CN116283667A - Functional isocyanate crosslinking agent and preparation method thereof - Google Patents
Functional isocyanate crosslinking agent and preparation method thereof Download PDFInfo
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- CN116283667A CN116283667A CN202310201592.2A CN202310201592A CN116283667A CN 116283667 A CN116283667 A CN 116283667A CN 202310201592 A CN202310201592 A CN 202310201592A CN 116283667 A CN116283667 A CN 116283667A
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- general formula
- crosslinking agent
- isocyanate crosslinking
- functional isocyanate
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- Granted
Links
- 239000012948 isocyanate Substances 0.000 title claims abstract description 57
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 57
- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims description 17
- -1 quaternary ammonium cations Chemical class 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 12
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 11
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 11
- WFACWTZLXIFJCM-UHFFFAOYSA-N 5-(chloromethyl)-2-hydroxybenzaldehyde Chemical compound OC1=CC=C(CCl)C=C1C=O WFACWTZLXIFJCM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000004985 diamines Chemical class 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 14
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 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
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- 239000003085 diluting agent Substances 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 125000000743 hydrocarbylene group Chemical group 0.000 claims description 5
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims description 2
- UPYPTOCXMIWHSG-UHFFFAOYSA-N 1-dodecylsulfanyldodecane Chemical compound CCCCCCCCCCCCSCCCCCCCCCCCC UPYPTOCXMIWHSG-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 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
- 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
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 10
- 229920002635 polyurethane Polymers 0.000 abstract description 6
- 239000004814 polyurethane Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 abstract description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006845 Michael addition reaction Methods 0.000 abstract description 4
- 238000007259 addition reaction Methods 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 238000010382 chemical cross-linking Methods 0.000 abstract description 2
- 238000005956 quaternization reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 239000004971 Cross linker Substances 0.000 description 11
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 11
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000011049 filling Methods 0.000 description 4
- 239000008204 material by function Substances 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 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 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000006203 ethylation Effects 0.000 description 3
- 238000006200 ethylation reaction Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-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 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 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
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 230000002429 anti-coagulating effect 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
- JUHORIMYRDESRB-UHFFFAOYSA-N benzathine Chemical class C=1C=CC=CC=1CNCCNCC1=CC=CC=C1 JUHORIMYRDESRB-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling 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
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001963 growth medium Substances 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
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 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
- 230000036961 partial effect Effects 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Chemical class 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a functional isocyanate crosslinking agent, in particular to an isocyanate crosslinking agent containing gemini quaternary ammonium cations in a molecular structure. The modified polyurethane is prepared from N, N' -disubstituted or unsubstituted alkyl organic diamine, hydroxyethyl methacrylate, polyisocyanate and 5-chloromethylsalicylaldehyde serving as raw materials through Michael addition reaction, addition reaction and quaternization reaction. The functional isocyanate crosslinking agent 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 functional isocyanate crosslinking agent is increased or the physical and mechanical stability of the functional isocyanate crosslinking agent is improved.
Description
Technical Field
The invention relates to a functional isocyanate crosslinking agent and a preparation method thereof, in particular to an isocyanate crosslinking agent containing gemini quaternary ammonium cations in a molecular structure and a preparation method thereof, belonging to the field of functional materials.
Technical Field
Functional substances refer to a class of compounds or polymers containing specific functional groups in their molecular structures, which are used for the preparation, production or processing of functional materials in specific fields. The isocyanate cross-linking agent can stably coexist with resin containing active groups (hydroxyl, amino and the like) for a long time at normal temperature, and after heat treatment, the-NCO group of the isocyanate cross-linking agent reacts with the hydroxyl, amino and the like on a resin molecular chain to form cross-linking, so that the adhesive force, color stability, steaming and boiling resistance and sterilizing capability of polyester, alkyd resin and acrylic resin can be obviously improved. The polyurethane prepolymer is a high molecular 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 such as isocyanate crosslinking agent, 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.
The invention provides a functional isocyanate crosslinking agent, in particular relates to an isocyanate crosslinking agent containing gemini quaternary ammonium cations in a molecular structure, which has partial structural units and reaction characteristics similar to isocyanate-terminated polyurethane prepolymer, can carry out post-chemical modification on an organic polymer material containing hydroxyl or amino in a chain structure, takes isocyanate groups as a spacer arm, uniformly bonds gemini quaternary ammonium cation units 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, anticoagulant property and structural stability; in addition, the isocyanate crosslinking agent containing the gemini quaternary ammonium cation can be used as a raw material for preparing the electroactive polyurethane material.
The isocyanate cross-linking agent containing gemini quaternary ammonium cations in the molecular structure is prepared from N, N' -disubstituted or unsubstituted alkyl organic diamine, polyethylene glycol mono-base acrylic ester, polyisocyanate and 5-chloromethyl salicylaldehyde serving as raw materials through Michael addition reaction, addition reaction and quaternary ammonium salt reaction. The isocyanate crosslinking agent containing the gemini quaternary ammonium cation in the molecular structure has the advantages of simple preparation method, pure product, no impurity, standard process technology, stable product quality, easy shaping of the product and convenient use.
Disclosure of Invention
The invention provides a functional isocyanate crosslinking agent and a preparation method thereof, in particular to an isocyanate crosslinking agent containing gemini quaternary ammonium cations in a molecular structure, which is characterized by having a structure shown in a general formula (A):
wherein R in the general formula (A) is selected from H or methyl, n is selected from natural numbers between 1 and 2000, R 1 And R is 2 Respectively selected from C 1 ～C 18 Hydrocarbon radicals, said
Selected from C 1 ～C 18 Hydrocarbylene radicals of the formula/>
Selected from C 1 ～C 18 Hydrocarbylene or
Wherein q is selected from natural numbers between 1 and 2000.
The isocyanate crosslinking agent containing gemini quaternary ammonium cations in the molecular structure comprises three types of functional groups, namely isocyanate groups (-NCO) which are groups for further chemical reaction; secondly, gemini quaternary ammonium salt which has hydrophilicity, conductivity, antibacterial property, antifogging or antifouling property; furthermore, the isocyanate crosslinking agent containing the gemini quaternary ammonium cations in the molecular structure has a chemical crosslinking function, and can chemically crosslink the chain structure containing O-H or N-H materials in the structure, so that the molecular weight of the isocyanate crosslinking agent is increased or the physical, chemical or mechanical stability of the isocyanate crosslinking agent is enhanced.
The specific preparation process of the isocyanate crosslinking agent containing the gemini quaternary ammonium cation in the molecular structure is as follows: at room temperature, dissolving the general formula (B) in an organic solvent, starting stirring, and slowly adding hydroxyl-terminated polyether monoacrylate, wherein the dosage of the hydroxyl-terminated polyether monoacrylate is 1.8-2.2 times of the molar quantity of the general formula (B); after finishing feeding hydroxyl-terminated polyether monoacrylate, raising the reaction temperature to 50-70 ℃, and continuing the reaction for 2-20 hours, and ending the Michael addition reaction process; keeping the reaction temperature, sequentially adding a catalyst, a diluent and polyisocyanate into a reaction system, continuously stirring, preserving heat and reacting for 2-20 hours, detecting that the NCO content in the materials in the reactor accords with a preset value, and then cooling the reaction product system to room temperature to finish the addition reaction process; slowly adding 5-chloromethyl salicylaldehyde solution, and stirring and reacting for 0.5-15 hours to obtain the isocyanate cross-linking agent solution containing gemini quaternary ammonium cations in the molecular 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, said
Selected from C 1 ～C 18 Hydrocarbylene or
Wherein q is selected from natural numbers between 1 and 2000.
The hydroxyl-terminated polyether 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 an organotin catalyst and comprises one of dibutyl tin dilaurate, stannous octoate, stannous oxalate, dibutyl tin dimaleate, dibutyl tin di (dodecyl sulfide) or dibutyl tin diacetate; 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 values of 1 to 5An integer of the following
Selected 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 polyisocyanate.
The mass ratio of the 5-chloromethyl salicylaldehyde solution to the organic solvent is 20-50:100, and the dosage of the 5-chloromethyl salicylaldehyde is 1.8-2.2 times of the molar quantity 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 gemini quaternary ammonium cations 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 preparation of functional isocyanate crosslinker of formula (1)
25 g of dehydrated N, N' -dibenzylethylenediamine 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 feeding of the hydroxyethyl methacrylate is finished, the reaction temperature is increased to 55-60 ℃, and the reaction is continued for 4 hours, so that an intermediate formula (1 a) solution is prepared; maintaining the temperature of reactants in a reaction kettle, adding 0.22 g of dibutyl tin dilaurate, 120 g of acetone and 36 g of toluene diisocyanate into the reaction kettle, continuing to perform heat preservation and stirring reaction, and detecting that the NCO value in a reaction product system is close to a preset value to prepare an intermediate formula (1 b) solution; then the temperature of the reaction product system is reduced to room temperature, and 120 g of acetone solution containing 36 g of 5-chloromethylsalicylaldehyde is added, and the mixture is stirred and reacted for 6 hours to prepare the isocyanate crosslinking agent solution containing gemini quaternary ammonium cations in the molecular structure shown in the formula (1).
The Michael addition reaction product in example 1 was purified by chromatography, and strong absorption peaks at 1736nm, 1128nm and 1108nm respectively appear in the IR spectrum of the intermediate of formula (1 a), belonging to c=o and C-O-C, indicating that the intermediate of formula (1 a) has carboxylate structural features. Compared with the intermediate in the formula (1 a), the IR spectrum of the intermediate in the formula (1 b) separated and purified by the chromatographic column has a characteristic absorption peak of NCO at 2272nm and a characteristic absorption peak of O-H in the formula (1 b) which is shown to be removed from the near 3342nm to 3484nm, and a characteristic absorption peak of carbamate N-H in the formula (1) which is shown to be removed from the near 3342nm, wherein the characteristic absorption peak of carbamate N-H in the formula (1) is shown to be 3484nm, and the structural characteristics of the formula (1) are met. It is clear from this that the chemical structure of the product of the above preparation process is identical to the theoretical design.
Detecting 3.78% of isocyanate groups in an isocyanate crosslinking agent solution containing gemini quaternary ammonium cations in a molecular structure shown in a formula (1) by using a GB/T29493.6-2013 stipulation method; after the sealing and standing for 180 days at room temperature by filling nitrogen, the isocyanate group mass percent content in the sample is 3.58 percent by sampling analysis and detection. The storage stability period of the functional isocyanate crosslinking agent of the formula (1) at room temperature can reach more than 3 months.
Example 2 functional isocyanate crosslinker of formula (2)
According to the method and operation procedure of example 1, N '-dibenzylethylenediamine in example 1 is changed to N, N' -didodecylethylenediamine to prepare an isocyanate crosslinker solution having a structure shown in formula (2) and containing a gemini quaternary ammonium cation.
The isocyanate crosslinker structure of formula (2) containing a gemini quaternary ammonium cation was confirmed by IR. Detecting 3.46% of isocyanate groups in an isocyanate crosslinking agent solution with a structure containing a gemini quaternary ammonium cation shown in a formula (2) by using a GB/T29493.6-2013 stipulation method; after the sealing and standing for 180 days at room temperature by filling nitrogen, the mass percent of isocyanate groups in the mixture is 3.25 percent by sampling analysis and detection. The stable storage period of the functional isocyanate crosslinking agent solution of the formula (2) at room temperature can reach more than 3 months.
Example 3 functional isocyanate crosslinker of formula (3)
According to the method and procedure of example 1, N '-dibenzylethylenediamine in example 1 was changed to N, N' -dibenzyl-1, 6-hexamethylenediamine to prepare an isocyanate crosslinker solution having a structure shown by formula (3) containing a gemini quaternary ammonium cation.
The isocyanate crosslinker structure of formula (3) containing a gemini quaternary ammonium cation was confirmed by IR. Detecting 3.29 percent of isocyanate groups in an isocyanate crosslinking agent solution with a structure containing a gemini quaternary ammonium cation shown in a formula (3) by using a GB/T29493.6-2013 stipulation method; after the sealing and standing for 180 days at room temperature by filling nitrogen, the mass percent of isocyanate groups in the mixture is 3.23 percent by sampling analysis and detection. The stable storage period of the functional isocyanate crosslinking agent solution of the formula (3) at room temperature can reach more than 3 months.
Example 4 functional isocyanate crosslinker of formula (4)
According to the method and operation procedure of example 1, N' -dibenzylethylenediamine in 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 an isocyanate crosslinker solution having a structure containing a gemini quaternary ammonium cation represented by formula (4) was prepared.
The isocyanate crosslinker structure of formula (4) containing a gemini quaternary ammonium cation was confirmed by IR. Detecting the percentage content of isocyanate groups in the isocyanate crosslinking agent solution with the structure containing the gemini quaternary ammonium cation shown in the formula (4) by using a GB/T29493.6-2013 stipulation method, wherein the percentage content of isocyanate groups in the isocyanate crosslinking agent solution is 0.35%; after the sealing and standing for 180 days at room temperature by filling nitrogen, the mass percentage of isocyanate groups in the sample is 0.32 percent. The stable storage period of the functional isocyanate crosslinking agent solution of the formula (4) at room temperature can reach more than 3 months.
Example 5 Properties of the functional isocyanate crosslinkers in examples 1-4
Taking 20 g of the functional isocyanate crosslinking agent solution in examples 1-4 respectively, adding 10 g of absolute ethyl alcohol, heating to 60 ℃ and stirring for 4 hours, and dissolving the obtained ethylation products in 100mL of deionized water, wherein the result shows that the four ethylation products are easy to dissolve in water; according to the dilution ratio of 1:2, 1:5, 1:10, 1:20, 1:50 and 1:100, 2mL of the ethylation product aqueous solution of the examples 1-4 is respectively mixed with 10mL of culture medium, 2 drops of pathogenic bacterial strain liquid are added, after uniform mixing, the mixture is placed at 37 ℃ for culturing for 24 hours, the growth condition of pathogenic bacteria is observed, and the Minimum Inhibitory Concentration (MIC) is calculated, wherein the experimental results are shown in Table 1.
Table 1 results of bacteriostasis experiments
Claims (7)
1. The functional isocyanate crosslinking agent is characterized by comprising a gemini quaternary ammonium cation in a molecular structure, and has a structure shown in a general formula (A):
wherein R in the general formula (A) is selected from H or methyl, n is selected from natural numbers between 1 and 2000, R 1 And R is 2 Respectively selected from C 1 ～C 18 Hydrocarbon radicals, said
Selected from C 1 ～C 18 Hydrocarbylene radicals, the->
Selected from C 1 ～C 18 Hydrocarbylene or->
Wherein q is selected from natural numbers between 1 and 2000.
2. The functional isocyanate crosslinking agent and the preparation method thereof according to claim 1, wherein the preparation method of the functional isocyanate crosslinking agent is as follows: at room temperature, dissolving the general formula (B) in an organic solvent, starting stirring, and slowly adding hydroxyl-terminated polyether monoacrylate, wherein the dosage of the hydroxyl-terminated polyether monoacrylate is 1.8-2.2 times of the molar quantity of the general formula (B); after finishing feeding hydroxyl-terminated polyether monoacrylate, raising the reaction temperature to 50-70 ℃, continuously reacting for 2-20 hours, keeping the reaction temperature, sequentially adding a catalyst, a diluent and polyisocyanate into a reaction system, continuously stirring and preserving heat for 2-20 hours, detecting that the NCO content in the materials in a reactor is consistent with a preset value, reducing the temperature of a reaction product system to room temperature, then slowly adding a 5-chloromethyl salicylaldehyde solution, and stirring and reacting for 0.5-15 hours to prepare an isocyanate cross-linking agent solution containing gemini quaternary ammonium cations in the molecular structure shown in the general formula (A);
wherein the general formula (B) has the structure shown below:
wherein R in the formula (C) 1 And R is 2 Respectively selected from C 1 ～C 18 Hydrocarbon radicals, said
Selected from C 1 ～C 18 Hydrocarbylene or
the hydroxyl-terminated polyether 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.
3. The functional isocyanate crosslinking agent according to claim 2 and a method for preparing the same, wherein 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, said
Selected from C1-C18 hydrocarbylene; the amount of the polyisocyanateIs 1.8 to 2.2 times of the molar quantity of the general formula (B).
4. The functional isocyanate crosslinking agent and the preparation method thereof according to claim 2, wherein the organic solvent is 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).
5. The functional isocyanate crosslinking agent and the preparation method thereof according to claim 2, wherein the catalyst is one of dibutyl tin dilaurate, stannous octoate, stannous oxalate, dibutyl tin dimaleate, dibutyl tin (dodecyl sulfide) or dibutyl tin diacetate; the catalyst is used in an amount of 0.05 to 5% by mass of the polyisocyanate of the general formula (D).
6. The functional isocyanate crosslinking agent and the preparation method thereof according to claim 2, wherein 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).
7. The functional isocyanate crosslinking agent and the preparation method thereof according to claim 2 are characterized in that the mass ratio of the 5-chloromethylsalicylaldehyde to the organic solvent in the 5-chloromethylsalicylaldehyde solution is 20-50:100, and the dosage of the 5-chloromethylsalicylaldehyde is 1.8-2.2 times of the molar quantity of the general formula (B).
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