Preparation method and application of carbon-sequestration and compatibilization type vegetable oil-based ether ester plasticizer

Abstract

The invention discloses a preparation method and application of a carbon sequestration and compatibilization type vegetable oil-based ether ester plasticizer, and the preparation method specifically comprises the following steps: (1) mixing vegetable oil acid, monoalkyl ether, a catalyst A and a dehydrating agent, and carrying out esterification reaction to obtain vegetable oil acid ether ester; (2) mixing the vegetable oleic acid ether ester, a catalyst B and organic acid, slowly dropwise adding H2O2, and carrying out epoxidation reaction to obtain epoxy vegetable oleic acid ether ester; and (3) carrying out catalytic cyclization reaction on the epoxy vegetable oil acid ether ester, a catalyst C and CO2, and carrying out extraction, washing and reduced pressure distillation to obtain the carbon-sequestration and compatibilization type vegetable oil-based ether ester plasticizer. The preparation method provided by the invention has the characteristics of easy operation, environmental protection, carbon sequestration and the like, and the prepared carbon sequestration and compatibilization type plant oil-based ether ester has the characteristics of good compatibility, high plasticizing efficiency and the like.

Description

Technical Field

[0001] The present application belongs to the technical field of novel plasticizer preparation, and in particular relates to a preparation method and application of a carbon-fixing and volume-enhancing vegetable oil-based ether ester plasticizer. Background Art

[0002] Carbon dioxide (CO2) is an important driver of a series of environmental problems such as accelerating global warming, climate change, frequent disasters, and melting of icebergs. The main application routes of CO2 in my country include chemical conversion into chemical products such as urea, inorganic carbonates, CO, salicylic acid, and carbonates, but the scale of conversion is far from meeting the requirements of my country's carbon neutrality goals. In recent years, it is necessary to research and develop new technologies for large-scale CO2 resource utilization, including CO2 hydrogenation to methanol, methane or oil products, CO2-methane reforming to synthesis gas, CO2-coke reduction to CO, CO2 and epoxide reaction to synthesize organic carbonates, CO2 electrocatalytic synthesis of chemicals and fuel technologies, etc.

[0003] Plasticizer is a polymer additive that can weaken the secondary bonds between material molecules, improve the processability, plasticity, flexibility, and stretchability of materials, reduce melt viscosity and glass transition temperature, and do not change the basic chemical properties of the plasticized materials. It has been widely used in many fields such as medical devices, automobile manufacturing, children's toys, food packaging, coatings, and electrical insulation. At present, the global consumption of plasticizers exceeds 8 million tons / a, and the market size exceeds US$19.5 billion. As the fastest-growing economy in the world, China is the world's largest producer and consumer of plasticizers, but the overall technical level of my country's plasticizer industry is relatively low, and toxic phthalate plasticizers account for more than 80% of the total production. Due to the lack of core preparation technology for high-quality and environmentally friendly plasticizers, many of my country's special and high-performance plasticizers are completely dependent on imports.

[0004] Vegetable oil is still considered one of the ideal raw materials for preparing bio-based plasticizers because of its wide availability, low price, non-toxicity and biodegradability. The structure of vegetable oil contains long-chain alkyl groups and active groups (carbon-carbon double bonds, carboxylates and hydrogen on the α carbon connected to the carboxylates). The former can improve the plasticizing performance by increasing the free volume of the plasticized material (PVC) resin; the latter can construct multifunctional PVC plasticizers through controllable chemical modification to meet different application requirements. However, the existing vegetable oil-based plasticizers have poor compatibility with PVC resins due to the high proportion of non-polar long-chain alkyl groups in their molecular structure. They are easy to migrate from the inside of PVC products to the surface, making them difficult to be used in high-end fields such as medical devices, food packaging, and children's toys.

[0005] Currently, the methods used to improve the compatibility of vegetable oil-based plasticizers with PVC can be divided into two categories according to their structure.The first is to introduce rigid aromatic groups: aromatic groups promote the increase of entropy (ΔS) of the plasticizer and PVC blending system (Bocqué, M.; Voirin, C.; Lapinte, V.; Caillol, S.; Robin, J. J. Petro-based and bio-based plasticizers: Chemical structures to plasticizing properties. J. Polym. Sci. Pol. Chem. 2016, 54, 11-33.), and polarized aromatic groups act as compatibilizers to give PVC long chains good elasticity; the second is to introduce polar polycarboxylate groups (Feng, G.; Hu, L.; Ma, Y.; Jia, P.; Hu, Y.; Zhang, M.; Liu, C.; Zhou, Y. Anefficient bio-based plasticizer for poly(vinyl chloride) from waste cooking oil and citric acid: Synthesis and evaluation in PVC films.J.Clean.Prod.2018,189,334–343.) or "hetero-oxy" groups (epoxy, phosphate, sulfate, etc.) [Omrain, L.; Ahmadi, A.; Farhadian, A.; Shendi, HK; Babanejad, N.; Nabid, M.R. Synthesis of a Bio-Based Plasticizer from Oleic Acid and Its Evaluation in PVC Formulations. Polym. Test2016,56,237–244; Jia, P.; Ma, Y.; Xia, H.; Zheng, M.; Feng, G.; Hu, L.; Zhang, M.; Zhou, Y. Clean Synthesis of Epoxidized Tung Oil Derivatives via Phase Transfer Catalyst and Thiol–ene Reaction: A Detailed Study. ACS Sustain.Chem.Eng.2018,6,13983–13994.] These polar groups interact with the polar part (CH-Cl) of PVC resin through Van der Waals force or hydrogen bond, promoting mutual dissolution, thereby improving the compatibility of plasticizer and PVC.However, the currently reported methods for modifying vegetable oil-derived plasticizers still have problems such as high dependence on the composition of vegetable oils (especially the content of linoleic acid and linolenic acid in the structure of vegetable oils), poor versatility, and complex preparation processes.

[0006] Therefore, developing core general preparation technologies for high-end, environmentally friendly bio-based plasticizers and breaking through the bottleneck of industry development are of great significance to promoting the upgrading of my country's plasticizer industry structure and meeting the high-quality development of industrial clusters such as medical devices, food / drug packaging, automobiles, and PLA green packaging. Summary of the invention

[0007] The technical problems to be solved by the present application include overcoming the problems of poor compatibility, easy migration and precipitation of plant oil-based plasticizers with plasticized materials (such as PVC or PLA, etc.) in the prior art; and also include solving the defects of the existing plant oil-based plasticizer modification methods such as high dependence on the composition of raw material plant oil, poor versatility, and complex preparation process, and providing a preparation method and application of a carbon-fixing and volume-enhancing plant oil-based ether ester plasticizer.

[0008] This application adopts the following technical solutions to solve the above technical problems:

[0009] First aspect:

[0010] The present application provides a method for preparing a carbon-fixing and compatibilizing vegetable oil-based ether ester plasticizer, which specifically comprises the following steps:

[0011] (1) mixing vegetable oil acid, monoalkyl ether, catalyst A and a dehydrating agent and performing an esterification reaction to obtain vegetable oil acid ether ester;

[0012] (2) slowly dropping H2O2 into the plant oil acid ether ester and catalyst B in an organic acid solution to carry out an epoxidation reaction to obtain an epoxidized plant oil acid ether ester;

[0013] (3) The epoxy plant oil acid ether ester, catalyst C and CO2 are subjected to a catalytic cyclization reaction, followed by extraction and washing to obtain a carbon-fixing and volume-enhancing plant oil-based ether ester plasticizer.

[0014] Preferably, the method for preparing the carbon-fixing and compatibilizing vegetable oil-based ether ester plasticizer is characterized by satisfying at least one of the following conditions:

[0015] The vegetable oleic acid includes one or more of soybean oleic acid, rubber seed oleic acid, eleostearic acid and rice bran oleic acid;

[0016] The monoalkyl ethers include polyol monoalkyl ethers;

[0017] The catalyst A comprises at least one of toluenesulfonic acid, sulfuric acid, cation exchange resin or activated carbon-supported sulfuric acid / p-toluenesulfonic acid;

[0018] The dehydrating agent includes at least one of cyclohexane and toluene;

[0019] The molar ratio of the vegetable oleic acid to the monoalkyl ether is 1:1-5;

[0020] The amount of the catalyst A is 1-5wt% of the mass of the vegetable oleic acid;

[0021] The amount of the dehydrating agent is 40-70wt% of the mass of the vegetable oleic acid;

[0022] The temperature of the esterification reaction is 110-140°C

[0023] The esterification reaction time is 5 to 8 hours;

[0024] The esterification reaction is followed by a refining treatment, wherein the refining treatment includes removing excess monoalkyl ether and dehydrating agent, adjusting pH to neutral, washing and dehydrating and drying operations.

[0025] Preferably, in the method for preparing the carbon-fixing and compatibilizing vegetable oil-based ether ester plasticizer, the general structural formula of the polyol monoalkyl ether is:

[0026]

[0027] In the formula, n is: 1 to 5, R1 is H or CH3, R2 is C 1-6 alkyl.

[0028] Preferably, the method for preparing the carbon-fixing and compatibilizing vegetable oil-based ether ester plasticizer is characterized by satisfying at least one of the following conditions:

[0029] The removing of excess monoalkyl ether and dehydrating agent comprises removing the low-boiling dehydrating agent and excess monoalkyl ether by a reduced pressure distillation method; the adjusting pH to neutral comprises: adjusting the pH of the system to neutral by using NaOH or NaHCO3 solution;

[0030] The dehydration includes removing the remaining water in the system by distillation under reduced pressure.

[0031] Preferably, the preparation method of the carbon-fixing and compatibilizing vegetable oil-based ether ester plasticizer satisfies at least one of the following conditions:

[0032] The catalyst B is a cation exchange resin;

[0033] The organic acid solution is formic acid or acetic acid solution;

[0034] The amount of the organic acid is 2-10% (based on the mass of vegetable oil ether ester);

[0035] The amount of H2O2 is 55-75% (based on the mass of vegetable oil ether ester);

[0036] The amount of the catalyst B is 0.2-1 wt % based on the mass of the vegetable oil ether ester;

[0037] The temperature of the epoxidation reaction is 60-70°C;

[0038] The epoxidation reaction time is 4 to 8 hours;

[0039] The epoxidation reaction is followed by a refining treatment, wherein the refining treatment includes washing, adjusting the pH to neutral, and dehydrating and drying operations.

[0040] Preferably, the preparation method of the carbon-fixing and compatibilizing vegetable oil-based ether ester plasticizer satisfies at least one of the following conditions:

[0041] The catalyst C includes one or more mixtures of Schiff base (Salen-Al) and CTAB;

[0042] The CO2 is industrial CO2;

[0043] The amount of the catalyst C is 2-6% based on the mass of the epoxy vegetable oil ether ester;

[0044] The catalytic cyclization reaction time is 12 to 24 hours;

[0045] The pressure of the catalytic cyclization reaction is 2 to 4 MPa;

[0046] The cyclization is carried out under stirring conditions, wherein the stirring speed is 800 r / min and the temperature of the catalytic cyclization reaction is 100-150° C.;

[0047] The extraction solvent is ethyl acetate;

[0048] The present application also provides a carbon-fixing and compatibilizing plant oil-based ether ester plasticizer, which is prepared by the above-mentioned preparation method of the carbon-fixing and compatibilizing plant oil-based ether ester plasticizer, and the carbon-fixing and compatibilizing plant oil-based ether ester plasticizer comprises the following general structural formula:

[0049]

[0050] Among them, R1=H or CH3, R2=C1-C6 alkyl, and n=1~5.

[0051] The present application also provides an application of the carbon-fixing and compatibilizing plant oil-based ether ester plasticizer as described in claim 7, which is used for plasticizing polylactic acid (PLA) plastics or plasticizing polyvinyl chloride (PVC) materials.

[0052] Second aspect:

[0053] In step (1), if the esterification reaction temperature is too high or the reaction time is too long, the product color will darken and the side reactions will increase; if the temperature is too low or the reaction time is too short, the esterification reaction will be incomplete, resulting in a lower yield of the target product. Excess diol monoalkyl ether and dehydrating agent are removed by refining treatment, and then the remaining liquid is washed with NaOH or NaHCO3 solution until the pH of the system is neutral; finally, dehydration is performed by reduced pressure distillation to obtain vegetable oil acid ether ester.

[0054] In step (2), if the amount of hydrogen peroxide is too little, the epoxy value of the product will be too low, and if the amount of hydrogen peroxide is too much, it will cause a waste of resources;

[0055] In step (3), during the cyclization process, the reaction mixture is heated to 120° C. and reacted for a certain period of time, then cooled to below 50° C., the gas is released, the pressure in the reactor is reduced, and the reactor is opened after cooling to room temperature to obtain a brown viscous liquid; the liquid is then extracted with ethyl acetate, washed with hot water, and finally distilled under reduced pressure to remove water to obtain a carbon-fixing and volume-enhancing vegetable oil-based ether ester plasticizer.

[0056] On the basis of conforming to the common sense in the art, the above-mentioned preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the present application.

[0057] The reagents and raw materials used in this application are commercially available.

[0058] The positive progress of the present application is that the present application provides a method for preparing a bio-based plasticizer using industrial CO2 and vegetable oil acid, which has the characteristics of easy operation, environmental protection, carbon fixation, etc., and the prepared carbon-fixing and compatibilizing vegetable oil-based ether ester has the characteristics of good compatibility and high plasticizing efficiency. Another purpose of the present invention is to provide the above-mentioned carbon-fixing and compatibilizing vegetable oil-based ether ester as a plasticizer for use in the plasticization of polylactic acid and PVC materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] The present application can be better understood by referring to the description given below in conjunction with the accompanying drawings. The accompanying drawings, together with the following detailed description, are included in this specification and form a part of this specification, and are used to further illustrate the preferred embodiments of the present application and explain the principles and advantages of the present application.

[0060] in:

[0061] Figure 1 For vegetable oleic acid (MA) 1 H NMR spectrum;

[0062] Figure 2 and vegetable oil ether esters (MA-n, n = 1,2,3,4) 1 H NMR spectrum;

[0063] Figure 3Epoxy vegetable oil ether ester (E-MA-n, n = 1,2,3,4) 1 H NMR spectrum;

[0064] Figure 4 It is a carbon-fixing and compatibilizing vegetable oil-based ether ester (C-MA-n, n=1,2,3,4). 1 H NMR spectrum. DETAILED DESCRIPTION

[0065] The present application is further described below by way of examples, but the present application is not limited to the scope of the examples. The experimental methods in the following examples without specifying specific conditions are selected according to conventional methods and conditions, or according to the product instructions.

[0066] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0067] The industrial-grade vegetable oil-derived acid (codenamed MA) in the following examples was provided by Anhui Hongtai New Materials Co., Ltd.;

[0068] The ethylene glycol methyl ether, diethylene glycol methyl ether, triethylene glycol methyl ether and tetraethylene glycol methyl ether in the following examples are all industrial grade and are produced by Jiangsu Yida Chemical Co., Ltd.;

[0069] The solid carbon-based catalysts in the following examples were prepared in the laboratory (the catalyst contained H + The loading amount was 8.03%); p-toluenesulfonic acid, cyclohexane, and H2O2 were provided by Nanjing Chemical Reagent Co., Ltd.;

[0070] NaOH and NaHCO3 in the following examples were provided by Nanjing Chemical Reagent Co., Ltd.; potassium hydrogen phthalate and anhydrous ethanol were provided by Xilong Scientific Co., Ltd.;

[0071] The concentrated sulfuric acid and ethyl acetate in the following examples were provided by Shanghai Aladdin Reagent Co., Ltd.; formic acid was provided by Shandong Pulis Chemical Co., Ltd.;

[0072] The ion exchange resins in the following examples were provided by Anhui Rongsheng Environmental Protection Water Treatment Co., Ltd.

[0073] In the following examples, hexadecyltrimethylammonium bromide (CTAB), aluminum chloride hexahydrate, and salicylaldehyde were provided by Sinopharm Chemical Reagent Co., Ltd.; polylactic acid (3052D) was provided by Nature Works; PVC powder (DG-1000K) was provided by Tianjin Dagu Chemical Co., Ltd.; dioctyl phthalate (DOP), epoxidized soybean oil (ESO), and diisononyl cyclohexane-1,2-dicarboxylate (DINCH) were provided by Shanghai MacLean Biochemical Technology Co., Ltd.

[0074] Example 1

[0075] The method for synthesizing vegetable oleic acid ethylene glycol monomethyl ether ester comprises the following steps: 113 g vegetable oleic acid and 152 g ethylene glycol monomethyl ether, 1.13 g p-toluenesulfonic acid as a catalyst, and 79.1 g dehydrating agent cyclohexane are added into a four-necked bottle, and the reaction is terminated after 8 hours at 110-120° C. The dehydrating agent cyclohexane and unreacted ethylene glycol methyl ether are recovered by vacuum distillation, and then the remaining liquid is washed with a 10 wt % NaHCO3 solution until the pH value of the system is neutral; finally, the vegetable oleic acid ethylene glycol monomethyl ether ester (MA-1) is dehydrated and dried by vacuum distillation, and the nuclear magnetic resonance image is as follows: Figure 1-Ⅰ -b as shown.

[0076] Example 2

[0077] The method for synthesizing vegetable oil diethylene glycol monomethyl ether ester comprises the following steps: 113g vegetable oil acid and 192g diethylene glycol monomethyl ether, 3.39g self-made solid acid catalyst, and 67.8g dehydrating agent toluene are added into a four-necked bottle, and the reaction is terminated after 7 hours at 110-120°C. The dehydrating agent toluene and unreacted diethylene glycol methyl ether are recovered by vacuum distillation, and then the remaining liquid is washed with 0.5mol / L NaOH solution until the pH of the system is neutral; finally, the vegetable oil diethylene glycol monomethyl ether ester (MA-2) is dehydrated and dried by vacuum distillation, and the nuclear magnetic resonance image is as follows: Figure 2-Ⅱ -b as shown.

[0078] Example 3

[0079] The method for synthesizing vegetable oil triethylene glycol monomethyl ether ester comprises the following steps: 113g vegetable oil acid and 131.26g triethylene glycol monomethyl ether, 4.52g self-made solid acid catalyst, and 56.5g dehydrating agent cyclohexane are added into a four-necked bottle, and the reaction is terminated after 6 hours at 110-140°C. The dehydrating agent cyclohexane and unreacted triethylene glycol methyl ether are recovered by vacuum distillation, and then the remaining liquid is washed with a 10wt% NaHCO3 solution until the pH of the system is neutral; finally, the vegetable oil triethylene glycol monomethyl ether ester (MA-3) is dehydrated and dried by vacuum distillation, and the nuclear magnetic resonance image is as follows: Figure 3-III -b as shown.

[0080] Example 4

[0081] The method for synthesizing vegetable oleic acid tetraethylene glycol monomethyl ether ester comprises the following steps: 113g vegetable oleic acid, 91.5g tetraethylene glycol monomethyl ether, 5.65g self-made solid acid catalyst, and 45.2g dehydrating agent toluene are added into a four-necked bottle, and the reaction is terminated after 5 hours at 110-140°C. The dehydrating agent toluene and unreacted tetraethylene glycol methyl ether are recovered by vacuum distillation, and then the remaining liquid is washed with 0.5mol / L NaOH solution until the pH of the system is neutral; finally, the vegetable oleic acid tetraethylene glycol monomethyl ether ester (MA-4) is dehydrated and dried by vacuum distillation, and the nuclear magnetic resonance image is as follows: Figure 4-IV -b as shown.

[0082] Example 5

[0083] Utilize the vegetable oil acid ethylene glycol monomethyl ether ester in Example 1 to synthesize epoxy vegetable oil acid ethylene glycol monomethyl ether ester, the steps are as follows: 120g of the above vegetable oil acid ethylene glycol monomethyl ether ester, 12g of formic acid and 0.24g of cation exchange resin are added to a four-necked bottle, the above mixed solution is heated to 60-65°C, 90g of H2O2 is slowly added dropwise using a constant pressure dropping funnel, and the reaction is terminated 8 hours after the addition is completed. Subsequently, the above mixed solution is added to a separating funnel for static stratification, the lower layer of formic acid and catalyst are removed, the upper layer of the crude oily product is neutralized (0.1mol / L NaOH) until the system is weakly alkaline, and then washed with warm water until neutral; finally, dehydrate and dry by means of reduced pressure distillation to obtain epoxy vegetable oil acid ethylene glycol monomethyl ether ester (E-MA-1), and the nuclear magnetic resonance image is as shown below Figure 1-Ⅰ -c.

[0084] Example 6

[0085] Utilize the vegetable oil acid diethylene glycol monomethyl ether ester in Example 2 to synthesize epoxy vegetable oil acid diethylene glycol monomethyl ether ester, the steps are as follows: 120g of the above vegetable oil acid diethylene glycol monomethyl ether ester, 10.8g of acetic acid and 0.36g of cation exchange resin are added to a four-necked bottle, the above mixed solution is heated to 60-65°C, 84g of H2O2 is slowly added dropwise using a constant pressure dropping funnel, and the reaction is terminated 7h after the addition is completed. Subsequently, the above mixed solution is added to a separating funnel for static stratification, the lower layer of acetic acid and catalyst are removed, the upper layer of the crude oil product is neutralized (0.1mol / L NaOH) until the system is weakly alkaline, and then washed with warm water until neutral; finally, dehydrated and dried by vacuum distillation to obtain epoxy vegetable oil acid diethylene glycol monomethyl ether ester (E-MA-2), and the nuclear magnetic spectrum is as shown in FIG. Figure 2-Ⅱ -c.

[0086] Example 7

[0087] Epoxy triethylene glycol monomethyl ether ester of vegetable oil acid is synthesized by using the triethylene glycol monomethyl ether ester of vegetable oil acid in Example 3, and the steps are as follows: 120g of the above triethylene glycol monomethyl ether ester of vegetable oil acid, 3.6g of formic acid and 1.08g of cation exchange resin are added to a four-necked bottle, the above mixed solution is heated to 65-70°C, 78g of H2O2 is slowly added dropwise using a constant pressure dropping funnel, and the reaction is terminated 5 hours after the addition is completed. Subsequently, the above mixed solution is added to a separating funnel for static stratification, the lower layer of formic acid and catalyst are removed, the upper layer of crude oil product is neutralized (0.1mol / L NaOH) until the system is weakly alkaline, and then washed with warm water until neutral; finally, dehydrate and dry by means of reduced pressure distillation to obtain epoxy triethylene glycol monomethyl ether ester of vegetable oil acid (E-MA-3), and the nuclear magnetic resonance image is as follows Figure 3-III -c.

[0088] Example 8

[0089] Utilize the vegetable oil acid tetraethylene glycol monomethyl ether ester in Example 4 to synthesize epoxy vegetable oil acid tetraethylene glycol monomethyl ether ester, the steps are as follows: 120g of the above vegetable oil acid tetraethylene glycol monomethyl ether ester, 2.4g of acetic acid and 1.20g of cation exchange resin are added to a four-necked bottle, the above mixed solution is heated to 65-70°C, 66g of H2O2 is slowly added dropwise using a constant pressure dropping funnel, and the reaction is terminated 4h after the addition is completed. Subsequently, the above mixed solution is added to a separating funnel for static stratification, the lower layer of acetic acid and catalyst are removed, the upper layer of the crude oil product is neutralized (0.1mol / L NaOH) until the system is weakly alkaline, and then washed with warm water until neutral; finally, dehydrated and dried by vacuum distillation to obtain epoxy vegetable oil acid tetraethylene glycol monomethyl ether ester (E-MA-4), and the nuclear magnetic spectrum is as follows Figure 4-IV -c.

[0090] Example 9

[0091] The epoxidized vegetable oil acid ethylene glycol monomethyl ether ester in Example 5 was used to synthesize the carbon-fixing and volume-enhancing vegetable oil-based ethylene glycol monomethyl ether ester, and the steps were as follows: 50g of epoxidized vegetable oil acid ethylene glycol monomethyl ether ester and 3.00g of catalyst were put into an autoclave (100mL) equipped with a thermocouple and a magnetic stirrer, and the air in the autoclave was removed by CO2 gas and then filled with CO2 gas to a pressure of 2.0MPa, and stirring was started (800r / min). After reacting at 100°C for 12h, the reactor was lowered to room temperature, and the remaining gas in the reactor was emptied to obtain a crude product. The crude product was separated by extraction with ethyl acetate to remove the catalyst, and the remaining liquid was washed with hot water (40-50°C), and finally the residual water was removed by reduced pressure distillation to obtain a carbon-fixing vegetable oil-based ethylene glycol monomethyl ether ester (C-MA-1), and the nuclear magnetic resonance image was as shown below. Figure 1-Ⅰ -d as shown.

[0092] Example 10

[0093] Using the epoxy vegetable oil acid diethylene glycol monomethyl ether ester in Example 6, carbon-fixing vegetable oil-based diethylene glycol monomethyl ether ester was synthesized, and the steps were as follows: 50g of epoxy vegetable oil acid diethylene glycol monomethyl ether ester and 2.50g of catalyst were put into an autoclave (100mL) equipped with a thermocouple and magnetic stirring, and the air in the autoclave was removed by CO2 gas, and then CO2 gas was filled to a pressure of 3.0MPa, and stirring was started (800r / min). After reacting at 120°C for 16h, the reactor was lowered to room temperature, and the remaining gas in the reactor was emptied to obtain a crude product. The crude product was separated by extraction with ethyl acetate to remove the catalyst, and the remaining liquid was washed with hot water (40-50°C), and finally the residual water was removed by reduced pressure distillation to obtain carbon-fixing vegetable oil-based diethylene glycol monomethyl ether ester (C-MA-2), and the nuclear magnetic resonance image was as shown below. Figure 2-Ⅱ -d as shown.

[0094] Embodiment 11

[0095] Using the epoxy vegetable oil triethylene glycol monomethyl ether ester in Example 7, carbon-fixing vegetable oil-based triethylene glycol monomethyl ether ester was synthesized, and the steps were as follows: 50g of epoxy vegetable oil triethylene glycol monomethyl ether ester and 1.50g of catalyst were put into an autoclave (100mL) with a thermocouple and magnetic stirring, and the air in the autoclave was removed by CO2 gas and then filled with CO2 gas to a pressure of 3.5MPa, and stirring was started (800r / min). After reacting at 140°C for 20h, the reactor was lowered to room temperature, and the remaining gas in the reactor was emptied to obtain a crude product. The crude product was separated by extraction with ethyl acetate to remove the catalyst, and the remaining liquid was washed with hot water (40-50°C), and finally the residual water was removed by reduced pressure distillation to obtain carbon-fixing vegetable oil triethylene glycol monomethyl ether ester (C-MA-3), and the nuclear magnetic resonance image was as follows Figure 3-III -d as shown.

[0096] Example 12

[0097] The epoxidized plant oil acid tetraethylene glycol monomethyl ether ester in Example 8 was used to synthesize carbon-fixing plant oil acid tetraethylene glycol monomethyl ether ester, and the steps were as follows: 50g of epoxidized plant oil acid tetraethylene glycol monomethyl ether ester and 1.00g of catalyst were put into an autoclave (100mL) equipped with a thermocouple and magnetic stirring, and the air in the autoclave was removed by CO2 gas, and then CO2 gas was filled in to a pressure of 4.0MPa, and stirring was started (800r / min). After reacting at 150°C for 24h, the reactor was lowered to room temperature, and the remaining gas in the reactor was emptied to obtain a crude product. The crude product was separated by extraction with ethyl acetate to remove the catalyst, and the remaining liquid was washed with hot water (40-50°C), and finally the residual water was removed by reduced pressure distillation to obtain carbon-fixing plant oil-based tetraethylene glycol monomethyl ether ester (C-MA-4), and the nuclear magnetic resonance image was as shown in the figure. Figure 4-IV -d as shown.

[0098] Effect Example 1

[0099] Put polylactic acid (PLA) particles (100 parts) and C-MA-1 (20 parts) prepared in Example 9 above into 60 ml of dichloromethane solvent, and stir thoroughly until a transparent and uniform liquid with a certain gloss, moderate viscosity is obtained. Pour the above solution into a polytetrafluoroethylene mold, and control the coating thickness to 1 mm. After the solvent evaporates, place the above product in an oven and dry it at 30-40°C to constant weight to obtain a transparent PLA film; then use a hot press to prepare 5 parallel PLA / C-MA-1 samples according to the test needs.

[0100] Put polylactic acid (PLA) particles (100 parts) and C-MA-2 (20 parts) prepared in Example 10 above into 60 ml of dichloromethane solvent, and stir thoroughly until a transparent and uniform liquid with a certain gloss, moderate viscosity is obtained. Pour the above solution into a polytetrafluoroethylene mold, and control the coating thickness to 1 mm. After the solvent evaporates, place the above product in an oven and dry it at 30-40°C to constant weight to obtain a transparent PLA film; then use a hot press to prepare 5 parallel PLA / C-MA-2 samples according to the test needs.

[0101] Put polylactic acid (PLA) particles (100 parts) and C-MA-3 (20 parts) prepared in Example 11 above into 60 ml of dichloromethane solvent, and stir thoroughly until a transparent and uniform liquid with a certain gloss, moderate viscosity is obtained. Pour the above solution into a polytetrafluoroethylene mold, and control the coating thickness to 1 mm. After the solvent evaporates, place the above product in an oven and dry it at 30-40°C to constant weight to obtain a transparent PLA film; then use a hot press to prepare 5 parallel PLA / C-MA-3 samples according to the test needs.

[0102] Put polylactic acid (PLA) particles (100 parts) and C-MA-4 (20 parts) prepared in Example 12 above into 60 ml of dichloromethane solvent, and stir thoroughly until a transparent and uniform liquid with a certain gloss, moderate viscosity is obtained. Pour the above solution into a polytetrafluoroethylene mold, and control the coating thickness to 1 mm. After the solvent evaporates, place the above product in an oven and dry it at 30-40°C to constant weight to obtain a transparent PLA film; then use a hot press to prepare 5 parallel PLA / C-MA-4 samples according to the test needs.

[0103] Comparative sample preparation

[0104] Put polylactic acid (PLA) particles (100 parts) and DOP (20 parts) into 60 ml of dichloromethane solvent and stir thoroughly until a transparent and uniform liquid with a certain gloss, moderate viscosity is obtained. Pour the above solution into a polytetrafluoroethylene mold and control the coating thickness to 1 mm. After the solvent evaporates, place the above product in an oven and dry it at 30-40°C to constant weight to obtain a transparent PLA film; then use a hot press to prepare 5 parallel PLA / DOP samples according to the test needs.

[0105] The application performance evaluation is shown in Table 1

[0106] Table 1. Application performance evaluation

[0107] Products <![CDATA[T g a (℃)]]> <![CDATA[Elongation at break (%) b > <![CDATA[Tensile strength (MPa) b > <![CDATA[Thermal decomposition temperature (°C) c > PLA / C-MA-1 39.2 281.5±19.3 8.9±0.7 240.1 PLA / C-MA-2 38.1 349.0±13.2 9.6±1.1 263.2 PLA / C-MA-3 37.3 365.4±23.2 11.3±1.2 267.9 PLA / C-MA-4 33.3 511.4±15.8 14.5±0.6 272.0 PLA / DOP 56.2 92.9±0.6 8.7±0.5 251.9

[0108] In Table 1, a Glass transition temperature (T g ) obtained from dynamic mechanical analysis (DMA) curve; b Elongation at break and tensile strength were determined by a universal testing machine; c Thermal decomposition temperature of PLA products after plasticization when the mass loss is 5%.

[0109] As shown in Table 1, the plasticizer prepared by the present invention can significantly improve the ductility of polylactic acid (PLA). Compared with the traditional petroleum-based DOP, the plasticizer prepared by the present application (C-MA-n, n = 2, 3, 4) can give PLA products better low temperature resistance, ductility and thermal stability, indicating that the plasticizer prepared by the present invention has the potential to completely replace DOP.

[0110] Effect Example 2

[0111] PVC powder (100 parts) and C-MA-1 (40 parts) prepared in Example 9 above, heat stabilizers: calcium stearate (1.5 parts) and zinc stearate (0.5 parts) were put into 60 mL of tetrahydrofuran solvent, stirred until the solution became a uniform transparent liquid, and then evenly spread on a glass surface dish. After standing at room temperature for 24 hours, it was moved to a vacuum drying oven and dried at 40°C for 72 hours to obtain a transparent PVC film. Finally, 5 parallel PVC / C-MA-1 samples were prepared according to the test needs.

[0112] PVC powder (100 parts) and C-MA-2 (40 parts) prepared in Example 10 above, heat stabilizers: calcium stearate (1.5 parts) and zinc stearate (0.5 parts) were put into 60 mL of tetrahydrofuran solvent, stirred until the solution became a uniform transparent liquid, and then evenly spread on a glass surface dish. After standing at room temperature for 24 hours, it was moved to a vacuum drying oven and dried at 40°C for 72 hours to obtain a transparent PVC film. Finally, 5 parallel PVC / C-MA-2 samples were prepared according to the test needs.

[0113] PVC powder (100 parts) and C-MA-3 (40 parts) prepared in Example 11 above, heat stabilizers: calcium stearate (1.5 parts) and zinc stearate (0.5 parts) were put into 60 mL of tetrahydrofuran solvent, stirred until the solution became a uniform transparent liquid, and then evenly spread on a glass surface dish. After standing at room temperature for 24 hours, it was moved to a vacuum drying oven and dried at 40°C for 72 hours to obtain a transparent PVC film. Finally, 5 parallel PVC / C-MA-3 samples were prepared according to the test needs.

[0114] PVC powder (100 parts) and C-MA-4 (40 parts) prepared in Example 12 above, heat stabilizers: calcium stearate (1.5 parts) and zinc stearate (0.5 parts) were put into 60 mL of tetrahydrofuran solvent, stirred until the solution became a uniform transparent liquid, and then evenly spread on a glass surface dish. After standing at room temperature for 24 hours, it was moved to a vacuum drying oven and dried at 40°C for 72 hours to obtain a transparent PVC film. Finally, 5 parallel PVC / C-MA-4 samples were prepared according to the test needs.

[0115] Comparative sample preparation

[0116] PVC powder (100 parts) and E-MA-3 (40 parts) prepared in Example 7 above, heat stabilizers: calcium stearate (1.5 parts) and zinc stearate (0.5 parts) were put into 60 mL of tetrahydrofuran solvent, stirred until the solution became a uniform transparent liquid, and then evenly spread on a glass surface dish. After standing at room temperature for 24 hours, it was moved to a vacuum drying oven and dried at 40°C for 72 hours to obtain a transparent PVC film. Finally, 5 parallel PVC / E-MA-3 samples were prepared according to the test needs.

[0117] PVC powder (100 parts) and DOP (40 parts), heat stabilizer: calcium stearate (1.5 parts), zinc stearate (0.5 parts) were put into 60mL tetrahydrofuran solvent, stirred until the solution was a uniform transparent liquid, evenly spread on a glass surface dish, left to volatilize at room temperature for 24 hours, and then moved to a vacuum drying oven at 40°C for 72 hours to obtain a transparent PVC film, and finally 5 parallel PVC / DOP samples were prepared according to the test needs. The application performance evaluation is shown in Table 2.

[0118] PVC powder (100 parts) and ESO (40 parts), heat stabilizer: calcium stearate (1.5 parts), zinc stearate (0.5 parts) were put into 60mL tetrahydrofuran solvent, stirred until the solution was a uniform transparent liquid, evenly spread in a glass surface dish, left to volatilize at room temperature for 24 hours, and then moved to a vacuum drying oven at 40°C for 72 hours to obtain a transparent PVC film, and finally 5 parallel PVC / ESO samples were prepared according to the test needs. The application performance evaluation is shown in Table 2.

[0119] PVC powder (100 parts) and DINCH (40 parts), heat stabilizer: calcium stearate (1.5 parts), zinc stearate (0.5 parts) were put into 60 mL of tetrahydrofuran solvent, stirred until the solution became a uniform transparent liquid, evenly spread on a glass surface dish, left to volatilize at room temperature for 24 hours, and then moved to a vacuum drying oven and dried at 40°C for 72 hours to obtain a transparent PVC film. Finally, 5 parallel PVC / DINCH samples were prepared according to the test needs, and the application performance evaluation is shown in Table 2.

[0120] Table 2. Application performance evaluation

[0121] Products <![CDATA[T g a (℃)]]> <![CDATA[Elongation at break (%) b > <![CDATA[Tensile strength (MPa) b > <![CDATA[Thermal decomposition temperature (°C) c > PVC / C-MA-1 -4.7 439.4±10.7 13.1±0.9 253.3 PVC / C-MA-2 -10.4 465.1±25.3 13.4±0.3 255.8 PVC / C-MA-3 -18.5 494.3±5.8 14.2±0.1 258.6 PVC / C-MA-4 -24.9 498.9±10.7 14.4±0.1 267.3 PVC / E-MA-3 0.9 481.6±11.4 13.1±0.7 247.1 PVC / DOP 17.6 359.7±6.0 13.6±0.3 228.3 PVC / ESO 15.1 350.8±1.6 13.0±1.3 245.1 PVC / DINCH 20.5 306.6±4.4 13.1±0.2 251.9

[0122] In the table, a Glass transition temperature (T g ) obtained from differential scanning calorimetry (DSC) curve; b Elongation at break and tensile strength were determined by a universal testing machine; c The thermal decomposition temperature of plasticized PVC products when the mass loss is 5%.

[0123] As shown in Table 2, the plasticizer prepared in the present invention can significantly improve the ductility of polyvinyl chloride (PVC). Compared with traditional petroleum-based DOP, DINCH and commercially available bio-based ESO, the plasticizer prepared in the present application can give PVC products better low temperature resistance, ductility and thermal stability, indicating that the plasticizer prepared in the present application has the potential to completely replace commercially available plasticizers.

[0124] Finally, it should be noted that in this application, the terms "comprises", "includes" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or apparatus that includes a series of elements includes not only those elements, but also other elements that are not explicitly listed, or also includes elements that are inherent to such process, method, article or apparatus.

[0125] Although the present application has been disclosed above through the description of the specific embodiments of the present application, it should be understood that those skilled in the art can design various modifications, improvements or equivalents to the present application within the spirit and scope of the attached scheme. These modifications, improvements or equivalents should also be considered to be included in the scope of protection claimed in the present application.

Claims

1. A method for preparing a carbon-fixing and compatibilizing vegetable oil-based ether ester plasticizer, characterized in that: The specific steps include: (1) mixing vegetable oil acid, monoalkyl ether, catalyst A and a dehydrating agent and performing an esterification reaction to obtain vegetable oil acid ether ester; (2) mixing the vegetable oil acid ether ester, catalyst B and organic acid solution, and then slowly dropping H2O2 into the mixture to carry out epoxidation reaction to obtain epoxy vegetable oil acid ether ester; (3) The epoxy plant oil acid ether ester, catalyst C and CO2 are subjected to a catalytic cyclization reaction, and then extracted, washed and distilled under reduced pressure to obtain a carbon-fixing and volume-enhancing plant oil-based ether ester plasticizer.

2. The method for preparing the carbon-fixing and compatibilizing vegetable oil-based ether ester plasticizer according to claim 1, characterized in that: At least one of the following conditions is met: The vegetable oleic acid includes one or more of soybean oleic acid, rubber seed oleic acid, eleostearic acid and rice bran oleic acid; The monoalkyl ethers include polyol monoalkyl ethers; The catalyst A comprises at least one of toluenesulfonic acid, sulfuric acid, cation exchange resin or activated carbon-supported sulfuric acid / p-toluenesulfonic acid; The dehydrating agent includes at least one of cyclohexane and toluene; The molar ratio of the vegetable oleic acid to the monoalkyl ether is 1:1-5; The amount of the catalyst A is 1-5 wt% of the vegetable oleic acid; The dehydrating agent is used in an amount of 40 to 70 wt% of the vegetable oleic acid; The temperature of the esterification reaction is 110-140°C The esterification reaction time is 5 to 8 hours; The esterification reaction is followed by a refining treatment, wherein the refining treatment includes removing excess monoalkyl ether and dehydrating agent, adjusting the pH to neutral, washing and dehydration operations.

3. The method for preparing the carbon-fixing and compatibilizing vegetable oil-based ether ester plasticizer according to claim 2, characterized in that: The general structural formula of the polyol monoalkyl ether is: In the formula, n is: 1 to 5, R1 is H or CH3, R2 is C 1-6 alkyl.

4. The method for preparing the carbon-fixing and volume-increasing vegetable oil acid ether ester plasticizer according to claim 2, characterized in that: At least one of the following conditions is met: The method for removing excess monoalkyl ether and dehydrating agent comprises removing the low-boiling-point dehydrating agent and excess monoalkyl ether by reduced pressure distillation; The adjusting the pH to neutral comprises: using NaOH or NaHCO3 solution to adjust the pH of the system to neutral; The dehydration includes removing the remaining water in the system by distillation under reduced pressure.

5. The method for preparing the carbon-fixing and compatibilizing vegetable oil-based ether ester plasticizer according to claim 1, characterized in that: At least one of the following conditions is met: The catalyst B is a cation exchange resin; The organic acid solution is formic acid or acetic acid solution; The amount of the organic acid is 2-10% based on the mass of the vegetable oil acid ether ester; The amount of H2O2 is 55-75% based on the mass of the vegetable oil ether ester; The amount of the catalyst B is 0.2-1 wt % based on the mass of the vegetable oil ether ester; The temperature of the epoxidation reaction is 60-70°C; The epoxidation reaction time is 4 to 8 hours; The epoxidation reaction is followed by a refining treatment, wherein the refining treatment includes washing, adjusting the pH to neutral, and dehydrating and drying operations.

6. The method for preparing the carbon-fixing and compatibilizing vegetable oil-based ether ester plasticizer according to claim 1, characterized in that: At least one of the following conditions is met: The catalyst C includes one or a mixture of Schiff base (Salen-Al) and CTAB; The CO2 is industrial CO2; The amount of the catalyst C is 2-6% based on the mass of the epoxy vegetable oil ether ester; The catalytic cyclization reaction time is 12 to 24 hours; The pressure of the catalytic cyclization reaction is 2 to 4 MPa; The cyclization is carried out under stirring, wherein the stirring speed is 800r / min; the catalytic cyclization reaction temperature is 100-150°C; The extraction solvent is ethyl acetate.

7. A carbon-fixing and compatibilizing plant oil-based ether ester plasticizer, which is prepared by the preparation method of the carbon-fixing and compatibilizing plant oil-based ether ester plasticizer according to any one of claims 1 to 6, wherein the carbon-fixing and compatibilizing plant oil-based ether ester plasticizer comprises the following general structural formula: in, R1=H or CH3, R2=C1-C6 alkyl, n=1~5.

8. An application of the carbon-fixing and compatibilizing plant oil-based ether ester plasticizer as claimed in claim 7, characterized in that: Used for plasticizing polylactic acid (PLA) plastics or plasticizing polyvinyl chloride (PVC) materials.

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