CN107417795B - Cellulose acetate sorbate and preparation method and application thereof - Google Patents
Cellulose acetate sorbate and preparation method and application thereof Download PDFInfo
- Publication number
- CN107417795B CN107417795B CN201710790730.XA CN201710790730A CN107417795B CN 107417795 B CN107417795 B CN 107417795B CN 201710790730 A CN201710790730 A CN 201710790730A CN 107417795 B CN107417795 B CN 107417795B
- Authority
- CN
- China
- Prior art keywords
- cellulose acetate
- sorbic acid
- sorbate
- chloride
- acid chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C08B3/16—Preparation of mixed organic cellulose esters, e.g. cellulose aceto-formate or cellulose aceto-propionate
Abstract
The invention belongs to the technical field of chemical cellulose, and relates to cellulose acetate sorbate as well as a preparation method and application thereof. The preparation method of the cellulose acetate sorbate comprises the following steps: (1) reacting sorbic acid with an acyl chlorination reagent to prepare sorbic acid chloride; (2) and (3) carrying out acyl chloride esterification reaction on the cellulose acetate and the sorbic acid chloride obtained in the step (1), and obtaining a product, namely the cellulose acetate sorbate. The cellulose acetate sorbate prepared by the method has mild reaction conditions and simple reaction process, and the product prepared by the method has excellent antibacterial effect.
Description
Technical Field
The invention belongs to the technical field of chemical cellulose, and relates to cellulose acetate sorbate as well as a preparation method and application thereof.
Background
Cellulose acetate is also called cellulose acetate (abbreviated as CA) and is an important organic ester, is derived from acetylation of cellulose, retains excellent performances of good biocompatibility, degradability and the like of the cellulose, has good stability, can be dissolved in common organic solvents such as acetone, DMAc (dimethylacetamide) and the like, has good melt rheological property and is easy to process, and the excellent performances of the cellulose acetate promote the cellulose acetate to gradually become a representative of cellulose materials, so that the cellulose acetate has wide application prospect.
Sorbic acid is an internationally recognized preservative, belongs to α and β unsaturated carbonyl compounds, pi bonds in two carbon-carbon double bonds in molecules are conjugated with pi bonds in carbon-oxygen double bonds, an electron relay system with a distance of about 0.25nm is formed by carbonyl oxygen and α carbon in the molecules, and the conjugated effect formed between carbonyl p electrons and adjacent olefinic bond pi electrons has strong electronic buffering capacity.
In recent years, researches on antibacterial modification and application of cellulose acetate are receiving more and more attention from the fiber field, and novel cellulose acetate fibers with antibacterial performance after modification can be widely applied to the fields of separation membranes, medical use, tobacco and the like. A method for preparing high-temperature resistant antibacterial cellulose acetate material from Sunchui comprises adding silver nitrate into solution, discharging to obtain nanometer silver loaded on fiber, and doping with photocatalytic antibacterial agent TiO 105525383A2The antibacterial cellulose acetate material having a high specific surface area and porosity is prepared by electrospinning, but the preparation process is complicated and the reaction cost is relatively high. Habib Etemadi (Habib Etemadi, Rezayegani, Valiollah Babaeibour. study on the reinforrning effect of nanodiamonds on the mechanical, thermal and antibacterial properties of cellulolacetate membranes, Diamond&Related Materials,2016,69, 166-176) by phase inversion method, adding pre-functionalized detonation method nano-diamond (DND) into a polymer matrix, thereby preparing a DND embedded CA nano-composite membrane, wherein the CA membrane prepared by the method has certain antibacterial activity to escherichia coli and staphylococcus aureus, but the reaction process has complicated steps, and because the miscibility between the polymer and the CA is poor, the nano-particle DND is easy to fall off, thereby influencing the antibacterial property.
Disclosure of Invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a cellulose acetate sorbate.
Another object of the present invention is to provide a process for preparing the above cellulose acetate sorbate.
The technical scheme of the invention is as follows:
a cellulose acetate sorbate, the cellulose acetate sorbate having the structural unit:
each structural unitR is H or
When R' is
The structural formulas of different structural units can be the same or different.
Further, the value range of n is 100-150; and/or the presence of a gas in the gas,
the degree of substitution of the cellulose acetate sorbate is 0.15 to 1.23.
The invention provides a preparation method of the cellulose acetate sorbate, which comprises the following steps:
(1) reacting sorbic acid with an acyl chlorination reagent to prepare sorbic acid chloride;
(2) and carrying out acyl chloride esterification reaction on the cellulose acetate and the sorbic acid chloride to prepare the cellulose acetate sorbate.
(3) And washing the cellulose acetate sorbate with deionized water, absolute ethyl alcohol and deionized water in sequence until the pH value is neutral to obtain the product.
The preparation method of the sorbic acid chloride in the step (1) comprises the following steps: and (2) placing sorbic acid in an acyl chlorination reagent, stirring and reacting for 2-3 hours at 60-80 ℃ under the action of a catalyst, and carrying out reduced pressure distillation after the reaction is finished to obtain the sorbic acid chloride.
The acyl chlorination reagent is thionyl chloride or PCl5Or oxalyl chloride, preferably thionyl chloride.
The molar ratio of sorbic acid to acyl chloride reagent is 1: 2-7, and can be more preferably 1:4.
The catalyst is one of DMF and pyridine.
The method for carrying out acyl chloride esterification reaction on cellulose acetate and sorbic acid chloride comprises the following steps: dissolving the cellulose acetate in an organic solvent, adding an acid-binding agent, then adding the sorbic acid chloride in an ice-water bath, reacting for 20-40 min, heating to 40-60 ℃, stirring and reacting for 18-24 h, and reacting to obtain cellulose acetate sorbate.
The substitution degree range of the cellulose acetate is 1.75-2.45.
The polymerization degree range of the cellulose acetate is 60-200.
The organic solvent is DMAc or acetone.
The concentration of the cellulose acetate in the organic solvent is 5-30 wt%.
The molar ratio of hydroxide ions of the cellulose acetate to the acid-binding agent is 1: 1-3;
the acid-binding agent is triethylamine, pyridine or K2CO3One kind of (1).
The molar ratio of hydroxide ions to sorbic acid chloride of the cellulose acetate is 1: 1-6, and can be further preferably 1: 1.5-6.
The invention also provides application of the cellulose acetate sorbate in the fields of separation membranes used for seawater desalination and sewage treatment, medical and health products such as baby diapers, medical surgical gowns, surgical sheets, food packaging and the like.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the sorbic acid chloride generated by activating sorbic acid by thionyl chloride has higher reaction activity than that of raw sorbic acid, is more favorable for reaction with CA, and improves the grafting rate.
2. The cellulose acetate with different substitution degrees can be grafted with sorbic acid with different amounts, so that the substitution degree range of the product is expanded, and the research on the antibacterial property and the relationship between the antibacterial property and the substitution degree of each product is facilitated to find out the product with the optimal antibacterial property. According to the invention, the cellulose acetate with the substitution degree range of 1.75-2.45 is adopted, and the obtained cellulose acetate sorbate has good antibacterial property.
3. The acid-binding agent adopted by the invention is triethylamine, pyridine or K2CO3The reaction can be performed in a forward direction by using the compound (A) which can react with HCl generated in the reaction process, so that the yield is improved, and the compound (A) is easy to remove.
4. According to the invention, ethanol and deionized water are adopted to wash the product, so that residual solvent, unreacted reagent, impurities and the like in the product can be removed, and a pure product, namely the cellulose acetate sorbate, is obtained, and the antibacterial property can be better exerted.
5. The preparation method disclosed by the invention is mild in reaction conditions and simple in reaction process, and the product prepared by the method has an excellent antibacterial effect.
6. The cellulose acetate sorbate obtained by the invention has good and stable antibacterial property, can be used for preparing separation membranes used for seawater desalination and sewage treatment, and can also be used in the fields of medical and health supplies such as diapers, medical surgical gowns and surgical bed sheets, food packaging and the like.
Drawings
FIG. 1 is a drawing showing the production of sorbic acid chloride in example 1 of the present invention1H NMR spectrum.
FIG. 2 shows cellulose acetate sorbate obtained in example 1 of the present invention1H NMR spectrum.
Detailed Description
The invention provides a preparation method and application of cellulose acetate sorbate.
< cellulose acetate sorbate >
A cellulose acetate sorbate, the cellulose acetate sorbate having the structural unit:
wherein the value range of n is 60-200;
r of each structural unit is H or
When R' is
The degree of substitution of the cellulose acetate sorbate is 0.15 to 1.23.
< preparation of cellulose acetate sorbate >
The preparation method of the cellulose acetate sorbate comprises the following steps:
(1) reacting sorbic acid with an acyl chlorination reagent to prepare sorbic acid chloride;
(2) and carrying out acyl chloride esterification reaction on the cellulose acetate and the sorbic acid chloride to prepare the cellulose acetate sorbate.
(3) And washing the cellulose acetate sorbate with deionized water to remove unreacted sorbic acid chloride, washing with absolute ethyl alcohol to remove impurities, and finally washing the product with deionized water to be neutral to obtain the cellulose acetate sorbate.
The preparation method of the sorbic acid chloride in the step (1) comprises the following steps: and (2) placing sorbic acid in an acyl chlorination reagent, stirring and reacting for 2-3 hours at 60-80 ℃ under the action of a catalyst, and carrying out reduced pressure distillation after the reaction is finished to obtain the sorbic acid chloride.
The acyl chlorination reagent is thionyl chloride or PCl5Or oxalyl chloride, preferably thionyl chloride.
The molar ratio of sorbic acid to acyl chloride reagent in the step (1) is 1: 2-7, and is preferably 1: 4;
the catalyst in the step (1) can be one of DMF and pyridine.
The step (2) of acyl chloride esterification reaction between cellulose acetate and sorbic acid chloride comprises the following steps: dissolving the cellulose acetate in an organic solvent, adding an acid-binding agent, then adding the sorbic acid chloride in an ice-water bath, reacting for 20-40 min, heating to 40-60 ℃, stirring and reacting for 18-24 h, and reacting to obtain cellulose acetate sorbate.
The substitution degree range of the cellulose acetate in the step (2) can be 1.75-2.45.
The polymerization degree of the cellulose acetate in the step (2) can be within the range of 60-200.
The organic solvent in the step (2) can be DMAc or acetone.
The concentration of the cellulose acetate in the organic solvent in the step (2) is 5-30 wt%.
In the step (2), the molar ratio of hydroxide ions of the cellulose acetate to the acid-binding agent is 1: 1-3.
The acid-binding agent adopts triethylamine, pyridine or K2CO3Is possible.
The molar ratio of hydroxide ions of the cellulose acetate to the sorbic acid chloride in the step (2) is 1: 1-6, preferably 1: 1.5-6.
The invention will be further described with reference to examples of embodiments shown in the drawings.
In the bacteriostasis test of the cellulose acetate sorbate obtained in the embodiment of the invention, the experimental group is the cellulose acetate sorbate obtained in each embodiment, the control group is the pure cellulose acetate without sorbic acid chemical grafting in the embodiment,
the bacteriostatic test is carried out at 25 deg.C, the oscillation frequency is 120rpm, the oscillation time is 4h, the experiment is repeated for 3 times to obtain an average value,
the bacteriostatic rate is [ (average colony count before sample oscillation-average colony count after sample oscillation)/colony count before sample oscillation ] × 100%
Example 1
(1) 40g of sorbic acid are added to 100ml of SOCl2Meso (sorbic acid and SOCl)2The molar ratio is 1:3.9), 2 drops of DMF is added dropwise as a catalyst, the mixture is stirred and reacted for 2 hours at the temperature of 60 ℃, reduced pressure distillation is carried out after the reaction is finished, and a light yellow oily liquid is evaporated out, namely, sorbic acid chloride;
shown in figure 1, by NMR1HNMR), the sorbic acid chloride1H NMR (DMSO, ppm) is 5.5-7.7;
(2) putting 40ml of DMAc into a four-neck flask, adding 5g of CA with the substitution degree of 2.45, the polymerization degree n of 143 and the number average molecular weight of 37878 under mechanical stirring at 40 ℃, dropwise adding 1.91g of triethylamine as an acid-binding agent after the CA is completely dissolved, slowly dropwise adding 3.7g of the sorbic acid chloride obtained in the step (1) under an ice water bath, transferring the whole reaction system into an oil bath at 40 ℃ after 20min, stirring and reacting for 18h, washing the obtained product with deionized water for three times after the reaction is finished, removing unreacted sorbic acid chloride, washing with absolute ethyl alcohol for several times, removing impurities, and finally, washing with deionized water until the product is neutral to obtain the cellulose acetate sorbate (namely the antibacterial cellulose acetate).
The cellulose acetate sorbate obtained in this example has the formula:
Shown in figure 2, by NMR spectrum (1HNMR) determination of the resulting cellulose acetate sorbate1H NMR (DMSO, ppm) was: 3.5-5.7 (H-1-H-6), 6.5-7.8 (H-7-H-10),1the appearance of a characteristic sorbic acid chloride peak in the H NMR spectrum indicates successful grafting to cellulose acetate.
By using1The Degree of Substitution (DS) of the cellulose acetate sorbate obtained in this example was 0.15 by H NMR, and the DS was calculated by:
ISAis composed of1Integral areas (H-7 to H-10) of characteristic peaks of sorbic acid chloride measured by an H NMR spectrum;
IAGUis composed of1H NMR spectrum of the integrated area of the peak of the characteristic peak on the cellulose acetate skeleton (H-1 to H-6).
The antibacterial properties of the cellulose acetate sorbate (antibacterial cellulose acetate) obtained in this example are shown in table 1.
TABLE 1
Example 2
(1) 40g of sorbic acid are added to 120ml of SOCl2(sorbic acid with SOCl)2The molar ratio is 1:4.6), 3 drops of DMF is dripped as a catalyst, the mixture is stirred and reacted for 3 hours at the temperature of 60 ℃, reduced pressure distillation is carried out after the reaction is finished, and a light yellow oily liquid is evaporated out, and the substance is sorbic acid chloride;
hydrogen spectrum by nuclear magnetic resonance (1HNMR), the sorbic acid chloride1H NMR(DMSO,ppm):5.7～7.9；
(2) Putting 40ml of DMAc into a four-neck flask, adding 5g of CA with the substitution degree of 2.01, the polymerization degree of 114 and the number average molecular weight of 27982 under mechanical stirring at 40 ℃, dropwise adding 2.05g of triethylamine as an acid-binding agent after the CA is completely dissolved, slowly dropwise adding 5.2g of the sorbic acid chloride obtained in the step (1) under an ice water bath, transferring the whole reaction system into an oil bath at 40 ℃ after 30min, stirring and reacting for 18h, washing the obtained product with deionized water for three times after the reaction is finished, removing unreacted sorbic acid chloride, washing the product with absolute ethyl alcohol for several times, removing impurities, washing the product with deionized water to be neutral, and obtaining the product, namely the cellulose acetate sorbate (namely the antibacterial cellulose acetate).
The cellulose acetate sorbate obtained in this example has the formula:
Hydrogen spectrum by nuclear magnetic resonance (1HNMR) determination of the resulting cellulose acetate sorbate1H NMR (DMSO, ppm) was: 3.5-5.3 (H-1-H-6), 6.4-7.8 (H-7-H-10),1the appearance of characteristic peaks in H NMR for sorbate indicates successful grafting to cellulose acetate.
By using1The Degree of Substitution (DS) of the cellulose acetate sorbate obtained in this example was 0.48 by HNMR (calculation method same as example 1).
The antibacterial properties of the cellulose acetate sorbate (antibacterial cellulose acetate) obtained in this example are shown in Table 2.
TABLE 2
Example 3
(1) 40g of sorbic acid are added to 140ml of SOCl2(sorbic acid with SOCl)2The molar ratio is 1:5.4), 4 drops of DMF is dripped as a catalyst, the mixture is stirred and reacted for 2 hours at the temperature of 70 ℃, reduced pressure distillation is carried out after the reaction is finished, and a light yellow oily liquid is evaporated out, and the substance is sorbic acid chloride;
hydrogen spectrum by nuclear magnetic resonance (1HNMR), the sorbic acid chloride1H NMR(DMSO,ppm):5.3～7.6；
(2) Putting 40ml of DMAc into a four-neck flask, adding 5g of CA with the substitution degree of 2.01, the polymerization degree of 114 and the number average molecular weight of 27982 under mechanical stirring at 50 ℃, dropwise adding 1.60g of acid-binding agent pyridine after the CA is completely dissolved, then slowly dropwise adding 10.5g of the sorbic acid chloride obtained in the step (1) under an ice water bath, transferring the whole system into an oil bath at 50 ℃ after 40min, stirring and reacting for 20h, washing the obtained product with deionized water for three times after the reaction is finished, removing unreacted sorbic acid chloride, washing the product with absolute ethyl alcohol for several times, removing impurities, washing the product with deionized water to be neutral, and obtaining the product, namely the cellulose acetate sorbate (namely the antibacterial cellulose acetate).
The cellulose acetate sorbate obtained in this example has the formula:
Hydrogen spectrum by nuclear magnetic resonance (1HNMR) determination of the resulting cellulose acetate sorbate1H NMR (DMSO, ppm) was: 3.5-5.5 (H-1-H-6), 6.3-7.7 (H-7-H-10),1the appearance of characteristic peaks of sorbic acid chloride in H NMR indicates successful grafting to acetate fibersOn the plain.
By using1The Degree of Substitution (DS) of the cellulose acetate sorbate obtained in this example was 0.92 by HNMR, and the DS was calculated in the same manner as in example 1.
The antibacterial properties of the cellulose acetate sorbate (antibacterial cellulose acetate) obtained in this example are shown in Table 3.
TABLE 3
Example 4
(1) 50g sorbic acid was added to 120ml PCl5(sorbic acid with PCl5The molar ratio is 1:4.6), 4 drops of pyridine is dripped as a catalyst, the mixture is stirred and reacted for 3 hours at the temperature of 70 ℃, reduced pressure distillation is carried out after the reaction is finished, and a light yellow oily liquid is evaporated out, namely, sorbic acid chloride;
hydrogen spectrum by nuclear magnetic resonance (1HNMR), the sorbic acid chloride1H NMR(DMSO,ppm):5.4～7.7；
(2) Putting 40ml of acetone into a four-neck flask, adding 5g of CA with the substitution degree of 1.75, the polymerization degree of 80 and the number average molecular weight of 18844 under the mechanical stirring at 50 ℃, dropwise adding 2.7g of triethylamine as an acid-binding agent after the CA is completely dissolved, then slowly dropwise adding 5.2g of the sorbic acid chloride obtained in the step (1) under an ice water bath, transferring the whole system into an oil bath at 50 ℃ after 20min, stirring and reacting for 20h, washing the product with deionized water for three times after the reaction is finished, removing the unreacted sorbic acid chloride, washing the product with absolute ethyl alcohol for several times, removing impurities, finally washing the product with the deionized water to be neutral, and obtaining the antibacterial cellulose sorbate (namely cellulose acetate).
The cellulose acetate sorbate obtained in this example has the formula:
Hydrogen spectrum by nuclear magnetic resonance (1HNMR) determination of the resulting cellulose acetate sorbate1H NMR (DMSO, ppm) was: 3.4-5.6 (H-1-H-6), 6.4-7.9 (H-7-H-10),1the appearance of characteristic peaks in H NMR for sorbate indicates successful grafting to cellulose acetate.
By using1The Degree of Substitution (DS) of the cellulose acetate sorbate obtained in this example was 0.75 by HNMR (calculation method same as example 1).
The antibacterial properties of the cellulose acetate sorbate (antibacterial cellulose acetate) obtained in this example are shown in Table 4.
TABLE 4
Example 5
(1) 50g of sorbic acid are added to 140ml of SOCl2(sorbic acid with SOCl)2The molar ratio is 1:4.3), 3 drops of pyridine is dripped as a catalyst, the mixture is stirred and reacted for 2 hours at the temperature of 80 ℃, reduced pressure distillation is carried out after the reaction is finished, and a light yellow oily liquid is evaporated out, namely, sorbic acid chloride;
hydrogen spectrum by nuclear magnetic resonance (1HNMR), the sorbic acid chloride1H NMR(DMSO,ppm):5.5～7.8；
(2) Putting 40ml of acetone into a four-neck flask, adding 5g of CA with the substitution degree of 1.75, the polymerization degree of 80 and the number average molecular weight of 18844 under mechanical stirring at 60 ℃, dropwise adding 3.1g of acid-binding agent pyridine after the CA is completely dissolved, then slowly dropwise adding 13.85g of the sorbic acid chloride obtained in the step (1) under an ice water bath, moving the whole system into an oil bath at 60 ℃ after 30min, stirring and reacting for 24h, washing the product with deionized water for three times after the reaction is finished, removing unreacted sorbic acid chloride, washing the product with absolute ethyl alcohol for several times, removing impurities, finally washing the product with deionized water to be neutral, and obtaining the product, namely the cellulose acetate sorbate (namely the antibacterial cellulose acetate).
The cellulose acetate sorbate obtained in this example has the formula:
Hydrogen spectrum by nuclear magnetic resonance (1HNMR) determination of the resulting cellulose acetate sorbate1H NMR (DMSO, ppm) was: 3.3-5.5 (H-1-H-6), 6.5-8.0 (H-7-H-10),1the appearance of characteristic peaks in H NMR for sorbate indicates successful grafting to cellulose acetate.
By using1HNMR measured the Degree of Substitution (DS) of the cellulose acetate sorbate obtained in this example to be 1.12, the DS was calculated in the same manner as in example 1.
The antibacterial properties of the cellulose acetate sorbate (antibacterial cellulose acetate) obtained in this example are shown in Table 5.
TABLE 5
Example 6
(1) Adding 50g sorbic acid into 160ml oxalyl chloride (the molar ratio of the sorbic acid to the oxalyl chloride is 1:4.2), dropwise adding 4 drops of pyridine as a catalyst, stirring and reacting at 80 ℃ for 3 hours, and carrying out reduced pressure distillation after the reaction is finished until light yellow oily liquid is evaporated out, wherein the substance is the sorbic acid chloride;
hydrogen spectrum by nuclear magnetic resonance (1HNMR), the sorbic acid chloride1H NMR(DMSO,ppm):5.4～7.8；
(2) Putting 40ml of acetone into a four-neck flask, adding 5g of CA with the substitution degree of 1.75, the polymerization degree of 80 and the number average molecular weight of 18844 under the mechanical stirring at 60 ℃, and dropwise adding an acid-binding agent K after the CA is completely dissolved2CO35.5g, then slowly dripping 20.80g of the sorbic acid chloride obtained in the step (1) in an ice water bath, transferring the whole system to an oil bath at 60 ℃ after 40min, stirring and reacting for 24h, washing a product for three times by deionized water after the reaction is finished, removing unreacted sorbic acid chloride,washing with anhydrous ethanol for several times, removing impurities, and washing with deionized water to neutral to obtain cellulose acetate sorbate.
The cellulose acetate sorbate obtained in this example has the formula:
Hydrogen spectrum by nuclear magnetic resonance (1HNMR) determination of the resulting cellulose acetate sorbate1H NMR (DMSO, ppm) was: 3.4-5.6 (H-1-H-6), 6.3-8.0 (H-7-H-10),1the appearance of characteristic peaks in H NMR for sorbate indicates successful grafting to cellulose acetate.
By using1The Degree of Substitution (DS) of the cellulose acetate sorbate obtained in this example was 1.20 by HNMR (the calculation was performed in the same manner as in example 1).
The antibacterial properties of the cellulose acetate sorbate (antibacterial cellulose acetate) obtained in this example are shown in Table 6.
TABLE 6
According to the bacteriostasis rate of the cellulose acetate sorbate (antibacterial cellulose acetate) obtained in each example, the bacteriostasis rate of the product tends to increase and then decrease with the increase of the degree of substitution, as sorbic acid is a hydrophobic substance, more and more hydrophilic hydroxyl groups on a sugar ring are esterified by sorbic acid with the increase of the degree of substitution, so that the hydrophobicity of the derivative is increased, and the cellulose acetate sorbate can freely enter cells through cell membranes, disturb the structure of the cells and inhibit a microbial enzyme system. However, when the degree of substitution reaches a certain degree, the steric hindrance effect by the high degree of substitution lowers the degree of freedom of the steric movement of the reaction active center, resulting in a decrease in the effective collision of cellulose acetate sorbate with the functional domain of the microorganism, thereby inhibiting the antibacterial activity.
The embodiments described above are intended to facilitate one of ordinary skill in the art in understanding and using the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (13)
1. A cellulose acetate sorbate characterized by: the cellulose acetate sorbate has the structural units as follows:
wherein the value range of n is 60-200;
r of each structural unit is H or
R' is
The degree of substitution of the cellulose acetate sorbate is 0.15 to 1.23.
2. The cellulose acetate sorbate of claim 1 further comprising: the value range of n is 100-150.
3. A method for producing cellulose acetate sorbate according to claim 1 or 2, characterized in that: the method comprises the following steps:
(1) reacting sorbic acid with an acyl chlorination reagent to prepare sorbic acid chloride;
(2) and carrying out acyl chloride esterification reaction on the cellulose acetate and the sorbic acid chloride to prepare the cellulose acetate sorbate.
4. The method of claim 3, wherein: the acyl chlorination reagent is thionyl chloride or PCl5Or oxalyl chloride.
5. The method of claim 3, wherein: the molar ratio of the sorbic acid to the acyl chlorination reagent is 1: 2-7.
6. The method of claim 3, wherein: the molar ratio of sorbic acid to acyl chloride reagent is 1:4.
7. The method of claim 3, wherein: the step (2) comprises the following steps: dissolving the cellulose acetate in an organic solvent, adding an acid-binding agent, then adding the sorbic acid chloride in an ice-water bath, and reacting to obtain the cellulose acetate sorbate.
8. The method of claim 7, wherein: the organic solvent is dimethylacetamide or acetone; and/or the presence of a gas in the gas,
the acid-binding agent is triethylamine, pyridine or K2CO3One of (1); and/or the concentration of the cellulose acetate in the organic solvent is 5-30 wt%; and/or the presence of a gas in the gas,
the molar ratio of hydroxide ions of the cellulose acetate to the acid-binding agent is 1: 1-3.
9. The production method according to claim 3 or 7, characterized in that: the molar ratio of hydroxide ions of the cellulose acetate to the sorbic acid chloride is 1: 1-6.
10. The production method according to claim 3 or 7, characterized in that: the molar ratio of hydroxide ions of the cellulose acetate to the sorbic acid chloride is 1: 1.5-6.
11. The production method according to claim 3 or 7, characterized in that: the substitution degree range of the cellulose acetate is 1.75-2.45; and/or the presence of a gas in the gas,
the degree of substitution of the cellulose acetate sorbate is 0.15 to 1.23; and/or the presence of a gas in the gas,
the polymerization degree range of the cellulose acetate is 60-200.
12. The method of claim 7, wherein: the method comprises the following steps: (3) and washing the cellulose acetate sorbate with deionized water, absolute ethyl alcohol and deionized water in sequence until the pH value is neutral.
13. Use of the cellulose acetate sorbate of claim 1 or 2 in separation membranes for desalination of sea water or treatment of sewage, medical and hygienic products, or food packaging materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710790730.XA CN107417795B (en) | 2017-09-05 | 2017-09-05 | Cellulose acetate sorbate and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710790730.XA CN107417795B (en) | 2017-09-05 | 2017-09-05 | Cellulose acetate sorbate and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107417795A CN107417795A (en) | 2017-12-01 |
| CN107417795B true CN107417795B (en) | 2020-06-05 |
Family
ID=60431845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710790730.XA Active CN107417795B (en) | 2017-09-05 | 2017-09-05 | Cellulose acetate sorbate and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107417795B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104645943A (en) * | 2014-12-26 | 2015-05-27 | 张红梅 | Method for preparing renewable anti-bacteria fiber for adsorbing heavy metal motes |
| CN105461814A (en) * | 2015-12-14 | 2016-04-06 | 上海交通大学医学院附属仁济医院 | Cellulose acetate derivative and preparation method and application thereof |
| CN107177004A (en) * | 2017-05-27 | 2017-09-19 | 天津工业大学 | Non-dissolving type antibiotic cellulose acetate and its production and use |
-
2017
- 2017-09-05 CN CN201710790730.XA patent/CN107417795B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104645943A (en) * | 2014-12-26 | 2015-05-27 | 张红梅 | Method for preparing renewable anti-bacteria fiber for adsorbing heavy metal motes |
| CN105461814A (en) * | 2015-12-14 | 2016-04-06 | 上海交通大学医学院附属仁济医院 | Cellulose acetate derivative and preparation method and application thereof |
| CN107177004A (en) * | 2017-05-27 | 2017-09-19 | 天津工业大学 | Non-dissolving type antibiotic cellulose acetate and its production and use |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107417795A (en) | 2017-12-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Carson et al. | Synthesis and characterization of chitosan–carbon nanotube composites | |
| JPS624702A (en) | Production of water-soluble acrylated chitosan | |
| JP2016537464A (en) | Composition for producing polysaccharide fibers | |
| CN111620966A (en) | Chitosan oligosaccharide-N-linalool copolymer and preparation method and application thereof | |
| CN102276663A (en) | Preparation method of glucosamine sulfate | |
| CN111732674A (en) | Chitosan oligosaccharide-M-cinnamyl alcohol derivative, preparation method and application thereof | |
| NO323216B1 (en) | Process for preparing ioversol | |
| CN113457564B (en) | Esterified SMA (styrene maleic anhydride) modified quaternary ammonium/phosphonium salt high-molecular antibacterial surfactant and application thereof | |
| CN107417795B (en) | Cellulose acetate sorbate and preparation method and application thereof | |
| CN114832143A (en) | Preparation method of chitosan grafted urushiol/graphene oxide composite material | |
| CN101343242A (en) | Acryloyl di-quaternary ammonium salt and preparation thereof | |
| CN107021989A (en) | A kind of preparation method for ozonizing Tea Saponin | |
| CN109134767B (en) | Antibacterial hydrogel material and preparation method thereof | |
| CN110452115B (en) | Synthesis method of poly 3-hydroxybutyrate oligomer, product obtained by synthesis method and application of oligomer | |
| CN103626979A (en) | Crosslinked liquid-state polycaprolactone and preparation method and application thereof | |
| CN111500010A (en) | Degradable polypropylene antibacterial mask material and preparation method thereof | |
| CN100376550C (en) | Quaternary bis-ammonium salt diamine fluoride and preparation method thereof | |
| CN114618332A (en) | Antibacterial polysulfone material and preparation method and application thereof | |
| CN103694377A (en) | Amphiphilic C-6-(4-(methyl amino)-1,2,3-triazole)deoxidized inulin derivatives and preparation and application thereof | |
| Ku et al. | Effect of oxidized alginate on its electrospinnability | |
| CN113445315A (en) | Preparation method of diphenolic acid antibacterial cotton fabric | |
| CN102834416A (en) | Substituted cyclodextrin derivatives useful as intermediates for producing biologically active materials | |
| CN101240061B (en) | Method for synthesizing polyracemic lactic acid for carrying medicament | |
| US10851214B2 (en) | Polymer gels, method of preparation and uses thereof | |
| JP6750778B2 (en) | Paramylon derivative and method for producing the same, and nanofiber and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |