CN113980228A - Macromolecular surface modifier and synthetic method thereof - Google Patents
Macromolecular surface modifier and synthetic method thereof Download PDFInfo
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- CN113980228A CN113980228A CN202111189160.1A CN202111189160A CN113980228A CN 113980228 A CN113980228 A CN 113980228A CN 202111189160 A CN202111189160 A CN 202111189160A CN 113980228 A CN113980228 A CN 113980228A
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- Prior art keywords
- hydroxyl
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- surface modifier
- macromolecular surface
- segment
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- 239000003607 modifier Substances 0.000 title claims abstract description 51
- 238000010189 synthetic method Methods 0.000 title description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 15
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012948 isocyanate Substances 0.000 claims abstract description 6
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000011159 matrix material Substances 0.000 claims description 12
- -1 polytetramethylene Polymers 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 9
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- FOWDZVNRQHPXDO-UHFFFAOYSA-N propyl hydrogen carbonate Chemical compound CCCOC(O)=O FOWDZVNRQHPXDO-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 150000003973 alkyl amines Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 claims description 2
- ANLVEXKNRYNLDH-UHFFFAOYSA-N 1,3-dioxonan-2-one Chemical compound O=C1OCCCCCCO1 ANLVEXKNRYNLDH-UHFFFAOYSA-N 0.000 claims description 2
- PBKFPDHTSQEJEJ-UHFFFAOYSA-N 2-benzofuran-1,3-dione;hexane-1,6-diol Chemical compound OCCCCCCO.C1=CC=C2C(=O)OC(=O)C2=C1 PBKFPDHTSQEJEJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002524 organometallic group Chemical group 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 2
- 229920005906 polyester polyol Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- FZWBABZIGXEXES-UHFFFAOYSA-N ethane-1,2-diol;hexanedioic acid Chemical compound OCCO.OC(=O)CCCCC(O)=O FZWBABZIGXEXES-UHFFFAOYSA-N 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000011368 organic material Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 8
- 229940113088 dimethylacetamide Drugs 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- 229960001484 edetic acid Drugs 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000012982 microporous membrane Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- IRTFYNWQADJCSC-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,5-undecafluoropentan-1-ol Chemical compound OC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F IRTFYNWQADJCSC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 210000001124 body fluid Anatomy 0.000 description 2
- 239000010839 body fluid Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012567 medical material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- FFLPBDJSZVOFJE-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecan-1-ol Chemical compound OC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F FFLPBDJSZVOFJE-UHFFFAOYSA-N 0.000 description 1
- PJDOLCGOTSNFJM-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctan-1-ol Chemical compound OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F PJDOLCGOTSNFJM-UHFFFAOYSA-N 0.000 description 1
- HAIVWDGLCRYQMC-UHFFFAOYSA-N 4-methylpentane-1,4-diol Chemical compound CC(C)(O)CCCO HAIVWDGLCRYQMC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000010836 blood and blood product Substances 0.000 description 1
- 229940125691 blood product Drugs 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000011100 viral filtration Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6576—Compounds of group C08G18/69
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a macromolecular surface modifier and a synthesis method thereof. The macromolecular surface modifier is composed of (A) a hydroxyl-containing base segment, (B) an isocyanate-containing segment and (G) a surface active group, and n is an integer of from 1 to 10. The macromolecular surface modifier is prepared by reacting a molecule containing isocyanate functional groups with a molecule containing hydroxyl functional groups through the action of an organic metal catalyst. The macromolecular surface modifier synthesized by the method has the molecular weight of 1000-10000, has higher thermal stability and better affinity with other macromolecular organic materials.
Description
Technical Field
The invention relates to the technical field of polymer synthesis, in particular to a macromolecular surface modifier and a synthesis method thereof.
Background
At present, as the requirements on the hydrophobic, oleophobic, hydrophilic and lipophilic properties of the surface of the material are increased, for example, blood product packaging materials or flow guide materials, materials which are in contact with body fluid and have the effects of resisting bacteria and infection, materials which are in contact with the body fluid and need to reduce the surface energy, materials which can block toxic substances such as organic solvents, aldehyde ketones and the like, materials which can increase the liquid permeability, materials which can increase the oil absorption property and the like; these materials are used in particular in medical garments, protective clothing, thermoplastic films, thermoplastic fibers, face masks, laboratory clothing, blood permeable membranes, virus filtration membranes, gas exchange membranes, etc. However, most matrix materials do not have specific surface hydrophobic, oleophobic, hydrophilic and oleophilic properties, and therefore, a macromolecular surface modifier needs to be added for modification.
The macromolecular surface modifier is a polymer with the molecular weight of more than 1000, and compared with the micromolecular modifier, the macromolecular surface modifier has the advantages of multiple structures, controllable molecular weight, various functional groups, functional diversity and the like. In recent years, due to the potential industrial and commercial utility of macromolecular surface modifiers, the development of macromolecular surface modifiers of different types and structures has been pursued and extensively studied by researchers as an industrially important raw material.
Common polymerization modes of the conventional macromolecular surface modifier include ring-opening polymerization, Group Transfer Polymerization (GTP), Atom Transfer Radical Polymerization (ATRP) and reversible addition fragmentation-chain transfer polymerization (RAFT). Wherein, the atom transfer radical polymerization can effectively control the reaction process and design the required molecular structure and molecular weight. The ATRP reaction is suitable for various monomers, has mild reaction conditions, and is convenient to operate and the like. In practical application, the molecules can be designed, and substances with different hydrophilicity/hydrophobicity, polarity/non-polarity and the like can be combined together to adapt to different environments. At the same time, the copolymerization or grafting of macromolecules is carried out to achieve the purpose of molecular design, so that the product has different properties for different substances, namely, the interfacial activity of reactants is changed, and certain substances with poor solubility can be better dissolved with the reactants.
In the known prior art, invention CN103131079B discloses a microporous membrane and a battery separator containing the same. The microporous membrane takes polyolefin as a main raw material, and macromolecular surface modifiers are dispersed in the microporous membrane; one end of the macromolecular surface modifier is provided with a polyolefin chain segment which is hydrophilic to a matrix, and the other end is provided with a polyester or polyether block or graft chain segment which is electrophilic electrolyte. The macromolecular surface modifier is mainly polyolefin-polyester or polyether triblock copolymer, but the structure of the macromolecular surface modifier is different from that of the macromolecular surface modifier containing a hydroxyl chain segment, an isocyanate chain segment and a surface active group, and the application field of the macromolecular surface modifier is different.
The invention CN1970649B discloses a macromolecular surface modifier for modifying ceramic nanometer surfaces, which is an oligomer with the molecular weight of 3000-9000 and is obtained by the free radical initiated copolymerization of monomers such as (methyl) acrylic esters, vinyl siloxane and (methyl) acrylic acid, maleic anhydride, styrene, vinyl acetate, acrylonitrile and the like in an organic solvent. The macromolecular surface modifier is also different from the molecular structure related to the invention, the invention is free radical initiated copolymerization in the synthesis method, and the invention is functional group polymerization in Atom Transfer Radical Polymerization (ATRP) and has different application fields.
Disclosure of Invention
In view of the above, it is necessary to provide a novel macromolecular surface modifier and a synthesis method thereof by applying a functional group polymerization method to polymer materials, especially medical materials, medical instruments, membrane materials and the like. The macromolecular surfactant disclosed by the invention is particularly applied to the fields of medical materials, medical instruments, membrane materials and the like, and has excellent thermal stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
a macromolecular surface modifying agent comprising the following structure (1):
G-[B-A]n-B-G (1)
wherein:
a is a hydroxyl-containing backbone segment;
b is an isocyanate group-containing segment;
g is a surface active group;
n is an integer of 1 to 10.
Further, the hydroxyl-containing matrix segment comprises poly (ethylene glycol hydroxy-terminated adipate); polydiallyl phthalate; hydroxyl-terminated polybutadiene; poly (diethylene glycol) adipic acid; poly (hexamethylene carbonate) diol; poly (ethylene-co-1, 2-butene) glycol; hydroxy-terminated polytetramethylene ether; hydroxyl-terminated hydrogenated polybutadiene; 1, 6-hexanediol phthalic anhydride polyester polyol; one or more of poly (2, 2-dimethyl-1, 3-propyl carbonate).
Further, the isocyanate group-containing segment includes isophorone diisocyanate; tetramethylxylylene diisocyanate; dicyclohexylmethane diisocyanate; hexamethylene diisocyanate; one or more of trimeric isophorone diisocyanate.
Further, the surface active group comprises alkyl monoalcohol of C1-C15; fluorinated alkyl mono-alcohols of C1 to C15; C1-C15 alkyl polyol; fluorinated alkyl polyols of C1-C15; C1-C15 alkylamine; one or more of C1-C15 fluorinated alkyl amines.
Preferably, in the macromolecular surface modifier, n is 1 or 2.
Further, the macromolecular surface modifier has a molecular weight of 1000-10000.
Further, the molecular weight of the hydroxyl-containing matrix segment A is between 1000 and 3500 Dalton.
Further, the molecular weight of the surface active group G is between 100 and 1500 daltons.
A method for synthesizing a macromolecular surface modifier comprises the following steps:
s1, respectively dissolving a hydroxyl-containing matrix chain segment A, an isocyanate-containing chain segment B and a catalyst in a solvent;
s2, mixing and reacting a hydroxyl-containing matrix chain segment A, an isocyanate-containing chain segment B and a catalyst solution under a nitrogen atmosphere and under anhydrous conditions at a certain temperature;
s3, adding the surface active group G into the mixed material in the S2 under the nitrogen atmosphere, mixing and reacting.
Further, the catalyst of S1 is an organometallic catalyst.
Preferably, the metal catalyst comprises one or more of an organic tin catalyst, an organic bismuth catalyst and an organic zinc catalyst.
Further, the solvent described in S1 is an organic high boiling point solvent.
Preferably, the organic high boiling point solvent comprises one or more of dimethylacetamide, dimethylsulfoxide, toluene, dimethylformamide and chlorobenzene.
Further, the temperature of S2 is 50-80 ℃.
When the temperature is too low as in S2, the reaction is not complete, and when the temperature is too high, the reaction by-products and polymers increase.
Further, A, B of S2 and the catalyst were mixed for 0.1 to 1 hour.
Further, the reaction time of S2 is 5 to 15 hours.
Further preferably, the reaction time of S2 is 5 to 8 hours.
Further, the temperature at which S3 is added to the surface active group G is 30 to 60 ℃. When the temperature of S3 added to the surface active group G is too low, the reaction is not complete, and when the temperature is too high, the by-products and polymers are increased.
Further, the mixing time of the mixed material of S3 and G was 0.1 to 1 hour. Too short mixing time causes increased side reactions and polymers, and too long mixing time causes decreased reaction efficiency and prolonged completion time.
Further, the reaction time of S3 is 12 to 20 hours.
Further, the molar ratio of the hydroxyl group-containing base segment a, the isocyanate group-containing segment B, and the surface active group G is 1: 1-3: 1-6.
The content of the catalyst is 1-10 wt% of the hydroxyl matrix chain segment A.
Further, the method comprises the steps of adding a poor solvent into the material obtained after the S3 reaction to precipitate a product, filtering, washing and drying to obtain the product.
Further, the poor solvent comprises one or more of water, methanol, ethanol and acetonitrile.
Further, the cleaning agent used for cleaning comprises one or more of tetrahydrofuran, methanol, water, ethanol, ethylene diamine tetraacetic acid, sodium ethylene diamine tetracetate, acetonitrile and acetone.
The invention has the beneficial effects that:
(1) provides a general skeleton of a macromolecular surface modifier, which can be connected with groups with different surface properties.
(2) Provides a high-efficiency and high-selectivity synthetic method of the target macromolecular surface modifier, so that the synthetic process is controllable and the target product is obtained.
(3) The synthesized macromolecular surface modifier not only obtains better substrate material affinity, but also has good thermal stability. The macromolecular surface modifying agent may have a pyrolysis temperature of at least 200 ℃.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be further clearly and completely described below with reference to the embodiments of the present invention. It should be noted that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
All vessels used for the synthesis of macromolecular surface-modifying agents were thoroughly dried at 110 ℃. A1000 ml glass-dried three-necked flask was charged with 72mmol of hydroxy-terminated poly (2, 2-dimethyl-1, 3-propyl carbonate), and the contents of the vessel were thoroughly purged with ultrapure nitrogen to dry and remove water overnight. 525ml of dimethylacetamide was measured out using a 1000ml measuring cylinder, sealed with a rubber stopper, and the solvent was pushed with ultrapure nitrogen. Dimethylacetamide was pushed into a three-necked flask with a double-ended needle to be miscible with hydroxy-terminated poly (2, 2-dimethyl-1, 3-propyl carbonate) and stirred uniformly. The temperature was maintained at 65-70 ℃ while stirring. To a 250ml glass-dried three-necked flask was added 151mmol of isophorone diisocyanate. 150ml of dimethylacetamide was measured out using a 250ml measuring cylinder, sealed with a rubber stopper and pushed with ultrapure nitrogen into the solvent. Dimethyl acetamide is pushed into a three-neck flask by a double-ended needle to be mixed and dissolved with isophorone diisocyanate and stirred uniformly. To a 50ml glass dried round bottom flask was added 8g (10% w/w weight of the hydroxyl terminated starting material) of organotin reagent, 26ml of dimethylacetamide was measured out using a 50ml graduated cylinder, sealed with a rubber stopper, and the solvent was pushed with ultrapure nitrogen. Dimethylacetamide was pushed into a round bottom flask with a double ended needle to be miscible with the organotin reagent and stirred uniformly. The solution containing isophorone diisocyanate was pushed through a double-ended needle with nitrogen into the solution containing hydroxyl terminated poly (2, 2-dimethyl-1, 3-propyl carbonate), followed immediately by the addition of the solution containing organotin reagent. The mixture system was stirred uniformly and maintained at 70 ℃ for 5 hours.
In another 50ml dry round bottom flask was added 180mmol perfluoropentanol, sealed with a rubber stopper and the reagent was pushed in with ultra pure nitrogen. Perfluoropentanol was added to the mixture system through a double-ended needle, and the mixture system was kept under uniform stirring at 45 ℃ for 18 hours. Finally synthesizing the macromolecular surface modifier A. The system was cooled to room temperature and was a milky white turbid liquid. Distilled water is added to the turbid solution to generate precipitate, and the precipitate is washed with isopropanol/ethylene diamine tetraacetic acid solution to remove unreacted raw materials, catalyst and solvent. Gradually heating and vacuum drying in an oven at 40-120 deg.C. The final product is obtained.
The structural formula of the macromolecular surface modifier A is as follows:
example 2
The procedure was as in example 1 using 74mmol of hydroxyl-terminated polybutadiene, 115mmol of isophorone diisocyanate, 111.18mmol of perfluoropentanediol, 5% w/w of an organozinc catalyst and anhydrous toluene as solvent. Adding methanol into the turbid solution after reaction to generate precipitate, and washing the precipitate with tetrahydrofuran/ethylene diamine tetraacetic acid solution to remove unreacted raw materials, catalyst and solvent. Gradually heating and vacuum drying in an oven at 40-120 deg.C. Obtaining the final product macromolecular surface modifier B.
The structural formula of the macromolecular surface modifier B is as follows:
example 3
The procedure is as in example 1, using 100mmol of hydroxy-terminated poly (2, 2-dimethyl-1, 3-propyl carbonate), 155mmol of dicyclohexylmethane diisocyanate, 125mmol of perfluorooctanol, 8% w/w of an organobismuth catalyst and dimethylacetamide as solvent. Obtaining the macromolecular surface modifier C which is the final product of the solid.
The structural formula of the macromolecular surface modifier C is as follows:
example 4
The procedure was as in example 1 using 84.8mmol of hydroxyl-terminated hydrogenated polybutadiene, 131.42mmol of trimeric isophorone diisocyanate, 254.36mmol of perfluorodecanol, 3% w/w of organotin catalyst and anhydrous toluene as solvent. Adding methanol into the turbid solution after reaction to generate precipitate, and washing the precipitate with tetrahydrofuran/ethylene diamine tetraacetic acid solution to remove unreacted raw materials, catalyst and solvent. Gradually heating and vacuum drying in an oven at 40-120 deg.C. Obtaining the final product macromolecular surface modifier D.
The structural formula of the macromolecular surface modifier D is as follows:
example 5
The procedure was as in example 1, using 4mmol of hydroxy terminated polytetramethylene ether, 8.4mmol of hexamethylene diisocyanate, 10mmol of dimethylbutylene glycol, 6% w/w of organobismuth catalyst and dimethylformamide as the reagent. Obtaining the final product macromolecular surface modifier E.
The structural formula of the macromolecular surface modifier E is as follows:
example 6
And carrying out thermogravimetric analysis on the five synthesized macromolecular surface modifiers. 2-10mg of the sample was loaded into an aluminum pan. The temperature range is from room temperature to 500 ℃, the heating rate is 50 ℃/min, and the temperature is 10 ℃/min when the temperature is close to the decomposition temperature. The test results are shown in the following table:
TABLE 1 thermogravimetric test results of macromolecular surface modifiers
| Name (R) | Td1/℃ | Td2/℃ | Appearance of the product |
| Macromolecular surface modifier A | 284 | 354 | White amorphous solid |
| Macromolecular surface modifier B | 288 | 379 | Colorless transparentMing semi-solid |
| Macromolecular surface modifier C | 326 | 401 | White waxy solid |
| Macromolecular surface modifier D | 283 | 407 | White solid |
| Macromolecular surface modifier E | 229 | 353 | Colorless transparent semisolid |
Claims (10)
1. A macromolecular surface modifying agent characterized by comprising the following structure (1):
G-[B-A]n-B-G (1) wherein:
a is a hydroxyl-containing backbone segment;
b is an isocyanate group-containing segment;
g is a surface active group;
n is an integer of 1 to 10.
2. The macromolecular surface-modifying agent according to claim 1, characterized in that the molecular weight of the hydroxyl-containing matrix segment A is between 1000 and 3500 daltons.
3. The macromolecular surface-modifying agent according to claim 1, characterized in that the molecular weight of the surface-active group G is between 100 and 1500 daltons.
4. The macromolecular surface-modifying agent according to claim 1,
the hydroxyl-containing matrix chain segment comprises poly (ethylene glycol adipate) with hydroxyl end; polydiallyl phthalate; hydroxyl-terminated polybutadiene; poly (diethylene glycol) adipic acid; poly (hexamethylene carbonate) diol; poly (ethylene-co-1, 2-butene) glycol; hydroxy-terminated polytetramethylene ether; hydroxyl-terminated hydrogenated polybutadiene; 1, 6-hexanediol phthalic anhydride polyester polyol; one or more of poly (2, 2-dimethyl-1, 3-propyl carbonate); the chain segment containing the isocyanate group comprises isophorone diisocyanate; tetramethylxylylene diisocyanate; dicyclohexylmethane diisocyanate; hexamethylene diisocyanate; one or more of trimeric isophorone diisocyanate;
the surface active group comprises alkyl monoalcohol of C1-C15; fluorinated alkyl mono-alcohols of C1 to C15;
C1-C15 alkyl polyol; fluorinated alkyl polyols of C1-C15; C1-C15 alkylamine; one or more of C1-C15 fluorinated alkyl amines.
5. A method for synthesizing a macromolecular surface modifier is characterized by comprising the following steps:
s1, respectively dissolving a hydroxyl-containing matrix chain segment A, an isocyanate-containing chain segment B and a catalyst in a solvent;
s2, mixing and reacting a hydroxyl-containing matrix chain segment A, an isocyanate-containing chain segment B and a catalyst solution under a nitrogen atmosphere and under anhydrous conditions at a certain temperature;
s3, adding the surface active group G into the mixed material in the S2 under the nitrogen atmosphere, mixing and reacting.
6. The method for synthesizing macromolecular surface modifier according to claim 5, characterized in that said catalyst S1 is an organometallic catalyst.
7. The method for synthesizing macromolecular surface modifier according to claim 5, characterized in that the solvent of S1 is organic high-boiling solvent.
8. A method for synthesizing a macromolecular surface modifying agent according to claim 5, wherein the molar ratio of the hydroxyl-containing base segment A, the isocyanate-containing segment B, and the surface active group G is 1: 1-3: 1-6.
The content of the catalyst is 1-10 wt% of the hydroxyl matrix chain segment A.
9. The method for synthesizing a macromolecular surface modifier according to claim 5, further comprising adding a poor solvent to the material after the S3 reaction to precipitate the product, filtering, washing, and drying to obtain the product.
10. The method for synthesizing a macromolecular surface modifier according to claim 9, wherein said poor solvent comprises one or more of water, methanol, ethanol, and acetonitrile.
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|---|---|---|---|---|
| US6127507A (en) * | 1995-08-03 | 2000-10-03 | Santerre; Paul J. | Fluoroligomer surface modifiers for polymers and articles made therefrom |
| US20080228253A1 (en) * | 2006-12-14 | 2008-09-18 | Sanjoy Mullick | Surface modifying macromolecules with high degradation temperatures and uses thereof |
| CN102203153A (en) * | 2008-08-28 | 2011-09-28 | 界面生物公司 | Thermally stable biuret and isocyanurate based surface modifying macromolecules and uses thereof |
| CN107709615A (en) * | 2015-06-26 | 2018-02-16 | Dic株式会社 | Surface of steel plate inorganic agent and the steel plate with its film |
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2021
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6127507A (en) * | 1995-08-03 | 2000-10-03 | Santerre; Paul J. | Fluoroligomer surface modifiers for polymers and articles made therefrom |
| US20080228253A1 (en) * | 2006-12-14 | 2008-09-18 | Sanjoy Mullick | Surface modifying macromolecules with high degradation temperatures and uses thereof |
| CN102203153A (en) * | 2008-08-28 | 2011-09-28 | 界面生物公司 | Thermally stable biuret and isocyanurate based surface modifying macromolecules and uses thereof |
| CN107709615A (en) * | 2015-06-26 | 2018-02-16 | Dic株式会社 | Surface of steel plate inorganic agent and the steel plate with its film |
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