Tung oil modified ethyl cellulose polymer and preparation method thereof

Abstract

Tung oil modified ethyl cellulose polymer and preparation method thereof, wherein the tung oil modified ethyl cellulose polymer is obtained by UV curing of methacrylated ethyl cellulose, tung oil ethyl methacrylate, acrylamide, etc. By adjusting the weight ratio of acrylated ethyl cellulose, tung oil ethyl methacrylate and acrylamide, a tung oil-based resin material with different mechanical properties, transparency, thermally induced recyclability and self-healing properties can be obtained. This material has broad application prospects in photosensitive coatings, foam plastics and adhesives.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer modification, and in particular relates to a tung oil-modified ethyl cellulose polymer and a preparation method thereof. Background Art

[0002] With the increasing depletion of petroleum resources, the biomass of chemical raw materials has become a research hotspot, and resin products are no exception. In recent years, new resins made of green plants have emerged in an endless stream. Using more renewable biomass resources to replace non-renewable resources, while reducing the consumption of petrochemical products in the plastics industry and alleviating environmental pollution caused by production, is an important development direction for polymer materials at present. Combining "green economy" and "low-carbon economy" has a higher development space.

[0003] Treating the abundant cellulose in plants with alkali can destroy its relatively inert structure to a certain extent and increase processing performance. On this basis, chlorohexane is added to react and some hydroxyl groups are replaced by ethoxy groups. The resulting ethyl cellulose (EC) is a white or light brown powder that has good compatibility with materials such as resins and plasticizers and has good film-forming properties. It can be used in coatings, adhesives, cross-linking agents, pharmaceutical tablets, etc. Ethyl cellulose is easily soluble in organic solvents such as tetrahydrofuran. The solubility varies with the degree of substitution of hydroxyl groups in cellulose by ethoxy groups. It also has a unique linear macromolecular structure, which is conducive to further modification of ethyl cellulose.

[0004] Tung oil is an industrial vegetable oil obtained by mechanically pressing and processing the fruit of the tung tree. It has excellent properties such as quick drying, high temperature resistance, corrosion resistance, and water resistance. It can be used to synthesize a wide variety of fine chemicals such as plasticizers, biodiesel, lubricants, and downstream products such as glycerol. It is widely used in construction, agricultural machinery, and the electronics industry. The main components are α-eleostearic acid triglyceride and some oleic acid, with less saturated fatty acids. The molecular structure is shown in the figure. It can be seen that the barrel oil molecule has conjugated double bonds, carboxyl groups and other functional groups, and can undergo chemical reactions such as Diels-Alder reaction, Friedel-Crafts reaction, free radical polymerization, oxidative polymerization, amidation, and transesterification. Because tung oil is highly toxic and cannot be eaten and has more active chemical properties than other vegetable oils, using tung oil as an industrial raw material can reduce the consumption of edible oil and alleviate the shortage of grain and oil resources in my country.

[0005] Combining the development and utilization of ethyl cellulose and tung oil resources with the modification of polymer materials will help promote the industrialization of biomass raw materials and develop them in a variety of high-performance directions. It will also help increase the added value of cellulose and tung oil products and expand their scope of application. Summary of the invention

[0006] Technical problem to be solved: The present invention provides a tung oil-modified ethyl cellulose polymer and a preparation method thereof. The material has the advantages of adjustable mechanical properties, repeatable processing, self-repairing, biocompatibility and degradability.

[0007] Technical solution: A method for preparing a tung oil-modified ethyl cellulose polymer, comprising the following steps: mixing methacrylated ethyl cellulose, acrylamide and tung oil ethyl methacrylate, heating to 30-150° C., wherein the mass ratio of methacrylated ethyl cellulose, acrylamide and tung oil ethyl methacrylate is (0-5):(5-0):5, and curing under ultraviolet light under the catalysis of a photoinitiator to obtain a tung oil-modified ethyl cellulose polymer.

[0008] The methacrylated ethyl cellulose is obtained by esterification reaction of methacrylic anhydride and ethyl cellulose.

[0009] The above-mentioned tung oil ethyl methacrylate is obtained by aminolysis of tung oil and ethanolamine and esterification with methacrylic anhydride.

[0010] Preferably, the temperature for blending the reactants is 90°C.

[0011] Preferably, the weight ratio of the methacrylated ethyl cellulose, acrylamide and ethyl methacrylate is 1:4:5.

[0012] Preferably, the photoinitiator is phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and the added amount is 2 wt.% of the total mass of the reaction system.

[0013] Preferably, the curing reaction time is 5-30 min.

[0014] Preferably, the above-mentioned ultraviolet light intensity is 50-200w.

[0015] The tung oil-modified ethyl cellulose polymer prepared by the above preparation method.

[0016] Beneficial effects: The present invention uses methacrylated ethyl cellulose, acrylamide and tung oil ethyl methacrylate to obtain a high-strength tung oil-modified ethyl cellulose polymer through UV curing. This type of tung oil-modified ethyl cellulose has adjustable mechanical properties. By changing the proportion of the solidified components, a series of polymer materials ranging from soft elastic to high toughness can be obtained. Its excellent self-healing, biocompatibility, degradability and relatively balanced mechanical properties make it have potential application value in various fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1The infrared spectra of tung oil, tung oil ethanol and tung oil ethyl methacrylate;

[0018] Figure 2 It is the H NMR spectrum of tung oil, tung oil ethanol and tung oil ethyl methacrylate;

[0019] Figure 3 The infrared spectra of ethyl cellulose and methyl acrylated ethyl cellulose are shown in Figure 1.

[0020] Figure 4 This is the H-NMR spectrum of ethyl cellulose and methyl acrylated ethyl cellulose;

[0021] Figure 5 Mechanical properties of tung oil modified ethyl cellulose polymer. DETAILED DESCRIPTION

[0022] Dissolve 10 g of ethyl cellulose in 100 ml of N,N-dimethylformamide, add 5 g of methacrylic anhydride and 0.1 g of 4-dimethylaminopyridine, stir and react at 60°C for 12 hours, then add 10 mL of water and continue the reaction for 1 hour, remove excess water to obtain methacrylated ethyl cellulose.

[0023] 100 g of tung oil, 25 g of ethanolamine and 0.43 g of sodium methoxide were added to a flask, stirred and reacted at 80°C for 4 hours, and tung oil ethanol was obtained after washing and drying. 100 g of tung oil ethanol, 50 g of methacrylic anhydride and 0.37 g of 4-dimethylaminopyridine were added to a flask, stirred and reacted at 60°C for 12 hours, 10 mL of water was added, and the reaction was continued for 1 hour. The excess water was removed to obtain tung oil ethyl methacrylate in a brown liquid state.

[0024] Example 1

[0025] The reactants methyl methacrylated ethyl cellulose, acrylamide and tung oil ethyl methacrylate were added into a reaction bottle in a weight ratio of 5:0:5, and phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide was added as a photoinitiator, with a total amount of 2 wt.% of the total mass of the reactants. After stirring at 90°C for 30 minutes and mixing evenly, the mixture was poured into a mold and cured by 100 W ultraviolet irradiation for 10 minutes to obtain tung oil-modified ethyl cellulose polymer.

[0026] Example 2

[0027] The reactants methyl methacrylated ethyl cellulose, acrylamide and tung oil ethyl methacrylate were added into a reaction bottle in a weight ratio of 4:1:5, and phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide was added as a photoinitiator, with a total amount of 2 wt.% of the total mass of the reactants. After stirring at 90°C for 30 minutes and mixing evenly, the mixture was poured into a mold and cured by 100 W ultraviolet irradiation for 10 minutes to obtain tung oil-modified ethyl cellulose polymer.

[0028] Example 3

[0029] The reactants methyl methacrylated ethyl cellulose, acrylamide and tung oil ethyl methacrylate were added into a reaction bottle in a weight ratio of 3:2:5, and phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide was added as a photoinitiator, with a total amount of 2 wt.% of the total mass of the reactants. After stirring at 90°C for 30 minutes and mixing evenly, the mixture was poured into a mold and cured by 100 W ultraviolet irradiation for 10 minutes to obtain tung oil-modified ethyl cellulose polymer.

[0030] Example 4

[0031] The reactants methyl methacrylated ethyl cellulose, acrylamide and tung oil ethyl methacrylate were added into a reaction bottle in a weight ratio of 2:3:5, and phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide was added as a photoinitiator, and the total amount was 2 wt.% of the total mass of the reactants. After stirring at 90°C for 30 minutes and mixing evenly, the mixture was poured into a mold and cured by 100 W ultraviolet irradiation for 10 minutes to obtain tung oil-modified ethyl cellulose polymer.

[0032] Example 5

[0033] The reactants methyl methacrylated ethyl cellulose, acrylamide and tung oil ethyl methacrylate were added into a reaction bottle in a weight ratio of 1:4:5, and phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide was added as a photoinitiator, with a total amount of 2 wt.% of the total mass of the reactants. After stirring at 90°C for 30 minutes and mixing evenly, the mixture was poured into a mold and cured by 100 W ultraviolet irradiation for 10 minutes to obtain tung oil-modified ethyl cellulose polymer.

Claims

1. A method for preparing tung oil-modified ethyl cellulose polymer, characterized in that: The preparation steps are as follows: methacrylated ethyl cellulose, acrylamide and tung oil ethyl methacrylate are mixed and heated to 30-150° C., wherein the mass ratio of methacrylated ethyl cellulose, acrylamide and tung oil ethyl methacrylate is (1-5):(4-0):5; under the catalysis of a photoinitiator, the mixture is irradiated and cured with an ultraviolet lamp to obtain a tung oil-modified ethyl cellulose polymer; the methacrylated ethyl cellulose is obtained by an esterification reaction between methacrylic anhydride and ethyl cellulose; and the tung oil ethyl methacrylate is obtained by an esterification reaction between tung oil and ethanolamine and methacrylic anhydride.

2. The method for preparing tung oil modified ethyl cellulose polymer according to claim 1, characterized in that: The temperature at which the reactants were blended was 90°C.

3. The method for preparing tung oil modified ethyl cellulose polymer according to claim 1, characterized in that: The methacrylated ethyl cellulose, acrylamide and elaiodoacetyl methacrylate are in a weight ratio of 1:4:

5.

4. The method for preparing tung oil modified ethyl cellulose polymer according to claim 1, characterized in that: The photoinitiator is phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and the amount added is 2 wt.% of the total mass of the reaction system.

5. The method for preparing tung oil modified ethyl cellulose polymer according to claim 1, characterized in that: The curing reaction time is 5-30 min.

6. The method for preparing tung oil modified ethyl cellulose polymer according to claim 1, characterized in that: The UV light intensity is 50-200W.

7. Tung oil-modified ethyl cellulose polymer obtained by the preparation method according to any one of claims 1 to 6.

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