CN115677998B - Functionalized polycarbonate and preparation method and application thereof - Google Patents
Functionalized polycarbonate and preparation method and application thereof Download PDFInfo
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- CN115677998B CN115677998B CN202211437816.1A CN202211437816A CN115677998B CN 115677998 B CN115677998 B CN 115677998B CN 202211437816 A CN202211437816 A CN 202211437816A CN 115677998 B CN115677998 B CN 115677998B
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- bisphenol
- sodium
- water
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- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 72
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 210000004369 blood Anatomy 0.000 claims abstract description 24
- 239000008280 blood Substances 0.000 claims abstract description 24
- 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 48
- 238000000034 method Methods 0.000 claims description 43
- -1 diallyl bisphenol compound Chemical class 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 229930185605 Bisphenol Natural products 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 229940047670 sodium acrylate Drugs 0.000 claims description 21
- 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 21
- 239000000203 mixture Substances 0.000 claims description 19
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 239000003795 chemical substances by application 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
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003146 anticoagulant agent Substances 0.000 claims description 10
- 229940127219 anticoagulant drug Drugs 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
- 239000003999 initiator Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 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 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 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 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
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000001631 haemodialysis Methods 0.000 claims description 4
- 230000000322 hemodialysis 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
- 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
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 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
- 230000010412 perfusion Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 6
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 claims 1
- 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 5
- 230000005764 inhibitory process Effects 0.000 abstract description 4
- 230000010100 anticoagulation Effects 0.000 abstract description 3
- 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 12
- 238000010521 absorption reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 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 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 5
- 108090000190 Thrombin Proteins 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000009835 boiling Methods 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
- 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
- 230000002411 adverse Effects 0.000 description 3
- 238000005102 attenuated total reflection Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 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
- 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
- 206010062713 Haemorrhagic diathesis Diseases 0.000 description 2
- 102100030304 Platelet factor 4 Human genes 0.000 description 2
- 208000007536 Thrombosis Diseases 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000001951 hemoperfusion Effects 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
- 238000005259 measurement Methods 0.000 description 2
- 238000010907 mechanical stirring Methods 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
- 239000002504 physiological saline solution Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000009467 reduction Effects 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
- 238000004483 ATR-FTIR spectroscopy Methods 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
- 108010022355 Fibroins Proteins 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 208000032843 Hemorrhage Diseases 0.000 description 1
- 229920000057 Mannan Polymers 0.000 description 1
- 238000005481 NMR spectroscopy Methods 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 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
- 239000012190 activator Substances 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 208000034158 bleeding Diseases 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 210000000601 blood cell Anatomy 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 230000008081 blood perfusion 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
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 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
- 150000004676 glycans Chemical class 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 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
- 238000002513 implantation Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- LUEWUZLMQUOBSB-GFVSVBBRSA-N mannan Chemical class O[C@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@@H](O[C@@H]2[C@H](O[C@@H](O[C@H]3[C@H](O[C@@H](O)[C@@H](O)[C@H]3O)CO)[C@@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O LUEWUZLMQUOBSB-GFVSVBBRSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 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
- 239000000843 powder 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
- 150000003384 small molecules Chemical class 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
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a function ofPolycarbonate and its preparation method and application are provided. The functional polycarbonate comprises carboxyl and sulfonic groups on the side chains of molecules, and has a structure shown as a formula (1):
Description
Technical Field
The invention belongs to the technical field of biomedical high polymer materials, and relates to a functional polycarbonate and a preparation method thereof, which can be used as a blood contact product.
Background
As medical technology has further advanced, the need for medical devices has further increased. Medical devices used in particular fields require materials with specific properties. In the course of blood treatment, such as extracorporeal hemodialysis, hemoperfusion and intravascular stent implantation, good blood compatibility is required
Polycarbonate (PC) is widely used as engineering plastic in the fields of automobiles, electronic equipment, buildings, office supplies, optical discs, sports equipment, medical care, computers, aerospace and the like due to its good mechanical properties, heat resistance, optical properties and chemical resistance. However, polycarbonate has less applications in the field of blood contact materials, and because of its poor blood compatibility, direct contact with blood can cause platelet aggregation activation to form thrombus and destroy blood cells.
There are studies indicating that the biocompatibility of polycarbonates is improved by means of blending with biologically active substances. For example, in patent CN105062029B, polycarbonate and chitin, hydroxypropyl methylcellulose were blended to prepare a biological purification material having polycarbonate. The patent CN108815590A is prepared by blending components such as corn starch, arabic gum, mannans, silk fibroin and the like with polyethylene carbonate and polycarbonate. However, blending is used to increase the biocompatibility of the polycarbonate, and small-molecule plasticizers are generally added to increase the compatibility between the components. There is a risk of migration and leakage of the small molecular plasticizer, which may adversely affect 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 the properties of the polycarbonate are adversely affected, such as reduction of modulus, deterioration of impact strength, reduction of thermal properties and the like.
Increasing the hemocompatibility of polycarbonates by copolymerization is a safer and more effective method. CN113402704a provides a method for preparing carboxyl functionalized polycarbonates, which improves the blood compatibility of the polycarbonates, so that the polycarbonates are not adversely affected by contact with blood. However, since it does not have self-anticoagulation property, it is still necessary to additionally add an anticoagulant to avoid thrombus formation when preparing an extracorporeal treatment such as a hemodialysis membrane or a blood perfusion microsphere for renal failure or liver failure. The traditional anticoagulant is directly injected and used, so that the anticoagulant still plays an anticoagulant role after treatment is finished along with blood circulation back into the body, and bleeding tendency exists for patients. Moreover, most anticoagulants are metabolized by the kidney or liver, whereas most patients undergoing blood purification are renal failure or liver failure patients, and the renal filtration rate or liver metabolic capacity is reduced, and the bleeding tendency is further exacerbated by prolonged in vivo anticoagulant clearance. In addition, clinicians often have difficulty determining anticoagulant tendencies due to the volume variability of each patient.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide a functionalized polycarbonate and a method for preparing the same, which have good blood compatibility, in particular self-anticoagulation, low hemolysis rate and inhibition of platelet activation, while maintaining the original properties of polycarbonate, have 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, liver failure blood, etc.
In order to achieve the above object, the present invention has the following technical scheme:
the invention provides a functionalized polycarbonate, which simultaneously comprises carboxyl and sulfonic groups on a molecular side chain and has a structure shown as a formula (1):
wherein m has a value of 1 to 10, preferably 4 to 7; n has a value of 1 to 10, preferably 3 to 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, and relates to two polymerization methods of free radical and polycondensation, and the preparation method has the advantages of mild reaction conditions, less energy consumption and stable product quality.
The preparation method of the functionalized polycarbonate specifically comprises the following steps:
(1) Mixing sodium acrylate, sodium p-styrenesulfonate, diallyl bisphenol compound, an initiator and water, and carrying out prepolymerization reaction for 2-24 hours, preferably 6-12 hours at 60-80 ℃ and preferably 70-75 ℃ under the protection of nitrogen to obtain a prepolymer;
(2) In a nitrogen environment, mixing the prepolymer, the bisphenol compound, the alkali metal hydroxide, the end capping agent and the water in the step (1), 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 at the same time, and carrying out polymerization reaction for 0.5-4h, preferably 2-3h at 25-35 ℃, preferably 30-32 ℃ to obtain the functionalized polycarbonate.
In the step (1) of the present invention, the diallyl bisphenol compound is at least one selected from diallyl bisphenol, diallyl bisphenol a, diallyl bisphenol Z, diallyl bisphenol F, diallyl bisphenol S, etc., preferably diallyl bisphenol a;
the initiator is at least one selected from ammonium persulfate, potassium persulfate and sodium persulfate, preferably ammonium persulfate.
In the step (1) of the invention, the molar ratio of the sodium acrylate to the sodium p-styrenesulfonate is 1 (1-5), preferably 1 (3-3.5);
the dosage of the diallyl bisphenol compound is 0.5-1.5%, preferably 1-1.2% of the total molar weight of sodium acrylate and sodium p-styrene sulfonate;
the initiator is used in an amount of 0.05 to 1%, preferably 0.1 to 0.5% of the total molar amount of sodium acrylate and sodium p-styrenesulfonate.
In the step (1) of the invention, the water is ultrapure water;
the ratio of the water to the total mass of sodium acrylate and sodium p-styrenesulfonate is (12.5-20): 1, preferably (16-16.5): 1.
in step (1) of the present invention, the prepolymer has a weight average molecular weight of 1000 to 10000g/mol, preferably 3000 to 5000g/mol.
In the step (2) of the present invention, the bisphenol compound is at least one selected from 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, preferably sodium hydroxide;
the end-capping agent is selected from at least one of phenol, p-methylphenol, p-isopropylphenol and p-tert-butylphenol, preferably p-tert-butylphenol;
the inert organic solvent is selected from at least one of dichloromethane, chloroform, dichloroethane and trichloroethane, preferably dichloromethane.
In the step (2) of the 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 is 1-3% of the mass of the bisphenol compound, preferably 1.5-2.5%;
the mass ratio of the bisphenol compound to water is 1: (12.5-20), preferably 1: (16-16.5);
the alkali metal hydroxide is present in the clarified solution in a mass concentration of from 2 to 8% by weight, preferably from 4 to 6% by weight.
The mass ratio of the water to the inert organic solvent is 1: (0.5-1.2), preferably 1 (1-1.05).
In the step (3) of the invention, the phosgene is introduced into the water-oil mixed system in the step (2), and the ratio of the total molar amount of the prepolymer and the bisphenol compound to the molar amount of the phosgene is 1 based on the total amount of the prepolymer and the bisphenol compound (namely the comonomer) in the water-oil mixed system in the step (2): (1-1.15), preferably 1: (1-1.12);
the phosgene is continuously fed in the reaction process, and the phosgene feeding time is the same as the reaction time.
In the step (3), the catalyst is at least one selected from triethylamine, tetrabutylammonium bromide and tetrabutylammonium chloride, preferably triethylamine;
the catalyst is used in an amount such that the mass ratio of the catalyst to the bisphenol compound is 0.0001 to 0.005:1, preferably 0.0002 to 0.0003:1, based on the bisphenol compound in the water-oil mixture system of step (2).
In the step (3) of the invention, the pH of the reaction system is kept between 11 and 12; the regulation and control can be carried out by adding sodium hydroxide aqueous solution and other conventional means, 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, and the polycarbonate copolymer emulsion obtained by the polymerization reaction is purified to obtain a functionalized polycarbonate product; the purification operation may be performed by a method conventional in the art, and is not particularly limited, and for example, a post-treatment method disclosed in patent CN202010666164.3 and CN202010698811.9 may be used, specifically, as follows: the copolymer emulsion is firstly subjected to oil-water separation, and then is washed, devolatilized, crushed and dried in sequence to obtain powder.
The functional polycarbonate is prepared by taking sodium acrylate, a prepolymer of sodium p-styrenesulfonate and a bisphenol compound as monomers and phosgene through a phosgene interface polycondensation method. The prepared functional polycarbonate has the performances of self anticoagulation, low hemolysis rate, platelet activation inhibition and the like, simultaneously keeps the original performances of the polycarbonate, can be used as a blood contact product, for example, can be used as a solid anticoagulant for blood purification materials, and can be used for preparing hemodialyzers, perfusion shells, hemodialysis membranes, hemoperfusion adsorption microspheres and the like.
The functionalized polycarbonates according to the invention exhibit an extended activation of partial prothrombin time compared to platelet-poor plasma, preferably 50-600s, more preferably 100-600s.
The functionalized polycarbonates according to the invention are at the same time characterized by an extended thrombin time, preferably from 20 to 180s, more preferably from 90 to 180s.
The functionalized polycarbonates according to the invention also have good hemocytocompatibility and exhibit 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:
according to the invention, the carboxyl and sulfonic groups with specific structures are simultaneously introduced into the side chains in a copolymerization mode, so that the polycarbonate has good blood compatibility, so that the polycarbonate has self anticoagulation property, low hemolysis rate and platelet activation inhibition, no anticoagulant is required to be additionally added during use, the risk of bleeding and complications of patients is reduced, the application field of the polycarbonate is widened, a material solution is provided for the development of the blood treatment field, and the polycarbonate has a wide application prospect in the blood contact material field.
The molecular weight and the composition of the functionalized polymer prepared by the invention can be regulated and controlled, and the method has simple steps, is convenient for realizing industrialization and has good industrial application prospect.
Detailed Description
For a better understanding of the technical solution of the present invention, the following examples are further described below, but the present invention is not limited to the following examples.
The main analytical evaluation methods employed in the examples and comparative examples of the present invention are as follows:
the molecular weight was measured by Gel Permeation Chromatography (GPC) using a gel permeation chromatograph model Waters 1515 with methylene chloride as the mobile phase at 30 ℃.
Tensile modulus and yield strength were tested by a universal tensile machine using a model Zwick, test standard ISO527.
Infrared testing was performed by attenuated total reflectance infrared (ATR-FTIR) spectroscopy using a Nicolet 560 test by sameifer (Thermo Fisher) company, usa.
Nuclear magnetic test is carried out by using a nuclear magnetic resonance spectrometer with the model of AV III HD 400MHz by Burker company.
The volume melt index (MVR) was measured by a melt fingermeter at 300℃under 1.2kg.
Coagulation response test Activated Partial Thrombin Time (APTT) and Thrombin Time (TT) were determined using a semi-automatic coagulation meter (Sysmex Corporation, kobe, japan);
the specific experimental steps are as follows: firstly, 1cm x 1cm PC film is soaked in physiological saline water overnight and incubated for 1h at 37 ℃; after this time, the saline was removed and 300. Mu.L of fresh Platelet Poor Plasma (PPP) was added to the plate containing the material and incubated for 30min at 37 ℃. For APTT testing, 50. Mu.L of incubated PPP, 50. Mu.L of APTT reagent, 50. Mu.L of 0.025M CaCl were added sequentially to the test cup 2 A solution. For TT testing, 50. Mu.L of incubated PPP was first added to the test cup, followed by 100. Mu.L of thrombin reagent.
The hemolysis rate was measured according to the standard for hemolysis rate of materials specified in ASTM F-756-08.
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: 1 cm. Times.1 cm PC film was first soaked overnight in physiological saline and incubated at 37℃for 1h, after which it was incubated with whole blood for 2h at 37 ℃. The treated whole blood was centrifuged at 1000rpm for 15min to obtain plasma for subsequent testing. Subsequent experimental steps were performed according to the specific requirements of the respective ELISA kit.
The raw materials in each of the examples and comparative examples of the present invention were common reagents purchased through commercial routes such as an Ara Ding Shiji mesh.
Example 1
The preparation method of the functionalized polycarbonate comprises the following steps:
(1) 94g (1 mol) of sodium acrylate, 618g (3 mol) of sodium p-styrenesulfonate, 0.912g (0.004 mol) of ammonium persulfate and 412.32g (0.04 mol) of diallyl bisphenol A are added to 11748g of ultrapure water, the mixture is protected by nitrogen atmosphere, the temperature is reduced to room temperature after the prepolymerization is carried out for 6 hours at 75 ℃, the nitrogen is removed, and the reaction is stopped by exposure to air, so as to obtain a prepolymer. The prepolymer obtained by GPC measurement had a weight average molecular weight of 3500.
FTIR test results showed 1720cm -1 There appears an absorption peak due to the carboxyl group on acrylic acid; in addition, 1163cm -1 And 1092cm -1 There was an absorption peak due to the sulfonic acid group on p-styrenesulfonic acid at 3350cm -1 An absorption peak, which is characteristic of the phenolic hydroxyl group of allyl bisphenol A, appears at 1650cm -1 No absorption peak was observed, indicating the disappearance of double bonds and the reaction 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 were charged into a reactor protected by nitrogen, and mixed with mechanical stirring until completely dissolved to give a clear solution, and then 3766.79g of methylene chloride was added and mechanically stirred to form a stable water-oil mixture system.
(3) To the water-oil mixture was added 0.046g of triethylamine as a catalyst, while 112.91g (1.14 mol) of phosgene was introduced at a rate of 0.94g/min to carry out polymerization. The pH of the system is maintained to be 11-12 by using a 32wt% sodium hydroxide aqueous solution in the whole reaction process, the reaction temperature is 30 ℃, and the reaction time is 120min. After the reaction is finished, performing alkali washing with 20wt% NaOH solution, acid washing with 0.5mol/L hydrochloric acid, washing with deionized water, devolatilizing (boiling water in a glass kettle at 40 ℃ for 2 h) and crushing and drying (drying in a blast oven at 120 ℃ for 4 h) to obtain the functionalized polycarbonate product.
The weight average molecular weight of the product was 24300 as measured by GPC, and the polydispersity index was 1.58.
The results of the nuclear magnetic test showed that the prepolymer content was 25.1wt%. Attenuated total reflection infrared test result shows 1163cm -1 And 1092cm -1 An absorption peak, which is typical of sulfonic acid groups, appears at 1720cm -1 The absorption peak of the carbonyl group was observed at 3350cm -1 No characteristic absorption peak of the phenolic hydroxyl group of allyl bisphenol a was observed.
The infrared test results show that the functional polycarbonate is prepared.
The nuclear magnetic result shows that m is 7 and n is 3 in the structure.
Example 2
The preparation method of the functionalized polycarbonate comprises the following steps:
(1) 94g (1 mol) of sodium acrylate, 206g (1 mol) of sodium p-styrenesulfonate, 0.238g (0.001 mol) of initiator sodium persulfate, 3.08g (0.01 mol) of diallyl bisphenol A were added to 6000g of ultrapure water, and the prepolymer was obtained by performing a prepolymerization reaction at 65℃for 4 hours under nitrogen atmosphere, cooling to room temperature, removing nitrogen, and terminating the reaction by exposure to air. The prepolymer obtained by GPC measurement had a weight average molecular weight of 1200.
(2) 15.39g (0.013 mol) of prepolymer, 228.29g of bisphenol A (1 mol), 5g of phenol as a capping agent, 136.974g of potassium hydroxide and 4565.8g of ultrapure water are added into a reactor protected by nitrogen, and the mixture is mechanically stirred until the mixture is completely dissolved to obtain a clear solution, then 2282.9g of dichloroethane as an inert organic solvent is added, and the mixture is mechanically stirred to form a stable water-oil mixed system.
(3) To the water-oil mixture was added 0.023g of tetrabutylammonium bromide as a catalyst, while 100.27g (1.013 mol) of phosgene was introduced at a rate of 3.342g/min to carry out polymerization. The pH of the system is maintained to be 11-12 by using a 32wt% sodium hydroxide aqueous solution in the whole reaction process, the reaction temperature is 25 ℃, and the reaction time is 30min. After the reaction is finished, performing alkali washing with 20wt% NaOH solution, acid washing with 0.5mol/L hydrochloric acid, washing with deionized water, devolatilizing (boiling water in a glass kettle at 40 ℃ for 2 h) and crushing and drying (drying in a blast oven at 120 ℃ for 4 h) to obtain the functionalized polycarbonate product.
The weight average molecular weight of the product was 23300 and the polydispersity index was 1.6 as determined by GPC.
The nuclear magnetic test result shows that the content of prepolymer is 6.05%,
the infrared test results show that the functional polycarbonate is prepared.
The nuclear magnetic result shows that m is 1 and n is 9 in the structure.
Example 3
The preparation method of the functionalized polycarbonate comprises 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 a prepolymerization reaction at 80℃for 24 hours under a nitrogen atmosphere, and 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 prepolymer obtained by GPC test had a weight average molecular weight of 10000.
(2) 51.30g (0.005 mol) of prepolymer, 228.29g of bisphenol A (1 mol), 5g of p-tert-butylphenol, 273.948g of sodium hydroxide and 3424.35 of ultrapure water were charged into a reactor protected by nitrogen gas, and mixed with mechanical stirring until completely dissolved to give a clear solution, and then 3595.58g of methylene chloride was added and stirred mechanically to form a stable water-oil mixture system.
(3) To the water-oil mixture was added 1.141g of triethylamine as a catalyst, while 114.43g (1.156 mol) of phosgene was introduced at a rate of 0.477g/min to carry out polymerization. The pH of the system is maintained to be 11-12 by using a 32wt% lithium hydroxide aqueous solution in the whole reaction process, the reaction temperature is 35 ℃, and the reaction time is 240min. After the reaction is finished, performing alkali washing with 20wt% NaOH solution, acid washing with 0.5mol/L hydrochloric acid, washing with deionized water, devolatilizing (boiling water in a glass kettle at 40 ℃ for 2 h) and crushing and drying (drying in a blast oven at 120 ℃ for 4 h) to obtain the functionalized polycarbonate product.
The weight average molecular weight of the product was 24300 as measured by GPC, and the polydispersity index was 1.58.
The results of the nuclear magnetic test showed that the prepolymer content was 20.1wt%.
The infrared test results show that the functional polycarbonate is prepared.
The nuclear magnetic result shows that m is 10 and n is 1 in the structure.
Example 4
The preparation method of the functionalized polycarbonate comprises 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 are added to 7590g of ultrapure water, the reaction is performed for 7 hours at 70 ℃ under the protection of nitrogen atmosphere, the temperature is reduced to room temperature, the nitrogen is removed, and the reaction is stopped by exposure in the air to obtain a prepolymer. The prepolymer obtained had a weight average molecular weight of 2800 by GPC.
(2) 119.27g (0.043 mol) of prepolymer, 268.35g (1 mol) of bisphenol Z,5.56g of p-tert-butylphenol, 201.26g of sodium hydroxide and 4025.25 of ultrapure water are mixed in a reactor protected by nitrogen, and the mixture is mechanically stirred until complete dissolution to give a clear solution, and then 4025.25g of methylene chloride is added and the mixture is mechanically stirred to form a stable water-oil mixture system.
(3) To the water-oil mixture was added 0.054g of triethylamine as a catalyst, and simultaneously 115.6g (1.167 mol) of phosgene was introduced at a rate of 0.963g/min to carry out polymerization. The pH of the system is maintained to be 11-12 by using a 32wt% sodium hydroxide aqueous solution in the whole reaction process, the reaction temperature is 30 ℃, and the reaction time is 120min. After the reaction is finished, performing alkali washing with 20wt% NaOH solution, acid washing with 0.5mol/L hydrochloric acid, washing with deionized water, devolatilizing (boiling water in a glass kettle at 40 ℃ for 2 h) and crushing and drying (drying in a blast oven at 120 ℃ for 4 h) to obtain the functionalized polycarbonate product.
The weight average molecular weight of the product was 24965 and the polydispersity index was 1.62 as determined by GPC.
The results of the nuclear magnetic test showed that the prepolymer content was 40wt%.
The infrared test results show that the functional polycarbonate is prepared.
The nuclear magnetic result shows that m is 5 and n is 5 in the structure.
Example 5
Preparation of functionalized polycarbonate by the method of example 1: the only differences are that: the amount of the capping agent p-tert-butylphenol added was 4.4g, and the rest was the same as in example 1.
The weight average molecular weight of the product was 28560 and the polydispersity index was 1.63 as determined by GPC. The result of the nuclear magnetic test shows that the content of the product A is 25.05wt%, and the m value is 4 and the n value is 6 in the structure.
Example 6
Preparation of functionalized polycarbonate by the method of example 2: except that the capping agent p-tert-butylphenol was added in an amount of 4.4g. The rest of the procedure is 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 the nuclear magnetic test shows that the content of the product A is 6.03 weight percent, the value of m in the structure is 8, and the value of n is 2.
Example 7
Preparation of functionalized polycarbonate by the method of example 3: except that the capping agent p-tert-butylphenol was added in an amount of 3.4g. The rest of the procedure is the same as in example 3. The weight average molecular weight of the product was 36200 as measured by GPC, and the polydispersity index was 1.61. The result of the nuclear magnetic test shows that the content of the product A is 20.1wt%, and the m value is 1 and the n value is 10 in the structure.
Comparative example 1
The preparation of polycarbonate comprises the following steps:
228.29g of bisphenol A,5g of p-tert-butylphenol, 188.34g of sodium hydroxide and 3766.785g of ultrapure water are added to a reactor protected by nitrogen and mixed, and the mixture is mechanically stirred until complete dissolution, and then 3766.785g of dichloromethane is added and mechanically stirred to form a stable water-oil mixed system. Thereafter, 0.046g of triethylamine as a catalyst was added, while 110.88g of phosgene was introduced into the above-mentioned system at a rate of 0.924 g/min. 32wt% sodium hydroxide aqueous solution is added in the whole reaction process to maintain the pH of the system to be 11-12, and the reaction temperature is 30 ℃. After the reaction is finished, the product is obtained through post-treatment (the treatment method is the same as in example 1).
The weight average molecular weight of the product was 24520 as measured by GPC and the polydispersity index was 1.71. Attenuated total reflection infrared spectra were shown at 1611cm -1 、1509cm -1 、1446cm -1 There is a distinct absorption peak, which is characteristic of benzene rings, and no observation is madeTypical absorption peaks to carboxyl and sulfonic groups.
Comparative example 2
The polycarbonate was prepared according to the method of example 1, except that: and (3) adding no sodium acrylate monomer in the step 1), and obtaining the polycarbonate without changing other operations and parameters.
Comparative example 3
The 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 unchanged, so that the polycarbonate is prepared.
Comparative example 4
The polycarbonate was prepared according to the method of example 1, except that: and (3) adding no sodium p-styrenesulfonate monomer in the step 1), and obtaining the polycarbonate without changing other operations and parameters.
Comparative example 5
The polycarbonate was prepared according to the method of example 1, except that: and (3) replacing the sodium p-styrenesulfonate monomer in the step (1) with a phenyl vinyl sulfone monomer, and preparing the polycarbonate without changing other operations and parameters.
Comparative example 6
Polycarbonate was prepared according to the method of example 1, except that: no catalyst is added in step 3).
The results of the performance test of the prepared polycarbonates of the above examples and comparative examples are shown in Table 1 below:
TABLE 1
Compared with the conventional polycarbonate, the polycarbonate copolymer has the advantages that the mechanical property and the flow property are basically maintained, the blood compatibility is improved, particularly the self-anticoagulation property is realized, the ATPP and TT time is obviously prolonged, the hemolysis rate is obviously reduced, the concentration of platelet activating activator is obviously reduced, the activation of platelets can be effectively inhibited, the performance of the polycarbonate is effectively improved, and the application field of materials is widened.
Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.
Claims (26)
1. A method for preparing a functionalized polycarbonate, comprising the steps of:
(1) Mixing sodium acrylate, sodium p-styrenesulfonate, diallyl bisphenol compound, an initiator and water, and carrying out prepolymerization reaction for 2-24h at 60-80 ℃ under the protection of nitrogen to obtain a prepolymer;
(2) In a nitrogen environment, mixing the prepolymer, the bisphenol compound, the alkali metal hydroxide, the end capping agent and the water in the step (1), stirring to obtain a clear solution, adding an inert organic solvent, and stirring to obtain a water-oil mixed system;
(3) Under the protection of nitrogen, introducing phosgene into the water-oil mixed system in the step (2), adding a catalyst at the same time, and carrying out polymerization reaction for 0.5-4h at 25-35 ℃ to obtain functionalized polycarbonate;
in the step (1), the molar ratio of the sodium acrylate to the sodium p-styrenesulfonate is 1 (1-5);
the dosage of the diallyl bisphenol compound is 0.5-1.5% of the total molar weight of the sodium acrylate and the sodium p-styrene sulfonate.
2. The process according to claim 1, wherein the prepolymerization in step (1) is carried out at a temperature of 70-75℃for a period of 6-12 hours.
3. The process according to claim 1, wherein the polymerization reaction in step (3) is carried out at a temperature of 30 to 32℃for a period of 2 to 3 hours.
4. The method according to claim 1, wherein in the step (1), the diallyl bisphenol compound is at least one selected from the group consisting of diallyl biphenol, diallyl bisphenol a, diallyl bisphenol Z, diallyl bisphenol F, and diallyl bisphenol S;
the initiator is at least one selected from ammonium persulfate, potassium persulfate and sodium persulfate.
5. The process according to claim 1, wherein in step (1),
the dosage of the initiator is 0.05-1% of the total molar weight of sodium acrylate and sodium p-styrenesulfonate; and/or
In the step (1), the water is ultrapure water;
the ratio of the water to the total mass of sodium acrylate and sodium p-styrenesulfonate is (12.5-20): 1, a step of; and/or
In step (1), the prepolymer has a weight average molecular weight of 1000 to 10000g/mol.
6. The method according to claim 1, wherein the molar ratio of sodium acrylate to sodium p-styrenesulfonate is 1 (3-3.5).
7. The method according to claim 1, wherein the diallyl bisphenol compound is used in an amount of 1 to 1.2% based on the total molar amount of sodium acrylate and sodium p-styrenesulfonate.
8. The method according to claim 5, wherein the initiator is used in an amount of 0.1 to 0.5% based on the total molar amount of sodium acrylate and sodium p-styrenesulfonate.
9. The method according to claim 5, wherein the ratio of the amount of water to the total mass of sodium acrylate and sodium p-styrenesulfonate is (16-16.5): 1.
10. the process according to claim 5, wherein the prepolymer has a weight average molecular weight of 3000 to 5000g/mol.
11. The method according to claim 1, wherein in the step (2), the bisphenol-type compound is at least one selected from bisphenol a, bisphenol B, bisphenol E, bisphenol F, bisphenol Z, bisphenol TMC;
the alkali metal hydroxide is at least one selected from potassium hydroxide, sodium hydroxide, lithium hydroxide and cesium hydroxide;
the end capping agent is at least one selected from phenol, p-methylphenol, p-isopropylphenol and p-tert-butylphenol;
the inert organic solvent is at least one selected from dichloromethane, chloroform, dichloroethane and trichloroethane.
12. The method according to claim 1, wherein in the step (2), the mass ratio of the prepolymer to the bisphenol-type compound is 1: (1.5-15.5);
the end capping agent accounts for 1-3% of the mass of the bisphenol compound;
the mass ratio of the bisphenol compound to water is 1: (12.5-20);
the mass concentration of the alkali metal hydroxide in the clarified solution is 3-8wt%;
the mass ratio of the water to the inert organic solvent is 1: (0.5-1.2).
13. The method of claim 12, wherein the mass ratio of prepolymer to bisphenol compound is 1: (3-4).
14. The method of claim 12, wherein the capping agent is 1.5-2.5% by mass of the bisphenol compound.
15. The method of claim 12, wherein the bisphenol-type compound to water mass ratio is 1: (16-16.5).
16. The preparation method according to claim 12, wherein the mass concentration of the alkali metal hydroxide in the clarified solution is 5 to 6wt%.
17. The preparation method according to claim 12, wherein the mass ratio of water to inert organic solvent is 1 (1-1.05).
18. The process according to claim 1, wherein in the step (3), the phosgene is introduced into the water-oil mixture system of the step (2) in an amount such that the ratio of the total molar amount of the prepolymer and the bisphenol-type compound to the molar amount of phosgene based on the total amount of the prepolymer and the bisphenol-type compound in the water-oil mixture system of the step (2) is 1: (1-1.15).
19. The method of claim 18, wherein the molar ratio of the total molar amount of prepolymer and bisphenol compound to phosgene is 1: (1-1.12).
20. The method according to claim 1, wherein in the step (3), the catalyst is at least one selected from the group consisting of triethylamine, tetrabutylammonium bromide and tetrabutylammonium chloride;
the dosage of the catalyst is 0.0001-0.005:1 based on the bisphenol compound in the water-oil mixed system in the step (2); and/or
In the step (3), the polymerization reaction is carried out, and the pH of the reaction system is kept at 11-12.
21. The method of claim 20, wherein the mass ratio of the catalyst to bisphenol-type compound is 0.0002 to 0.0003:1.
22. The method of claim 1, wherein the weight average molecular weight is 23000-36000g/mol.
23. The process of claim 22, wherein the weight average molecular weight is 25000 to 28000g/mol.
24. Use of a functionalized polycarbonate prepared by the method of any one of claims 1-23 in the field of blood contact products.
25. Use according to claim 24 as a solid anticoagulant for blood purification materials.
26. The use according to claim 24 for the preparation of hemodialyzers, the housing of a perfusion apparatus, hemodialysis membranes, hemodiafiltration 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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