CN116478439A - Application of functional isocyanate crosslinking agent in surface modification of polyvinyl chloride material - Google Patents
Application of functional isocyanate crosslinking agent in surface modification of polyvinyl chloride material Download PDFInfo
- Publication number
- CN116478439A CN116478439A CN202310485543.6A CN202310485543A CN116478439A CN 116478439 A CN116478439 A CN 116478439A CN 202310485543 A CN202310485543 A CN 202310485543A CN 116478439 A CN116478439 A CN 116478439A
- Authority
- CN
- China
- Prior art keywords
- polyvinyl chloride
- functional isocyanate
- crosslinking agent
- general formula
- isocyanate crosslinking
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 172
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 172
- 239000000463 material Substances 0.000 title claims abstract description 78
- 239000012948 isocyanate Substances 0.000 title claims abstract description 57
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 57
- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 52
- 230000004048 modification Effects 0.000 title claims abstract description 25
- 238000012986 modification Methods 0.000 title claims abstract description 25
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 22
- 229920000570 polyether Polymers 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229940117986 sulfobetaine Drugs 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 31
- 239000012528 membrane Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- -1 Hydrocarbyl radicals Chemical class 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 17
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 8
- 229920001228 polyisocyanate Polymers 0.000 claims description 8
- 239000005056 polyisocyanate Substances 0.000 claims description 8
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 8
- 125000000743 hydrocarbylene group Chemical group 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000003085 diluting agent Substances 0.000 claims description 6
- 230000000051 modifying effect Effects 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000004971 Cross linker Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 239000008280 blood Substances 0.000 claims description 5
- 210000004369 blood Anatomy 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 5
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- 230000002152 alkylating effect Effects 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000009832 plasma treatment Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims description 2
- UPYPTOCXMIWHSG-UHFFFAOYSA-N 1-dodecylsulfanyldodecane Chemical compound CCCCCCCCCCCCSCCCCCCCCCCCC UPYPTOCXMIWHSG-UHFFFAOYSA-N 0.000 claims description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- FKPSBYZGRQJIMO-UHFFFAOYSA-M benzyl(triethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC1=CC=CC=C1 FKPSBYZGRQJIMO-UHFFFAOYSA-M 0.000 claims description 2
- 230000001680 brushing effect Effects 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 210000000056 organ Anatomy 0.000 claims description 2
- RFIOZSIHFNEKFF-UHFFFAOYSA-M piperazine-1-carboxylate Chemical compound [O-]C(=O)N1CCNCC1 RFIOZSIHFNEKFF-UHFFFAOYSA-M 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims 1
- 125000002947 alkylene group Chemical group 0.000 claims 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 8
- 230000004913 activation Effects 0.000 abstract description 7
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 7
- 230000010100 anticoagulation Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 238000005461 lubrication Methods 0.000 abstract description 3
- 125000006850 spacer group Chemical group 0.000 abstract description 2
- 238000010382 chemical cross-linking Methods 0.000 abstract 1
- 238000009736 wetting Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 17
- 235000019441 ethanol Nutrition 0.000 description 6
- HTTJABKRGRZYRN-UHFFFAOYSA-N Heparin Chemical compound OC1C(NC(=O)C)C(O)OC(COS(O)(=O)=O)C1OC1C(OS(O)(=O)=O)C(O)C(OC2C(C(OS(O)(=O)=O)C(OC3C(C(O)C(O)C(O3)C(O)=O)OS(O)(=O)=O)C(CO)O2)NS(O)(=O)=O)C(C(O)=O)O1 HTTJABKRGRZYRN-UHFFFAOYSA-N 0.000 description 5
- 229920000669 heparin Polymers 0.000 description 5
- 229960002897 heparin Drugs 0.000 description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 229960003237 betaine Drugs 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000033444 hydroxylation Effects 0.000 description 2
- 238000005805 hydroxylation reaction Methods 0.000 description 2
- YHHSONZFOIEMCP-UHFFFAOYSA-O phosphocholine Chemical compound C[N+](C)(C)CCOP(O)(O)=O YHHSONZFOIEMCP-UHFFFAOYSA-O 0.000 description 2
- 229950004354 phosphorylcholine Drugs 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 230000002485 urinary effect Effects 0.000 description 2
- 230000004584 weight gain Effects 0.000 description 2
- 235000019786 weight gain Nutrition 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000001631 haemodialysis Methods 0.000 description 1
- 229940003953 helium / oxygen Drugs 0.000 description 1
- 230000000322 hemodialysis Effects 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- YFRQBLYSYSHFLU-UHFFFAOYSA-N n-ethyl-n-[2-(hydroxyamino)ethyl]hydroxylamine Chemical compound CCN(O)CCNO YFRQBLYSYSHFLU-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/04—Macromolecular materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/467—Compounds containing quaternary nitrogen atoms derived from polyamines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/53—Polyethers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/22—Polymers or copolymers of halogenated mono-olefins
Abstract
The invention provides a functional isocyanate cross-linking agent for surface modification of polyvinyl chloride materials. The functional isocyanate crosslinking agent has a polyether chain in a molecular structure, and two ends of the polyether chain are respectively connected with sulfobetaine and isocyanate groups. Wherein the isocyanate group can carry out chemical crosslinking modification on the polyvinyl chloride material with the surface subjected to activation treatment; meanwhile, isocyanate groups are used as spacer arms, and sulfobetaine units are bonded on the surface of the polyvinyl chloride material in a comb-shaped manner through polyether chains, so that the polyvinyl chloride surface has strong hydrophilicity, wet lubrication after water wetting, conductivity, antibacterial property, fog resistance, pollution resistance, anticoagulation and mechanical property enhancement effects.
Description
Technical Field
The invention relates to application of a functional isocyanate cross-linking agent in surface modification of a polyvinyl chloride material, in particular to application of the functional isocyanate cross-linking agent containing disulfobetaine, gemini quaternary ammonium salt and polyether chains in molecular structure in hydrophilic, antibacterial, anticoagulation and biocompatibility enhancement of the surface of the polyvinyl chloride material, and belongs to the field of functional polymer materials.
Technical Field
Polyvinyl chloride is a thermoplastic synthetic material with excellent mechanical properties and low cytotoxicity, and is commonly used as a production raw material for medical catheters, hemodialysis pipe fittings, blood storage bags, urine storage bags and the like due to low cost, but the hydrophobicity of the surface of the polyvinyl chloride material influences the contact of human tissues or blood with water lubrication of the human tissues or blood. When other types such as polyvinyl chloride catheters are placed on a human body for a long time, it is a frequent occurrence that infection is caused by bacteria adhering to and growing on the surface of the catheters. For this reason, the problems of hydrophilicity, antibacterial property, biocompatibility, anticoagulation and the like of the surface of the polyvinyl chloride material are constantly researched and developed.
The main method for improving the hydrophilicity, antibacterial property, anticoagulation and biocompatibility of the surface of the polyvinyl chloride material is to graft three hydrophilic substances such as polyethylene glycol, carboxyl betaine/sulfobetaine/phosphorylcholine or heparin on the surface of the polyvinyl chloride material. Polyethylene glycol is a hydrophilic polymer, and is widely applied to antibacterial adhesion on the surface of polyvinyl chloride materials due to good antibacterial adhesion performance. The principle is that the polyvinyl chloride material can form a hydration layer by combining a large number of water molecules through hydrogen bonds on the surface of the polyvinyl chloride material, and the hydration layer is a physical barrier for protein and microorganism adhesion, so that adhesion, colonization and growth of bacteria on the surface of the polyvinyl chloride material can be effectively prevented. The zwitterions containing units such as carboxybetaines, sulfobetaines or phosphorylcholine have higher hydrophilicity and biocompatibility, and generate hydration layers through strong interaction between ion solvation and water molecules instead of hydrogen bonds used by polyethylene glycol to bond with water molecules. Meanwhile, the exposure of negative charges also shows that the negative charge carrying proteins and bacteria are repulsed with each other like poles, so that the zwitterionic units are grafted on the surface of the polyvinyl chloride, and the polyvinyl chloride shows remarkable antifouling function. Heparin is a polysaccharide molecule containing a large number of sulfonic acid groups and carboxyl groups and being unevenly distributed, the molecular weight of the heparin is about 20000, the sulfur content is about 9-12.9%, the heparin is acidic, and the heparin is easy to absorb moisture and dissolve in water, and has excellent anticoagulation performance.
To date, many reports have been made to confirm the chemical modification of polyvinyl chloride materials after surface activation treatment, which is the preferred method for maintaining the surface modification firmness of polyvinyl chloride materials. The surface activation treatment of polyvinyl chloride material mainly comprises (1) the surface activation treatment of polyvinyl chloride material in O 2 、NH 3 Performing plasma treatment in a mixed atmosphere of air, helium/oxygen or argon/oxygen and the like to obtain the activation effect of surface hydroxylation, amination or carboxylation; (2) also, polyvinyl chloride materials are immersed in dilute alkali liquor for alkali hydrolysis treatment, so that the activation effect of surface hydroxylation is obtained; (3) the surface of the activated polyvinyl chloride is treated by a silane coupling agent, and O-H, NH is introduced on the surface 2 Functional groups such as epoxy, NCO, c=c double bond, etc., and then covalently or graft-polymerizing to attach the hydrophilic material.
According to the molecular design principle, the inventor designs a functional isocyanate cross-linking agent applied to the modification of the surface of a polyvinyl chloride material by fusing the surface structural characteristics of surface-activated polyvinyl chloride, the structural characteristics of polyethylene glycol and sulfobetaine and the functional application. The functional isocyanate crosslinking agent is a functional isocyanate crosslinking agent containing double sulfobetaines, gemini quaternary ammonium salt and polyether chains, wherein both ends of the polyether chains in the molecular structure are respectively connected with the sulfobetaines, the quaternary ammonium salt and isocyanate groups. Wherein the isocyanate groups can carry out covalent bonding on the polyvinyl chloride material with the surface subjected to the activation treatment; meanwhile, isocyanate groups are used as spacer arms, and sulfobetaine and gemini quaternary ammonium salt are bonded on the surface of the polyvinyl chloride material in a brush-like manner through polyether chains, so that the polyvinyl chloride surface is endowed with the effects of strong hydrophilicity, wet lubrication, conductivity, antibacterial property, fog resistance, pollution resistance, anticoagulation and mechanical property enhancement. The functional isocyanate crosslinking agent is used for modifying the surface of the polyvinyl chloride material, is simple and convenient to implement, and has obvious modifying effect.
Disclosure of Invention
The invention provides a functional isocyanate crosslinking agent containing disulfobetaine, gemini quaternary ammonium salt and polyether chain in a molecular structure, which is applied to the modification of the surface of a polyvinyl chloride material, and is realized by adopting the following steps: at room temperature, immersing the surface-activated polyvinyl chloride material into a functional isocyanate crosslinking agent solution containing disulfobetaine, gemini quaternary ammonium salt and polyether chains in a molecular structure, and uniformly dipping the surface-activated polyvinyl chloride material fully; or spraying, rolling and brushing the functional isocyanate cross-linking agent solution on the surface-activated polyvinyl chloride material, then sending the polyvinyl chloride material into a reactor at 60-130 ℃ for heat treatment for 0.2-20 hours, and then taking out and cooling the polyvinyl chloride material to prepare the polyvinyl chloride material with the surface bonded with the disulfobetaine, the gemini quaternary ammonium salt and the polyether chain, which is called as the surface-modified polyvinyl chloride material.
Wherein the surface activated polyvinyl chloride material refers to a surface clean polyvinyl chloride material which generates-OH (hydroxyl) groups or-NH on the surface of the clean polyvinyl chloride material after plasma treatment in a plasma chamber with oxygen, ammonia or air atmosphere, wherein the gas pressure in the chamber is 30-50 Pa, the temperature in the chamber is 10-40 ℃, the power of a radio frequency power supply is 50-500 watts, and the irradiation time is 50-500 seconds 2 An (amino) group, known as a surface-activated polyvinyl chloride material; or immersing the surface clean polyvinyl chloride material into alkali solution with the mass percentage concentration of 0.01-10%, carrying out ultrasonic hydrolysis for 2-200 minutes at room temperature, taking out, using deionized water to wash to neutrality, and carrying out vacuum drying at 60 ℃, wherein-OH (hydroxyl) groups are generated on the surface of the clean polyvinyl chloride material, namely the surface activated polyvinyl chloride material.
The clean polyvinyl chloride material is prepared by sequentially washing a polyvinyl chloride raw material with ethanol and deionized water, and vacuum drying at a temperature of 60 ℃ to constant weight;
wherein the polyvinyl chloride raw material comprises one of polyvinyl chloride artificial organs, a polyvinyl chloride catheter, a polyvinyl chloride blood storage bag, a polyvinyl chloride vessel, polyvinyl chloride foam, a polyvinyl chloride film, a polyvinyl chloride filter membrane, a polyvinyl chloride filter screen, a polyvinyl chloride non-woven fabric or a polyvinyl chloride fiber.
The alkali solution refers to one of potassium hydroxide, sodium hydroxide, N, N, N-trimethyl-N-benzyl ammonium hydroxide, N, N, N-triethyl-N-benzyl ammonium hydroxide or aqueous solution of N, N, N, N-tetrabutylammonium hydroxide.
The functional isocyanate crosslinking agent has a structure shown in a general formula (A):
wherein R in formula (A) is selected from H or methyl, R 1 And R is 2 Respectively selected from C 1 ～C 18 A hydrocarbon group, n is selected from natural numbers between 1 and 2000,and Y is independently selected from C 1 ～C 18 Hydrocarbylene,/->Selected from C 1 ～C 18 Hydrocarbylene or->Q is selected from C 1 ～C 18 Hydrocarbyl radicals or->Wherein p is selected from natural numbers between 0 and 2000, X - Refers to Cl - 、Br - 、I - Or p-CH 3 C 6 H 4 SO 3 - One of them.
The weight percentage concentration of the functional isocyanate crosslinking agent in the functional isocyanate crosslinking agent solution is 0.5-50%, and the dosage of the functional isocyanate crosslinking agent solution is 5-500% of the weight of the surface activated polyvinyl chloride material.
The preparation of the functional isocyanate crosslinking agent comprises the following steps: at room temperature, dihydroxydiamine of the general formula (B) is dissolved in an organic solvent, stirring is started, the acryloyloxy polyether sulfobetaine is slowly added, the dosage of the acryloyloxy polyether sulfobetaine is 2.0-2.2 times of the molar quantity of the general formula (B), and after the material addition of the acryloyloxy polyether sulfobetaine is finished, the reaction temperature is increased to 50-90 ℃ and the reaction is carried out for 2-20 hours; maintaining the reaction temperature, adding an alkylating reagent into the reaction system, wherein the dosage of the alkylating reagent is 1.8-2.2 times of the molar quantity of the general formula (B), and reacting for 2-20 hours; sequentially adding a catalyst, a diluent and polyisocyanate into a reaction system, continuing to perform heat preservation and stirring reaction, detecting that the NCO content in materials in a reactor accords with a preset value, and cooling the reaction product system to room temperature to prepare a solution of a functional isocyanate crosslinking agent containing disulfobetaine, gemini quaternary ammonium salt and polyether chains in a molecular structure.
Wherein the general formula (B) refers to dihydroxydiamine having a structure represented by the general formula (B):
wherein in the general formula (B)Selected from C 1 ～C 18 Hydrocarbylene or->Wherein p is selected from a natural number between 0 and 2000 and Y is selected from C 1 ～C 18 Hydrocarbylene groups.
The acryloyloxy polyether sulfobetaine has a structure shown in a general formula (C):
wherein R in formula (C) is selected from H or methyl, R 1 And R is 2 Respectively selected from C 1 ～C 18 And (3) hydrocarbon group, wherein n is selected from natural numbers between 1 and 2000.
The organic solvent is one or more than two of tetrahydrofuran, 1, 4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide, N-diethylformamide or hexamethylphosphoramide; the dosage of the organic solvent is 1 to 10 times of the mass of the dihydroxydiamine in the general formula (B).
The catalyst refers to a compound of organotin and organic amine; wherein the organotin refers to one of dibutyl tin dilaurate, stannous octoate, stannous oxalate, dibutyl tin dimaleate, dibutyl tin di (dodecyl sulfide) or dibutyl tin diacetate; the organic amine refers to one of triethylamine, p-dimethylaminopyridine, N-dimethylformamide, triethylene diamine, dialkyl piperazine, alkyl imidazole, 1, 8-diazabicyclo [5.4.0] undec-7-ene, triethylene diamine carboxylate, dialkyl piperazine carboxylate or alkyl imidazole carboxylate; the mass ratio of the organic tin to the organic amine is 1:0-1.5; the catalyst is used in an amount of 0.05 to 5% by mass of the polyisocyanate of the general formula (D).
The polyisocyanate has a structure represented by the general formula (D):
wherein q in the general formula (D) is selected from positive integers of 1 to 5, saidSelected from C 1 ～C 18 Hydrocarbylene radicals;
the amount of the polyisocyanate is 2.02 to 2.25 times the molar amount of the dihydroxydiamine of the general formula (B).
The diluent is one or more than two of acetone, butanone, cyclohexanone, methyl acetate, ethyl acetate, diethyl ether, tetrahydrofuran, 1, 4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, toluene, xylene, dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide, N-diethylformamide or hexamethylphosphoramide; the amount of the diluent is 1 to 10 times of the mass of the dihydroxydiamine in the general formula (B).
The invention provides N in the molecular structure of the functional isocyanate crosslinking agent containing the disulfobetaine, the gemini quaternary ammonium salt and the polyether chain + Upper R 1 And R is 2 Can be selected from C along with the change of the performance according to the actual functional modification requirement of the polyvinyl chloride material 1 ～C 18 A hydrocarbon group; secondly, if the main purpose is to crosslink and strengthen the tensile strength of the polyvinyl chloride material, whereinAnd the polyether chain of the acryloxypolyether betaine of the general formula (C) can be chosen to be shorter; if the modification is mainly aimed at hydrophilic, anti-fouling, biocompatible etc., said +.>And the polyether chain in the acryloxypolyether betaine of the general formula (C) can be selected to be longer. The concentration of the modified polyvinyl chloride material by using the functional isocyanate crosslinking agent solution is adjustable, and the number of modification treatment times can be increased and reduced. In summary, the invention provides a flexible and effective preferred method for modifying the surface of the polyvinyl chloride material by using the functional isocyanate crosslinking agent.
Detailed Description
For a further understanding of the present invention, it is to be understood that the present invention is specifically described by way of examples, and is for the purpose of better understanding of the present invention. Therefore, the use of the functional isocyanate crosslinking agent not shown in the examples for the surface modification of polyvinyl chloride materials should not be construed as limiting the scope of the invention.
Example 1 modified polyvinyl chloride film (I-1)
Preparing and activating a polyvinyl chloride membrane: 5 g of SH-200 polyvinyl chloride powder produced by Shanghai chloralkali chemical industry Co., ltd are dissolved in 55 g of tetrahydrofuran to prepare a solution, the polyvinyl chloride solution is poured into a flat-plate mold, after the solvent is naturally volatilized completely, a film with the thickness of 0.2mm is prepared, a film with the thickness of 80mm is sheared, ultrasonic washing is sequentially carried out by using ethanol and deionized water, and vacuum drying is carried out at 60 ℃ for 10 hours, thus obtaining the surface clean polyvinyl chloride film.
Placing the surface clean polyvinyl chloride membrane into a plasma chamber, wherein O is arranged in the chamber 2 The pressure is 30 Pa, the temperature in the chamber is 35 ℃, the power of the radio frequency power supply is 100 watts, and the irradiation time is 100 seconds, so that the surface activated polyvinyl chloride membrane is prepared.
Preparation of functional isocyanate crosslinker solution of formula (A-1): dissolving 20 g of N, N' -dihydroxyethyl ethylenediamine in 180 g of tetrahydrofuran, putting the mixture into a reaction kettle, starting stirring, slowly adding 90 g of formula (c-1) at room temperature, heating to 45-50 ℃, reacting for 4 hours, adding 28 g of benzyl chloride into the reaction kettle, heating to 70 ℃ for reacting for 12 hours, putting 0.22 g of dibutyl tin dilaurate, 0.15 g of triethylenediamine, 120 g of toluene and 45 g of toluene diisocyanate into the reaction kettle, continuously stirring and preserving heat for reacting, detecting that the NCO value in a reaction product system is within the range of 4.55-4.88%, and cooling to stop the reaction to obtain the solution of the isocyanate cross-linking agent with the structure of the formula (A-1) and containing disulfobetaine, gemini quaternary ammonium salt and polyether chains.
The infrared spectrum test shows that the product of the formula (A-1) has strong NCO peak near 2270nm, characteristic absorption peak belonging to carbamate N-H at 3482nm and characteristic carbamate C=O at 1726nm, and the structural characteristic of the formula (A-1) is met, and the chemical structure of the product is confirmed to be identical with the theoretical design of the formula (A-1). The percentage content of isocyanate groups in the solution of the isocyanate crosslinking agent containing the disulfo-betaine and having the structure shown in the formula (1) is detected by using a method specified in GB/T29493.6-2013 to be 4.78 percent.
Surface modification of polyvinyl chloride membrane: at room temperature, immersing the surface-activated polyvinyl chloride membrane into the functional isocyanate crosslinking agent solution of the formula (A-1), uniformly dipping the surface-activated polyvinyl chloride membrane fully, then sending the surface-activated polyvinyl chloride membrane into a reactor at 80-90 ℃ for 6 hours, and then taking out the surface-activated polyvinyl chloride membrane for cooling to obtain the surface-modified polyvinyl chloride membrane I-1.
After diluting the functional isocyanate crosslinking agent solution of the formula (A-1) by 1 time by using ethylene glycol dimethyl ether, treating the polyvinyl chloride membrane to be modified by adopting the same method to prepare the surface modified polyvinyl chloride membrane I-2.
And diluting the functional isocyanate crosslinking agent solution of the formula (1) by using ethylene glycol dimethyl ether for 1 time, and repeatedly treating the modified polyvinyl chloride membrane I-2 by adopting the same method to prepare the surface secondary modified polyvinyl chloride membrane I-3.
Example 2 modified polyvinyl chloride film (II-1)
Preparing a functional isocyanate crosslinking agent of formula (2): according to the method and operation procedure of example 1, N' -dihydroxyethyl ethylenediamine in example 1 was changed to N, N-bis (6-hydroxyhexyl) -p-xylylenediamine, formula (c-1) was changed to formula (c-2), benzyl chloride was changed to methoxypolyethylene glycol-2000 p-toluenesulfonate, and toluene diisocyanate was changed to diphenylmethane diisocyanate, to prepare a solution of the functional isocyanate crosslinking agent of formula (2).
Through infrared spectrum test, strong peak of NCO appears near 2271nm of IR spectrum of formula (A-2), characteristic absorption peak belonging to carbamate N-H appears at 3487nm, characteristic peak of carbamate C=O appears at 1728nm, structural feature of formula (A-2) is met, and chemical structure of product is confirmed to be identical with theoretical design of formula (A-2). The percentage content of isocyanate groups in the functional isocyanate crosslinking agent solution of the formula (A-2) is detected to be 1.32% by adopting a GB/T29493.6-2013 stipulated method.
Surface modification of polyvinyl chloride membrane: and (3) immersing the surface-activated polyvinyl chloride membrane into the functional isocyanate crosslinking agent solution of the formula (A-2) at room temperature, uniformly dipping and standing for 3 minutes, then sending the surface-activated polyvinyl chloride membrane into a reactor at 80-90 ℃ for 10 hours, and then taking out and cooling the surface-activated polyvinyl chloride membrane to obtain the modified polyvinyl chloride membrane II-1.
Example 3 modified polyvinyl chloride urinary catheter (I-1)
According to the method and procedure of example 1, a polyvinyl chloride catheter manufactured by Jiangsu Jiading Cheng medical instruments Co., ltd was ultrasonically washed with ethanol and deionized water in sequence, and vacuum-dried at 60℃for 10 hours to obtain a surface-cleaned polyvinyl chloride catheter.
Placing the surface cleaning polyvinyl chloride catheter into a plasma chamber, wherein O is arranged in the chamber 2 The pressure is 40 Pa, the temperature in the chamber is 25 ℃, the power of the radio frequency power supply is 100 watts, and the irradiation time is 100 seconds, so that the surface activated polyvinyl chloride catheter is prepared.
At room temperature, immersing the surface-activated polyvinyl chloride catheter into the functional isocyanate cross-linking agent solution of the formula (A-1), uniformly dipping the surface-activated polyvinyl chloride catheter fully, feeding the surface-activated polyvinyl chloride catheter into a reactor at 80-90 ℃ for 10 hours, and then taking out the surface-activated polyvinyl chloride catheter for cooling to obtain the modified polyvinyl chloride catheter I-1.
Example 4 modified polyvinyl chloride urinary catheter (II-1)
According to the method and procedure of example 1, a polyvinyl chloride catheter manufactured by Jiangsu Jiading Cheng medical instruments Co., ltd was ultrasonically washed with ethanol and deionized water in sequence, and vacuum-dried at 60℃for 10 hours to obtain a surface-cleaned polyvinyl chloride catheter.
Placing the surface cleaning polyvinyl chloride catheter into a plasma chamber, wherein O is arranged in the chamber 2 The pressure is 40 Pa, the temperature in the chamber is 25 ℃, the power of the radio frequency power supply is 100 watts, and the irradiation time is 150 seconds, so that the surface activated polyvinyl chloride catheter is prepared.
At room temperature, immersing the surface-activated polyvinyl chloride catheter into the functional isocyanate cross-linking agent solution of the formula (A-2), uniformly dipping the surface-activated polyvinyl chloride catheter fully, feeding the surface-activated polyvinyl chloride catheter into a reactor at 80-90 ℃ for 10 hours, and then taking out the surface-activated polyvinyl chloride catheter for cooling to obtain the modified polyvinyl chloride catheter II-1.
Example 5 modified polyvinyl chloride fishing net (I-1)
According to the method and procedure of example 1, polyvinyl chloride fishing net produced by star plastics Co., ltd. In Liyun Kong, was sequentially ultrasonically washed with ethanol and deionized water, and vacuum-dried at 60℃for 10 hours to obtain a surface-cleaned polyvinyl chloride fishing net.
Placing the surface clean polyvinyl chloride fishing net into a plasma chamber, wherein O is arranged in the chamber 2 The pressure is 30 Pa, the temperature in the chamber is 25 ℃, the power of the radio frequency power supply is 100 watts, and the irradiation time is 80 seconds, so that the surface activated polyvinyl chloride fishing net is prepared.
At room temperature, immersing the surface-activated polyvinyl chloride fishing net into the functional isocyanate crosslinking agent solution of the formula (1), uniformly dipping and fully feeding the solution into a reactor at 80-90 ℃ for 10 hours, and then taking out and cooling the solution to obtain the modified polyvinyl chloride fishing net I-1.
Example 6 modified polyvinyl chloride fishing net (II-1)
According to the method and procedure of example 1, polyvinyl chloride fishing net produced by star plastics Co., ltd. In Liyun Kong, was sequentially ultrasonically washed with ethanol and deionized water, and vacuum-dried at 60℃for 10 hours to obtain a surface-cleaned polyvinyl chloride fishing net.
Placing the surface clean polyvinyl chloride fishing net into a plasma chamber, wherein O is arranged in the chamber 2 The pressure is 30 Pa, the temperature in the chamber is 25 ℃, the power of the radio frequency power supply is 100 watts, and the irradiation time is 100 seconds, so that the surface activated polyvinyl chloride fishing net is prepared.
At room temperature, immersing the surface-activated polyvinyl chloride fishing net into the functional isocyanate crosslinking agent solution of the formula (A-2), uniformly dipping the surface-activated polyvinyl chloride fishing net fully, feeding the surface-activated polyvinyl chloride fishing net into a reactor at 80-90 ℃ for 10 hours, and then taking out the surface-activated polyvinyl chloride fishing net and cooling the surface-activated polyvinyl chloride fishing net to obtain the modified polyvinyl chloride fishing net II-1.
Example 7 examples 1 to 6 changes in characteristics of polyvinyl chloride materials before and after modification
Respectively taking the polyvinyl chloride materials before and after modification in examples 1-6, putting the polyvinyl chloride materials into absolute ethyl alcohol for ultrasonic washing, then drying the polyvinyl chloride materials at 60 ℃ in vacuum until the weight is constant, and measuring the weight gain and the water contact angle, wherein the results are shown in Table 1.
TABLE 1 Properties of polyvinyl chloride Material before and after modification
As can be seen from the data in Table 1, the polyvinyl chloride film is modified by the functional isocyanate crosslinking agent, the weight of the polyvinyl chloride film is increased, and the water contact angle of the surface of the material is reduced. The polyvinyl chloride membrane is repeatedly treated by using the functional isocyanate crosslinking agent, so that similar modification effect can be obtained. Under the same conditions, the weight gain rate of the polyvinyl chloride fishing net after being treated by the functional isocyanate crosslinking agent is obviously higher than that of the polyvinyl chloride catheter and the polyvinyl chloride membrane, which indicates that the larger the specific surface area of the material to be modified is, the better the surface modification effect is, and the higher the grafting efficiency is.
Claims (9)
1. The application of the functional isocyanate crosslinking agent in the surface modification of the polyvinyl chloride material is characterized by comprising the following steps: immersing the surface-activated polyvinyl chloride material into the functional isocyanate cross-linking agent solution at room temperature, and then uniformly dipping, or spraying, rolling and brushing the functional isocyanate cross-linking agent solution on the surface-activated polyvinyl chloride material, then sending the surface-activated polyvinyl chloride material into a reactor at 60-130 ℃ for heat treatment for 0.2-20 hours, and then taking out and cooling to obtain the surface-modified polyvinyl chloride material;
wherein the surface activated polyvinyl chloride material refers to a surface clean polyvinyl chloride material which generates-OH groups or-NH groups on the surface after plasma treatment in a plasma chamber with oxygen, ammonia or air atmosphere, the gas pressure in the chamber is 30-50 Pa, the temperature in the chamber is 10-40 ℃, the power of a radio frequency power supply is 50-500 watts, and the irradiation time is 50-500 seconds 2 A group, known as a surface-activated polyvinyl chloride material; or immersing the surface clean polyvinyl chloride material into an alkali solution with the mass percentage concentration of 0.01-10%, carrying out ultrasonic hydrolysis for 2-200 minutes at room temperature, taking out, using deionized water to wash to neutrality, and carrying out vacuum drying at 60 ℃, wherein-OH groups are generated on the surface of the clean polyvinyl chloride material, namely the surface activated polyvinyl chloride material;
the functional isocyanate crosslinking agent has a structure shown in a general formula (A):
wherein R in formula (A) is selected from H or methyl, R 1 And R is 2 Respectively selected from C 1 ～C 18 Hydrocarbyl groups, n being selected from natural numbers between 1 and 2000, and Y being independently selected from C 1 ～C 18 An alkylene group,selected from C 1 ～C 18 Hydrocarbylene or->Q is selected from C 1 ～C 18 Hydrocarbyl radicals or->Wherein p is selected from natural numbers between 0 and 2000, X - Refers to Cl - 、Br - 、I - Or p-CH 3 C 6 H 4 SO 3 - One of the following;
the weight percentage concentration of the functional isocyanate crosslinking agent in the functional isocyanate crosslinking agent solution is 0.5-50%, and the dosage of the functional isocyanate crosslinking agent solution is 5-500% of the weight of the surface activated polyvinyl chloride material.
2. The application of the functional isocyanate crosslinking agent in the surface modification of the polyvinyl chloride material according to claim 1, which is characterized in that the surface cleaning polyvinyl chloride material is prepared by sequentially washing a polyvinyl chloride raw material with ethanol and deionized water, and drying the polyvinyl chloride raw material in vacuum at a temperature of 60 ℃ to constant weight;
wherein the polyvinyl chloride raw material refers to one of polyvinyl chloride artificial organs, a polyvinyl chloride catheter, a polyvinyl chloride blood storage bag, a polyvinyl chloride vessel, a polyvinyl chloride foam, a polyvinyl chloride film, a polyvinyl chloride filter membrane, a polyvinyl chloride filter screen, a polyvinyl chloride non-woven fabric or a polyvinyl chloride fiber.
3. The use of a functional isocyanate crosslinker according to claim 1 for modifying the surface of polyvinyl chloride materials, characterized in that the alkaline solution is potassium hydroxide, sodium hydroxide, N, one or more of N, N-trimethyl-N-benzylammonium hydroxide, N, N, N-triethyl-N-benzylammonium hydroxide or N, N, N, N-tetrabutylammonium hydroxide.
4. The use of a functional isocyanate crosslinker according to claim 1 for modifying the surface of polyvinyl chloride materials, characterized in that the preparation method of the functional isocyanate crosslinker is as follows: at room temperature, dihydroxydiamine of the general formula (B) is dissolved in an organic solvent, stirring is started, and acryloyloxy polyether sulfobetaine is slowly added, wherein the dosage of the acryloyloxy polyether sulfobetaine is 2.0-2.2 times of the molar quantity of the general formula (B); after the addition of the acryloyloxy polyether sulfobetaine is finished, the reaction temperature is increased to 50-90 ℃ and the reaction is carried out for 2-20 hours; maintaining the reaction temperature, adding an alkylating reagent into a reaction system, wherein the dosage of the alkylating reagent is 1.8-2.2 times of the molar quantity of the general formula (B), continuously stirring and reacting for 2-20 hours, after the quaternary ammonium salt reaction is finished, sequentially adding a catalyst, a diluent and polyisocyanate into the reaction system, continuously preserving heat and stirring for reaction, detecting that the NCO content in materials in the reactor accords with a preset value, and cooling the reaction product system to room temperature to prepare a solution of the functional isocyanate crosslinking agent;
wherein the dihydroxydiamine has a structure represented by the general formula (B):
wherein in the general formula (B)Selected from C 1 ～C 18 Hydrocarbylene or->Wherein p is selected from a natural number between 0 and 2000 and Y is selected from C 1 ～C 18 Hydrocarbylene groups.
5. The use of a functional isocyanate crosslinking agent according to claim 4 for surface modification of polyvinyl chloride materials, wherein the organic solvent is one or more of tetrahydrofuran, 1, 4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide, N-diethylformamide or hexamethylphosphoramide; the dosage of the organic solvent is 1 to 10 times of the mass of the dihydroxydiamine in the general formula (B).
6. The use of a functional isocyanate crosslinking agent according to claim 4 for the surface modification of polyvinyl chloride materials, characterized in that the acryloxypolyether sulfobetaine has the structure of general formula (C):
wherein R in formula (C) is selected from H or methyl, R 1 And R is 2 Respectively selected from C 1 ～C 18 And (3) hydrocarbon group, wherein n is selected from natural numbers between 1 and 2000.
7. The use of a functional isocyanate crosslinker according to claim 4 for modifying the surface of polyvinyl chloride materials, characterized in that the catalyst is a complex of organotin and an organic amine;
wherein the organotin refers to one of dibutyl tin dilaurate, stannous octoate, stannous oxalate, dibutyl tin dimaleate, dibutyl tin di (dodecyl sulfide) or dibutyl tin diacetate; the organic amine refers to one of triethylamine, p-dimethylaminopyridine, N-dimethylformamide, triethylene diamine, dialkyl piperazine, alkyl imidazole, 1, 8-diazabicyclo [5.4.0] undec-7-ene, triethylene diamine carboxylate, dialkyl piperazine carboxylate or alkyl imidazole carboxylate; the mass ratio of the organic tin to the organic amine is 1:0-1.5; the catalyst is used in an amount of 0.05 to 5% by mass of the polyisocyanate of the general formula (D).
8. A functional isocyanate crosslinking agent according to claim 4 on a polyvinyl chloride material surface
Use in the modification of a surface, characterized in that the polyisocyanate has a structure according to general formula (D):
wherein q in formula (D) is selected from positive integers from 1 to 5, said positive integers being selected from C 1 ～C 18 Hydrocarbylene radicals;
the amount of polyisocyanate used is 2.02 to 2.25 times the molar amount of the general formula (B).
9. A functional isocyanate crosslinking agent according to claim 4 on a polyvinyl chloride material surface
The application in surface modification is characterized in that the diluent refers to one or more than two of acetone, butanone, cyclohexanone, methyl acetate, ethyl acetate, diethyl ether, tetrahydrofuran, 1, 4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, toluene, xylene, dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide, N-diethylformamide or hexamethylphosphoramide; the amount of the diluent is 1 to 10 times of the mass of the general formula (B).
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