CN107383414A - 表面改性方法 - Google Patents
表面改性方法 Download PDFInfo
- Publication number
- CN107383414A CN107383414A CN201710276803.3A CN201710276803A CN107383414A CN 107383414 A CN107383414 A CN 107383414A CN 201710276803 A CN201710276803 A CN 201710276803A CN 107383414 A CN107383414 A CN 107383414A
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- CN
- China
- Prior art keywords
- hydrophilic monomer
- wavelength
- polymerization
- radical polymerization
- photoepolymerizationinitiater initiater
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000000178 monomer Substances 0.000 claims abstract description 45
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 25
- 230000000977 initiatory effect Effects 0.000 claims abstract description 18
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 14
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 8
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 21
- 239000012965 benzophenone Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 230000010148 water-pollination Effects 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 229920005672 polyolefin resin Polymers 0.000 claims description 3
- QAVGKCMDOKZSBK-UHFFFAOYSA-N 1-morpholin-4-ylbut-2-en-1-one Chemical compound CC=CC(=O)N1CCOCC1 QAVGKCMDOKZSBK-UHFFFAOYSA-N 0.000 claims description 2
- PQJUJGAVDBINPI-UHFFFAOYSA-N 9H-thioxanthene Chemical compound C1=CC=C2CC3=CC=CC=C3SC2=C1 PQJUJGAVDBINPI-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229920001225 polyester resin Polymers 0.000 claims description 2
- 239000004645 polyester resin Substances 0.000 claims description 2
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 206010028980 Neoplasm Diseases 0.000 abstract description 22
- 201000011510 cancer Diseases 0.000 abstract description 22
- 238000010521 absorption reaction Methods 0.000 abstract description 17
- 102000004169 proteins and genes Human genes 0.000 abstract description 11
- 108090000623 proteins and genes Proteins 0.000 abstract description 11
- 210000004027 cell Anatomy 0.000 description 36
- 239000000243 solution Substances 0.000 description 23
- -1 polycyclic alkene Chemical class 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 229920000139 polyethylene terephthalate Polymers 0.000 description 9
- 239000005020 polyethylene terephthalate Substances 0.000 description 9
- 238000005507 spraying Methods 0.000 description 9
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 8
- 239000002953 phosphate buffered saline Substances 0.000 description 8
- 230000036541 health Effects 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 210000004369 blood Anatomy 0.000 description 6
- 239000008280 blood Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920001477 hydrophilic polymer Polymers 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 210000001772 blood platelet Anatomy 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004425 Makrolon Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000002054 inoculum Substances 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- VLTYTTRXESKBKI-UHFFFAOYSA-N (2,4-dichlorophenyl)-phenylmethanone Chemical class ClC1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 VLTYTTRXESKBKI-UHFFFAOYSA-N 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- NSXOFALHYZPMNH-UHFFFAOYSA-N 1-(3-methylmorpholin-4-yl)prop-2-en-1-one Chemical compound CC1COCCN1C(=O)C=C NSXOFALHYZPMNH-UHFFFAOYSA-N 0.000 description 1
- IQHHBXCEQVIZEF-UHFFFAOYSA-N 2,3-diethylthioxanthen-9-one Chemical class S1C2=CC=CC=C2C(=O)C2=C1C=C(CC)C(CC)=C2 IQHHBXCEQVIZEF-UHFFFAOYSA-N 0.000 description 1
- UGZADCUCQJGKFX-UHFFFAOYSA-N 2,4-bis(ethenyl)thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC(C=C)=CC(C=C)=C3SC2=C1 UGZADCUCQJGKFX-UHFFFAOYSA-N 0.000 description 1
- LOEUTAUAOGBXIL-UHFFFAOYSA-N 2,4-diphenylthioxanthen-9-one Chemical class C1=C2C(=O)C3=CC=CC=C3SC2=C(C=2C=CC=CC=2)C=C1C1=CC=CC=C1 LOEUTAUAOGBXIL-UHFFFAOYSA-N 0.000 description 1
- FIMVHLLUSOFQSR-UHFFFAOYSA-N 2-cyclohexylthioxanthen-9-one Chemical class C1=C2C(=O)C3=CC=CC=C3SC2=CC=C1C1CCCCC1 FIMVHLLUSOFQSR-UHFFFAOYSA-N 0.000 description 1
- KHDGCKOTVWKNMB-UHFFFAOYSA-N 2-ethenylthioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC(C=C)=CC=C3SC2=C1 KHDGCKOTVWKNMB-UHFFFAOYSA-N 0.000 description 1
- NCLVBVXPXLVABY-UHFFFAOYSA-N 4-cyclohexylthioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1C1CCCCC1 NCLVBVXPXLVABY-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 201000008808 Fibrosarcoma Diseases 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- RVWADWOERKNWRY-UHFFFAOYSA-N [2-(dimethylamino)phenyl]-phenylmethanone Chemical compound CN(C)C1=CC=CC=C1C(=O)C1=CC=CC=C1 RVWADWOERKNWRY-UHFFFAOYSA-N 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000001194 anti-hemostatic effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004104 aryloxy group Chemical group 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
- 230000000903 blocking effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000002558 medical inspection Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical class COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical class CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/08—Materials for coatings
- A61L29/085—Macromolecular materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
- B05D3/065—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F120/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
本发明提供了用于表面改性热塑性树脂的方法,所述方法制备的表面不仅具有对蛋白质和细胞的低吸附性,而且还选择性吸附或粘附特定细胞如癌细胞,并且还具有优异的耐久性。一种用于表面改性由热塑性树脂制成的物体的方法,所述方法包括:步骤1,在物体的表面上形成聚合引发点;以及步骤2,通过用波长为300~400nm的紫外光照射,从聚合引发点开始使至少一种亲水性单体发生自由基聚合,从而在物体的表面上形成厚度为2~100nm的接枝层。
Description
技术领域
本发明涉及用于表面改性的方法,该方法制备的表面不仅表现出对来自血液或生物流体的蛋白质和细胞的低吸附性,而且还显示出对特定细胞如癌细胞的选择性吸附或粘附。本发明还涉及用于医疗和保健用途的基质,过滤器,通道,管和其它装置的表面改性体,其表面的至少一部分通过该方法改性。
背景技术
用于医疗和保健用途或其他用途的基质(例如测试用基板,芯片,仪器),过滤器,通道,管和其他装置具有缺陷,因为它们在使用时在身体内部或外部与血液或生物流体接触,血液或生物流体中的蛋白质和细胞可以粘附或吸附到装置的表面,从而损害装置的原始功能。为了捕获用于诊断或治疗的特定细胞如癌细胞,需要这些装置选择性地吸附和收集特定的细胞。然而,不幸的是,这些装置还难以选择性地吸附这些特定细胞。
专利文献1提出用亲水性单体的聚合物涂覆用于医疗和保健用途的基质,过滤器,通道或管的表面,以解决上述问题。然而,该方法具有耐久性问题,因为涂层由于其亲水性而可能剥离或分离。
引用列表
专利文献1:JP 2005-523981 T。
发明内容
技术问题
本发明的目的在于解决上述问题,提供用于表面改性热塑性树脂的方法,该方法制备的表面不仅具有对蛋白质和细胞的低吸附性,还具有对特定细胞如癌细胞的选择性吸附或粘附,并且更进一步具有出色的耐久性。本发明还旨在提供用于医疗和保健用途的基质,过滤器,通道,管和其它装置的表面改性体,其表面的至少一部分通过该方法改性。
解决问题的技术方案
本发明的第一方面涉及用于表面改性由热塑性树脂制成的物体的方法,该方法包括:
步骤1:在物体的表面上形成聚合引发点;和
步骤2:通过用波长为300~400nm的紫外光照射,从聚合引发点使至少一种亲水性单体发生自由基聚合,以在物体表面上形成厚度为2~100nm的接枝层。
本发明的第二方面涉及一种用于表面改性由热塑性树脂制成的物体的方法,所述方法包括:
步骤I:在光聚合引发剂的存在下,通过用波长为300-400nm的紫外光照射,使至少一种亲水性单体发生自由基聚合,以在物体的表面上形成厚度为2至100nm的接枝层。
步骤1优选包括将光聚合引发剂吸附到物体的表面,任选地随后用波长为300-400nm的紫外光照射,以在表面上由光聚合引发剂形成聚合引发点。
光聚合引发剂优选为二苯甲酮化合物或噻吨酮化合物中的至少一种。
优选地,将惰性气体引入装有亲水性单体溶液的反应容器或管中,使得单体在由惰性气体替代的气氛中进行自由基聚合。
亲水性单体优选为选自丙烯酸,丙烯酸酯,甲基丙烯酸,甲基丙烯酸酯,丙烯酰基吗啉和甲基丙烯酰基吗啉中的至少一种。
优选地,使用含有阻聚剂的亲水性单体的溶液,以及在阻聚剂的存在下使单体自由基聚合。
热塑性树脂优选为选自丙烯酸树脂、环烯烃树脂、碳酸酯树脂、苯乙烯树脂和聚酯树脂中的至少一种。
发明的有益效果
根据本发明的第一和第二方面的表面改性方法,亲水性单体被自由基聚合以在待改性的物体的表面上形成具有预定厚度的薄的接枝层(由亲水性聚合物链形成的接枝层)。因此,物体的表面不仅具有对血液或生物流体中的蛋白质和细胞的低吸附性,而且还具有对特定细胞如癌细胞的选择性吸附或粘附性。此外,由于亲水性聚合物被固定在表面上,所以也赋予该表面经反复使用的耐久性,从而能够降低低吸附性或者选择性吸附或粘附性的劣化。因此,通过使用该方法在物体表面上形成具有预定厚度的亲水性聚合物链(接枝层),可以制备上述性能优异的用于医疗和保健用途的基质,过滤器,通道,管和其它装置的表面改性体。
附图说明
图1显示具有腔室区的通道的示例性示意图。
附图标记列表:
1:医疗检测装置
11:通道
12:腔室区
具体实施方式
本发明的第一方面是一种用于表面改性由热塑性树脂制成的物体的方法,其包括:步骤1:在物体的表面上形成聚合引发点;以及步骤2:通过用波长为300~400nm的紫外光照射,从聚合引发点使至少一种亲水性单体发生自由基聚合,以在物体表面上形成厚度为2~100nm的接枝层。
在步骤1中,在形成的热塑性树脂(待改性物体)的表面上形成聚合引发点。例如,步骤1可以通过如下方式进行:将光聚合引发剂吸附到物的表面以形成聚合引发点,或者将光聚合引发剂吸附到物体的表面,然后用波长为300~400nm的紫外光照射该表面,从而在表面上由光聚合引发剂形成聚合引发点。
用作待改性物体的热塑性树脂的实例包括丙烯酸树脂(聚丙烯酸树脂)如聚甲基丙烯酸酯,聚甲基丙烯酸甲酯,聚丙烯酸和聚甲基丙烯酸,环烯烃树脂(聚环烯烃),碳酸酯树脂(聚碳酸酯),苯乙烯树脂(聚苯乙烯),聚酯树脂如聚对苯二甲酸乙二醇酯(PET),和聚二甲基硅氧烷。
光聚合引发剂的实例包括羰基化合物,有机硫化合物如二硫化四乙基秋兰姆,过硫化物,氧化还原化合物,偶氮化合物,重氮化合物,卤素化合物和光还原染料。其中优选羰基化合物。
优选地,用作光聚合引发剂的羰基化合物是二苯甲酮及其衍生物(二苯甲酮化合物)。例如,适合的是由下式表示的二苯甲酮化合物:
其中R1至R5和R1'至R5'彼此相同或不同,各自表示氢原子,烷基,卤素(氟,氯,溴或碘),羟基,伯氨基,仲氨基或叔氨基,巯基或任选含有氧,氮或硫原子的烃基,并且R1至R5和R1'至R5'的任何两个相邻基团可以与它们所连接的碳原子结合在一起以形成环。
二苯甲酮化合物的具体实例包括二苯甲酮,呫吨酮,9-芴酮,2,4-二氯二苯甲酮,邻苯甲酰基苯甲酸甲酯,4,4'-双(二甲基氨基)二苯甲酮和4,4'-双(二乙基氨基)二苯甲酮。其中特别优选的是二苯甲酮,呫吨酮和9-芴酮,因为它们有助于良好地形成聚合物刷。
光聚合引发剂也可以合适地为噻吨酮化合物,因为它具有高的聚合速率并易于被吸附和/或反应。例如,合适的是由下式表示的化合物:
其中R6至R9和R6'至R9'彼此相同或不同,各自表示氢原子,卤素原子或烷基,环烷基,芳基,烯基,烷氧基或芳氧基。
由上式表示的噻吨酮化合物的实例包括噻吨酮,2-异丙基噻吨酮,4-异丙基噻吨酮,2,3-二乙基噻吨酮,2,4-二乙基噻吨酮,2,4-二氯噻吨酮,2-甲氧基噻吨酮,1-氯-4-丙氧基噻吨酮,2-环己基噻吨酮,4-环己基噻吨酮,2-乙烯基噻吨酮,2,4-二乙烯基噻吨酮,2,4-二苯基噻吨酮,2-丁烯基-4-苯基噻吨酮,2-甲氧基噻吨酮和2-对辛氧基苯基-4-乙基噻吨酮。其中,优选R6至R9和R6'至R9'中的一个或两个,特别是两个被烷基取代的那些化合物。更优选2,4-二乙基噻吨酮。
聚合引发剂如二苯甲酮或噻吨酮化合物在物体表面上的吸附可以按如下进行。在二苯甲酮或噻吨酮化合物的情况下,例如将二苯甲酮或噻吨酮化合物溶解在有机溶剂中以制备溶液;用该溶液处理待改性物体的表面部分,使化合物吸附在表面上;以及视需要,将有机溶剂干燥并蒸发,从而形成聚合引发点。表面处理方法可以是使二苯甲酮或噻吨酮化合物的溶液与物体的表面接触的任何方法。合适的方法包括例如涂布或喷涂二苯甲酮或噻吨酮化合物溶液;或者浸入溶液中。此外,如果仅需要改性表面的一部分,则仅将光聚合引发剂吸附到表面的需要部分即是充足的。在这种情况下,例如,溶液的涂布或喷涂是合适的。溶剂的实例包括甲醇,乙醇,丙酮,苯,甲苯,甲基乙基酮,乙酸乙酯和THF。优选为丙酮,因为它不会使待改性物体膨胀,并且它会迅速干燥并蒸发。
如上所述,在光聚合引发剂被吸附到物体的表面之后,可以用波长为300~400nm的紫外光照射该表面,从而在表面上由光聚合引发剂形成聚合引发点。该紫外光照射可以通过已知的方法进行,例如,如下所述的用于步骤2中的紫外光照射的方法。
在步骤2中,通过用波长为300~400nm的紫外光照射,至少一种亲水性单体从步骤1中形成的聚合引发点开始被自由基聚合,以在物体表面上形成厚度为2~100nm的接枝层(或生长聚合物链)。
亲水性单体可以是含有亲水基团的各种单体中的任一种。亲水基团的实例包括已知的亲水基团,例如酰胺基,硫酸基,磺酸基,羧酸基,羟基,氨基和氧乙烯基。
亲水性单体的具体实例包括(甲基)丙烯酸,(甲基)丙烯酸酯((甲基)丙烯酸烷氧基烷基酯如(甲基)丙烯酸甲氧基乙基酯,和(甲基)丙烯酸羟烷基酯如(甲基)丙烯酸羟乙酯),(甲基)丙烯酰胺,和具有环状基团的(甲基)丙烯酰胺衍生物(如(甲基)丙烯酰基吗啉)。其中优选的是(甲基)丙烯酸,(甲基)丙烯酸酯和(甲基)丙烯酰基吗啉。更优选(甲基)丙烯酸烷氧基烷基酯,特别优选丙烯酸2-甲氧基乙酯。
在步骤2中,只要不抑制亲水性单体的效果,可以共聚除亲水性单体以外的第二单体。第二单体的实例包括可赋予温度响应性的芳族单体如苯乙烯,乙酸乙烯酯和N-异丙基丙烯酰胺。
在步骤2中亲水性单体的自由基聚合可以通过例如如下方式进行:(1)将亲水性单体的溶液涂布(喷涂)到其上吸附了二苯甲酮或噻吨酮化合物的物体的表面(外表面和/或内表面)上,然后用紫外光照射;(2)将物体浸渍在亲水性单体的溶液中,然后用紫外光照射;或(3)将亲水性单体的溶液注入到物体(例如管或通道的形状)的内部,然后用紫外光照射,由此允许进行自由基聚合(光自由基聚合)以在物体的表面(外表面和/或内表面)上形成接枝层。在涂布(喷涂),浸渍或注入之后,可以用玻璃,PET,聚碳酸酯或其他材料的透明盖子进一步覆盖表面,然后用紫外光透过透明盖子照射以允许自由基聚合(光自由基聚合)进行,从而使聚合物链在物体的表面上生长。
用于涂布(喷涂)的溶剂,用于涂布(喷涂)的方法,用于浸渍的方法,用于注入的方法,用于照射的条件,以及其他条件可以是传统已知的材料或方法。亲水性单体的溶液可以是例如可自由基聚合的单体的水溶液,或在不溶解所使用的光聚合引发剂(例如二苯甲酮或噻吨酮化合物)的有机溶剂中的可自由基聚合的单体的溶液。此外,亲水性单体的溶液可以含有已知的阻聚剂如4-甲基苯酚。
在本发明中,在涂布或注入或浸渍在亲水性单体溶液中之后,通过光照射进行亲水性单体的自由基聚合。在光照射中,可以适当地使用发射波长主要在紫外线区域中的紫外(UV)光源,例如高压汞灯,金属卤化物灯和LED灯。考虑到聚合时间和反应的均匀进行,可以选择合适的光剂量。此外,为了防止由于反应容器和反应管中的氧等活性气体引起的对聚合的抑制,优选在光照射期间或之前从反应容器,反应管和反应溶液(亲水性单体溶液)中除去氧。为此,可以执行适当的操作;例如,将惰性气体如氮气或氩气引入反应容器或反应管和反应溶液中以从反应体系中排出活性气体如氧气,并用惰性气体代替反应体系中的气氛。此外,为了防止由于氧和其他气体导致的对反应的抑制,例如也可以适当地采取措施,其中将UV光源设置成使得空气层(氧含量为15%以上)不存在于由玻璃,塑料或其他材料制成的反应容器和反应溶液或待改性物体之间。
使用的紫外光的波长为300~400nm。这样的波长使聚合物链(接枝层)能够在待改性物体的表面上良好地形成。可以使用的光源的实例包括高压汞灯,中心波长为365nm的LED和中心波长为375nm的LED。更优选照射波长为355~380nm的LED光。特别地,考虑到效率,例如,优选接近于二苯甲酮的激发波长(366nm)的中心波长为365nm的LED。波长小于300nm的光可以裂解并破坏物体的分子。因此,优选波长为300nm以上的光。更优选的是波长为355nm以上的光,因为它对物体产生很小的破坏。然而,波长大于400nm的光不太可能激活光聚合引发剂,使得聚合反应不易进行。因此,优选波长为400nm以下的光。LED灯是适合的,因为LED光的波长范围窄,使得不发射除中心波长以外的波长,但如果使用滤光器来遮挡波长短于300nm的光线,则汞灯或其他光源也可以实现与LED灯类似的效果。
本发明的第二方面是一种用于对由热塑性树脂制成的物体进行表面改性的方法,该方法包括:步骤I:在光聚合引发剂的存在下,通过波长为300-400nm的紫外光照射,使至少一种亲水性单体进行自由基聚合,以在物体的表面上形成厚度为2至100nm的接枝层。具体地说,亲水性单体在用作引发剂的光聚合引发剂存在下,通过紫外光照射进行自由基聚合以形成聚合物链(接枝层),从而可以制备表面改性体,其中由亲水性聚合物链形成的接枝层被设置在待改性物体的表面上。步骤I中使用的待改性物体,光聚合引发剂和亲水性单体可以如上所述。
例如,步骤I可以通过如下方式进行:使物体的表面与光聚合引发剂和亲水性单体接触,然后用波长为300~400nm的LED光照射表面,从而由光聚合引发剂形成聚合引发点,同时使亲水性单体从聚合引发点开始进行自由基聚合以生长聚合物链(或形成接枝层)。
步骤I中亲水性单体的自由基聚合可以通过例如如下方式进行:(1)将含有光聚合引发剂的亲水性单体(例如二苯甲酮或噻吨酮化合物)的溶液涂布(喷涂)到物体表面上,然后用紫外光照射;(2)将物体浸渍在含有光聚合引发剂的亲水性单体的溶液中,然后用紫外光照射;或(3)将含有光聚合引发剂的亲水性单体的溶液注入到物体(例如管或通道的形状)的内部,然后用紫外光照射,由此允许进行自由基聚合(光自由基聚合)以在物体的表面(外表面和/或内表面)上形成接枝层。此外,例如,可以用玻璃,PET,聚碳酸酯或其它材料的透明盖覆盖表面,然后如上所述用紫外光透过透明盖进行照射。用于涂布(喷涂)的溶剂,用于涂布(喷涂)的方法,用于浸渍的方法,用于注入的方法,用于照射的条件以及其他条件可以是上述材料或方法。
在步骤2或步骤I中形成的接枝层(由亲水性聚合物链形成的接枝层)的厚度为2~100nm,优选为2~50nm,更优选为2~30nm。如果厚度小于2nm,则蛋白质和细胞的低吸附和癌细胞的选择性吸附或粘附趋于不能很好地实现。如果厚度超过100nm,则蛋白质和细胞的低吸附以及癌细胞的选择性吸附或粘附倾向于恶化。
步骤2或步骤I中的紫外照射的持续时间优选为15~250分钟,更优选为30~200分钟,进一步优选为30~150分钟。当持续时间小于15分钟时,蛋白质和细胞的低吸附和癌细胞的选择性吸附或粘附趋于不能很好地实现。当持续时间超过250分钟时,蛋白质和细胞的低吸附和癌细胞的选择性吸附或粘附趋于恶化。
在步骤2或步骤I中,两种或更多种类型的单体可以同时自由基聚合。此外,可以在物体的表面上生长多种类型的聚合物链。在本发明的表面改性方法中,聚合物链可以彼此交联。在这种情况下,聚合物链可以通过离子交联,通过含有氧原子的亲水基团的交联或通过卤素基团如碘的交联而相互交联。
表面改性方法可以应用于热塑性树脂以产生其表面的至少一部分被改性的表面改性体。具体地,可以生产用于医疗和保健用途的基质(例如用于测试的基底,芯片,仪器),过滤器,通道,管和其它装置。该改性可以优选地应用于用于医疗和保健用途的装置中与血液或生物流体接触的至少一部分表面,该装置为例如基质(例如用于收集和吸附来自血液样品或生物流体样品的特定蛋白质或特定细胞例如癌细胞的基质),过滤器,通道或管。整个表面也可以被改性。通过根据所需的性质适当选择亲水性单体的种类,可以防止血液或生物流体中的蛋白质和细胞粘附或吸附到表面,并且表面可以选择性地粘附或吸附特定细胞如癌细胞。此外,也获得了优异的耐久性,这是由于聚合物链被固定在表面上,使得该聚合物链即使在该表面用化学物质洗涤或处理时也不会剥落。
实施例
以下参考实施例更详细地描述本发明,但本发明不限于此。
(实施例1)
将3质量%二苯甲酮的丙酮溶液涂布到待改性的聚对苯二甲酸乙二醇酯(PET)物体的表面上,使得二苯甲酮被吸附在表面上,然后干燥。
随后,在玻璃反应容器中将该表面浸渍在10质量%的丙烯酸2-甲氧基乙酯的水和乙醇(水:乙醇=1:1)混合溶液中。用橡胶塞密封反应容器,引入氩气,使其通入溶液鼓泡120分钟以除去氧气。在旋转的同时,用波长365nm的LED光照射玻璃反应容器60分钟,进行自由基聚合,由此在PET表面上生长接枝层。从而,制备了表面改性体。
(实施例2)
除了将LED光照射的持续时间变更为30分钟以外,与实施例1同样地制作表面改性体。
(实施例3)
除了将LED光照射的持续时间变更为120分钟以外,与实施例1同样地制作表面改性体。
(实施例4)
除了将LED光照射的持续时间变更为180分钟以外,与实施例1同样地制作表面改性体。
(实施例5)
除了使用聚环烯烃代替PET以外,与实施例1同样地制作表面改性体。
(实施例6)
除了使用聚甲基丙烯酸甲酯代替PET以外,与实施例1同样地制作表面改性体。
(实施例7)
将3质量%二苯甲酮的丙酮溶液注入到如图1所示具有腔室区的由聚环烯烃制成的通道中,使得二苯甲酮被吸附,接着将丙酮溶液排出,然后干燥。
随后,将通过氩气鼓泡预先除去氧气的10质量%丙烯酸2-甲氧基乙酯的水和乙醇(水:乙醇=1:1)的混合溶液注入通道,然后用波长365nm的LED光照射60分钟以进行自由基聚合,由此在聚环烯烃表面(腔室内表面)上生长接枝层。从而制备了表面改性体。
(实施例8)
按照实施例7制备表面改性体,不同之处在于,将由聚环烯烃制成的通道用具有腔室区但由聚甲基丙烯酸甲酯制成的相似通道代替。
(对比例1)
使用未处理的PET。
(对比例2)
除了将LED光照射的持续时间变更为300分钟以外,与实施例1同样地制作表面改性体。
对实施例和对比例中制备的表面改性体进行如下评价。
(接枝层的厚度)
表面改性体的表面上的接枝层的厚度在15kV的加速电压和1000的放大倍数下,通过使用TEM测定(拍摄)其上形成有接枝层(亲水性聚合物链)的表面改性体的截面来确定。
(血小板的吸附量)
通过混合血浆和血小板以将血小板浓度(接种密度(plating density))调节至4×107细胞/cm2而制备的液体与样品(表面改性体)的表面接触,然后使样品在37℃下静置1小时。用磷酸盐缓冲盐水洗涤样品表面,然后用1%戊二醛固定(在37℃下静置2小时)。此后,用磷酸盐缓冲盐水和蒸馏水再次洗涤样品的表面。
通过SEM观察该样品,计数吸附的血小板数。血小板的数量表示为相对于对比例1取为1的值。
(癌细胞的吸附量)
使人纤维肉瘤(HT1080:一种癌细胞)(FBS,接种密度:1×104细胞/cm2)的悬浮液与样品(表面改性体)的表面接触,然后使样品在37℃下静置1小时。用磷酸盐缓冲盐水洗涤样品表面,然后用1%戊二醛固定(在37℃下静置2小时)。此后,用磷酸盐缓冲盐水和蒸馏水再次洗涤样品的表面。
通过SEM观察该样品,计数附着的癌细胞的数目。癌细胞的数目表示为相对于对比例1取为1的值。
表1
选择性=癌细胞的吸附量/血小板的吸附量
使用各自具有特定厚度的接枝层的实施例的表面改性体,可吸附少量的血小板,同时附着大量的癌细胞,并且还获得超过10的良好选择性(癌细胞的吸附量/血小板的吸附量))。相反,在使用未处理的PET表面的对比例1中,粘附有大量的癌细胞,但也吸附了大量的血小板,因此选择性低。具有较厚接枝层的对比例2的表面改性体在选择性方面大大差于实施例的,这是由于血小板的吸附量略大,并且癌细胞的吸附量略小。这些结果表明,血小板的低吸附性和癌细胞高粘附性高度依赖于接枝层的厚度(聚合物链的长度),并且太大的厚度导致极大降低的选择性。
因此,通过将接枝层的厚度调整在2~100nm的特定范围内,提高选择性,从而可以预期提供诸如从血液中选择性捕获癌细胞等性质。
Claims (8)
1.一种用于表面改性由热塑性树脂制成的物体的方法,其特征在于,所述方法包括:
步骤1:在所述物体的表面上形成聚合引发点;以及
步骤2:通过用波长为300~400nm的紫外光照射,从所述聚合引发点使至少一种亲水性单体发生自由基聚合,以在所述物体的表面上形成厚度为2~100nm的接枝层。
2.一种用于表面改性由热塑性树脂制成的物体的方法,其特征在于,所述方法包括:
步骤I:在光聚合引发剂的存在下,通过用波长为300-400nm的紫外光照射,使至少一种亲水性单体发生自由基聚合,以在所述物体的表面上形成厚度为2~100nm的接枝层。
3.根据权利要求1所述的方法,其中,所述步骤1包括,将光聚合引发剂吸附到所述物体的表面,任选地随后用波长为300~400nm的紫外光照射,从而在所述表面上由所述光聚合引发剂形成聚合引发点。
4.根据权利要求2或3所述的方法,其中,所述光聚合引发剂是二苯甲酮化合物或噻吨酮化合物中的至少一种。
5.根据权利要求1至4中任一项所述的方法,
其中,将惰性气体引入到含有亲水性单体溶液的反应容器或管中,使得亲水性单体在用惰性气体替代的气氛中自由基聚合。
6.根据权利要求1至5中任一项所述的方法,其中,所述亲水性单体是选自于丙烯酸,丙烯酸酯,甲基丙烯酸,甲基丙烯酸酯,丙烯酰基吗啉和甲基丙烯酰基吗啉中的至少一种。
7.根据权利要求1至6中任一项所述的方法,
其中,使用含有阻聚剂的亲水性单体的溶液,并且在阻聚剂的存在下使亲水性单体进行自由基聚合。
8.根据权利要求1至7中任一项所述的方法,
其中,所述热塑性树脂是选自于丙烯酸树脂、环烯烃树脂、碳酸酯树脂、苯乙烯树脂和聚酯树脂中的至少一种。
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CN110157671A (zh) * | 2018-02-14 | 2019-08-23 | 住友橡胶工业株式会社 | 用于捕获特定细胞的方法 |
CN114702901A (zh) * | 2020-12-17 | 2022-07-05 | 中国石油化工股份有限公司 | 覆膜胶塞用喷涂液组合物与接枝型胶塞喷涂液和覆膜胶塞及其制备方法 |
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WO2019151535A1 (ja) * | 2018-02-05 | 2019-08-08 | 株式会社エースネット | ポリマー成形体への目的分子の選択的な結合方法、およびそれを用いた目的分子結合型ポリマー成形体の製造方法 |
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CN110157671A (zh) * | 2018-02-14 | 2019-08-23 | 住友橡胶工业株式会社 | 用于捕获特定细胞的方法 |
CN114702901A (zh) * | 2020-12-17 | 2022-07-05 | 中国石油化工股份有限公司 | 覆膜胶塞用喷涂液组合物与接枝型胶塞喷涂液和覆膜胶塞及其制备方法 |
CN114702901B (zh) * | 2020-12-17 | 2023-03-14 | 中国石油化工股份有限公司 | 覆膜胶塞用喷涂液组合物与接枝型胶塞喷涂液和覆膜胶塞及其制备方法 |
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US10618996B2 (en) | 2020-04-14 |
JP6362224B2 (ja) | 2018-07-25 |
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JP2017203057A (ja) | 2017-11-16 |
US20170320990A1 (en) | 2017-11-09 |
EP3243862A1 (en) | 2017-11-15 |
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