CN115505079A - Temperature-sensitive keratin, catalyst, preparation method and application - Google Patents
Temperature-sensitive keratin, catalyst, preparation method and application Download PDFInfo
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- CN115505079A CN115505079A CN202211223255.5A CN202211223255A CN115505079A CN 115505079 A CN115505079 A CN 115505079A CN 202211223255 A CN202211223255 A CN 202211223255A CN 115505079 A CN115505079 A CN 115505079A
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- 102000011782 Keratins Human genes 0.000 title claims abstract description 129
- 108010076876 Keratins Proteins 0.000 title claims abstract description 129
- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000010949 copper Substances 0.000 claims abstract description 47
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 claims abstract description 36
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000017 hydrogel Substances 0.000 claims abstract description 17
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 9
- 150000001879 copper Chemical class 0.000 claims abstract description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 36
- 150000001728 carbonyl compounds Chemical group 0.000 claims description 31
- 239000000047 product Substances 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 21
- -1 ketone compound Chemical class 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 8
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- 238000007334 copolymerization reaction Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 5
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000000499 gel Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 4
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 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
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 238000000502 dialysis Methods 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 claims description 2
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 claims description 2
- 125000006275 3-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C([H])C(*)=C1[H] 0.000 claims description 2
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 claims description 2
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 2
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 2
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical group NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 2
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical group C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 claims description 2
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical group OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 claims description 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Chemical group NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004472 Lysine Chemical group 0.000 claims description 2
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims description 2
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Chemical group CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004473 Threonine Chemical group 0.000 claims description 2
- 125000000637 arginyl group Chemical group N[C@@H](CCCNC(N)=N)C(=O)* 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000007306 functionalization reaction Methods 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 125000003607 serino group Chemical group [H]N([H])[C@]([H])(C(=O)[*])C(O[H])([H])[H] 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Chemical group OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 30
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052796 boron Inorganic materials 0.000 abstract description 14
- 238000007259 addition reaction Methods 0.000 abstract description 12
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 abstract description 6
- 235000005513 chalcones Nutrition 0.000 abstract description 6
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 description 19
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 14
- 238000006555 catalytic reaction Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- 125000003700 epoxy group Chemical group 0.000 description 2
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- 229910021645 metal ion Inorganic materials 0.000 description 2
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- 239000000203 mixture Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920003213 poly(N-isopropyl acrylamide) Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
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- 210000001519 tissue Anatomy 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
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- 239000012620 biological material Substances 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 230000010478 bone regeneration Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- UNXISIRQWPTTSN-UHFFFAOYSA-N boron;2,3-dimethylbutane-2,3-diol Chemical compound [B].[B].CC(C)(O)C(C)(C)O UNXISIRQWPTTSN-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
- C07K14/435—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
- C07K14/46—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from vertebrates
- C07K14/47—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from vertebrates from mammals
- C07K14/4701—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from vertebrates from mammals not used
- C07K14/4741—Keratin; Cytokeratin
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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Abstract
The invention relates to temperature-sensitive keratin, a catalyst, a preparation method and application, and specifically comprises the following steps: (1) Functionalizing keratin powder by using 1, 2-epoxy-4-vinylcyclohexane, reacting the obtained product with N-isopropyl acrylamide to obtain temperature-sensitive hydrogel, and loading copper salt to obtain a temperature-sensitive keratin copper catalyst; (2) characterizing the prepared catalyst; (3) Applying the prepared catalyst to boron addition reaction of chalcone; and (4) carrying out a catalyst recycling test. The temperature-sensitive type keratin copper catalyst PNKCu obtained by the invention has low critical temperature, can realize solid-liquid conversion at 25-35 ℃, has good repeatability and recoverability, and has high reaction activity in boron addition reaction of chalcone.
Description
Technical Field
The invention belongs to the technical field of production of beta-borate substituted carbonyl compounds, and particularly relates to temperature-sensitive keratin, a catalyst, a preparation method and application.
Background
Boron addition reaction plays an important role in synthesis, and means that diborane is dissociated into borane in an ether solution and then reacts with unsaturated bonds of alkyne and alkene in the form of B-H bonds to generate an organoboron compound. The product generated by the reaction exists as an important intermediate in synthesis, and can be converted into a plurality of very important functional groups such as hydroxyl, aryl, alkenyl and the like through Suzuki coupling reaction. Has important value in the fields of fine chemicals, pharmacy, materials and the like. Recently, the literature (Nanomaterials, 2018 (5)) catalyzed the conversion of α, β -unsaturated ketones to β -boronate substituted carbonyls using divalent copper (1 mol%, mass percent relative to the template reaction substrate) by using chalcone as the template substrate, 1.2 equivalents of pinacol bisboronate reagent, a mixed solution of acetone and water as the solvent, and reacting at room temperature to obtain a higher yield of β -boronate substituted carbonyls, followed by NaBO 3 ·4H 2 And O is an oxidant, and the hydroxyl substituted carbonyl compound can be obtained by oxidizing for 4 hours at room temperature. However, the material has relatively low reactivity compared with other copper (II) homogeneous catalysis materials using the reaction, and the preparation method of the catalysis material is more complicated compared with other heterogeneous catalysis. Therefore, it is urgent to develop a new green and environment-friendly method which is simple and easy to operate and can directly convert the alpha, beta-unsaturated ketone compound into the beta-borate substituted carbonyl compound with high yield.
Keratin has applications in many fields due to its excellent properties. For example, in the food industry, keratin is rich in umami amino acids and can be made into food additives. In the biomedical field, keratin is used alone or in combination with other biomaterials to produce materials such as bone regeneration, wound healing, hemostasis, peripheral nerve repair, etc. In the cosmetic industry, the characteristics of high resistance, special biological action and the like can be utilized to prepare certain daily required cosmetics such as sunscreen cream, shampoo and the like by taking the plant extract as a raw material. In the aspect of tissue engineering, the compound is expected to be a substitute of tissue engineering due to excellent biocompatibility and activity. In addition, keratin also has important effects in the aspects of fertilizers, pesticides, environmental protection and the like.
At around the critical temperature (LCST), PNIPAAm hydrogels have hydrophobic/hydrophilic, chain-coil/stretch volume phase transition properties. Due to these characteristics, the catalyst formed by the PNIPAAm hydrogel complex metal ions is easy to recover near the LCST. When the temperature of the reaction system is lower than the LCST, the catalyst will be dissolved in the aqueous solution to form a transparent solution. When the temperature of the reaction system is higher than LCST, the catalyst can be separated out, so that the effective reuse and convenient recovery of the catalyst are realized, and the catalyst is more economic, green and environment-friendly. At present, no report is found about the research of the application of the temperature-sensitive keratin-loaded copper catalyst in the boron addition reaction for constructing C-B bonds.
Disclosure of Invention
In order to prepare a green catalyst with high reaction activity and easy recovery, functionalized keratin and N-isopropylacrylamide (NIPAAm) are used for reaction to prepare a temperature-sensitive hydrogel PNK for experiments, and a dried hydrogel is loaded with copper salt to prepare the temperature-sensitive keratin copper catalyst PNKCu.
The invention adopts the technical conception that temperature-sensitive materials N-isopropyl acrylamide and functionalized keratin are polymerized to prepare hydrogel with thermal responsiveness, cupric salt is loaded to ensure that the hydrogel has catalytic activity, the divalent cupric salt can be uniformly dissolved in a solvent in the catalytic reaction process, and the catalyst can be separated by changing the integral temperature of the catalyst after the reaction is finished.
A temperature-sensitive keratin has the following structural formula,
wherein R represents serine, threonine, tyrosine, lysine and arginine residues in keratin molecules, and a + b = 12-13.
Further, m: N =50 to 90, 90 represents the degree of polymerization of N-isopropylacrylamide, and 10 represents the degree of polymerization of keratin.
Further, a: b is less than or equal to 3.
A preparation method of temperature-sensitive keratin comprises the following preparation methods,
step 1.1 functionalization of keratin: dissolving keratin powder and 1,2 epoxy-4-vinyl cyclohexane in ionized water, stirring to obtain a mixed solution, dropwise adding the mixed solution into acetone, filtering to obtain a precipitate, repeatedly washing the precipitate with acetone, and finally performing vacuum drying at 50-70 ℃ to obtain functionalized keratin;
step 1.2, polymerization of the temperature-sensitive material: dissolving and polymerizing the product obtained in the step 1.1 and a temperature-sensitive material N-isopropylacrylamide (NIPAAm) in deionized water to obtain a temperature-sensitive hydrogel solution, adding an initiator to carry out copolymerization reaction, placing the product of the copolymerization reaction in a dialysis bag, dialyzing with deionized water, and finally drying in an oven to obtain the temperature-sensitive keratin gel.
Further, in the step 1.2, the initiator is ammonium persulfate, the initiation temperature is 60 ℃, and the polymerization time is 24 hours.
Further, the acetone content in the acetone solution in the step 1.1 is as follows: the mass ratio of the solution =10:1, in the step 1.1, the stirring temperature is 60 ℃, and the stirring time is 24 hours.
A catalyst containing temperature-sensitive keratin is prepared by dissolving water-soluble divalent copper salt in deionized water, mixing with temperature-sensitive keratin gel, stirring at room temperature for 24 hr, and freeze drying to obtain temperature-sensitive keratin copper catalyst.
Further, the water-soluble divalent copper salt is one or more of copper sulfate, copper nitrate and copper chloride.
Further, cu in the catalyst 2+ The molar ratio of the temperature-sensitive keratin to keratin in the temperature-sensitive keratin is 1:10.
the application of the catalyst containing the temperature-sensitive keratin in synthesizing a beta-borate substituted carbonyl compound is characterized in that an alpha, beta-unsaturated ketone compound and a pinacol bisborate ester are used as raw materials, the catalyst containing the temperature-sensitive keratin is used as a catalyst, and the raw materials are uniformly stirred at room temperature to prepare the beta-borate substituted carbonyl compound;
the structural formula of the alpha, beta-unsaturated ketone compound is shown in the specification
The structural formula of the corresponding beta-boric acid ester substituted carbonyl compound is shown as
Wherein R is 1 Is one of phenyl, p-methylphenyl and p-methoxyphenyl, R 2 Is one of phenyl, p-methylphenyl, p-methoxyphenyl, p-fluorophenyl, p-chlorophenyl, p-bromophenyl, o-chlorophenyl, m-bromophenyl and m-chlorophenyl.
Further, the preparation method of the beta-boric acid ester substituted carbonyl compound comprises the following steps:
step P1, mixing and adding an alpha, beta-unsaturated ketone compound, polyboronate pinacol ester and a temperature-sensitive keratin-containing catalyst into a solvent according to the mass ratio of 1: 0.01; the amount of the substance of the temperature-sensitive keratin copper catalyst is Cu 2+ As a benchmark;
step P2, extracting the product obtained in the step P1 by using an organic solvent, drying, performing rotary evaporation, and finally performing column chromatography separation to obtain a beta-borate ester substituted carbonyl compound;
in the step P2, the volume ratio of ethyl acetate to petroleum ether used for column chromatography is 1.
Compared with the prior art, the invention has the following beneficial effects:
1. the temperature-sensitive keratin prepared by the invention is prepared on the basis of the catalyst loaded with a large amount of metallic copper, and finally the temperature-sensitive keratin copper catalyst is obtained, and the keratin can be grafted with a group containing C = C after the reaction of the keratin and 1, 2-epoxy-4-vinylcyclohexane, so that the functionalized keratin can be grafted and copolymerized with a hydrophilic monomer N-isopropylacrylamide (NIPAAm) better, and the formed copolymerization product has rich pore structures, the diameter is 5-10 mu m, the size is larger, and the copolymerization products are stacked together, so that the loading of a large amount of metallic copper can be realized, and the catalyst has stronger catalytic activity.
2. The invention also provides application of the temperature-sensitive keratin-based copper catalyst, which takes the alpha, beta-unsaturated ketone compound and the pinacol diborate as raw materials and utilizes the temperature-sensitive keratin-based copper catalyst to prepare the beta-borate substituted carbonyl compound. The reaction condition of the whole preparation process is mild, no alkali is needed to be added, methanol is used as a solvent, the reaction is carried out at room temperature, and the preparation method is simple and easy to operate. Due to the high activity of the catalyst, the yield of the beta-borate ester substituted carbonyl compound prepared based on the catalyst is high, and is over 80 percent, and the yield of the specific beta-borate ester substituted carbonyl compound is as high as 92 percent. In addition, the catalyst can catalyze various different types of alpha, beta-unsaturated ketone compounds to complete boron addition reaction, and the substrate application range is wide.
3. The catalyst provided by the invention has the characteristic of low critical temperature after the graft copolymerization of the keratin and the temperature-sensitive material, the solid-liquid conversion can be realized by adjusting the temperature to 25-35 ℃ when the catalyst is recovered, namely, the product and the catalyst can realize solid-liquid separation through simple temperature change, the catalyst has good repeatability and recoverability, and the recovered catalyst still has very high catalytic activity and longer cycle service life, so the catalyst has very low cost in the production preparation and later use processes, is environment-friendly and avoids the problem of environmental pollution.
Drawings
FIG. 1 shows SEM morphology of temperature sensitive material PN90K10 Cu;
FIG. 2 is an XRD pattern of temperature sensitive material keratin powder, functionalized keratin, PN90K10 Cu;
FIG. 3 is an LCST test spectrum of temperature sensitive material PN90K10 Cu;
FIG. 4 is a nuclear magnetic hydrogen spectrum of the target product in application example 1;
FIG. 5 is a nuclear magnetic carbon spectrum of a target product in application example 1;
FIG. 6 is a diagram of the repeatability and recovery performance study of the thermo-sensitive material PN90K10 Cu.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. For a better understanding of the present invention, reference will now be made in detail to the present invention, which is illustrated in the accompanying drawings and specific examples. The method specifically shows the preparation and the application of the temperature-sensitive type keratin copper catalyst, and the catalytic performance test and the recoverable performance test of the temperature-sensitive type keratin copper catalyst material.
Example 1
In the temperature-sensitive type keratin copper catalyst provided by the embodiment, the carrier is functionalized keratin powder, N-isopropylacrylamide is a hydrophilic monomer, and Ammonium Persulfate (APS) is used as an initiator to prepare the catalyst in deionized water and then adsorb copper ions, so that the temperature-sensitive type keratin copper catalyst is formed. The preparation method comprises the following steps:
s1, weighing 1.9987g of dry hydrolyzed keratin powder (keratin), weighing 20mL of deionized water, pouring into a 100mL round-bottom flask, putting a stirrer with a proper size, plugging the bottle mouth with a rubber stopper, and stirring at 60 ℃ for 24 hours to dissolve the keratin powder (10 wt% solution); 0.3618g of 1, 2-epoxy-4-vinylcyclohexane is then added and reacted for 24h at 50-70 ℃ with magnetic stirring, and the reaction medium is then transferred dropwise into acetone with vigorous stirring (acetone: solution mass ratio = 10. Collecting the precipitate, washing with acetone for several times, and vacuum drying at 60 deg.C for 24 hr to obtain functionalized keratin; in this step, the molar ratio of keratin to 1, 2-epoxy-4-vinylcyclohexane is 10:3.
s2, weighing 1.7985g of N-isopropylacrylamide (NIPAAm) and 0.2019g of functionalized keratin prepared in the step S1 into a round-bottom flask, and measuring 20mL of deionized water to dissolve the functionalized keratin in the round-bottom flask to obtain a 10wt% NIPAAm solution containing the keratin; free radical polymerization was carried out at 60 ℃ for 24h with NIPAAm solution containing keratin using 0.1039g Ammonium Persulfate (APS) as initiator. The adding amount of the ammonium persulfate is 5 percent of the total amount of N-isopropyl acrylamide, the polymerization is less than incomplete, and the excessive amount can cause the molecular weight of the polymer to be smaller and can not form a hole structure.
After the reaction is finished, pouring the reaction product into a dialysis bag, dialyzing with deionized water for 24 hours, and then putting into an oven to dry for 4 hours to obtain the temperature-sensitive keratin hydrogel; in this step, the molar ratio of N-isopropylacrylamide to keratin was 90.
S3, weighing 0.499g of CuSO by using an electronic balance 4 Dissolving the crystal in 50mL of deionized water to prepare CuSO 4 Measuring 25mL of prepared CuSO in the water solution 4 Pouring the solution into a beaker, weighing 0.1002g of dried temperature-sensitive keratin hydrogel prepared in the step S2, pouring the dried temperature-sensitive keratin hydrogel into the beaker to enable the hydrogel to adsorb metal copper ions, stirring the mixture at normal temperature for 24 hours, then carrying out freeze drying on the mixture, and obtaining a freeze-dried temperature-sensitive keratin copper catalyst after 24 hours, wherein in the step, cu is used as the Cu catalyst 2+ The molar ratio of the temperature-sensitive keratin to keratin in the temperature-sensitive keratin is 1:10.
in this example, 1, 2-epoxy-4-vinylcyclohexane may be replaced with other organic substance a having a C = C double bond and an epoxy group, the C = C double bond may be polymerized with N-isopropylacrylamide, and the epoxy group may be linked to the carboxyl group of the amino acid after ring opening.
If the structural formula of the organic matter A is:
x is = CH-or =N-, Y is-NH-, -NR 4 -、-S-、-O-、-CH＝N-、-N＝CH-、-N＝N-、-CH＝CH-、
R 1 Is H, or optionally substituted lower alkyl, R 5 、R 6 Or R 7 Is optionally substituted lower aryl, optionally substituted lower N-atom-containing heterocycle, optionally substituted lower alkoxy, or optionally substituted amino.
The keratin and 1, 2-epoxy-4-vinylcyclohexane provided in this example were purchased from Shanghai Bigdi medical science and technology, inc., N-isopropylacrylamide (NIPAAm) was purchased from Shanghai Michelin medical science and technology, inc., and copper sulfate was purchased from Tianjin Kaiton chemical reagent, inc. The carboxylic acid group in the keratin has good reactivity, can be conveniently modified and grafted, and the keratin can be used for immobilizing metal ions through coordination and electrostatic action. However, keratin does not have temperature-sensitive property, so that the keratin can obtain the temperature-sensitive characteristic by polymerizing the keratin with N-isopropyl acrylamide (NIPAAm), and the solid-liquid separation can be realized by changing the temperature. The water-soluble cupric salt is one of copper sulfate, copper nitrate and copper chloride.
As shown in FIG. 1, a SEM scanning electron microscope image of the temperature sensitive material PN90K10Cu prepared in example 1, and a drawing b in the drawing is a partial view of a drawing a, and the keratin with a pore structure, the diameter of which is 5-10 μm, the size of which is larger, is stacked together and has some aggregates can be seen.
FIG. 2 is an XRD pattern of PN90K10Cu prepared as a temperature sensitive material in example 1, according to the XRD curve analysis, the keratin powder (a) has a large diffraction intensity and a blunt crystalline peak appearing at 12.4 degrees, which is an overlapping peak of an alpha-helical structure and a beta-sheet structure; the peaks with duller diffraction intensity at 18.9 degrees and 26 degrees are respectively an alpha-helix characteristic peak and an alpha-folding characteristic peak, and the arrangement of the keratin can be analyzed by an XRD curve of the keratin in a main mode of an alpha-helix structure, a beta-helix structure and an amorphous arrangement. The functionalized keratin (b) exhibits a diffraction peak at the same position as compared to the keratin powder (a), but is relatively low and broad.
This is because keratin reacts with 1, 2-epoxy-4-vinylcyclohexane to reduce intermolecular forces, increase intermolecular distances, slightly interfere with the degree of molecular chain order, weaken crystalline properties, and react with 1, 2-epoxy-4-vinylcyclohexane as shown in formula 1 below:
1, 2-epoxy-4-vinylcyclohexane may be grafted onto keratin. On one hand, the ring formation structure of carboxyl and amino in the keratin is disturbed, the original smaller ring formation structure is changed, so that the structure of the grafting product in the formula is formed, and the functionalized keratin is subjected to ring formation by virtue of the hydroxyl of 1, 2-epoxy-4-vinylcyclohexane, so that a larger ring structure can be formed. On the other hand, the functionalized keratin is rich in double bonds, so that the functionalized keratin can better follow the temperature-sensitive material and simultaneously is grafted and copolymerized with N-isopropyl acrylamide (NIPAAm) of a hydrophilic monomer, and the integral stability of the catalyst is stronger. The structure of the temperature-sensitive type keratin gel is as shown in formula 2, wherein a: b =3, 10,m, N =90, a + b = 12-13, and the molar ratio of the keratin to 1, 2-epoxy-4-vinylcyclohexane and N-isopropyl acrylamide is 10:3:90, when the functionalized keratin forms a ring structure in the interior of the keratin, the cavity is proper in size, and the functionalized keratin is loaded with proper amount of Cu 2+ And secondly, a cavity is left to participate in catalytic reaction, so that the catalytic efficiency is higher. If the amount of 1, 2-epoxy-4-vinylcyclohexane is increased, the formation of cyclic structures of the functionalized keratin becomes larger or disappears.
As shown in fig. 2, the PN90K10 (c) peak appears at substantially the same and slightly wider position than the functionalized keratin (b), but the 26 ° peak disappears, indicating that the chemical bond between the functionalized keratin (b) and the keratin structure after NIPAAm polymerization is broken, so that more amorphous regions are generated during PN90K10 formation. Compared with PN90K10 (b), PN90K10Cu (d) has a plurality of sharp and moderate-strength peaks at a plurality of angles of 18 degrees, 22 degrees, 24 degrees and the like, which indicates that the crystallization performance of the hydrogel is enhanced due to the copper loaded in the hydrogel, and possibly that the copper ions are not completely loaded, and the XRD curve shows high crystallinity due to the residual copper sulfate crystals after freeze drying.
FIG. 3 is a LCST test spectrum of the thermosensitive material PN90K10 in example 1, wherein the critical solution temperature is 30 ℃, the material shows good solubility below LCST, and forms a uniform and transparent aqueous solution, and above LCST, the hydrogel shows hydrophobicity and can be separated out from the aqueous phase, and the property can realize effective reuse and convenient recovery of the catalyst prepared by using the thermosensitive hydrogel as a carrier.
Application example 1
This application example used the temperature sensitive copper keratin catalyst of example 1 above to prepare a beta-borate ester substituted carbonyl compound. The method comprises the following specific steps:
p1, taking chalcone (0.2 mmol), pinacol diboron (0.24 mmol) and temperature-sensitive type keratin copper catalyst 0.002mmol (Cu is used) 2+ Calculated by the substance) is mixed and added into 2mL of methanol solvent, stirred for 12h at room temperature to obtain a boron addition product, and the Cu in the temperature-sensitive type keratin copper catalyst 2+ The content of (A) is 1 percent of the substance of the chalcone serving as the reaction raw material;
and P2, extracting by using ethyl acetate, drying, performing rotary evaporation, and finally performing column chromatography separation to obtain the carbonyl compound substituted by the beta-borate. The product yield was 92%. The reaction process is as follows:
the nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are shown as follows, and the spectra are shown in figures 4 and 5.
1 H NMR(400MHz,Chloroform-d)；δ＝8.01–7.98(m,2H),7.59–7.56(m,1H),7.55–7.48(m,2H),7.46–7.44(m,4H),7.25–7.14(m,1H),3.62–3.40(m,2H),2.80(dd,J＝11.0,5.0Hz,1H),1.27(s,6H),1.19(s,6H).
13 C NMR(100MHz,Chloroform-d)；δ＝199.5,141.7,136.5,132.7,128.3,128.2,128.1,127.8,125.4,83.1,43.1,24.38,24.33.
Application example 2
This application example used the temperature-sensitive copper keratin catalyst of example 1 above to prepare a β -borate ester-substituted carbonyl compound in substantially the same manner as in application example 1. The only difference is that the alpha, beta-unsaturated ketone compound selected by the application example is (E) -3- (4-p-chlorophenyl) -1-2-alkene-1-ketone. Finally, the beta-boric acid ester substituted carbonyl compound is obtained, and the yield of the product is 92%. The reaction process is as follows:
the nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1 H NMR(400MHz,Chloroform-d)；δ＝7.99–7.96(m,2H),7.59–7.54(m,1H),7.49–7.42(m,2H),7.27–7.25(m,4H),3.57–3.35(m,2H),2.81(dd,J＝10.3,5.3Hz,1H),1.26(s,6H),1.19(s,6H).
13 C NMR(100MHz,Chloroform-d)；δ＝199.5,140.1,136.5,133.1,131.2,129.6,128.6,128.5,128.2,83.4,43.1,24.6,24.5.
the application example shows that under the catalysis condition of the temperature-sensitive type keratin copper catalyst provided by the embodiment of the invention, the conversion rate of (E) -3- (4-p-chlorophenyl) -1-2-alkene-1-ketone is also high, and the yield of the boron addition reaction product reaches 92%.
Application example 3
This application example used the temperature-sensitive copper keratin catalyst of example 1 above to prepare a β -borate ester-substituted carbonyl compound in substantially the same manner as in application example 1. The only difference is that the alpha, beta-unsaturated ketone compound selected by the application example is (E) -3- (4-p-bromophenyl) -1-2-alkene-1-ketone. Finally, the beta-boric acid ester substituted carbonyl compound is obtained, and the product yield is 83%. The reaction process is as follows:
the nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1 H NMR(400MHz,Chloroform-d)；δ＝7.90–7.86(m,2H),7.50–7.44(m,1H),7.39-7.31(m,2H),7.34–7.31(m,2H),7.12–7.08(m,2H),3.47–3.31(m,2H),2.69(dd,J＝10.3,5.4Hz,1H),1.17(s,6H),1.09(s,6H).
13 C NMR(100MHz,Chloroform-d)；δ＝199.5,141.2,136.7,133.2,131.6,130.3,128.7,128.2,119.5,83.6,42.9,24.7,24.6.
the application example shows that under the catalysis condition of the temperature-sensitive keratin copper catalyst provided by the embodiment of the invention, the conversion rate of (E) -3- (4-p-bromophenyl) -1-2-alkene-1-ketone is also high, and the yield of the boron addition reaction product reaches 83%.
Application example 4
This application example used the temperature-sensitive copper keratin catalyst of example 1 above to prepare a β -borate ester-substituted carbonyl compound in substantially the same manner as in application example 1. The only difference is that the alpha, beta-unsaturated ketone compound selected by the application example is (E) -3- (4-p-methoxyphenyl) -1-2-alkene-1-ketone. Finally, the beta-boric acid ester substituted carbonyl compound is obtained, and the product yield is 86%. The reaction process is as follows:
the nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1 H NMR(400MHz,Chloroform-d)；δ＝7.97(d,J＝8.8Hz,2H),7.38–7.28(m,4H),7.18(t,J＝6.9Hz,1H),6.95(d,J＝8.9Hz,2H),3.89(s,3H),3.57–3.39(m,2H),2.80(dd,J＝10.8,5.2Hz,1H),1.27(s,6H),1.19(s,6H).
13 C NMR(100MHz,Chloroform-d)；δ＝198.1,163.2,142.0,130.2,129.8,128.4,128.3,125.4,113.5,83.2,55.4,43.0,24.58,24.55.
the application example shows that under the catalysis condition of the temperature-sensitive keratin copper catalyst provided by the embodiment of the invention, the conversion rate of (E) -3- (4-p-methoxyphenyl) -1-2-alkene-1-ketone is also high, and the yield of the boron addition reaction product reaches 86%.
Application example 5
This application example used the temperature-sensitive copper keratin catalyst of example 1 above to prepare a β -borate ester-substituted carbonyl compound in substantially the same manner as in application example 1. The only difference is that the alpha, beta-unsaturated ketone compound selected by the application example is (E) -1- (4-m-methylphenyl) -1-2-alkene-3-ketone. Finally, the beta-boric acid ester substituted carbonyl compound is obtained, and the yield of the product is 80%. The reaction process is as follows:
the nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1 H NMR(400MHz,Chloroform-d)；δ＝7.92–7.87(m,2H),7.48–7.44(m,1H),7.39–7.34(m,2H),7.13–7.01(m,3H),6.93(d,J＝7.4Hz,1H),3.51–3.31(m,2H),2.68(dd,J＝11.0,4.9Hz,1H),2.25(s,3H),1.18(s,6H),1.10(s,6H).
13 C NMR(100MHz,Chloroform-d)；δ＝199.7,141.7,138.0,136.7,132.8,129.2,128.4,128.3,128.0,126.3,125.2,83.3,43.3,24.5,21.4.
the application example shows that under the catalysis condition of the temperature-sensitive type keratin copper catalyst provided by the embodiment of the invention, the conversion rate of (E) -1- (4-m-methylphenyl) -1-2-alkene-3-ketone is also high, and the yield of the boron addition reaction product reaches 80%.
Application example 6
This application example used the temperature-sensitive copper keratin catalyst of example 1 above to prepare a β -borate ester-substituted carbonyl compound in substantially the same manner as in application example 1. The only difference is that the alpha, beta-unsaturated ketone compound selected by the application example is (E) -1- (4-p-methoxyphenyl) -1-2-alkene-3-ketone. Finally, the beta-boric acid ester substituted carbonyl compound is obtained, and the product yield is 84%. The reaction process is as follows:
the nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1 H NMR(400MHz,Chloroform-d)；δ＝7.99–7.96(m,2H),7.35–7.27(m,4H),7.21–7.16(m,1H),6.94–6.91(m,2H),3.88(s,3H),3.58–3.38(m,2H),2.80(dd,J＝10.8,5.2Hz,1H),1.27(s,6H),1.19(s,6H).
13 C NMR(100MHz,Chloroform-d)；δ＝198.3,163.3,142.2,130.2,129.8,128.4,128.3,125.4,113.5 83.2,55.5,43.0,24.58,24.55.
the application example shows that under the catalysis condition of the temperature-sensitive keratin copper catalyst provided by the embodiment of the invention, the conversion rate of (E) -1- (4-p-methoxyphenyl) -1-2-alkene-3-ketone is also high, and the yield of the boron addition reaction product reaches 84%.
Application example 7
This application example used the temperature-sensitive copper keratin catalyst of example 1 above to prepare a β -borate ester-substituted carbonyl compound in substantially the same manner as in application example 1. The only difference is that the alpha, beta-unsaturated ketone compound selected by the application example is (E) -1- (4-p-methylphenyl) -1-2-alkene-3-ketone. Finally, the beta-borate ester substituted carbonyl compound is obtained, and the yield of the product is 85%. The reaction process is as follows:
the nuclear magnetic hydrogen spectrum and carbon spectrum of the target product are shown below
1 H NMR(400MHz,Chloroform-d)；δ＝7.78–7.77(m,2H),7.24–7.16(m,4H),7.15(d,J＝8.0Hz,2H),7.11–7.06(m,1H),3.48–3.27(m,2H),2.70(dd,J＝10.9,5.0Hz,1H),2.30(s,3H),1.16(s,6H),1.08(s,6H).
13 C NMR(100MHz,Chloroform-d)；δ＝199.4,143.8,142.2,134.2,129.1,128.4,128.3,128.3,125.5,83.3,43.1,24.60,24.57,21.7.
The application example shows that the conversion rate of (E) -1- (4-p-methylphenyl) -1-2-alkene-3-ketone is high under the catalysis condition of the temperature-sensitive type keratin copper catalyst provided by the embodiment of the invention, and the yield of the boron addition product reaches 85%.
From the application examples 1 to 7, it can be known that the alpha, beta-unsaturated ketone compound can be prepared into a corresponding beta-borate ester substituted carbonyl compound by using various different alpha, beta-unsaturated ketone compounds and adopting the temperature-sensitive keratin copper catalyst provided by the invention, and the yield is high.
Application example 8
The temperature of application example 1 was repeatedly increased and decreased to check the recyclability of the catalyst, as shown in fig. 6a, and the results showed that the transmittance did not change significantly after a plurality of temperature increases and decreases, indicating that the catalyst has good recyclability. Fig. 6b shows that the catalyst was used in 5 times repeatedly to catalyze the boron addition reaction using chalcone as a substrate, and the yield of the boron addition reaction was not significantly reduced.
Application example 8 illustrates that the catalyst has good recoverability and efficient repeatability.
Claims (11)
1. A temperature-sensitive keratin is characterized by having the following structural formula,
wherein, R represents serine, threonine, tyrosine, lysine and arginine residue in keratin molecules, and a + b = 12-13.
2. The temperature-sensitive keratin according to claim 1, wherein m: N =50-90, 10, 90 represents the degree of polymerization of N-isopropylacrylamide, and 10 represents the degree of polymerization of keratin.
3. The temperature-sensitive keratin according to claim 2, wherein a: b ≦ 3.
4. A preparation method of temperature-sensitive keratin is characterized by comprising the following preparation methods,
step 1.1 functionalization of keratin: dissolving keratin powder and 1, 2-epoxy-4-vinylcyclohexane in ionized water, stirring to obtain a mixed solution, dropwise adding the mixed solution into acetone, filtering to obtain a precipitate, repeatedly washing the precipitate with acetone, and finally performing vacuum drying at 50-70 ℃ to obtain functionalized keratin;
step 1.2, polymerization of the temperature-sensitive material: dissolving and polymerizing the product obtained in the step 1.1 and a temperature-sensitive material N-isopropylacrylamide (NIPAAm) in deionized water to obtain a temperature-sensitive hydrogel solution, adding an initiator to carry out copolymerization reaction, placing the product of the copolymerization reaction in a dialysis bag, dialyzing with deionized water, and finally drying in an oven to obtain the temperature-sensitive keratin gel.
5. The preparation method of the temperature-sensitive keratin according to claim 4, wherein the initiator in step 1.2 is ammonium persulfate, the initiation temperature is 60 ℃, and the polymerization time is 24 hours.
6. The method for preparing temperature-sensitive keratin according to claim 4, wherein the ratio of acetone in the acetone solution in step 1.1: the mass ratio of the solution =10:1, the stirring temperature in the step 1.1 is 60 ℃, and the stirring time is 24 hours.
7. A catalyst containing the temperature-sensitive keratin according to claim 3, characterized in that a water-soluble divalent copper salt is dissolved in deionized water, and then mixed with the temperature-sensitive keratin gel, stirred for 24 hours at normal temperature, and then freeze-dried to obtain the temperature-sensitive keratin copper catalyst.
8. The catalyst of claim 7, wherein the water-soluble divalent copper salt is one or more of copper sulfate, copper nitrate, and copper chloride.
9. The catalyst of claim 7, wherein Cu is in the catalyst 2+ The molar ratio of the temperature-sensitive keratin to keratin in the temperature-sensitive keratin is 1:10.
10. the application of the catalyst containing the temperature-sensitive keratin in synthesizing a carbonyl compound substituted by beta-borate according to any one of claims 7-9, characterized in that the carbonyl compound substituted by the beta-borate is prepared by taking an alpha, beta-unsaturated ketone compound and a pinacol diborate as raw materials and taking the catalyst containing the temperature-sensitive keratin as a catalyst and uniformly stirring at room temperature;
the structural formula of the alpha, beta-unsaturated ketone compound is shown in the specification
The structural formula of the corresponding beta-boric acid ester substituted carbonyl compound is shown as
Wherein R is 1 Is one of phenyl, p-methylphenyl and p-methoxyphenyl, R 2 Is one of phenyl, p-methylphenyl, p-methoxyphenyl, p-fluorophenyl, p-chlorophenyl, p-bromophenyl, o-chlorophenyl, m-bromophenyl and m-chlorophenyl.
11. Use according to claim 9, wherein the preparation of the β -boronate substituted carbonyl compound comprises the steps of:
step P1, taking alpha, beta-unsaturated ketone compound, polyboronic acid pinacol ester and temperature-sensitive keratinThe catalyst (A) is mixed and added into the solvent according to the mass ratio of 1.2; the amount of the substance of the temperature-sensitive type keratin copper catalyst is Cu 2+ Is taken as a reference;
step P2, extracting the product obtained in the step P1 by using an organic solvent, drying, performing rotary evaporation, and finally performing column chromatography separation to obtain a beta-borate ester substituted carbonyl compound;
in the step P2, the volume ratio of ethyl acetate to petroleum ether used for column chromatography is 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116393172A (en) * | 2023-04-03 | 2023-07-07 | 湖北工程学院 | Preparation method of temperature-sensitive chitosan aerogel catalytic material and application of temperature-sensitive chitosan aerogel catalytic material in boron addition reaction |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116393172A (en) * | 2023-04-03 | 2023-07-07 | 湖北工程学院 | Preparation method of temperature-sensitive chitosan aerogel catalytic material and application of temperature-sensitive chitosan aerogel catalytic material in boron addition reaction |
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