CN116284839A - Method for preparing phenolized lignin by transesterification of lignin and dihydrocoumarin - Google Patents
Method for preparing phenolized lignin by transesterification of lignin and dihydrocoumarin Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 29
- VMUXSMXIQBNMGZ-UHFFFAOYSA-N 3,4-dihydrocoumarin Chemical compound C1=CC=C2OC(=O)CCC2=C1 VMUXSMXIQBNMGZ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- DMSHWWDRAYHEBS-UHFFFAOYSA-N dihydrocoumarin Natural products C1CC(=O)OC2=C1C=C(OC)C(OC)=C2 DMSHWWDRAYHEBS-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000005809 transesterification reaction Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
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- 230000035484 reaction time Effects 0.000 claims description 5
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
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- 238000003756 stirring Methods 0.000 description 3
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
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- 239000000523 sample Substances 0.000 description 2
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- Engineering & Computer Science (AREA)
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Abstract
The invention discloses a method for preparing phenolized lignin by transesterification of lignin and dihydrocoumarin, which comprises the following steps: (1) Mixing lignin, organic alkali and dihydrocoumarin with an organic solvent, and reacting for 0.5-24 hours in a reaction kettle with the temperature of 80-140 ℃ to obtain phenolized lignin crude liquid; (2) Adding C1-C4 lower fatty alcohol or water into the phenolized lignin solution, filtering the mixed solution, and washing and purifying the solid mixture obtained by filtering with C1-C4 lower fatty alcohol or water, and drying to obtain the phenolized lignin. The preparation process has the characteristics of mild reaction conditions, simple process and low cost, and is beneficial to industrialized implementation; meanwhile, the phenolized lignin prepared by the process is novel in structure and has important significance for expanding the functionalization and high-value utilization of lignin; in addition, the phenolized lignin has the characteristics of better solubility, oxidation resistance and ultraviolet resistance.
Description
Technical Field
The invention relates to a preparation method of phenolized lignin, in particular to a method for preparing phenolized lignin by transesterification of lignin and dihydrocoumarin.
Background
Lignin is a second largest biobased resource next to cellulose but is far from being fully utilized. In cellulose-based pulping black liquor, lignin is more discharged as a waste. According to incomplete statistics, the annual lignin yield is 5000 ten thousand tons, while the lignin actually utilized is only 2%, and more lignin only provides heat for combustion.
Lignin has a large and complex polymer network structure including methoxy groups, phenolic hydroxyl groups, alcoholic hydroxyl groups, and some terminal aldehyde groups on side chains. Unfortunately, lignin is generally brittle due to its aromaticity and highly complex three-dimensional structure, has poor compatibility, low dispersity, poor processability, etc. when used directly as a polymer or composite component. It is widely believed that chemical modification of lignin by its structural features can significantly improve the above-mentioned shortcomings, thereby expanding its application range. For example, lignin can be modified by alkylation, alkoxylation, nitration, and esterification of hydroxyl, methoxy, carbonyl, and carboxyl groups without destroying its inherent structure. The material with great application potential is obtained in the fields of cosmetics, energy catalysis, surfactants, enhancers and the like. Among them, lignin phenolization has been studied extensively in lignin functionalization.
Phenolated lignin can be largely divided into three pathways:
1. the addition of a lewis acid after dissolution of lignin with DMF may cause cleavage of methyl groups in methoxy groups on lignin to form phenolic hydroxyl groups to obtain phenolized lignin. Of these, the most common are the haloacids (ACS Sustainable Chemistry Engineering,5,5424).
2. In the publication No. CN111286041A, alkali lignin is dissolved under acidic conditions (pH 4.0 or 6.0), and 2,2' -diaza-bis-3-ethylbenzothiazoline-6-sulfonic acid is added with a fungal laccase of Coriolus versicolor to obtain phenolized lignin. Secondly, phenol monooxygenase also can phenolize lignin.
3. In the publication CN104004479a, alkali lignin is dehydrated under strong acid conditions, and then electrophilically substituted with alpha or gamma carbocations at a lower pH, and grafted to lignin to form phenolized lignin.
Among the above strategies for phenolizing lignin, strategies 1 and 3 require high temperatures and pressures, which are not conducive to industrial production and safety. Strategy 2, although the reaction conditions are milder, the process of extracting the enzyme is more complex and the cost is higher.
Disclosure of Invention
The invention aims to provide a method for preparing phenolized lignin by transesterification of lignin and dihydrocoumarin. The preparation process has the characteristics of mild reaction conditions, simple process and low cost, and is beneficial to industrialized implementation; meanwhile, the phenolized lignin prepared by the process is novel in structure and has important significance for expanding the functionalization and high-value utilization of lignin; in addition, the phenolized lignin has the characteristics of better solubility, oxidation resistance and ultraviolet resistance.
The technical scheme of the invention is as follows: a method for preparing phenolized lignin by transesterification of lignin and dihydrocoumarin comprises the following steps:
(1) Mixing lignin, organic alkali and dihydrocoumarin with an organic solvent, and reacting for 0.5-24 hours in a reaction kettle with the temperature of 80-140 ℃ to obtain a phenolized lignin solution;
(2) Adding C1-C4 lower fatty alcohol or water into the phenolized lignin solution, filtering the mixed solution, and washing and purifying the solid mixture obtained by filtering with C1-C4 lower fatty alcohol or water, and drying to obtain the phenolized lignin.
The preparation method of the phenolized lignin comprises the following steps: one or any combination of several of alkali lignin, enzymolysis lignin, lignin sulfonate, steam explosion lignin or lignin separated from agriculture and forestry lignocellulose waste, and the basic unit of the structural formula is as follows:
in the preparation method of the phenolized lignin, the mass concentration of lignin in the mixture in the step (1) is 1-20wt%, the mass concentration of organic alkali is 0.5-30wt%, and the balance is organic solvent.
In the preparation method of the phenolated lignin, the organic base has the following structural characteristics:
wherein: r is independently hydrogen, methyl or ethyl; r is R 1 Is independent hydrogen or alkyl with 1-6 carbon atoms; r is R 2 ，R 3 ，R 4 R is R 5 Is independently hydrogen, methyl or ethyl.
In the preparation method of the phenolized lignin, the organic solvent is one or more than two of dimethyl sulfoxide, N-methylpyrrolidone, tetramethylguanidine, N-dimethyl imidazolinone, N-dimethylformamide, N-dimethylacetamide, N-diethylacetamide, 2-pyrrolidone, 2-azahexacyclic ketone, epsilon-caprolactam, N-dimethylpropenyl urea, sulfolane or piperylene sulfone or any mixture of more than two of the above.
The temperature of the preparation method of the phenolized lignin is 110 ℃ and the reaction time is 12 hours.
According to the preparation method of the phenolated lignin, the molar ratio of the dihydrocoumarin to the lignin hydroxyl is 0.5-10:1.
In the preparation method of the phenolized lignin, when the C1-C4 lower fatty alcohol or water is added into the phenolized lignin solution in the step (3), the volume ratio of the C1-C4 lower fatty alcohol or water to the phenolized lignin solution is 0.5-10:1.
The preparation method of the phenolized lignin comprises the following structural characteristics:
the beneficial effects of the invention are that
1. The method is based on the system of the organic solvent and the organic alkali to dissolve and activate lignin, and simultaneously, the organic alkali is used for ring-opening the dihydrocoumarin and preparing the phenolized lignin through transesterification, so that the reaction condition of the whole process is mild, the process steps are simple, and the method is very beneficial to industrial popularization and implementation.
2. The preparation method is based on an organic solvent and organic base system, the reaction reagent is cheap and easy to obtain, the preparation process is simple, and the reaction condition is mild, so that the preparation cost of the phenolized lignin is greatly reduced.
3. The invention prepares the phenolized lignin by using the lignin and the dihydrocoumarin to carry out transesterification reaction, and the obtained phenolized lignin has novel structure and has important significance for expanding the functionalization and high-value utilization of lignin.
4. According to the invention, the phenolized lignin is prepared after the transesterification reaction of lignin, and compared with the log lignin, the solubility, the antioxidation and the anti-ultraviolet performance of the phenolized lignin are greatly improved; meanwhile, the phenolated lignin has a lower glass transition temperature, so that the phenolated lignin has better processing and dispersing performance in the subsequent application process; the characteristics lead the application prospect of the product of the invention in the industrial fields of biological medicine, environmental protection, coating, packaging material and the like to be better.
Drawings
FIG. 1 is an ATR spectrum of a phenolated lignin of the present invention;
FIG. 2 is a schematic representation of phenolated lignin according to the present invention 1 H NMR spectrum;
FIG. 3 is a schematic representation of the phenolated lignin of the present invention 13 C NMR spectrum;
FIG. 4 is a two-dimensional spectrum of phenolated lignin of the present invention;
FIG. 5 is a schematic illustration of phenolized lignin according to the present invention 31 P NMR spectrum
FIG. 6 is a TGA spectrum of phenolated lignin of the present invention;
FIG. 7 is a DSC profile of a phenolized lignin of the present invention;
FIG. 8 is a UV spectrum of a phenolized lignin of the present invention;
FIG. 9 is an antioxidant spectrum of phenolated lignin of the present invention;
Detailed Description
The invention is further illustrated by the following examples, which are not intended to be limiting.
Embodiments of the invention
It is to be noted that the content of phenolic hydroxyl groups is defined by 31 The P NMR test result shows that the content of the phenolic hydroxyl groups of the unmodified lignin is 1.732mmol/g. The phenolic hydroxyl content units are mmol/g.
The formula for radical scavenging (DPPH Scavenging acitivity) is as follows:
wherein Abs sample ，Abs blank Abs control The absorbance of the sample, the blank and the control sample are shown, respectively.
Example 1:
a method for preparing phenolized lignin by transesterification of lignin and dihydrocoumarin comprises the following steps:
(1) Alkali lignin, 1, 8-diazabicyclo [5.4.0]-7-undecene, dihydrocoumarin and tetramethylguanidine in a mass concentration of 10 wt.% of alkali lignin, 1, 8-diazabicyclo [5.4.0]The mass concentration of the-7-undecene is 15wt%, the balance is tetramethylguanidine, the mol ratio of the dihydrocoumarin to the hydroxyl on the alkali lignin is 2:1, and the mixture is kept at N 2 Reacting in a reaction kettle at 110 ℃ for 12 hours under atmosphere to obtain a phenolized lignin solution;
(2) Adding 5 times of C1-C4 lower fatty alcohol into the phenolized lignin solution, filtering the mixed solution, washing and purifying the solid mixture obtained by filtering with the C1-C4 lower fatty alcohol, and drying to obtain the phenolized lignin.
Example 2:
a method for preparing phenolized lignin by transesterification of lignin and dihydrocoumarin comprises the following steps:
(1) Lignosulfonate, 1, 8-diazabicyclo [5.4.0]-7-undecene, dihydrocoumarin and N, N-diethylacetamide in a mass concentration of 1wt%,1, 8-diazabicyclo [5.4.0]The mass concentration of the 7-undecene is 0.5wt percent, the rest is N, N-diethyl acetamide, and the dihydrocoumarin and the woodinessThe molar ratio of hydroxyl groups on the su sulfonate salt was 0.5:1, and the mixture was maintained at N 2 Reacting in an atmosphere at 80 ℃ for 24 hours to obtain a phenolized lignin solution;
(2) Adding 0.5 times of C1-C4 lower fatty alcohol into the phenolized lignin solution, filtering the mixed solution, washing the solid mixture obtained by filtering with the C1-C4 lower fatty alcohol, purifying and drying to obtain the phenolized lignin.
Example 3:
a method for preparing phenolized lignin by transesterification of lignin and dihydrocoumarin comprises the following steps:
(1) Enzymatic hydrolysis of lignin, 1, 8-diazabicyclo [5.4.0 ]]-7-undecene, dihydrocoumarin and epsilon-caprolactam in a mass concentration of 20 wt.% of enzymatically hydrolyzed lignin, 1, 8-diazabicyclo [5.4.0]The mass concentration of the-7-undecene is 30wt%, the balance is epsilon-caprolactam, the mol ratio of the dihydrocoumarin to the hydroxyl on the enzymatic lignin is 3:1, and the mixture is kept at N 2 Reacting in a reaction kettle at 140 ℃ for 0.5 hour under atmosphere to obtain a phenolized lignin solution;
(2) Adding 10 times of C1-C4 water into the phenolized lignin solution, filtering the mixed solution, washing the solid mixture obtained by filtering with water, purifying and drying to obtain the phenolized lignin.
Example 4:
weighing lignin of different types 2g each, and respectively mixing with 1, 8-diazabicyclo [5.4.0 ] in the same manner as in example 1]0.3164g of 7-undecene (DBU) and 10g of N, N-Dimethylformamide (DMF) and 1.0267g of dihydrocoumarin are added into a reaction kettle, the reaction kettle is covered, and N is filled and discharged 2 Circulating for three times, removing air, and finally adding N under 0Mpa 2 The mixture was stirred at 120℃for 6 hours under an atmosphere. And (3) obtaining a black homogeneous solution after the reaction is finished, separating out a solid product by using 100mL of pure water as an antisolvent, washing, filtering for 3 times, and freeze-drying to obtain the product. The products obtained from different lignin in this example were tested and the relevant results are shown in the following table:
table 1 study of lignin from different sources
| Numbering device | Lignin | Phenolic hydroxyl group content |
| 1 | Alkali lignin | 2.78 |
| 2 | Enzymatic hydrolysis lignin | 3.01 |
| 3 | Lignin sulfonate | 2.56 |
| 4 | Lignin by steam explosion | 2.17 |
This example is a full illustration of the fact that phenolated lignin products can be prepared for lignin of different sources, and is a full illustration of the versatility of this patent with respect to lignin species.
Example 5:
2g of enzymatically hydrolyzed lignin is weighed out and the organic base 1, 8-diazabicyclo [5.4.0 ] is taken out according to the procedure of example 1]-7-undecene (DBU), triethylamine (TEA) or 1, 5-diazabicyclo [4.3.0]Non-5-ene (DBN), taking organic solvent dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF) or N-methylpyrrolidone (NMP), and respectively subjecting to enzymolysis ligninMixing one of organic alkali and one of organic solvent, adding into the reaction kettle, covering the reaction kettle, and charging and discharging N 2 Circulating for three times, removing air, and finally adding N under 0Mpa 2 Stirring for 6 hours at 120 ℃ in atmosphere to obtain a homogeneous phenolized lignin solution. And (3) separating out a solid product by using 100mL of pure water as an antisolvent, washing, filtering for 3 times, and freeze-drying to obtain the product. The products prepared from different organic bases and organic solvents in this example were tested and the relevant results are shown in the following table:
table 2 study of certain lignin content, different organic bases and organic solvents
This example is fully illustrative of the fact that phenolated lignin can be prepared for different lignin concentration levels as well as for different strong organic bases and levels, and for different organic solvents.
Example 6:
2g of enzymatically hydrolyzed lignin was weighed out in the same manner as in example 1, and was reacted with 1, 8-diazabicyclo [5.4.0, respectively]0.3164g of 7-undecene (DBU), 1.0267g of dihydrocoumarin and 10g of N, N-Dimethylformamide (DMF) are added into a reaction kettle, the reaction kettle is covered, and N is filled and discharged 2 Circulating for three times, exhausting air, and keeping N 2 Stirring for 1-24 hours at 80-140 ℃ in atmosphere to obtain a homogeneous phenolized lignin solution. The solid product was precipitated by using 100mL of pure water, washed and suction-filtered 3 times, and freeze-dried to obtain the product. The products produced in this example at different reaction times and temperatures were tested and the results are shown in the following table:
TABLE 3 investigation of the influence of different reaction times and reaction temperatures
This example is a full illustration of the fact that phenolated lignin can be prepared for different reaction times and temperatures.
Example 7:
2g of enzymatically hydrolyzed lignin was weighed out in the same manner as in example 1, and was reacted with 1, 8-diazabicyclo [5.4.0, respectively]0.3164g of 7-undecene (DBU) and 10g of N, N-Dimethylformamide (DMF) are added into a reaction kettle, the reaction kettle is covered, and N is filled and discharged 2 Circulating for three times, exhausting air, and keeping N 2 Stirring for 6 hours at 120 ℃ in atmosphere to obtain a phenolized lignin solution. The solid product was precipitated using 100mL of different antisolvents, washed, suction filtered 3 times and freeze dried to give the product. The products obtained from the different antisolvents in this example were tested and the relevant results are shown in the following table:
table 4 study of the effect of different antisolvents
| Numbering device | Antisolvents | Phenolic hydroxyl group content | Yield(％) |
| 1 | Water and its preparation method | 3.02 | 98 |
| 2 | Methanol | 2.34 | 70 |
| 3 | Ethanol | 2.27 | 65 |
| 4 | Isopropyl alcohol | 2.48 | 80 |
| 5 | Tert-butanol | 2.44 | 80 |
The example fully shows that the phenolic lignin can be precipitated for different antisolvents, and the regenerated yield of the product is higher, thus showing that different antisolvents have good effects.
While the invention has been described with reference to the preferred embodiments, it should be understood that the invention is not limited to the embodiments described above, but is intended to cover modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (9)
1. The method for preparing phenolized lignin by transesterification of lignin and dihydrocoumarin is characterized by comprising the following steps:
(1) Mixing lignin, organic alkali and dihydrocoumarin with an organic solvent, and reacting for 0.5-24 hours in a reaction kettle with the temperature of 80-140 ℃ to obtain a phenolized lignin reaction crude liquid;
(2) Adding C1-C4 lower fatty alcohol or water into the phenolized lignin solution, filtering the mixed solution, and washing and purifying the solid mixture obtained by filtering with C1-C4 lower fatty alcohol or water, and drying to obtain the phenolized lignin.
2. The method for preparing phenolized lignin according to claim 1, wherein: the lignin is as follows: one or any combination of several of alkali lignin, enzymolysis lignin, lignin sulfonate, steam explosion lignin or lignin separated from agriculture and forestry lignocellulose waste, and the structural formula is as follows:
3. the method for preparing phenolized lignin according to claim 1, wherein: the mass concentration of lignin in the mixture in the step (1) is 1-20wt%, the mass concentration of organic alkali is 0.5-30wt% and the balance is organic solvent.
4. The method for preparing phenolized lignin according to claim 1, wherein: the organic base has the following structural characteristics:
wherein: r is independently hydrogen, methyl or ethyl; r is R 1 Is independent hydrogen or alkyl with 1-6 carbon atoms; r is R 2 ，R 3 ，R 4 R is R 5 Is independently hydrogen, methyl or ethyl.
5. The method for preparing phenolized lignin according to claim 1, wherein: the organic solvent is one or a mixture of two or more of dimethyl sulfoxide, N-methyl pyrrolidone, tetramethyl guanidine, N-dimethyl imidazolinone, N-dimethyl formamide, N-dimethyl acetamide, N-diethyl acetamide, 2-pyrrolidone, 2-azacyclic ketone, epsilon-caprolactam, N-dimethyl propenyl urea, sulfolane or piperylene sulfone.
6. The method for preparing phenolized lignin according to claim 1, wherein: the molar ratio of the dihydrocoumarin to the hydroxyl groups on lignin in the lignin solution is 0.5-3:1.
7. The method for preparing phenolized lignin according to claim 1, wherein: the reaction temperature of the step (2) is 110 ℃, and the reaction time is 12 hours.
8. The method for preparing phenolized lignin according to claim 1, wherein: and (3) adding C1-C4 lower fatty alcohol or water into the phenolized lignin solution, wherein the volume ratio of the C1-C4 lower fatty alcohol or water to the phenolized lignin solution is 0.5-10:1.
9. The method for preparing phenolated lignin according to any one of claims 1 to 8, wherein: the phenolated lignin has the following structural characteristics:
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| CN105431466A (en) * | 2013-06-26 | 2016-03-23 | 植物材料工业公司 | Phenolic resin obtained by polycondensation of formaldehyde, phenol and lignin |
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| CN112441885A (en) * | 2020-12-04 | 2021-03-05 | 华中科技大学 | Method for preparing 4-vinylphenol by using lignin at high yield |
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| CN107722127A (en) * | 2017-09-27 | 2018-02-23 | 贵州大学 | The preparation method of cellulose esters |
| CN111171336A (en) * | 2020-02-18 | 2020-05-19 | 广西博世科环保科技股份有限公司 | Lignin modification method |
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