CN116987259A - Multifunctional allylammonium crosslinking agent and preparation method thereof - Google Patents
Multifunctional allylammonium crosslinking agent and preparation method thereof Download PDFInfo
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- CN116987259A CN116987259A CN202310967481.2A CN202310967481A CN116987259A CN 116987259 A CN116987259 A CN 116987259A CN 202310967481 A CN202310967481 A CN 202310967481A CN 116987259 A CN116987259 A CN 116987259A
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- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims description 19
- -1 acryloyloxy Chemical group 0.000 claims abstract description 33
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 26
- 229920000570 polyether Polymers 0.000 claims abstract description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 claims description 13
- 125000001424 substituent group Chemical group 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- 239000004971 Cross linker Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 9
- 125000006325 2-propenyl amino group Chemical group [H]C([H])=C([H])C([H])([H])N([H])* 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000743 hydrocarbylene group Chemical group 0.000 claims description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-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
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 0.000 claims 5
- 125000000746 allylic group Chemical group 0.000 claims 1
- 239000002861 polymer material Substances 0.000 abstract description 20
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 14
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 abstract description 11
- 229940117986 sulfobetaine Drugs 0.000 abstract description 11
- 230000004048 modification Effects 0.000 abstract description 10
- 238000012986 modification Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 8
- 229920000098 polyolefin Polymers 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000010100 anticoagulation Effects 0.000 abstract description 3
- 230000003373 anti-fouling effect Effects 0.000 abstract description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 12
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 9
- 229960003237 betaine Drugs 0.000 description 9
- 238000013461 design Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 150000003863 ammonium salts Chemical group 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 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 2
- 238000006845 Michael addition reaction Methods 0.000 description 2
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 2
- FMWSPIAZAHDSBL-UHFFFAOYSA-N [O].NC(=O)C=C Chemical compound [O].NC(=O)C=C FMWSPIAZAHDSBL-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229960002897 heparin Drugs 0.000 description 2
- 229920000669 heparin Polymers 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
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 239000002473 artificial blood Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- BUZRUIZTMOKRPB-UHFFFAOYSA-N carboxycarbamic acid Chemical compound OC(=O)NC(O)=O BUZRUIZTMOKRPB-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000007547 defect Effects 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
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- RHUCQDQRNUUMKY-UHFFFAOYSA-N n-benzylprop-2-en-1-amine Chemical compound C=CCNCC1=CC=CC=C1 RHUCQDQRNUUMKY-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
- C08G65/33306—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino 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
- C08G65/334—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
- C08G65/3346—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur having sulfur bound to carbon and oxygen
-
- 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
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention takes allylamine, acryloyloxy polyether sulfobetaine and bridging molecules as raw materials to prepare the multifunctional allylammonium cross-linking agent containing disulfobetaine plus quaternary ammonium cations or dicarboxybetaine plus quaternary ammonium cations, which not only can be used for the surface modification of various organic high polymer materials with high grafting efficiency, such as hydrophilicity, conductivity, antibacterial property, antifogging, antifouling property, anticoagulation property and the like, but also can be used as the cross-linking agent for preparing electroactive polyolefin materials to endow the polyolefin materials with hydrophilic, conductive or antibacterial functions.
Description
Technical Field
The invention relates to a multifunctional allylammonium crosslinking agent and a preparation method thereof, in particular to a multifunctional allylammonium crosslinking agent containing disulfonic betaine and gemini quaternary ammonium cations or dicarboxylammonium betaine and gemini quaternary ammonium cations, gemini quaternary ammonium cations and a preparation method thereof, and belongs to the field of functional polymer materials.
Technical Field
The polymer materials such as polyester, polyethylene, polyvinyl chloride, polyurethane, polysilane and the like have excellent rebound, flexibility, wear resistance, chemical stability, no toxicity, no stimulation, no variation, biocompatibility and the like, and are suitable for manufacturing medical and sanitary instruments such as artificial organs, artificial skin, artificial blood vessels, bone adhesives, surgical sutures, medical dressings, interventional catheters, drug carriers, living goods and the like. However, the polymer materials have two major defects in the field of medical and health and need to be overcome. Firstly, the surface of the high polymer material is hydrophobic, which affects the water lubrication type contact between the high polymer material and human tissues or blood. Secondly, when the high molecular materials are placed on some human body parts for a long time, the proteins or bacteria are attached to the surfaces of the high molecular materials, and the high molecular materials grow to cause infection. Therefore, it is necessary to increase the hydrophilicity, antibacterial property, anticoagulation property, biocompatibility and the like of the polymer material surface in all directions. At present, the main method for modifying the surface of the polymer material is to bond three hydrophilic antibacterial substances such as polyethylene glycol, carboxyl betaine/sulfobetaine/phosphorylcholine or heparin on the surface of the polymer material.
The method for bonding three major hydrophilic antibacterial substances such as polyethylene glycol, carboxyl betaine/sulfobetaine/phosphorylcholine or heparin on the surface of the polymer material is various, wherein the most suitable method is that ethylene monomer carrying the hydrophilic antibacterial substances is grafted and polymerized on the surface of the polymer material. However, it has also been found that the problem of homo-polymerization of the vinyl monomer carrying the hydrophilic antibacterial substance on the surface of the polymer material is unavoidable, resulting in serious loss of the vinyl monomer raw material and complicated post-treatment. In order to improve the grafting efficiency of the vinyl monomer carrying the hydrophilic antibacterial substance on the surface of the polymer material, development of a technique and a method for improving the grafting efficiency of the surface of the polymer material have been desired. For example, WO 2008/022062,US 20150210627,CN 104086511,CN110204710,CN104086512,CN108385415,CN107574691,CN105218688,US10280148 discloses a batch of monoquaternary ammonium salts with multiple epoxy groups, polyquaternary ammonium salts with multiple epoxy groups or polyquaternary ammonium salts with multiple epoxy groups, which are used as cationic etherifying agents or modifying agents, for cationizing and crosslinking modifying materials such as cellulose fibers, starch or polyamide, and the like, so that the surface grafting reaction efficiency is greatly improved by 100%.
Based on the principle of molecular design, the present inventors created a multi-vinyl compound containing disulfobetaine+gemini quaternary ammonium cation, dicarboxybtaine+gemini quaternary ammonium cation or gemini quaternary ammonium cation+gemini quaternary ammonium cation in the molecular structure as a multi-functional allylammonium cross-linking agent by Michael addition reaction and nucleophilic substitution reaction based on the structural characteristics and functional applications of polyethylene glycol, sulfobetaine, carboxybetaine and quaternary ammonium salt and the modification requirements of the application field of the polymer materials. The invention provides the multifunctional allylammonium crosslinking agent, which is used for modifying the hydrophilicity, conductivity, antibacterial property, antifogging, antifouling property, anticoagulation property, biocompatibility and the like of the surface of a high polymer material based on a plurality of vinyl groups in a molecular structure to improve grafting efficiency; it can also be used as a functional cross-linking agent for preparing electroactive polyolefin materials, and endows the polyolefin materials with hydrophilicity, conductivity, antibacterial property and the like; the functional allylammonium crosslinking agent with different functional characteristics can be prepared by adjusting the length of the polyether chain, and the functional allylammonium crosslinking agent is suitable for the surface modification requirements of polymer materials in multiple fields. The multifunctional allylammonium crosslinking agent containing disulfo betaine and gemini quaternary ammonium cations, dicarboxy betaine and gemini quaternary ammonium cations or gemini quaternary ammonium cations and gemini quaternary ammonium cations has the advantages of novel structural design, simple preparation method and remarkable function modification effect.
Disclosure of Invention
The invention provides a multifunctional allylammonium crosslinking agent which is characterized by having a structure shown in a general formula (I) or a general formula (II):
wherein R in the general formula (I) or the general formula (II) is selected fromTaking C 1 ～C 18 Hydrocarbon radicals or radicalsR 1 Selecting H or CH 3 ，R 2 、R 3 C is selected respectively 1 ～C 18 Hydrocarbon group, n is selected from natural number between 0 and 2000, when Y is C 1 ～C 18 Hydrocarbon radicals or radicalsWhen X is 1 - And X 2 - Respectively select Cl - 、Br - 、I - Or p-CH 3 C 6 H 4 SO 3 - One of the following; when Y selects-CH 2 CH 2 CH 2 SO 3 - or-CH 2 CH 2 CH 2 CO 2 - When X is 1 - Selecting Cl - 、Br - 、I - Or p-CH 3 C 6 H 4 SO 3 - One of, X 2 - Not selecting any, said->Refers to C 1 ～C 18 Hydrocarbylene or->
Wherein R is 4 C is selected respectively 1 ～C 18 Hydrocarbyl groups, m is selected from natural numbers between 0 and 2000.
The invention provides a specific preparation method of a multifunctional allylammonium crosslinking agent containing disulfobetaine, gemini quaternary ammonium cations, dicarboxybtaine, gemini quaternary ammonium cations or gemini quaternary ammonium cations and gemini quaternary ammonium cations in a molecular structure, which comprises the following steps:
step one: preparation of allylamino polyether ammonium
Sequentially weighing a solvent and the acrylamide oxygen polyether ammonium with the general formula (III), adding the solvent and the acrylamide oxygen polyether ammonium with the general formula (III) into a reaction kettle, stirring and dissolving uniformly, controlling the temperature to be 0-100 ℃, adding diallylamine or N- (substituent) allylamine into the reaction kettle, and carrying out Michael addition reaction for 2-48 hours to prepare an allylamino polyether ammonium solution for later use;
wherein the acryloyloxy polyether ammonium has a structure shown in a general formula (III):
wherein R in the formula (III) 1 Selecting H or CH 3 ，R 2 And R is 3 C is selected respectively 1 ～C 18 Hydrocarbon group, when Y is C 1 ～C 18 Hydrocarbon radicals or radicalsWhen X is 2 - Selected from Cl - 、Br - 、I - Or p-CH 3 C 6 H 4 SO 3 - One of the following; when Y selects-CH 2 CH 2 CH 2 SO 3 - or-CH 2 CH 2 CH 2 CO 2 - When X is 2 - No selection is made. Wherein R is 4 C is selected respectively 1 ～C 18 Hydrocarbyl groups, m is selected from natural numbers between 0 and 2000. Wherein the amount of the acryloyloxypolyether ammonium of the general formula (III) is 1.0 to 1.2 times of the molar amount of the diallylamine or the N- (substituent) allylamine.
The allylamine polyether ammonium has a structure shown in a general formula (IV) or a general formula (V):
wherein R in formula (IV) or formula (V) is C 1 ～C 18 Hydrocarbon radicals or radicalsR 1 Selecting H or CH 3 ，R 2 And R is 3 Respectively selectTaking C 1 ～C 18 Hydrocarbon group, when Y is C 1 ～C 18 Hydrocarbyl radicals or->When X is 2 - Selected from Cl - 、Br - 、I - Or p-CH 3 C 6 H 4 SO 3 - One of the following; when Y selects-CH 2 CH 2 CH 2 SO 3 - or-CH 2 CH 2 CH 2 CO 2 - When X is 2 - Any is not selected; wherein R is 4 C is selected respectively 1 ～C 18 Hydrocarbyl groups, m is selected from natural numbers between 0 and 2000.
The substituent in the N- (substituent) allylamine refers to R, and the R is C 1 ～C 18 Hydrocarbon radicals or radicalsWherein R is 4 Selecting C 1 ～C 18 Hydrocarbyl groups, m is selected from natural numbers between 0 and 2000.
The solvent is selected from one or more than two of water, methanol, ethanol, butanol, butanone, 1, 4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, toluene, xylene, anisole, chlorobenzene, toluene, chloroform, carbon tetrachloride, 1, 2-dichloroethane, tetrahydrofuran, ethyl acetate, methyl acetate, butyl acetate, N-dimethylformamide, dimethyl sulfoxide or methylcyclohexane; the solvent is 50-500% of the total mass of diallylamine or N- (substituent) allylamine and the ammonium acryloyloxy polyether of the general formula (III).
Step two: preparation of multifunctional allylammonium crosslinking agent
Adding a bridge molecule and hydroquinone, N, into the allylamino polyether ammonium solution of the general formula (IV) or the allylamino polyether ammonium solution of the general formula (V) 2 Under the protection, the temperature is controlled to be 20-100 ℃, the stirring reaction is carried out for 2-20 hours, then the mixture is concentrated by rotary evaporation, the solid is separated out after the temperature is reduced, and the mixture is filtered, washed and dried to obtain the structure multifunctional shown in the general formula (I) or the general formula (II)Can be allylammonium type crosslinking agent.
Wherein the bridge molecule refers to a dialkylating agent having a structure of the formula (VI):
wherein saidSelected from C 1 ～C 18 Hydrocarbylene, -, and->One of, X 1 Refers to Cl, br, I or p-CH 3 C 6 H 4 SO 3 One of them. Wherein m is selected from natural numbers between 0 and 2000.
The dosage of the bridge molecule is 0.5 to 0.55 times of the mol weight of the diallyl amine or the N- (substituent) allylamine;
the dosage of the hydroquinone is 0.25-5% of the mass of the diallyl amine or the N- (substituent) allylamine.
The invention provides a multifunctional allylammonium crosslinking agent containing disulfo betaine and gemini quaternary ammonium cations, dicarboxybtaine and gemini quaternary ammonium cations or gemini quaternary ammonium cations and gemini quaternary ammonium cations, which has the following characteristics:
(1) the preparation method of the multifunctional allylammonium crosslinking agent belongs to classical organic chemical reaction, is simple and easy to operate, and has rich raw material sources and low cost; in addition, the main raw materials (including the acryloxypolyether ammonium) and the intermediates (including the intermediates in the general formula (IV) or the intermediates in the general formula (V)) used for preparing the multifunctional ethylene cross-linking agent have the chemical characteristics and the application functions of the grafting polymerization or copolymerization reaction of the target compounds.
(2) According to the application field and the use requirement of the high polymer material to be modified, the length of the polyether chain in the multifunctional allylammonium crosslinking agent structure can be adjusted, so that the hydrophilic modification of the multifunctional allylammonium crosslinking agent structure is mainly achieved, or the hydrophilic and biocompatible modification of the multifunctional allylammonium crosslinking agent structure is mainly achieved; secondly, the bridge molecular structure can be redesigned to obtain various combined effects of disulfo betaine, gemini quaternary ammonium cation, dicarboxybetaine, gemini quaternary ammonium cation or gemini quaternary ammonium cation and gemini quaternary ammonium cation, so as to meet the main purposes of antibacterial and hydrophilic modification, or the main purposes of antibacterial, hydrophilic and biocompatible modification, or the main purposes of biocompatibility, hydrophilic and antibacterial modification.
(3) More importantly, after the multifunctional allylammonium crosslinking agent is adopted to modify the high polymer material, the hydrophilic property, the antibacterial function and the like of the high polymer material after the surface modification are not reduced after severe conditions and environments are encountered in the use process.
(4) The multifunctional allylammonium crosslinking agent disclosed by the invention is soluble in water or alcohol solvents, so that the application process of the multifunctional allylammonium crosslinking agent does not generate toxic VOC.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The multifunctional allylammonium type crosslinking agent containing disulfobetaine + gemini quaternary ammonium cation, dicarboxybtaine + gemini quaternary ammonium cation or gemini quaternary ammonium cation + gemini quaternary ammonium cation and the preparation method provided by the present invention are further described by the following examples, and the purpose of the present invention is better understood. Therefore, the multifunctional allylammonium type crosslinking agents and the preparation methods thereof, which are not listed in the examples, should not be construed as limiting the scope of the present invention. Any improvement to the present invention falls into the act of infringing intellectual property.
EXAMPLE 1 preparation of multifunctional allylammonium Cross-linker of formula (I-1)
Adding 9.5 g of diallylamine into 80 g of absolute ethyl alcohol, stirring, slowly adding 55 g of methacryloxypolyether sulfobetaine of formula (V-1) at room temperature, continuously reacting for 24 hours after the addition of formula (V-1), adding 30 g of ethanol solution containing 9.0 g of p-dichlorobenzene and 0.15 g of hydroquinone into a reaction system, and adding N 2 Under the protection, the reaction temperature is raised to 70-80 ℃ again, stirring is carried out for 12 hours, then rotary evaporation concentration, cooling crystallization,Filtering, washing and drying to obtain the multifunctional allylammonium crosslinking agent of the formula (I-1) with the yield of 89.5%.
The unsaturation degree of the multifunctional allylammonium crosslinking agent shown in the formula (I-1) is 1.7755mol/Kg by adopting a GB/T12008.7-1992 method, and the unsaturation degree is basically consistent with a theoretical calculated value 1.7801mol/Kg, which shows that the structure of the multifunctional vinyl crosslinking agent shown in the formula (I-1) is consistent with the theoretical design.
EXAMPLE 2 preparation of multifunctional allylammonium Cross-linker of formula (I-2)
According to the method and the steps of example 1, the methacryloxypolyether sulfobetaine of the formula (V-1) is changed into the methacryloxypolyether sulfobetaine of the formula (V-2), the dichlorobenzene is changed into polyethylene glycol-200 bis-p-toluenesulfonate, and the multifunctional allylammonium crosslinking agent of the formula (I-2) is prepared, and the unsaturation degree of the multifunctional allylammonium crosslinking agent of the formula (I-2) is 0.7044mol/Kg by sampling analysis through a GB/T12008.7-1992 method and basically coincides with a theoretical calculation value of 0.7048mol/Kg, so that the structure of the multifunctional allylammonium crosslinking agent of the formula (I-2) accords with the theoretical design.
Example 3 preparation of multifunctional allylammonium Cross-linker of formula (II-1)
According to the method and procedure of example 1, diallylamine was changed to N-benzyl allylamine, the methacryloxypolyether sulfobetaine of formula (V-1) was changed to methacryloxypolyether sulfobetaine of formula (V-2), and p-dichlorobenzene was changed to polyethylene glycol-200 bis-p-toluenesulfonate to prepare a multifunctional allylammonium crosslinker of formula (II-1). The unsaturation degree of the multifunctional allylammonium crosslinking agent of the formula (II-1) is 0.3575mol/Kg by adopting a GB/T12008.7-1992 method, and the unsaturation degree is basically consistent with a theoretical calculated value 0.3587mol/Kg, which shows that the multifunctional allylammonium crosslinking agent of the formula (II-1) accords with the theoretical design.
EXAMPLE 4 preparation of multifunctional allylammonium Cross-linker of formula (II-2)
According to the method and the steps of example 1, diallyl amine is changed into omega-allylamino tetraglycol methyl ether, methacrylic acyloxy polyether sulfobetaine of the formula (V-1) is changed into methacrylic acyloxy polyether carboxyl betaine of the formula (V-3), and the multifunctional allyl ammonium cross-linking agent of the formula (II-2) is prepared, and the method of GB/T12008.7-1992 is adopted, wherein the unsaturation degree of the multifunctional allyl ammonium cross-linking agent of the formula (II-2) is 0.7601mol/Kg by sampling analysis and basically coincides with a theoretical calculated value 0.7591mol/Kg, so that the structure of the multifunctional allyl ammonium cross-linking agent of the formula (II-2) accords with the theoretical design.
EXAMPLE 5 preparation of multifunctional allylammonium Cross-linker of formula (III-1)
According to the method and procedure of example 1, the methacryloxy polyether sulfobetaine of formula (V-1) is changed to a methacryloxy polyether quaternary ammonium salt of formula (V-4) to produce a multifunctional allylammonium crosslinking agent of formula (III-1);
the unsaturation degree of the multifunctional allylammonium crosslinking agent shown in the formula (III-1) is 1.8065mol/Kg by adopting a GB/T12008.7-1992 method, and the unsaturation degree is basically consistent with a theoretical calculated value 1.8026mol/Kg, which shows that the structure of the multifunctional allylammonium crosslinking agent shown in the formula (III-1) is consistent with the theoretical design.
Example 6 Properties of multifunctional allylammonium Cross-linking Agents 1-5
The multifunctional allylammonium crosslinking agents in examples 1-5 can be dissolved in deionized water to prepare respective saturated aqueous solutions, 2mL of each concentration aqueous solution in examples 1-5 are mixed with 10mL of culture medium according to the dilution ratio of 1:2, 1:5, 1:10, 1:20, 1:50, 1:100 and 1:1000, 2 drops of pathogenic bacterial strain liquid are added, and after the mixture is fully mixed, the mixture is placed 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 (5)
1. The multifunctional allylammonium crosslinking agent is characterized by having a structure shown in a general formula (I) or a general formula (II):
wherein R in the general formula (I) or the general formula (II) is C 1 ～C 18 Hydrocarbon radicals or radicalsR 1 Selecting H or CH 3 ，R 2 And R is 3 C is selected respectively 1 ～C 18 Hydrocarbon group, n is selected from natural number between 0 and 2000, when Y is C 1 ～C 18 Hydrocarbon radicals or radicalsWhen X is 1 - And X 2 - Respectively select Cl - 、Br - 、I - Or p-CH 3 C 6 H 4 SO 3 - One of the following; when Y selects-CH 2 CH 2 CH 2 SO 3 - or-CH 2 CH 2 CH 2 CO 2 - When X is 1 - Selecting and removing Cl - 、Br - 、I - Or p-CH 3 C 6 H 4 SO 3 - One of, X 2 - Not selecting any, said->Refers to C 1 ～C 18 Hydrocarbylene or->
Wherein R is 4 Selecting C 1 ～C 18 Hydrocarbyl groups, m is selected from natural numbers between 0 and 2000.
2. A method for preparing a multifunctional allylammonium crosslinker, characterized in that the preparation method of the multifunctional allylammonium crosslinker is as follows:
step one: preparation of allylamino polyether ammonium
Sequentially weighing a solvent and the acryloyloxy polyether ammonium, adding the solvent and the acryloyloxy polyether ammonium into a reaction kettle, uniformly stirring and dissolving, controlling the temperature to be 0-100 ℃, adding diallyl amine or N- (substituent) allyl amine into the reaction kettle, and reacting for 2-48 hours to prepare an allylamino polyether ammonium solution for later use;
wherein the acryloyloxy polyether ammonium has a structure shown in a general formula (III):
wherein R in the formula (III) 1 Selecting H or CH 3 ，R 2 And R is 3 C is selected respectively 1 ～C 18 Hydrocarbon group, when Y is C 1 ～C 18 Hydrocarbon radicals or radicalsWhen X is 2 - Selected from Cl - 、Br - 、I - Or p-CH 3 C 6 H 4 SO 3 - One of the following; when Y selects-CH 2 CH 2 CH 2 SO 3 - or-CH 2 CH 2 CH 2 CO 2 - When X is 2 - Any is not selected;
wherein R is 4 Selecting C 1 ～C 18 A hydrocarbon group, m is selected from natural numbers between 0 and 2000;
the allylamine polyether ammonium has a structure shown in a general formula (IV) or a general formula (V):
wherein R in formula (IV) or formula (V) is C 1 ～C 18 Hydrocarbon radicals or radicalsR 1 Selecting H or CH 3 ，R 2 And R is 3 C is selected respectively 1 ～C 18 Hydrocarbon group, when Y is C 1 ～C 18 Hydrocarbyl radicals or->When X is 2 - Selecting Cl - 、Br - 、I - Or p-CH 3 C 6 H 4 SO 3 - One of the following; when Y selects-CH 2 CH 2 CH 2 SO 3 - or-CH 2 CH 2 CH 2 CO 2 - When X is 2 - Any is not selected;
wherein R is 4 Selecting C 1 ～C 18 A hydrocarbon group, m is selected from natural numbers between 0 and 2000;
the dosage of the acryloyloxy polyether ammonium is 1.0 to 1.2 times of the mol of diallyl amine or N- (substituent) allylamine;
step two: preparation of multifunctional allylammonium crosslinking agent
Adding a bridge molecule and hydroquinone, N, into the allylamino polyether ammonium solution of the general formula (IV) or the allylamino polyether ammonium solution of the general formula (V) 2 Under the protection, controlling the temperature to be 20-100 ℃, stirring and reacting for 2-20 hours, then concentrating by rotary evaporation, cooling and separating out solid, filtering, washing and drying to prepare the multifunctional allylammonium cross-linking agent with the structure shown in the general formula (I) or the general formula (II);
wherein the amount of the bridge molecule is 0.5 to 0.55 times the molar amount of the diallylamine or the N- (substituent) allylamine;
the dosage of the hydroquinone is 0.25-5% of the mass of the diallylamine.
3. A process for preparing a multifunctional allylammonium-type crosslinking agent as claimed in claim 2, wherein the substituent in the N- (substituent) allylamine is R, and R is C 1 ～C 18 Hydrocarbon radicals or radicals
Wherein R is 4 Selecting C 1 ～C 18 Hydrocarbyl groups, m is selected from natural numbers between 0 and 2000.
4. A process for preparing a multifunctional allylic ammonium crosslinker according to claim 2, characterized in that the bridge molecule is referred to as a dialkylating agent having the structure of formula (vi):
wherein saidSelected from C 1 ～C 18 Hydrocarbylene, -, and->Wherein m is selected from natural numbers between 0 and 2000, X 1 Refers to Cl, br, I or p-CH 3 C 6 H 4 SO 3 One of the following;
wherein m is selected from natural numbers between 0 and 2000.
5. A method for preparing a multifunctional allylammonium-type crosslinking agent according to claim 2, characterized in that the solvent is selected from one or more of water, methanol, ethanol, butanol, butanone, 1, 4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, toluene, xylene, anisole, chlorobenzene, toluene, chloroform, carbon tetrachloride, 1, 2-dichloroethane, tetrahydrofuran, ethyl acetate, methyl acetate, butyl acetate, N-dimethylformamide, dimethyl sulfoxide or methylcyclohexane; the solvent is 50-500% of the total mass of diallyl amine or N- (substituent) allyl amine and the acryloyloxy polyether ammonium in the general formula (III).
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