CN110724232A - Method for synthesizing active bagasse xylan citrate-g-GMA - Google Patents
Method for synthesizing active bagasse xylan citrate-g-GMA Download PDFInfo
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Abstract
The invention discloses a method for synthesizing bagasse xylan citrate-g-GMA with biological activity. Taking bagasse xylan as a main raw material, firstly, taking potassium persulfate as an initiator, and carrying out graft copolymerization with glycidyl methacrylate under a water phase condition to obtain a bagasse xylan-g-GMA derivative; then, sodium hypophosphite monohydrate is used as an esterification catalyst, citric acid is used as an esterification agent, and the target product bagasse xylan citrate-g-GMA is obtained through catalytic esterification reaction in an ionic liquid chlorination-1-allyl-3-methylimidazole solvent. The target product synthesized by the process improves the stability of the bagasse xylan, and introduces active groups of functional monomers GMA and citric acid to further improve the biological activities of the bagasse xylan, such as cancer resistance and the like.
Description
Technical Field
The invention relates to the field of fine chemical engineering and biomass materials, in particular to a method for synthesizing bagasse xylan citrate-g-GMA with bioactivity.
Background
In recent years, the application of renewable biomass resources as a novel industrial polymer instead of traditional industrial petrochemical materials has become a focus of attention of researchers. The xylan is used as a renewable and degradable polysaccharide, and can be deeply processed by adopting esterification, etherification, graft copolymerization and other modes due to more hydroxyl groups distributed in macromolecules, so that the xylan has a wide development prospect. At present, chemical modification of xylan is mainly single modification research, for example, by selecting different monomers, improving the spatial structure of xylan through grafting reaction, and synthesizing products such as slow-release materials and additives.
On the basis of one-step modification of xylan, a second step of grafting, esterification and other reactions can provide more active groups for xylan. The method has the advantages that the initiator is adopted to control Glycidyl Methacrylate (GMA) to be grafted and copolymerized to the bagasse xylan side chain, so that the bioactivity of the bagasse xylan can be effectively improved, citric acid with high activity and hydrophilicity is introduced through esterification reaction to serve as a second active group of the bagasse xylan, the hydrogen bond effect of molecules is reduced, and meanwhile, the ionic liquid is adopted as an esterification reaction solvent to enable the esterification reaction of the citric acid and a xylan derivative to be homogeneous esterification, so that the esterification effect is improved, the basic physical and chemical properties of the bagasse xylan are improved, and the bioactivity of the bagasse xylan is enhanced.
The method comprises the steps of taking bagasse xylan as a main raw material, firstly, taking potassium persulfate as an initiator, and carrying out graft copolymerization with glycidyl methacrylate under a water phase condition to obtain a bagasse xylan-g-GMA derivative; then, sodium hypophosphite monohydrate is used as an esterification catalyst, citric acid is used as an esterification agent, and the target product bagasse xylan citrate-g-GMA is obtained through catalytic esterification reaction in an ionic liquid chlorination-1-allyl-3-methylimidazole (AmimCl) solvent.
Disclosure of Invention
The invention aims to improve the basic physicochemical property of bagasse xylan and enhance the biological activity of the bagasse xylan, and provides a method for synthesizing bagasse xylan citrate-g-GMA with biological activity.
The method comprises the following specific steps:
(1) and (3) drying 5-10 g of bagasse xylan in a vacuum constant-temperature drying oven at 60 ℃ for 24 hours to constant weight to obtain the dry-based bagasse xylan.
(2) And (3) weighing 3-8 g of the dry bagasse xylan obtained in the step (2), adding into a 250mL four-neck flask, and then adding 15-20 mL of deionized water. Stirring for 10-15 minutes at room temperature to obtain the xylan suspension.
(3) Weighing 0.2-0.3 g of potassium persulfate in a 50mL beaker, adding 10-15 mL of deionized water into the beaker, stirring until the deionized water is dissolved to obtain an initiator solution, and pouring the initiator solution into a 50mL constant-pressure dropping funnel for later use.
(4) Heating the system obtained in the step (2) to 70-90 ℃, dropwise adding the initiator solution obtained in the step (3), and controlling the time for dropwise adding 1/4 of the total mass of the initiator solution within 10-20 minutes.
(5) Placing 5-10 mL of analytically pure monomer Glycidyl Methacrylate (GMA) into a 50mL constant-pressure dropping funnel, and beginning to drop the analytically pure monomer GMA when the initiator potassium persulfate solution total mass is 1/4 after the system in the step (4) is dropped; and controlling the reaction time to be 3-4 hours, and simultaneously finishing the dropwise addition, continuously stirring and reacting for 1-2 hours, and cooling the materials to room temperature.
(6) And (5) carrying out suction filtration on the material obtained in the step (5), and sequentially washing and carrying out suction filtration for 3-4 times by using 25-30 mL of analytically pure absolute ethyl alcohol and 25-30 mL of analytically pure acetone respectively. And (3) putting the filter cake into a watch glass, and putting the watch glass in a vacuum constant-temperature drying oven at 60 ℃ for drying for 24 hours to constant weight to obtain a bagasse xylan-g-GMA crude product.
(7) And (3) extracting the crude product obtained in the step (6) with 30-50 mL of analytically pure acetone in a Soxhlet extractor for 24 hours, and drying the extracted sample in a vacuum constant-temperature drying oven at 60 ℃ for 24 hours to constant weight to obtain the bagasse xylan-g-GMA pure graft copolymer.
(8) Weighing 40-45 mL of analytically pure allyl chloride and 30-35 mL of analytically pure 1-methylimidazole, placing the analytically pure allyl chloride and the 1-methylimidazole into a 250mL round-bottom flask sealing system provided with a stirrer, a reflux condensing device and a thermometer, controlling the temperature to be 55-60 ℃, and stirring and reacting the system for 7-9 hours under a continuous vacuum-pumping state by adopting a circulating water type vacuum pump. Evaporating excessive allyl chloride in the obtained crude product by a rotary evaporator to obtain ionic liquid chloro-1-allyl-3-methylimidazole, cooling the ionic liquid to room temperature, and pouring the ionic liquid chloro-1-allyl-3-methylimidazole into a 100mL beaker for later use.
(9) Weighing 23-30 g of ionic liquid chloro-1-allyl-3-methylimidazole in a 250mL four-neck flask, heating to 70-90 ℃, and melting the ionic liquid into yellow transparent liquid under stirring.
(10) And (3) weighing 3-5 g of dried bagasse xylan-g-GMA, adding the dried bagasse xylan-g-GMA into the system obtained in the step (9), and stirring for 40-60 minutes until the bagasse xylan-g-GMA is completely dissolved in the chlorinated-1-allyl-3-methylimidazole solvent.
(11) 0.7-1 g of sodium hypophosphite monohydrate and 1.2-2.2 g of citric acid are weighed and added into the system obtained in the step (10), and the temperature is controlled to be 70-90 ℃ for reaction for 3-4 hours. The material was cooled to room temperature to obtain a reaction product solution.
(12) And (3) carrying out suction filtration on the reaction liquid obtained in the step (11) to obtain a filter cake, and sequentially washing and carrying out suction filtration for 3-4 times by using 25-30 mL of analytically pure acetone and 25-30 mL of analytically pure anhydrous ethanol respectively. And (3) putting the filter cake into a watch glass, and putting the watch glass into a vacuum constant-temperature drying oven at 60 ℃ for drying for 24 hours to constant weight to obtain the product of bagasse xylan citrate-g-GMA.
(13) And (3) measuring the esterification substitution degree of the bagasse xylan citrate-g-GMA obtained in the step (12) by adopting an acid-base titration method, wherein the method comprises the following specific steps: accurately weighing about 0.2g of sample, putting the sample into a 250mL conical flask, adding 5mL of deionized water, shaking the sample uniformly, and dripping 3 drops of phenolphthalein indicator. 2.5mL of 0.5mol/L sodium hydroxide solution was added and shaken. Saponification was performed at room temperature for 1 hour with shaking. The stopper and the inner wall of the conical flask were rinsed with 10mL of deionized water, followed by 0.1mol/L hydrochloric acidAnd titrating the standard solution until the standard solution is colorless, and obtaining an end point. Recording the volume V of the standard solution of hydrochloric acid consumed1. Under the same condition, blank titration is carried out by using bagasse xylan before esterification, and the volume V of the consumed hydrochloric acid standard solution is recorded0. The calculation formula of the mass fraction w of acetyl groups and the degree of substitution DS is as follows:
in the formula:
w-average mass fraction,%, of acetyl groups contained in each unit of the citric acid esterified bagasse xylan graft derivative;
V0titrating the volume of HCl standard solution consumed by bagasse xylan-g-GMA in unit of mL;
V1titrating the volume of HCl standard solution consumed by the citric acid esterified bagasse xylan graft derivative in units of mL;
CHCl-the concentration of the hydrochloric acid standard solution in mol/L;
m is the mass of the target product sample in g;
132-relative molecular mass of anhydroxylose units;
43-relative molecular mass of the citrayl groups;
DS-degree of substitution of citric acid esterified bagasse xylan-g-GMA;
relative molecular mass of the M-acyl anhydroxylose graft derivative units.
The target product synthesized by the process improves the stability of the bagasse xylan, and introduces active groups of functional monomers GMA and citric acid to further improve the biological activities of the bagasse xylan, such as cancer resistance and the like.
Drawings
FIG. 1 is an IR chart of raw bagasse xylan.
FIG. 2 is an IR chart of bagasse xylan citrate-g-GMA.
Figure 3 is an XRD pattern of raw bagasse xylan.
FIG. 4 is an XRD pattern of bagasse xylan citrate-g-GMA.
FIG. 5 is a graph showing TG and DTG curves of raw bagasse xylan.
FIG. 6 is a TG-DTG plot of bagasse xylan citrate-g-GMA.
Fig. 7 is an SEM photograph of bagasse xylan.
FIG. 8 is an SEM image of bagasse xylan citrate-g-GMA.
FIG. 9 shows the production of bagasse xylan citrate-g-GMA1H NMR chart.
Detailed Description
Example (b):
(1) and (3) drying 6g of bagasse xylan in a vacuum constant-temperature drying oven at 60 ℃ for 24 hours to constant weight to obtain dry-based bagasse xylan.
(2) Weighing 5g of the dry bagasse xylan obtained in the step (2) and adding the dry bagasse xylan into a 250mL four-neck flask, and then adding 15mL of deionized water. Stirring at room temperature for 10 minutes gave a xylan suspension.
(3) 0.3g of potassium persulfate is weighed into a 50mL beaker, 15mL of deionized water is added into the beaker, the mixture is stirred until the deionized water is dissolved to obtain an initiator solution, and the initiator solution is poured into a 50mL constant-pressure dropping funnel for later use.
(4) Heating the system obtained in the step (2) to 70 ℃, starting to dropwise add the initiator solution obtained in the step (3), and controlling the dropwise addition of 1/4 based on the total mass of the initiator solution within 15 minutes.
(5) Weighing 5mL of analytically pure monomer Glycidyl Methacrylate (GMA), placing the 5mL of analytically pure monomer GMA into a 50mL constant-pressure dropping funnel, and beginning to drop the analytically pure monomer GMA when the total mass of the initiator potassium persulfate solution is 1/4 after the system in the step (4) is dropped; after the dropwise addition was completed while controlling for 4 hours, the reaction was continued for 2 hours with stirring, and the material was cooled to room temperature.
(6) And (5) carrying out suction filtration on the material obtained in the step (5), washing with 25mL of analytically pure absolute ethyl alcohol and 25mL of analytically pure acetone in sequence, and carrying out suction filtration for 4 times. And (3) putting the filter cake into a watch glass, and putting the watch glass in a vacuum constant-temperature drying oven at 60 ℃ for drying for 24 hours to constant weight to obtain a bagasse xylan-g-GMA crude product.
(7) And (3) extracting the crude product obtained in the step (6) by using 50mL of analytically pure acetone in a Soxhlet extractor for 24 hours, and drying the extracted sample in a vacuum constant-temperature drying oven at 60 ℃ for 24 hours to constant weight to obtain the bagasse xylan-g-GMA pure graft copolymer.
(8) 40mL of analytically pure allyl chloride and 30mL of analytically pure 1-methylimidazole are weighed and placed in a 250mL round-bottom flask sealed system provided with a stirrer, a reflux condenser and a thermometer, the temperature is controlled at 60 ℃, and the system is stirred and reacted for 9 hours under the condition of continuous vacuum pumping by adopting a circulating water type vacuum pump. Evaporating excessive allyl chloride in the obtained crude product by a rotary evaporator to obtain ionic liquid chloro-1-allyl-3-methylimidazole, cooling the ionic liquid to room temperature, and pouring the ionic liquid chloro-1-allyl-3-methylimidazole into a 100mL beaker for later use.
(9) 23g of ionic liquid chloro-1-allyl-3-methylimidazole is weighed into a 250mL four-neck flask, the temperature is raised to 90 ℃, and the ionic liquid is melted into yellow transparent liquid under stirring.
(10) And (3) weighing 5g of dried bagasse xylan-g-GMA, adding the dried bagasse xylan-g-GMA into the system obtained in the step (9), and stirring for 60 minutes until the bagasse xylan-g-GMA is completely dissolved in the chlorinated-1-allyl-3-methylimidazole solvent.
(11) 1.0g of sodium hypophosphite monohydrate and 2.2g of citric acid are weighed into the system obtained in the step (10), and the temperature is controlled to be 90 ℃ for reaction for 4 hours. The material was cooled to room temperature to obtain a reaction product solution.
(12) And (4) carrying out suction filtration on the reaction liquid obtained in the step (11) to obtain a filter cake, and sequentially washing and carrying out suction filtration for 4 times by using 30mL of analytically pure acetone and 30mL of analytically pure absolute ethyl alcohol respectively. And (3) putting the filter cake into a watch glass, and putting the watch glass into a vacuum constant-temperature drying oven at 60 ℃ for drying for 24 hours to constant weight to obtain the product of bagasse xylan citrate-g-GMA.
(14) And (3) measuring the substitution degree of the product obtained in the step (12) by citric acid esterification by an acid-base titration method to obtain the DS of 0.35.
The product bagasse xylan citrate-g-GMA was analyzed by FTIR at 1727.65cm-1The peak is the C ═ O stretching vibration peak of glycidyl methacrylate, 2935.35cm-1Point C-The H absorption peak is flanked by smaller peaks, which are caused by the C-H stretching vibrations of the methylene group in citric acid. Changes in the XRD of the product indicate changes in the crystalline regions and degree of the grafted esterification product. The TG-DTG curve of an analysis product is mainly divided into three parts, but the mass loss in the first stage is only about 8%, the cooling rate at 200-410 ℃ in the second stage is higher, and the mass loss is about 78% of the total mass; the mass loss in the third stage was about 2% and the final bagasse xylan citrate-g-GMA residual was about 8%. SEM photos show that after xylan is grafted by glycerol methacrylate, a plurality of large spherical bulges are added on the surface, but the surface is still smooth like the litchi rind surface, and the surface changes after the xylan is esterified by citric acid show that the grafting and esterification modification of the xylan are successful.1H NMR further demonstrated the macromolecular structural changes of the synthesized product bagasse xylan citrate-g-GMA.
Claims (1)
1. A method for synthesizing bagasse xylan citrate-g-GMA with bioactivity is characterized by comprising the following specific steps:
(1) drying 5 ~ 10g of bagasse xylan in a vacuum constant-temperature drying oven at 60 ℃ for 24 hours to constant weight to obtain dry-based bagasse xylan;
(2) weighing 3 ~ 8g of the dry bagasse xylan obtained in the step (2), adding the dry bagasse xylan into a 250mL four-neck flask, adding 15 ~ 20mL deionized water, and stirring at room temperature for 10 ~ 15 minutes to obtain a xylan suspension;
(3) weighing 0.2 ~ 0.3.3 g of potassium persulfate in a 50mL beaker, adding 10 ~ 15mL of deionized water into the beaker, stirring until the deionized water is dissolved to obtain an initiator solution, and pouring the initiator solution into a 50mL constant-pressure dropping funnel for later use;
(4) heating the system obtained in the step (2) to 70 ~ 90 ℃, starting to dropwise add the initiator solution obtained in the step (3), and controlling the time to be 10 ~ 20 minutes, and dropwise adding 1/4 of the total mass of the initiator solution;
(5) weighing 5 ~ 10mL of analytically pure monomer Glycidyl Methacrylate (GMA) and placing the monomer GMA in a 50mL constant-pressure dropping funnel, beginning to drop the analytically pure monomer GMA when the total mass of the initiator potassium persulfate solution is 1/4 after the system in the step (4) is dropped, controlling the dropping to be 3 ~ 4 hours and the dropping to be completed, continuously stirring and reacting for 1 ~ 2 hours, and cooling the material to the room temperature;
(6) carrying out suction filtration on the material obtained in the step (5), sequentially washing with 25 ~ 30mL of analytically pure absolute ethyl alcohol and 25 ~ 30mL of analytically pure acetone, and carrying out suction filtration for 3 ~ 4 times, putting the filter cake into a watch glass, and drying in a vacuum constant-temperature drying oven at 60 ℃ for 24 hours until the weight is constant, thus obtaining a bagasse xylan-g-GMA crude product;
(7) extracting the crude product obtained in the step (6) with 30 ~ 50mL of analytically pure acetone in a Soxhlet extractor for 24 hours, and drying the extracted sample in a vacuum constant-temperature drying oven at 60 ℃ for 24 hours to constant weight to obtain a bagasse xylan-g-GMA pure graft copolymer;
(8) weighing 40 ~ 45mL of analytically pure allyl chloride and 30 ~ 35mL of analytically pure 1-methylimidazole, placing the analytically pure allyl chloride and the 1-methylimidazole in a 250mL round-bottom flask sealing system provided with a stirrer, a reflux condensing device and a thermometer, controlling the temperature to be 55 ~ 60 ℃, adopting a circulating water type vacuum pump to stir the system for reaction for 7 ~ 9 hours under the continuous vacuum-pumping state, evaporating excessive allyl chloride by using a rotary evaporator to obtain ionic liquid chloro-1-allyl-3-methylimidazole, cooling the ionic liquid chloro-1-allyl-3-methylimidazole to room temperature, and pouring the ionic liquid chloro-1-allyl-3-methylimidazole into a 100mL beaker for later use;
(9) weighing 23 ~ 30g of ionic liquid chloro-1-allyl-3-methylimidazole in a 250mL four-neck flask, heating to 70 ~ 90 ℃, and melting the ionic liquid into yellow transparent liquid under stirring;
(10) weighing 3 ~ 5g of dried bagasse xylan-g-GMA, adding the dried bagasse xylan-g-GMA into the system obtained in the step (9), and stirring for 40 ~ 60 minutes until the bagasse xylan-g-GMA is completely dissolved in the chlorinated-1-allyl-3-methylimidazole solvent;
(11) 0.7 ~ 1g of sodium hypophosphite monohydrate and 1.2 g of 1.2 ~ 2.2.2 g of citric acid are weighed and added into the system obtained in the step (10), the temperature is controlled to be 70 ~ 90 ℃, the reaction is carried out for 3 ~ 4 hours, and the materials are cooled to room temperature to obtain reaction product solution;
(12) and (3) carrying out suction filtration on the reaction liquid obtained in the step (11) to obtain a filter cake, sequentially washing with 25 ~ 30mL of analytically pure acetone and 25 ~ 30mL of analytically pure absolute ethyl alcohol, and carrying out suction filtration for 3 ~ 4 times, putting the filter cake into a watch glass, and drying in a vacuum constant-temperature drying oven at 60 ℃ for 24 hours to constant weight to obtain the bagasse xylan citrate-g-GMA.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111560097A (en) * | 2020-06-25 | 2020-08-21 | 桂林理工大学 | Synthesis method of active cross-linked bagasse xylan/camellia nitidissima shikimate-g-NVP |
| CN113842373A (en) * | 2021-08-28 | 2021-12-28 | 桂林理工大学 | Preparation method of curcumin-coated LTBX-g-EGDMA/HEMA/IMA nanoparticles |
| CN113861345A (en) * | 2021-08-31 | 2021-12-31 | 桂林理工大学 | Synthesis method of bagasse xylan/naringin-g-HPMA malate with anticancer activity |
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| CN110128593A (en) * | 2019-05-28 | 2019-08-16 | 桂林理工大学 | The method of bagasse xylan vanilla acid esters-g-HEMA/MAA is synthesized in ionic liquid |
| CN110194817A (en) * | 2019-05-28 | 2019-09-03 | 桂林理工大学 | A kind of synthetic method of activity bagasse xylan vanilla acid esters-g-HEMA/MAA/EA |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111560097A (en) * | 2020-06-25 | 2020-08-21 | 桂林理工大学 | Synthesis method of active cross-linked bagasse xylan/camellia nitidissima shikimate-g-NVP |
| CN113842373A (en) * | 2021-08-28 | 2021-12-28 | 桂林理工大学 | Preparation method of curcumin-coated LTBX-g-EGDMA/HEMA/IMA nanoparticles |
| CN113861345A (en) * | 2021-08-31 | 2021-12-31 | 桂林理工大学 | Synthesis method of bagasse xylan/naringin-g-HPMA malate with anticancer activity |
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