CN114853914B - Thermoplastic cellulose ester derivative and preparation method thereof - Google Patents
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Abstract
The invention belongs to the field of high molecular compounds, and particularly relates to a cellulose ester derivative and a preparation method thereof. The invention provides a method for preparing a thermoplastic cellulose ester derivative, which comprises the following steps: performing one-step esterification reaction on cellulose, a co-reactant trifluoroacetic anhydride and an esterifying agent, and then purifying to obtain the thermoplastic cellulose ester derivative. The preparation method of the cellulose ester derivative provided by the invention is simple and easy to implement, an organic solvent is not used, the prepared cellulose ester has high degree of substitution, the cellulose ester with high degree of substitution can show certain thermoplasticity, and the cellulose ester has lower glass transition temperature, and can be prepared into a transparent film by a thermoforming method.
Description
Technical Field
The invention belongs to the field of high molecular compounds, and particularly relates to a cellulose ester derivative and a preparation method thereof.
Background
The modern society faces two problems of environmental pollution and resource shortage, on one hand, the waste plastic products seriously pollute soil and ocean resources, and on the other hand, the shortage of petroleum resources hinders the economic development. Therefore, the search for renewable resources to replace petroleum resources is one of the most important issues at present.
Cellulose (Cellulose) is a natural polymer material with the most abundant yield on the earth, is low in price and has excellent performances of regeneration, biodegradation and the like. The cellulose is formed by connecting D-glucose structural units (AGU) through beta-1,4-bonds, and each repeating unit is provided with three hydroxyl groups (-OH), so that cellulose molecular chains can form a large number of strong intermolecular and intramolecular hydrogen bond network structures, and due to the existence of the hydrogen bond network and the regular chain structure of the cellulose, the cellulose has extremely high crystallinity, and the cellulose cannot be dissolved in common solvents and cannot be melted, so that the cellulose is difficult to process in a traditional mode.
The current research on melt processing of cellulose is mainly divided into physical and chemical methods, and recent research is mainly focused on chemical modification methods because physical methods require high energy and are not ideal.
The chemical modification is to substitute hydroxyl groups on the cellulose into other groups so as to destroy the hydrogen bonding network and the crystal structure of the cellulose, such as Cellulose Acetate (CA), cellulose Nitrate (NC) and hydroxyethyl cellulose (HEC) which have already been prepared in industrial production systems. Although cellulose esters formed by small-group substitution can be dissolved in common solvents, they cannot be processed by conventional methods due to a too narrow processing window. And the hydroxyl on the cellulose is replaced by a larger and longer side chain, so that the content of the hydroxyl can be reduced, the molecular chain of the cellulose can be isolated, the hydrogen bond can be reduced, and the crystal structure can be damaged. In addition, the side chain can also endow the cellulose with other performances except meltability, thereby enlarging the application range of the cellulose and improving the utilization rate. However, limited by the low reactivity of cellulose, finding a general method for efficiently preparing cellulose ester derivatives in a green color has become a major and difficult point of research on the application problems of cellulose nowadays.
Cellulose was dissolved in N, N' -dimethylacetamide/lithium chloride (DMAc/LiCl) by Kevin j. Edgar et al as early as 1998, and cellulose fatty acid esters of various degrees of substitution and side chain lengths were prepared by reacting fatty acid chlorides with cellulose under homogeneous conditions using 4-pyrrolidinopyridine (PP) and Dicyclohexyldiimide (DCC) as catalysts. Research shows that the prepared Cellulose fatty acid ester can be dissolved in nonpolar solvents such as chloroform, and the long-chain side group has plasticizing effect on Cellulose (Kevin J. Edgar, et al. ACS Symposium series Vol.688: cellulose Derivatives,1998,38-60.). In addition to the DMAc/LiCl described above, ionic liquids (Raj K.Singh, et al, journal of Industrial and Engineering Chemistry,2015, 24.
Tuomas Kulomaa et al placed the pulp crumb in pyridine at 100 ℃ and soaked for 1h, then added the suspension into toluene solution containing unsaturated fatty acid chloride, stirred and reacted for 2-3 days at 90-100 ℃ in homogeneous solution system, and finally purified to obtain cellulose unsaturated fatty acid ester. The results show that the unsaturated fatty acid-modified cellulose derivative exhibits stronger thermal stability and a glass transition temperature (Tg) in the range of 104 to 119 ℃ than cellulose. In addition, the cellulose ester derivative also shows excellent hydrophobicity and mechanical properties, which provides possibility for practical application of the cellulose unsaturated fatty acid ester derivative (T.Kulomaa, J, et al.RSC Advances,5 (2015) 80702-80708).
The above examples fully illustrate that bulky side-chain modified cellulose ester derivatives are an effective way to achieve melt processing of cellulose. However, the homogeneous method requires a large amount of solvent, which not only increases the cost, but also causes some environmental damage, and thus a method for preparing cellulose ester in a heterogeneous system needs to be explored.
Huang Zujiang et al (chinese patent CN 103435702B) reported a method for preparing cellulose higher fatty acid esters in a heterogeneous system. The mixture of lauric acid and caprylic acid is used as an esterifying agent, trichloroacetic anhydride is used as a co-reactant, and a relatively ideal cellulose ester product can be prepared by virtue of high-efficiency mixing and high mechanical energy of ball milling. The method can reduce the usage amount of organic solvent in the esterification reaction process and shorten the reaction time; however, the pretreatment of the cellulose before the reaction is required, and the pretreatment time even exceeds the time required for the subsequent esterification reaction step, which seriously affects the efficiency of the reaction.
In addition, with trichloroacetic anhydride as the co-reactant, most of the hydroxyl groups on the cellulose chain are replaced by short-chain acetyl groups, and a large amount of long-chain fatty acids cannot be grafted onto the cellulose backbone. Furthermore, there is a document (Huang Lang, et al. ACS Sustainable Chemistry & Engineering,2019,19:1, the highest degree of substitution was obtained, but the problem of imbalance in the long and short chain reactions still existed, in which the degree of substitution of acetyl was 1.67 and the degree of substitution of the long-chain oleic acid side chain was only 0.041. This method is not ideal for obtaining highly substituted cellulose higher fatty acid esters, and further, melt-processable cellulose esters cannot be obtained.
Therefore, the existing research using ball-milling modified cellulose cannot really realize the one-step method for preparing the cellulose derivative with high substitution degree; therefore, there is a need to find a method for more efficiently producing thermoplastic cellulose ester derivatives having a high degree of substitution.
Disclosure of Invention
Aiming at the defects of large amount of solvents, low reaction degree, long reaction time, complex experimental process and the like in the existing research of cellulose derivatization, the invention provides a preparation method of cellulose ester derivatives, which is simple and easy to implement, does not use organic solvents, has high substitution degree of the prepared cellulose ester, can show certain thermoplasticity, has lower glass transition temperature (Tg), and can be prepared into a transparent film by a thermoforming method; the invention provides theoretical and practical basis for preparing cellulose ester derivatives and realizing cellulose melt processing.
The technical scheme of the invention is as follows:
the first technical problem to be solved by the invention is to provide a method for preparing a thermoplastic cellulose ester derivative, which comprises the following steps: and carrying out one-step esterification reaction on cellulose, a co-reactant trifluoroacetic anhydride and an esterifying agent, and then purifying to obtain the thermoplastic cellulose ester derivative.
Further, the molar ratio of the cellulose to the esterifying agent to the trifluoroacetic anhydride is as follows: 1:1 to 12:1 to 6.
Further, the esterifying agent is a carboxyl-containing esterifying agent selected from: at least one of Stearic Acid (Stearic Acid, C18), palmitic Acid (Palmitic Acid, C16), myristic Acid (Myristic Acid, C14), lauric Acid (Lauric Acid, C12), capric Acid (Capric Acid, C10), caprylic Acid (octanic Acid, C8), 2-butylcaprylic Acid (2-butylcaprylanoic Acid, BA), 4-n-pentylbenzoic Acid (4-pentaylben Acid, PA), formic Acid (Formic Acid), acetic Acid (Acetic Acid), oxalic Acid (Oxalic Acid), malonic Acid (propaedoic Acid), benzoic Acid (Benzoic Acid), succinic Acid (Amber Acid), butenedioic Acid (butenedioic Acid), phthalic Acid (Phthalic Acid), or alpha-Naphthylacetic Acid (1-naphylacetic Acid).
Further, the cellulose is selected from: at least one of sugarcane cellulose, cassava cellulose, rice straw cellulose, corn straw cellulose, wood cellulose, cotton cellulose, flax cellulose, ramie cellulose, bacterial cellulose, microcrystalline cellulose, nano cellulose or regenerated cellulose.
Further, the preparation method comprises the following steps: firstly, carrying out esterification reaction on cellulose, an esterifying agent and trifluoroacetic anhydride by ball milling; then dissolving, precipitating, washing and filtering the obtained product to obtain the thermoplastic cellulose ester derivative.
Further, in the ball milling process, the ball milling speed is 100-1000 rpm, preferably 300-1000 rpm; the ball milling time is 0.1 to 12 hours, preferably 3 to 12 hours.
Further, the method for obtaining the thermoplastic cellulose ester derivatives by precipitating, washing and filtering the obtained product comprises the following steps: dissolving the product in a solvent, adding an anti-solvent for full precipitation, repeatedly washing for at least 3 times, performing suction filtration to obtain a crude product, and performing Soxhlet extraction for 1-72 hours to obtain different cellulose ester derivatives.
Further, in the method for obtaining the thermoplastic cellulose ester derivatives by precipitating, washing and filtering the obtained product, the solvent is selected from the group consisting of: at least one of dichloromethane, chloroform, acetone, DMF, DMSO, 1,4-dioxane, tetrahydrofuran, benzene, toluene or hexane.
Further, in the method for obtaining the thermoplastic cellulose esters and derivatives thereof by precipitating, washing and filtering the obtained product, the anti-solvent is selected from the group consisting of: at least one of ethanol, methanol, water, formamide, acetonitrile, or propanol.
Further, the solvent for Soxhlet extraction is at least one of ethanol, methanol, water, formamide, acetonitrile or propanol.
The second technical problem to be solved by the invention is to provide a thermoplastic cellulose ester derivative prepared by the method.
Further, the degree of substitution of the long chain of the thermoplastic cellulose ester derivative is 1.5 to 3. There are three hydroxyl groups on each repeat unit of cellulose, and the degree of substitution refers to the average number of hydroxyl groups on all repeat units that are chemically reacted.
Further, the thermoplastic cellulose ester derivatives have melt processability.
Further, the melting temperature of the thermoplastic cellulose ester derivative is 50-170 ℃.
The third technical problem to be solved by the present invention is to provide a method for increasing the degree of substitution of cellulose ester derivatives (cellulose higher fatty acid esters), the method comprising: trifluoroacetic anhydride is selected as a coreactant, and is subjected to esterification reaction with cellulose and an esterifying agent; then purifying to obtain the cellulose ester derivatives.
Further, the molar ratio of the cellulose to the esterifying agent to the trifluoroacetic anhydride is as follows: 1:1 to 12:1 to 6.
Further, the cellulose is selected from: at least one of sugarcane cellulose, cassava cellulose, rice straw cellulose, corn straw cellulose, wood cellulose, cotton cellulose, flax cellulose, ramie cellulose, bacterial cellulose, microcrystalline cellulose, nanocellulose or regenerated cellulose.
Further, the esterifying agent is a carboxyl-containing esterifying agent selected from: at least one of Stearic Acid (Stearic Acid, C18), palmitic Acid (Palmitic Acid, C16), myristic Acid (Myristic Acid, C14), lauric Acid (Lauric Acid, C12), capric Acid (Capric Acid, C10), caprylic Acid (octanic Acid, C8), 2-butylcaprylic Acid (2-butylcaprylic Acid, BA), 4-n-pentylbenzoic Acid (4-Pentylben Acid, PA), formic Acid (Formic Acid), acetic Acid (Acetic Acid), oxalic Acid (Oxalic Acid), malonic Acid (propanodic Acid), benzoic Acid (Benzoic Acid), succinic Acid (Amber Acid), butenedioic Acid (butenedioic Acid), phthalic Acid (Phthalic Acid), or alpha-Naphthylacetic Acid (1-napthylacetic Acid).
Further, the method for improving the degree of substitution of the cellulose ester derivatives comprises the following steps: the cellulose, esterifying agent and trifluoroacetic anhydride are processed by esterification reaction through ball milling, and then the obtained product is deposited, washed and filtered to prepare the thermoplastic cellulose ester derivative.
Compared with the prior art, the invention has the following characteristics and beneficial effects:
1) The reaction system of the invention is a one-step reaction, does not need to pretreat cellulose or an esterification agent before the esterification reaction, and has simple and convenient reaction process.
2) The reaction process of the present invention does not require additional control of the temperature and pressure of the reaction system.
3) The esterification reaction process of the invention completely does not need to use expensive aprotic solvents or other cellulose solvents, and has low cost and environmental protection.
4) The invention can be used for preparing cellulose ester with high substitution degree and different types of side chains.
5) The thermoplastic cellulose ester of the invention has low melting temperature, good flexibility and high transparency.
Description of the drawings:
FIG. 1 is a flow chart of a process for preparing a cellulose higher fatty acid ester according to the present invention.
FIG. 2 is an infrared spectrum of the product obtained in examples 1 to 4 of the present invention; as can be seen from fig. 2: the cellulose is positioned at 3000-3500 cm -1 The broad peak at which-OH is represented disappears in the following four products, and newly appears at 2800-3000 cm -1 represents-CH 2 And at 1750cm -1 The peak represents-C = O, which indicates that most of hydroxyl groups on the cellulose are converted into ester groups, and aliphatic side chains are grafted on the cellulose, so that the cellulose fatty acid ester is successfully prepared.
FIG. 3 shows the results of degree of substitution of the product obtained in example 5 of the present invention; as can be seen from the figure: FIG. 3 shows the degree of substitution of products prepared by using different types of side chains at different ratios of the amounts of substances (acid/cellulose), and using the solid NMR spectrum to characterize the products, it can be seen that as the ratio of the amounts of substances gradually increases, the degree of substitution of the products also gradually increases, so we can prepare products with different degrees of substitution by changing the reaction parameters.
FIG. 4 is an optical microscope photograph of the products obtained in examples 1 to 4 of the present invention; the lower left panel represents the temperature at which the product begins to melt, and the large panel represents the temperature at which the product is completely melted; as can be seen, all the products can be completely melted at a certain temperature, and the type of side chain affects the melting temperature of the product.
FIG. 5 is a photograph of a film obtained by hot-pressing the product obtained in example 1; as can be seen from the figure: the cellulose ester prepared by the examples can be used for preparing transparent and flexible films by a simple hot-press forming method.
FIG. 6 is a graph of mechanical properties of MCC-SA product bars tested at different degrees of substitution using a universal tester: FIG. 6a shows the results of elongation at break and tensile stress, and FIG. 6b shows the results of Young's modulus and tensile strength.
FIG. 7 is a photograph showing the products obtained in comparative example 1 (left) and example 1 (right) dissolved in methylene chloride; trichloroacetic anhydride is used in the comparative example, trifluoroacetic anhydride is used in the example, and the operation of other experiments is completely the same; as can be seen, the product obtained using trichloroacetic anhydride is hardly soluble in the dichloromethane solvent; in contrast, the solution prepared from the product of trifluoroacetic anhydride was very clear, indicating that the product had a high solubility in dichloromethane; this shows that the degree of substitution is higher for the trifluoroacetic anhydride product (example 1) and lower for the trichloroacetic anhydride product (comparative example 1).
FIG. 8 is a chart of IR spectra of products obtained in comparative example 1 (MCC-TClAA-SA) and example 1 (MCC-TFAA-SA); from 2800 to 3000cm -1 Represents a methylene group and is located at 1750cm -1 Comparative example 1 is almost unchanged from the peak representing carbonyl; in contrast, example 1 shows a distinct peak indicating that trifluoroacetic anhydride is superior to trichloroacetic anhydride.
FIG. 9 is an optical micrograph of a product obtained in comparative example 1 during temperature elevation; as can be seen from the figure, trichloroacetic anhydride gives a product with no melting behavior.
Detailed Description
In the invention, trifluoroacetic anhydride is selected as a coreactant, a substance with carboxyl is selected as an esterifying agent, and the mechanism is as follows: trifluoroacetic anhydride and an esterifying agent generate asymmetric anhydride, and then the asymmetric anhydride reacts with hydroxyl on cellulose; both sides of the asymmetric anhydride may react with cellulose, but the reaction tendency (side reaction direction) on the trifluoroacetic acid side is particularly low, so that cellulose ester mostly using an esterifying agent (main reaction direction) can be produced.
The invention discovers for the first time that when trifluoroacetic anhydride is used as a co-reactant, cellulose trifluoroacetate formed with cellulose in the reaction process is extremely unstable, is easily decomposed under the action of ball milling and is then substituted by a group with larger steric hindrance; the invention utilizes the characteristics that trifluoroacetic anhydride, cellulose and carboxylic acid with different chain lengths and different configurations are used as esterifying agents to directly prepare the high-substitution cellulose ester without trifluoroacetic acid side groups by a one-step method without pretreatment. Therefore, the method can omit the pretreatment step and really realize the one-step method for efficiently preparing the cellulose derivative; and the resulting product has melt characteristics.
The present invention is further illustrated by the following examples, which are provided only for the purpose of facilitating understanding of the present invention and are not intended to limit the scope of the present invention.
To illustrate the effects of the examples, the structure of the obtained thermoplastic cellulose stearate was analyzed by infrared spectroscopy and nuclear magnetic hydrogen spectroscopy, and the melting temperature of the thermoplastic cellulose stearate was observed by an Optical Microscope (OM) equipped with a temperature-controlled hot stage. In addition, thermoplastic cellulose grafted stearate was hot-pressed into a film to observe melt characteristics, transparency and flexibility.
The cellulose used in the following examples is: microcrystalline cellulose powder (MCC, 50 μm, aladdin), available from shanghai alatin biochemical science co ltd, has an average Degree of Polymerization (DP) of MCC of 215 as measured by the viscometry according to international standards (ISO 5351.
Example 1
Adding 0.16g (1 mmol) of cellulose, 0.85g (3 mmol) of Stearic Acid (SA) and 1.26g (6 mmol) of trifluoroacetic anhydride into a planetary ball mill, reacting for 4h at the rotating speed of 450rpm to obtain a reaction product, and fully stirring and dissolving the reaction product by using dichloromethane; precipitating with ethanol repeatedly for three times, and filtering the precipitate; performing Soxhlet extraction with ethanol at 90 ℃ for 24-48 h to obtain pure cellulose stearate, and performing nuclear magnetic hydrogen spectrum characterization to obtain the long-chain substitution degree of 2.86.
Further, using the product obtained in example 1, a film having a thickness of 300. + -. 20 μm was obtained by hot pressing at 160 ℃ under 10MPa using a plate vulcanizer (BL-6170-B, takara Kogyo precision measuring instruments Co., ltd., china) for a hot pressing duration of 5min. The mechanical properties of the sample strips were further tested using a universal tester, and the results are shown in FIG. 6. As can be seen from FIG. 6 (a), the elongation at break and tensile stress of the samples of 1h to 4h both gradually increased with the increase in the degree of substitution. Probably because the cellulose stearate with high substitution degree has higher content of side chains, the existence of the side chains improves the flexibility of the cellulose on one hand and further improves the elongation at break, and the side chains on the other hand can be tangled and crystallized, so that the tensile stress is improved; FIG. 6 (b) is the Young's modulus and tensile strength of the sample, the Young's modulus gradually decreasing with increasing degree of substitution.
Example 2
0.16g (1 mmol) of cellulose, 0.60g (3 mmol) of Lauric Acid (LA) and 1.26g (6 mmol) of trifluoroacetic anhydride are added into a planetary ball mill and reacted for 4 hours at the rotating speed of 450rpm to obtain a reaction product, the reaction product is fully washed and dried to obtain pure cellulose laurate, and the long-chain substitution degree is 2.96 by using nuclear magnetic hydrogen spectrum characterization.
Example 3
0.16g (1 mmol) of cellulose, 0.60g (3 mmol) of 2-Butyloctanoic Acid (BA) and 1.26g (6 mmol) of trifluoroacetic anhydride are added into a planetary ball mill and reacted for 4 hours at the rotating speed of 450rpm to obtain a reaction product, the reaction product is fully washed and dried to obtain pure cellulose stearate, and the long-chain substitution degree is 2.57 by using nuclear magnetic hydrogen spectrum characterization.
Example 4
0.16g (1 mmol) of cellulose, 0.60g (3 mmol) of 4-n-Pentylbenzoic Acid (PA) and 1.26g (6 mmol) of trifluoroacetic anhydride are added into a planetary ball mill and reacted for 4h at the rotating speed of 450rpm to obtain a reaction product, the reaction product is fully washed and dried to obtain pure cellulose stearate, and the long-chain substitution degree is 2.68, the short-chain substitution degree is 0.22 and the total substitution degree is 2.90 by using nuclear magnetic hydrogen spectrum characterization.
Example 5
0.16g (1 mmol) of cellulose, 4-n-pentylbenzoic acid, 2-butyloctanoic acid and stearic acid with different molar ratios (cellulose: acid) of 1:1, 1:2 and 1:3 as esterifying agents and 1.26g (6 mmol) of trifluoroacetic anhydride are added into a planetary ball mill to react for 4h at the rotating speed of 450rpm to obtain a reaction product, the reaction product is fully washed and dried to obtain pure cellulose ester, and the long chain substitution degree is obtained by using nuclear magnetic spectrum characterization, and the result is shown in figure 3.
Comparative example 1
The other steps are the same as in example 1, except that 1.85g (6 mmol) of trichloroacetic anhydride is used instead of 1.26g (6 mmol) of trifluoroacetic anhydride; it was found experimentally that the resulting product was insoluble in dichloromethane and therefore the degree of substitution of the product could not be characterized.
The results of the degree of substitution, the characteristics of the product, the melting temperature, and other properties of the products obtained in examples 1 to 5 and comparative example 1 are shown in Table 1. Therefore, different carboxylic acids are used as esterification agents to carry out derivatization reaction with cellulose, so that the cellulose derivative with good thermoplasticity can be obtained, and the preparation method has universality and can be used for preparing various cellulose ester derivatives. In addition, the cellulose derivatives with different degrees of substitution can be obtained by changing the time, the rotating speed and the reactant proportion, and the method has a certain guiding function on improving the utilization rate of cellulose and preparing degradable materials.
In the invention, the substitution degree is tested and calculated as follows: the MCC-g-SA was recorded at room temperature using a nuclear magnetic resonance spectrometer (AV-400, bruker, germany) 1 H NMR; 5mg of the sample was dissolved in 0.6mL of a solution containing tetramethylDeuterated chloroform (CDCl) of silane (TMS, 0.03%) 3 ) In the method, TMS is used as an internal standard to record the chemical shift of a sample, and the scanning times are 64 times; and to 1 Calculating the Degree of Substitution (DS) of-OH on MCC-g-SA by performing integration treatment on an H NMR spectrum; specifically calculated according to the following formula: DS =7I H-MCC /35I H-SA。
TABLE 1 results of Properties of the products obtained in examples 1-5 and comparative example 1
-represents: the signal is not obvious and cannot be calculated.
Claims (12)
1. A method for preparing thermoplastic cellulose ester derivatives is characterized in that the preparation method comprises the following steps: carrying out one-step esterification reaction on cellulose, a coreactant trifluoroacetic anhydride and an esterifying agent by ball milling, and then purifying to obtain the thermoplastic cellulose ester derivatives; the esterifying agent is a carboxyl-containing esterifying agent; the molar ratio of the cellulose to the esterifying agent to the trifluoroacetic anhydride is as follows: 1:1 to 12:1 to 6.
2. The method of claim 1, wherein said esterifying agent is selected from the group consisting of: at least one of stearic acid, palmitic acid, myristic acid, lauric acid, capric acid, caprylic acid, 2-butylcaprylic acid, 4-n-pentylbenzoic acid, formic acid, acetic acid, oxalic acid, malonic acid, benzoic acid, succinic acid, butenedioic acid, phthalic acid, or alpha-naphthylacetic acid.
3. The process of claim 1 or 2, wherein the cellulose is selected from the group consisting of: at least one of sugarcane cellulose, cassava cellulose, rice straw cellulose, corn straw cellulose, wood cellulose, cotton cellulose, flax cellulose, ramie cellulose, bacterial cellulose, microcrystalline cellulose, nano cellulose or regenerated cellulose.
4. The method of claim 1 or 2, wherein the method comprises: firstly, performing an esterification reaction on cellulose, an esterifying agent and trifluoroacetic anhydride through ball milling; then dissolving, precipitating, washing and filtering the obtained product to obtain the thermoplastic cellulose ester derivative.
5. The method of claim 4, wherein during said ball milling, said ball milling speed is in the range of 100 to 1000rpm; the ball milling time is 0.1-12 h.
6. The method of claim 5, wherein during said ball milling, said ball milling speed is in the range of 300 to 1000rpm; the ball milling time is 3-12 h.
7. The method of claim 4, wherein the dissolving, precipitating, washing and filtering the obtained product to obtain the thermoplastic cellulose ester derivatives comprises: dissolving the product in a solvent, adding an anti-solvent for full precipitation, repeatedly washing for at least 3 times, performing suction filtration to obtain a crude product, and performing Soxhlet extraction for 1 to 72 hours to obtain different cellulose ester derivatives.
8. The method of claim 7, wherein said solvent is selected from the group consisting of: at least one of dichloromethane, chloroform, acetone, DMF, DMSO, 1,4-dioxane, tetrahydrofuran, benzene, toluene or hexane;
the antisolvent is selected from: at least one of ethanol, methanol, water, formamide, acetonitrile, or propanol;
the solvent for Soxhlet extraction is selected from the group consisting of: at least one of ethanol, methanol, water, formamide, acetonitrile or propanol.
9. A derivative of a thermoplastic cellulose ester, which is obtained by the method according to any one of claims 1 to 8.
10. The derivative according to claim 9, wherein the degree of substitution of the long chain of the derivative is 1.5 to 3.
11. The derivative of thermoplastic cellulose ester according to claim 9, wherein the derivative of thermoplastic cellulose ester is melt processable.
12. The thermoplastic cellulose ester derivative according to claim 9, wherein the thermoplastic cellulose ester derivative has a melting temperature of 50 to 170 ℃.
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