CN112898439B - Amino cellulose and preparation method thereof - Google Patents
Amino cellulose and preparation method thereof Download PDFInfo
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- CN112898439B CN112898439B CN202110208103.7A CN202110208103A CN112898439B CN 112898439 B CN112898439 B CN 112898439B CN 202110208103 A CN202110208103 A CN 202110208103A CN 112898439 B CN112898439 B CN 112898439B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/08—Preparation of cellulose esters of organic acids of monobasic organic acids with three or more carbon atoms, e.g. propionate or butyrate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/14—Preparation of cellulose esters of organic acids in which the organic acid residue contains substituents, e.g. NH2, Cl
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/22—Post-esterification treatments, including purification
Abstract
The invention discloses amino cellulose and a preparation method thereof, cellulose, a double bond introducing agent and a catalyst react for 1-24 hours at 0-70 ℃ in a good solvent system according to a certain molar ratio to prepare a cellulose-based acrylic acid macromonomer; the second step: dissolving cellulose-based acrylic acid macromonomer, mercaptoethylamine and an initiator in a good solvent according to a certain proportion, reacting for 1-15 h at 10-100 ℃ or under the irradiation of an ultraviolet lamp, precipitating the product in deionized water, filtering and drying to obtain the amino cellulose. The invention can conveniently and efficiently prepare the amino cellulose, and the obtained amino cellulose has better solubility and can be used as a Schiff base chemical macromolecular cross-linking agent and an epoxy resin curing agent.
Description
Technical Field
The invention relates to cellulose and a preparation method thereof, in particular to amino cellulose and a preparation method thereof.
Background
With the increasing consumption of fossil raw materials, the use of renewable resources for the preparation of functional chemicals, polymer materials, adsorption materials, etc. has received great attention. Cellulose is a renewable resource with the most abundant reserves, has the advantages of environmental friendliness, degradability, low price and the like, is widely used in various fields of industrial production, and has a prospect of replacing corresponding petroleum-based products.
The amino cellulose serving as a nitrogen-containing cellulose derivative is widely applied to the fields of agriculture, food industry, textile industry, daily chemical industry and the like, particularly the amino group of the amino cellulose in the field of environmental protection can form a coordinate bond through extremely strong coordination of transition metal ions, so that heavy metal ions in a solution can be effectively adsorbed or trapped to achieve the effect of removing toxic heavy metal ions such as lead, mercury, chromium and the like in a water body, and the amino cellulose is widely used as a water treatment agent for treating heavy metals in industrial wastewater. However, most of the currently reported methods for preparing amino cellulose have the disadvantages of complex production process, long time consumption, harsh reaction conditions, high production cost and the like. Therefore, more and more people are paying more attention to the preparation of the amino cellulose by a convenient and efficient method.
Disclosure of Invention
The purpose of the invention is as follows: one of the purposes of the invention is to provide the amino cellulose which has better solubility and can be used as a Schiff base chemical macromolecular cross-linking agent and an epoxy resin curing agent, thereby further improving the additional value of the cellulose and expanding the application range of the cellulose; the second purpose of the invention is to provide a preparation method of amino cellulose, which has the characteristics of convenience and high efficiency.
The technical scheme is as follows: the amino cellulose has the following structural general formula:
wherein R is a functional group characteristic of the cellulose in the first step and is H or-CH3、-CH2CH3、-COCH3、-CH2CH2OH、-CH2CH2CH2Any one of OH, R1is-CH3Or H.
The invention also provides a preparation method of the amino cellulose, which comprises the following steps:
(1) reacting cellulose, a double bond introducing agent and a catalyst in a good solvent system to prepare a cellulose-based acrylic acid macromonomer;
(2) carrying out sulfhydryl-alkene click reaction on cellulose-based acrylic acid macromonomer, mercaptoethylamine and an initiator in a good solvent system, then precipitating a product in deionized water, filtering and drying to obtain the amino cellulose.
In the step (1), the molar ratio of the cellulose to the double bond introducing agent to the catalyst is 1: 0.1-2. The reaction temperature is 0-70 ℃, and the reaction time is 1-24 h. When the reaction temperature exceeds 70 ℃, an additional polymerization inhibitor is required, and the product yield is lowered.
Wherein the cellulose is any one of nano cellulose, microcrystalline cellulose, ethyl cellulose, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose; the double bond introducing agent is any one of methacrylic anhydride, acrylic anhydride, methacryloyl chloride and acryloyl chloride; the catalyst is 4-dimethylamino pyridine or triethylamine; the good solvent system is any one of DMF, DMSO, DMAc/LiCl, tetrahydrofuran and water.
In the step (2), the molar ratio of the cellulose-based acrylic acid macromonomer, the mercaptoethylamine and the initiator is 1: 0.1-3: 0.01-0.05.
In the step (2), the reaction is initiated by heat or light, and the reaction time is 1-15 h; wherein the thermal initiation is heating to 10-100 deg.C, and the photo initiation is with light intensity of 0.01-5 mW/cm2Is irradiated by the ultraviolet lamp. When the reaction time is too long, the product can generate self-polymerization when the temperature is too high; too low a temperature will reduce the reaction rate and affect the yield.
The initiator is one of azodiisobutyronitrile, dibenzoyl peroxide, a photoinitiator 907 and a photoinitiator 2959; the good solvent is any one of methanol, ethanol, DMF, DMSO and DMAc.
Wherein, when thermal initiation is adopted, the initiator is selected from azobisisobutyronitrile and dibenzoyl peroxide; when the ultraviolet lamp is used for irradiation, the other two photoinitiators are selected.
The method combines esterification and sulfydryl-alkene click reaction, and realizes the preparation of the amino cellulose under mild conditions, thereby further reducing the production cost of the amino cellulose and further expanding the application value of the amino cellulose in the fields of self-repairing polymers, epoxy resin curing agents and the like.
Has the advantages that:
(1) the amino cellulose and the preparation method thereof have the characteristics of greenness, convenience and high efficiency, and the obtained amino cellulose has high yield which can reach 90.4 percent at most.
(2) The preparation method has the characteristics of convenience and high efficiency, and the prepared amino cellulose has good solubility in organic solvents such as dichloromethane, tetrahydrofuran, ethanol and the like, and can be used as a Schiff base chemical macromolecular cross-linking agent and an epoxy resin curing agent, so that the additional value of the cellulose is further improved, and the application range of the cellulose is expanded.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of an ethylcellulose acrylic macromonomer and an amino cellulose in example 1;
FIG. 2 is an infrared spectrum of ethylcellulose acrylic macromonomer and amino cellulose in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples.
The starting materials and the actual materials in the following examples are all commercially available.
A preparation method of amino cellulose comprises the following steps: the first step is as follows: reacting cellulose, a double bond introducing agent and a catalyst for 1-24 hours at 0-70 ℃ in a good solvent system according to a certain molar ratio to prepare a cellulose-based acrylic acid macromonomer; the second step is that: dissolving cellulose-based acrylic acid macromonomer, mercaptoethylamine and an initiator in a good solvent according to a certain proportion, reacting for 1-15 h at 10-100 ℃ or under the irradiation of an ultraviolet lamp, precipitating the product in deionized water, filtering and drying to obtain the amino cellulose.
Example 1: preparation of amino cellulose from ethyl cellulose
The first step is as follows: dissolving ethyl cellulose, methacrylic anhydride and 4-dimethylaminopyridine in a molar ratio of [ ethyl cellulose ], [ methacrylic anhydride ], [ 4-dimethylaminopyridine ] =1:1.2:0.3 in tetrahydrofuran, and reacting at 50 ℃ for 5 hours to prepare an ethyl cellulose acrylic macromonomer;
the second step is that: dissolving ethyl cellulose acrylic acid macromonomer, mercaptoethylamine and azobisisobutyronitrile into ethanol according to the molar ratio of [ ethyl cellulose acrylic acid macromonomer ], [ mercaptoethylamine ], [ azobisisobutyronitrile ] =1:1: 0.03, heating and reacting for 5 hours at 75 ℃, precipitating the product in deionized water, filtering and drying to obtain the amino cellulose, wherein the yield is 90.4%.
The preparation process of this example is represented by the following reaction formula:
wherein R is a functional group characteristic of the cellulose in the first step and is H or-CH3、-CH2CH3、-COCH3、-CH2CH2OH、-CH2CH2CH2One of OH, R1is-CH3Or H.
In this embodiment, R is H or-CH3、-CH2CH3Any one of the above.
The structure of the amino cellulose prepared in this example is as follows:
FIG. 1 is a nuclear magnetic hydrogen spectrum of an ethylcellulose acrylic macromonomer and an amino cellulose in example 1, from which it can be found that a peak of methylene protons corresponding to C = C double bonds of the ethylcellulose acrylic macromonomer at a chemical shift of 5.45-6.20 ppm; after sulfydryl-alkene click reaction, the methylene proton peak of the C = C double bond at the chemical shift of 5.45-6.20 ppm disappears, and the peak corresponding to the amino proton appears at the chemical shift of 1.5 ppm, which indicates that the amino cellulose is successfully prepared.
FIG. 2 is an infrared spectrum of ethylcellulose acrylic macromonomer and amino cellulose in example 1, from which it can be found that 1650 cm is obtained after mercapto-ene click reaction-1The intensity of the characteristic peak corresponding to the ethylcellulose acrylic macromer-C = C-is significantly reduced, indicating that the amino cellulose was successfully prepared.
Example 2: preparation of amino cellulose from ethyl cellulose
The first step is as follows: dissolving ethyl cellulose, methacryloyl chloride and triethylamine in tetrahydrofuran according to the mol ratio of [ ethyl cellulose ], [ methacrylic anhydride ], [ triethylamine ] =1:1:0.3, and reacting for 5 hours at 10 ℃ to prepare an ethyl cellulose acrylic acid macromonomer;
the second step is that: ethyl cellulose acrylic acid macromonomer, mercaptoethylamine,Photoinitiator 907 is added according to molar ratio [ ethyl cellulose acrylic acid macromonomer ]]Mercapto ethylamine][ photoinitiator 907 ]]Dissolve in ethanol at a concentration of 2 mW/cm =1:0.5: 0.042After 12 h under ultraviolet lamp irradiation, the product was precipitated in deionized water, filtered and dried to obtain amino cellulose with a yield of 89.2%.
Example 3: the microcrystalline cellulose is used for preparing the amino cellulose.
In this embodiment, R is H or-CH3Any one of the above.
The first step is as follows: dissolving microcrystalline cellulose, methacrylic anhydride and triethylamine in a DMAc/LiCl system according to the mol ratio of [ microcrystalline cellulose ], [ methacrylic anhydride ], [ triethylamine ] =1:1:0.3, and reacting for 5 hours at 40 ℃ to prepare a microcrystalline cellulose acrylic acid macromonomer;
the second step is that: dissolving microcrystalline cellulose acrylic acid macromonomer, mercaptoethylamine and azobisisobutyronitrile in DMSO according to a molar ratio of [ ethyl cellulose acrylic acid macromonomer ], [ mercaptoethylamine ], [ azobisisobutyronitrile ] =1:2: 0.04, heating and reacting for 5 hours at 60 ℃, precipitating a product in deionized water, filtering and drying to obtain the amino cellulose, wherein the yield is 86.0%.
Example 4: the nanocellulose is used for preparing the amino cellulose.
In this embodiment, R is H or-CH3Any one of the above.
The first step is as follows: dissolving nano-cellulose, methacryloyl chloride and 4-dimethylaminopyridine in a molar ratio of [ microcrystalline cellulose ], [ methacryloyl chloride ], [ 4-dimethylaminopyridine ] =1:2:0.5 in a DMF system, and reacting at 20 ℃ for 24 hours to prepare a nano-cellulose-based acrylic macromonomer;
the second step is that: nano cellulose acrylic acid macromonomer, mercaptoethylamine and photoinitiator 2959 are added according to molar ratio]Mercapto ethylamine][ photoinitiator 2959 ]]Dissolve in DMF system at ratio of 5 mW/cm =1:1: 0.032The product was precipitated in deionized water, filtered and dried to give amino cellulose in 84.3% yield.
Example 5: preparation of amino cellulose from ethyl cellulose
The first step is as follows: dissolving ethyl cellulose, methacrylic anhydride and 4-dimethylaminopyridine in a molar ratio of [ ethyl cellulose ]: [ methacrylic anhydride ]: [ 4-dimethylaminopyridine ] =1:0.5:0.1 in tetrahydrofuran, and reacting at 60 ℃ for 3 hours to prepare an ethyl cellulose acrylic macromonomer;
the second step is that: ethyl cellulose acrylic acid macromonomer, mercaptoethylamine and photoinitiator 2959 are mixed according to molar ratio]Mercapto ethylamine][ photoinitiator 2959 ]]Dissolve in ethanol at a ratio of 5 mW/cm =1: 3: 0.052The product was precipitated in deionized water, filtered and dried to give amino cellulose in 89.7% yield.
Example 6: the amino cellulose is prepared by using hydroxyethyl cellulose.
In this embodiment, R is H or-CH3、-CH2CH2Any one of OH.
The first step is as follows: dissolving hydroxyethyl cellulose, methacrylic anhydride and 4-dimethylaminopyridine in a molar ratio of [ hydroxyethyl cellulose ], [ methacrylic anhydride ], [ 4-dimethylaminopyridine ] =1:0.5:0.1 in water, and reacting at 60 ℃ for 5 hours to prepare a hydroxyethyl cellulose acrylic macromonomer;
the second step is that: dissolving hydroxyethyl cellulose acrylic acid macromonomer, mercaptoethylamine and dibenzoyl peroxide in DMSO according to molar ratio [ hydroxyethyl cellulose acrylic acid macromonomer ], [ mercaptoethylamine ], [ dibenzoyl peroxide ] =1:1: 0.05, heating and reacting for 8 hours at 60 ℃, precipitating a product in deionized water, filtering and drying to obtain the amino cellulose, wherein the yield is 85.1%.
Example 7: the amino cellulose is prepared by using hydroxypropyl cellulose.
In this embodiment, R is H or-CH3、-CH2CH2CH2Any one of OH.
The first step is as follows: dissolving hydroxypropyl cellulose, acryloyl chloride and triethylamine in a molar ratio of [ hydroxypropyl cellulose ], [ acryloyl chloride ], [ triethylamine ] =1:1.5:1 in water, and reacting at 60 ℃ for 8 hours to prepare a hydroxypropyl cellulose acrylic acid macromonomer;
the second step: dissolving hydroxypropyl cellulose acrylic acid macromonomer, mercaptoethylamine and azobisisobutyronitrile into DMSO according to the molar ratio of [ hydroxyethyl cellulose acrylic acid macromonomer ], [ mercaptoethylamine ], [ azobisisobutyronitrile ] =1:1: 0.03, heating and reacting for 10 hours at 60 ℃, precipitating a product in deionized water, filtering and drying to obtain the amino cellulose, wherein the yield is 83.7%.
Example 8: preparation of amino cellulose from ethyl cellulose
The first step is as follows: dissolving ethyl cellulose, methacrylic anhydride and 4-dimethylaminopyridine in a molar ratio of [ ethyl cellulose ], [ methacrylic anhydride ], [ 4-dimethylaminopyridine ] =1:0.1:2 in tetrahydrofuran, and reacting at 0 ℃ for 1 h to prepare an ethyl cellulose acrylic macromonomer;
the second step is that: dissolving ethyl cellulose acrylic acid macromonomer, mercaptoethylamine and azobisisobutyronitrile in ethanol according to molar ratio [ ethyl cellulose acrylic acid macromonomer ], [ mercaptoethylamine ], [ azobisisobutyronitrile ] =1:0.1: 0.01, heating and reacting for 5 hours at 75 ℃, precipitating a product in deionized water, filtering and drying to obtain the amino cellulose, wherein the yield is 90.4%.
Tests show that the amino cellulose prepared in the above examples 1 to 8 has good solubility in organic solvents such as dichloromethane, tetrahydrofuran, ethanol and the like, and can be used as a Schiff base chemical macromolecular cross-linking agent and an epoxy resin curing agent.
Claims (9)
1. An amino cellulose characterized by: the structural general formula is as follows:
wherein R is1is-CH3Or H, R is H, -CH3、-CH2CH3、-COCH3、-CH2CH2OH or-CH2CH2CH2Any one of OH.
2. A process for producing an amino cellulose according to claim 1, characterized in that: the method comprises the following steps:
(1) reacting cellulose, a double bond introducing agent and a catalyst in a good solvent system to prepare a cellulose-based acrylic acid macromonomer, wherein the double bond introducing agent is any one of methacrylic anhydride, acrylic anhydride, methacryloyl chloride and acryloyl chloride;
(2) carrying out sulfhydryl-alkene click reaction on cellulose-based acrylic acid macromonomer, mercaptoethylamine and an initiator in a good solvent system, then precipitating a product in deionized water, filtering and drying to obtain the amino cellulose.
3. The method for producing amino cellulose according to claim 2, characterized in that: in the step (1), the molar ratio of the cellulose to the double bond introducing agent to the catalyst is 1: 0.1-2.
4. The method for producing amino cellulose according to claim 2, characterized in that: in the step (1), the reaction temperature is 0-70 ℃, and the reaction time is 1-24 h.
5. The method for producing amino cellulose according to claim 2, characterized in that: in the step (2), the molar ratio of the cellulose-based acrylic acid macromonomer, the mercaptoethylamine and the initiator is 1: 0.1-3: 0.01-0.05.
6. The method for producing amino cellulose according to claim 2, characterized in that: in the step (2), thermal initiation or photo initiation is adopted for reaction, and the reaction time is 1-15 h; wherein the thermal initiation is heating to 10-100 deg.C, and the photo initiation is with light intensity of 0.01-5 mW/cm2Is irradiated by the ultraviolet lamp.
7. The method for producing amino cellulose according to claim 2, characterized in that: the cellulose is any one of nanocellulose, microcrystalline cellulose, ethyl cellulose, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose.
8. The method for producing amino cellulose according to claim 2, characterized in that: the catalyst is 4-dimethylamino pyridine or triethylamine.
9. The method for producing amino cellulose according to claim 2, characterized in that: the initiator is any one of azobisisobutyronitrile, dibenzoyl peroxide, a photoinitiator 907 and a photoinitiator 2959.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS61211302A (en) * | 1985-03-18 | 1986-09-19 | Agency Of Ind Science & Technol | Cellulose having pendant diethylenetriamine group and its production |
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| GB1081732A (en) * | 1964-02-28 | 1967-08-31 | Ici Ltd | New cellulose derivatives |
| US6596809B2 (en) * | 2001-07-20 | 2003-07-22 | Symyx Technologies, Inc. | Cellulose copolymers that modify fibers and surfaces and methods of making same |
| WO2010138069A1 (en) * | 2009-05-27 | 2010-12-02 | Swetree Technologies Ab | A polymer made of a primary amine functionalized polymer and a hemicellulose |
| EP2526121A4 (en) * | 2010-01-19 | 2013-11-13 | Organoclick Ab | Heterogeneous thiol-ene click modifications of solid polysaccharide-based materials |
| DE102013005184A1 (en) * | 2013-03-20 | 2014-09-25 | fzmb GmbH, Forschungszentrum für Medizintechnik und Biotechnologie | Method for functionalizing a surface |
| WO2017075417A1 (en) * | 2015-10-28 | 2017-05-04 | Innotech Materials, Llc | Preparation of modified cellulose and its derivatives |
| CN108360080A (en) * | 2018-02-12 | 2018-08-03 | 天津工业大学 | A kind of cellulose-acrylate base solid-solid phase transition material and preparation method thereof |
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