulfonate is 1 (1-5), preferably 1 (3-3.5);
the amount of the diallyl bisphenol compound is 0.5-1.5 percent, preferably 1-1.2 percent of the total molar amount of the sodium acrylate and the sodium p-styrene sulfonate;
the dosage of the initiator is 0.05-1%, preferably 0.1-0.5% of the total molar weight of the sodium acrylate and the sodium p-styrene sulfonate.
In the step (1), the water is ultrapure water;
the proportion of the amount of the water to the total mass of the sodium acrylate and the sodium p-styrene sulfonate is (12.5-20): 1, preferably (16-16.5): 1.
in step (1) of the present invention, the weight average molecular weight of the prepolymer is 1000 to 10000g/mol, preferably 3000 to 5000g/mol.
In step (2) of the present invention, the bisphenol-type compound is at least one selected from the group consisting of bisphenol a, bisphenol B, bisphenol E, bisphenol F, bisphenol Z, bisphenol TMC, preferably bisphenol a;
the alkali metal hydroxide is at least one selected from potassium hydroxide, sodium hydroxide, lithium hydroxide and cesium hydroxide, and is preferably sodium hydroxide;
the end capping agent is selected from at least one of phenol, p-methyl phenol, p-isopropyl phenol and p-tert-butyl phenol, preferably p-tert-butyl phenol;
the inert organic solvent is at least one selected from dichloromethane, trichloromethane, dichloroethane and trichloroethane, and is preferably dichloromethane.
In step (2) of the present invention, the mass ratio of the prepolymer to the bisphenol compound is 1: (1.5-15.5), preferably 1: (3-4);
the end capping agent accounts for 1 to 3 percent of the mass of the bisphenol compound, and preferably 1.5 to 2.5 percent;
the mass ratio of the bisphenol compound to water is 1: (12.5-20), preferably 1: (16-16.5);
the mass concentration of the alkali metal hydroxide in the clear solution is 2 to 8 wt.%, preferably 4 to 6 wt.%.
The mass ratio of the water to the inert organic solvent is 1: (0.5-1.2), preferably 1 (1-1.05).
In step (3) of the present invention, the phosgene is introduced into the water-oil mixture system in step (2) in an amount such that, based on the total amount of the prepolymer and the bisphenol compound (i.e., the comonomer) in the water-oil mixture system in step (2), the ratio of the total molar amount of the prepolymer and the bisphenol compound to the molar amount of phosgene is 1: (1-1.15), preferably 1: (1-1.12);
and the phosgene is continuously fed in the reaction process in a continuous feeding mode, and the phosgene feeding time is the same as the reaction time.
In step (3), the catalyst is at least one selected from triethylamine, tetrabutylammonium bromide and tetrabutylammonium chloride, preferably triethylamine;
the mass ratio of the catalyst to the bisphenol compound in the water-oil mixture system in the step (2) is 0.0001-0.005, preferably 0.0002-0.0003.
In the step (3) of the invention, the pH of the reaction system is kept between 11 and 12 in the polymerization reaction; the regulation and control can be carried out by a conventional means such as adding an aqueous solution of sodium hydroxide, and the invention is not particularly limited.
In the step (3), the method further comprises a post-treatment process after the polymerization reaction is finished, wherein a functionalized polycarbonate product is obtained after the polycarbonate copolymer emulsion obtained by the polymerization reaction is purified; the purification operation can adopt the conventional method in the field without special requirements, for example, the post-treatment method disclosed in patents CN202010666164.3 and CN202010698811.9 can be adopted, specifically as follows: the copolymer emulsion is firstly subjected to oil-water separation, and then is sequentially subjected to washing, devolatilization, crushing and drying to obtain powder.
The functionalized polycarbonate is prepared by taking sodium acrylate, a prepolymer of sodium p-styrene sulfonate and a bisphenol compound as monomers and reacting the monomers with phosgene by a phosgene interfacial polycondensation method. The prepared functional polycarbonate has the performances of self-anticoagulation, low hemolysis rate, platelet activation inhibition and the like, maintains the original performance of the polycarbonate, can be used as a blood contact product, and can be used as a solid anticoagulant for blood purification materials, and can be used for preparing shells of hemodialyzers and perfusion devices, hemodialysis membranes, hemoperfusion adsorption microspheres and the like.
The functionalized polycarbonates according to the invention exhibit a prolonged activated partial prothrombin time, preferably in the range from 50 to 600s, more preferably in the range from 100 to 600s, compared with platelet-poor plasma.
The functionalized polycarbonates of the present invention also exhibit extended thrombin times, preferably from 20 to 180 seconds, more preferably from 90 to 180 seconds.
The functionalized polycarbonates according to the invention also have good hemocytocompatibility, which is manifested by a low hemolysis rate, preferably < 5%, more preferably < 1%. Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
the invention introduces carboxyl and sulfonic group with specific structure on the side chain by copolymerization mode, endows the polycarbonate with good blood compatibility, makes it have self-anticoagulation, low hemolysis rate and inhibits the activation of blood platelet, does not need to add anticoagulant additionally when in use, reduces the risk of bleeding and complication of patients, widens the application field of polycarbonate, provides a material solution for the development of blood treatment field, and has wide application prospect in the field of blood contact material.
The molecular weight and the composition of the functional polymer prepared by the invention can be regulated, and the method has simple steps, is convenient for realizing industrialization and has good industrial application prospect.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
The main analytical evaluation methods employed in the examples of the present invention and comparative examples were as follows:
the molecular weight was determined by Gel Permeation Chromatography (GPC) using a gel permeation chromatograph model Waters 1515, dichloromethane as mobile phase and 30 ℃ temperature.
The tensile modulus and the yield strength are tested by a universal tensile machine, and the test standard ISO527 is adopted with the model Zwick.
The infrared test was carried out by means of an attenuated total reflectance infrared (ATR-FTIR) spectrometer, using a Nicolet 560 from Thermo Fisher, USA.
The nuclear magnetic resonance test is carried out by a nuclear magnetic resonance spectrometer with the model number of AV III HD 400MHz of Burker company.
The volume melt index (MVR) was measured by a melt index meter under the conditions of 300 ℃ and 1.2kg.
Coagulation response test Activated Partial Thrombin Time (APTT) and Thrombin Time (TT) were measured using a semi-automatic coagulometer (Sysmex Corporation, kobe, japan);
the specific experimental procedure is as follows: firstly, soaking a 1cm by 1cm PC film in normal saline overnight and incubating for 1h at 37 ℃; the saline was then removed and 300. Mu.L of fresh Platelet Poor Plasma (PPP) was added to the well plate containing the material and incubated at 37 ℃ for 30min. Testing for APTTAdding 50 μ L of incubated PPP, 50 μ L of APTT reagent, and 50 μ L of 0.025M CaCl into the test cup in sequence 2 And (3) solution. For testing of TT, 50 μ L of incubated PPP was added first to the test cup, followed by 100 μ L of thrombin reagent.
The test for the hemolysis rate was carried out according to the hemolysis rate test standard for materials specified in ASTM F756-08.
Platelet factor 4 (PF 4) was used to study platelet activation of the material, and the concentration of PF4 was tested by enzyme-linked immunosorbent assay (ELISA) kit;
the specific experimental steps are as follows: 1cm by 1cm PC films were first soaked overnight in physiological saline and incubated at 37 ℃ for 1h, after which they were co-incubated with whole blood at 37 ℃ for 2h. The treated whole blood was centrifuged at 1000rpm for 15min to obtain plasma for subsequent testing. The subsequent experimental steps were performed according to the specific requirements of the respective ELISA kits.
In the examples of the present invention and the comparative examples, each raw material was a general reagent purchased from a commercial source such as an alatin reagent net.
Example 1
Preparing functional polycarbonate, comprising the following steps:
(1) 94g (1 mol) of sodium acrylate, 618g (3 mol) of sodium p-styrene sulfonate, 0.912g (0.004 mol) of ammonium persulfate and 412.32g (0.04 mol) of diallyl bisphenol A are added into 11748g of ultrapure water, the mixture is subjected to prepolymerization reaction at 75 ℃ under the protection of nitrogen atmosphere for 6 hours, then the temperature is reduced to room temperature, the nitrogen is removed, and the reaction is terminated by exposure in the air, so that a prepolymer is obtained. The weight average molecular weight of the prepolymer was 3500 by GPC measurement.
FTIR test result shows 1720cm -1 An absorption peak appears due to the carboxyl group on acrylic acid; besides, 1163cm -1 And 1092cm -1 An absorption peak is shown, which is attributed to the sulfonic group on p-styrenesulfonic acid, at 3350cm -1 An absorption peak, which is a characteristic absorption peak of the phenolic hydroxyl group of allyl bisphenol A, appeared at 1650cm -1 No absorption peak was observed indicating disappearance of the double bond and occurrence of polymerization.
(2) 64.13g of prepolymer (0.018 mol), 228.29g (1 mol) of bisphenol A,5g of p-tert-butylphenol, 188.34g of sodium hydroxide and 3766.79 of ultrapure water are added into a reactor protected by nitrogen and mixed, and mechanically stirred until completely dissolved to obtain a clear solution, and then 3766.79g of dichloromethane are added and mechanically stirred to form a stable water-oil mixed system.
(3) 0.046g of catalyst triethylamine is added into the water-oil mixed system, and 112.91g (1.14 mol) of phosgene is introduced at the rate of 0.94g/min for polymerization reaction. In the whole reaction process, 32wt% of sodium hydroxide aqueous solution is used for maintaining the pH value of the system to be 11-12, the reaction temperature is 30 ℃, and the reaction time is 120min. After the reaction is finished, performing 20wt% NaOH solution alkali washing, 0.5mol/L hydrochloric acid washing, deionized water washing, devolatilization (boiling in water in a glass kettle at 40 ℃ for preparing powder for 2 hours), crushing, and drying (drying in a blast oven at 120 ℃ for 4 hours) to obtain a functionalized polycarbonate product.
The weight average molecular weight of the product was 24300 and the polydispersity index was 1.58 as determined by GPC.
The results of the nuclear magnetic test showed that the content of the prepolymer was 25.1wt%. The result of the attenuated total reflection infrared test shows 1163cm -1 And 1092cm -1 An absorption peak is shown, which is a typical absorption peak of sulfonic acid group, at 1720cm -1 An absorption peak of carbonyl group was observed at 3350cm -1 The characteristic absorption peak of the phenolic hydroxyl group of allyl bisphenol A was not observed.
The infrared test result shows that the functionalized polycarbonate is prepared.
The nuclear magnetic results show that m in the structure is 7,n which is 3.
Example 2
Preparing functional polycarbonate, comprising the following steps:
(1) 94g (1 mol) of sodium acrylate, 206g (1 mol) of sodium p-styrene sulfonate, 0.238g (0.001 mol) of initiator sodium persulfate and 3.08g (0.01 mol) of diallyl bisphenol A are added into 6000g of ultrapure water, the temperature is reduced to room temperature under the protection of nitrogen atmosphere after prepolymerization reaction for 4h at 65 ℃, the nitrogen is removed, and the reaction is terminated by exposure to the air, so that a prepolymer is obtained. The weight average molecular weight of the prepolymer was 1200 by GPC measurement.
(2) 15.39g (0.013 mol) of prepolymer, 228.29g of bisphenol A (1 mol), 5g of end-capping agent phenol, 136.974g of potassium hydroxide, 4565.8g of ultrapure water are mixed in a reactor with nitrogen protection, mechanically stirred until completely dissolved to obtain a clear solution, 2282.9g of inert organic solvent dichloroethane is added, and mechanically stirred to form a stable water-oil mixed system.
(3) 0.023g of tetrabutylammonium bromide catalyst is added into the water-oil mixture system, and 100.27g (1.013 mol) of phosgene is introduced for polymerization at the same time according to the rate of 3.342 g/min. In the whole reaction process, 32wt% of sodium hydroxide aqueous solution is used for maintaining the pH value of the system to be 11-12, the reaction temperature is 25 ℃, and the reaction time is 30min. After the reaction is finished, performing 20wt% NaOH solution alkali washing, 0.5mol/L hydrochloric acid washing, deionized water washing, devolatilization (boiling in water in a glass kettle at 40 ℃ for preparing powder for 2 hours), crushing, and drying (drying in a blast oven at 120 ℃ for 4 hours) to obtain a functionalized polycarbonate product.
The weight average molecular weight of the product was 23300 and the polydispersity index was 1.6, determined by GPC.
The results of the nuclear magnetic test showed that the content of the prepolymer was 6.05%,
the infrared test result shows that the functionalized polycarbonate is prepared.
The nuclear magnetic results show that m in the structure is 1,n which is 9.
Example 3
Preparing functional polycarbonate, comprising the following steps:
(1) 94g (1 mol) of sodium acrylate, 1030g (5 mol) of sodium p-styrenesulfonate, 16.2g (0.06 mol) of potassium persulfate and 27.27g (0.09 mol) of diallyl bisphenol A were added to 14050g of ultrapure water, and the mixture was subjected to prepolymerization at 80 ℃ for 24 hours under a nitrogen atmosphere, then the temperature was lowered to room temperature, the nitrogen was removed, and the reaction was terminated by exposure to air to obtain a prepolymer. The weight average molecular weight of the prepolymer was 10000 by GPC measurement.
(2) 51.30g (0.005 mol) prepolymer, 228.29g bisphenol A (1 mol), 5g p-tert-butylphenol, 273.948g sodium hydroxide and 3424.35 ultrapure water are added into a reactor with nitrogen protection and mixed, and the mixture is mechanically stirred until completely dissolved to obtain a clear solution, then 3595.58g dichloromethane is added, and the mixture is mechanically stirred to form a stable water-oil mixed system.
(3) 1.141g of catalyst triethylamine is added into the water-oil mixed system, and 114.43g (1.156 mol) of phosgene is introduced for polymerization at the rate of 0.477 g/min. In the whole reaction process, 32wt% of lithium hydroxide aqueous solution is used for maintaining the pH of the system to be 11-12, the reaction temperature is 35 ℃, and the reaction time is 240min. After the reaction is finished, performing 20wt% NaOH solution alkali washing, 0.5mol/L hydrochloric acid washing, deionized water washing, devolatilization (boiling in water in a glass kettle at 40 ℃ for preparing powder for 2 hours), crushing, and drying (drying in a blast oven at 120 ℃ for 4 hours) to obtain a functionalized polycarbonate product.
The weight average molecular weight of the product was 24300 and the polydispersity index was 1.58 as determined by GPC.
The results of the nuclear magnetic test showed that the content of the prepolymer was 20.1wt%.
The infrared test result shows that the functionalized polycarbonate is prepared.
The nuclear magnetic results show that m takes the value of 10 and n takes the value of 1 in the structure.
Example 4
Preparing functional polycarbonate, comprising the following steps:
(1) 94g (1 mol) of sodium acrylate, 412g (2 mol) of sodium p-styrenesulfonate, 0.684g (0.003 mol) of ammonium persulfate and 7.98g (0.03 mol) of diallyl bisphenol S were added to 7590g of ultrapure water, and after prepolymerization at 70 ℃ for 7 hours under a nitrogen atmosphere, the temperature was lowered to room temperature, the nitrogen was removed, and the reaction was terminated by exposure to air to obtain a prepolymer. The weight average molecular weight of the prepolymer was 2800 by GPC measurement.
(2) 119.27g (0.043 mol) prepolymer, 268.35g (1 mol) bisphenol Z,5.56g p-tert-butylphenol, 201.26g sodium hydroxide, 4025.25 ultrapure water are added into a reactor with nitrogen protection and mixed, mechanically stirred until completely dissolved to obtain clear solution, then 4025.25g dichloromethane is added, and mechanically stirred to form a stable water-oil mixed system.
(3) 0.054g of catalyst triethylamine is added into the water-oil mixed system, and at the same time, 115.6g (1.167 mol) of phosgene is introduced at the rate of 0.963g/min for polymerization. In the whole reaction process, 32wt% of sodium hydroxide aqueous solution is used for maintaining the pH value of the system to be 11-12, the reaction temperature is 30 ℃, and the reaction time is 120min. After the reaction is finished, performing 20wt% NaOH solution alkali washing, 0.5mol/L hydrochloric acid washing, deionized water washing, devolatilization (boiling in water in a glass kettle at 40 ℃ for preparing powder for 2 hours), crushing, and drying (drying in a blast oven at 120 ℃ for 4 hours) to obtain a functionalized polycarbonate product.
The weight average molecular weight of the product was 24965 by GPC, with a polydispersity index of 1.62.
The results of the nuclear magnetic test showed that the content of the prepolymer was 40wt%.
The infrared test result shows that the functionalized polycarbonate is prepared.
The nuclear magnetic results show that m in the structure is 5,n which is 5.
Example 5
Functionalized polycarbonate was prepared according to the method of example 1: the difference is only that: the same procedure as in example 1 was repeated except that the amount of the terminal-blocking agent added was 4.4g.
The product has a weight average molecular weight of 28560 and a polydispersity index of 1.63 as determined by GPC. The result of nuclear magnetic test shows that the content of the product A is 25.05wt%, and the value of m in the structure is 4,n is 6.
Example 6
Functionalized polycarbonate was prepared according to the method of example 2: except that the amount of the terminal-capping agent added was 4.4g p-tert-butylphenol. The rest of the operation was the same as in example 2. The weight average molecular weight of the product was 29200 and the polydispersity index was 2.05 as determined by GPC. The result of nuclear magnetic test shows that the content of the product A is 6.03wt%, and the value of m in the structure is 8,n is 2.
Example 7
Functionalized polycarbonate was prepared according to the method of example 3: except that the amount of the added end-capping agent p-tert-butylphenol was 3.4g. The rest of the operation was the same as in example 3. The product had a weight average molecular weight of 36200 and a polydispersity index of 1.61 as determined by GPC. The result of nuclear magnetic test shows that the content of the product A is 20.1wt%, and the value of m in the structure is 1,n and is 10.
Comparative example 1
Preparing polycarbonate by the following steps:
228.29g bisphenol A,5g p-tert-butylphenol, 188.34g sodium hydroxide and 3766.785g ultrapure water are added into a reactor protected by nitrogen and mixed, and mechanically stirred until completely dissolved, and then 3766.785g dichloromethane is added and mechanically stirred to form a stable water-oil mixed system. Then 0.046g of catalyst triethylamine was added while 110.88g of phosgene were passed into the system at a rate of 0.924 g/min. In the whole reaction process, 32wt% of sodium hydroxide aqueous solution is added to maintain the pH of the system to be 11-12, and the reaction temperature is 30 ℃. After the reaction was completed, the product was obtained by post-treatment (the treatment method was the same as in example 1).
The product has a weight average molecular weight of 2450 and a polydispersity index of 1.71 as determined by GPC. The attenuated total reflection infrared spectrum was 1611cm -1 、1509cm -1 、1446cm -1 There was a clear absorption peak, which is a characteristic peak of the benzene ring, and no absorption peak typical of the carboxyl group and the sulfonic acid group was observed.
Comparative example 2
Polycarbonate was prepared according to the method of example 1, except that: in the step 1), no sodium acrylate monomer is added, and other operations and parameters are unchanged, so that the polycarbonate is prepared.
Comparative example 3
Polycarbonate was prepared according to the method of example 1, except that: in the step 1), the sodium acrylate monomer is replaced by trans-2 hexenoic acid, and other operations and parameters are not changed, so that the polycarbonate is prepared.
Comparative example 4
Polycarbonate was prepared according to the method of example 1, except that: in the step 1), sodium p-styrenesulfonate monomer is not added, and other operations and parameters are not changed, so that the polycarbonate is prepared.
Comparative example 5
Polycarbonate was prepared according to the method of example 1, except that: in the step 1), the sodium p-styrenesulfonate monomer is replaced by a phenyl vinyl sulfone monomer, and other operations and parameters are unchanged, so that the polycarbonate is prepared.
Comparative example 6
Polycarbonate was prepared by referring to the method of example 1, except that: no catalyst was added in step 3).
The results of the performance tests on the polycarbonates prepared in the above examples and comparative examples are shown in the following table 1:
TABLE 1
The comparison of the data shows that compared with the conventional polycarbonate, the polycarbonate copolymer disclosed by the invention basically maintains the mechanical property and the flow property, improves the blood compatibility, particularly has the self-anticoagulation property, and has the effects of obviously prolonging the ATPP and TT time, obviously reducing the hemolysis rate, obviously reducing the concentration of platelet activating factors, effectively inhibiting the activation of platelets, effectively improving the performance of the polycarbonate and widening the application field of materials.
It will be appreciated by those skilled in the art that modifications and adaptations to the invention may be made in light of the teachings of the present disclosure. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (10)
1. A functionalized polycarbonate having a structure according to formula (1):
wherein m is 37-51, preferably 4-50; n is 1-13, preferably 2-6.
2. Functionalized polycarbonate according to claim 1, characterized in that the weight average molecular weight is 23000-36000g/mol, preferably 25000-28000g/mol.
3. A process for the preparation of the functionalized polycarbonate of claim 1 or 2, comprising the steps of:
(1) Mixing sodium acrylate, sodium p-styrene sulfonate, a diallyl bisphenol compound, an initiator and water, and carrying out prepolymerization reaction for 2-24h, preferably 6-12h at 60-80 ℃, preferably 70-75 ℃ under the protection of nitrogen to obtain a prepolymer;
(2) Mixing the prepolymer in the step (1), a bisphenol compound, an alkali metal hydroxide, a capping agent and water in a nitrogen environment, stirring to obtain a clear solution, adding an inert organic solvent, and stirring to obtain a water-oil mixed system;
(3) And (3) introducing phosgene into the water-oil mixed system in the step (2) under the protection of nitrogen, adding a catalyst, and carrying out polymerization reaction at the temperature of 25-35 ℃, preferably 30-32 ℃ for 0.5-4h, preferably 2-3h to obtain the functionalized polycarbonate.
4. The method according to claim 3, wherein in the step (1), the diallyl bisphenol compound is at least one selected from diallyl diphenol, diallyl bisphenol A, diallyl bisphenol Z, diallyl bisphenol F and diallyl bisphenol S, preferably diallyl bisphenol A;
the initiator is selected from at least one of ammonium persulfate, potassium persulfate and sodium persulfate, and preferably ammonium persulfate.
5. The preparation method according to claim 3 or 4, wherein in the step (1), the molar ratio of the sodium acrylate to the sodium p-styrene sulfonate is 1 (1-5), preferably 1 (3-3.5);
the amount of the diallyl bisphenol compound is 0.5-1.5 percent, preferably 1-1.2 percent of the total molar amount of the sodium acrylate and the sodium p-styrene sulfonate;
the amount of the initiator is 0.05-1%, preferably 0.1-0.5% of the total molar amount of the sodium acrylate and the sodium p-styrene sulfonate; and/or
In the step (1), the water is ultrapure water;
the proportion of the using amount of the water to the total mass of the sodium acrylate and the sodium p-styrene sulfonate is (12.5-20): 1, preferably (16-16.5): 1; and/or
In step (1), the weight average molecular weight of the prepolymer is 1000 to 10000g/mol, preferably 3000 to 5000g/mol.
6. The production method according to any one of claims 3 to 5, wherein in the step (2), the bisphenol-type compound is selected from at least one of bisphenol A, bisphenol B, bisphenol E, bisphenol F, bisphenol Z, bisphenol TMC, preferably bisphenol A;
the alkali metal hydroxide is at least one selected from potassium hydroxide, sodium hydroxide, lithium hydroxide and cesium hydroxide, and is preferably sodium hydroxide;
the end capping agent is selected from at least one of phenol, p-methyl phenol, p-isopropyl phenol and p-tert-butyl phenol, preferably p-tert-butyl phenol;
the inert organic solvent is at least one selected from dichloromethane, trichloromethane, dichloroethane and trichloroethane, and is preferably dichloromethane.
7. The production method according to any one of claims 3 to 6, wherein in the step (2), the mass ratio of the prepolymer to the bisphenol compound is 1: (1.5-15.5), preferably 1: (3-4);
the end capping agent accounts for 1 to 3 percent of the mass of the bisphenol compound, and preferably 1.5 to 2.5 percent of the mass of the bisphenol compound;
the mass ratio of the bisphenol compound to water is 1: (12.5-20), preferably 1: (16-16.5);
the mass concentration of the alkali metal hydroxide in the clear solution is 3 to 8 wt.%, preferably 5 to 6 wt.%.
The mass ratio of the water to the inert organic solvent is 1: (0.5-1.2), preferably 1 (1-1.05).
8. The preparation method according to any one of claims 3 to 7, wherein in the step (3), the phosgene is introduced into the water-oil mixing system in the step (2) in an amount that the ratio of the total molar amount of the prepolymer and the bisphenol compound to the molar amount of the phosgene is 1: (1-1.15), preferably 1: (1-1.12).
9. The method according to any one of claims 3 to 8, wherein in the step (3), the catalyst is at least one selected from triethylamine, tetrabutylammonium bromide and tetrabutylammonium chloride, preferably triethylamine;
the mass ratio of the catalyst to the bisphenol compound is 0.0001-0.005, preferably 0.0002-0.0003, based on the bisphenol compound in the water-oil mixture system in the step (2); and/or
In the step (3), the pH of the reaction system is kept between 11 and 12 in the polymerization reaction.
10. Use of the functionalized polycarbonate of claim 1 or 2 or prepared by the preparation process of any one of claims 3 to 9 in the field of blood contact products, preferably as a solid anticoagulant for blood purification materials, for example for the preparation of hemodialyzers, cartridge housings, hemodialysis membranes, hemoperfusion adsorption microspheres.
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| CN113045695A (en) * | 2020-05-18 | 2021-06-29 | 武汉杨森生物技术有限公司 | Preparation method and application of anticoagulant copolymer |
| CN113402704A (en) * | 2021-07-09 | 2021-09-17 | 万华化学集团股份有限公司 | Polycarbonate copolymer and preparation method and application thereof |
| CN113929894A (en) * | 2021-11-30 | 2022-01-14 | 万华化学集团股份有限公司 | High-temperature-resistant polycarbonate copolymer and preparation method and application thereof |
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| CN113045695A (en) * | 2020-05-18 | 2021-06-29 | 武汉杨森生物技术有限公司 | Preparation method and application of anticoagulant copolymer |
| CN113402704A (en) * | 2021-07-09 | 2021-09-17 | 万华化学集团股份有限公司 | Polycarbonate copolymer and preparation method and application thereof |
| CN113929894A (en) * | 2021-11-30 | 2022-01-14 | 万华化学集团股份有限公司 | High-temperature-resistant polycarbonate copolymer and preparation method and application thereof |
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