CN115368559A - Hydrogen bond induced bio-based fluorescent polyamide and preparation method thereof - Google Patents
Hydrogen bond induced bio-based fluorescent polyamide and preparation method thereof Download PDFInfo
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 55
- 229920002647 polyamide Polymers 0.000 title claims abstract description 55
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 21
- 239000001257 hydrogen Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
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- 238000001514 detection method Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 150000001412 amines Chemical class 0.000 claims description 21
- 150000002527 isonitriles Chemical class 0.000 claims description 21
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000002541 furyl group Chemical group 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 9
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 229910001447 ferric ion Inorganic materials 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 229920006021 bio-based polyamide Polymers 0.000 abstract description 13
- 229910021645 metal ion Inorganic materials 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 3
- 229920001109 fluorescent polymer Polymers 0.000 abstract description 2
- 239000008235 industrial water Substances 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 36
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 34
- FAGLEPBREOXSAC-UHFFFAOYSA-N tert-butyl isocyanide Chemical compound CC(C)(C)[N+]#[C-] FAGLEPBREOXSAC-UHFFFAOYSA-N 0.000 description 12
- 150000001299 aldehydes Chemical class 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000002189 fluorescence spectrum Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000006452 multicomponent reaction Methods 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000012716 precipitator Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 150000001408 amides Chemical group 0.000 description 4
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 4
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- 229940040102 levulinic acid Drugs 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 108010043958 Peptoids Proteins 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000003745 diagnosis Methods 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
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- 239000012467 final product Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
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- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- 238000006257 total synthesis reaction Methods 0.000 description 1
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- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/145—Heterocyclic containing oxygen as the only heteroatom
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- Chemical & Material Sciences (AREA)
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Abstract
The invention provides a preparation method of hydrogen bond induced bio-based fluorescent polyamide, belonging to the technical field of fluorescent polymer materials. The reaction process needs no catalyst, the condition is mild, and the atom economy is high. The bio-based polyamide prepared by the multi-component polymerization reaction contains abundant hydrogen bonds, so that fluorescence is generated. The bio-based fluorescent polyamide has good solubility, has a strong fluorescence emission peak at the wavelength of 460-480 nm, and can be applied to the detection of metal ions in industrial water, domestic water and biological systems.
Description
Technical Field
The invention belongs to the field of fluorescent polymer materials, and particularly relates to a preparation method of hydrogen bond induced bio-based fluorescent polyamide.
Background
Polyamides are an important class of polymeric materials in nature and in industrial applications. Natural polyamides are essential building blocks for polypeptides and proteins in the living body, and synthetic polyamides are receiving attention because of their excellent mechanical properties and thermal stability. In the current commercialized polyamide products, the bio-based polyamide only accounts for about 1 percent, so that the synthesis of the bio-based polyamide with high added value by using the cheap and renewable furfural-based monomer has important significance. The bio-based polyamide is mainly divided into two types according to different synthetic precursor structures, wherein one type is polyamide formed by condensation polymerization of amino acid or ring-opening polymerization of lactam; another class is polyamides formed by the polycondensation of diamines and diacids. Both polyamide (usually aliphatic) synthetic routes require high temperatures (170-260 ℃), high pressures and even high vacuum.
The multi-component reaction refers to a synthesis strategy of synthesizing a final product by three or more reactants through a one-pot method, and the structure of the multi-component reaction contains all reactant fragments, so that the multi-component reaction has wide application prospect in the fields of drug synthesis and total synthesis of natural products. The multi-component reaction has a series of advantages of simple and convenient operation, high reaction efficiency, mild conditions, no need of a catalyst and the like, and is favored by polymer chemists. The multi-component reaction is attracted by the advantages of convergence, selectivity (regio, stereo) and high yield, and provides an ideal choice for the synthesis of high molecular materials. Therefore, the polyamide with various structures and high added value can be prepared by utilizing multi-component reaction under mild conditions, and the application prospect is good.
The invention adopts multi-component polymerization reaction to prepare the bio-based polyamide, has the characteristics of wide monomer source, mild reaction condition, simple reaction system, convenient operation, wide substrate applicability and the like, conforms to the green chemical reaction concept and has important application value.
Disclosure of Invention
The invention aims to solve the technical problem of providing hydrogen bond induced bio-based fluorescent polyamide, a preparation method and application thereof, and solves the problem that the existing polyamide synthesis conditions are harsh and are endowed with high added value.
The technical scheme for realizing the invention is as follows: a hydrogen bond induced bio-based fluorescent polyamide has a structural formula as follows:
wherein n is an integer of 2 to 200; r 1 Selected from alkyl, furyl and phenyl with 1 to 6 carbon atoms; r 2 Selected from alkyl, furyl and phenyl with 1 to 10 carbon atoms; r is 3 Selected from alkyl, furanyl, benzyl of 1 to 6 carbon atoms; r is 4 Selected from alkyl, cycloalkyl, ester group and benzyl with 1 to 6 carbon atoms; r 5 Selected from alkyl, furyl and benzyl with 1 to 6 carbon atoms; r is 6 Selected from alkyl, furyl and benzyl with 1 to 6 carbon atoms; r is 7 Selected from alkyl, furyl and benzyl with 1 to 6 carbon atoms; the bio-based fluorescent polyamide has the non-traditional fluorescent characteristic, and the fluorescence emission wavelength is 460-480 nm.
The invention also aims to provide a preparation method of the hydrogen bond induced bio-based fluorescent polyamide, which comprises the steps of reacting aldehyde, amine, carboxylic acid and an isonitrile monomer in an organic solvent, and carrying out subsequent treatment to obtain the bio-based fluorescent polyamide; when aldehyde, amine, carboxylic acid and isonitrile monomers are reacted, the specific reaction formula is as follows:
(1) When aldehyde, amine, carboxylic acid and isonitrile monomers are reacted, the aldehyde is R 1 -CHO, amine NH 2 -R 2 - NH 2 The carboxylic acid is COOH-R 3 -COOH, isonitrile R 4 -NC, of the formula:
(2) The aldehyde being R 1 -CHO, amine is NH 2 -R 2 -NH 2 The carboxylic acid is R 5 -COOH, isonitrile CN-R 6 -NC, of the formula:
(3) The aldehyde being R 1 -CHO, amine R 7 -NH 2 The carboxylic acid is COOH-R 3 -COOH, isonitrile CN-R 6 -NC, of the formula:
specifically, aldehyde and amine are used as initial raw materials, and are stirred in an organic solvent to form an imine intermediate; continuously adding carboxylic acid and isonitrile monomers, and continuously reacting; after the reaction is finished, precipitating the product in water to remove the solvent, washing the product with acetone, and precipitating the product with normal hexane or petroleum ether to obtain the bio-based fluorescent polyamide.
Preferably, the monoaldehyde R 1 -CHO is selected from any one of the following 1 to 6; diamine NH 2 -R 2 -NH 2 Any one selected from the following 7 to 11; dicarboxylic acid COOH-R 3 -COOH is selected from any one of the following 12 to 16; the monoisonitrile R 4 -NC is selected from any one of the following 17-21; monocarboxylic acids R 5 -COOH is selected from any one of the following 22-26; binary isonitrile CN-R 6 -NC is selected from any one of the following 27-29; monoamine R 7 -NH 2 Any one selected from the following 30-34:
in the above synthesis method, the organic solvent is one or more of methanol, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and Tetrahydrofuran (THF), and preferably methanol.
Further characterized in that the aldehyde R 1 -CHO, amine NH 2 -R 2 -NH 2 Carboxylic acid COOH-R 3 -COOH, isonitrile R 4 -the molar ratio of NC to (2 to 3): 1:1: (2-3); aldehyde R 1 -CHO, amine NH 2 -R 2 - NH 2 Carboxylic acid R 5 -COOH, isonitrile CN-R 6 -the molar ratio of NC is (2 to 3): 1: (2-3): 1; aldehyde R 1 -CHO, amine R 7 -NH 2 Carboxylic acid COOH-R 3 -COOH, isonitrile CN-R 6 -the molar ratio of NC is (2 to 3): (2-3): 1:1.
the preparation method of the bio-based polyamide has the reaction time of 48 to 96 hours and the reaction temperature of 0 to 60 ℃.
The invention further aims to provide application of the hydrogen bond induced bio-based fluorescent polyamide in iron ion detection.
The preparation method provided by the invention selects multi-component polymerization reaction to prepare the bio-based fluorescent polyamide, and the material has stronger fluorescence luminescence characteristic and can be applied to detection of metal ions in industrial water, domestic water and a biological system. Compared with the prior art, the invention has the beneficial effects that:
1. the hydrogen bond induced bio-based fluorescent polyamide has high-efficiency fluorescence luminescence characteristics and a peptoid structure with high biological affinity, can be used for detecting metal ions in an environmental system and a biological system, and is expected to carry out cell imaging and disease diagnosis;
2. the invention utilizes multi-component polymerization reaction to prepare the hydrogen bond-containing bio-based fluorescent polyamide, does not need a catalyst, and has simple synthesis method, mild reaction condition and higher yield;
3. the invention utilizes various bio-based monomers as substrates of multi-component polymerization reaction, and has the characteristics of rich and various raw material structures, low price, environmental friendliness, greenness, reproducibility and the like.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the bio-based fluorescent polyamide synthesized in example 1 of the present invention.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the bio-based fluorescent polyamide synthesized in example 2 of the present invention.
FIG. 3 is a Fourier transform infrared spectrum of a bio-based fluorescent polyamide synthesized in examples 1-3 of the present invention.
FIG. 4 is a DSC curve of bio-based fluorescent polyamides synthesized in examples 1-3 of the present invention.
FIG. 5 is a fluorescence spectrum of bio-based fluorescent polyamide synthesized in examples 1 to 3 of the present invention.
FIG. 6 is a graph showing the response of the bio-based fluorescent polyamide synthesized in example 1 of the present invention to metal ions.
FIG. 7 shows the bio-based fluorescent polyamide synthesized in example 1 of the present invention for different concentrations of Fe 3+ Fluorescence spectrum of response.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1:
furfural, decamethylene diamine, 2,5-furandicarboxylic acid and tert-butyl isonitrile as raw materials, the reaction formula and experimental steps are as follows:
the monomers furfural, decamethylenediamine, 2,5-furandicarboxylic acid, and t-butyl isonitrile are commercially available; furfural (369mg, 3.84mmol, 3.0eq.), decamethylenediamine (220mg, 1.28mmol, 1.0eq.) were taken, added to a 10mL reaction tube containing 1.28mL of methanol, stirred at room temperature for 30 minutes, and then 2,5-furandicarboxylic acid (200mg, 1.28mmol, 1.0eq.) and tert-butylisonitrile (319mg, 3.84mmol, 3.0eq.) were added, followed by a further reaction for 72 hours. After the reaction is finished, water is used as a precipitator, acetone washing and normal hexane secondary precipitation are carried out, and the bio-based fluorescent polyamide compound is obtained after drying, wherein the yield is 93%, the number average molecular weight is 7600g/mol, and the molecular weight distribution index is 1.70.
The NMR spectrum of the bio-based fluorescent polyamide P1 prepared in this example is shown in FIG. 1. From FIG. 1, it can be seen that the chemical shift of the carboxyl group in the monomer 2,5-furandicarboxylic acid is knownUpon disappearance, the-CH-shift in the monomeric furfural, directly connected to the furan ring, was reduced to 5.98ppm. The infrared absorption spectrum of the bio-based fluorescent polyamide P1 prepared in the example is shown in FIG. 3, and it can be seen from FIG. 3 that characteristic peaks of the amide structure in P1 appear at 1625 and 1570cm -1 And the stretching vibration peak of N-H in amide appears at 3417 and 3326cm -1 This indicates that the polymerization reaction proceeded smoothly. The DSC curve of the bio-based fluorescent polyamide prepared in this example under nitrogen is shown in fig. 4. FIG. 4 shows that the glass transition temperature of the resulting polymer was 90.5 ℃. The fluorescence emission spectrum of the bio-based fluorescent polyamide prepared in the embodiment is shown in FIG. 5 under the excitation wavelength of 387nm, and the maximum emission wavelength of the polymer appears at 484nm. FIG. 6 shows fluorescence emission spectra (excitation wavelength 387 nm) of bio-based fluorescent polyamide P1 prepared in example 1 after different metal ions were added. As can be seen from FIG. 6, the bio-based polyamide P1 is coupled with Fe 2+ And Fe 3+ All have obvious fluorescence quenching effect. FIG. 7 shows the addition of Fe at various concentrations to the bio-based polyamide P1 prepared in example 1 3+ Fluorescence emission spectrum (excitation wavelength is 387 nm) after metal ion. As can be seen from FIG. 7, with Fe 3+ The polymer solution gradually decreases in luminescence with an increase in the concentration of the metal ions.
Example 2:
furfural, pentamethylene diamine, 2,5-furandicarboxylic acid and tert-butyl isonitrile are used as raw materials, and the reaction formula and the experimental steps are as follows:
the monomers furfural, pentanediamine, 2,5-furandicarboxylic acid and t-butyl isonitrile are commercially available; furfural (369mg, 3.84mmol, 3.0eq.), pentamethylenediamine (131mg, 1.28mmol, 1.0eq.) were added to a 10mL reaction tube containing 1.28mL of methanol, and stirred at room temperature for 30 minutes, followed by addition of 2,5-furandicarboxylic acid (200mg, 1.28mmol, 1.0eq.) and t-butylisonitrile (319mg, 3.84mmol, 3.0eq.) and continued reaction for 72 hours. After the reaction is finished, water is used as a precipitator, acetone washing and secondary precipitation are carried out by normal hexane, and the bio-based polyamide compound is obtained after drying, wherein the yield is 91%, the number average molecular weight is 2100g/mol, and the molecular weight distribution index is 1.45.
The NMR spectrum of the bio-based fluorescent polyamide P2 prepared in this example is shown in FIG. 2, and it can be seen from FIG. 2 that the chemical shift of the carboxyl group in the monomer 2,5-furandicarboxylic acid has disappeared, and the-CH-shift directly connected to the furan ring in the monomer furfural is reduced to 5.78-6.00ppm. The infrared absorption spectrum of the bio-based fluorescent polyamide P2 prepared in the example is shown in FIG. 3, and it can be seen from FIG. 3 that characteristic peaks of the amide structure in P1 appear at 1625 and 1570cm -1 . The DSC curve of the bio-based fluorescent polyamide prepared in this example under nitrogen atmosphere is shown in FIG. 4. FIG. 4 shows that the glass transition temperature of the resulting polymer was 117 ℃. The fluorescence emission spectrum of the bio-based fluorescent polyamide prepared in the embodiment is shown in FIG. 5 at an excitation wavelength of 387nm, and FIG. 5 shows that the maximum emission wavelength of the obtained polymer appears at 484nm.
Example 3:
furfural, polyether amine (D230), 2,5-furandicarboxylic acid and tert-butyl isonitrile as raw materials, and the reaction formula and the experimental steps are as follows:
the monomers furfural, polyetheramine (D230), 2,5-furandicarboxylic acid and tert-butylisonitrile are commercially available; furfural (369mg, 3.84mmol, 3.0eq.), polyetheramine (294mg, 1.28mmol, 1.0eq.) were taken, added to a 10mL reaction tube containing 1.28mL of methanol, stirred at room temperature for 30 minutes, and then 2,5-furandicarboxylic acid (200mg, 1.28mmol, 1.0eq.) and t-butylisonitrile (319mg, 3.84mmol, 3.0eq.) were added, and the reaction was continued for 72 hours. After the reaction is finished, water is used as a precipitator, acetone washing and normal hexane secondary precipitation are carried out, and the bio-based polyamide compound is obtained after drying, wherein the yield is 80%, the number average molecular weight is 6600g/mol, and the molecular weight distribution index is 1.31.
Bio-based fluorescent polyamides prepared in this exampleThe IR absorption spectrum of P3 is shown in FIG. 3, and it can be seen from FIG. 3 that characteristic peaks of the amide structure in P1 appear at 1625 and 1570cm -1 . The DSC curve of the bio-based fluorescent polyamide prepared in the example under the nitrogen atmosphere is shown in FIG. 4. FIG. 4 shows that the glass transition temperature of the resulting polymer is 99 ℃. The fluorescence emission spectrum of the bio-based fluorescent polyamide prepared in the embodiment is shown in fig. 5 at an excitation wavelength of 387nm, and fig. 5 shows that the maximum emission wavelength of the obtained polymer appears at 460nm.
Example 4:
benzaldehyde, pentanediamine, 2,5-furandicarboxylic acid and tert-butyl isonitrile are taken as raw materials, and the reaction formula and the experimental steps are as follows:
the monomers benzaldehyde, pentanediamine, 2,5-furandicarboxylic acid and t-butylisonitrile are commercially available; benzaldehyde (407mg, 3.84mmol, 3.0eq.), pentanediamine (131mg, 1.28mmol, 1.0eq.) were added to a 10mL reaction tube containing 1.28mL of methanol, and the mixture was stirred at room temperature for 30 minutes, and then 2,5-furandicarboxylic acid (200mg, 1.28mmol, 1.0eq.) and t-butylisonitrile (319mg, 3.84mmol, 3.0eq.) were added, and the reaction was continued for 72 hours. After the reaction is finished, washing the mixture by using a water precipitator through acetone, carrying out secondary precipitation by using n-hexane, and drying the mixture to obtain the bio-based polyamide compound, wherein the yield is 90%, the number average molecular weight is 4590g/mol, and the molecular weight distribution index is 1.75.
Example 5:
the method takes furfural, decamethylene diamine, levulinic acid and hexamethylene dinitrile as raw materials, and comprises the following reaction formula and experimental steps:
the monomers furfural, decamethylenediamine, levulinic acid and hexamethylene dinitrile are commercially available; furfural (369 mg,3.84mmol,3.0 eq.), decamethylenediamine (220mg, 1.28mmol,1.0 eq.) were added to a 10mL reaction tube containing 1.28mL of methanol, stirred at room temperature for 30 minutes, and then levulinic acid (446 mg,3.84mmol,3.0 eq.) and adiponitrile (174mg, 1.28mmol,1.0 eq.) were added and the reaction was continued for 72 hours. After the reaction is finished, washing the reaction product by using a water precipitator through acetone, carrying out secondary precipitation through n-hexane, and drying the reaction product to obtain the bio-based polyamide compound, wherein the yield is 89%, the number average molecular weight is 5320g/mol, and the molecular weight distribution index is 1.74.
Example 6:
furfural, n-butylamine, 2,5-furandicarboxylic acid and hexamethylene dinitrile are used as raw materials, and the reaction formula and the experimental steps are as follows:
the monomers furfural, n-butylamine, 2,5-furandicarboxylic acid, and adiponitrile are commercially available; furfural (369 mg,3.84mmol, 3.0eq.), n-butylamine (281mg, 3.84mmol, 3.0eq.) were added to a 10mL reaction tube containing 1.28mL methanol, stirred at room temperature for 30 minutes, and then 2,5-furandicarboxylic acid (200 mg,1.28mmol, 1.0eq.) and diisocyanatohexane (174mg, 1.28mmol, 1.0eq.) were added, and the reaction was continued for 72 hours. After the reaction is finished, washing the reaction product by using a water precipitator through acetone, carrying out secondary precipitation through n-hexane, and drying the reaction product to obtain the bio-based polyamide compound with the side group containing the furan ring, wherein the yield is 90%, the number-average molecular weight is 5570 g/mol, and the molecular weight distribution index is 1.71.
While the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the details of the embodiments, and various equivalent modifications can be made within the technical spirit of the present invention, and the scope of the present invention is also within the scope of the present invention.
Claims (8)
1. A hydrogen bond induced bio-based fluorescent polyamide is characterized in that the structural formula is as follows:
wherein n is an integer of 2 to 200; r 1 Selected from alkyl, furyl and phenyl with 1 to 6 carbon atoms; r 2 Selected from alkyl, furyl and phenyl with 1 to 10 carbon atoms; r is 3 Selected from alkyl, furyl and benzyl with 1 to 6 carbon atoms; r 4 Selected from alkyl, cycloalkyl, ester group and benzyl with 1 to 6 carbon atoms; r 5 Selected from alkyl, furyl and benzyl with 1 to 6 carbon atoms; r 6 Selected from alkyl, furyl and benzyl with 1 to 6 carbon atoms; r is 7 Selected from alkyl, furyl and benzyl with 1 to 6 carbon atoms; the bio-based fluorescent polyamide has the non-traditional fluorescent characteristic, and the fluorescence emission wavelength is 460-480 nm.
2. The method for preparing hydrogen bond-induced bio-based fluorescent polyamide as claimed in claim 1, wherein: the method comprises the following steps:
reacting aldehyde, amine, carboxylic acid and an isonitrile monomer in an organic solvent, and performing subsequent treatment to obtain the bio-based fluorescent polyamide; when aldehyde, amine, carboxylic acid and isonitrile monomers are reacted,
(1) The aldehyde being R 1 -CHO, amine NH 2 -R 2 -NH 2 Carboxylic acid is COOH-R 3 -COOH, isonitrile R 4 -NC, of the formula:
(2) The aldehyde being R 1 -CHO, amine NH 2 -R 2 -NH 2 The carboxylic acid is R 5 -COOH, isonitrile CN-R 6 -NC, of the formula:
(3) The aldehyde being R 1 -CHO, amine R 7 -NH 2 Carboxylic acid is COOH-R 3 -COOH, isonitrile CN-R 6 -NC, inverseThe formula is as follows:
3. the method for preparing hydrogen bond-induced bio-based fluorescent polyamide according to claim 2, characterized in that: aldehyde R 1 -CHO is selected from any one of the following 1 to 6; amine NH 2 -R 2 -NH 2 Any one selected from the following 7 to 11; carboxylic acid COOH-R 3 -COOH is selected from any one of the following 12-16; isonitrile R 4 -NC is selected from any one of the following 17-21; carboxylic acids R 5 -COOH is selected from any one of the following 22-26; isonitrile CN-R 6 -NC is selected from any one of the following 27-29; amine R 7 -NH 2 Any one selected from the following 30-34:
4. the method for preparing hydrogen bond-induced bio-based fluorescent polyamide as claimed in claim 2, wherein: the organic solvent is selected from one or more of methanol, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or Tetrahydrofuran (THF).
5. The method for preparing hydrogen bond-induced bio-based fluorescent polyamide as claimed in claim 2, wherein: the aldehyde R 1 -CHO, amine NH 2 -R 2 -NH 2 Carboxylic acid COOH-R 3 -COOH, isonitrile R 4 -the molar ratio of NC is (2 to 3): 1:1: (2-3); aldehyde R 1 -CHO, amine NH 2 -R 2 -NH 2 Carboxylic acid R 5 -COOH, isonitrile CN-R 6 -the molar ratio of NC is (2 to 3): 1: (2-3): 1; aldehyde R 1 -CHO, amine R 7 -NH 2 Carboxylic acid COOH-R 3 -COOH, isonitrile CN-R 6 of-NCThe molar ratio is (2-3): (2-3): 1:1.
6. the method for preparing hydrogen bond-induced bio-based fluorescent polyamide as claimed in claim 2, wherein: the reaction time is 48 to 96 hours, and the reaction temperature is 0 to 60 ℃.
7. The method for preparing hydrogen bond-induced bio-based fluorescent polyamide as claimed in claim 2, wherein: and the subsequent treatment is to precipitate the reaction solution in water after the reaction is finished, wash the reaction solution with acetone, and precipitate the reaction solution in petroleum ether or n-hexane to obtain the bio-based fluorescent polyamide.
8. The use of the hydrogen bond-induced bio-based fluorescent polyamide of claim 1 in ferric ion detection.
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| US3277033A (en) * | 1962-03-15 | 1966-10-04 | Bayer Ag | Polyamides from an isonitrile, a carboxylic acid, an amino and a carbonyl compound and a process for their manufacture |
| US3285992A (en) * | 1962-04-04 | 1966-11-15 | Bayer Ag | Polyesteramide prepared by reacting a carboxyl containing copolymer with an isonitrile, and an aldehyde or a ketone |
| DE102014011402A1 (en) * | 2014-08-06 | 2016-02-11 | Basf Se | Process for the preparation of polyamides by multicomponent reaction |
| CN110563943A (en) * | 2019-09-09 | 2019-12-13 | 中国科学院长春应用化学研究所 | Bio-based polymer and preparation method thereof |
| CN111393647A (en) * | 2020-03-12 | 2020-07-10 | 香港科技大学深圳研究院 | Non-traditional luminous polymer and preparation method and application thereof |
| CN113121781A (en) * | 2021-04-20 | 2021-07-16 | 西北工业大学 | Preparation method of self-repairable thermosetting film based on multi-component Ugi polymerization reaction and dynamic oxime urethane bond exchange |
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| US3277033A (en) * | 1962-03-15 | 1966-10-04 | Bayer Ag | Polyamides from an isonitrile, a carboxylic acid, an amino and a carbonyl compound and a process for their manufacture |
| US3285992A (en) * | 1962-04-04 | 1966-11-15 | Bayer Ag | Polyesteramide prepared by reacting a carboxyl containing copolymer with an isonitrile, and an aldehyde or a ketone |
| DE102014011402A1 (en) * | 2014-08-06 | 2016-02-11 | Basf Se | Process for the preparation of polyamides by multicomponent reaction |
| CN110563943A (en) * | 2019-09-09 | 2019-12-13 | 中国科学院长春应用化学研究所 | Bio-based polymer and preparation method thereof |
| CN111393647A (en) * | 2020-03-12 | 2020-07-10 | 香港科技大学深圳研究院 | Non-traditional luminous polymer and preparation method and application thereof |
| CN113121781A (en) * | 2021-04-20 | 2021-07-16 | 西北工业大学 | Preparation method of self-repairable thermosetting film based on multi-component Ugi polymerization reaction and dynamic oxime urethane bond exchange |
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