CN110128589B - Preparation method of amino acid modified microspheres and product thereof - Google Patents
Preparation method of amino acid modified microspheres and product thereof Download PDFInfo
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- CN110128589B CN110128589B CN201910469795.3A CN201910469795A CN110128589B CN 110128589 B CN110128589 B CN 110128589B CN 201910469795 A CN201910469795 A CN 201910469795A CN 110128589 B CN110128589 B CN 110128589B
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- 150000001413 amino acids Chemical class 0.000 title claims abstract description 49
- 239000004005 microsphere Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000003446 ligand Substances 0.000 claims abstract description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 239000002815 homogeneous catalyst Substances 0.000 claims abstract description 6
- 239000003999 initiator Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 18
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 7
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 7
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 7
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 7
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 7
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 150000001408 amides Chemical group 0.000 claims description 4
- 239000004088 foaming agent Substances 0.000 claims description 3
- 229920000136 polysorbate Polymers 0.000 claims description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 description 5
- 238000002791 soaking Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical group [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- APPOKADJQUIAHP-GGWOSOGESA-N (2e,4e)-hexa-2,4-diene Chemical group C\C=C\C=C\C APPOKADJQUIAHP-GGWOSOGESA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
Classifications
-
- B01J35/51—
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- 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
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
- C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
Abstract
Under the protection of nitrogen, a monomer containing double bonds and an amino acid ligand containing double bonds are initiated by a thermal initiator, the double bonds are polymerized, and the amino acid ligand is grafted on the surface of the microsphere, so that a homogeneous catalyst is converted into a heterogeneous catalyst, the heterogeneous catalyst is easy to separate from a reaction system, and the heterogeneous catalyst does not swell in an organic solvent, and the industrial application value of the heterogeneous catalyst is improved. The particle size of the amino acid microsphere is about 0.25-0.30 mm through microscopic detection, and the amino acid microsphere can be separated only through a filtration mode.
Description
Technical Field
The invention relates to a preparation method of amino acid modified microspheres and a product thereof, belonging to the technical field of organic polymer material preparation.
Background
Researches show that in the traditional reaction for introducing the planar chiral structure into the ferrocene structure, a catalyst is expensive and reaction conditions are harsh, and equivalent lithium reagent, chiral alkali and the like are needed, however, the catalyst with the amino acid ligand is beneficial to introducing the planar chiral structure into the ferrocene skeleton, and the conditions are relatively mild, but as most of the catalysts are homogeneous catalysts, certain difficulty is brought to the recovery of the catalyst after the reaction. Meanwhile, the research finds that amino acid ligands can be grafted on the surface of the polystyrene microsphere, but the microsphere can swell in an organic solvent.
Therefore, in order to solve the defects of the catalyst, the amino acid ligand is initiated to polymerize by a thermal initiator and grafted on the surface of the organic microsphere of the invention, so that the homogeneous catalyst is converted into the heterogeneous catalyst which is easy to separate from a reaction system.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of amino acid modified microspheres.
Yet another object of the present invention is to: provides an amino acid modified microsphere product prepared by the method.
The purpose of the invention is realized by the following scheme: a preparation method of amino acid modified microspheres is characterized in that under the protection of nitrogen, a monomer containing double bonds and an amino acid ligand containing double bonds are initiated by a thermal initiator, the double bonds are polymerized, and the amino acid ligand is grafted on the surfaces of the microspheres, so that a homogeneous catalyst is converted into a heterogeneous catalyst, the heterogeneous catalyst is easy to separate from a reaction system, and the heterogeneous catalyst does not swell in an organic solvent, and the industrial application value of the heterogeneous catalyst is improved, and the preparation method comprises the following steps:
(1) placing a dispersing agent into n-heptane, and fully and uniformly stirring, wherein the mass ratio of the dispersing agent to the n-heptane is 0.5-1.0: 82;
(2) gradually adding a monomer, a functional ligand, a cross-linking agent and a pore-foaming agent formamide into the solution obtained in the step (1), uniformly stirring the mixture, wherein the monomer is an amide containing propenyl, the functional ligand is an amino acid ligand containing vinyl, and the cross-linking agent is an amide containing dipropenyl, and the mass ratio of the monomer to the functional ligand to the cross-linking agent to the pore-foaming agent is 0.7:1.0-2.0:4.0: 17.6;
(3) adding an initiator azobisisobutyronitrile into the solution obtained in the step (2), introducing nitrogen, and exhausting by using a vacuum pump to remove air in the system while removing the nitrogen so as to enable the reaction process to be in a nitrogen protection state;
(4) and (3) raising the reaction temperature to 50-80 ℃, stirring at the speed of 300-400 rpm, stirring for 2-4 hours, filtering to obtain white particles, and drying in an oven at the temperature of 50-80 ℃ to obtain the amino acid modified microspheres.
The preparation method of the amino acid modified microspheres is characterized in that the particle size of the amino acid microspheres is about 0.25-0.30 mm, and the amino acid microspheres can be separated from a reaction system only by a filtration mode.
The dispersant is one or the combination of span and tween.
The mass ratio of the azodiisobutyronitrile to the functional monomer is 0.70: 0.10-0.20.
An amino acid modified microsphere prepared according to any one of the methods described above.
The invention has the following advantages:
(1) the raw materials used in the invention are all commercially available and have wide and easily available sources;
(2) the preparation process of the microsphere has mild conditions and is easy for industrial application;
(3) the invention grafts the amino acid ligand on the surface of the microsphere, so that the homogeneous catalyst is heterogenized and is easy to separate from the reaction system.
(4) The microsphere is synthesized in an organic solvent, so that the microsphere can not swell in the organic solvent.
Detailed Description
The following is a detailed description with reference to specific examples: the present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.
Example 1
An amino acid modified microsphere is prepared by the following steps:
(1) placing 0.07 g of span-60 and 0.03 g of Tween-20 into a three-neck flask, adding 12 ml of n-heptane, setting the stirring speed to 325 r/min, and uniformly dispersing;
(2) gradually adding 0.07 g of methacrylamide, 0.15 g of amino acid ligand, 0.4 g of N, N' -methylene bisacrylamide and 1.76 g of formamide, and stirring until a transparent solution is obtained;
(3) adding 0.07 g of azodiisobutyronitrile into the solution obtained in the step (2) for dissolving, and then introducing nitrogen while exhausting by using a vacuum pump to remove air in the system so as to enable the reaction process to be in a nitrogen protection state;
(4) and (3) raising the reaction temperature to 70 ℃, stirring at the speed of 300-400 rpm, stirring for 4 hours, filtering to obtain white particles, fully washing with ethanol, and drying in a 70 ℃ oven to obtain the amino acid modified microspheres.
The particle size is 0.30 mm by microscope detection, and the particle size is still 0.30 mm by microscope detection after the soaking in ethanol solution for 12 hours.
The structure of the amino acid ligand is shown below:
example 2
An amino acid modified microsphere is prepared by the following steps:
(1) placing 0.07 g of span-60 and 0.03 g of Tween-20 into a three-neck flask, adding 12 ml of n-heptane, setting the stirring speed to 325 r/min, and uniformly dispersing;
(2) gradually adding 0.07 g of methacrylamide, 0.20 g of amino acid ligand, 0.4 g of N, N' -methylene bisacrylamide and 1.76 g of formamide, and stirring until a transparent solution is obtained;
(3) adding 0.07 g of azodiisobutyronitrile into the solution obtained in the step (2) for dissolving, and then introducing nitrogen while exhausting by using a vacuum pump to remove air in the system so as to enable the reaction process to be in a nitrogen protection state;
(4) and (3) raising the reaction temperature to 70 ℃, stirring for 4 hours, filtering to obtain white particles, fully washing with ethanol, and drying in a 70 ℃ oven to obtain the amino acid modified microspheres.
The particle size is about 0.27 mm by microscope detection, and the particle size is still 0.27 mm by microscope detection after the soaking in ethanol solution for 12 hours. The structure of the amino acid ligand is shown below:
example 3
An amino acid modified microsphere is prepared by the following steps:
(1) placing 0.07 g of span-60 and 0.03 g of Tween-20 into a three-neck flask, adding 12 ml of n-heptane, setting the stirring speed to 325 r/min, and uniformly dispersing;
(2) gradually adding 0.07 g of methacrylamide, 0.10 g of amino acid ligand, 0.4 g of N, N' -methylene bisacrylamide and 1.76 g of formamide, and stirring until a transparent solution is obtained;
(3) adding 0.07 g of azodiisobutyronitrile into the solution obtained in the step (2) for dissolving, and then introducing nitrogen while exhausting by using a vacuum pump to remove air in the system so as to enable the reaction process to be in a nitrogen protection state;
(4) and (3) raising the reaction temperature to 70 ℃, stirring for 4 hours, filtering to obtain white particles, fully washing with ethanol, and drying in a 70 ℃ oven to obtain the amino acid modified microspheres.
The particle size is about 0.29 mm by microscopic detection, and the particle size is still 0.29 mm by microscopic detection after the soaking in ethanol solution for 12 hours. The structure of the amino acid ligand is shown below:
comparative example
0.07 g of span-60 and 0.03 g of Tween-20 are placed in a three-neck flask, 12 ml of N-heptane is added, the stirring speed is set to 325 revolutions per minute, the dispersion is uniform, then 0.07 g of methacrylamide, 0.4 g of N, N' -methylene bisacrylamide and 1.76 g of formamide are gradually added, the transparent solution is stirred, 0.07 g of azobisisobutyronitrile is added for dissolution, and then, the nitrogen is introduced, the vacuum pump is used for air extraction while the nitrogen is pumped, the air in the system is removed, and the reaction process is in a nitrogen protection state. Raising the reaction temperature to 70 ℃, stirring for 4 hours, filtering to obtain white particles, fully washing with ethanol, putting into a 70 ℃ oven, and drying to obtain microspheres, wherein the particle size is about 0.29 mm by microscopic detection.
Claims (5)
1. A preparation method of amino acid modified microspheres is characterized in that under the protection of nitrogen, a monomer containing double bonds and a functional ligand containing double bonds are polymerized by initiating double bonds through an initiator, so that the functional ligand is grafted on the surfaces of the microspheres, and a homogeneous catalyst is converted into a heterogeneous catalyst, so that the heterogeneous catalyst is easy to separate from a reaction system and cannot swell in an organic solvent, and comprises the following steps:
(1) placing the dispersing agent into n-heptane, wherein the mass ratio of the dispersing agent to the n-heptane is (0.5-1.0) to 82, and fully and uniformly stirring;
(2) gradually adding a monomer, a functional ligand, a cross-linking agent and a pore-foaming agent formamide into the solution in the step (1) according to the mass ratio of 0.7:1.0-2.0:4.0:17.6, uniformly stirring, wherein the monomer is an amide containing propenyl, the functional ligand is an amino acid ligand containing vinyl, and the cross-linking agent is an amide containing bi-propenyl;
(3) adding an initiator azobisisobutyronitrile into the solution obtained in the step (2), wherein the mass ratio of the azobisisobutyronitrile to the functional ligand is 0.70:0.10-0.20, introducing nitrogen while exhausting by using a vacuum pump to remove air in the system, and keeping the reaction process in a nitrogen protection state;
(4) raising the reaction temperature to 50-80 ℃, stirring at the speed of 300-400 rpm, stirring for 2-4 hours, filtering to obtain white particles, and drying in a 50-80 ℃ oven to obtain the amino acid modified microspheres; wherein the content of the first and second substances,
the particle size of the amino acid modified microspheres is 0.25-0.30 mm, and the amino acid modified microspheres can be separated from a reaction system only by a filtration mode;
the dispersant in the step (1) is one or the combination of span and tween.
2. The method for preparing amino acid modified microspheres according to claim 1, wherein the method comprises the following steps:
(1) placing 0.07 g of span-60 and 0.03 g of Tween-20 into a three-neck flask, adding 12 ml of n-heptane, setting the stirring speed to 325 r/min, and uniformly dispersing;
(2) gradually adding 0.07 g of methacrylamide, 0.15 g of amino acid ligand, 0.4 g of N, N' -methylene bisacrylamide and 1.76 g of formamide, and stirring until a transparent solution is obtained;
(3) adding 0.07 g of azodiisobutyronitrile into the solution obtained in the step (2) for dissolving, and then introducing nitrogen while exhausting by using a vacuum pump to remove air in the system so as to enable the reaction process to be in a nitrogen protection state;
(4) and (3) raising the reaction temperature to 70 ℃, stirring at the speed of 300-400 rpm, stirring for 4 hours, filtering to obtain white particles, fully washing with ethanol, and drying in a 70 ℃ oven to obtain the amino acid modified microspheres.
3. The method for preparing amino acid modified microspheres according to claim 1, wherein the method comprises the following steps:
(1) placing 0.07 g of span-60 and 0.03 g of Tween-20 into a three-neck flask, adding 12 ml of n-heptane, setting the stirring speed to 325 r/min, and uniformly dispersing;
(2) gradually adding 0.07 g of methacrylamide, 0.20 g of amino acid ligand, 0.4 g of N, N' -methylene bisacrylamide and 1.76 g of formamide, and stirring until a transparent solution is obtained;
(3) adding 0.07 g of azodiisobutyronitrile into the solution obtained in the step (2) for dissolving, and then introducing nitrogen while exhausting by using a vacuum pump to remove air in the system so as to enable the reaction process to be in a nitrogen protection state;
(4) and (3) raising the reaction temperature to 70 ℃, stirring for 4 hours, filtering to obtain white particles, fully washing with ethanol, and drying in a 70 ℃ oven to obtain the amino acid modified microspheres.
4. The method for preparing amino acid modified microspheres according to claim 1, wherein the method comprises the following steps:
(1) placing 0.07 g of span-60 and 0.03 g of Tween-20 into a three-neck flask, adding 12 ml of n-heptane, setting the stirring speed to 325 r/min, and uniformly dispersing;
(2) gradually adding 0.07 g of methacrylamide, 0.10 g of amino acid ligand, 0.4 g of N, N' -methylene bisacrylamide and 1.76 g of formamide, and stirring until a transparent solution is obtained;
(3) adding 0.07 g of azodiisobutyronitrile into the solution obtained in the step (2) for dissolving, and then introducing nitrogen while exhausting by using a vacuum pump to remove air in the system so as to enable the reaction process to be in a nitrogen protection state;
(4) and (3) raising the reaction temperature to 70 ℃, stirring for 4 hours, filtering to obtain white particles, fully washing with ethanol, and drying in a 70 ℃ oven to obtain the amino acid modified microspheres.
5. An amino acid modified microsphere, characterized in that it is prepared according to the method of any one of claims 1 to 4.
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