CN116672515A - Coating system comprising hydrophilic polymers, bilayer coating system, hydrophilic coating and use - Google Patents
Coating system comprising hydrophilic polymers, bilayer coating system, hydrophilic coating and use Download PDFInfo
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- CN116672515A CN116672515A CN202310833983.6A CN202310833983A CN116672515A CN 116672515 A CN116672515 A CN 116672515A CN 202310833983 A CN202310833983 A CN 202310833983A CN 116672515 A CN116672515 A CN 116672515A
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- coating system
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- hydrophilic polymer
- reactive monomer
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- 238000000576 coating method Methods 0.000 title claims abstract description 331
- 239000011248 coating agent Substances 0.000 title claims abstract description 321
- 229920001477 hydrophilic polymer Polymers 0.000 title claims abstract description 213
- 239000000178 monomer Substances 0.000 claims abstract description 187
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 49
- 230000001050 lubricating effect Effects 0.000 claims abstract description 39
- 238000004132 cross linking Methods 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 239000003999 initiator Substances 0.000 claims description 118
- -1 methylene, 1, 2-ethylene, 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, 1, 6-hexylene, 1, 7-heptylene Chemical group 0.000 claims description 105
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 69
- 239000002904 solvent Substances 0.000 claims description 68
- 125000002947 alkylene group Chemical group 0.000 claims description 66
- 125000000217 alkyl group Chemical group 0.000 claims description 62
- 230000037452 priming Effects 0.000 claims description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- 239000002987 primer (paints) Substances 0.000 claims description 42
- 229920000642 polymer Polymers 0.000 claims description 38
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 36
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 36
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 35
- 229920001223 polyethylene glycol Polymers 0.000 claims description 35
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 34
- 239000002202 Polyethylene glycol Substances 0.000 claims description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 22
- 125000005647 linker group Chemical group 0.000 claims description 21
- 229920000570 polyether Polymers 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 229920003023 plastic Polymers 0.000 claims description 15
- 239000004033 plastic Substances 0.000 claims description 15
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229920000180 alkyd Polymers 0.000 claims description 12
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000012965 benzophenone Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000004814 polyurethane Substances 0.000 claims description 11
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 239000004743 Polypropylene Substances 0.000 claims description 10
- 150000001408 amides Chemical class 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 10
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 10
- 125000004386 diacrylate group Chemical group 0.000 claims description 9
- 150000002170 ethers Chemical class 0.000 claims description 9
- 229920002635 polyurethane Polymers 0.000 claims description 9
- 238000010546 Norrish type I reaction Methods 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 7
- 239000012949 free radical photoinitiator Substances 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 6
- 229920002873 Polyethylenimine Polymers 0.000 claims description 6
- 244000028419 Styrax benzoin Species 0.000 claims description 6
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 6
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 6
- 150000008062 acetophenones Chemical class 0.000 claims description 6
- 229960002130 benzoin Drugs 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 6
- 150000004676 glycans Chemical class 0.000 claims description 6
- 235000019382 gum benzoic Nutrition 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 229920001184 polypeptide Polymers 0.000 claims description 6
- 229920001282 polysaccharide Polymers 0.000 claims description 6
- 239000005017 polysaccharide Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 6
- 102000004196 processed proteins & peptides Human genes 0.000 claims description 6
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 4
- OKQKDCXVLPGWPO-UHFFFAOYSA-N sulfanylidenephosphane Chemical compound S=P OKQKDCXVLPGWPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 claims description 4
- 125000003275 alpha amino acid group Chemical group 0.000 claims description 3
- 239000008199 coating composition Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 39
- 239000010410 layer Substances 0.000 description 68
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 32
- 239000000047 product Substances 0.000 description 31
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 28
- 239000000203 mixture Substances 0.000 description 26
- 238000009472 formulation Methods 0.000 description 23
- 229920001577 copolymer Polymers 0.000 description 22
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 20
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 20
- 238000012360 testing method Methods 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- 235000019441 ethanol Nutrition 0.000 description 18
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 16
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 16
- 238000005859 coupling reaction Methods 0.000 description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 14
- 238000005227 gel permeation chromatography Methods 0.000 description 14
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 14
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 125000000524 functional group Chemical group 0.000 description 11
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 10
- 239000002356 single layer Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 235000019400 benzoyl peroxide Nutrition 0.000 description 9
- 239000011247 coating layer Substances 0.000 description 9
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 229920002614 Polyether block amide Polymers 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 8
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 7
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- 210000001519 tissue Anatomy 0.000 description 7
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
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- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
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- 125000003396 thiol group Chemical class [H]S* 0.000 description 5
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 4
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 description 4
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 4
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- 238000004090 dissolution Methods 0.000 description 4
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- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
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- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 208000037816 tissue injury Diseases 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- ZJIFDEVVTPEXDL-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) hydrogen carbonate Chemical group OC(=O)ON1C(=O)CCC1=O ZJIFDEVVTPEXDL-UHFFFAOYSA-N 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- VIESAWGOYVNHLV-UHFFFAOYSA-N 1,3-dihydropyrrol-2-one Chemical compound O=C1CC=CN1 VIESAWGOYVNHLV-UHFFFAOYSA-N 0.000 description 1
- CQYYGCVORGQMEQ-UHFFFAOYSA-N 2,5-dioxopyrrolidine-1-carboxylic acid Chemical compound OC(=O)N1C(=O)CCC1=O CQYYGCVORGQMEQ-UHFFFAOYSA-N 0.000 description 1
- 125000004398 2-methyl-2-butyl group Chemical group CC(C)(CC)* 0.000 description 1
- 125000004918 2-methyl-2-pentyl group Chemical group CC(C)(CCC)* 0.000 description 1
- 125000004922 2-methyl-3-pentyl group Chemical group CC(C)C(CC)* 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000004917 3-methyl-2-butyl group Chemical group CC(C(C)*)C 0.000 description 1
- 125000004919 3-methyl-2-pentyl group Chemical group CC(C(C)*)CC 0.000 description 1
- 125000004921 3-methyl-3-pentyl group Chemical group CC(CC)(CC)* 0.000 description 1
- 125000004920 4-methyl-2-pentyl group Chemical group CC(CC(C)*)C 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241001631457 Cannula Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 102100035235 Coiled-coil domain-containing protein 141 Human genes 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 101000737219 Homo sapiens Coiled-coil domain-containing protein 141 Proteins 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 125000000777 acyl halide group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000002399 angioplasty Methods 0.000 description 1
- 230000010100 anticoagulation Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000013211 curve analysis Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000010339 dilation Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 210000003709 heart valve Anatomy 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical group CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002324 minimally invasive surgery Methods 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 230000000451 tissue damage Effects 0.000 description 1
- 231100000827 tissue damage Toxicity 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/08—Materials for coatings
- A61L31/10—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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/452—Lubricants
-
- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
- A61L2300/606—Coatings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application relates to a coating system containing hydrophilic polymers, a double-layer coating system, a hydrophilic coating and application. The hydrophilic polymer-containing coating system comprises a reactive hydrophilic polymer Poly1 and a reactive monomer Rm1, can be used as a top coating system of a double-layer coating system or singly, wherein the Poly1 has a plurality of carbon-carbon double bonds, can form a compact crosslinked network, and Rm1 can further provide a more compact crosslinked network of physical interpenetrating or chemical secondary crosslinking, so that the formed coating can form a plurality of chemical bond connection with a base coat layer or a substrate layer; the hydrophilic polymer-containing bilayer coating further comprises a primer system comprising a reactive hydrophilic polymer Poly2 and a reactive monomer Rm2, which further enhances the adhesion robustness of the hydrophilic coating. The hydrophilic coating prepared from the coating system and the double-layer coating system can be used as a hydrophilic lubricating layer of a medical instrument, and has good lubricity, low friction and high firmness.
Description
RELATED APPLICATIONS
The present application is a divisional application of chinese patent application, filed on month 12 of 2022, 26, with application number CN202211676225X, entitled "hydrophilic polymer-containing coating system and bilayer coating system, hydrophilic coating and application", which is incorporated herein by reference in its entirety.
Technical Field
The invention relates to the technical field of medical hydrophilic coatings, in particular to a coating system containing a hydrophilic polymer, a double-layer coating system containing the hydrophilic polymer, a hydrophilic coating and application.
Background
In the field of medical devices, interventional therapy is becoming more and more accepted. For many interventional medical devices, such as catheters, balloon dilation catheters, central venous catheters, intravascular contrast catheters, and the like, due to insufficient surface smoothness, there is a large resistance to insertion or extraction into the body, causing pain and lifting injuries. Wherein, the medical catheter (or guide wire) is mainly guided into the human body through a natural duct of the human body or a micro-wound of puncture, and needs to be contacted with human tissue for a short term or a long term. The catheter (or guide wire) is rubbed with the tissue in direct contact during insertion or extraction, which leads to frequent burning and pain feeling of the patient, and is easy to cause tissue damage and adhesion, which leads to easy occurrence of complications.
Lubricating oil (such as paraffin oil, silicone oil and vaseline) is often used for coating the surface of a catheter or a guide wire clinically so as to reduce the problems; however, in clinical use, silicone oil cannot be stably attached to the surface of a catheter or a guide wire, has poor lubrication effect, is difficult to last, and still causes damage to tissues when inserted into or pulled out of the body. Accordingly, related researchers have been working on developing a method capable of forming a stable hydrophilic lubricating layer on the surface of a medical catheter, a guide wire, and hope to achieve multiple effects as follows: 1. the discomfort of a patient is relieved, and the damage to mucous membranes and tissue cells caused in the inserting process is avoided; 2. reducing biological pollution, such as reducing adsorption accumulation of proteins, cells, bacteria, microorganisms and the like on the surface of the substrate; 3. anticoagulation and reduced effects on the blood flow environment; 4. improving the biocompatibility of the device, such as improving blood compatibility; 5. the medical instrument is endowed with good trafficability, and the operation safety is improved; 6. the hydrophilic coating is suitable for nylon, PEBAX (block polyether amide resin), PU (polyurethane), PET (polyethylene terephthalate), PVC (polyvinyl chloride), PMMA (polymethyl methacrylate), PEEK (polyether ether ketone), PDMS (polydimethylsiloxane), PE (polyethylene), PP (polypropylene), PTFE (polytetrafluoroethylene) and other substrates. In general, hydrophilic coatings are required to have lubricity, resistance to biofouling, good adhesion, biocompatibility, and reliability.
At present, few products capable of meeting the comprehensive performance requirements of a hydrophilic lubricating layer are available on the market, and the formula is complex. Therefore, there is still a need to further develop hydrophilic lubricating layers that have clinical application value.
Disclosure of Invention
Based on the above, the invention aims to provide a coating system containing hydrophilic polymer and a double-layer coating system thereof, wherein the two systems can be applied to the surface of a plastic substrate of a medical device, and the formed hydrophilic coating can be used as a hydrophilic lubricating layer to provide lower friction force, better lubricity and higher adhesion firmness for the medical device, so that important technical support can be provided for developing implantable medical device products.
The above object of the present invention can be achieved by the following means.
In a first aspect of the invention, there is provided a hydrophilic polymer-containing coating system comprising, on a dry weight basis, 100 parts by weight: 45 to 90 weight parts of reactive hydrophilic polymer Poly1, 9.9 to 50 weight parts of reactive monomer Rm1, 0.1 to 5 weight parts of initiator In1 and solvent So1;
the reactive hydrophilic polymer Poly1 has a general structure shown in a formula (1);
the reactive monomer Rm1 is capable of intermolecular crosslinking;
The initiator In1 is Norrish type I initiator or free radical photoinitiator;
the mass percentage of the solvent So1 in the coating system is more than or equal to 50%;
in the formula (1), the components are as follows,
m is an integer selected from 9 to 100;
n is an integer selected from 1 to 40;
each R 1 Independently a hydrophilic group;
each A 1 Independently H or C 1-19 An alkyl group;
each A 2 Independently C 1-18 An alkylene group;
each L 11 independently-O-or-NH-;
l is a divalent linking group, each L is independently a linking group containing a heteroatom selected from one or more of O, S, N and P;
each B is 2 Independently C 1-18 An alkylene group;
each L 13 independently-O-or NH;
each B is 1 Independently H or C 1-19 An alkyl group;
", indicates the site of attachment to the end group.
In a second aspect of the invention, there is provided a bilayer coating system comprising a hydrophilic polymer, comprising a top coating system and a bottom coating system; the top coating system may be selected from the hydrophilic polymer containing coating systems of the first aspect of the invention.
In some embodiments, the priming system comprises the following components, on a dry weight basis of 100 parts by weight: 45 to 90 weight parts of reactive hydrophilic polymer Poly2, 9.9 to 50 weight parts of reactive monomer Rm2, 0.1 to 5 weight parts of initiator In2 and solvent So2;
The reactive hydrophilic polymer Poly2 has a general structure shown in a formula (4)
The reactive monomer Rm2 is capable of intermolecular crosslinking, the reactive monomer Rm2 having a polymer chain and a plurality of reactive groups F covalently linked to the polymer chain 2 ；
The initiator In2 is Norrish type I initiator or free radical photoinitiator;
the mass percentage of the solvent So2 in the bottom coating system is more than or equal to 50%;
in the formula (4), the amino acid sequence of the compound,
each X is independently-O-or-NH-or-N (CH) 3 )-；
Each Z is independently C 1-18 An alkylene group;
L 21 and L 22 Each independently selected from: absence, -C (=o) -and-C (=o) NH-; wherein X is directed to X;
B 21 and B 22 Each independently is C 1-18 An alkylene group;
L 31 and L 32 Each independently is-O-or-NH-;
B 11 and B 12 Each independently is H, methyl, ethyl or C 3-6 An alkyl group;
k is an integer selected from 1 to 220.
In a third aspect of the invention, there is provided a hydrophilic coating which can be prepared according to the hydrophilic polymer-containing coating system of the first aspect of the invention or according to the hydrophilic polymer-containing bilayer coating system of the second aspect of the invention. The hydrophilic coating may act as a hydrophilic lubricating layer.
In a fourth aspect of the invention there is provided the use of a hydrophilic polymer containing coating system according to the first aspect of the invention, or a hydrophilic polymer containing bilayer coating system according to the second aspect of the invention, for the preparation of a hydrophilic lubricating layer for a medical device, or the use of a hydrophilic coating according to the third aspect of the invention as a hydrophilic lubricating layer for a medical device.
In some embodiments, the hydrophilic coating is laminated to the surface of the plastic substrate of the implantable medical device.
The coating system containing the hydrophilic polymer provided by the first aspect of the invention is a coating system which can prepare a hydrophilic coating and has a simple formula, and can be used as a top coating system of a double-layer coating system or can be used independently to prepare the hydrophilic coating. The reactive hydrophilic polymer Poly1 has a large number of carbon-carbon double bonds to form a compact crosslinking network, the reactive monomer Rm1 has polymerization and crosslinking capability, and can further provide a more compact crosslinking network of physical interpenetrating or chemical secondary crosslinking, so that the formed coating can form a large number of chemical bond connection with the base coat or the substrate, and high lubricity and low friction force are provided, and meanwhile, high adhesiveness is also provided. When preparing a bilayer hydrophilic coating, the reactive components of the coating system (including but not limited to Poly 1) can also chemically couple or even crosslink with the reactive groups of the primer layer (including but not limited to carbon-carbon double bonds), thereby imparting excellent adhesion robustness to the bilayer hydrophilic coating.
The bilayer coating system provided by the second aspect of the present invention may comprise the hydrophilic polymer-containing coating system of the first aspect of the present invention and any suitable primer system, thereby producing a bilayer hydrophilic coating having a bilayer structure, which may be used as a bilayer hydrophilic lubricating layer, wherein the coating system of the first aspect may form a top coating layer of the hydrophilic lubricating layer and the primer system may form a primer layer of the hydrophilic lubricating layer, which may achieve high lubricity, low friction and high adhesion strength at the same time. Further, the primer coating system can comprise a reactive hydrophilic polymer Poly2 and a reactive monomer Rm2, and the two components have polymerization and crosslinking capabilities, so that the lubricity of the hydrophilic lubricating layer can be further improved, the friction force can be reduced, and the adhesion firmness of the hydrophilic lubricating layer can be enhanced. The primer coating system containing the reactive hydrophilic polymer Poly2 can form a primer coating with a crosslinked network, and after being further coated with the polymer containing the reactive hydrophilic polymer Poly1, the polymer network can be formed, and meanwhile, chemical bond connection can be formed between the polymer network and the primer coating formed by the primer coating system, so that the adjustable controllability of the bonding firmness of the hydrophilic coating is improved more finely.
The hydrophilic polymer coating system and the hydrophilic coating made of the hydrophilic polymer-containing double-layer coating system can be used as a hydrophilic lubricating layer of medical devices, including but not limited to a hydrophilic lubricating layer on the surface of implantable medical devices, and have good lubricity, low friction and high firmness. When the hydrophilic lubricating layer is used on the surface of the implantable medical device, the problems that the existing implantable medical device is easy to rub with body tissues when being removed, the patient is often accompanied with burning and pain feeling, tissue injury and adhesion are easy to cause, and complications are easy to occur can be solved or remarkably relieved.
The hydrophilic polymer-containing coating system and the double-layer coating system can be applied to different substrates, and further, can provide better adhesion to plastic substrates.
Drawings
In order to more clearly illustrate the technical solution in the embodiments of the present application and to more fully understand the present application and its advantageous effects, the following brief description will be given with reference to the accompanying drawings, which are required to be used in the description of the embodiments. It is evident that the figures in the following description are only some embodiments of the application, from which other figures can be obtained without inventive effort for a person skilled in the art.
FIG. 1 shows a hydrophilic polymer P (VP-HEMA) in one embodiment of the invention 1 H NMR spectrum, axis of abscissa is chemical shift δ (noted as f 1), unit ppm;
FIG. 2 is a reactive hydrophilic polymer P (VP- (HEMA-g-IEM)) in one embodiment of the invention 1 H NMR spectrum, the axis of abscissa is chemical shift delta (noted as f 1),unit ppm;
FIG. 3 shows a hydrophilic polymer P (VP-HEMA) in one embodiment of the invention 1 H NMR spectrum, axis of abscissa is chemical shift δ (noted as f 1), unit ppm;
FIG. 4 shows a reactive hydrophilic polymer P (VP- (HEMA-g-IEM)) in one embodiment of the invention 1 H NMR spectrum, axis of abscissa is chemical shift δ (noted as f 1), unit ppm;
FIG. 5 shows a hydrophilic polymer P (VP-HEMA) in one embodiment of the invention 1 H NMR spectrum, axis of abscissa is chemical shift δ (noted as f 1), unit ppm;
FIG. 6 is a reactive hydrophilic polymer P (VP- (HEMA-g-IEM)) in one embodiment of the invention 1 H NMR spectrum, axis of abscissa is chemical shift δ (noted as f 1), unit ppm;
FIG. 7 is a schematic diagram of a reactive hydrophilic polymer IEM-PTMG-IEM in one embodiment of the invention 1 H NMR spectra, the axis of abscissa is the chemical shift δ (noted as f 1), in ppm.
Detailed Description
The present invention will be described in further detail with reference to the drawings, embodiments and examples. It should be understood that these embodiments and examples are provided solely for the purpose of illustrating the invention and are not intended to limit the scope of the invention in order that the present disclosure may be more thorough and complete. It will also be appreciated that the present invention may be embodied in many different forms and is not limited to the embodiments and examples described herein, but may be modified or altered by persons skilled in the art without departing from the spirit of the invention, and equivalents thereof are also intended to fall within the scope of the invention. For example, features illustrated or described as part of one embodiment can be combined with another embodiment in a suitable manner to yield a new embodiment. Furthermore, in the following description, numerous specific details are set forth in order to provide a more thorough understanding of the invention, it being understood that the invention may be practiced without one or more of these details.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing the embodiments and examples only and is not intended to be limiting of the invention.
Terminology
Unless otherwise indicated or contradicted, terms or phrases used herein have the following meanings:
the term "and/or," "and/or," as used herein, includes any one of two or more of the listed items in relation to each other, as well as any and all combinations of the listed items in relation to each other, including any two of the listed items in relation to each other, any more of the listed items in relation to each other, or all combinations of the listed items in relation to each other. It should be noted that, when at least three items are connected by a combination of at least two conjunctions selected from the group consisting of "and/or", "and/or", it should be understood that, in the present application, the technical solutions include technical solutions that all use "logical and" connection, and also include technical solutions that all use "logical or" connection. For example, "a and/or B" includes A, B and "a and B in combination" three parallel schemes. For another example, the technical schemes of "a, and/or B, and/or C, and/or D" include any one of A, B, C, D (i.e., the technical scheme of "logical or" connection), and also include any and all combinations of A, B, C, D, i.e., any two or three of A, B, C, D, and also include four combinations of A, B, C, D (i.e., the technical scheme of "logical and" connection).
The term "plural", and the like in the present invention refers to, unless otherwise specified, a number of 2 or more. For example, "one or more" means one kind or two or more kinds.
As used herein, "a combination thereof," "any combination thereof," and the like include all suitable combinations of any two or more of the listed items.
The "suitable" in the "suitable combination manner", "suitable manner", "any suitable manner" and the like herein refers to the fact that the technical scheme of the present invention can be implemented, the technical problem of the present invention is solved, and the technical effect expected by the present invention is achieved.
Herein, "preferred", "better", "preferred" are merely to describe better embodiments or examples, and it should be understood that they do not limit the scope of the invention. If there are multiple "preferences" in a solution, if there is no particular description and there is no conflict or constraint, then each "preference" is independent of the others.
In the present invention, "further", "particularly" and the like are used for descriptive purposes to indicate differences in content of different technical solutions, but should not be construed as limiting the scope of the invention.
In the present application, "optional" means optional or not, that is, means any one selected from two parallel schemes of "with" or "without". If multiple "alternatives" occur in a technical solution, if no particular description exists and there is no contradiction or mutual constraint, then each "alternative" is independent. In the present application, "optionally containing", and the like are described, meaning "containing or not containing". "optional component X" means that component X is present or absent.
In the present application, the terms "first", "second", "third", "fourth", etc. are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity, nor as implying an importance or quantity of a technical feature being indicated. Moreover, the terms "first," "second," "third," "fourth," and the like are used for non-exhaustive list description purposes only, and are not to be construed as limiting the number of closed forms.
In the application, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
In the present invention, a numerical range (i.e., a numerical range) is referred to, and, unless otherwise indicated, a distribution of optional values within the numerical range is considered to be continuous and includes two numerical endpoints (i.e., a minimum value and a maximum value) of the numerical range, and each numerical value between the two numerical endpoints. Where a numerical range merely refers to integers within the numerical range, unless otherwise stated, integers from both endpoints of the range, and each integer between the two endpoints, are equivalent to the direct list of each integer, e.g., t is an integer selected from 1 to 10, and t is any integer selected from the group consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. When multiple numerical ranges are provided to describe a feature or characteristic, the numerical ranges may be combined. In other words, unless otherwise indicated, the numerical ranges disclosed herein are to be understood as including any and all subranges subsumed therein. The "numerical value" in the numerical interval may be any quantitative value, such as a number, a percentage, a proportion, or the like. "numerical intervals" allows for the broad inclusion of numerical interval types such as percentage intervals, proportion intervals, ratio intervals, and the like.
The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or may vary within a predetermined temperature range. It should be appreciated that the constant temperature process described allows the temperature to fluctuate within the accuracy of the instrument control. Allows for fluctuations within a range such as + -5 ℃, + -4 ℃, + -3 ℃, + -2 ℃, + -1 ℃.
In the present invention, the term "room temperature" or "normal temperature" generally means 4℃to 35℃such as 20.+ -. 5 ℃. In some embodiments of the invention, "room temperature" or "normal temperature" refers to 10 ℃ to 30 ℃. In some embodiments of the invention, "room temperature" or "normal temperature" refers to 20 ℃ to 30 ℃.
In the present invention, referring to a unit of a data range, if a unit is only carried behind a right end point, the units indicating the left and right end points are the same. For example, 3 to 5h means that the units of the left end point "3" and the right end point "5" are both h (hours).
The mass or weight of the related components mentioned in the description of the embodiments of the present invention may refer not only to the specific content of each component, but also to the proportional relationship of the mass or weight of each component, so long as the content of the related component in the description of the embodiments of the present invention is scaled up or down within the scope of the disclosure of the embodiments of the present invention. Specifically, the mass or weight described in the specification of the embodiment of the present invention may be a unit well known in the chemical industry such as μ g, mg, g, kg.
In the present invention, the method flow involves a plurality of steps, and the steps are not strictly limited in order to be performed in other orders than that shown unless explicitly stated otherwise herein. Moreover, any step may include a plurality of sub-steps or a plurality of stages, which are not necessarily performed at the same time, but may be performed at different times, the order of which is not necessarily sequential, and may be performed in rotation or alternately or simultaneously with other steps or a part of the sub-steps or stages of other steps.
Herein, the term "alkyl" refers to a monovalent residue of a saturated hydrocarbon containing a primary (positive) carbon atom, or a secondary carbon atom, or a tertiary carbon atom, or a quaternary carbon atom, or a combination thereof, losing one hydrogen atom. Phrases containing this term, e.g., "C 1 ～ 9 Alkyl "means an alkyl group containing from 1 to 9 carbon atoms, which at each occurrence may be, independently of one another, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 Alkyl, C 7 Alkyl, C 8 Alkyl or C 9 An alkyl group. Suitable examples include, but are not limited to: methyl (Me, -CH) 3 ) Ethyl (Et, -CH) 2 CH 3 ) 1-propyl (n-Pr, n-propyl, -CH 2 CH 2 CH 3 ) 2-propyl (i-Pr, i-propyl, -CH (CH) 3 ) 2 ) 1-butyl (n-Bu, n-butyl, -CH) 2 CH 2 CH 2 CH 3 ) 2-methyl-1-propyl (i-Bu, i-butyl)CH 2 CH(CH 3 ) 2 ) 2-butyl (s-Bu, s-butyl, -CH (CH) 3 )CH 2 CH 3 ) 2-methyl-2-propyl (t-Bu, t-butyl, -C (CH) 3 ) 3 ) 1-pentyl (n-pentyl, -CH) 2 CH 2 CH 2 CH 2 CH 3 ) 2-pentyl (-CH (CH 3) CH2CH2CH 3), 3-pentyl (-CH (CH) 2 CH 3 ) 2 ) 2-methyl-2-butyl (-C (CH) 3 ) 2 CH 2 CH 3 ) 3-methyl-2-butyl (-CH (CH) 3 )CH(CH 3 ) 2 ) 3-methyl-1-butyl (-CH) 2 CH 2 CH(CH 3 ) 2 ) 2-methyl-1-butyl (-CH) 2 CH(CH 3 )CH 2 CH 3 ) 1-hexyl (-CH) 2 CH 2 CH 2 CH 2 CH 2 CH 3 ) 2-hexyl (-CH (CH) 3 )CH 2 CH 2 CH 2 CH 3 ) 3-hexyl (-CH (CH) 2 CH 3 )(CH 2 CH 2 CH 3 ) 2-methyl-2-pentyl (-C (CH) 3 ) 2 CH 2 CH 2 CH 3 ) 3-methyl-2-pentyl (-CH (CH) 3 )CH(CH 3 )CH 2 CH 3 ) 4-methyl-2-pentyl (-CH (CH) 3 )CH 2 CH(CH 3 ) 2 ) 3-methyl-3-pentyl (-C (CH) 3 )(CH 2 CH 3 ) 2 ) 2-methyl-3-pentyl (-CH (CH) 2 CH 3 )CH(CH 3 ) 2 ) 2, 3-dimethyl-2-butyl (-C (CH) 3 ) 2 CH(CH 3 ) 2 ) 3, 3-dimethyl-2-butyl (-CH (CH) 3 )C(CH 3 ) 3 And octyl (- (CH) 2 ) 7 CH 3 )。
As used herein, the term "alkylene" refers to a hydrocarbon group derived from the removal of one more hydrogen atom on an alkyl basis having two monovalent radical centers, which may be a saturated branched alkyl group or a saturated straight chain alkyl group. For example, "C 1 ～C 9 Alkylene "means that the alkyl moiety contains from 1 to 9 carbon atoms and, at each occurrence, can be independently of each other C 1 Alkylene, C 2 Alkylene, C 3 Alkylene, C 4 Alkylene, C 5 Alkylene, C 6 Alkylene, C 7 Alkylene, C 8 Alkylene or C 9 An alkylene group. Suitable examples include, but are not limited to: methylene (-CH) 2 (-), 1-ethyl (-CH (CH) 3 ) (-), 1, 2-ethyl (-CH) 2 CH 2 (-), 1-propyl (-CH (CH) 2 CH 3 ) (-), 1, 2-propyl (-CH) 2 CH(CH 3 ) (-), 1, 3-propyl (-CH) 2 CH 2 CH 2 (-) and 1, 4-butyl (-CH) 2 CH 2 CH 2 CH 2 -)。
As used herein, "polymer" refers to a polymer having multiple (. Gtoreq.2) repeating units. The molecular weight of the polymer herein means the average molecular weight, as not particularly limited.
As used herein, "small molecule" refers to a molecular weight of less than 1000Da.
As used herein, "hydrophilic group" refers to the group having an atom group that is soluble in or readily compatible with water, which may attract water molecules or dissolve in water, and the solid surface having such functional groups is readily wettable by water.
As used herein, "reactive group" and "functional group" all refer to groups capable of undergoing a coupling reaction to form a covalent bond.
As used herein, a "pair of functional groups" is a pair of functional groups consisting of two identical or different functional groups, the two functional groups that make up the "pair of functional groups" being capable of undergoing a coupling reaction to form a covalent bond.
Herein, unless otherwise specified, "about" means that the fluctuation range is within a range of a certain amplitude above and below the present number, and the fluctuation range may be different depending on the type and the numerical value of the present number. For example, it is allowed to be within a range of + -10%, + -5%, + -2%, + -1%, etc. Such as about 600Da, may represent a member selected from 600.+ -. 60Da.
In a first aspect of the present invention, a hydrophilic polymer containing coating system is provided comprising a reactive hydrophilic polymer Poly1 and a reactive monomer Rm1, which can be used to form a hydrophilic coating, providing lower friction, better hydrophilic lubricity and higher coating firmness. The coating system containing the hydrophilic polymer can be used as a top coating system of a double-layer coating system, can also be used independently to provide a hydrophilic coating with a single-layer structure, and correspondingly, the formed hydrophilic coating can be used as a top coating of a double-layer hydrophilic lubricating layer, and can also be used as a hydrophilic lubricating layer with a single-layer structure.
In the present invention, a "coating system" refers to a combined system of related components, which may be packaged in one piece, and the components may be packaged separately in multiple containers. The components of the "coating system" can be mixed in a suitable manner to form a coating composition, which is coated to form the corresponding coating structure.
In the present invention, the term "coating" refers to a structural layer made of the relevant components after coating, and the coating may be dried after coating, and may be in an undried or partially dried state, or may be a structural layer in the final product.
In the present invention, "coating layer" refers to a liquid layer of a coating composition that is applied to a structured surface.
In some embodiments, a hydrophilic polymer-containing coating system is provided that includes a reactive hydrophilic polymer Poly1 and a reactive monomer Rm1, further including an initiator In1 and a solvent (denoted as solvent So 1); the coating system can be used alone to form a hydrophilic coating with a single-layer structure, or can be used as a top coating system of a double-layer hydrophilic coating to form a hydrophilic coating with a double-layer structure. In the coating system, poly1 has a large number of carbon-carbon double bonds, a compact crosslinking network can be formed, rm1 can further provide a more compact crosslinking network of physical interpenetrating or chemical secondary crosslinking, so that the formed coating can form a large number of chemical bond connection with an undercoat or a substrate, and high lubricity and low friction force are provided, and meanwhile, high adhesiveness is also provided. When preparing a bilayer hydrophilic coating, a bilayer hydrophilic lubricating layer can be prepared by using the bilayer hydrophilic lubricating layer together with a primer coating system, at the moment, reactive components (including but not limited to Poly 1) in the coating system can also be chemically coupled or even crosslinked with reactive groups (including but not limited to carbon-carbon double bonds) in the primer coating, a large number of chemical bond connections can be formed between the top coating and the primer coating, and the bilayer hydrophilic lubricating layer has excellent adhesion firmness and is good in lubricity, low in friction and high in adhesion firmness. Based on this, it is applicable to surface hydrophilic coating modifications, including but not limited to hydrophilic lubricious layers on the surface of implantable medical devices. In addition, the hydrophilic polymer-containing coating system can realize excellent combination of high lubricity, low friction and high adhesion firmness without adding a benzophenone initiator and an adhesion promoter (such as PAcA, poly (acrylic-co-acrylic acid) copolymer).
In some embodiments, the hydrophilic polymer-containing coating system provided in the first aspect of the present application comprises the following components: 45 to 90 weight parts of reactive hydrophilic polymer Poly1, 9.9 to 50 weight parts of reactive monomer Rm1, 0.1 to 5 weight parts of initiator In1 and solvent So1; further, based on 100 parts by weight of dry weight; furthermore, the mass percent of the solvent So1 in the coating system is more than or equal to 50 percent.
In the present application, reference to "dry weight of the coating system", unless otherwise indicated, refers to the sum of the weights of the other components than the solvent. The dry weight components of the coating system of the first aspect may comprise the reactive hydrophilic polymer Poly1, the reactive monomer Rm1 and the initiator In1. The dry weight components of the coating system can be formulated as a mixture using a solvent at the concentrations described for coating, or the dry weight components of the coating system can be formulated as a concentrate using less solvent for storage and transportation, and the solvent can be added to dilute to the desired concentration prior to use.
In some embodiments, the application provides a reactive hydrophilic polymer Poly1 with high crosslinking capability, and the hydrophilicity, polarity and reactivity of the reactive hydrophilic polymer can be regulated and controlled by regulating the equivalent ratio of monomers.
In some embodiments, the reactive hydrophilic polymer Poly1 has m repeat units U1 and n repeat units U2 therein; wherein m may be an integer selected from 9 to 100; n may be an integer selected from 2 to 40; r is R 1 Is a hydrophilic group; a is that 1 May be H or alkyl; l (L) 11 Can be-O-or-NH-; a is that 2 May be an alkylene group; l may be a divalent linking group; b (B) 2 May be an alkylene group; l (L) 13 Can be-O-or-NH-; b (B) 1 May be H or alkyl; "[]"brackets indicate the minimum unit structure of the repeating unit. At this time, the reactive hydrophilic polymer Poly1 may be represented by the structure shown in formula (1). It is understood that the expression of formula (1) is merely to clearly show the repeating units of the copolymer and does not limit the arrangement of the repeating units, for example, the copolymer of formula (1) may be a random copolymer, that is, the repeating units U1 and U2 may be randomly distributed in formula (1).
When L 11 And L 13 When both are O, the repeating unit U2 may be represented by the structure shown as U2 a.
The following groups are present in the formula (1) in an amount greater than 1: r is R 1 、A 1 、L 11 、A 2 、L、B 2 、L 13 And B 1 Groups of the same sign may be the same or different from each other in the same molecule. When the number of any one of the groups is larger than 1, the plurality of groups may be the same or different from each other. In some preferred embodiments, R 1 、A 1 、L 11 、A 2 、L、B 2 、L 13 And B 1 Each of which, independently, may have the same structure. In the same molecule, R 1 May be independently the same; a is that 1 May be independently the same; l (L) 11 May be independently the same; a is that 2 May be independently the same; l may independently be the same; b (B) 2 May be independently the same; l (L) 13 May be independently the same; b (B) 1 May be independently identical.
In some preferred embodiments, R in the same molecule 1 Are all the same; a is that 2 Are all the same; b (B) 2 Are all the same; b (B) 1 All the same.
In some preferred embodiments, L is the same in the same molecule.
In some preferred embodiments, L in the same molecule 11 All the same.
In some preferred embodiments, L in the same molecule 13 All the same.
In some embodiments, the reactive hydrophilic polymer Poly1 has a general structure represented by formula (1); in the formula (1), the components are as follows,
m is an integer selected from 9 to 100;
n is an integer selected from 1 to 40;
each R 1 Independently a hydrophilic group;
each A 1 Independently H or C 1-19 An alkyl group;
each A 2 Independently C 1-18 An alkylene group;
each L 11 independently-O-or-NH-;
l is a divalent linking group, each L is independently a linking group containing a heteroatom selected from one or more of O, S, N and P;
Each B is 2 Independently C 1-18 An alkylene group;
each L 13 independently-O-or NH;
each B is 1 Independently H or C 1-19 An alkyl group;
", indicates the site of attachment to the end group.
In the present invention, the polymer end groups attached in a "", unless otherwise indicated, refer to end groups formed by the carbon-carbon double bond radical polymerization reaction system, and may be formed in either the initiation stage or the termination stage. The structure of the corresponding end groups can be known to the person skilled in the art. In the present invention, the structural formula such as formula (1) and its end groups formed by polymerization of monomers containing carbon-carbon double bonds will be apparent to those skilled in the art.
When L in formula (1) 11 And L 13 When both are O, the structure represented by formula (1) can be represented by formula (1 a).
When R in formula (1) 1 Is N-pyrroleAlkanonyl groupIn this case, the structure of formula (1) can be represented by formula (1 b). Further, L 11 And L 13 When both are O, the structures of the formula (1) and the formula (1 b) can be represented by the formula (1 c).
In some embodiments, L is-O-, -O-C (=o) -or-O-C (=o) -NH-, L is preferably-O-C (=O) -NH-, and the-O-terminus is with A 2 And (5) connection.
When L in formula (1) is-R 3 -C (O) -NH and R 3 And A is a 2 When connected, the structure of formula (1) can be represented by formula (2). The reactive hydrophilic polymer Poly1 has a general structure shown in formula (2), and further, each R 3 independently-O-or-NH-. In some embodiments, R 3 Can be either-O-or-NH-. In some embodiments, R 3 is-O-. In some embodiments, R 3 is-NH-.
R in formula (2) 1 Is N-pyrrolidone groupIn this case, the structure of formula (2) can be represented by formula (2 a). Further, when L in formula (2 a) 11 And L 13 When both are O, the structures of the formula (2) and the formula (2 a) can be represented by the formula (2 b). In some embodiments, the reactive hydrophilic polymer Poly1 has a general structure represented by formula (2 b), further, A 1 Can be methyl, A 2 Can be 1, 2-ethylene, R 3 Can be-O-, B 2 Can be 1, 2-ethylene, B 1 May be methyl. In some embodiments, in formula (2 b), A 1 Is methyl, A 2 Is 1, 2-ethylene，R 3 is-O-, B 2 Is 1, 2-ethylene, B 1 Is methyl.
In some embodiments, the initiator In1 is a Norrish type I initiator or a free radical photoinitiator.
In some embodiments, reactive monomer Rm1 is capable of intermolecular crosslinking. In some preferred examples, the reactive monomer Rm1 has a polymer chain and a plurality of reactive groups F covalently attached to the polymer chain 1 。
In some embodiments, the reactive hydrophilic polymer Poly1 has a general structure represented by formula (1), and the repeating units U1 and U2 are randomly distributed in formula (1).
In some embodiments, the number average molecular weight of the reactive hydrophilic polymer Poly1 is selected from 1.5kDa to 22kDa, further may be selected from 2kDa to 20kDa, further may be 3kDa to 6kDa. The number average molecular weight of the reactive hydrophilic polymer Poly1 is not limited to 2kDa, 3kDa, 4kDa, 5kDa, 6kDa, 7kDa, 8kDa, 9kDa, 10kDa, 11kDa, 12kDa, 13kDa, 14kDa, 15kDa, 16kDa, 17kDa, 18kDa, 19kDa, 20kDa, etc., and may be selected from the interval consisting of any two of the foregoing molecular weights.
In some embodiments, the weight average molecular weight of the reactive hydrophilic polymer Poly1 is selected from 1.5kDa to 25kDa, further may be selected from 2kDa to 20kDa, further may be 3kDa to 6kDa. The weight average molecular weight of the reactive hydrophilic polymer Poly1 is not limited to 2kDa, 3kDa, 4kDa, 5kDa, 6kDa, 7kDa, 8kDa, 9kDa, 10kDa, 11kDa, 12kDa, 13kDa, 14kDa, 15kDa, 16kDa, 17kDa, 18kDa, 19kDa, 20kDa, 21kDa, 22kDa, 23kDa, 24kDa, 25kDa, etc., and may be selected from the interval consisting of any two of the foregoing molecular weights.
In some embodiments, m is an integer selected from 9 to 100, m may be any one of the following integers: 9. 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, etc., may also be selected from integer intervals of any two suitable integers as described above, some non-limiting examples being 10-50, 15-40, etc.
In some embodiments, n is an integer selected from 1 to 40, n may be any one of the following integers: 1. 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39 and 40, may also be selected from integer intervals of any two suitable integers as described above, some non-limiting examples being 4-30, 4-20, etc.
Herein, m and n may be combined in any suitable manner. In some embodiments, m is an integer selected from 10 to 50; n is an integer selected from 4 to 30. In some embodiments, m is an integer selected from 15 to 40; n is an integer selected from 4 to 20.
In some embodiments, the ratio of m to n is selected from (1-99): 1 (i.e., 1:1 to 99:1), and may be selected from any of the following ratios: 1:1, 1.5:1, 2:1, 7:3, 2.5:1, 3:1, 3.5:1, 4:1, 5:1, 6:1, 8:1, 10:1, 12:1, 15:1, 16:1, 18:1, 19:1, 20:1, 25:1, 30:1, 40:1, 50:1, etc., may also be selected from intervals consisting of any two suitable ratios of the foregoing, some non-limiting examples being (1-19): 1 (i.e., 1:1 to 19:1), (1-12): 1, (1-2): 1, (2-2.5): 1, etc.).
Herein, m, n and their ratio m: n may be combined in any suitable manner. In some embodiments, m is an integer selected from 10 to 50; n is an integer selected from 4 to 30; the ratio of m to n is selected from 1:1 to 99:1. In some embodiments, m is an integer selected from 15 to 40; n is an integer selected from 4 to 20; the ratio of m to n is selected from (1-19): 1.
In some embodiments, the reactive hydrophilic polymer Poly1 has a number average molecular weight with m: the n-ratio may be combined in any suitable manner. In some embodiments, the reactive hydrophilic polymer Poly1 has a number average molecular weight selected from the range of 1.5kDa to 25kDa (further may be any suitable range herein, e.g., 3kDa to 6 kDa), and a ratio of m to n of 1:1 to 99:1 (further may be any suitable ratio herein, e.g., the ratio of m to n may be 19:1).
In some embodiments, R in the same molecule 1 independently-CHO, -COOH, -OH, -NH 2 、And an equivalent hydrophilic group. In some embodiments, R in the same molecule 1 All the same. In some embodiments, R 1 is-CHO, -COOHH, -OH, -NH 2 、/>And any of the hydrophilic groups. In some preferred embodiments, R 1 Is->
In some embodiments, each A in the same molecule 1 Independently H or alkyl, further independently H or C 1-19 An alkyl group; further can be independently H, methyl, ethyl or- (CH) 2 ) j1 -CH 3 J1 is an integer selected from 2 to 18; still further may be independently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, or nonadecyl; further, it may be independently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl, further, it may be independently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, further, it may be independently H, methyl, ethyl, propyl, butyl, pentyl or hexyl. In some embodiments, each A 1 Independently H, methyl, ethyl or C 3-6 An alkyl group. In some preferred embodiments, A 1 Is alkyl, further can be C 1-19 An alkyl group; further can be methyl, ethyl or- (CH) 2 ) j1 -CH 3 J1 is an integer selected from 2 to 18. In some preferred embodiments, A 1 Is C 1-18 An alkyl group. In some preferred embodiments, A 1 Is C 1-16 An alkyl group. In some preferred embodiments, A 1 Is C 1-12 An alkyl group. In some preferred embodiments, A 1 Is C 1-10 An alkyl group. In some preferred embodiments, A 1 Is C 1-8 An alkyl group. In some preferred embodiments, A 1 Is C 1-6 Alkyl (which may be selected from methyl, ethyl, propyl, butyl, pentyl and hexyl). In some preferred embodiments, A 1 Is C 1-3 Alkyl (in particular methyl, ethyl or propyl). In some embodiments, each A 1 Independently H or methyl. In some embodiments, a 1 Is either H or methyl. In some preferred embodiments, A 1 H. In some preferred embodiments, A 1 Is methyl. In embodiments herein, A in the same molecule 1 May be identical.
In some embodiments, each A in the same molecule 2 Independently alkylene, further independently C 1-18 Alkylene groups, further independently C 1-16 Alkylene groups, further independently C 1-12 Alkylene groups, further independently C 1-10 Alkylene groups, further independently C 1-8 Alkylene (which may be in particular methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene or octylene), further may be independently C 1-6 Alkylene (which may be in particular methylene, ethylene, propylene, butylene, pentylene or hexylene) and further may independently be C 1-3 Alkylene (which may be in particular methylene, ethylene or propylene). In some embodiments, each A 2 Independently C 2-8 An alkylene group. In some preferred embodiments, each A 2 Can be independently- (CH) 2 ) q1 -; wherein q1 is an integer selected from 2 to 18 (specifically, may be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18), further may be selected from 2 to 16, further may be selected from 2 to 12, further may be selected from 2 to 10, and further may be 2, 3, 4, 5 or 6; in some embodimentsWherein q1 is 4. In some embodiments, each A 2 Independently is methylene, 1, 2-ethylene, 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, 1, 6-hexylene, 1, 7-heptylene or 1, 8-octylene. In some preferred embodiments, A 2 is-CH 2 CH 2 -. In embodiments herein, A in the same molecule 2 May be identical.
In some embodiments, each L in the same molecule 11 independently-O-or-NH-. In some embodiments, L 11 Is either-O-or-NH-. In some embodiments, L 11 is-O-. In some embodiments, L 11 is-NH-.
In the present invention, L is a divalent linking group. Further, L is preferably a divalent linking group resulting from a coupling reaction of the reactive groups. In some embodiments, each L is independently a heteroatom-containing linker in the same molecule, further the heteroatoms may be selected from one or more of O, S, N and P. In some embodiments, each L is independently-NH containing 2 Or a divalent linking group of the coupling reaction residue of-OH. In some embodiments, each L is independently NH 2 Or coupling reaction residues of-OH. For example, -NH 2 Can be combined with-COOH and succinimidocarbonyl (-CO-NHS), wherein NHS is) Succinimidyl carbonate group (-OC (=O) -NHS, < >>) Coupling of acid halides (e.g. acid chlorides), -NCO, etc. to form divalent linking groups such as-NH-C (=o) -, -NH-C (=o) -O, -NH-C (=o) -NH-, etc. -NH 2 The coupling reaction residue of (C) is-NH-. For example, -OH may be coupled with-COOH, succinimidocarbonyl (-CO-NHS), succinimidocarbonyl (-OC (=O) -NHS), acyl halide (such as acyl chloride), -NCO, etc. to form-O-C (=O) -, -O-C (=O) -NH-, etcDivalent linking groups, in which case the coupling reaction residue of-OH is-O-. In some embodiments, each L is independently a group comprising R 0 Divalent linking group of R 0 is-O-or-NH-, and R 0 And A is a 2 Is connected with each other. In some embodiments, L is a divalent linking group comprising-O-and-O-is with A 2 Is connected with each other. In some embodiments, L is a divalent linking group containing-NH-and-NH-is with A 2 Is connected with each other. In some embodiments, each L may be independently selected from any one of-NH-, -NH-C (=o) -NH-, -O-C (=o) -and-O-C (=o) -NH-, wherein x represents the direction a 2 Is a ligation site of (2). In some embodiments, each L may be independently-R 3 -C (=o) -NH, wherein R 3 And A is a 2 Is connected with each other; further, each R 3 And may independently be-O-or-NH-. In some embodiments, R 3 is-O-, where L is-O-C (=O) -NH, wherein-O-segment is identical to A 2 Is connected with each other. In embodiments herein, L in the same molecule may be identical. In some embodiments, L is selected from any of-NH-, -NH-C (=o) -NH-, -O-C (=o) -and-O-C (=o) -NH-, wherein x represents the direction a 2 Is a ligation site of (2).
In some embodiments, each B in the same molecule 2 Independently alkylene, further independently C 1-18 Alkylene groups, further independently C 1-16 Alkylene groups, further independently C 1-12 Alkylene groups, further independently C 1-10 Alkylene groups, further independently C 1-8 Alkylene (which may be in particular methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene or octylene), further may be independently C 1-6 Alkylene (which may be in particular methylene, ethylene, propylene, butylene, pentylene or hexylene) and further may independently be C 1-3 Alkylene (which may be in particular methylene, ethylene or propylene). In some embodiments, each B 2 Independently C 2-8 An alkylene group. In some preferred embodimentsEach B is 2 Can be independently- (CH) 2 ) q2 -; wherein q2 is an integer selected from 2 to 18 (specifically, may be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18), further may be selected from 2 to 16, further may be selected from 2 to 12, further may be selected from 2 to 10, and further may be 2, 3, 4, 5 or 6; in some embodiments, q2 is 4. In some embodiments, each B 2 Independently is methylene, 1, 2-ethylene, 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, 1, 6-hexylene, 1, 7-heptylene or 1, 8-octylene. In some preferred embodiments, B 2 is-CH 2 CH 2 - (i.e. 1, 2-ethylene). In some preferred embodiments, B 2 Is 1, 4-butylene. In embodiments herein, B in the same molecule 2 May be identical.
In some embodiments, each L in the same molecule 13 independently-O-or-NH-. In some embodiments, L 13 Is either-O-or-NH-. In some embodiments, L 13 is-O-. In some embodiments, L 13 is-NH-.
In some embodiments, each B in the same molecule 1 Independently H or alkyl, further independently H or C 1-19 An alkyl group; further can be independently H, methyl, ethyl or- (CH) 2 ) j2 -CH 3 J2 is an integer selected from 2 to 18; still further may be independently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, or nonadecyl; further, it may be independently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl, further, it may be independently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, further, it may be independently H, methyl, ethyl, propyl, butyl, pentyl or hexyl. In some embodiments, each B 1 Independently H, methyl,Ethyl or C 3-6 An alkyl group. In some preferred embodiments, each B 1 Independently alkyl, further independently C 1-19 An alkyl group; further can be independently methyl, ethyl or- (CH) 2 ) j2 -CH 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein j2 is an integer selected from 2 to 18. In some preferred embodiments, B 1 Is alkyl. In some preferred embodiments, B 1 Is C 1-18 An alkyl group. In some preferred embodiments, B 1 Is C 1-16 An alkyl group. In some preferred embodiments, B 1 Is C 1-12 An alkyl group. In some preferred embodiments, B 1 Is C 1-10 An alkyl group. In some preferred embodiments, B 1 Is C 1-8 An alkyl group. In some preferred embodiments, B 1 Is C 1-6 Alkyl (which may be selected from methyl, ethyl, propyl, butyl, pentyl and hexyl). In some preferred embodiments, B 1 Is C 1-3 Alkyl (in particular methyl, ethyl or propyl). In some embodiments, each B 1 Independently H or methyl. In some embodiments, B 1 Is either H or methyl. In some preferred embodiments, B 1 H. In some preferred embodiments, B 1 Is methyl. In embodiments herein, B in the same molecule 1 May be identical.
In the present invention, R 1 、A 1 、A 2 、L、L 11 、L 13 、B 1 、B 2 、R 3 M, n are allowed to be combined in any suitable manner, and further may be combined in any suitable manner in any of the structural formulae herein.
In some embodiments, a 2 Is 1, 2-ethylene, R 3 is-O-.
In some embodiments, B 2 Is 1, 2-ethylene, B 1 Is methyl.
In some embodiments, a 1 Is methyl, B 1 Is methyl.
In some embodiments, a 2 Is 1, 2-ethylene, B 2 Is 1, 2-ethylene.
In some embodiments of the invention, formula (1) satisfies any one or more of the following features:
each R 1 independently-CHO, -COOH, -OH, -NH 2 Or (b)
Each A 1 Independently H, methyl, ethyl or C 3-6 An alkyl group;
each A 2 Independently C 2-8 An alkylene group;
L 11 is-O-;
each L is independently R-containing 0 Divalent linking group of R 0 is-O-or-NH-, and R 0 And A is a 2 Is connected with each other;
each B is 2 Independently C 2-8 An alkylene group;
L 13 is-O-;
each B is 1 Independently H, methyl, ethyl or C 3-6 An alkyl group.
In some embodiments of the invention, formula (1) satisfies any one or more of the following features:
each R 1 independently-CHO, -COOH, -OH, -NH 2 Or (b)
A 1 Is H, methyl, ethyl or- (CH) 2 ) j1 -CH 3 J1 is an integer selected from 2 to 18;
A 2 is- (CH) 2 ) q1 Q1 is an integer selected from 2 to 18;
l is R-containing 0 Divalent linking group of R 0 is-O-or-NH-, and R 0 And A is a 2 Is connected with each other;
B 2 is- (CH) 2 ) q2 Q2 is an integer selected from 2 to 18;
B 1 is H, methyl, ethyl or- (CH) 2 ) j2 -CH 3 J2 isSelected from integers from 2 to 18.
In some embodiments of the invention, A 1 Is H or methyl; b (B) 1 Is H or methyl. Further, in some embodiments of the invention, A 1 Is methyl; b (B) 1 Is methyl.
In some embodiments of the invention, A 2 Is methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene or octylene; and/or B 2 Is methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene or octylene.
In some preferred embodiments of the invention, L is-R 3 -C (=o) -NH-, wherein, -R 3 -and A 2 Is connected with each other; at this time, the reactive hydrophilic polymer Poly1 has a general structure represented by formula (2):
further, in some preferred embodiments, R 3 is-O-or-NH-. The definition of the remaining parameters can be found in the foregoing.
In some preferred embodiments of the invention, R 3 is-O-, and the reactive hydrophilic polymer Poly1 has a general structure shown in a formula (2 d):
the definition of the parameters in formula (2 d) can be found in the foregoing.
In some preferred embodiments of the present invention, the reactive hydrophilic polymer Poly1 has a general structure represented by formula (3 a), in which case A 1 Is methyl; further, B 1 May be methyl, in which case it is represented by formula (3 b). The definition of the parameters can be found in the foregoing.
In some embodiments, the reactive hydrophilic polymer Poly1 comprises 45% to 90% by weight of the dry weight of the hydrophilic polymer-containing coating system of the first aspect of the present invention, and may be selected from any of the following: 45%, 47%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, etc., may also be selected from the interval consisting of any two percentages mentioned above, some non-limiting examples being 45% -85%, 47% -80%, 70% -90%, 75% -85%, 45% -54%, etc.
In the present application, "mass percent in dry weight of the coating system" is based on 100% dry weight of the coating system, unless otherwise indicated. "percent by mass in the coating system", unless otherwise indicated, is based on 100% by weight of the total weight of the coating system including the solvent.
In some embodiments, the reactive hydrophilic polymer Poly1 is present in the hydrophilic polymer containing coating system of the first aspect of the present application in an amount of 4% to 30% by mass, and may be selected from any of the following: 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12%, 15%, 16%, 18%, 20%, 22%, 24%, 25%, 26%, 8%, 30%, etc., may also be selected from the interval consisting of any two percentages mentioned above, some non-limiting examples being 5% -12%, 5% -8%, 8% -15%, 6% -10%, 4% -6%, etc.
In the present application, the reactive monomer Rm1 is capable of intermolecular crosslinking. In some embodiments, reactive monomer Rm1 may also act as a cross-linking agent. In some embodiments, reactive monomer Rm1 has a polymer chain and a plurality of (+.2 or+.3) reactive groups F covalently attached to the polymer chain 1 . In some embodiments, the polymer chain in the reactive monomer Rm1 is selected from one or more structures from the group consisting of: polyethers, polyurethanes, polyethylenes, polypropylenes, polyvinylchlorides, polyethylene oxides, polyamides, polyacrylamides, poly (meth) acrylic acid, polyvinyl alcohols, polyethylenimines, polyesters and alkyd copolymers, polypeptides, polysaccharides, and the like. In some embodiments, the reactive group F 1 One or more groups selected from the group consisting of: unsaturated bond of carbon and carbon, -NH 2 、-CONH 2 and-SH, which may preferably be carbon-freeSaturated bonds. When the reactive monomer Rm1 includes a carbon-carbon unsaturated bond, the reactive monomer Rm1 may include one or more structures of an alkenyl group, an unsaturated ester, an unsaturated ether, an unsaturated amide, and a dry alkyd resin. In some embodiments of the invention, the carbon-carbon unsaturation in Rm1 is provided by alkenyl. In some embodiments of the invention, the carbon-carbon unsaturation is provided by an unsaturated structure selected from the group consisting of: unsaturated esters, acrylic acid esters, methacrylic acid esters, unsaturated ethers, unsaturated amides, and the like. In some suitable examples, reactive monomer Rm1 is a polymer having an unsaturated ester, an unsaturated amide, an unsaturated ether, an unsaturated thiol, or an unsaturated thiol.
In some embodiments, reactive monomer Rm1 is selected from one or more of a plurality of carbon-carbon unsaturated bond modified polyethers. In some embodiments, the plurality of carbon-carbon unsaturated bond modified polyethers include a plurality of carbon-carbon unsaturated bond modified polyethylene glycols and a plurality of carbon-carbon unsaturated bond modified polytetrahydrofurans. In some embodiments, the reactive monomer Rm1 is polyethylene glycol diacrylate or polyethylene glycol dimethacrylate. In some embodiments, the reactive monomer Rm1 is polyethylene glycol diacrylate.
In some embodiments, the reactive monomer Rm1 has a number average molecular weight of about 600Da to about 10000Da, further may be about 600Da to about 5000Da, and still further may be about 1000Da to about 5000Da. The number average molecular weight of the reactive monomer Rm1 may be selected from any of the following molecular weights: 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1800, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5100, 5200, 5300, 5400, 5500, 5600, 5800, 6000, etc., may also be selected from the interval of any two of the foregoing molecular weights, some non-limiting examples being 800-2000 Da.
In some embodiments, the reactive monomer Rm1 is present in the dry weight of the hydrophilic polymer containing coating system of the first aspect of the invention in a mass percentage of 9.9% to 50%, and may be selected from any of the following percentages: 9.9%, 10%, 14.5%, 15%, 18%, 19%, 20%, 25%, 30%, 35%, 40%, 42%, 45%, 48%, 50%, etc., may also be selected from the interval consisting of any two percentages mentioned above, some non-limiting examples being 14.5% -50%, 19% -48%, 9.9% -25%, 14.5% -20%, 42% -50%, etc.
In some embodiments, the reactive monomer Rm1 is present in the hydrophilic polymer-containing coating system of the first aspect of the invention in an amount of 1.9% to 19% by mass, and may be selected from any of the following percentages: 1.9%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 9.9%, 10%, 14.5%, 15%, 18%, 19% etc., may also be selected from the intervals consisting of any two percentages mentioned above, some non-limiting examples being 2% to 8%, 2% to 5%, 1.9% to 4.8%, 1% to 4%, 4% to 6% etc.
In the present invention, the initiator In1 may initiate the polymerization of the reactive hydrophilic polymer Poly 1.
In some embodiments, the initiator In1 is a Norrish type I initiator or a free radical photoinitiator, in which case the reaction rate is faster. In some embodiments, the initiator In1 is selected from one or more of benzoin-based initiators, 4-benzoyl-1, 3-dioxolane-based initiators, benzyl ketal (benzolket al), α -dialkoxyacetophenone, α -hydroxyalkyl benzophenone (α -hydroxy alkylphenone), α -aminoalkylbenzophenone, acylphosphine oxide, diacylphosphine oxide, acylphosphine sulfide, halogenated acetophenone-based initiators, and the like. Examples of initiator In1 include, but are not limited to, the following products: irgacure 2959 (2-hydroxy-4' - (2-hydroxyethoxy) -2-methylphenyl ethyl ketone), irgacure651 (benzyl dimethyl ketal or 2, 2-dimethoxy-1, 2-diphenylethanone), irgacure184 (1-hydroxy-cyclohexyl-phenyl methanone as an active ingredient), and the like. The initiator In1 may be one initiator or a combination of a plurality of initiators.
In some embodiments, the initiator In1 comprises 0.1% to 5% by weight of the dry weight of the hydrophilic polymer containing coating system of the first aspect of the present invention, based on dry weight, and may be selected from any of the following: 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.2%, 1.5%, 1.6%, 1.8%, 1.9%, 2%, 2.2%, 2.4%, 2.5%, 2.6%, 2.8%, 3%, 3.2%, 3.5%, 3.6%, 4%, 4.5%, 4.8%, 5%, etc., may also be selected from the interval consisting of any two percentages mentioned above, some non-limiting examples being 0.5% to 5%, 0.9% to 5%, 0.1% to 3%, 0.5% to 2%, 4% to 5%, etc.
In some embodiments, the initiator In1 is present In the hydrophilic polymer-containing coating system of the first aspect of the present invention In an amount of 0.05% to 1% by mass, and may be selected from any of the following: 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.12%, 0.15%, 0.16%, 0.18%, 0.2%, 0.22%, 0.24%, 0.25%, 0.26%, 0.28%, 0.3%, 0.32%, 0.35%, 0.36%, 0.38%, 0.4%, 0.42%, 0.45%, 0.48%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 0.95%, 1% etc., and may be selected from the interval constituted by any two percentages mentioned above, some non-limiting examples being 0.1% to 0.6%, 0.1% to 0.5%, 0.1% to 0.2%, 0.05% to 0.15%, 0.1% to 0.8% etc.
In some embodiments, the solvent So1 is selected from one or more of alcohol, acetone, methyl ethyl ketone, tetrahydrofuran, methylene chloride, and toluene, or is a solution or emulsion of one or more of alcohol, acetone, methyl ethyl ketone, tetrahydrofuran, methylene chloride, and toluene with water, or is water. In some embodiments, the alcohol is methanol, ethanol, propanol, butanol. In some embodiments, the alcohol is any suitable isomer. In some embodiments, the alcohol is methanol, ethanol, propanol, butanol, or isomers thereof.
In some embodiments, the solvent So1 is present in the hydrophilic polymer-containing coating system of the first aspect of the present invention in an amount of 50% to 90% by mass, and may be selected from any of the following percentages: 50%, 55%, 60%, 65%, 70%, 80%, 82%, 84%, 85%, 86%, 86.5%, 87.2%, 88%, 90%, etc., may also be selected from the interval consisting of any two percentages mentioned above, some non-limiting examples being 80% -90%, 86.5% -90%, 86% -90%, 87.2% -90%, etc.
In the present invention, the mass percentages of the reactive hydrophilic polymer Poly1, the reactive monomer Rm1 and the initiator In1 In the dry weight of the hydrophilic polymer containing coating system In the first aspect of the invention may be combined In any suitable way.
In some embodiments, the reactive hydrophilic polymer Poly1 is 45% to 90%, the reactive monomer Rm1 is 9.9% to 50% and the initiator In1 is 0.1% to 5% by mass of the dry weight of the hydrophilic polymer-containing coating system In the first aspect of the invention; in some embodiments, the reactive hydrophilic polymer Poly1 is 45% to 85%, the reactive monomer Rm1 is 14.5% to 50% and the initiator In1 is 0.5% to 5%; in some embodiments, the reactive hydrophilic polymer Poly1 is 47% to 80%, the reactive monomer Rm1 is 19% to 48% and the initiator In1 is 0.9% to 5%; in some embodiments, the reactive hydrophilic polymer Poly1 is 70% to 90%, the reactive monomer Rm1 is 9.9% to 25% and the initiator In1 is 0.1% to 3%; in some embodiments, the reactive hydrophilic polymer Poly1 is 75% to 85%, the reactive monomer Rm1 is 14.5% to 20% and the initiator In1 is 0.5% to 2%; in some embodiments, the reactive hydrophilic polymer Poly1 is 45% to 54%, the reactive monomer Rm1 is 42% to 51% and the initiator In1 is 4% to 5%.
In some embodiments, in the hydrophilic polymer-containing coating system of the first aspect, the weight proportions of the reactive hydrophilic polymer Poly1, the initiator In1, and the reactive monomer Rm1 are as follows: 45 to 90 parts by weight of reactive hydrophilic polymer Poly1, 9.9 to 50 parts by weight of reactive monomer Rm1 and 0.1 to 5 parts by weight of initiator In1. The reactive hydrophilic polymer Poly1 may be selected from the range consisting of any two of the foregoing parts by weight, for example, 45, 46, 47, 48, 50, 52, 54, 55, 56, 58, 60, 65, 68, 70, 72, 75, 76, 78, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, etc. parts by weight. The parts by weight of the reactive monomer Rm1 may be 9.9, 10, 11, 12, 13, 14, 14.5, 15, 16, 17, 18, 19, 20, 24, 25, 28, 30, 32, 35, 36, 38, 40, 42, 45, 46, 47, 48, 50, or the like, and may be selected from any two of the above-mentioned parts by weight. The parts by weight of the initiator In1 may be, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, etc., and may be selected from the ranges consisting of any two of the foregoing parts by weight. Reference is also made to the aforementioned mass percentages in dry weight of the coating system comprising hydrophilic polymer in the first aspect of the invention.
In the present invention, the mass percentages of the reactive hydrophilic polymer Poly1, the reactive monomer Rm1, the initiator In1 and the solvent So1 In the hydrophilic polymer containing coating system of the first aspect of the present invention may be combined In any suitable way.
In some embodiments, the reactive hydrophilic polymer Poly1 is 4% to 30%, the reactive monomer Rm1 is 1.9% to 19%, the initiator In1 is 0.05% to 1%, and the solvent So1 is 50% to 90% based on the mass percent In the hydrophilic polymer-containing coating system of the first aspect of the present invention; in some embodiments, the reactive hydrophilic polymer Poly1 is 5% to 12%, the reactive monomer Rm1 is 2% to 8%, the initiator In1 is 0.1% to 0.6%, and the solvent So1 is 80% to 90%; in some embodiments, the reactive hydrophilic polymer Poly1 is 5% to 8%, the reactive monomer Rm1 is 2% to 5%, the initiator In1 is 0.1% to 0.5%, and the solvent So1 is 86.5% to 90%; in some embodiments, the reactive hydrophilic polymer Poly1 is 8% to 15%, the reactive monomer Rm1 is 1.9% to 4.8%, the initiator In1 is 0.1% to 0.2%, and the solvent So1 is 80% to 90%; in some embodiments, the reactive hydrophilic polymer Poly1 is 6% to 10%, the reactive monomer Rm1 is 1% to 4%, the initiator In1 is 0.05% to 0.15%, and the solvent So1 agent is 86% to 90%; in some embodiments, the reactive hydrophilic polymer Poly1 is 4% to 6%, the reactive monomer Rm1 is 4% to 6%, the initiator In1 is 0.1% to 0.8%, and the solvent So1 is 87.2% to 90%.
In some embodiments, the coating system of the first aspect satisfies one or more of the following characteristics:
the initiator In1 is selected from one or more of benzoin initiator, 4-benzoyl-1, 3-dioxavaleric initiator, benzyl ketal, alpha-dialkoxyacetophenone, alpha-hydroxy alkyl benzophenone, alpha-amino alkyl benzophenone, acyl phosphorus oxide, diacyl phosphine oxide, acyl phosphine sulfide and halogenated acetophenone initiator;
the reactive monomer Rm1 has a polymer chain and a plurality of reactive groups F covalently linked to the polymer chain 1 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the polymer chain in the reactive monomer Rm1 is selected from one or more structures in the group consisting of: polyethers, polyurethanes, polyethylenes, polypropylenes, polyvinylchlorides, polyethylene oxides, polyamides, polyacrylamides, poly (meth) acrylic acid, polyvinyl alcohols, polyethylenimines, polyesters and alkyd copolymers, polypeptides and polysaccharides; the reactive group F in the reactive monomer Rm1 1 One or more groups selected from the group consisting of: unsaturated bond of carbon and carbon, -NH 2 、-CONH 2 and-SH; when the reactive monomer Rm1 comprises a carbon-carbon unsaturation, the reactive monomer Rm1 comprises one or more structures of alkenyl groups, unsaturated esters, unsaturated ethers, unsaturated amides, and drying alkyds;
The solvent So1 is selected from one or more of alcohol, acetone, methyl ethyl ketone, tetrahydrofuran, dichloromethane and toluene, or is a solution or emulsion formed by one or more of alcohol, acetone, methyl ethyl ketone, tetrahydrofuran, dichloromethane and toluene and water, or is water.
In some embodiments, the coating system of the first aspect satisfies one or more of the following characteristics:
the reactive monomer Rm1 is selected from one or more of a plurality of polyethers modified by carbon-carbon unsaturated bonds; wherein the polyether modified by the plurality of carbon-carbon unsaturated bonds comprises polyethylene glycol modified by the plurality of carbon-carbon unsaturated bonds and polytetrahydrofuran modified by the plurality of carbon-carbon unsaturated bonds;
the number average molecular weight of the reactive monomer Rm1 is 600-5000 Da.
In some embodiments, the coating system of the first aspect satisfies one or more of the following characteristics:
the reactive monomer Rm1 is polyethylene glycol diacrylate or polyethylene glycol dimethacrylate;
the number average molecular weight of the reactive monomer Rm1 is 800-2000 Da.
In a second aspect of the invention, there is provided a two-layer coating system comprising a hydrophilic polymer, comprising a top coating system and a bottom coating system; the top coating system may be selected from the hydrophilic polymer-containing coating systems of the first aspect of the invention.
The priming system used in the third aspect of the invention may be suitably selected from existing priming systems or priming formulations.
The bilayer coating system provided by the second aspect of the present invention may comprise the hydrophilic polymer-containing coating system of the first aspect of the present invention and any suitable primer system, thereby producing a bilayer hydrophilic coating having a bilayer structure, which may be used as a bilayer hydrophilic lubricating layer, wherein the coating system of the first aspect may form a top coating layer of the hydrophilic lubricating layer and the primer system may form a primer layer of the hydrophilic lubricating layer, which may achieve high lubricity, low friction and high adhesion strength at the same time.
In some embodiments, the priming system comprises the following components: the reactive hydrophilic polymer Poly2, the reactive monomer Rm2, further comprises an initiator In2 and a solvent (denoted as solvent So 2).
The priming coating system can comprise a reactive hydrophilic polymer Poly2 and a reactive monomer Rm2, and the two components have polymerization and crosslinking capabilities, so that the lubricity of the hydrophilic lubricating layer can be further improved, the friction force is reduced, and the adhesion firmness of the hydrophilic lubricating layer is enhanced. The primer coating system containing the reactive hydrophilic polymer Poly2 can form a primer coating with a crosslinked network, and after being further coated with the polymer containing the reactive hydrophilic polymer Poly1, the polymer network can be formed, and meanwhile, chemical bond connection can be formed between the polymer network and the primer coating formed by the primer coating system, so that the adjustable controllability of the bonding firmness of the hydrophilic coating is improved more finely.
In some embodiments, the priming system comprises the following components: 45 to 90 weight parts of reactive hydrophilic polymer Poly2, 9.9 to 50 weight parts of initiator In2, 0.1 to 5 weight parts of reactive monomer Rm2 and solvent So2; further, based on 100 parts by weight of dry weight; furthermore, the mass percentage of the solvent So2 in the priming coating system is more than or equal to 50 percent.
In the present application, reference to "dry weight of the priming system", unless otherwise indicated, refers to the sum of the weights of the other components than the solvent. The dry weight components of the priming system of the second aspect may comprise the reactive hydrophilic polymer Poly2, the reactive monomer Rm2 and the initiator In2. The dry weight components of the priming system can be prepared into a mixture by using a solvent according to the concentration when the priming system is coated, or the dry weight components of the priming system can be prepared into a concentrated solution by using less solvent, so that the priming system is convenient to store and transport, and the solvent is added to dilute the priming system to the required concentration before the priming system is used.
In some embodiments, reactive monomer Rm2 is capable of intermolecular crosslinking and may also act as a crosslinking agent, in some preferred embodiments, reactive monomer Rm2 has a polymer chain and a plurality of reactive groups F covalently attached to the polymer chain 2 。
In some embodiments, the initiator In2 may be a Norrish type I initiator or a radical photoinitiator.
In some embodiments, the present invention provides a reactive hydrophilic polymer Poly2 with certain cross-linking capability, comprising hydrophilic polymer chains. In some embodiments, the repeat units of the hydrophilic polymer segment are [ Z-X ]]Wherein Z may be an alkylene group (e.g., C 1-18 Alkylene), X may be-O-or-NH-or-N (CH) 3 ) X may further be-O-or-NH-, further, X may be-O- (corresponding polyether segment). Further, the reactive hydrophilic polymer Poly2 also comprises 2 carbon-carbon double bonds. In some embodiments, the 2 carbon-carbon double bonds are each independently CH 2 =ch-or CH 2 ＝C(CB 10 ) -, wherein B 10 Is H orC 1-6 Alkyl, further, two carbon-carbon double bonds are structurally identical. In some embodiments, poly2 is a linear polyethylene glycol derivative double-bonded at both ends, and further may be a linear polyethylene glycol derivative modified at both ends with an acryl or methacryl group. In some embodiments, poly2 is a linear polytetrahydrofuran derivative doubly linked at both ends, further can be modified at both ends with an acryl group (CH 2 =ch-C (=o) -) or methacryloyl (CH) 2 ＝C(CH 3 ) -linear polytetrahydrofuran derivatives of C (=o) -). In some embodiments, poly2 is modified at both ends with acrylate groups (CH 2 =ch-C (=o) O-) or methacrylate (CH 2 ＝C(CH 3 ) -linear polytetrahydrofuran derivatives of C (=o) O-. In some embodiments, poly2 is modified at both ends with an acrylamide group (CH 2 =ch-C (=o) NH-) and methacrylamide group (CH 2 ＝C(CH 3 ) -linear polytetrahydrofuran derivatives of C (=o) NH-).
In some embodiments, the degree of polymerization for the repeating units [ Z-X ] in the reactive hydrophilic polymer Poly2 can be noted as k.
In some embodiments, the reactive hydrophilic polymer Poly2 has a general structure represented by formula (4)
In the formula (4), the amino acid sequence of the compound,
each X is independently-O-or-NH-or-N (CH) 3 )-；
Each Z is independently C 1-18 An alkylene group;
L 21 and L 22 Each independently selected from: absence, -C (=o) -and-C (=o) NH-; wherein X is directed to X;
B 21 and B 22 Each independently is C 1-18 An alkylene group;
L 31 and L 32 Each independently is-O-or-NH-;
B 11 and B 12 Each independently is H or C 1-6 Alkyl groups, further independently of one another, may be H, methyl, ethyl or C 3-6 An alkyl group;
k is an integer selected from 1 to 220.
In some embodiments, L 31 And L 32 In the case of-O-, the formula (4) has a structure represented by the formula (4 a):
in some embodiments, each Z is independently alkylene, further may be independently C, in the same molecule 1-18 Alkylene groups, further independently C 1-16 Alkylene groups, further independently C 1-12 Alkylene groups, further independently C 1-10 Alkylene groups, further independently C 1-8 Alkylene (which may be in particular methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene or octylene), further may be independently C 1-6 Alkylene (which may be in particular methylene, ethylene, propylene, butylene, pentylene or hexylene) and further may independently be C 1-3 Alkylene (which may be in particular methylene, ethylene or propylene). In some embodiments, each Z is independently C 2-8 Alkylene groups, further independently, may be C 2-6 Alkylene groups, further independently, may be C 2-4 Alkylene (i.e., may independently be ethylene, propylene, or butylene). In some preferred embodiments, each Z is independently- (CH) 2 ) q3 -; wherein q3 is an integer selected from 2 to 18, further selected from 2 to 16 (specifically, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18), further selected from 2 to 12, further selected from 2 to 10, and further selected from 2, 3, 4, 5 or 6; in some embodiments, q3 is 2 or 4; in some embodiments, q3 is 2; in some embodiments, q3 is 4. In some embodiments, each Z is independently methylene, ethylene, methylene Propyl, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene or octadecylene. In some embodiments, each Z is independently methylene, 1, 2-ethylene, 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, 1, 6-hexylene, 1, 7-heptylene, or 1, 8-octylene. In some preferred embodiments, Z is-CH 2 CH 2 - (i.e. 1, 2-ethylene). In some preferred embodiments, Z is 1, 4-butylene. In embodiments herein, Z in the same molecule may be the same.
In some embodiments, each X may independently be-O-or-NH-or-N (CH) 3 ) -, further X may independently be-O-or-NH-, still further, X may be-O-. In some preferred embodiments, X is-O-or-NH-. At this time, each Z may be the same or different. In some preferred embodiments, X is-O-. In some preferred embodiments, X is-NH-.
In some embodiments, the repeating unit [ Z-X ]]is-CH 2 CH 2 O-in which case Poly2 contains a polyethylene glycol (PEG) segment.
In some embodiments, the repeating unit [ Z-X ] ]is-CH 2 CH 2 CH 2 CH 2 O-Poly 2 contains Polytetrahydrofuran (PTMG) segments.
In some embodiments, k may be an integer selected from 1-220, some non-limiting examples being 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 15, 16, 18, 20, 22, 23, 24, 25, 26, 28, 30, 35, 36, 37, 38, 40, 41, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, etc., and may be an integer interval selected from any two integers described above, such as 2-100, 3-65, 4-51, 4-50, 7-24, 7-20.
In some embodiments, the reactive hydrophilic polymer is Poly 2- (Z-X) k The number average molecular weight of the segments is selected from 500-7500 Da, and can be selected from any of the following molecular weights: 500Da, 600Da, 800Da, 1000Da, 1100Da,1300kDa, 1500Da, 1750Da, 2000Da, 2200Da, 2500Da, 3000Da, 3300Da, 3500Da, 4000Da, 4400Da, 4500Da, 5000Da, 5500Da, 6000Da, 6500Da, 6600Da, 7000Da, 7500Da, etc., and can be selected from the interval consisting of any two of the foregoing molecular weights, some non-limiting examples being 500-5000 Da, 600-4000 Da, 800-2000 Da, 800-2200 Da, 800-1750 Da, etc.
In some embodiments, the number average molecular weight of the reactive hydrophilic polymer Poly2 is selected from 500 to 7500Da, and may also be selected from any of the following molecular weights: 500Da, 600Da, 800Da, 1000Da, 1100Da, 1300 Da, 1500Da, 1750Da, 2000Da, 2200Da, 2500Da, 3000Da, 3300Da, 3500Da, 4000Da, 4400Da, 4500Da, 5000Da, 5500Da, 6000Da, 6500Da, 6600Da, 7000Da, 7500Da, etc., and can also be selected from the interval formed by any two of the foregoing molecular weights, such as 500-5000 Da, 600-4000 Da, 800-2000 Da, 800-2200 Da, 800-1750 Da, etc.
In some embodiments, L 21 And L 22 Each independently selected from: absence, -C (=o) -and-C (=o) NH-; wherein X is directed to X. In the same molecule, L 21 And L 22 May be the same or different.
In some embodiments, L 21 And L 22 Are all-C (=o) -. In this case, the formula (4 a) has a structure represented by the formula (4 b):
in some embodiments, L 21 And L 22 Are all-C (=O) NH-; wherein-C (=o) -is attached to X. In this case, the formula (4 a) has a structure represented by the formula (4 c):
in some embodiments, B in the same molecule 21 And B 22 Can be each independently alkylene, further can each independently The ground is C 1-18 Alkylene groups, further independently of one another, may be C 1-16 Alkylene groups, further independently of one another, may be C 1-12 Alkylene groups, further independently of one another, may be C 1-10 Alkylene groups, further independently of one another, may be C 1-8 Alkylene (which may be in particular methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene or octylene), further may each independently be C 1-6 Alkylene (which may be in particular methylene, ethylene, propylene, butylene, pentylene or hexylene) groups, further may each independently be C 1-3 Alkylene (which may be in particular methylene, ethylene or propylene). In some embodiments, B 21 And B 22 Can each independently be C 2-8 Alkylene groups, further independently of one another, may be C 2-6 Alkylene groups, further independently of one another, may be C 2-4 Alkylene (i.e., may independently be ethylene, propylene, or butylene). In some preferred embodiments, B 21 And B 22 Can each independently be- (CH) 2 ) q4 -; wherein q4 is an integer selected from 2 to 18, further selected from 2 to 16 (specifically, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18), further selected from 2 to 12, further selected from 2 to 10, and further selected from 2, 3, 4, 5 or 6; in some embodiments, q4 is 2 or 4; in some embodiments, q4 is 2; in some embodiments, q4 is 4. In some embodiments, B 21 And B 22 And may each independently be methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene or octadecylene. In some embodiments, B 21 And B 22 May each independently be methylene, 1, 2-ethylene, 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, 1, 6-hexylene, 1, 7-heptylene or 1, 8-octylene. In some preferred embodiments, B 21 And B 22 Are all-CH 2 CH 2 - (i.e. 1, 2-ethylene). In some preferred embodiments, B 21 And B 22 Are all 1, 4-butylene. In embodiments herein, B in the same molecule 21 And B 22 May be the same.
In some embodiments, L 31 And L 32 Each independently contains R 02 ，R 02 is-O-or-NH-, and R 02 And CH (CH) 2 ＝C(B 11 ) -C (O) -or CH 2 ＝C(B 12 ) -C (O) -phase connection. In some embodiments, L 31 And L 32 Each independently is-O-or-NH-. In some embodiments, L 31 And L 32 is-O-. In some embodiments, L 31 And L 32 is-NH-.
In some embodiments, B in the same molecule 11 And B 12 Each independently is H or alkyl, further independently can be H or C 1-10 An alkyl group; further can be independently H, methyl, ethyl or- (CH) 2 ) j4 -CH 3 J4 is an integer selected from 2 to 9; further, it may be independently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl, further, it may be independently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, further, it may be independently H, methyl, ethyl, propyl, butyl, pentyl or hexyl. In some embodiments, B 11 And B 12 Each independently is H, methyl, ethyl or C 3-6 An alkyl group. In some preferred embodiments, B 11 And B 12 Each independently is alkyl, further may each independently be C 1-10 An alkyl group; further can each independently be methyl, ethyl or- (CH) 2 ) j4 -CH 3 J4 is an integer selected from 2 to 9. In some preferred embodiments, B 11 And B 12 Each independently is C 1-10 An alkyl group. In some preferred embodiments, B 11 And B 12 Each independently is C 1-8 An alkyl group. In some preferred embodiments, B 11 And B 12 Each independently is C 1-6 Alkyl (which may be selected from methyl, ethyl, propyl, butyl, pentyl and hexyl). In some preferred embodiments, B 11 And B 12 Each independently is C 1-3 Alkyl (in particular methyl, ethyl or propyl). In some embodiments, B 11 And B 12 Each independently is H or methyl. In some embodiments, B 11 And B 12 Each independently is any one of H or methyl. In some preferred embodiments, B 11 And B 12 H. In some preferred embodiments, B 11 And B 12 Is methyl. In embodiments herein, B in the same molecule 11 And B 12 May be the same.
In some embodiments, the weight percentage of the reactive hydrophilic polymer Poly2 in the dry weight of the priming system is 45% to 90%, and may also be selected from any of the following percentages: 45%, 47%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, etc., may also be selected from the interval consisting of any two percentages mentioned above, some non-limiting examples being 45% -85%, 47% -80%, 70% -90%, 75% -85%, 45% -54%, etc.
In the present application, "mass percent in dry weight of the priming system" is based on 100% dry weight of the priming system, unless otherwise specified. "percent by weight in the primer system", unless otherwise indicated, is based on 100% total weight of the primer system including solvent.
In some embodiments, the mass percentage of the reactive hydrophilic polymer Poly2 in the priming system is 4% -30%, and may also be selected from any one of the following percentages: 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12%, 15%, 16%, 18%, 20%, 22%, 24%, 25%, 26%, 8%, 30%, etc., may also be selected from the interval consisting of any two percentages mentioned above, some non-limiting examples being 5% -12%, 5% -8%, 8% -15%, 6% -10%, 4% -6%, etc.
In the present invention, the reactive monomer Rm2 is capable of intermolecular crosslinking. In some embodiments, reactive monomer Rm2 may also act as a cross-linking agent. In some embodimentsWherein the reactive monomer Rm2 has a polymer chain and a plurality of (. Gtoreq.2 or. Gtoreq.3) reactive groups F covalently linked to said polymer chain 2 . In some embodiments, the polymer chain in reactive monomer Rm2 is selected from one or more structures in the group consisting of: polyethers, polyurethanes, polyethylenes, polypropylenes, polyvinylchlorides, polyethylene oxides, polyamides, polyacrylamides, poly (meth) acrylic acid, polyvinyl alcohols, polyethylenimines, polyesters and alkyd copolymers, polypeptides, polysaccharides, and the like. In some embodiments, reactive group F of the backbone side group of reactive monomer Rm2 2 One or more groups selected from the group consisting of: unsaturated bond of carbon and carbon, -NH 2 、-CONH 2 and-SH, which may preferably be a carbon-carbon unsaturated bond. When the reactive monomer Rm2 includes a carbon-carbon unsaturated bond, the reactive monomer Rm2 may include one or more structures of an alkenyl group, an unsaturated ester, an unsaturated ether, an unsaturated amide, and a dry alkyd resin. In some embodiments of the invention, the carbon-carbon unsaturation in Rm2 is provided by alkenyl. In some embodiments of the invention, the carbon-carbon unsaturation in Rm2 is provided by an unsaturated structure selected from the group consisting of: unsaturated esters, acrylic acid esters, methacrylic acid esters, unsaturated ethers, unsaturated amides, and the like. In some suitable examples, the reactive monomer Rm2 is a polymer having an unsaturated ester, amide, ether, thiol, or thiol group.
In some embodiments, reactive monomer Rm2 is selected from one or more of a plurality of carbon-carbon unsaturated bond modified polyethers. In some embodiments, the plurality of carbon-carbon unsaturated bond modified polyethers include a plurality of carbon-carbon unsaturated bond modified polyethylene glycols and a plurality of carbon-carbon unsaturated bond modified polytetrahydrofurans. In some embodiments, the reactive monomer Rm2 is polyethylene glycol diacrylate or polyethylene glycol dimethacrylate. In some embodiments, the reactive monomer Rm2 is polyethylene glycol diacrylate.
In some embodiments, the reactive monomer Rm2 has a number average molecular weight of about 600Da to about 10000Da, further may be about 600Da to about 5000Da, and still further may be about 1000Da to about 5000Da. The number average molecular weight of the reactive monomer Rm2 may be selected from any of the following molecular weights: 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1800, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5100, 5200, 5300, 5400, 5500, 5600, 5800, 6000, etc., may also be selected from the interval of any two of the foregoing molecular weights, some non-limiting examples being 800-2000 Da.
In some embodiments, the weight percentage of the reactive monomer Rm2 in the dry weight of the priming system is 9.9% to 50%, and may be selected from any one of the following percentages: 9.9%, 10%, 14.5%, 15%, 18%, 19%, 20%, 25%, 30%, 35%, 40%, 42%, 45%, 48%, 50%, etc., may also be selected from the interval consisting of any two percentages mentioned above, some non-limiting examples being 14.5% -50%, 19% -48%, 9.9% -25%, 14.5% -20%, 42% -50%, etc.
In some embodiments, the mass percentage of the reactive monomer Rm2 in the priming system is 1.9% -19%, and may be selected from any one of the following percentages: 1.9%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 9.9%, 10%, 14.5%, 15%, 18%, 19% etc., may also be selected from the intervals consisting of any two percentages mentioned above, some non-limiting examples being 2% to 8%, 2% to 5%, 1.9% to 4.8%, 1% to 4%, 4% to 6% etc.
In some embodiments, the initiator In2 is a Norrish type I initiator or a free radical photoinitiator, in which case the reaction rate is faster. In some embodiments, the initiator In2 is selected from one or more of benzoin-based initiators, 4-benzoyl-1, 3-dioxolane-based initiators, benzyl ketal (benzolket al), α -dialkoxyacetophenone, α -hydroxyalkyl benzophenone (α -hydroxy alkylphenone), α -aminoalkylbenzophenone, acylphosphine oxide, diacylphosphine oxide, acylphosphine sulfide, halogenated acetophenone-based initiators, and the like. Examples of initiator In2 include, but are not limited to, the following products: irgacure 2959 (2-hydroxy-4' - (2-hydroxyethoxy) -2-methylphenyl ethyl ketone), irgacure651 (benzyl dimethyl ketal or 2, 2-dimethoxy-1, 2-diphenylethanone), irgacure184 (1-hydroxy-cyclohexyl-phenyl methanone as an active ingredient), and the like. The initiator In2 may be one initiator or a combination of a plurality of initiators.
In some embodiments, the initiator In2 comprises 0.1 to 5% by weight of the dry weight of the priming system, and may be selected from any of the following percentages: 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.2%, 1.5%, 1.6%, 1.8%, 1.9%, 2%, 2.2%, 2.4%, 2.5%, 2.6%, 2.8%, 3%, 3.2%, 3.5%, 3.6%, 4%, 4.5%, 4.8%, 5%, etc., may also be selected from the interval consisting of any two percentages mentioned above, some non-limiting examples being 0.5% to 5%, 0.9% to 5%, 0.1% to 3%, 0.5% to 2%, 4% to 5%, etc.
In some embodiments, the mass percentage of the initiator In2 In the primer coating system is 0.05% -1%, and may be selected from any one of the following percentages: 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.12%, 0.15%, 0.16%, 0.18%, 0.2%, 0.22%, 0.24%, 0.25%, 0.26%, 0.28%, 0.3%, 0.32%, 0.35%, 0.36%, 0.38%, 0.4%, 0.42%, 0.45%, 0.48%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 0.95%, 1% etc., and may be selected from the interval constituted by any two percentages mentioned above, some non-limiting examples being 0.1% to 0.6%, 0.1% to 0.5%, 0.1% to 0.2%, 0.05% to 0.15%, 0.1% to 0.8% etc.
In some embodiments, the solvent So2 is selected from one or more of alcohol, acetone, methyl ethyl ketone, tetrahydrofuran, methylene chloride, and toluene, or is a solution or emulsion of one or more of alcohol, acetone, methyl ethyl ketone, tetrahydrofuran, methylene chloride, and toluene with water, or is water. In some embodiments, the alcohol is methanol, ethanol, propanol, butanol. In some embodiments, the alcohol is any suitable isomer. In some embodiments, the alcohol is methanol, ethanol, propanol, butanol, or isomers thereof.
In some embodiments, the solvent So2 is 50% -90% by mass of the priming system, and may be selected from any of the following percentages: 50%, 55%, 60%, 65%, 70%, 80%, 82%, 84%, 85%, 86%, 86.5%, 87.2%, 88%, 90%, etc., may also be selected from the interval consisting of any two percentages mentioned above, some non-limiting examples being 80% -90%, 86.5% -90%, 86% -90%, 87.2% -90%, etc.
In the present invention, the mass percentages of the reactive hydrophilic polymer Poly2, the reactive monomer Rm2 and the initiator In2 In the dry weight of the priming system may be combined In any suitable way.
In some embodiments, the reactive hydrophilic polymer Poly2 is 45% to 90%, the reactive monomer Rm2 is 9.9% to 50% and the initiator In2 is 0.1% to 5% by mass percent In the dry weight of the priming system; in some embodiments, the reactive hydrophilic polymer Poly2 is 45% to 85%, the reactive monomer Rm2 is 14.5% to 50% and the initiator In2 is 0.5% to 5%; in some embodiments, the reactive hydrophilic polymer Poly2 is 47% to 80%, the reactive monomer Rm2 is 19% to 48% and the initiator In2 is 0.9% to 5%; in some embodiments, the reactive hydrophilic polymer Poly2 is 70% to 90%, the reactive monomer Rm2 is 9.9% to 25% and the initiator In2 is 0.1% to 3%; in some embodiments, the reactive hydrophilic polymer Poly2 is 75% to 85%, the reactive monomer Rm2 is 14.5% to 20% and the initiator In2 is 0.5% to 2%; in some embodiments, the reactive hydrophilic polymer Poly2 is 45% to 54%, the reactive monomer Rm2 is 42% to 51% and the initiator In2 is 4% to 5%.
In some embodiments, in the priming system of the second aspect, the weight proportions of reactive hydrophilic polymer Poly2, initiator In2 and reactive monomer Rm2 are as follows: 45 to 90 parts by weight of reactive hydrophilic polymer Poly2, 9.9 to 50 parts by weight of reactive monomer Rm2 and 0.1 to 5 parts by weight of initiator In2. The reactive hydrophilic polymer Poly2 may be selected from the range consisting of any two of the foregoing parts by weight, for example, 45, 46, 47, 48, 50, 52, 54, 55, 56, 58, 60, 65, 68, 70, 72, 75, 76, 78, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, etc. parts by weight. The parts by weight of the reactive monomer Rm2 may be 9.9, 10, 11, 12, 13, 14, 14.5, 15, 16, 17, 18, 19, 20, 24, 25, 28, 30, 32, 35, 36, 38, 40, 42, 45, 46, 47, 48, 50, or the like, and may be selected from any two of the above-mentioned parts by weight. The parts by weight of the initiator In2 may be, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, etc., and may be selected from the ranges consisting of any two of the foregoing parts by weight. Reference is also made to the aforementioned mass percentages in dry weight of the priming system.
In the present invention, the mass percentages of the reactive hydrophilic polymer Poly2, the reactive monomer Rm2, the initiator In2 and the solvent So2 In the priming system of the second aspect of the present invention may be combined In any suitable way.
In some embodiments, the reactive hydrophilic polymer Poly3 is 4% to 30%, the reactive monomer Rm3 is 1.9% to 19%, the initiator In3 is 0.05% to 1%, and the solvent So2 is 50% to 90% by mass In the priming system; in some embodiments, the reactive hydrophilic polymer Poly1 is 5% to 12%, the reactive monomer Rm1 is 2% to 8%, the initiator In2 is 0.1% to 0.6%, and the solvent So2 is 80% to 90%; in some embodiments, the reactive hydrophilic polymer Poly2 is 5% to 8%, the reactive monomer Rm2 is 2% to 5%, the initiator In2 is 0.1% to 0.5%, and the solvent So2 is 86.5% to 90%; in some embodiments, the reactive hydrophilic polymer Poly2 is 8% to 15%, the reactive monomer Rm2 is 1.9% to 4.8%, the initiator In2 is 0.1% to 0.2%, and the solvent So2 is 80% to 90%; in some embodiments, the reactive hydrophilic polymer Poly2 is 6% to 10%, the reactive monomer Rm2 is 1% to 4%, the initiator In2 is 0.05% to 0.15%, and the solvent So2 is 86% to 90%; in some embodiments, the reactive hydrophilic polymer Poly2 is 4% to 6%, the reactive monomer Rm2 is 4% to 6%, the initiator In2 is 0.1% to 0.8%, and the solvent So2 is 87.2% to 90%.
In some embodiments, the priming system of the second aspect meets one or more of the following characteristics:
the reactive monomer Rm2 has a polymer chain and a plurality of reactive groups F covalently linked to the polymer chain 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the polymer chain in the reactive monomer Rm2 is selected from one or more structures in the group consisting of: polyethers, polyurethanes, polyethylenes, polypropylenes, polyvinylchlorides, polyethylene oxides, polyamides, polyacrylamides, poly (meth) acrylic acid, polyvinyl alcohols, polyethylenimines, polyesters and alkyd copolymers, polypeptides and polysaccharides; the reactive group F in the reactive monomer Rm2 2 One or more groups selected from the group consisting of: unsaturated bond of carbon and carbon, -NH 2 、-CONH 2 and-SH; when the reactive monomer Rm2 comprises a carbon-carbon unsaturation, the reactive monomer Rm2 comprises one or more structures of alkenyl groups, unsaturated esters, unsaturated ethers, unsaturated amides, and drying alkyds;
the initiator In2 is selected from one or more solvents of benzoin initiator, 4-benzoyl-1, 3-dioxavaleric initiator, benzyl ketal, alpha-dialkoxyacetophenone, alpha-hydroxy alkyl benzophenone, alpha-amino alkyl benzophenone, acyl phosphorus oxide, diacyl phosphine oxide, acyl phosphine sulfide and halogenated acetophenone initiator;
So2 is selected from one or more of alcohol, acetone, methyl ethyl ketone, tetrahydrofuran, methylene dichloride and toluene, or is a solution or emulsion of one or more of alcohol, acetone, methyl ethyl ketone, tetrahydrofuran, methylene dichloride and toluene and water, or is water.
In some embodiments, the reactive monomer Rm2 is selected from one or more of a plurality of carbon-carbon unsaturated bond modified polyethers; wherein the polyether modified by the plurality of carbon-carbon unsaturated bonds comprises polyethylene glycol modified by the plurality of carbon-carbon unsaturated bonds and polytetrahydrofuran modified by the plurality of carbon-carbon unsaturated bonds;
further, the number average molecular weight of the reactive monomer Rm2 may be 600 to 5000Da, and more preferably 800 to 2000Da.
In some embodiments, the reactive monomer Rm2 is polyethylene glycol diacrylate or polyethylene glycol dimethacrylate;
further, the number average molecular weight of the reactive monomer Rm2 is 600 to 5000Da, and more preferably 800 to 2000Da.
In a third aspect of the invention, there is provided a hydrophilic coating which can be prepared according to the hydrophilic polymer-containing coating system of the first aspect of the invention or according to the hydrophilic polymer-containing bilayer coating system of the second aspect of the invention. The hydrophilic coating may act as a top coating for the hydrophilic lubricating layer.
In some embodiments, the hydrophilic coating is laminated to the surface of the medical device; in some embodiments, the hydrophilic coating may be laminated to the plastic substrate surface of the medical device; in some embodiments, the medical device may be an implantable medical device.
In some embodiments of the invention, the hydrophilic coating may be laminated to the surface of the implantable medical device, and further, the hydrophilic coating may be laminated to the surface of the plastic substrate of the implantable medical device.
In the present invention, unless otherwise specified, "surface" of the "medical device (e.g., a plastic substrate surface)", and "surface of the" implantable medical device (e.g., a plastic substrate surface) "include at least surfaces that may contact and rub against tissue in the body at the implantation site.
In the present invention, unless otherwise stated, an "implantable medical device" may be used as an implantable medical device, but is also permitted to be used as a non-implantable medical device.
In some embodiments, the hydrophilic polymer-containing coating system according to the first aspect of the present invention may be used to prepare a hydrophilic coating of a single layer structure (which may be used as a hydrophilic lubricating layer having a single layer structure), or may be used in combination with any suitable priming system to prepare a hydrophilic coating of a double layer structure (which may be used as a hydrophilic lubricating layer having a double layer structure).
In some embodiments, the bilayer coating system comprising a hydrophilic polymer according to the second aspect of the invention produces a bilayer hydrophilic coating that can be used as a hydrophilic lubricating layer having a bilayer structure.
The hydrophilic coating of the foregoing single-layer structure can be obtained by the following preparation method: coating the hydrophilic polymer-containing coating system of the first aspect on the surface of a substrate, and drying to form a hydrophilic coating with a single-layer structure.
The hydrophilic coating of the aforementioned bilayer structure can be obtained by the following preparation method: the method comprises the steps of firstly coating a base coating system on the surface of a substrate to form a base coating layer, drying to form a base coating layer, then coating a top coating system (including but not limited to the coating system containing the hydrophilic polymer according to the first aspect of the invention) on the surface of the base coating layer to form a top coating layer, and drying to form the top coating layer, thereby obtaining the hydrophilic coating layer with a double-layer structure (which can be used as a hydrophilic lubricating layer with a double-layer structure). During the preparation process, the reactive groups (including but not limited to carbon-carbon double bonds) in the top coat layer may be capable of forming chemical bonds with the residual reactive groups (including but not limited to double bonds) in the primer layer, thereby forming a strong chemical bond between the re-primer layer and the top coat layer.
In a fourth aspect of the invention there is provided the use of a hydrophilic polymer containing coating system according to the first aspect of the invention, or a hydrophilic polymer containing bilayer coating system according to the second aspect of the invention, for the preparation of a hydrophilic lubricating layer for a medical device, or the use of a hydrophilic coating according to the third aspect of the invention as a hydrophilic lubricating layer for a medical device.
The hydrophilic polymer coating system and the hydrophilic coating made of the hydrophilic polymer-containing double-layer coating system can be used as a hydrophilic lubricating layer of medical devices, including but not limited to a hydrophilic lubricating layer on the surface of implantable medical devices, and have good lubricity, low friction and high firmness. When the hydrophilic lubricating layer is used on the surface of the implantable medical device, the problems that the existing implantable medical device is easy to rub with body tissues when being removed, the patient is often accompanied with burning and pain feeling, tissue injury and adhesion are easy to cause, and complications are easy to occur can be solved or remarkably relieved.
The hydrophilic polymer-containing coating system and the double-layer coating system can be applied to different substrates, and further, can provide better adhesion to plastic substrates.
In some embodiments, the hydrophilic coating is formed on the surface of the medical device; in some embodiments, the hydrophilic coating may be formed on a surface of a plastic substrate of a medical device; in some embodiments, the medical device may be an implantable medical device.
In some embodiments of the invention, the hydrophilic coating is formed on a surface of the implantable medical device, and further, the hydrophilic coating is formed on a surface of a plastic substrate of the implantable medical device.
In some embodiments of the invention, the substrate coated with the hydrophilic coating is a plastic substrate. Suitable plastic substrates include, but are not limited to: nylon, PEBAX (block polyether amide resin product), PU (polyurethane), PET (polyethylene terephthalate), PVC (polyvinyl chloride), PMMA (polymethyl methacrylate), PEEK (polyether ether ketone), PDMS (polydimethylsiloxane), PE (polyethylene), PP (polypropylene), PTFE (polytetrafluoroethylene), and the like.
It should be understood that the term "medical device" as used herein may be a stand-alone medical device product or may be a component or a portion of a structure of a medical device product.
In some embodiments of the invention, examples of medical devices include, but are not limited to: tubes (e.g., catheters, drainage tubes, shunt tubes, cannulas, ear tubes d. Mu.m), stents, connectors, patches, electrodes, leads, sutures, medical needles, wires, sensors, angioplasty spheres, sleeves, blood-filled oxygen generators, heart valves, surgical clips, surgical staples, pacemakers, implantable defibrillators, medical pumps (e.g., implantable drug pumps), cages, artificial discs, artificial lenses, and the like.
In some embodiments, any of the foregoing medical devices may be implantable medical devices involved in minimally invasive surgery.
In a fifth aspect of the present invention, there is provided a method for preparing a reactive hydrophilic polymer, which can prepare the reactive hydrophilic polymer Poly1 in the hydrophilic polymer containing coating system according to the first aspect of the present invention.
In some embodiments, the reactive hydrophilic polymer Poly1 is prepared from a hydrophilic polymer Poly having a structure shown in formula (6) and a small molecule compound SM having a structure shown in formula (7).
In the formula (7), B 1 And B 2 Is defined as above;
R 21 and R is 22 Are reactive groups and R 21 And R is 22 To the functional group pair capable of coupling reaction, further R 21 And R is 22 Capable of undergoing a coupling reaction to form a valence linking group L; m, n, R 1 、A 1 、L 11 、A 2 、L、B 2 、L 13 And B 1 Any one parameter or any suitable combination of parameters may be as defined in any implementation or example herein; ", indicates the site of attachment to the end group.
Further, SM is overdosed relative to repeat unit U3 such that all R 21 Grafted with a small molecule compound SM represented by the formula (7).
In some embodiments, R 21 And R is 22 Is carboxyl (-COOH), activated carboxyl (such as succinimidocarboxylate (-C (O) NHS)), hydrohalate (-COOH. HX, X is halogen such as F, cl, br or I), acyl halide (-C (=O) X, X is halogen such as Cl or Br), active carbonate (such as succinimidocarbonate (-OC (O) NHS)), amino (-NH) 2 ) Hydroxyl (-OH), mercapto (-SH), aldehyde (-CHO), isocyanate (-NCO), halo (such as F, cl, br or I), etc. In some embodiments, R 21 And R is 22 In combination of-OH and carboxyl, halogen acid salt of carboxyl, acyl halide, isocyanate or halogen, can be respectively subjected to coupling reaction to generate ester group (-COO-or-OC (=O) -), ester group,An ester group, a carbamate group (-NHCOO-or-OC (=O) NH-)) or an ether linkage (-O-). In some embodiments, R 21 And R is 22 is-NH 2 In combination with a carboxyl group, an activated carboxyl group, a hydrohalate of a carboxyl group, an acyl halide group, an activated carbonate group, an isocyanate group or a halogen group (e.g., F, cl, br or I), a coupling reaction may be performed to form an amide group (-CONH-or-NHC (=O) -), an amide group, a carbamate group (-NHCOO-or-OC (=O) NH-), a urea group (-NHC (=O) NH-) or a divalent amino group (-NH-), respectively. In some embodiments, R 21 is-OH or-NH 2 Further, R 22 May be-NCO. In some embodiments, R 21 is-OH, R 22 is-NCO. In some embodiments, R 22 is-OH, R 21 is-NCO. The conditions under which these functional groups undergo the coupling reaction are well known to those skilled in the art and will not be described in detail herein.
In some embodiments, small molecule compound SM is isocyanoalkyl methacrylate (IEM), at which point B 1 Is methyl, L 13 is-O-, B 2 Is alkylene, R 22 is-NCO.
In some embodiments, small molecule compound SM is isocyanoethyl methacrylate (IEM), in which case B 1 Is methyl, L 13 is-O-, B 2 Is 1, 2-ethylene, R 22 is-NCO.
In some embodiments, the reactive hydrophilic polymer Poly1 is copolymerized from monomers M1 and M3, and further, is randomly copolymerized. The monomer M3 may be represented by any one of structures M3a, M3b, M3c, M3d, and M3 e. R is R 1 、A 1 、L 11 、A 2 、R 21 Any one parameter or any suitable combination of parameters may be as defined in any implementation or example herein. In some embodiments, M1 is vinyl pyrrolidone. In some embodiments, M3 is a hydroxyalkyl methacrylate, such as A in formula M3e 2 Is an alkylene group. In some embodiments, M3 is hydroxyalkyl ethyl methacrylate, as A in formula M3e 2 Is 1, 2-ethylene. In some embodiments, M1Is vinyl pyrrolidone and M3 is hydroxyalkyl ethyl methacrylate. The amount of M1 and M3 may be selected appropriately according to the polymerization degree of the repeating units (e.g., U1 and U2) in the target copolymer and the ratio thereof. In some embodiments, the feed ratio of M1 to M3 is M: n.
In some embodiments, the reactive hydrophilic polymer Poly1 may be copolymerized from monomers M1 and M2. Further, the molar ratio of the monomers M1 and M2 is M to n. Wherein R is 1 、A 1 、L 11 、A 2 、L、B 2 、L 13 、B 1 (m: n) with reference to the preceding definition. When L 11 And L 13 In the case of-O-, the structure of M2 is shown as M2 a. When A is 1 And B 1 In the case of methyl, the structure of M2 is shown as M2 b. In some embodiments, M2 has a structure as shown in M2 c. In some embodiments, M2 has a structure as shown in M2 d. In some embodiments, M2 has a structure as shown in M2 e.
In the present invention, the hydrophilic polymer Poly and the reactive hydrophilic polymer Poly1 can each independently be tested for molecular weight by selecting a suitable method from Gel Permeation Chromatography (GPC), matrix assisted laser Desorption ionization time of flight mass spectrometry (MALDI-TOF) and the like, and can also be combined with hydrogen nuclear magnetic resonance [ (] 1 H NMR), fourier infrared (FT-IR), ultraviolet (UV) and the like. One skilled in the art can confirm whether the target structure is obtained according to conventional analytical methods.
In a sixth aspect of the present invention, there is provided a reactive hydrophilic polymer (Poly 1) which can be selected from any of the reactive hydrophilic polymers Poly1 according to the first aspect of the present invention, or any of the reactive hydrophilic polymers Poly1 prepared by the preparation method according to the fifth aspect of the present invention.
In some embodiments, the reactive hydrophilic polymer has a structure represented by formula (1), wherein m, n, R 1 、A 1 、L 11 、A 2 、L、B 2 、L 13 And B 1 May be as defined in any embodiment or example herein; ", indicates the site of attachment to the end group.
In a seventh aspect of the present invention, there is provided a method for preparing a reactive hydrophilic polymer, which can prepare the reactive hydrophilic polymer Poly2 in the hydrophilic polymer-containing bilayer coating system according to the second aspect of the present invention.
In some embodiments, the reactive hydrophilic polymer Poly2 may be modified by double-ended by the reactive group R 41 The modified polyether derivative (LP) and the carbon-carbon double bond compound (SM 2). In some embodiments, the structure of LP is as shown in formula (8), wherein X, Z and k can be defined as previously described. In some embodiments, X is-O-, where LP is a polyether glycol. In some embodiments, LP is polytetrahydrofuran diol, X is-O-, and Z is 1, 4-butylene. In some embodiments, LP is polyethylene glycol X is-O-, and Z is 1, 2-ethylene. In some embodiments, the carbon-carbon double bonded compound (SM 2) may have a structure represented by formula (9). Wherein R is 41 And R is 42 Are reactive groups and R 41 And R is 42 For a functional group pair capable of undergoing a coupling reaction (refer to the aforementioned R 21 And R is 22 A pair of functional groups formed), further R 41 And R is 42 Capable of undergoing a coupling reaction to form a valence linking group L 21 Or L 22 ；B 12 、L 31 And B 21 Any one parameter or any suitable combination of parameters may be as defined in any implementation or example herein; ", indicates the site of attachment to the end group.
If not otherwise stated, in the coupling reaction of LP and SM-NCO in the present invention, the SM-NCO is in excess so that both ends of LP are modified with carbon-carbon double bonds.
In some embodiments, R 41 is-NH 2 . In some preferred embodiments, R 42 is-OH.
In some embodiments, R 41 is-NH 2 X is-NH-, in which case the compound of formula (8) is a polyamine.
In some embodiments, R 41 In the case of-OH, X is-O-, in which case the compound of formula (8) is polyethylene glycol.
In some embodiments, in formula (8), R 41 is-NH 2 or-OH; z is alkylene; x is-O-or-NH-.
In some embodiments, R 42 is-NCO.
In some embodiments, SM2 is isocyanoethyl methacrylate.
In some embodiments, R 41 is-OH, R 42 is-NCO.
In the invention, the reactive hydrophilic polymer Poly2 can be used for testing the molecular weight by selecting a proper method in a Gel Permeation Chromatography (GPC) method, a matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF) method and the like, and can also be combined with hydrogen spectrum nuclear magnetic resonance 1 H NMR), fourier infrared (FT-IR), ultraviolet (UV) and the like. One skilled in the art can confirm whether the target structure is obtained according to conventional analytical methods.
In an eighth aspect of the present invention, there is provided a reactive hydrophilic polymer (Poly 2) which can be selected from any of the reactive hydrophilic polymers Poly2 according to the second aspect of the present invention, or any of the reactive hydrophilic polymers Poly2 prepared by the preparation method according to the seventh aspect of the present invention.
In some embodiments, the reactive hydrophilic polymer has a structure represented by formula (4), wherein B 11 、B 12 、L 31 、L 32 、B 21 、B 22 、L 21 、L 22 X, Z and k may be as in any embodiment or example hereinDefined as; ", indicates the site of attachment to the end group.
Some specific examples are provided below.
Embodiments of the present invention will be described in detail below with reference to examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental methods in the following examples, in which specific conditions are not noted, are preferably referred to the guidelines given in the present invention, and may be according to the experimental manual or conventional conditions in the art, the conditions suggested by the manufacturer, or the experimental methods known in the art.
In the following examples, the measurement parameters relating to the raw materials may have fine deviations within the weighing accuracy range unless otherwise specified. Temperature and time parameters are involved, allowing acceptable deviations from instrument testing accuracy or operational accuracy. The materials or reagents in each of the examples below, unless otherwise indicated, may be obtained by commercially available routes or prepared by known methods.
In the following examples, unless otherwise stated,
IEM: isocyanoethyl methacrylate;
PTMG: polytetrahydrofuran; PTMG (PTMG) 1000 、IEM-PTMG 1000 The numbers in IEM et al represent molecular weights, further index average molecular weights;
PEGDA: polyethylene glycol (diol) diacrylate; PEGTA: three-arm polyethylene glycol (triol) triacrylate; PEGDA 800 、PEGDA 2000 、PEGDA 5000 、PEGDA 5000 、PEGTA 3000 、PEGTA 2400 、IEM-PEG 2000 The numbers in IEM et al represent molecular weights, further index average molecular weights;
HEMA: hydroxyethyl methacrylate;
BPO, dibenzoyl peroxide;
VP: vinyl pyrrolidone; that is, NVP: n-vinylpyrrolidone;
Methanol-d 4 : deuterated methanol;
PEBAX, block polyether amide resin.
Relates to light-proof low-temperature preservation, if no other description exists, the preservation is carried out under the light-proof condition and the temperature is less than or equal to 4 ℃. The term "preservation at normal temperature in the absence of light" refers to preservation at 20-30℃under the condition of light protection unless otherwise stated. If no other description exists, the reaction monomer is preserved in a dark place at low temperature, and the coating system is preserved in a dark place at normal temperature.
1 The H NMR nuclear magnetic resonance detection conditions were (unless otherwise specified): nuclear magnetic instrument bruk AVANCE III, scanning power 400MHz.
The molecular weight detection method comprises the following steps: gel Permeation Chromatography (GPC). The following instrumentation and test adjustments were used, if not otherwise stated: waters1515 gel permeation chromatograph, detector waters 2414, column Agilent PLgel 5 μm MIXED-C, mobile phase chloroform, mobile phase flow rate 1mL/min, column temperature 35 ℃, standard Polystyrene (PS).
Example 1 Synthesis of a reactive hydrophilic Polymer P (VP- (HEMA-g-IEM))
In this example, a structural compound of formula (S1) was prepared with a monomer ratio NVP of hema=99:1.
(1) 5g (about 45 mmol) of vinylpyrrolidone (NVP), 59mg (about 0.45 mmol) of hydroxyethyl methacrylate (HEMA) are weighed out and dissolved in 100mL of isopropanol, followed by the addition of 1mg of dibenzoyl peroxide (BPO) and the reaction is carried out in an oil bath at 75℃for 20h under nitrogen. After the reaction is finished, spin-drying isopropanol by a rotary evaporator, precipitating and drying the product in diethyl ether to obtain a white solid P (VP-HEMA) copolymer (P01 a), wherein the structural formula is shown as a formula (100 a).
Intermediate P01a 1 The H NMR spectrum is shown in FIG. 1. According to the chemical shift characteristic peak (-CH-N-CH) of vinyl pyrrolidone (NVP) monomer unit in formula (100 a) 2 -CH 2 -CH 2 -C(=o) -, characteristic peaks of hydrogen atoms adjacent to N of 3.20 to 3.50 ppm), characteristic peaks of chemical shift of hydroxyethyl methacrylate (HEMA) monomer units (CH 3 -C-C(＝O)O-CH 2 -CH 2 -OH, 1.10 to 1.25ppm of methyl characteristic peak), and calculating the quantitative ratio of two monomer units of NVP and HEMA in formula (100 a) to about 99:1.
(2) The copolymer P01a (5 g) obtained above was dissolved in 100mL of chloroform, after complete dissolution, 70mg of isocyanatoethyl methacrylate ((about 0.45 mmol)) was slowly added dropwise thereto, the reaction was completed for 2 hours, the trichloromethyl chloride was dried by spinning after the completion of the reaction, and the product was precipitated in diethyl ether and dried to give copolymer P (VP- (HEMA-g-IEM)), which was designated as copolymer P01, and the structure was represented by formula (100).
According to GPC measurement, the weight average molecular weight of product P01 was about 11.3kDa, and the number average molecular weight was about 11.1kDa.
Product P01 1 The H NMR spectrum is shown in FIG. 2, and the solvent is Methanol-d 4 . According to the chemical shift characteristic peak (-CH-N-CH) of vinyl pyrrolidone (NVP) monomer unit in formula (100) 2 -CH 2 -CH 2 -C (=o) -, characteristic peaks of hydrogen atoms adjacent to N3.20-3.50 ppm), characteristic peaks of chemical positions of methacrylate groups grafted in this step (-OC (=o) -C (CH) 3 )＝CH 2 The ratio analysis of the correlation peak areas of the characteristic peaks of two hydrogen atoms on the double bond of 5.65ppm and 6.14 ppm) calculated m in the formula (100): the n ratio is about 99:1. It is estimated that the grafting ratio of isocyanatoethyl methacrylate is substantially 100%. In combination with the molecular weight results from GPC testing, m in formula (100) is about 99 and n is about 1.
EXAMPLE 2 Synthesis of a reactive hydrophilic Polymer P (VP- (HEMA-g-IEM))
In this case, a structural compound represented by the formula (100) (as shown in example 1) was prepared, and monomer units having the same structure as in example 1 were prepared in a monomer ratio of NVP: hema=19:1.
(1) 5g (about 45 mmol) of vinylpyrrolidone (NVP), 308mg (about 2.37 mmol) of hydroxyethyl methacrylate (HEMA) are weighed out and dissolved in 100mL of isopropanol, followed by the addition of 8.2mg of dibenzoyl peroxide (BPO) and the reaction is carried out in an oil bath at 75℃for 20h under nitrogen. After the reaction is finished, spin-drying isopropanol by a rotary evaporator, precipitating and drying the product in diethyl ether to obtain a white solid P (VP-HEMA) copolymer (P02 a), wherein the structural formula is shown as a formula (100 a).
According to the chemical shift characteristic peak (-CH-N-CH) of vinyl pyrrolidone (NVP) monomer unit in formula (100 a) 2 -CH 2 -CH 2 -C (=o) -, characteristic peaks of hydrogen atoms adjacent to N3.20-3.50 ppm), characteristic peaks of chemical shift (CH) of hydroxyethyl methacrylate (HEMA) monomer units 3 -C-C(＝O)O-CH 2 -CH 2 -OH, 1.10 to 1.25ppm of methyl characteristic peak), and calculating the quantitative ratio of two monomer units of NVP and HEMA in formula (100 a) to about 19:1.
(2) The copolymer P02a (5 g) obtained above was dissolved in 100ml of N, N-dimethylformamide, after complete dissolution, 367mg of isocyanatoethyl methacrylate (about 2.37 mmol) was slowly added dropwise thereto, the reaction was carried out for 2 hours, chloroform was dried by spinning after the completion of the reaction, and the product was precipitated in diethyl ether and dried to give copolymer P (VP- (HEMA-g-IEM)), which was designated as copolymer P02, and the structure was represented by formula (100).
According to GPC measurement, the weight average molecular weight of product P02 was about 11.2kDa, and the number average molecular weight was about 4.48kDa.
According to the chemical shift characteristic peak (-CH-N-CH) of vinyl pyrrolidone (NVP) monomer unit in formula (100) 2 -CH 2 -CH 2 -C (=o) -, characteristic peaks of hydrogen atoms adjacent to N3.20-3.50 ppm), characteristic peaks of chemical positions of methacrylate groups grafted in this step (-OC (=o) -C (CH) 3 )＝CH 2 The ratio analysis of the correlation peak areas of the characteristic peaks of two hydrogen atoms on the double bond of 5.65ppm and 6.14 ppm) calculated m in the formula (100): the n ratio is about 19:1. It is estimated that the grafting ratio of isocyanatoethyl methacrylate is substantially 100%. In combination with the molecular weight results from GPC testing, m in formula (100) is about 38 and n is about 2.
EXAMPLE 3 Synthesis of a reactive hydrophilic Polymer P (VP- (HEMA-g-IEM))
In this case, a structural compound represented by the formula (100) (as shown in example 1) was prepared, and monomer units having the same structure as in example 1 were prepared in a monomer ratio of NVP: hema=7:3.
(1) 5g (about 45 mmol) of vinylpyrrolidone, 2.51g (about 19.3 mmol) of hydroxyethyl methacrylate, were weighed out in 100mL of isopropanol, and 74mg of dibenzoyl peroxide (BPO) was added thereto, followed by an oil bath under nitrogen protection at 75℃for 20 hours. After the reaction is finished, spin-drying isopropanol by a rotary evaporator, precipitating and drying the product in diethyl ether to obtain a P (VP-HEMA) copolymer, namely a copolymer P03a, wherein the structural general formula of the copolymer P03a is shown as a formula (100 a).
Intermediate P03a 1 The H NMR spectrum is shown in FIG. 3. According to the chemical shift characteristic peak (-CH-N-CH) of vinyl pyrrolidone (NVP) monomer unit in formula (100 a) 2 -CH 2 -CH 2 -C (=o) -, characteristic peaks of hydrogen atoms adjacent to N3.20-3.50 ppm), characteristic peaks of chemical shift (CH) of hydroxyethyl methacrylate (HEMA) monomer units 3 -C-C(＝O)O-CH 2 -CH 2 -OH, methyl characteristic peak 1.10-1.28 ppm), the quantitative ratio of two monomer units NVP and HEMA in formula (100 a) was calculated to be about 7:3.
(2) The copolymer P03a (5 g) obtained in the above step was dissolved in 100mL of chloroform, after complete dissolution, 3.9g of isocyanatoethyl methacrylate (IEM, about 25.2mmol, excess) was slowly added dropwise thereto, reacted for 2 hours, after the completion of the reaction, chloroform was dried by spinning, and the product was precipitated in diethyl ether and dried to obtain a P (VP- (HEMA-g-IEM)) copolymer, which was designated as copolymer P03, having the structural formula shown in formula (100).
According to GPC measurement, the weight average molecular weight of product P03 was about 12.6kDa, and the number average molecular weight was about 4.67kDa.
Product P03 1 The H nuclear magnetic resonance spectrum is shown in FIG. 4 (400 MHz, methanol-d) 4 ). According to the chemical shift characteristic peak (-CH-N-CH) of vinyl pyrrolidone (NVP) monomer unit in formula (100) 2 -CH 2 -CH 2 -C (=o) -, characteristic peaks of hydrogen atoms adjacent to N3.25-3.50 ppm, characteristic peaks of chemical positions (-OC (=o) -C (CH) of methacrylate groups grafted in this step 3 )＝CH 2 Characteristic peaks for two hydrogen atoms at double bonds of 5.65ppm and 6.14ppmAnd (2) calculating m in the formula (100) by analyzing the ratio of the relevant peak areas: the n ratio is about 7:3. It is estimated that the grafting ratio of isocyanatoethyl methacrylate is substantially 100%. In combination with the molecular weight results from GPC testing, m in formula (100) was calculated to be about 28, and n was calculated to be about 12.
EXAMPLE 4 Synthesis of a reactive hydrophilic Polymer P (VP- (HEMA-g-IEM))
In this example, a structural compound of formula (100) (as shown in example 1) was prepared, and monomer units having the same structure as in example 1, and design parameters of the structure included: monomer ratio NVP, hema=5:5.
(1) 5g (about 45 mmol) of vinylpyrrolidone, 5.86g (about 45 mmol) of hydroxyethyl methacrylate, were weighed out into 100mL of isopropanol, and then 74mg of phthalimide (BPO) was added thereto, and the mixture was reacted for 20 hours at 75℃in an oil bath under nitrogen. After the reaction is finished, spin-drying isopropanol by a rotary evaporator, precipitating and drying the product in diethyl ether to obtain a P (VP-HEMA) copolymer, namely a copolymer P04a, wherein the structural formula is shown as a formula (100 a).
Intermediate P04a 1 The H NMR spectrum is shown in FIG. 5. According to the chemical shift characteristic peak (-CH-N-CH) of vinyl pyrrolidone (NVP) monomer unit in formula (100 a) 2 -CH 2 -CH 2 -C (=o) -, characteristic peaks of hydrogen atoms adjacent to N3.15-3.50 ppm), characteristic peaks of chemical shift (CH) of hydroxyethyl methacrylate (HEMA) monomer units 3 -C-C(＝O)O-CH 2 -CH 2 OH, methyl characteristic peak 1.08-
1.26 ppm) and calculating the quantitative ratio of two monomer units of NVP and HEMA in formula (100 a) to about 5:5.
(2) The copolymer P04a (5 g) obtained above was dissolved in 100mL of chloroform, after complete dissolution, 7.1g of isocyanatoethyl methacrylate (IEM, about 45 mmol) was slowly added dropwise thereto, the reaction was completed for 2 hours, the chloroform was dried after completion of the reaction, and the product was precipitated in diethyl ether and dried to obtain a P (VP- (HEMA-g-IEM)) copolymer, which was designated as copolymer P04, having the structural formula shown in formula (100).
According to GPC measurement, the weight average molecular weight of product P04 was about 11.66kDa, and the number average molecular weight was about 4.82kDa.
Product P04 1 The H NMR spectrum is shown in FIG. 6 (400 MHz, methanol-d) 4 ). According to the chemical shift characteristic peak (-CH-N-CH) of vinyl pyrrolidone (NVP) monomer unit in formula (100) 2 -CH 2 -CH 2 -C (=o) -, characteristic peaks of hydrogen atoms adjacent to N3.25-3.55 ppm, characteristic peaks of chemical positions (-OC (=o) -C (CH) of methacrylate groups grafted in this step 3 )＝CH 2 The ratio analysis of the correlation peak areas of the characteristic peaks of two hydrogen atoms on the double bond of 5.63ppm and 6.14 ppm) calculated m in the formula (100): the n ratio is about 5:5. It is estimated that the grafting ratio of isocyanatoethyl methacrylate is substantially 100%. In combination with the molecular weight results from GPC testing, m in formula (100) is calculated to be about 20, and n is calculated to be about 20.
Coating system preparation examples 1-7: formulation of a Top coating System (coating System for preparing a Top coating)
Top coating System preparation examples 1-7: the following top coating system formulation was used to prepare top coating systems 1-7 according to the coating system formulations of tables 1-6:
(1) According to the formula, adding the metered absolute ethyl alcohol into a container with magnetic stirring, and starting stirring;
(2) According to the formulation, a metered amount of the reactive hydrophilic polymer P (VP- (HEMA-g-IEM)) is added to the vessel, stirring being continued;
(3) According to the formula, adding a metered amount of reactive monomer Rm1 into a container, and stirring for 1h in a dark place after the addition is finished;
(4) And adding an initiator (according to the formula) after stirring, stirring for 1h in a dark place, and preserving at normal temperature in a dark place for later use.
Top coating System preparation example 8: according to the formula of Table 8, the reactive parent monomer PEGDA and the photoinitiator are uniformly dissolved in absolute ethyl alcohol to prepare a top coating system 7, and the top coating system is preserved at normal temperature in a dark place for later use.
Top coating System preparation examples 9-10: according to the formulation of tables 9-10, the reactive hydrophilic polymer P (VP- (HEMA-g-IEM)) and the photoinitiator were uniformly dissolved in absolute ethanol to prepare a top coating system 8-9, which was stored at normal temperature in the absence of light for use.
TABLE 1 Top coating System 1 formulation
TABLE 2 Top coating System 2 formulation
TABLE 3 Top coating System 3 formulation
TABLE 4 Top coating System 4 formulation
TABLE 5 Top coating System 5 formulation
TABLE 6 Top coating System 6 formulation
TABLE 7 Top coating System 7 formulation
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TABLE 8 Top coating System 8 formulation
Table 9. Top coating System 9 formulation (without addition of reactive hydrophilic Polymer Poly 1)
| Top coating system raw materials | Top coating system 9 | Mass percent |
| Reactive monomer Rm1 | PEGDA 1000 | 10％ |
| Initiator (photoinitiator) | Irgacure2959 | 0.1％ |
| Solvent(s) | Absolute ethyl alcohol | 89.9％ |
TABLE 10 Top coating System 10 formulation (without reactive monomer Rm1 added)
TABLE 11 Top coating System 11 formulation (without reactive monomer Rm1 added)
EXAMPLE 5 Synthesis of IEM-PTMG-IEM
(1) 20g of polytetrahydrofuran 1000 (PTMG) were weighed out 1000 ，M n About 1000Da,20 mmol) in a 100mL round bottom flask, heating to 80 ℃ in an oil bath under the protection of nitrogen to completely dissolve, slowly dropwise adding 6.2g (about 40 mmol) of isocyanatoethyl methacrylate (IEM) into the flask, and stopping heating after 3h of nitrogen protection reaction to obtain a colorless transparent product P05 (IEM-PTMG-IEM), wherein the structural formula is shown in a formula (200), and k is about 13.
Product P05 1 The H NMR spectrum is shown in FIG. 7 (400 MHz, solvent deuterated chloroform). Peaks (-OCH) characteristic to chemical shift of tetrahydrofuran monomer units according to formula (200) 2 CH 2 CH 2 CH 2 -,4H,3.30-3.60 ppm) and-OCH 2 CH 2 CH 2 CH 2 -,4H,1.50-1.80 ppm), chemical position characteristic peak (-OC (=O) -C (CH) of methacrylate group with two end modification 3 )＝CH 2 It is also inferred from the analysis of the ratio of the peak areas of the characteristic peaks of two hydrogen atoms on the double bond of 4H, 5.59ppm and 6.12 ppm) that both ends of polytetrahydrofuran were modified with methacrylate groups. The data molecular weight of product P05 was about 1.3kDa.
EXAMPLE 6 Synthesis of IEM-PEG-IEM
(1) 40g of polyethylene glycol 2000 (PEG) was weighed out 1000 ，M n About 2000Da,20 mmol) was heated to 80℃in a 100mL round bottom flask under nitrogen protection to dissolve completely, then 6.2g (about 40 mmol) of isocyanatoethyl methacrylate (IEM) was slowly added dropwise thereto, and after 3 hours of nitrogen protection reaction, the heating was stopped to obtain colorless and transparent product P06 (IEM-PEG-IEM) having the structural formula shown in formula (300).
The product P06 is subjected to 1 H NMR test, 400MHz, solvent deuterated chloroform. According to 1 H NMR spectrum, chemical shift characteristic peak (-OCH) of ethylene glycol monomer unit in formula (300) 2 CH 2 -,4H,3.40-3.80 ppm), chemical position characteristic peak (-OC (=O) -C (CH) of methacrylate group with two end modification 3 )＝CH 2 It is also inferred from the analysis of the ratio of the peak areas of the characteristic peaks of two hydrogen atoms on the double bond of 4H, about 5.5ppm and 6.1 ppm) that both ends of the polyethylene glycol were modified with methacrylate groups. Thus, the product P06 IEM-PEG 2000 The number average molecular weight of the IEM is about 2.3kDa.
Primer coating System preparation examples 12-16: preparation of priming System (priming System for use in double-layer coating System)
Primer coating System preparation examples 12-16: the following priming systems 12-16 were prepared according to the coating system formulations of tables 12-16 using the following priming system formulation method:
(1) According to the formula, adding the metered absolute ethyl alcohol into a container with magnetic stirring, and starting stirring;
(2) Adding a metered amount of a reactive hydrophilic polymer Poly2 into the vessel according to the formulation, and continuing to stir;
(3) According to the formula, adding a metered amount of reactive monomer Rm2 into a container, and stirring for 1h in a dark place after the addition is finished;
(4) And adding an initiator (according to the formula) after stirring, stirring for 1h in a dark place, and preserving at normal temperature in a dark place for later use.
Top coating System preparation example 17: according to the formula of Table 17, the reactive parent monomer PEGDA and the photoinitiator are uniformly dissolved in absolute ethyl alcohol to prepare a base coat system 17, and the base coat system is preserved at normal temperature in a dark place for later use.
Top coating System preparation example 18: according to the formulation of Table 18, the reactive hydrophilic polymer IEM-PTMG was prepared 1000 IEM (prepared in example 4) and photoinitiator were dissolved uniformly in absolute ethanol to give a top coating system 18 which was stored at ambient temperature protected from light for use.
Table 12.
| Raw materials of bottom coating system | Primer coating system 12 | Mass percent |
| Reactive hydrophilic polymer Poly2 | IEM-PTMG-IEM (example 5) | 8％ |
| Reactive monomer Rm2 | PEGDA 1000 | 2％ |
| Initiator (photoinitiator) | Irgacure2959 | 0.1％ |
| Solvent(s) | Absolute ethyl alcohol | 89.9％ |
Table 13.
| Raw materials of bottom coating system | Primer coating system 13 | Mass percentPercentage of |
| Reactive hydrophilic polymer Poly2 | IEM-PEG 2000 IEM (example 6) | 8％ |
| Reactive monomer Rm2 | PEGDA 1000 | 2％ |
| Initiator (photoinitiator) | Irgacure2959 | 0.1％ |
| Solvent(s) | Absolute ethyl alcohol | 89.9％ |
Table 14.
| Raw materials of bottom coating system | Primer coating system 14 | Mass percent |
| Reactive hydrophilic polymer Poly2 | IEM-PTMG-IEM (example 5) | 5％ |
| Reactive monomer Rm2 | PEGDA 1000 | 5％ |
| Initiator (photoinitiator) | Irgacure2959 | 0.5％ |
| Solvent(s) | Absolute ethyl alcohol | 89.5％ |
Table 15.
| Raw materials of bottom coating system | Primer coating system 15 | Mass percent |
| Reactive hydrophilic polymer Poly2 | IEM-PTMG-IEM (example 5) | 20％ |
| Reactive monomer Rm2 | PEGDA 2000 | 10％ |
| Initiator (photoinitiator) | Irgacure2959 | 0.3％ |
| Solvent(s) | Absolute ethyl alcohol | 69.7％ |
Table 16.
| Raw materials of bottom coating system | Primer coating system 16 | Mass percent |
| Reactive hydrophilic polymer Poly2 | IEM-PTMG-IEM (example 5) | 30％ |
| Reactive monomer Rm2 | PEGTA 2400 | 19％ |
| Initiator (photoinitiator) | Irgacure2959 | 1％ |
| Solvent(s) | Absolute ethyl alcohol | 50％ |
Table 17 under-coating System 17 formulation (without addition of reactive hydrophilic Polymer Poly 2)
| Raw materials of bottom coating system | Primer coating system 17 | Mass percent |
| Reactive monomer Rm1 | PEGDA 1000 | 10％ |
| Initiator (photoinitiator) | Irgacure2959 | 0.1％ |
| Solvent(s) | Absolute ethyl alcohol | 89.9％ |
TABLE 18 under-coating System 18 formulation (without addition of reactive monomer Rm 2)
| Raw materials of bottom coating system | Primer coating system 18 | Mass percent |
| Reactive hydrophilic polymer Poly2 | IEM-PTMG 1000 IEM (example 5) | 10％ |
| Initiator (photoinitiator) | Irgacure2959 | 0.1％ |
| Solvent(s) | Absolute ethyl alcohol | 89.9％ |
Test examples coating of pipes and test of frictional force in Water
The top coating systems 1-11 in tables 1-11 are abbreviated as top coatings 1-11, respectively; the priming systems in tables 12-18 are abbreviated as priming 12-18, respectively.
1. Preparation of Single-layer hydrophilic coating (Top coating System)
A plastic base material: PEBAX tubing (tubing not modified with hydrophilic coating).
The preparation method comprises the following steps: the top coating systems of coating examples 1-8 in Table 19 were used, and the tubing was immersed in the liquid of the top coating system for 1min and exposed to light for 3min to give tubing with a single layer of hydrophilic coating. The hydrophilic coatings formed are designated as coatings 1-8, respectively.
2. Preparation of double-layer hydrophilic coating (combination of base coating system and top coating system)
A plastic base material: PEBAX tubing (tubing not modified with hydrophilic coating).
The preparation method comprises the following steps: the top coating system and the bottom coating system of coating examples 9-19 in Table 19 are adopted, (1) the pipe is immersed in the bottom coating system for 1min and exposed to ultraviolet light for 30s; (2) Immersing the pipe in a top coating system for 1min, and exposing for 3min to obtain the pipe with the double-layer hydrophilic coating. The hydrophilic coatings formed are designated as coatings 9-19, respectively.
3. Comparative example
Comparative example 1: tubing that was not modified with a hydrophilic coating.
Comparative example 2: commercial product 1, a double-layer coating system, wherein the base coat consists of waterborne polyurethane, a photoinitiator and a solvent; the top coat consists of polyvinylpyrrolidone, a cross-linking agent, an adhesion promoter PAcA, a photoinitiator and a solvent.
Comparative example 3: commercial product 2, double-layer coating system, the base coat is composed of polyamide, photoinitiator and solvent; the top coating consists of polyethylene glycol, a cross-linking agent, a photoinitiator, an adhesion promoter PAcA and a solvent.
Comparative examples 4 to 6 were conducted in substantially the same manner as in coating example 1 except that: the top coating systems 9-11 were used in place of the top coating system 1, respectively. Wherein, the reactive hydrophilic polymer Poly1 is not added to the top coating system 9, and the reactive monomer Rm1 is not added to the top coating systems 10-11.
Comparative examples 7 to 8 were conducted in substantially the same manner as in coating example 8 except that: primer systems 17-18 were used in place of primer system 12 in coating example 9, respectively. Wherein the priming system 17 is not added with the reactive hydrophilic polymer Poly2 and the priming system 18 is not added with the reactive monomer Rm2.
Test method
The test for friction, number of effective repetitions and firmness is as follows: referring to the T/CAMDI 021-2019 single-use hydrophilic coating guide wire; standard test model for evaluating YY/T1536-2017 non-intravascular catheter surface sliding performance; the method for evaluating the lubricating performance of the hydrophilic coating of the T/CSBME 021-2020 catheter; YY 0285.1-2017 intravascular catheter disposable sterile catheter first portion: the test methods mentioned in the standards of the general requirements and the like.
1. Friction test method: the hydrophilic coating sample catheter to be tested is soaked in a constant-temperature water bath for 30-60 seconds, a clamping force of 300g is set for the catheter through a friction device after the hydrophilic coating sample catheter is fully soaked, the catheter is circularly pulled for 25 times, in the process, a friction tester can display real-time data of the friction force of the catheter, a friction force-displacement curve is recorded, and a data table is automatically generated through a program. The average friction per cycle of the test catheter was compared from the friction-displacement curve analysis.
The average of the 25 cycles of average friction was calculated and recorded as the "friction" test result for the hydrophilic coating, as shown in table 18.
Physical meaning of friction: the average friction reflects the level of lubrication of the coating after curing, with smaller values indicating better lubricity of the coating.
2. Effective repetition number test: repeated test for 25 times
The method of section 1, "friction test method", was repeated 25 times under the same clamping force.
3. Fastness degree
Firmness refers to the difference between the number average of the average friction values of the last three times and the number average of the average friction values of the first three times, for 25 repeated friction tests.
Physical meaning of "firmness": reflecting the durability of the coating, the smaller the difference, the better the coating firmness.
The testing method comprises the following steps: the method of section 1, "friction test method", was repeated at least 25 times under the same clamping force.
Test results
The test results can be seen in table 19.
Among them, the single-layer hydrophilic coatings (coating examples 1 to 8) prepared using the top coating system all had a low friction level and excellent firmness. The coating efficiency was higher than that of the commercial products (comparative example 2 and comparative example 3) on the premise that the friction and the firmness were not inferior to those of the commercial products.
The double layer hydrophilic coatings (coating examples 9-18) prepared using the basecoat system and the topcoat system both have a low level of friction and excellent fastness. There was no significant difference from the commercial products (comparative example 2 and comparative example 3).
In comparative example 1, the pipe without the "hydrophilic coating" modification of the present invention had poor lubricity.
The top coating system of comparative example 4 was free of the addition of reactive hydrophilic polymer Poly1 and, as a result, was found to be poor in both lubricity and firmness. Presumably due to the failure to form a crosslinked network of coating that meets the friction and firmness requirements.
The top coating systems of comparative examples 5-6 did not add reactive monomer Rm1, and as a result, the coatings were found to fail prematurely. Presumably due to the low degree of crosslinking of the coating network.
The primer system of comparative example 7 was free of the addition of the reactive hydrophilic polymer Poly2, and as a result, it was found that the friction was high and the firmness was poor. Presumably due to the lower degree of crosslinking of the coating.
The primer system of comparative example 8 was found to have a higher friction and poor firmness without the addition of reactive monomer Rm 2. Presumably due to the lower degree of crosslinking of the coating.
Table 19.
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In Table 18, the effective number of repetitions is less than 25, indicating that at this value, the friction has reached the upper range limit of the device, and has exceeded a friction level suitable for clinical use.
The technical features of the above embodiments and examples may be combined in any suitable manner, and for brevity of description, all of the possible combinations of the technical features of the above embodiments and examples are not described, however, as long as there is no contradiction between the combinations of the technical features, they should be considered to be within the scope described in the present specification.
The above examples merely illustrate several embodiments of the present invention, which facilitate specific and detailed understanding of the technical solutions of the present invention, but should not be construed as limiting the scope of protection of the present invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Further, it is understood that various changes and modifications of the present invention may be made by those skilled in the art after reading the above teachings, and equivalents thereof are intended to fall within the scope of the present invention. It should also be understood that, based on the technical solutions provided by the present invention, those skilled in the art obtain technical solutions through logical analysis, reasoning or limited experiments, all of which are within the scope of protection of the appended claims. The scope of the patent is therefore intended to be covered by the appended claims, and the description and drawings may be interpreted as illustrative of the contents of the claims.
Claims (17)
1. A coating system comprising a hydrophilic polymer, characterized by comprising the following components in 100 parts by weight on a dry weight basis: 45 to 90 weight parts of reactive hydrophilic polymer Poly1, 9.9 to 50 weight parts of reactive monomer Rm1, 0.1 to 5 weight parts of initiator In1 and solvent So1;
the reactive hydrophilic polymer Poly1 has a general structure shown in a formula (1);
the reactive monomer Rm1 is capable of intermolecular crosslinking;
the initiator In1 is Norrish type I initiator or free radical photoinitiator;
the mass percentage of the solvent So1 in the coating system is more than or equal to 50%;
in the formula (1), the components are as follows,
m is an integer selected from 10 to 50;
n is an integer selected from 4 to 30;
the ratio of m to n is selected from 1:1 to 8:1;
each R 1 Independently a hydrophilic group;
each A 1 Independently H or C 1-19 An alkyl group;
each A 2 Independently C 1-18 An alkylene group;
each L 11 independently-O-or-NH-;
l is a divalent linking group, each L is independently a linking group containing a heteroatom selected from one or more of O, S, N and P;
each B is 2 Independently C 1-18 An alkylene group;
each L 13 independently-O-or NH;
each B is 1 Independently H or C 1-19 An alkyl group;
". Times" indicates the site of attachment to the end group;
The number average molecular weight of the reactive monomer Rm1 is 900-5000 Da.
2. The coating system of claim 1, wherein formula (1) satisfies any one or more of the following characteristics:
m is an integer selected from 15 to 40;
n is an integer selected from 4 to 20;
the ratio of m to n is selected from 1:1 to 7:3;
each R 1 independently-CHO, -COOH, -OH, -NH 2 Or (b)
Each A 1 Independently H, methyl, ethyl or C 3-6 An alkyl group;
each A 2 Independently C 2-8 An alkylene group;
L 11 is-O-;
each L is independently R-containing 0 Divalent linking group of R 0 is-O-or-NH-, and R 0 And A is a 2 Is connected with each other;
each B is 2 Independently C 2-8 An alkylene group;
L 13 is-O-;
each B is 1 Independently H, methyl, ethyl or C 3-6 An alkyl group;
the number average molecular weight of the reactive hydrophilic polymer Poly1 is selected from 1.5kDa to 15kDa.
3. The coating system of claim 1, wherein formula (1) satisfies any one or more of the following characteristics:
m is an integer selected from 20 to 28;
n is an integer selected from 12 to 20;
the ratio of m to n is selected from 1:1 to 7:3;
R 1 is that
Each A 1 Independently H or methyl;
each B is 1 Independently H or methyl;
each A 2 Independently methylene, 1, 2-ethylene, 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, 1, 6-hexylene, 1, 7-heptylene or 1, 8-octylene;
Each L is independently selected from any one of-NH-, -NH-C (=o) -NH-, -O-C (=o) -and-O-C (=o) -NH-, wherein x represents the direction a 2 Is a ligation site of (2);
each B is 2 Is independently methylene, 1, 2-ethylene, 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, 1, 6-hexylene, 1, 7-heptylene or 1, 8-octylene;
the number average molecular weight of the reactive hydrophilic polymer Poly1 is selected from 3kDa to 10kDa.
4. The coating system of claim 1, wherein one or more of the following characteristics are satisfied:
in the same molecule, R 1 Are all the same; a is that 2 Are all the same; b (B) 2 Are all the same; b (B) 1 Are all the same;
in the same molecule, L are the same;
in the same molecule, L 11 Are all the same;
in the same molecule, L 13 Are all the same;
the number average molecular weight of the reactive hydrophilic polymer Poly1 is selected from 3kDa to 6kDa.
5. The coating system of any one of claims 1-4, wherein the reactive hydrophilic polymer Poly1 has a general structure represented by formula (2):
wherein each R 3 independently-O-or-NH-.
6. The coating system of claim 5, wherein the reactive hydrophilic polymer Poly1 has a general structure represented by formula (2 b):
Wherein A is 1 Is methyl, A 2 Is 1, 2-ethylene, R 3 is-O-, B 2 Is 1, 2-ethylene, B 1 Is methyl.
7. The coating system of any one of claims 1-4, wherein one or more of the following characteristics are satisfied:
1) The reactive monomer Rm1 has a polymer chain and a plurality of reactive groups F covalently linked to the polymer chain 1 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the polymer chain in the reactive monomer Rm1 is selected from one or more structures in the group consisting of: polyethers, polyurethanes, polyethylenes, polypropylenes, polyvinylchlorides, polyethylene oxides, polyamides, polyacrylamides, poly (meth) acrylic acid, polyvinyl alcohols, polyethylenimines, polyesters and alkyd copolymers, polypeptides and polysaccharides; the reactive group F in the reactive monomer Rm1 1 One or more groups selected from the group consisting of: unsaturated bond of carbon and carbon, -NH 2 、-CONH 2 and-SH; when the reactive monomer Rm1 includes a carbon-carbon unsaturated bond, the reactive monomer Rm1 includes one or more structures of alkenyl groups, unsaturated esters, unsaturated ethers, unsaturated amides, and drying alkyds;
2) The number average molecular weight of the reactive monomer Rm1 is 900-2000 Da;
3) The initiator In1 is selected from one or more of benzoin initiator, 4-benzoyl-1, 3-dioxavaleric initiator, benzyl ketal, alpha-dialkoxyacetophenone, alpha-hydroxy alkyl benzophenone, alpha-amino alkyl benzophenone, acyl phosphorus oxide, diacyl phosphine oxide, acyl phosphine sulfide and halogenated acetophenone initiator;
4) The solvent So1 is selected from one or more of alcohol, acetone, methyl ethyl ketone, tetrahydrofuran, dichloromethane and toluene, or is a solution or emulsion formed by one or more of alcohol, acetone, methyl ethyl ketone, tetrahydrofuran, dichloromethane and toluene and water, or is water;
5) The mass percentage of the reactive hydrophilic polymer Poly1 in the dry weight of the coating system is 45-85%;
6) The mass percentage of the reactive monomer Rm1 in the dry weight of the coating system is 14.5-50%;
7) The mass percentage of the initiator In1 In the dry weight of the coating system is 0.5-5 percent;
8) The mass percentage of the reactive hydrophilic polymer Poly1 in the coating system is 4% -30%;
9) The mass percentage of the reactive monomer Rm1 in the coating system is 1.9-19%;
10 The mass percentage of the initiator In1 In the coating system is 0.05-1 percent;
11 The mass percentage of the solvent So1 in the coating system is 50-90%.
8. The coating system of claim 7, wherein one or more of the following characteristics are satisfied:
The reactive monomer Rm1 is selected from one or more of a plurality of polyethers modified by carbon-carbon unsaturated bonds; wherein the polyether modified by the plurality of carbon-carbon unsaturated bonds comprises polyethylene glycol modified by the plurality of carbon-carbon unsaturated bonds and polytetrahydrofuran modified by the plurality of carbon-carbon unsaturated bonds;
the number average molecular weight of the reactive monomer Rm1 is 900-1100 Da;
the mass percentage of the reactive hydrophilic polymer Poly1 in the dry weight of the coating system is 75-85-80%;
the mass percentage of the reactive monomer Rm1 in the dry weight of the coating system is 14.5-20%;
the mass percentage of the initiator In1 In the dry weight of the coating system is 0.5-2%;
the mass percentage of the reactive hydrophilic polymer Poly1 in the coating system is 6% -10%;
the mass percentage of the reactive monomer Rm1 in the coating system is 1-4%;
the mass percentage of the initiator In1 In the coating system is 0.05-0.15%;
the mass percentage of the solvent So1 in the coating system is 86% -90%.
9. The coating system of claim 7, wherein one or more of the following characteristics are satisfied:
1) The reactive monomer Rm1 is polyethylene glycol diacrylate or polyethylene glycol dimethacrylate;
2) The number average molecular weight of the reactive monomer Rm1 is 900-1100 Da;
3) The mass percentage of the reactive hydrophilic polymer Poly1 in the dry weight of the coating system is 47% -80%;
4) The mass percentage of the reactive monomer Rm1 in the dry weight of the coating system is 19-48%;
5) The mass percentage of the initiator In1 In the dry weight of the coating system is 0.9-5%;
6) The mass percentage of the reactive hydrophilic polymer Poly1 in the coating system is 5% -8%;
7) The mass percentage of the reactive monomer Rm1 in the coating system is 2% -5%;
8) The mass percentage of the initiator In1 In the coating system is 0.1-0.5%;
9) The mass percentage of the solvent So1 in the coating system is 86.5% -90%.
10. A bilayer coating system comprising a hydrophilic polymer, comprising a top coating system and a bottom coating system; the top coating system is selected from the hydrophilic polymer containing coating systems of any one of claims 1 to 9.
11. The two-layer coating system according to claim 10, characterized in that the primer coating system comprises the following components, based on 100 parts by weight of dry weight: 45 to 90 weight parts of reactive hydrophilic polymer Poly2, 9.9 to 50 weight parts of reactive monomer Rm2, 0.1 to 5 weight parts of initiator In2 and solvent So2;
The reactive hydrophilic polymer Poly2 has a general structure shown in a formula (4)
The reactive monomer Rm2 is capable of intermolecular crosslinking, the reactive monomer Rm2 having a polymer chain and a plurality of reactive groups F covalently linked to the polymer chain 2 ；
The initiator In2 is Norrish type I initiator or free radical photoinitiator;
the mass percentage of the solvent So2 in the bottom coating system is more than or equal to 50%;
in the formula (4), the amino acid sequence of the compound,
each X is independently-O-or-NH-or-N (CH) 3 )-；
Each Z is independently C 1-18 An alkylene group;
L 21 and L 22 Each independently selected from: absence, -C (=o) -and-C (=o) NH-; wherein X is directed to X;
B 21 and B 22 Each independently is C 1-18 An alkylene group;
L 31 and L 32 Each independently is-O-or-NH-;
B 11 and B 12 Each independently is H, methyl, ethyl or C 3-6 An alkyl group;
k is an integer selected from 1 to 220.
12. The bilayer coating system of claim 11, wherein formula (4) satisfies one or more of the following characteristics:
each X is independently-O-;
each Z is independently 1, 2-ethylene or 1, 4-butylene;
L 21 and L 22 All are-C (=o) NH-; wherein X is directed to X;
B 21 and B 22 Each independently is methylene, 1, 2-ethylene, 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, 1, 6-hexylene, 1, 7-heptylene, or 1, 8-octylene;
B 11 And B 12 Each independently is H or methyl;
k is an integer selected from 2 to 100;
the number average molecular weight of the reactive hydrophilic polymer Poly2 is 500-5000 Da.
13. The bilayer coating system of claim 11, wherein the coating composition comprises,
k is an integer selected from 4 to 50;
the reactive monomer Rm2 has a polymer chain and a plurality of reactive groups F covalently linked to the polymer chain 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the polymer chain in the reactive monomer Rm2 is selected from one or more structures in the group consisting of: polyether, polyurethane, polyethylene, polypropylene, polyvinyl chloride, polyethylene oxide, polyamide,Polyacrylamides, poly (meth) acrylic acid, polyvinyl alcohol, polyethylenimine, polyesters and alkyd copolymers, polypeptides and polysaccharides; the reactive group F in the reactive monomer Rm2 2 One or more groups selected from the group consisting of: unsaturated bond of carbon and carbon, -NH 2 、-CONH 2 and-SH; when the reactive monomer Rm2 comprises a carbon-carbon unsaturation, the reactive monomer Rm2 comprises one or more structures of alkenyl groups, unsaturated esters, unsaturated ethers, unsaturated amides, and drying alkyds;
the number average molecular weight of the reactive monomer Rm2 is 600-4000 Da;
The initiator In2 is selected from one or more of benzoin initiator, 4-benzoyl-1, 3-dioxavaleric initiator, benzyl ketal, alpha-dialkoxyacetophenone, alpha-hydroxy alkyl benzophenone, alpha-amino alkyl benzophenone, acyl phosphorus oxide, diacyl phosphine oxide, acyl phosphine sulfide and halogenated acetophenone initiator;
the solvent So2 is selected from one or more of alcohol, acetone, methyl ethyl ketone, tetrahydrofuran, dichloromethane and toluene, or is a solution or emulsion formed by one or more of alcohol, acetone, methyl ethyl ketone, tetrahydrofuran, dichloromethane and toluene and water, or is water;
the mass percentage of the reactive hydrophilic polymer Poly2 in the dry weight of the priming coating system is 75-85%;
the mass percentage of the reactive monomer Rm2 in the dry weight of the priming coating system is 14.5-20%;
the mass percentage of the initiator In2 In the dry weight of the priming coating system is 0.5-2%;
the mass percentage of the reactive hydrophilic polymer Poly2 in the priming coating system is 4% -30%;
the mass percentage of the reactive monomer Rm2 in the primer coating system is 1.9-19%;
The mass percentage of the initiator In2 In the primer coating system is 0.05% -1%;
the mass percentage of the solvent So2 in the priming coating system is 50% -90%.
14. The bilayer coating system of claim 13, wherein one or more of the following characteristics are satisfied:
k is an integer selected from 7 to 20;
the reactive monomer Rm2 is selected from one or more of a plurality of polyethers modified by carbon-carbon unsaturated bonds; wherein the polyether modified by the plurality of carbon-carbon unsaturated bonds comprises polyethylene glycol modified by the plurality of carbon-carbon unsaturated bonds and polytetrahydrofuran modified by the plurality of carbon-carbon unsaturated bonds;
the number average molecular weight of the reactive monomer Rm2 is 800-2000 Da;
the reactive monomer Rm2 is polyethylene glycol diacrylate or polyethylene glycol dimethacrylate;
the mass percentage of the reactive hydrophilic polymer Poly2 in the dry weight of the priming coating system is 47% -80%;
the mass percentage of the reactive monomer Rm2 in the dry weight of the priming coating system is 19-48%;
the mass percentage of the initiator In2 In the dry weight of the priming coating system is 0.9-5%;
the mass percentage of the reactive hydrophilic polymer Poly2 in the priming coating system is 5% -8%;
The mass percentage of the reactive monomer Rm2 in the primer coating system is 2% -5%;
the mass percentage of the initiator In2 In the primer coating system is 0.1-0.5%;
the mass percentage of the solvent So2 in the priming coating system is 86.5% -90%.
15. Hydrophilic coating, characterized in that it is prepared according to the hydrophilic polymer-containing coating system according to any one of claims 1 to 9 or according to the hydrophilic polymer-containing bilayer coating system according to any one of claims 10 to 14.
16. Use of a hydrophilic polymer containing coating system according to any one of claims 1 to 9, or a hydrophilic polymer containing bilayer coating system according to any one of claims 10 to 14, for the preparation of a hydrophilic lubricating layer for a medical device, or use of a hydrophilic coating according to claim 15 as a hydrophilic lubricating layer for a medical device.
17. The use of claim 16, wherein the hydrophilic coating is laminated to the surface of the plastic substrate of the implantable medical device.
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| US5135297A (en) * | 1990-11-27 | 1992-08-04 | Bausch & Lomb Incorporated | Surface coating of polymer objects |
| AR009439A1 (en) * | 1996-12-23 | 2000-04-12 | Novartis Ag | AN ARTICLE THAT INCLUDES A SUBSTRATE WITH A PRIMARY POLYMERIC COATING THAT CARRIES REACTIVE GROUPS PREDOMINANTLY ON ITS SURFACE, A METHOD FOR PREPARING SUCH AN ARTICLE, AN ARTICLE THAT HAS A HYBRID-TYPE COATING AND A CONTACT LENS |
| US6723815B2 (en) * | 1999-09-02 | 2004-04-20 | Alcon, Inc. | Covalently-bound, hydrophilic coating compositions for surgical implants |
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| CN102597028B (en) * | 2009-10-29 | 2015-07-01 | 关西涂料株式会社 | Copolymer, aqueous coating composition containing copolymer, and method for forming multilayer coating film |
| CN103709691B (en) * | 2012-10-09 | 2016-11-23 | 上海微创医疗器械（集团）有限公司 | Biodegradable crosslinking polymer and preparation method thereof |
| CN110845666B (en) * | 2019-11-07 | 2022-03-04 | 北京美中双和医疗器械股份有限公司 | Functionalized hydrophilic polymer, hydrophilic coating solution and medical catheter comprising the same |
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