Bio-based plasticizer, polymer composition containing plasticizer and application

Abstract

The invention discloses a bio-based plasticizer, a polymer composition containing the plasticizer and application, and belongs to the technical field of polymer processing aids. The structure of the furyl plasticizer is shown as a general formula (A1), (A2), (A3) or (A4), the plasticizer is compatible with a polymer, meanwhile, the thermal stability and the mechanical property of the plasticizer are improved, the compatibility with the polymer is improved, the migration rate of the plasticizer in a polymer matrix is remarkably reduced, and the plasticizer has a good application prospect. The problems of toxicity and migration of the existing orthophthalic plasticizers and the problems of poor compatibility, high volatility and insufficient outstanding mechanical properties of the existing bio-based plasticizers for plasticizing polymer materials are solved. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the technical field of polymer processing aids, and in particular relates to a bio-based plasticizer and a polymer composition containing the plasticizer and application thereof. Background Art

[0002] Plasticizers are a class of polymer material additives widely used in industrial production. They can increase the plasticity of polymers, thereby improving the processing properties and physical properties of materials. The mechanism of action of plasticizers is mainly to increase the mobility of polymer molecular chains and reduce the crystallinity of polymer molecular chains by weakening the secondary bonds between polymer molecules, thereby improving the plasticity of polymers. This is manifested in the decrease of hardness, modulus, softening temperature and brittle temperature of polymers, while the elongation, flexibility and toughness are improved. At present, hundreds of plasticizers have been introduced, among which phthalates are the most widely used plasticizers (e.g. dioctyl phthalate) due to their good plasticizing effect and relatively low cost, accounting for more than 80% of the total amount of plasticizers. However, commercial phthalate plasticizers will migrate from the inside of the product to the surface during use and eventually enter the surrounding environment, thereby polluting the environment and having a negative impact on human health, such as disrupting the endocrine system and causing cancer.

[0003] Furanic acid is an important bio-based platform compound and the only bio-based rigid aromatic ring structure monomer. It is expected to be used as a raw material for synthesizing biosafety and new environmentally friendly bio-based plasticizers. CN117946043A discloses a preparation method and application of a fully bio-based furandicarboxylate plasticizer for PLA, which uses bio-based platform compound 2,5-furandicarboxylic acid and natural fatty alcohol as raw materials, and obtains furandicarboxylate by esterification reaction under the action of a catalyst. The fully bio-based furandicarboxylate plasticizer has a bio-based content of 100%, a high boiling point, good stability, and is non-toxic and green. It is very similar to the structure of phthalate plasticizers and is a perfect substitute for phthalate plasticizers. It can be used in the preparation of polymer composite materials to replace traditional phthalate plasticizers. However, the plasticizer is highly volatile and has poor mechanical properties. Summary of the invention

[0004]

Technical issues

[0005] Aiming at the toxicity and migration problems of existing orthophthalic plasticizers and the problems of poor compatibility, high volatility and insufficient mechanical properties of existing bio-based plasticizer-plasticized polymer materials, the present invention provides a method for preparing a furan-based plasticizer and a polymer composition containing the plasticizer. The furan-based plasticizer with excellent performance is prepared by using fatty acid ester, furanic acid and acetic anhydride as raw materials. The furan-based plasticizer contains a long fatty chain structure, a furan ring structure and an ester branched structure, and thus has special plasticizing properties. The compatibility of the plasticizer with the polymer is increased while the thermal stability, mechanical properties and migration resistance of the plasticizer are increased.

[0006]

Technical solution

[0007] The present invention provides a bio-based plasticizer, the structure of which is shown in the general formula (A1), (A2), (A3) or (A4):

[0008]

[0009] In the formula, R 1 C 1-10 alkyl;

[0010] n1 is a substituent R on the furan ring 2 The number of substitutions is 0 or 1;

[0011] R 2 -CH 2 OC(=O)CH 3 ;

[0012] n2 is -CH on the fatty chain 2 - is 1, 2, 3, 4, 5, 6, 7 or 8;

[0013] n3 is -CH on the fatty chain 2 - is 1, 2, 3, 4, 5, 6, 7 or 8;

[0014] n3 is -CH on the fatty chain 2 - is 1, 2, 3, 4, 5, 6, 7 or 8;

[0015] n4 is -CH on the fatty chain 2 - is 1, 2, 3, 4, 5, 6, 7 or 8.

[0016] In an embodiment of the present invention, the structure of the bio-based plasticizer may be:

[0017]

[0018] In the formula, R 1 C 1-10 alkyl;

[0019] n1 is a substituent R on the furan ring 2 The number of substitutions is 0 or 1;

[0020] R 2 -CH 2 OC(=O)CH 3 .

[0021] The above-mentioned bio-based plasticizers are mainly composed of a long fatty chain structure, a furan ring structure, a polyester structure, and an ester branched structure.

[0022] The present invention provides a method for preparing the above-mentioned bio-based plasticizer, using fatty acid ester, furanic acid and acetic anhydride as raw materials, and obtaining the plasticizer through three steps of epoxidation, ring-opening esterification and acetylation, and the specific steps are as follows:

[0023] S1, using fatty acid ester and catalyst 1 as raw materials to prepare epoxy fatty acid ester through epoxidation;

[0024] S2, preparing furanoic acid fatty acid ester by ring-opening reaction of epoxy fatty acid ester, furanoic acid and ring-opening agent;

[0025] S3, finally, furanoic acid fatty acid ester, acetic anhydride and catalyst 2 undergo acetylation reaction to obtain the corresponding bio-based plasticizer.

[0026] In one embodiment of the present invention, the fatty acid ester is a fatty acid ester containing 1 to 3 unsaturated double bonds, specifically selected from: methyl oleate, ethyl oleate, butyl oleate, hexyl oleate, octyl oleate, decyl oleate, methyl linoleate, ethyl linoleate, butyl linoleate, hexyl linoleate, octyl linoleate, decyl linoleate, methyl linoleate, ethyl linoleate, butyl linoleate, hexyl linoleate, octyl linoleate, decyl linoleate, methyl linolenate, ethyl linolenate, butyl linoleate, hexyl linoleate, octyl linoleate and decyl linoleate.

[0027] In one embodiment of the present invention, the furanic acid is furan monoacid or furan diacid; wherein the furan diacid is 2,5-furandicarboxylic acid, and the furan monoacid is selected from any one of 2-furancarboxylic acid, 5-hydroxymethyl-2-furancarboxylic acid, and 3-hydroxymethyl-2-furancarboxylic acid.

[0028] Further:

[0029] In one embodiment of the present invention, a bio-based plasticizer having a structure represented by the general formula (A1) is prepared by using a fatty acid ester containing one unsaturated double bond and furan monoacid as raw materials according to the above steps.

[0030] In one embodiment of the present invention, a bio-based plasticizer having a structure represented by the general formula (A2) is prepared by using a fatty acid ester containing two unsaturated double bonds and furan monoacid as raw materials according to the above steps.

[0031] In one embodiment of the present invention, a bio-based plasticizer having a structure represented by the general formula (A3) is prepared by using a fatty acid ester containing three unsaturated double bonds and furan monoacid as raw materials according to the above steps.

[0032] In one embodiment of the present invention, a bio-based plasticizer having a structure represented by the general formula (A4) is prepared by using a fatty acid ester containing one unsaturated double bond and furan dicarboxylic acid as raw materials according to the above steps.

[0033] In an embodiment of the present invention, the catalyst 1 is any one of meta-chloroperbenzoic acid and hydrogen peroxide.

[0034] In one embodiment of the present invention, the ring-opening agent is any one of tetrabutylammonium chloride and tetrabutylammonium bromide.

[0035] In one embodiment of the present invention, the catalyst 2 is any one of a strongly acidic cation exchange resin and concentrated sulfuric acid.

[0036] In one embodiment of the present invention, in S1, the molar ratio of fatty acid ester to catalyst 1 is 1:1.2-3.2.

[0037] In one embodiment of the present invention, in S1, fatty acid ester and meta-chloroperbenzoic acid are dissolved in dichloromethane, reacted in an ice-water bath first and then at room temperature, washed to neutrality after the reaction, purified and dried to obtain the product epoxy fatty acid ester.

[0038] In one embodiment of the present invention, in S1, an acidic ion exchange resin and formic acid are added to the fatty acid ester, and then hydrogen peroxide is added dropwise to react. After the reaction is completed, the mixture is washed to neutrality, purified and dried to obtain epoxy fatty acid ester.

[0039] In one embodiment of the present invention, in S2, the molar ratio of epoxy fatty acid ester to furanic acid is 1:0.5-4.5.

[0040] In one embodiment of the present invention, in S2, the amount of the ring-opening agent added is 0.1 wt%-5 wt% of the epoxy fatty acid ester, and can further be 4 wt%-5 wt%.

[0041] In one embodiment of the present invention, in S2, epoxy fatty acid ester, furanic acid and a ring-opening agent are mixed and heated to 120-140° C., and the reaction is continued for 4-7 hours. After the reaction is completed, the mixture is washed to neutrality, purified and dried to obtain the product furanic acid fatty acid ester.

[0042] In one embodiment of the present invention, in S3, the amount of acetic anhydride added is 50 wt%-90 wt% of the furanoic acid fatty acid ester.

[0043] In one embodiment of the present invention, in S3, the added amount of catalyst 2 is 5wt%-15wt% of the furanoic acid fatty acid ester.

[0044] In one embodiment of the present invention, in S3, furanic acid fatty acid ester, acetic anhydride and catalyst 2 are mixed and heated to 60°C-90°C, and the reaction is continued for 18-24 hours. After the reaction is completed, the mixture is washed to neutrality, purified and dried to obtain the final product, furan-based plasticizer.

[0045] The invention also provides the use of the above bio-based plasticizer in polyvinyl chloride, polyester, rubber and thermoplastic elastomer products.

[0046] The present invention also provides a polymer composition comprising a polymer substrate and the bio-based plasticizer.

[0047] In one embodiment of the present invention, the polymer substrate includes at least one of polyvinyl chloride, polyester, rubber and thermoplastic elastomer.

[0048] In one embodiment of the present invention, the amount of the bio-based plasticizer added to the polymer substrate is 2 wt%-60 wt%; further, 10 wt%-40 wt%.

[0049]

Beneficial Effects

[0050] (1) The present invention utilizes the special structure (carboxyl group) of furanic acid and the ring-opening reaction of epoxy fatty acid ester to prepare a bioplasticizer having a long fatty chain structure, a furan ring structure, and an ester branched structure; while improving its compatibility with polymers, it also improves the tensile strength, elongation at break, thermal stability, and migration resistance of the material.

[0051] (2) The non-polar long alkyl chain is inserted into the polymer to increase the free volume and act as a lubricant. The presence of the polar furan ring structure improves the compatibility of the plasticizer with the polymer while increasing its thermal stability and mechanical properties. The multiple ester groups contained in it interact with the polymer to offset part of the interaction force between the polymer macromolecules, thereby increasing compatibility. The ester branched structure increases the interaction and physical interpenetration between molecules, significantly reducing the mobility of the plasticizer in the polymer matrix, and can replace traditional phthalate plasticizers.

[0052] (3) The raw materials used in the present invention are derived from bio-based materials, which are green and environmentally friendly. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 The infrared spectra of epoxy oleic acid methyl ester, 2,5-furandicarboxylic acid methyl oleate and the final product acetyl 2,5-furandicarboxylic acid methyl oleate in Example 1;

[0054] Figure 2 The infrared spectra of epoxy oleic acid methyl ester, 2-furancarboxylic acid methyl oleate and the final product acetyl 2-furancarboxylic acid methyl oleate are shown in Example 2;

[0055] Figure 3 The thermogravimetric curves of the product of Example 1 and the comparative plasticizer are shown below: methyl oleate, diisononyl cyclohexane-1,2-dicarboxylate (DINCH) and acetyl 2,5-furandicarboxylic acid methyl oleate.

[0056] Figure 4 The color changes of PVC samples of Comparative Examples 1-4 and Application Example 1 at 200°C over time. DETAILED DESCRIPTION

[0057] The present invention is described in detail below in conjunction with the accompanying drawings and embodiments.

[0058] Example 1

[0059] (1) 37 g of m-chloroperbenzoic acid was dissolved in 150 mL of dichloromethane and stirred under ice-water bath conditions, and then 100 mL of dichloromethane solution containing 50 g of methyl oleate was added dropwise, and the reaction system formed above was first reacted in an ice-water bath for 0.5 h, and then reacted at room temperature for 24 h. After the reaction was completed, it was washed with sodium thiosulfate solution and sodium bicarbonate solution until neutral, and then washed with sodium chloride solution for 3 times, and finally washed with deionized water for 3 times, and then dichloromethane was removed by vacuum distillation at -0.1 MPa and 35° C. to obtain the product epoxy methyl oleate;

[0060] (2) 50 g (0.16 mol) of the product methyl epoxyoleate obtained in step (1), 15.6 g (0.1 mol) of 2,5-furandicarboxylic acid and 2 g of tetrabutylammonium chloride are added to a reactor under a nitrogen atmosphere, the raw materials are mixed and heated to 140° C., and the reaction is continued for 5 hours. After the reaction is completed, the organic phase is washed with deionized water until neutral, and the organic phase is then vacuum distilled under -0.1 MPa and 75° C. to remove water to obtain the product methyl 2,5-furandicarboxylate;

[0061] (3) Add 50 g of the product of step (2), 25 g of acetic anhydride and 2.5 g of a strongly acidic cation exchange resin into a reactor, mix the above raw materials, heat to 85° C., and continue the reaction for 24 hours. After the reaction is completed, first remove the acetic anhydride by vacuum distillation at -0.1 MPa and 120° C., then wash with deionized water to neutrality, and then remove the water by vacuum distillation at -0.1 MPa and 75° C. to obtain the final product, bio-based plasticizer acetyl 2,5-furandicarboxylic acid methyl oleate.

[0062] (General formula A4, R 1 =Me, n2=7, n3=7)

[0063] The infrared spectrum test of epoxy oleic acid methyl ester, 2,5-furandicarboxylic acid methyl ester and the final product acetyl 2,5-furandicarboxylic acid methyl ester in Example 1 was performed. The test results are as follows: Figure 1 shown.

[0064] Figure 1 From top to bottom are epoxy oleic acid methyl ester, 2,5-furandicarboxylic acid methyl ester and the final product acetyl 2,5-furandicarboxylic acid methyl ester. In the first step of the epoxidation reaction, the infrared curve of epoxy oleic acid methyl ester at 928cm -1 The formation of epoxy bond (COC) proved the successful preparation of epoxy oleic acid methyl ester. -1 The stretching vibration peak of the epoxy bond (COC) at 3527cm -1 The appearance of the stretching vibration peak of the hydroxyl group (-OH) at 3527 cm -1 The stretching vibration peak of the hydroxyl group (-OH) disappeared, which proved that the acetylation reaction was successful and acetyl 2,5-furandicarboxylic acid methyl ester was successfully synthesized.

[0065] Example 2

[0066] (1) 40 g of m-chloroperbenzoic acid was dissolved in 150 mL of dichloromethane and stirred under ice-water bath conditions, and then 100 mL of dichloromethane solution containing 50 g of methyl oleate was added dropwise to the above system, and the above raw materials were first reacted in an ice-water bath for 0.5 h, and then reacted at room temperature for 24 h. After the reaction, the mixture was washed with sodium thiosulfate solution and sodium bicarbonate solution until neutral, and then washed with sodium chloride solution for 3 times, and finally washed with deionized water for 3 times, and then dichloromethane was removed by vacuum distillation at -0.1 MPa and 35° C. to obtain the product epoxy methyl oleate;

[0067] (2) 50 g (0.16 mol) of the product methyl epoxyoleate obtained in step (1), 26 g (0.24 mol) of 2-furandicarboxylic acid and 0.1 g of tetrabutylammonium chloride are added to a reactor under a nitrogen atmosphere, the raw materials are mixed and heated to 140° C., and the reaction is continued for 5 hours. After the reaction is completed, the organic phase is washed with deionized water until neutral, and the organic phase is then vacuum distilled under -0.1 MPa and 75° C. to remove water to obtain the product methyl 2-furandicarboxylate;

[0068] (3) Add 50 g of the product of step (2), 25 g of acetic anhydride and 2.5 g of a strongly acidic cation exchange resin into a reactor, mix the above raw materials, heat to 85° C., and continue the reaction for 24 hours. After the reaction is completed, first remove the acetic anhydride by vacuum distillation at -0.1 MPa and 120° C., then wash with deionized water to neutrality, and then remove the water by vacuum distillation at -0.1 MPa and 75° C. to obtain the final product, a bio-based environmentally friendly plasticizer, acetyl 2-furancarboxylic acid methyl oleate.

[0069] (General formula A1, R 1 =Me, n1=0, n2=7, n3=7)

[0070] The epoxy oleic acid methyl ester, 2-furancarboxylic acid methyl ester and the final product acetyl 2-furancarboxylic acid methyl ester in Example 1 were subjected to infrared spectrum test. The test results are as follows: Figure 2 shown.

[0071] Figure 2 From top to bottom are epoxy oleic acid methyl ester, 2-furancarboxylic acid methyl ester and the final product acetyl 2-furancarboxylic acid methyl ester. In the first step of the epoxidation reaction, the infrared curve of epoxy oleic acid methyl ester at 928cm -1 The formation of epoxy bond (COC) proved the successful preparation of epoxy oleic acid methyl ester. -1 The stretching vibration peak of the epoxy bond (COC) at 3501cm -1 The appearance of the stretching vibration peak of the hydroxyl group (-OH) at 3501 cm -1 The stretching vibration peak of the hydroxyl group (-OH) disappeared, which proved that the acetylation reaction was successful and acetyl 2-furancarboxylic acid methyl ester was successfully synthesized.

[0072] Example 3

[0073] (1) 43 g of m-chloroperbenzoic acid was dissolved in 150 mL of dichloromethane and stirred under ice-water bath conditions, and then 100 mL of dichloromethane solution containing 50 g of methyl oleate was added dropwise to the above system, and the above raw materials were first reacted in an ice-water bath for 0.5 h, and then reacted at room temperature for 24 h. After the reaction, the mixture was washed with sodium thiosulfate solution and sodium bicarbonate solution until neutral, and then washed with sodium chloride solution for 3 times, and finally washed with deionized water for 3 times, and then dichloromethane was removed by vacuum distillation at -0.1 MPa and 35° C. to obtain the product epoxy methyl oleate;

[0074] (2) 50 g (0.16 mol) of the product epoxy oleic acid methyl ester obtained in step (1), 30 g (0.24 mol) of 5-hydroxymethyl-2-furancarboxylic acid and 0.05 g of tetrabutylammonium chloride are added to a reactor under a nitrogen atmosphere, the above raw materials are mixed and heated to 140° C., and the reaction is continued for 5 hours. After the reaction is completed, the organic phase is washed with deionized water until neutral, and the organic phase is then vacuum distilled under -0.1 MPa and 75° C. to remove water to obtain the product 5-hydroxymethyl-2-furancarboxylic acid methyl oleate;

[0075] (3) 50 g of the product of step (2), 40 g of acetic anhydride and 7.5 g of a strongly acidic cation exchange resin were added to a reactor, the raw materials were mixed and heated to 85° C., and the reaction was continued for 24 h. After the reaction was completed, the acetic anhydride was first removed by vacuum distillation at -0.1 MPa and 120° C., then washed with deionized water until neutral, and then vacuum distilled at -0.1 MPa and 75° C. to remove water to obtain the final product, a bio-based environmentally friendly plasticizer, acetyl 5-acetoxymethyl-2-furancarboxylic acid methyl oleate (general formula A1, R 1 =Me, n1=1, R 2 =-CH 2 OC(=O)CH 3 , n2=7, n3=7).

[0076] Example 4

[0077] (1) 37 g of m-chloroperbenzoic acid was dissolved in 150 mL of dichloromethane and stirred under ice-water bath conditions, and then 100 mL of dichloromethane solution containing 50 g of methyl oleate was added dropwise to the above system, and the above raw materials were first reacted in an ice-water bath for 0.5 h, and then reacted at room temperature for 24 h. After the reaction, the mixture was washed with sodium thiosulfate solution and sodium bicarbonate solution until neutral, and then washed with sodium chloride solution for 3 times, and finally washed with deionized water for 3 times, and then dichloromethane was removed by vacuum distillation at -0.1 MPa and 35° C. to obtain the product epoxy methyl oleate;

[0078] (2) adding 50 g (0.16 mol) of the product epoxy oleic acid methyl ester obtained in step (1), 30 g (0.24 mol) of 3-hydroxymethyl-2-furancarboxylic acid and 2.5 g of tetrabutylammonium chloride into a reactor under a nitrogen atmosphere, mixing the above raw materials and heating them to 140° C., and continuing the reaction for 5 h. After the reaction is completed, washing with deionized water until neutral, and then vacuum distilling the organic phase at -0.1 MPa and 75° C. to remove water to obtain the product 3-hydroxymethyl-2-furancarboxylic acid methyl oleate;

[0079] (3) 50 g of the product of step (2), 35 g of acetic anhydride and 5 g of a strongly acidic cation exchange resin were added to a reactor, the raw materials were mixed and heated to 85° C., and the reaction was continued for 24 h. After the reaction was completed, the acetic anhydride was first removed by vacuum distillation at -0.1 MPa and 120° C., and then washed with deionized water until neutral, and then vacuum distilled at -0.1 MPa and 75° C. to remove water to obtain the final product, a bio-based environmentally friendly plasticizer, acetyl 3-acetoxymethyl-2-furancarboxylic acid methyl oleate (general formula A1, R 1 =Me, n1=1, R 2 -CH 2 OC(=O)CH 3 , n2=7, n3=7).

[0080] Example 5

[0081] (1) 37 g of m-chloroperbenzoic acid was dissolved in 150 mL of dichloromethane and stirred under ice-water bath conditions, and then 100 mL of dichloromethane solution containing 50 g of ethyl oleate was added dropwise to the above system, and the above raw materials were first reacted in an ice-water bath for 0.5 h, and then reacted at room temperature for 24 h. After the reaction, the mixture was washed with sodium thiosulfate solution and sodium bicarbonate solution until neutral, and then washed with sodium chloride solution for 3 times, and finally washed with deionized water for 3 times, and then dichloromethane was removed by vacuum distillation at -0.1 MPa and 35° C. to obtain the product epoxy ethyl oleate;

[0082] (2) 50 g (0.16 mol) of the product ethyl oleate obtained in step (1), 37 g (0.24 mol) of 2,5-furandicarboxylic acid and 2 g of tetrabutylammonium chloride are added to a reactor under a nitrogen atmosphere, the above raw materials are mixed and heated to 140° C., and the reaction is continued for 5 hours. After the reaction is completed, the organic phase is washed with deionized water until neutral, and the organic phase is then vacuum distilled under -0.1 MPa and 75° C. to remove water to obtain the product ethyl oleate of 2,5-furandicarboxylate;

[0083] (3) 50 g of the product of step (2), 40 g of acetic anhydride and 7.5 g of a strongly acidic cation exchange resin were added to a reactor, the raw materials were mixed and heated to 85° C., and the reaction was continued for 24 h. After the reaction was completed, the acetic anhydride was first removed by vacuum distillation at -0.1 MPa and 120° C., then washed with deionized water until neutral, and then vacuum distilled at -0.1 MPa and 75° C. to remove water to obtain the final product, bio-based plasticizer acetyl 2,5-furandicarboxylic acid ethyl ester (general formula A4, R 1 =Et, n2=7, n3=7).

[0084] Example 6

[0085] (1) 37 g of m-chloroperbenzoic acid was dissolved in 150 mL of dichloromethane and stirred under ice-water bath conditions, and then 100 mL of dichloromethane solution containing 50 g of ethyl oleate was added dropwise to the above system, and the above raw materials were first reacted in an ice-water bath for 0.5 h, and then reacted at room temperature for 24 h. After the reaction, the mixture was washed with sodium thiosulfate solution and sodium bicarbonate solution until neutral, and then washed with sodium chloride solution for 3 times, and finally washed with deionized water for 3 times, and then dichloromethane was removed by vacuum distillation at -0.1 MPa and 35° C. to obtain the product epoxy ethyl oleate;

[0086] (2) adding 50 g (0.16 mol) of the product ethyl epoxy oleate obtained in step (1), 26 g (0.24 mol) of 2-furancarboxylic acid and 2 g of tetrabutylammonium chloride into a reactor under a nitrogen atmosphere, mixing the above raw materials and heating them to 140° C., and continuing the reaction for 5 h. After the reaction is completed, washing with deionized water until neutral, and then vacuum distilling the organic phase at -0.1 MPa and 75° C. to remove water to obtain the product ethyl 2-furancarboxylate;

[0087] (3) Add 50 g of the product of step (2), 35 g of acetic anhydride and 5 g of a strongly acidic cation exchange resin into a reactor, mix the above raw materials, heat to 85° C., and continue the reaction for 24 h. After the reaction is completed, acetic anhydride is first removed by vacuum distillation at -0.1 MPa and 120° C., then washed with deionized water until neutral, and then vacuum distilled at -0.1 MPa and 75° C. to remove water to obtain the final product, a bio-based environmentally friendly plasticizer, acetyl 2-furancarboxylic acid ethyl oleate (general formula A1, R 1 =Et, n1=0, n2=7, n3=7).

[0088] Example 7

[0089] (1) 37 g of m-chloroperbenzoic acid was dissolved in 150 mL of dichloromethane and stirred under ice-water bath conditions, and then 100 mL of dichloromethane solution containing 50 g of ethyl oleate was added dropwise to the above system, and the above raw materials were first reacted in an ice-water bath for 0.5 h, and then reacted at room temperature for 24 h. After the reaction, the mixture was washed with sodium thiosulfate solution and sodium bicarbonate solution until neutral, and then washed with sodium chloride solution for 3 times, and finally washed with deionized water for 3 times, and then dichloromethane was removed by vacuum distillation at -0.1 MPa and 35° C. to obtain the product epoxy ethyl oleate;

[0090] (2) adding 50 g (0.16 mol) of the product ethyl epoxy oleate obtained in step (1), 30 g (0.24 mol) of 5-hydroxymethyl-2-furancarboxylic acid and 2 g of tetrabutylammonium chloride into a reactor under a nitrogen atmosphere, mixing the above raw materials and heating to 140° C., and continuing the reaction for 5 h. After the reaction is completed, washing with deionized water until neutral, and then vacuum distilling the organic phase under -0.1 MPa and 75° C. to remove water to obtain the product ethyl 5-hydroxymethyl-2-furancarboxylate;

[0091] (3) Add 50 g of the product of step (2), 35 g of acetic anhydride and 5 g of a strongly acidic cation exchange resin into a reactor, mix the above raw materials, heat to 85° C., and continue the reaction for 24 h. After the reaction is completed, acetic anhydride is first removed by vacuum distillation at -0.1 MPa and 120° C., then washed with deionized water until neutral, and then vacuum distilled at -0.1 MPa and 75° C. to remove water to obtain the final product, a bio-based environmentally friendly plasticizer, acetyl 5-acetoxymethyl-2-furancarboxylic acid ethyl oleate (general formula A1, R 1 =Et,n1=1,R 2 -CH 2 OC(=O)CH 3 , n2=7, n3=7).

[0092] Example 8

[0093] (1) 37 g of m-chloroperbenzoic acid was dissolved in 150 mL of dichloromethane and stirred under ice-water bath conditions, and then 100 mL of dichloromethane solution containing 50 g of ethyl oleate was added dropwise to the above system, and the above raw materials were first reacted in an ice-water bath for 0.5 h, and then reacted at room temperature for 24 h. After the reaction, the mixture was washed with sodium thiosulfate solution and sodium bicarbonate solution until neutral, and then washed with sodium chloride solution for 3 times, and finally washed with deionized water for 3 times, and then dichloromethane was removed by vacuum distillation at -0.1 MPa and 35° C. to obtain the product epoxy ethyl oleate;

[0094] (2) adding 50 g (0.16 mol) of the product ethyl epoxy oleate obtained in step (1), 30 g (0.24 mol) of 3-hydroxymethyl-2-furancarboxylic acid and 1 g of tetrabutylammonium chloride into a reactor under a nitrogen atmosphere, mixing the above raw materials and heating to 140° C., and continuing the reaction for 5 h. After the reaction is completed, washing with deionized water until neutral, and then vacuum distilling the organic phase under -0.1 MPa and 75° C. to remove water to obtain the product ethyl 2-hydroxymethyl-3-furancarboxylate;

[0095] (3) Add 50 g of the product of step (2), 35 g of acetic anhydride and 5 g of a strongly acidic cation exchange resin into a reactor, mix the above raw materials, heat to 85° C., and continue the reaction for 24 h. After the reaction is completed, acetic anhydride is first removed by vacuum distillation at -0.1 MPa and 120° C., then washed with deionized water until neutral, and then vacuum distilled at -0.1 MPa and 75° C. to remove water to obtain the final product, a bio-based environmentally friendly plasticizer, acetyl 3-acetoxymethyl-2-furancarboxylic acid ethyl oleate (general formula A1, R 1 =Et,n1=1,R 2 -CH 2 OC(=O)CH 3 , n2=7, n3=7).

[0096] Example 9

[0097] (1) 37 g of m-chloroperbenzoic acid was dissolved in 150 mL of dichloromethane and stirred under ice-water bath conditions, and then 100 mL of dichloromethane solution containing 50 g of butyl oleate was added dropwise to the above system, and the above raw materials were first reacted in an ice-water bath for 0.5 h, and then reacted at room temperature for 24 h. After the reaction, the mixture was washed with sodium thiosulfate solution and sodium bicarbonate solution until neutral, and then washed with sodium chloride solution for 3 times, and finally washed with deionized water for 3 times, and then dichloromethane was removed by vacuum distillation at -0.1 MPa and 35° C. to obtain the product epoxy butyl oleate;

[0098] (2) 50 g (0.14 mol) of the product butyl oleate obtained in step (1), 15.6 g (0.1 mol) of 2,5-furandicarboxylic acid and 2 g of tetrabutylammonium chloride are added to a reactor under a nitrogen atmosphere, the raw materials are mixed and heated to 140° C., and the reaction is continued for 5 hours. After the reaction is completed, the organic phase is washed with deionized water until neutral, and the organic phase is vacuum distilled under -0.1 MPa and 75° C. to remove water to obtain the product butyl oleate of 2,5-furandicarboxylate;

[0099] (3) 50 g of the product of step (2), 35 g of acetic anhydride and 5 g of a strongly acidic cation exchange resin were added to a reactor, the raw materials were mixed and heated to 85° C., and the reaction was continued for 24 h. After the reaction was completed, the acetic anhydride was first removed by vacuum distillation at -0.1 MPa and 120° C., and then washed with deionized water until neutral, and then vacuum distilled at -0.1 MPa and 75° C. to remove water to obtain the final product, bio-based plasticizer acetyl 2,5-furandicarboxylic acid butyl oleate (general formula A4, R 1 =n-butyl, n2=7, n3=7).

[0100] Example 10

[0101] (1) 37 g of m-chloroperbenzoic acid was dissolved in 150 mL of dichloromethane and stirred under ice-water bath conditions, and then 100 mL of dichloromethane solution containing 50 g of butyl oleate was added dropwise to the above system, and the above raw materials were first reacted in an ice-water bath for 0.5 h, and then reacted at room temperature for 24 h. After the reaction, the mixture was washed with sodium thiosulfate solution and sodium bicarbonate solution until neutral, and then washed with sodium chloride solution for 3 times, and finally washed with deionized water for 3 times, and then dichloromethane was removed by vacuum distillation at -0.1 MPa and 35° C. to obtain the product epoxy butyl oleate;

[0102] (2) 50 g (0.14 mol) of the product epoxy oleic acid butyl ester obtained in step (1), 26 g (0.24 mol) of 2-furancarboxylic acid and 2 g of tetrabutylammonium chloride are added to a reactor under a nitrogen atmosphere, the above raw materials are mixed and heated to 140° C., and the reaction is continued for 5 hours. After the reaction is completed, the organic phase is washed with deionized water until neutral, and the organic phase is then vacuum distilled under -0.1 MPa and 75° C. to remove water to obtain the product 2-furancarboxylic acid butyl oleate;

[0103] (3) 50 g of the product of step (2), 35 g of acetic anhydride and 5 g of a strongly acidic cation exchange resin were added to a reactor, the raw materials were mixed and heated to 85° C., and the reaction was continued for 24 h. After the reaction was completed, the acetic anhydride was first removed by vacuum distillation at -0.1 MPa and 120° C., then washed with deionized water until neutral, and then vacuum distilled at -0.1 MPa and 75° C. to remove water to obtain the final product, a bio-based environmentally friendly plasticizer, acetyl 2-furancarboxylic acid butyl oleate (general formula A1, R 1 =n-butyl, n1=0, n2=7, n3=7).

[0104] Embodiment 11

[0105] (1) adding 0.5 g of formic acid and 0.05 g of acidic ion exchange resin to 50 g of hexyl linoleate, and dripping 35% hydrogen peroxide at 60-75° C. while stirring. The dripping is completed within 4 hours, and then reacted for 1 hour. After the reaction is completed, the mixture is cooled to below 50° C., washed with sodium carbonate solution and deionized water until neutral, and then vacuum distilled at -0.1 MPa and 100° C. to remove impurities to obtain the product hexyl linoleate;

[0106] (2) adding 50 g (0.13 mol) of the product obtained in step (1), 39 g (0.28 mol) of 5-hydroxymethyl-2-furancarboxylic acid and 2 g of tetrabutylammonium chloride into a reactor under a nitrogen atmosphere, mixing the above raw materials and heating them to 140° C., and continuing the reaction for 5 h. After the reaction is completed, washing with deionized water until neutral, and then vacuum distilling the organic phase at -0.1 MPa and 75° C. to remove water to obtain the product 5-hydroxymethyl-2-furancarboxylic acid hexyl linoleate;

[0107] (3) Add 50 g of the product of step (2), 40 g of acetic anhydride and 5 g of strongly acidic cation exchange resin into a reactor, mix the above raw materials, heat to 85° C., and continue the reaction for 24 hours. After the reaction is completed, first remove the acetic anhydride by vacuum distillation at -0.1 MPa and 120° C., then wash with deionized water to neutrality, and then remove the water by vacuum distillation at -0.1 MPa and 75° C. to obtain the final product, bio-based environmentally friendly plasticizer acetyl 5-acetoxymethyl-2-furancarboxylic acid hexyl linoleate.

[0108] (General formula A2, R 1 = hexyl, n1 = 1, R 2 -CH 2 OC(=O)CH 3 , n2=7, n3=1, n4=4).

[0109] Example 12

[0110] (1) Add 0.5 g of formic acid and 0.05 g of acidic ion exchange resin to 50 g of decyl linolenate, and drip 35% hydrogen peroxide at 60-75° C. while stirring. The dripping is completed within 4 hours, and then reacted for 1 hour. After the reaction is completed, cool to below 50° C., wash with sodium carbonate solution and deionized water until neutral, and then vacuum distill at -0.1 MPa and 100° C. to remove impurities to obtain the product decyl epoxy linolenate;

[0111] (2) adding 50 g (0.11 mol) of the product epoxy linolenic acid decyl ester obtained in step (1), 48 g (0.34 mol) of 3-hydroxymethyl-2-furancarboxylic acid and 2 g of tetrabutylammonium chloride into a reactor under a nitrogen atmosphere, mixing the above raw materials and heating to 140° C., and continuing the reaction for 5 h. After the reaction is completed, washing with deionized water until neutral, and then vacuum distilling the organic phase under -0.1 MPa and 75° C. to remove water to obtain the product 2-hydroxymethyl-3-furancarboxylic acid linolenic acid decyl ester;

[0112] (3) Add 50 g of the product of step (2), 45 g of acetic anhydride and 5 g of a strongly acidic cation exchange resin into a reactor, mix the above raw materials, heat to 85° C., and continue the reaction for 24 hours. After the reaction is completed, first remove the acetic anhydride by vacuum distillation at -0.1 MPa and 120° C., then wash with deionized water to neutrality, and then remove the water by vacuum distillation at -0.1 MPa and 75° C. to obtain the final product, a bio-based environmentally friendly plasticizer, acetyl 3-acetoxymethyl-2-furancarboxylic acid linolenic acid decyl ester.

[0113] (General Formula A3, R 1 = decyl, n1 = 1, R 2 -CH2 OC(=O)CH 3 , n2=7, n3=1, n4=1, n5=1).

[0114] Application Examples 1-4 and Comparative Examples 1-4

[0115] The preparation of the plasticized PVC composition comprises the following specific steps:

[0116] (1) adding 100 parts by weight of PVC paste resin powder, 40 parts by weight of plasticizer, 3 parts of heat stabilizer (environmentally friendly liquid calcium zinc heat stabilizer), 0.2 parts of lubricant (paraffin), and 10 parts of calcium carbonate into an internal mixer and melt blending at 160° C. for 6 minutes to obtain a plasticized PVC composition material;

[0117] (2) The blended material is placed in a mold at 170° C. and hot-pressed to obtain a PVC film with uniform thickness.

[0118] The formulations of Application Examples 1-4 and Comparative Examples 1-4 are shown in Table 1.

[0119] Table 1 Formulations of plasticized PVC compositions of Application Examples 1-4 and Comparative Examples 1-4

[0120]

[0121]

[0122] In the table: MO represents methyl oleate, DINCH represents diisononyl cyclohexane-1,2-dicarboxylate, plasticizer A represents furandicarboxylate mentioned in the existing document CN117946043A (Example 1 in the document), and plasticizer B represents acetoxy fatty acid methyl ester mentioned in the existing document CN117986692A (Example 6 in the document).

[0123] Application Examples 5-8 and Comparative Examples 5-6

[0124] The preparation of the plasticized PLA composition, the specific steps are as follows:

[0125] (1) adding 100 parts by weight of PLA and 10 parts by weight of plasticizer into an internal mixer and melt blending at 180° C. for 8 minutes to obtain a plasticized PLA composite material;

[0126] (2) The blended material is placed in a mold at 190° C. and hot-pressed to obtain a PLA film with uniform thickness.

[0127] The formulations of Application Examples 5-8 and Comparative Examples 5-6 are shown in Table 2.

[0128] Table 2 Formulations of plasticized PLA compositions of Application Examples 5-8 and Comparative Examples 5-6

[0129]

[0130] “ / ” in the table means no plasticizer is added.

[0131] Application Examples 9-12 and Comparative Example 7

[0132] The preparation of the plasticized rubber composition comprises the following specific steps:

[0133] (1) Plasticize the raw rubber at a temperature of 50-60°C for 10-20 minutes, with a roller distance of 3-4 mm and 2-5 passes;

[0134] (2) adding the above-mentioned plasticized rubber, carbon black, plasticizer, co-crosslinking agent and vulcanizing agent in sequence at a temperature of 70-80° C. and mixing and kneading for 10-15 minutes, with a roller distance of 1-2 mm, and thin-passing 2-5 times to obtain a mixed rubber;

[0135] (3) The mixed rubber is placed in a mold for compression vulcanization at 170°C to obtain a rubber material.

[0136] The formulations of Application Examples 9-12 and Comparative Example 5 are shown in Table 3.

[0137] Table 3 Formulations of plasticized rubber compositions of Application Examples 9-12 and Comparative Example 7

[0138]

[0139] Performance Testing:

[0140] N 2 Thermogravimetric analysis of plasticizer and plasticized PVC film was carried out with the carrier gas at a flow rate of 50 mL / min, the test temperature range of 100-500°C, the heating rate of 20°C / min, and the sample mass of 5-10 mg.

[0141] The mechanical properties of the materials were tested according to GB / T 1040-2006, the tensile rate was 50 mm / min, and five samples were tested in parallel in each group.

[0142] According to GB / T9349-2002 Polyvinyl chloride, related chlorine-containing homopolymers and copolymers and their blends - Determination of thermal stability - Color change method, observe and record the color change of the sample. By observing the color change of PVC samples at 200°C over time, the stability and aging speed of thermal PVC products can be judged.

[0143] According to the standard "ISO 176-2005 activated carbon adsorption method", PVC samples with a size of 20×20×1.0mm were completely buried in ceramic crucibles filled with activated carbon powder, and then the ceramic crucibles were placed in a forced air hot oven at a temperature of 100±1℃. After 24 hours, the samples were taken out to test their mass loss. The initial mass of the sample was weighed, recorded as W0; at the end of the test, the sample was weighed, recorded as W. Each group of tests was performed three times in parallel to obtain the average value as the final loss rate result. The volatility of the PVC sample was calculated by formula (1),

[0144] The performance test results of plasticized PVC of Application Examples 1-4 and Comparative Examples 1-4 are shown in Table 4.

[0145] Table 4

[0146]

[0147]

[0148] T d-50％ It indicates the thermal degradation temperature corresponding to 50% mass loss of plasticized PVC film.

[0149] The performance test results of plasticized PLA of Application Examples 5-8 and Comparative Examples 5-6 are shown in Table 5.

[0150] Table 5

[0151] Tensile strength(MPa) Elongation at break (%) volatility(%) <![CDATA[T d-50％ (℃)]]> Application Example 5 42.7 287.7 1.2 355.7 Application Example 6 41.2 826.8 1.4 357.2 Application Example 7 37.8 292.3 1.5 355.8 Application Example 7 41.7 289.6 1.9 354.9 Comparative Example 5 65.1 6.3 / 353.9 Comparative Example 6 38.7 219.8 2.4 354.3

[0152] The “ / ” in the formula means no plasticizer is added and the product is non-volatile.

[0153] The performance test results of the plasticized rubber of Application Examples 9-12 and Comparative Example 7 are shown in Table 6.

[0154] Table 6

[0155] Tensile strength(MPa) Elongation at break (%) Shore A Hardness Mooney viscosity / (Pa·s) Example 9 18.2 440 64 54.7 Example 10 17.3 437 68 55.6 Embodiment 11 18.1 427 65 51.9 Example 12 18.3 436 63 50.6 Comparative Example 7 16.4 398 74 62.9

[0156] Function and effect:

[0157] Thermogravimetric analysis of three plasticizers, methyl oleate (MO), diisononyl cyclohexane-1,2-dicarboxylate (DINCH), and methyl oleate of acetyl 2,5-furandicarboxylate, showed that Figure 2As shown in the figure, when the mass loss is 50%, the temperature corresponding to acetyl 2,5-furandicarboxylic acid methyl oleate is higher than that of other plasticizers, indicating that the synthesized acetyl 2,5-furandicarboxylic acid methyl oleate has higher thermal stability. Because methyl oleate only contains a long fatty chain structure and has a small molecular weight, its thermal stability is the worst; the environmentally friendly plasticizer cyclohexane-1,2-dicarboxylic acid diisononyl ester contains a six-membered ring, two ester groups and two long fatty chains, and its thermal stability is relatively high; acetyl 2,5-furandicarboxylic acid methyl oleate contains a furan ring structure, a long fatty chain structure, multiple ester groups and ester branched structures and its molecular weight is higher than that of other plasticizers, so it has the best thermal stability.

[0158] From the data in Table 4, it can be seen that the tensile strength, elongation at break (plasticizing efficiency) and volatility resistance of the furanoate-based plasticizer plasticized PVC prepared in the examples of the present invention are much better than those of methyl oleate and environmentally friendly plasticizer diisononyl cyclohexane-1,2-dicarboxylate (DINCH), as well as existing plasticizers A and B. When the mass loss is 50%, the degradation temperature corresponding to the plasticized PVC in the examples is higher than that of the comparative samples, indicating that the PVC samples plasticized by the furanoate-based plasticizer show better thermal stability. This is because furanate-based environmentally friendly plasticizers have a long fatty chain structure, a furan ring structure and an ester branch structure. The non-polar long alkyl chain is inserted into PVC to increase the free volume and act as a lubricant. The presence of the furan ring structure improves the compatibility of the plasticizer with PVC while increasing its thermal stability and mechanical properties. The multiple polar ester groups contained in it produce dipole-dipole interactions with the α-H on the polar PVC molecules, which offset part of the interaction force between PVC, increase compatibility with PVC, and the ester branch structure increases the interaction and physical interpenetration between molecules, and the volatility of the plasticizer in the PVC matrix is ​​significantly reduced.

[0159] From the data in Table 5, it can be seen that the tensile strength of pure PLA is generally 65.1 MPa, and the elongation at break is 6.3%. Compared with pure PLA, the elongation at break of the PLA composite film increases after adding 10 parts of plasticizer. Compared with methyl oleate, when 10 parts of the furanoic acid ester-based plasticizer prepared in the embodiment are added, the strength and toughness can be improved at the same time, and the volatility and the degradation temperature corresponding to the mass loss of 50% are higher than those of the PLA plasticized by the comparative sample. It can be seen that the comprehensive performance of the prepared furanoic acid ester-based plasticizer is improved as a whole. This is because the furanoic acid ester-based environmentally friendly plasticizer has a long fatty chain structure, a furan ring structure and an ester branched structure. The non-polar long alkyl chain is inserted into the PLA molecule to increase the free volume and play a lubricating role. The presence of the furan ring structure improves the compatibility of the plasticizer with the PLA molecule while increasing its thermal stability and mechanical properties. The multiple polar ester groups contained in the plasticizer interact with the ester groups on the PLA molecule to produce hydrogen bonds to offset the interaction force between part of the polyester molecules, increase the compatibility with the polyester molecules, and the short ester branched structure increases the interaction and physical interpenetration between molecules, and the volatility of the plasticizer in the polyester molecule matrix is ​​significantly reduced.

[0160] It can be seen from the results in Table 6 that the rubber material obtained by using the plasticizer of the embodiment of the present invention has excellent mechanical properties. Compared with the plasticizer of the comparative example, the tensile strength and elongation at break of the rubber material obtained by the plasticizer of the embodiment of the present invention are increased at the same time, and the hardness and Mooney viscosity are reduced to varying degrees. This is because the furanoate-based plasticizer enters between the molecular chains, only improves the mobility of the molecular chains, does not destroy the chain segments between the macromolecules, and maintains the good tensile strength of the composite material. The more polar groups present in the furanoate-based plasticizer of the present invention enhance the compatibility between the plasticizer and the rubber matrix, effectively reduce the interaction force between the rubber molecular chains, and make the rubber molecular chains easier to slide, thereby enhancing the mechanical properties of the rubber material, reducing the hardness and Mooney viscosity, and improving the processing performance of the rubber material.

[0161] By observing the color change of PVC samples at 200°C over time, comparative example 1 turned black within 5 minutes, and a large number of small bubbles were generated on the surface. Its thermal stability was very poor and hydrogen chloride was released during heating; comparative example 2 turned black within 10 minutes and small bubbles were generated on the surface; comparative example 3 turned black in about 30 minutes but no small bubbles were generated on the surface; comparative example 4 gradually turned black after 10 minutes and a small number of small bubbles were generated on the surface; application example 1 did not turn dark until 50 minutes later and no small bubbles were generated on the surface, and had good color retention and heat aging properties. This is because furanate-based plasticizers have a long fatty chain structure, a furan ring structure and an ester branch structure. The non-polar long alkyl chain is inserted into PVC to increase the free volume and act as a lubricant. The presence of the furan ring structure improves the compatibility of the plasticizer with PVC while increasing its thermal stability and mechanical properties. The multiple polar ester groups contained in it produce dipole-dipole interactions with the α-H on the polar PVC molecules, which offset part of the interaction force between PVCs and increase compatibility with PVC. The ester branch structure increases the interaction and physical interpenetration between molecules, so furanate-based environmentally friendly plasticizers have the best color retention and thermal aging properties.

[0162] The embodiments provided above are not intended to limit the scope of the present invention, and the steps described are not intended to limit the execution order thereof. Those skilled in the art may make obvious improvements to the present invention in combination with existing common knowledge, which also fall within the scope of protection defined by the claims of the present invention.

Claims

1. A bio-based plasticizer, the structure of which is shown in general formula (A1), (A2), (A3) or (A4): In the formula, R1 is C 1-10 alkyl; n1 is the number of substitutions of the substituent R2 on the furan ring, which is 0 or 1; R2 is -CH2O-C(=O)CH3; n2 is the number of -CH2- groups on the aliphatic chain, which is 1, 2, 3, 4, 5, 6, 7 or 8; n3 is the number of -CH2- groups on the aliphatic chain, which is 1, 2, 3, 4, 5, 6, 7 or 8; n4 is the number of -CH2- groups on the aliphatic chain, which is 1, 2, 3, 4, 5, 6, 7 or 8; n5 is the number of -CH2- on the aliphatic chain, which is 1, 2, 3, 4, 5, 6, 7 or 8.

2. The bio-based plasticizer according to claim 1, characterized in that The structure of the bio-based plasticizer is specifically: In the formula, R1 is C 1-10 alkyl; n1 is the number of substitutions of the substituent R2 on the furan ring, which is 0 or 1; R2 is -CH2O-C(=O)CH3.

3. A method for preparing the bio-based plasticizer according to claim 1, characterized in that: The plasticizer is obtained by using fatty acid ester, furanic acid and acetic anhydride as raw materials through three steps of epoxidation, ring-opening esterification and acetylation. The specific steps are as follows: S1, using fatty acid ester and catalyst 1 as raw materials to prepare epoxy fatty acid ester by epoxidation; S2, preparing furanoic acid fatty acid ester by ring-opening reaction of epoxy fatty acid ester, furanoic acid and ring-opening agent; S3, finally, furanoic acid fatty acid ester, acetic anhydride and catalyst 2 undergo acetylation reaction to obtain the corresponding bio-based plasticizer.

4. The method according to claim 3, characterized in that The fatty acid ester is at least one of methyl oleate, ethyl oleate, butyl oleate, hexyl oleate, octyl oleate, decyl oleate, methyl linoleate, ethyl linoleate, butyl linoleate, hexyl linoleate, octyl linoleate, decyl linoleate, methyl linoleate, ethyl linoleate, butyl linoleate, hexyl linoleate, octyl linoleate and decyl linoleate; the molar ratio of the fatty acid ester to the catalyst 1 is 1:1.2-3.

2.

5. The method according to claim 3, characterized in that: The furanoic acid is at least one of 2,5-furandicarboxylic acid, 2-furancarboxylic acid, 5-hydroxymethyl-2-furancarboxylic acid and 3-hydroxymethyl-2-furancarboxylic acid; the molar ratio of the epoxy fatty acid ester to the furanoic acid is 1:0.5-4.

5.

6. The method according to claim 3, characterized in that The catalyst 1 is any one of meta-chloroperbenzoic acid and hydrogen peroxide; the ring-opening agent is any one of tetrabutylammonium chloride and tetrabutylammonium bromide; and the added amount of the ring-opening agent is 0.1wt%-5wt% of the epoxy fatty acid ester.

7. The method according to any one of claims 3 to 6, characterized in that: The catalyst 2 is any one of an acidic cation exchange resin and concentrated sulfuric acid; the added amount of the catalyst 2 is 5wt%-15wt% of the furanic acid fatty acid ester; the added amount of acetic anhydride is 50wt%-90wt% of the furanic acid fatty acid ester.

8. A polymer composition, characterized in that It comprises a polymer substrate and the bio-based plasticizer according to claim 1 or 2.

9. The polymer composition according to claim 8, characterized in that The polymer substrate includes at least one of polyvinyl chloride, a polymer containing an ester group, rubber and a thermoplastic elastomer.

10. The polymer composition according to claim 8, characterized in that The amount of the bio-based plasticizer added relative to the polymer substrate is 2 wt%-60 wt%.

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