WO2021068443A1 - Preparation method for and application of tung oil-based polymer, and preparation method for tung oil-based polymer derivatives - Google Patents

Abstract

A method for preparing a tung oil-based polymer, which uses methyl tungate as a raw material, olive oil, palm oil or coconut oil as a reaction solvent, and a Lewis acid as a catalyst to perform a cationic polymerization reaction to prepare the tung oil-based polymer. The preparation method for the tung oil-based polymer has raw materials that have numerous sources and are renewable. During the preparation process, renewable vegetable oil is used as a reaction solvent to replace traditional petroleum-based solvents such as halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons. The present invention is environmentally friendly, and the prepared tung oil-based polymer is safe and non-toxic, and can be used to prepare plasticizers.

Description

Preparation method and application of tung oil-based polymer, and preparation method of tung oil-based polymer derivative Technical field

The invention belongs to the technical field of polymer materials, and specifically relates to a preparation method and application of a tung oil-based polymer, and a preparation method of a tung oil-based polymer derivative.

Background technique

Cationic polymerization is an important polymerization reaction, which is similar to free radical polymerization. It consists of elementary reactions such as chain initiation, chain extension, chain transfer, and chain termination. However, because it is prone to chain transfer reactions, it is usually difficult to obtain high Molecular polymers. Industrially, polymers obtained by cationic polymerization of monomers such as isobutylene and piperylene have a wide range of applications, such as rubber, coatings and adhesives.

Chinese patent CN103881027B discloses a method for synthesizing piperylene resin by copolymerizing piperylene, monoolefin, and isoprene in a weight ratio of 1:(0.1-1.0):(0.1-0.5) Raw material, under the action of catalyst Lewis acid, with inert aliphatic hydrocarbon as solvent, cationic polymerization reaction at 40-70℃ under anaerobic conditions, it has good viscosity, oxidation stability and compatibility. Performance of piperylene petroleum resin. The raw materials for the preparation of the above resins are all derived from petroleum.

At present, most of the polymers used in coatings, adhesives, plasticizers and other industries are derived from petroleum-based products. Petroleum is a non-renewable resource. Its exploitation, transportation and consumption will bring environmental pollution such as air pollution and marine pollution. Pollution. Due to the frequent price fluctuations of petroleum resources and people’s increasing attention to environmental protection, it is urgent to develop bio-based materials from renewable biological resources to replace petroleum-based materials. In addition, "using renewable resources" is an important principle in green chemistry. Many renewable resources have been developed for bio-based materials, such as lignin, sugars, terpenes, natural polyphenols, and vegetable oils. Unlike petroleum, biomass is renewable and does not cause environmental pollution, so it is of great significance to apply biomass to the preparation of polymers.

Chinese patent CN105658685B discloses a β-phellandrene polymer, which is obtained by cationic polymerization of β-phellandrene using Lewis acid as a catalyst. The organic solvent constituting the reaction solution can be halogenated hydrocarbons, aromatic hydrocarbons, and Aliphatic hydrocarbons, etc., with a reaction temperature of -90°C to 100°C, and a β-phellandrene polymer with a high degree of polymerization excellent in heat resistance and light transmittance can be obtained.

At present, the reaction solvents used in cationic polymerization are generally halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons. The above-mentioned solvents are all derived from non-renewable petroleum resources, and their boiling points are generally low and easy to volatilize. One of the reasons for the increase of volatile organic compounds (VOC), in addition, chlorinated hydrocarbons can also cause harm to the human body.

Summary of the invention

The first object of the present invention is to provide a method for preparing a tung oil-based polymer to solve at least one of the above technical problems.

The second object of the present invention is to provide the application of the tung oil-based polymer prepared by the above preparation method in the preparation of plasticizers, so as to solve at least one of the above technical problems.

The third object of the present invention is to provide a method for preparing tung oil-based polymer derivatives to solve at least one of the above technical problems.

According to one aspect of the present invention, there is provided a method for preparing a tung oil-based polymer, which includes the following steps:

S1. Add methyl eletronate and reaction solvent into the reaction vessel, and after blowing nitrogen into the reaction vessel, add Lewis acid to carry out cationic polymerization reaction;

S2. After the reaction is completed, the first solvent and the second solvent are sequentially added, and the precipitate is collected by centrifugation to obtain a tung oil-based polymer;

Wherein, the reaction solvent is selected from at least one of olive oil, palm oil and coconut oil, the first solvent is selected from at least one of ethyl acetate, dichloromethane and tetrahydrofuran; the second solvent is selected from acetic acid, acetone and ethanol At least one of them.

In the method for preparing the tung oil-based polymer provided by the present invention, the prepared tung oil-based polymer is represented by the following formula (1). In the cationic polymerization reaction, among the three carbon-carbon double bonds of methyl eletronate, when only the carbon-carbon double bond at the C9 position is reacted, the resulting tung oil-based polymer is soluble in the first solvent and can be dissolved again. Adding the second solvent can precipitate the tung oil-based polymer. When there are two or three double bonds participating in the reaction, a product with a cross-linked structure is generated, which is difficult to dissolve in the first solvent. In the present invention, the first solvent and the second solvent are sequentially added after the cationic polymerization reaction is completed, which is also beneficial to improve the purity of the tung oil-based polymer.

In the present invention, the addition amount of the first solvent can be determined according to the actual situation, so as to fully dissolve the reaction product in step S1; the second solvent is mainly used to precipitate the polymer, and the addition amount can also be determined according to the actual situation. The polymer can be charged and analyzed.

Methyl tellonic acid has a conjugated triene structure. In theory, it can be polymerized by cationic polymerization without other chemical modification. Therefore, the inventors performed cationic polymerization of methyl tellonic acid to prepare a tung oil-based polymer. Researched. Through a comparative study of different reaction conditions, the inventors found that: in addition to using aliphatic hydrocarbons such as ethyl acetate and dimethyl carbonate as the reaction solvent and Lewis acid as the catalyst, the tung oil-based polymer represented by formula (I) can be prepared. Using olive oil, palm oil or coconut oil as the reaction solvent and Lewis acid as the catalyst can also carry out cationic polymerization to prepare the tung oil-based polymer represented by formula (I).

In addition, the inventor further researched and found that the above-mentioned tung oil-based polymer has no obvious plasticizing effect when used as a plasticizer alone, and when it is combined with dioctyl phthalate as a plasticizer, the plasticizer The effect is significantly better than the plasticizing effect when using dioctyl phthalate alone as the plasticizer. Based on the above findings, the present invention has been completed.

Among the raw materials for the preparation of the polymer provided by the present invention, methyl elenate is prepared from tung oil, the reaction solvents are olive oil, palm oil, and coconut oil as renewable bio-based materials, and methyl elenate is used as the polymerized monomer and double bond. The low content of vegetable oil is the reaction solvent and the Lewis acid is the catalyst. The cationic polymerization reaction is carried out under anaerobic conditions to prepare the tung oil-based polymer. The raw material source is wide and renewable. The preparation process is green and environmentally friendly. The prepared tung oil-based polymer is safe and non-oxygen Toxic, can be used to prepare plasticizers.

In some embodiments, the weight ratio of the reaction solvent to methyl eletronate may be (1-5):1.

In some embodiments, the reaction temperature of the cationic polymerization reaction may be 30-60° C., and the reaction time may be 0.5-10 h. Under this reaction condition, two or three double bonds in methyl eleonic acid can be avoided to participate in the reaction, and the obtained reaction product can be completely dissolved in the first solvent, thereby improving the reaction yield.

In some embodiments, the Lewis acid may be selected from at least one of aluminum trichloride, boron trifluoride ether and titanium tetrachloride, and its addition amount may be 1-10% of the weight of methyl eletronate.

In some embodiments, the volume ratio of the first solvent and the second solvent is 1: (5-10).

The tung oil-based polymer prepared by the method for preparing the tung oil-based polymer provided by the present invention can be used to prepare plasticizers, in particular, it can be compounded with dioctyl phthalate as a plasticizer and applied to plastics, coatings, and adhesives. And other industries, the plasticizing effect is excellent.

According to another aspect of the present invention, there is provided a method for preparing a derivative of a tung oil-based polymer, which includes the following steps:

S1. Add methyl eletronate and the reaction solvent into the reaction vessel, and after blowing nitrogen into the reaction vessel, add Lewis acid, and react for 0.5-10h at a temperature of 30-60℃; wherein, the reaction solvent can be selected from At least one of olive oil, palm oil and coconut oil;

S2, after the reaction of step S1 is completed, add an aqueous alkali solution, and react for 3 to 5 hours at a temperature of 70 to 90°C;

After the reaction in step S3 and step S2 is completed, acid is added until the pH of the solution is acidic, washed with water and organic solvent, and then dried, filtered, and rotary steamed to obtain the product.

The present invention utilizes a one-pot method to first carry out cationic polymerization reaction, and then directly hydrolyze the reaction product (ie tung oil-based polymer) obtained by carrying out cationic polymerization reaction under acid-base catalysis and heating to prepare tung oil-based polymer derivatives. The reaction process does not require separation of intermediate products, which is economical and environmentally friendly. In addition, in the preparation method of the derivative of tung oil-based polymer provided by the present invention, methyl elenate prepared from the bio-based material tung oil is used as the raw material to prepare the tung oil-based polymer, and the renewable bio-based material olive oil, Palm oil or coconut oil replaces organic solvents as reaction solvents, and raw materials have a wide range of sources and are renewable, and the preparation process is green and environmentally friendly. The derivative of the tung oil-based polymer provided by the present invention is a polycarboxyl polymer with the structural formula shown in the following formula (II), which can be applied to the fields of coatings, adhesives, water reducing agents and the like.

In some embodiments, the weight ratio of the reaction solvent to methyl eletronate may be (1-5):1.

In some embodiments, the Lewis acid may be selected from at least one of aluminum trichloride, boron trifluoride ether and titanium tetrachloride, and its addition amount may be 1-10% of the weight of methyl eletronate.

In some embodiments, in step S2, the base may be selected from at least one of potassium hydroxide, sodium hydroxide and sodium carbonate, and the molar ratio of base to methyl elenate may be (1 to 3):1. The concentration of the aqueous solution can be 0.5-8mol/L.

In some embodiments, in step S3, the acid may be selected from at least one of sulfuric acid, acetic acid, and hydrochloric acid; the organic solvent may be selected from at least one of ethyl acetate, ethanol, and ether.

Compared with the prior art, the present invention has the following beneficial effects:

(1) In the present invention, methyl elenate is used as a raw material for cationic polymerization, biomass is used in the preparation of polymers, and the prepared tung oil-based polymer can be applied to prepare plasticizers.

(2) The present invention uses renewable vegetable oils as polymerization solvents, instead of traditional petroleum-based solvents such as halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons. Vegetable oil is a renewable resource. Compared with petroleum-based solvents, it has the advantages of wide sources, low price, non-toxic, harmless, and non-depleted. In addition, vegetable oils have high boiling points, are not volatile, and will not cause an increase in VOC. Moreover, vegetable oil is biodegradable and will not bring additional burden to the environment.

(3) The tung oil-based polymer provided by the present invention can be used to prepare plasticizers, partially replacing traditional petroleum-based plasticizers. At present, most of the commonly used plasticizers on the market belong to the phthalates. Among them, dioctyl phthalate is widely used because of its high plasticizing efficiency. However, these phthalate plasticizers are easy to migrate. , Damage to human reproductive system and other hazards, and these plasticizers are all derived from non-renewable petroleum resources. Partial replacement of tung oil-based polymers with phthalate petroleum-based plasticizers can reduce the harm caused by plasticizers to human health.

(4) When the tung oil-based polymer and dioctyl phthalate compound provided by the present invention are used as a plasticizer to prepare polyvinyl chloride (PVC) film, the glass transition temperature (T _g ) of the prepared PVC film Not more than 50℃, the tensile strength is greater than 18MPa, and the elongation at break is greater than 560%. Compared with the PVC film made by using dioctyl phthalate alone as the plasticizer, the tensile strength and elongation at break are both Significant improvement, indicating that the plasticizing effect of tung oil-based polymer and dioctyl phthalate as a plasticizer is significantly improved than that of dioctyl phthalate.

Description of the drawings

Figure 1 is an infrared spectrogram of the tung oil methyl polymer prepared in Example 1 of the present invention;

Figure 2 is a gel permeation chromatogram of tung oil methyl polymer prepared in Examples 1-7 of the present invention;

Figure 3 is an infrared spectrogram of a tung oil methyl polymer derivative prepared in Example 8 of the present invention;

Fig. 4 is a stress-strain graph of a PVC film prepared by using a plasticizer composed of a tung oil-based polymer and dioctyl phthalate in a mass ratio of 1:1 in Example 1.

Detailed ways

The present invention will be further described in detail below with reference to specific embodiments and drawings, but the implementation of the present invention is not limited to this. The reagents used in the examples can be conventionally purchased from the market unless otherwise specified.

Example 1 Preparation of tung oil-based polymer

Including the following steps:

S1. Add methyl tellonic acid and olive oil into the reaction vessel, then pour nitrogen into the reaction vessel, then add 10% boron trifluoride ether by weight of methyl eletronate, heat up to 60°C, stir and react for 0.5h ; Among them, the weight ratio of methyl eletronate and olive oil is 1:1;

S2. After the reaction, a sufficient amount of the first solvent dichloromethane is added, the reaction product is fully dissolved, and the second solvent, acetone, is added to precipitate the tung oil-based polymer, centrifuged, and the precipitate is taken to obtain the tung oil-based polymer; The volume ratio of the solvent and the second solvent is 1:5.

The yield of the polymer is 75% (about 20% of the methyl eletronate is non-conjugated fatty acid ester), and the purity is 95%.

The tung oil-based polymer was coated on the KBr film, and then placed on the Nicolet iS10 Fourier Transform Infrared Spectrometer of Thermo Fisher Scientific Company for testing. The scanning wave number range is 4000～400cm ^-1 , the resolution is 4cm ^-1 , and the scanning is 32 After the average value was taken, the FTIR spectrum of the tung oil-based polymer was obtained, as shown in Figure 1. By comparing with the infrared spectrum of methyl eletronate, it can be seen that 991cm ^-1 is the peak of conjugated double bond of methyl ^{eletronate. After polymerization, the peak of anti-anticonjugated double bond appears at 989cm -1} , and the intensity of the peak decreases. Prove that the tung oil-based polymer has been successfully prepared.

The tung oil-based polymer was dissolved in tetrahydrofuran to prepare a 2mg/ml solution, and then injected into a Waters gel permeation chromatograph. The mobile phase is tetrahydrofuran, the chromatographic columns are Styragel HR 2, HR 4 and HR 6, and the flow rate is 0.5 ml/min. The standard curve is obtained from polystyrene standards. The gel permeation chromatography (GPC) chart of the tung oil-based polymer is shown in Figure 2. The number average molecular weight of the tung oil-based polymer is 38,000 and the polydispersity index is 2.1.

Example 2 Preparation of tung oil-based polymer

Including the following steps:

S1. Add methyl eletronate and palm oil into the reaction vessel, then pour nitrogen into the reaction vessel, then add 1% aluminum trichloride by weight of methyl eletronate, raise the temperature to 30°C, stir and react for 10 hours; , The weight ratio of palm oil to methyl eletronate is 5:1;

S2. After the reaction is completed, add ethyl acetate and ethanol in sequence, the volume ratio of ethyl acetate and ethanol is 1:8, and the precipitate is centrifuged to obtain a tung oil-based polymer. The yield of the polymer is 77% and the purity is 94%. .

The FTIR spectrum of the tung oil-based polymer was obtained by the Nicolet iS10 Fourier Transform Infrared Spectrometer of Thermo Fisher Scientific, and the characteristic peaks obtained were the same as those in Example 1.

The GPC chart of the tung oil-based polymer measured by Waters gel permeation chromatography is shown in Figure 2. The number average molecular weight of the tung oil-based polymer was measured to be 37,850, and the polydispersity index was 1.9.

Example 3 Preparation of tung oil-based polymer

Including the following steps:

S1. Add methyl eletronate and coconut oil into the reaction vessel, then pour nitrogen into the reaction vessel, and then add 10% titanium tetrachloride by weight of methyl eletronate, raise the temperature to 50°C, stir and react for 8h; , The weight ratio of coconut oil and methyl eletronate is 5:1;

S2. After the reaction is completed, tetrahydrofuran and acetic acid are sequentially added, the volume ratio of tetrahydrofuran and acetic acid is 1:6, and the precipitate is collected by centrifugation to obtain a tung oil-based polymer. The yield of the polymer is 76% and the purity is 96%.

The FTIR spectrum of the tung oil-based polymer was obtained by the Nicolet iS10 Fourier Transform Infrared Spectrometer of Thermo Fisher Scientific, and the characteristic peaks obtained were the same as those in Example 1.

The GPC chart of the tung oil-based polymer measured by Waters gel permeation chromatograph is shown in Figure 2. The number average molecular weight of the tung oil-based polymer is 35,000 and the polydispersity index is 1.9.

Example 4 Preparation of tung oil-based polymer

Including the following steps:

S1. Add methyl eletronate and olive oil into the reaction vessel, and then pour nitrogen into the reaction vessel, then add 5% aluminum trichloride by weight of methyl eletronate, heat up to 60°C, stir and react for 5h; , The weight ratio of olive oil and methyl eletronate is 3:1;

S2. After the reaction is completed, ethyl acetate and acetic acid are sequentially added, the volume ratio of ethyl acetate and acetic acid is 1:10, and the tung oil-based polymer is obtained by centrifugal separation. The yield of the polymer is 74% and the purity is 95%.

The FTIR spectrum of the tung oil-based polymer was obtained by the Nicolet iS10 Fourier Transform Infrared Spectrometer of Thermo Fisher Scientific, and the characteristic peaks obtained were the same as those in Example 1.

The GPC chart of the tung oil-based polymer measured by Waters gel permeation chromatograph is shown in Figure 2. The number average molecular weight of the tung oil-based polymer is 39744 and the polydispersity index is 2.0.

Example 5 Preparation of tung oil-based polymer

Including the following steps:

S1. Add methyl eletronate and olive oil into the reaction vessel, then pour nitrogen into the reaction vessel, and then add 5% boron trifluoride ether by weight of methyl eletronate, raise the temperature to 30°C, stir and react for 8h; Among them, the weight ratio of olive oil and methyl eletronate is 3:1;

S2. After the reaction is completed, dichloromethane and acetone are sequentially added, the volume ratio of dichloromethane and acetone is 1:5, and the tung oil-based polymer is obtained by centrifugal separation. The yield of the polymer is 73% and the purity is 93%.

The FTIR spectrum of the tung oil-based polymer was obtained by the Nicolet iS10 Fourier Transform Infrared Spectrometer of Thermo Fisher Scientific, and the characteristic peaks obtained were the same as those in Example 1.

The GPC chart of the tung oil-based polymer measured by Waters gel permeation chromatography is shown in Figure 2. The number average molecular weight of the tung oil-based polymer was measured to be 37,800, and the polydispersity index was 2.0.

Example 6 Preparation of tung oil-based polymer

Including the following steps:

S1. Add methyl eletronate and palm oil into the reaction vessel, then pour nitrogen into the reaction vessel, and then add 10% aluminum trichloride by weight of methyl eletronate, raise the temperature to 60°C, and stir to react for 1 hour; , The weight ratio of palm oil and methyl eletronate is 1:1;

S2. After the reaction is completed, ethyl acetate and ethanol are sequentially added, and the volume ratio of ethyl acetate and ethanol is 1:8, and the tung oil-based polymer is obtained by centrifugal separation. The yield of the polymer is 75% and the purity is 96%.

The FTIR spectrum of the tung oil-based polymer was obtained by the Nicolet iS10 Fourier Transform Infrared Spectrometer of Thermo Fisher Scientific, and the characteristic peaks obtained were the same as those in Example 1.

The GPC chart of the tung oil-based polymer measured by Waters gel permeation chromatograph is shown in Figure 2. The number average molecular weight of the tung oil-based polymer measured is 37823, and the polydispersity index is 2.0.

Example 7 Preparation of tung oil-based polymer

Including the following steps:

S1. Add methyl eletronate and olive oil into the reaction vessel, then pour nitrogen into the reaction vessel, and then add 1% aluminum trichloride by weight of methyl eletronate, heat up to 60°C, stir and react for 8h; where , The weight ratio of olive oil and methyl elenate is 5:1;

S2. After the reaction is completed, ethyl acetate and acetic acid are sequentially added, the volume ratio of ethyl acetate and acetic acid is 1:8, and the tung oil-based polymer is obtained by centrifugal separation. The yield of the polymer is 78% and the purity is 94%.

The FTIR spectrum of the tung oil-based polymer was obtained by the Nicolet iS10 Fourier Transform Infrared Spectrometer of Thermo Fisher Scientific, and the characteristic peaks obtained were the same as those in Example 1.

The GPC chart of the tung oil-based polymer measured by Waters gel permeation chromatography is shown in Figure 2. The number average molecular weight of the tung oil-based polymer was measured to be 37857, and the polydispersity index was 2.0.

Example 8 Preparation of derivatives of tung oil-based polymers

Including the following steps:

S1. Add methyl eletronate and coconut oil into the reaction vessel, and after blowing nitrogen into the reaction vessel, add 10% titanium tetrachloride by weight of methyl eletronate, heat up to 50°C, stir and react for 8h; wherein, The weight ratio of coconut oil and methyl elenate is 5:1;

S2. After the reaction of step S1 is completed, an aqueous solution of sodium hydroxide is added, and the reaction is carried out at a temperature of 90°C for 3 hours; wherein the molar ratio of sodium hydroxide to methyl eletronate is 2:1, and the sodium hydroxide solution is The concentration is 0.5mol/L;

S3. After the reaction of step S2 is completed, add hydrochloric acid to the reaction product of step S2 until the pH of the reaction product is acidic, and then wash with water and ethyl acetate respectively, and then dry with anhydrous magnesium sulfate, filter, and rotatory steam to obtain The tung oil-based polymer derivative has a yield of 95% and a purity of 97%.

Infrared spectroscopy test, test conditions and methods refer to Example 1, and the results are shown in Figure 3. It can be seen from Figure 3 ^{that carboxyl peaks appear at 2500-3500 cm -1} and 1712 cm ^-1 , which proves that the tung oil-based polymer derivatives have been successfully prepared.

Example 9 Preparation of derivatives of tung oil-based polymer

Including the following steps:

S1. Add methyl eletronate and palm oil into the reaction vessel, and after blowing nitrogen into the reaction vessel, add 1% boron trifluoride ether by weight of methyl eletronate, raise the temperature to 40°C, and stir for 10 hours; where , The weight ratio of palm oil to methyl eletronate is 2:1;

S2. After the reaction of step S1 is completed, an aqueous solution of potassium hydroxide is added to the reaction product of step S1, and the reaction is carried out at a temperature of 70°C for 4 hours; wherein the molar ratio of potassium hydroxide to methyl eletronate is 1: 1. The concentration of potassium hydroxide aqueous solution is 1mol/L;

S3. After the reaction of step S2 is completed, add acetic acid to the reaction product of step S2 until the pH of the reaction product is acidic, and then wash with water and ethanol respectively, and then dry with anhydrous magnesium sulfate, filter, and rotate to obtain a tung oil base. The polymer derivative has a yield of 96% and a purity of 96%.

Test example 1

The tung oil-based polymers prepared in Examples 1-7 were mixed with polyvinyl chloride (PVC), dioctyl phthalate (DOP) and tetrahydrofuran, respectively. The quality of the tung oil-based polymer, PVC, DOP and tetrahydrofuran The ratio is 1:4.7:1:10, then dried at room temperature for 12 hours, heated at 80°C for 5 hours, and finally dried in vacuum at 50°C for 5 hours to make a PVC film. In addition, PVC, DOP and tetrahydrofuran are mixed in a mass ratio of 2:4.7:10 to make a PVC film.

The glass transition temperature (T _g ) analysis of the film was tested with a NETZSCH DMA 242E dynamic mechanical analyzer. The test frequency was 1Hz, the temperature range was -60-110°C, and the heating rate was 5°C/min.

The tensile strength of the film is analyzed, and the mechanical properties of the PVC film are measured using the UTM4204 universal electronic testing machine. The crosshead speed is 10mm/min.

The test results of each sample are shown in Table 1. The stress-strain diagram of the PVC film prepared by using the tung oil-based polymer prepared in Example 1 and the plasticizer composed of DOP at a mass ratio of 1:1 is shown in FIG. 4.

Table 1 Comprehensive performance test results of PVC film

To	T g /℃	Tensile strength/MPa	Elongation at break/%
Example 1	48	21.0	651.2
Example 2	46	20.5	601.2
Example 3	43	19.8	610.1
Example 4	48	22.4	598.5
Example 5	49	23.0	580.7
Example 6	43	18.9	620.2
Example 7	50	24.5	569.3
DOP	12	11.0	309.1

The key performance parameters of plasticized PVC are T _g and elongation at break. From the results in Table 1, it can be seen that the PVC film prepared by using the tung oil-based polymer provided by the present invention and the plasticizer composed of DOP at a mass ratio of 1:1 The T _{g of the product is} not greater than 50°C, the tensile strength is greater than 18MPa, and the elongation at break is greater than 560%. It has good elongation and ductility, and its performance fully meets the needs of practical applications.

What has been described above are only some embodiments of the present invention. For those of ordinary skill in the art, without departing from the inventive concept of the present invention, several modifications and improvements can be made, and these all fall within the protection scope of the present invention.

Claims (10)

1. The preparation method of tung oil-based polymer is characterized in that it comprises the following steps:

   S1. Add methyl eletronate and reaction solvent into the reaction vessel, and after blowing nitrogen into the reaction vessel, add Lewis acid to carry out cationic polymerization reaction;

   S2. After the reaction is completed, the first solvent and the second solvent are sequentially added, and the precipitate is collected by centrifugation to obtain a tung oil-based polymer;

   Wherein, the reaction solvent is selected from at least one of olive oil, palm oil and coconut oil; the first solvent is selected from at least one of ethyl acetate, dichloromethane and tetrahydrofuran; the second solvent is selected From at least one of acetic acid, acetone, and ethanol.
2. The method for preparing a tung oil-based polymer according to claim 1, wherein the weight ratio of the reaction solvent to methyl eletronate is (1-5):1.
3. The method for preparing a tung oil-based polymer according to claim 1, wherein the reaction temperature of the cationic polymerization reaction is 30-60°C, and the reaction time is 0.5-10h.
4. The method for preparing a tung oil-based polymer according to claim 1, wherein the Lewis acid is selected from at least one of aluminum trichloride, boron trifluoride ether and titanium tetrachloride, and its addition amount is 1-10% of the weight of methyl eletronate.
5. The method for preparing a tung oil-based polymer according to claim 1, wherein the volume ratio of the first solvent and the second solvent is 1: (5-10).
6. The use of the tung oil-based polymer prepared by the method for preparing the tung oil-based polymer according to any one of claims 1 to 5 in the preparation of plasticizers.
7. The application according to claim 6, wherein the plasticizer further comprises dioctyl phthalate.
8. The preparation method of the derivative of tung oil-based polymer is characterized in that it comprises the following steps:

   S1. Add methyl eletronate and reaction solvent into the reaction vessel, and after blowing nitrogen into the reaction vessel, add Lewis acid, and react for 0.5-10h at a temperature of 30-60°C; wherein, the reaction solvent is selected From at least one of olive oil, palm oil and coconut oil;

   S2, after the reaction of step S1 is completed, add an aqueous alkali solution, and react for 3 to 5 hours at a temperature of 70 to 90°C;

   After the reaction in step S3 and step S2 is completed, acid is added until the pH of the solution is acidic, washed with water and organic solvent, and then dried, filtered, and rotary steamed to obtain the product.
9. The method for preparing a derivative of a tung oil-based polymer according to claim 8, wherein the Lewis acid is selected from at least one of aluminum trichloride, boron trifluoride ether and titanium tetrachloride. The addition amount is 1-10% of the weight of methyl eletronate.
10. The method for preparing tung oil-based polymer derivatives according to claim 8, wherein in step S2, the alkali is selected from at least one of potassium hydroxide, sodium hydroxide and sodium carbonate, and the alkali The molar ratio with the methyl eletronate is (1～3):1, and the concentration of the aqueous alkali solution is 0.5～8mol/L; in step S3, the acid is selected from at least one of sulfuric acid, acetic acid and hydrochloric acid. One; the organic solvent is selected from at least one of ethyl acetate, ethanol and ether.

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