CN116283674B - Isocyanate crosslinking agent containing disulfo betaine and preparation method thereof - Google Patents
Isocyanate crosslinking agent containing disulfo betaine and preparation method thereof Download PDFInfo
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- CN116283674B CN116283674B CN202310201593.7A CN202310201593A CN116283674B CN 116283674 B CN116283674 B CN 116283674B CN 202310201593 A CN202310201593 A CN 202310201593A CN 116283674 B CN116283674 B CN 116283674B
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- betaine
- isocyanate
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- 239000012948 isocyanate Substances 0.000 title claims abstract description 53
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 53
- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 44
- 229960003237 betaine Drugs 0.000 title claims abstract description 38
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 title claims abstract description 13
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 19
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 19
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 11
- 150000004985 diamines Chemical class 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 23
- -1 Hydrocarbon radicals Chemical class 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- 229940117986 sulfobetaine Drugs 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000004971 Cross linker Substances 0.000 claims description 9
- 125000000743 hydrocarbylene group Chemical group 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 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
- 239000003085 diluting agent Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 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 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 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
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 238000001816 cooling Methods 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
- 150000007942 carboxylates Chemical class 0.000 claims 2
- WCRDXYSYPCEIAK-UHFFFAOYSA-N dibutylstannane Chemical compound CCCC[SnH2]CCCC WCRDXYSYPCEIAK-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 16
- 238000007259 addition reaction Methods 0.000 abstract description 11
- 238000007142 ring opening reaction Methods 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 7
- 125000005442 diisocyanate group Chemical group 0.000 abstract description 6
- 229920002635 polyurethane Polymers 0.000 abstract description 6
- 239000004814 polyurethane Substances 0.000 abstract description 6
- 238000006845 Michael addition reaction Methods 0.000 abstract description 5
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 3
- 230000003373 anti-fouling effect Effects 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 230000002429 anti-coagulating effect Effects 0.000 abstract description 2
- 238000010382 chemical cross-linking Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 11
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 10
- 238000003860 storage Methods 0.000 description 7
- 239000002861 polymer material Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- JUHORIMYRDESRB-UHFFFAOYSA-N benzathine Chemical compound C=1C=CC=CC=1CNCCNCC1=CC=CC=C1 JUHORIMYRDESRB-UHFFFAOYSA-N 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- 230000006203 ethylation Effects 0.000 description 3
- 238000006200 ethylation reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000011017 operating method Methods 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 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 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 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 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UPYPTOCXMIWHSG-UHFFFAOYSA-N 1-dodecylsulfanyldodecane Chemical compound CCCCCCCCCCCCSCCCCCCCCCCCC UPYPTOCXMIWHSG-UHFFFAOYSA-N 0.000 description 1
- XYZIUGPCJRYTCP-UHFFFAOYSA-N 1-n-benzyl-3-phenylpropane-1,2-diamine Chemical compound C=1C=CC=CC=1CC(N)CNCC1=CC=CC=C1 XYZIUGPCJRYTCP-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000010100 anticoagulation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- ALZARSJEJMWPOM-UHFFFAOYSA-N n,n'-didodecylethane-1,2-diamine Chemical compound CCCCCCCCCCCCNCCNCCCCCCCCCCCC ALZARSJEJMWPOM-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- RFIOZSIHFNEKFF-UHFFFAOYSA-M piperazine-1-carboxylate Chemical compound [O-]C(=O)N1CCNCC1 RFIOZSIHFNEKFF-UHFFFAOYSA-M 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/16—Preparation of derivatives of isocyanic acid by reactions not involving the formation of isocyanate groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C265/00—Derivatives of isocyanic acid
- C07C265/12—Derivatives of isocyanic acid having isocyanate groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/13—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
- C07C309/14—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/3311—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group
- C08G65/3312—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33396—Polymers modified by chemical after-treatment with organic compounds containing nitrogen having oxygen in addition to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
- C08G65/3344—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur
Abstract
The invention relates to an isocyanate crosslinking agent containing disulfo-betaine in a molecular structure, belongs to a small molecular compound, and is a gemini zwitterionic compound containing terminal isocyanate groups in the molecule. The modified polyurethane is prepared from N, N' -disubstituted or unsubstituted alkyl organic diamine, polyethylene glycol monoacrylate, gamma-propane sultone and polyisocyanate serving as raw materials through Michael addition reaction, ring opening reaction and addition reaction. The molecular structure of the isocyanate cross-linking agent containing the disulfo-betaine has three functional groups, namely an isocyanate group (-NCO) which is a group for further chemical reaction; secondly, gemini betaine, which has hydrophilic, conductive, antibacterial, antifogging, antifouling or anticoagulant properties; furthermore, the gemini betaine containing diisocyanate groups has a chemical crosslinking function, and can chemically crosslink a chain structure containing O-H or N-H materials in the structure, so that the molecular weight of the gemini betaine is increased or the physical and mechanical stability of the gemini betaine is improved.
Description
Technical Field
The invention relates to an isocyanate cross-linking agent containing disulfo-betaine in a molecular structure and a preparation method thereof, belonging to the field of functional polymer materials.
Technical Field
The polyurethane prepolymer is a functional polymer material with a reaction function, and is a polyurethane semi-finished product with the reaction function, which is prepared by taking polyisocyanate and polyol as main raw materials and reacting under certain conditions. According to the end group reaction characteristics of polyurethane prepolymers, it can be classified as: isocyanate-terminated prepolymers, hydroxyl-terminated prepolymers, prepolymers containing blocking groups, and polyurethane prepolymers containing other groups such as silane-terminated, alkyl acrylate-terminated. Among them, the terminal NCO polyurethane prepolymer is the most abundant type of products, and can be used as polyurethane adhesive, polyurethane coating, polyurethane impregnant, polyurethane fixing agent and other fields with chemical activity. The polyol in the raw material of the NCO-terminated polyurethane prepolymer has the characteristics of easy molecular structure design and adjustable performance, so that a certain functional group is generally introduced into the polyol structure to form the functional polyurethane prepolymer, and the polyurethane prepolymer is endowed with unique biological, optical, electric, magnetic, thermal and other physical and chemical characteristics or functions on the basis of keeping a plurality of characteristics of the polyurethane prepolymer, and can be used as the raw material of functional materials such as optical, electric, magnetic, thermal, medical, medicine or biology. Meanwhile, when the structures of the base materials such as organic or inorganic materials contain O-H or N-H groups, the NCO-terminated functional polyurethane prepolymer can also be used as a chemical modifier of the base materials, so that the base materials are endowed with new functions and application characteristics, the application fields of the base materials are widened, the new requirements of different fields are further met, and the functional material is one of the main development directions of innovation of the functional materials.
Based on the above, the invention provides an isocyanate crosslinking agent containing disulfobetaine in a molecular structure, which belongs to a small molecular compound, and is prepared from N, N' -disubstituted or unsubstituted alkyl organic diamine, hydroxyethyl methacrylate, gamma-propane sultone and polyisocyanate serving as raw materials through Michael addition reaction, ring opening reaction and addition reaction. The isocyanate crosslinking agent containing the disulfo betaine in the molecular structure has structural units and reaction characteristics similar to those of isocyanate-terminated polyurethane prepolymer, and is also a zwitterionic compound which can be used as a raw material for preparing an electroactive polyurethane material, can be used for carrying out post-chemical modification on an organic polymer material with a hydroxyl group or an amino group on the surface, takes the isocyanate group as a spacer arm, uniformly bonds the disulfo betaine unit on the chain structure of the organic polymer material, and carries out crosslinking on the chain structure of the organic polymer material so as to endow the organic polymer material with hydrophilicity, conductivity, antibacterial property, antifogging, antifouling property, anticoagulation property and structural stability. The preparation method of the gemini betaine containing the diisocyanate group in the molecular structure is simple, the product is pure and free of impurities, the process technology is standard, the product quality is stable, the product is easy to shape, and the use is convenient.
Disclosure of Invention
The invention provides an isocyanate crosslinking agent containing disulfo-betaine in a molecular structure, which is characterized by having 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 Hydrocarbon radicals, saidSelected from C 1 ～C 18 Alkylene, wherein n is selected from natural numbers between 1 and 2000, said +.>Selected from C 1 ～C 18 Hydrocarbylene orWherein q is selected from natural numbers between 1 and 2000.
The molecular structure of the isocyanate cross-linking agent containing the disulfo-betaine has three functional groups, namely isocyanate groups (-NCO) which are groups for further chemical reaction; secondly, gemini betaine, which has hydrophilic, conductive, antibacterial, antifogging, antifouling or anticoagulant properties; furthermore, the diisocyanate-containing disulfobetaine has a chemical crosslinking function, and can chemically crosslink the chain structure of O-H or N-H-containing materials in the structure, so that the molecular weight of the diisocyanate-containing disulfobetaine is increased or the physical, chemical or mechanical stability of the diisocyanate-containing disulfobetaine is improved.
The preparation raw materials of the isocyanate cross-linking agent containing the disulfo-betaine in the molecular structure comprise: organic diamines, polyethylene glycol monoacrylates, gamma-propane sultone and polyisocyanates.
Wherein the organic diamine refers to N, N' -di (substituted or unsubstituted hydrocarbon group) organic diamine, and has a structure shown in a general formula (B):
wherein R in the formula (B) 1 And R is 2 Respectively selected from C 1 ～C 18 Hydrocarbon radicals, saidSelected from C 1 ～C 18 Hydrocarbylene orWherein q is selected from natural numbers between 1 and 2000;
the polyethylene glycol monoacrylate has a structure shown in a general formula (C):
wherein R in the general formula (C) is selected from H or methyl, and n is selected from natural numbers between 1 and 2000.
The polyisocyanate has a structure represented by the general formula (D):
wherein p in the general formula (D) is selected from positive integers of 1 to 5, saidSelected from C 1 ～C 18 Hydrocarbylene groups.
According to the organic synthesis chemistry principle, the preparation process of the isocyanate crosslinking agent containing the disulfo-betaine in the molecular structure can have two technical routes, and the following is detailed by taking hydroxyethyl acrylate as an example: in the solution, firstly, the Michael addition reaction between the organic diamine and hydroxyethyl acrylate is finished to prepare the di-tertiary amine with the structure shown in the general formula (E):
and secondly, carrying out addition reaction on the general formula (E) and polyisocyanate of the general formula (D), and then carrying out ring opening reaction on the obtained addition reaction product and gamma-propane sultone to obtain the isocyanate crosslinking agent containing the disulfo-betaine in the molecular structure of the general formula (A).
The general formula (E) is a tertiary amine organic base, can be used as a catalyst for the addition reaction of hydroxyl and polyisocyanate of the general formula (D), so that the addition reaction between the general formula (E) and the general formula (D) belongs to an autocatalytic chemical reaction, can save an additional catalyst, and has significance for simplifying the purification of products and reducing the cost. However, the addition reaction product of formula (E) with formula (D) is of formula (F), after which the ring opening reaction of formula (F) with gamma-propane sultone occurs at two reaction points, one being the tertiary amine N atom in formula (F) and the other being the N-H group of the carbamate. The ring-opening reaction of the N-H group of the carbamate with gamma-propane sultone is not expected, but even if such side reaction occurs, the obtained product does not influence the application characteristics and the use requirements of the general formula (A) product.
If the molecular structure of the structure shown in the general formula (G) contains dihydroxyl gemini betaine through the ring opening reaction of the general formula (E) and gamma-propane sultone, and then the molecular structure of the structure shown in the general formula (G) and polyisocyanate of the general formula (D) are subjected to addition reaction, so that the synthesis of the isocyanate cross-linking agent containing the disulfo betaine in the structure shown in the general formula (A) is completed. It is theorized that the zwitterionic unit in the structure of the general formula (G) does not affect the ring-opening reaction of the tertiary amine N atom (the only reaction point) and gamma-propane sultone, but a catalyst is needed to ensure that the addition reaction of the polyisocyanate group of the general formula (D) and the hydroxyl group of the general formula (G) is successfully completed, and no other side reaction exists. If the catalyst of the formula (A) is used immediately without transport and storage, the catalyst added in the process is just the catalyst in the application process of the formula (A). However, if the formula (A) is to be transported and stored, the catalyst added in the process is a breaker of the stability of the formula (A) and must be removed or deactivated. In summary, the present invention preferably adopts a synthesis technology process of the general formula (a) with ring opening and then addition, and the preparation reaction process is shown in the following reaction formula:
wherein R in the reaction scheme 1 And R is 2 Respectively selected from C 1 ～C 18 Hydrocarbon radicals, saidSelected from C 1 ～C 18 Hydrocarbylene orWherein q is selected from a natural number between 1 and 2000, said +.>Selected from C 1 ～C 18 Hydrocarbylene groups.
The polyisocyanate has a structure represented by the general formula (D):
wherein p in the general formula (D) is selected from positive integers of 1 to 5, saidSelected from C 1 ～C 18 Hydrocarbylene groups.
The specific preparation process of the isocyanate cross-linking agent containing the disulfo-betaine in the molecular structure comprises the following steps: at room temperature, dissolving the general formula (B) in an organic solvent, starting stirring, and slowly adding polyethylene glycol monoacrylate, wherein the dosage of the polyethylene glycol monoacrylate is 1.8-2.2 times of the molar quantity of the general formula (B); after finishing the feeding of the polyethylene glycol monoacrylate, raising the reaction temperature to 50-70 ℃, and after continuing the reaction for 2-6 hours, ending the Michael addition reaction process; the reaction temperature is kept, gamma-propane sultone is added into a reaction system, the dosage of the gamma-propane sultone is 1.8 to 2.2 times of the molar quantity of the general formula (B), and the ring-opening reaction process is finished after the reaction is carried out for 2 to 6 hours; sequentially adding a catalyst, a diluent and polyisocyanate of the general formula (D) into a reaction system, continuing stirring and heat-preserving reaction, detecting that the NCO content in materials in a reactor is consistent with a preset value, cooling the reaction product system to room temperature, and ending the addition reaction process to prepare a solution of the isocyanate cross-linking agent containing the disulfo-betaine in the molecular structure of the general formula (A).
Wherein the general formula (B) has the structure shown below:
wherein R in the formula (B) 1 And R is 2 Respectively selected from C 1 ～C 18 Hydrocarbon radicals, saidSelected from C 1 ～C 18 Hydrocarbylene orWherein q is selected from natural numbers between 1 and 2000.
The polyethylene glycol monoacrylate has a structure shown in a general formula (C):
wherein R in the general formula (C) is selected from H or methyl, and n is selected from natural numbers between 1 and 2000.
The organic solvent refers to one or more than two of diethyl ether, 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 diamine 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 p 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 polyisocyanate used is 1.8 to 2.2 times the molar amount 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 general formula (B).
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 isocyanate crosslinking agents containing disulfobetaine in the molecular structures not shown in the examples and the preparation method thereof should not be construed as limiting the scope of the invention.
Example 1 formula (1) bis-sulfobetaine containing isocyanate crosslinker
25 g of N, N' -dibenzyl ethylenediamine is dissolved in 80 g of 1, 4-dioxane, the mixture is put into a reaction kettle, stirring is started, 30 g of hydroxyethyl methacrylate is slowly added at room temperature, after the material addition of the hydroxyethyl methacrylate is completed, the reaction temperature is increased to 55-60 ℃, and the reaction is continued for 4 hours, so that an intermediate formula (1 a) is obtained; maintaining the temperature of reactants in a reaction kettle, adding 26 g of gamma-propane sultone into the reaction kettle, and reacting for 6 hours to obtain an intermediate formula (1 b); adding 0.22 g of dibutyl tin dilaurate, 0.15 g of triethylene diamine, 120 g of acetone and 40 g of toluene diisocyanate into a reaction kettle, continuously carrying out heat preservation and stirring reaction, reducing the temperature of a reaction product system to room temperature after detecting that the NCO value in the reaction product system is close to a preset value, and ending the addition reaction process to prepare the solution of the isocyanate cross-linking agent containing the disulfobetaine, which is shown in the formula (1).
The Michael addition reaction product in example 1 was separated and purified by a chromatographic column, and strong absorption peaks respectively appear at 1738nm and 1127nm in the IR spectrum of the intermediate of formula (1 a), belonging to the vibration absorption of ester groups c=o and C-O-C, respectively, indicating that the intermediate of formula (1 a) has the structural characteristics of carboxylic esters. The IR spectrum of the intermediate (1 b) separated and purified by the chromatographic column is not obviously different from that of the intermediate (1 a), which shows that the IR characteristic peak which is not shown in the sulfonic acid group of the intermediate (1 b) can be submerged in the characteristic peak of the ester group. The isocyanate cross-linking agent solution with the structure containing the disulfo-betaine shown in the formula (1) is subjected to negative pressure concentration and chromatographic column separation and purification, wherein a strong peak of NCO appears near an IR spectrum 2270nm, a peak near 3340nm is shifted to 3482nm, the characteristic absorption peak 3340nm of O-H shown in the formula (1 b) disappears, a characteristic absorption peak of 3482nm belonging to carbamate N-H appears, and a characteristic peak of carbamate C=O appears at 1726nm, and the structural characteristics of the formula (1) are met. Therefore, the chemical structure of the product in the preparation process of the invention is consistent with the theoretical design.
Detecting 3.83% of isocyanate groups in the isocyanate crosslinking agent solution containing the disulfo-betaine and having the structure shown in the formula (1) by using a GB/T29493.6-2013 stipulation method; after 180 days of sealing and standing at room temperature, the mass percent of isocyanate groups in the sample is 3.52 percent. The stable storage period of the isocyanate cross-linking agent solution with the structure containing the disulfo-betaine shown in the formula (1) at room temperature can reach more than 3 months.
Example 2 formula (2) bis-sulfobetaine containing isocyanate crosslinker
According to the method and operation procedure of example 1, N '-dibenzylethylenediamine in example 1 was changed to N, N' -didodecylethylenediamine to prepare an isocyanate crosslinking agent solution having a structure represented by formula (2) containing disulfobetaine.
The structure of the disulfo-betaine containing a diisocyanate group of the formula (2) was confirmed by IR. Detecting 3.78% of isocyanate groups in the solution of the isocyanate crosslinking agent containing the disulfo-betaine and having the structure shown in the formula (2) by using a GB/T29493.6-2013 stipulation method; after 180 days of sealing and standing at room temperature, the mass percent of isocyanate groups in the sample is 3.45 percent. The stable storage period of the isocyanate cross-linking agent solution with the structure containing the disulfo-betaine shown in the formula (2) at room temperature can reach more than 3 months.
Example 3 formula (3) bis-sulfobetaine containing isocyanate crosslinker
Following the procedure and operating procedures of example 1, the N, N '-dibenzylethylenediamine of example 1 was changed to N, N' -dibenzyl-1, 6-hexamethylenediamine to prepare a solution of the isocyanate crosslinking agent having the structure of bis-sulfobetaine represented by formula (3).
The structure of the isocyanate crosslinking agent containing the disulfobetaine of the formula (3) was confirmed by IR. Detecting 3.56% of isocyanate groups in the solution of the isocyanate crosslinking agent containing the disulfo-betaine and having the structure shown in the formula (3) by using a GB/T29493.6-2013 stipulation method; after 180 days of sealing and standing at room temperature, the mass percent of isocyanate groups in the sample is 3.15 percent. The stable storage period of the isocyanate cross-linking agent solution with the structure containing the disulfo-betaine shown in the formula (3) at room temperature can reach more than 3 months.
Example 4 formula (4) bis-sulfobetaine containing isocyanate crosslinker
According to the method and the operation procedure of example 1, toluene diisocyanate in example 1 was changed to diphenylmethane diisocyanate to prepare an isocyanate crosslinking agent solution having a structure containing bis-sulfobetaine represented by formula (4).
The structure of the isocyanate crosslinking agent containing bis-sulfobetaine of the formula (4) was confirmed by IR. Detecting 3.75% of isocyanate groups in the solution of the isocyanate crosslinking agent containing the disulfo-betaine and having the structure shown in the formula (4) by using a GB/T29493.6-2013 stipulation method; after 180 days of sealing and standing at room temperature, the mass percent of isocyanate groups in the sample is 3.59 percent. The stable storage period of the isocyanate cross-linking agent solution with the structure containing the disulfo-betaine shown in the formula (4) at room temperature can reach more than 3 months.
Example 5 formula (5) bis-sulfobetaine containing isocyanate crosslinker
Following the procedure and operating procedures of example 1, the N, N' -dibenzylethylenediamine of example 1 was changed to α, ω -dibenzylaminopolyene oxide-2000 to produce a solution of the isocyanate crosslinking agent having the structure of bis-sulfobetaine of formula (5).
The structure of the isocyanate crosslinking agent containing bis-sulfobetaine of the formula (5) was confirmed by IR. Detecting the percentage content of isocyanate groups in the isocyanate crosslinking agent solution containing the disulfo-betaine and having the structure shown in the formula (5) by using a GB/T29493.6-2013 stipulation method; after 180 days of sealing and standing at room temperature, the mass percent of isocyanate groups in the sample is 0.32 percent. The stable storage period of the isocyanate cross-linking agent solution containing the disulfo-betaine in the structure shown in the formula (5) at room temperature can reach more than 3 months.
Example 6 formula (6) bis-sulfobetaine containing isocyanate crosslinker
Following the procedure and operating procedures of example 1, the N, N' -dibenzylethylenediamine of example 1 was changed to α, ω -dibenzylaminopolyethylene oxide-2000, hydroxyethyl methacrylate was changed to polyethylene glycol-2000 monomethacrylate, toluene diisocyanate was changed to diphenylmethane diisocyanate, and a solution of an isocyanate crosslinking agent containing disulfobetaine of the structure shown in formula (6) was prepared.
The structure of the isocyanate crosslinking agent containing bis-sulfobetaine of the formula (6) was confirmed by IR. Detecting the percentage content of isocyanate groups in the isocyanate crosslinking agent solution containing the disulfo-betaine and having the structure shown in the formula (6) by using a GB/T29493.6-2013 stipulation method; after 180 days of sealing and standing at room temperature, the mass percent of isocyanate groups in the sample is 0.29 percent. The stable storage period of the isocyanate cross-linking agent solution with the structure containing the disulfo-betaine shown in the formula (6) at room temperature can reach more than 3 months.
Example 7 Properties of the isocyanate crosslinkers containing bis-sulfobetaines of examples 1-6
20 g of the isocyanate crosslinking agent solution containing the disulfo-betaine in each of examples 1 to 6 is taken, 10 g of absolute ethyl alcohol is added, and after the temperature is raised to 60 ℃ and stirring is carried out for 4 hours, the obtained ethylation products are dissolved in 100mL of deionized water, and the result shows that the ethylation products of the isocyanate crosslinking agent containing the disulfo-betaine in each of examples 1 to 6 can be dissolved in water; according to the dilution ratio of 1:2, 1:5, 1:10, 1:20, 1:50 and 1:100, respectively taking 2mL of the ethylation product aqueous solution of the examples 1-6 to be mixed with 10mL of culture medium, adding 2 drops of pathogenic bacterial strain liquid, fully mixing, and placing in a 37 ℃ incubator for culturing for 24 hours; the growth of pathogenic bacteria was observed, the Minimum Inhibitory Concentration (MIC) was calculated, and the test results are shown in table 1.
Table 1 results of bacteriostasis experiments
Claims (3)
1. An isocyanate crosslinker containing bis-sulfobetaine characterized by:
the isocyanate crosslinking agent containing the disulfo betaine 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 Hydrocarbon radicals, saidSelected from C 1 ～C 18 Alkylene, wherein n is selected from natural numbers between 1 and 2000, said +.>Selected from C 1 ～C 18 Hydrocarbylene or->Wherein q is selected from natural numbers between 1 and 2000.
2. A process for preparing an isocyanate crosslinker containing bis-sulfobetaines according to claim 1, characterized in that the preparation process is as follows: dissolving the general formula (B) in an organic solvent at room temperature, stirring and slowly adding polyethylene glycol monoacrylate, wherein the dosage of the polyethylene glycol monoacrylate is 1.8-2.2 times of the molar quantity of the general formula (B), after the polyethylene glycol monoacrylate is completely added, raising the reaction temperature to 50-70 ℃, continuing to react for 2-6 hours, keeping the reaction temperature, adding gamma-propane sultone into a reaction system, wherein the dosage of the gamma-propane sultone is 1.8-2.2 times of the molar quantity of the general formula (B), reacting for 2-6 hours, sequentially adding a catalyst, a diluent and polyisocyanate into the reaction system, continuing to stir and keep the temperature for reaction, detecting that the NCO content in the materials in a reactor is consistent with a preset value, and then cooling the reaction temperature of a reaction product system to room temperature to obtain the isocyanate cross-linking agent solution containing the disulfobetaine with the structure shown in the general formula (A);
wherein the general formula (B) has the structure shown below:
wherein R in the formula (B) 1 And R is 2 Respectively selected from C 1 ～C 18 Hydrocarbon radicals, saidSelected from C 1 ～C 18 Hydrocarbylene orWherein q is selected from natural numbers between 1 and 2000;
the polyethylene glycol monoacrylate has a structure shown in a general formula (C):
wherein R in the general formula (C) is selected from H or methyl, and n is selected from natural numbers between 1 and 2000;
the polyisocyanate has a structure represented by the general formula (D):
wherein p 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 of the general formula (D) is 1.8 to 2.2 times of the molar amount of the polyisocyanate of the general formula (B);
the catalyst refers to a compound of organotin and organic amine;
wherein the organotin is dibutyl tin dilaurate, stannous octoate, stannous oxalate,
One of dibutyltin dimaleate, dibutyltin dilaurate or dibutyltin diacetate;
the organic amine refers to triethylamine, p-dimethylaminopyridine, N-dimethylformamide,
One of triethylenediamine, dialkylpiperazine, alkylimidazole, 1, 8-diazabicyclo [5.4.0] undec-7-ene, triethylenediamine carboxylate, dialkylpiperazine carboxylate, or alkylimidazole 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 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 general formula (B).
3. The method for preparing the isocyanate crosslinking agent containing the disulfobetaine according to claim 2, wherein the organic solvent is one or more of diethyl ether, 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 diamine in the general formula (B).
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| CN105503649A (en) * | 2016-01-08 | 2016-04-20 | 淮海工学院 | Polyols containing quaternary ammonium cations and Salen or Salophen functional groups and preparation method thereof |
| CN109354706A (en) * | 2018-10-12 | 2019-02-19 | 淮海工学院 | A kind of application of multifunctional polyurethane prepolymer in medical catheter surface is modified |
| CN109331667A (en) * | 2018-11-05 | 2019-02-15 | 长治学院 | A kind of surface modifying method of aromatic polyamides composite membrane |
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