Bio-based isosorbide carbonate plasticizer as well as preparation method and application thereof

Abstract

The invention discloses a bio-based isosorbide carbonate plasticizer and a preparation method and application thereof, and relates to the technical field of plastic processing assistants.The preparation method of the bio-based isosorbide carbonate plasticizer comprises the steps that in the atmosphere of protective gas, diester carbonate and isosorbide serve as raw materials to be subjected to transesterification with a catalyst; and after the reaction is completed, carrying out post-treatment to obtain the isosorbide carbonate plasticizer. The isosorbide carbonate plasticizer disclosed by the invention can effectively reduce the melting temperature and melt viscosity of a material, improve the processability of the material, increase the flexibility of the material and improve the optical transmittance of the material. The preparation method disclosed by the invention has the characteristics of being simple in process, green and environment-friendly, easily available in raw materials, easy in catalyst separation and relatively high in product yield, and is an efficient and environment-friendly preparation process of isosorbide carbonate.

Description

Technical Field

[0001] The invention relates to the technical field of plastic processing aids, and more particularly to a bio-based isosorbide carbonate plasticizer and a preparation method and application thereof. Background Art

[0002] With the growth of the world population and the progress of social economy, oil resources are decreasing day by day, which is not conducive to the sustainable development of society. As a bio-based renewable resource, isosorbide can be directly converted from glucose and cellulose, which has attracted the attention of researchers at home and abroad. With the deepening of research, it is found that isosorbide and isosorbide derivatives have excellent performance and good compatibility, and are gradually applied to food, medicine, plastics, cosmetics, liquid crystal materials, polymer modification and other fields. At present, the preparation of isosorbide esters is mainly obtained by esterification of isosorbide and carboxylic acid. As a new type of bio-based plasticizer, its addition can weaken the interaction between polymer molecules, reduce the melting temperature and melt viscosity, and is often used to improve the processing properties of polymer materials. At the same time, it also has a certain improvement on the flexibility and optical transmittance of the materials.

[0003] CN 10868998 A discloses a method for preparing a carboxylic acid isosorbide plasticizer, wherein sorbitol is used as a raw material, and a dehydration reaction is carried out under the action of an acidic catalyst to obtain isosorbide; and the isosorbide and fatty acids are mixed at 100-180°C for esterification reaction. However, this esterification reaction usually uses a strong acid as a catalyst, such as concentrated sulfuric acid, p-toluenesulfonic acid, etc. After the reaction is completed, p-toluenesulfonic acid and sulfuric acid will be mutually soluble in the esterification product. In the process of product purification, multiple steps such as washing and extraction with a saturated sodium chloride aqueous solution, pH adjustment, reduced pressure distillation, purification, and activated carbon decolorization are required to remove the strong acid in the product and obtain isosorbide ester.

[0004] CN 114085231 A discloses a method for preparing a synthetic carboxylic acid isosorbide ester plasticizer, which uses isosorbide as a raw material, adds a monocarboxylic acid and an acidic catalyst, stirs and performs nitrogen purging, reacts at 40-95° C., and after the reaction is completed, performs extraction washing, reduced pressure distillation and other methods to obtain the isosorbide plasticizer. However, the reaction process and post-treatment process are complicated and cumbersome, and a lot of acidic waste liquid will be generated, which is not environmentally friendly.

[0005] Therefore, developing a method for efficiently preparing isosorbide ester plasticizer has important scientific significance and research value. Summary of the invention

[0006] In order to solve the problems existing in the prior art, the present invention provides a bio-based isosorbide carbonate plasticizer and a preparation method and application thereof. The isosorbide carbonate plasticizer of the present invention can effectively reduce the melting temperature and melt viscosity of the material, improve the processing performance of the material, increase the flexibility of the material, and enhance the optical transmittance of the material. The preparation method of the present invention has the characteristics of simple process, green and environmental protection, easy availability of raw materials, easy separation of catalysts, and high product yield, and is an efficient and environmentally friendly preparation process of isosorbide carbonate.

[0007] One of the purposes of the present invention is to provide a bio-based isosorbide carbonate plasticizer, the isosorbide carbonate plasticizer having the structural formula:

[0008]

[0009] wherein R1 and R2 are independently selected from -CH3, -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3, -(CH2)4CH3, -(CH2)5CH3, -(CH2)6CH3, -(CH2)7CH3, -(CH2)2OH, -(CH2)3OH, -CH2CH(CH3)OH, -C(CH3)3, R1 and R2 may be the same or different.

[0010] The second object of the present invention is to provide a method for preparing a bio-based isosorbide carbonate plasticizer, the method comprising:

[0011] In a protective gas atmosphere, carbonic acid diester and isosorbide are used as raw materials and a catalyst to carry out an ester exchange reaction; after the reaction is completed, post-treatment is performed to obtain the isosorbide carbonate plasticizer.

[0012] Preferably,

[0013] The molar ratio of isosorbide to carbonic acid diester is 1:(0.5-14), preferably 1:(1-8);

[0014] The mass ratio of isosorbide to catalyst is 100:(0.001-1), preferably 100:(0.01-0.1).

[0015] Preferably,

[0016] The carbonic acid diester is at least one of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, di-n-butyl carbonate, dipentyl carbonate, dihexyl carbonate, diheptyl carbonate, dioctyl carbonate, diethyl oxalate, di-tert-butyl dicarbonate, ethylene carbonate, propylene carbonate, trimethylene carbonate, and diphenyl carbonate.

[0017] Preferably,

[0018] The catalyst is a supported solid base catalyst;

[0019] Preferably,

[0020] The loading amount of the alkali metal compound of the supported solid base catalyst on the surface of the carrier is 1%-80%, preferably 20%-60%;

[0021] The calcination temperature of the carrier of the supported solid base catalyst is 100°C-800°C, preferably 200°C-600°C.

[0022] Preferably,

[0023] The carrier of the supported solid base catalyst is at least one of magnesium oxide, calcium oxide, zinc oxide, aluminum oxide, lanthanum oxide, titanium dioxide and tin dioxide; and / or,

[0024] The alkali metal compound supported on the surface of the carrier of the supported solid base catalyst is at least one or more of alkali metal hydroxides, alkali metal bicarbonates, alkali metal carbonates, alkali metal halides, alkali metal bisulfites, alkali metal sulfites, and alkali metal acetates, preferably at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, lithium fluoride, sodium fluoride, potassium fluoride, lithium bisulfite, sodium bisulfite, potassium bisulfite, lithium sulfite, sodium sulfite, potassium sulfite, lithium acetate, sodium acetate, potassium acetate, cesium acetate, lithium acetylacetonate, and sodium acetylacetonate.

[0025] The supported solid base catalyst can be specifically prepared by the method disclosed in CN 110003458 A, and the invention name is a supported solid base catalyst and its application: using the impregnation method, adding alkali metal compounds of different concentrations to the carrier, adding deionized water and magnetic stirring for three hours, and then placing it in a 100°C oven to stand and dry for 12 hours to obtain a solid. After grinding, the solid powder is placed in a muffle furnace and roasted at a temperature set at 200 to 800 degrees for 5 hours to obtain a supported solid base catalyst. The loading amount and calcination temperature are quantitative indicators of the active substance content and morphological characteristics in the catalyst. The appropriate calcination temperature and loading amount can cause the catalyst to react in situ to generate new strong alkaline active centers such as KMgF3 and K2MgF4, improve the strength and quantity of the carrier surface, and improve the stability of the alkaline site.

[0026] Preferably,

[0027] The temperature of the transesterification reaction is 90-150°C, preferably 90-120°C;

[0028] The transesterification reaction time is 1-15h, preferably 6-8h;

[0029] The stirring speed of the transesterification reaction is 10-60 rpm, preferably 15-30 rpm.

[0030] Preferably,

[0031] The post-treatment includes suction filtration and reduced pressure distillation of the reaction solution after the reaction is completed.

[0032] The specific plan is as follows:

[0033] 1) In a protective gas atmosphere, carbonic acid diester and isosorbide are used as raw materials and a supported solid base is used as a catalyst and added into a reaction kettle, and an ester exchange reaction is carried out at a reaction temperature of 90-150° C. to obtain an ester exchange reaction liquid, and the reaction formula thereof is shown in the following formula;

[0034] 2) The ester exchange reaction liquid is filtered and distilled under reduced pressure to obtain isosorbide carbonate plasticizer.

[0035]

[0036] The third object of the present invention is to provide a bio-based isosorbide carbonate plasticizer prepared by the preparation method.

[0037] A fourth object of the present invention is to provide an application of a bio-based isosorbide carbonate plasticizer as a plastic processing aid.

[0038] Compared with the prior art, the present invention has the following beneficial effects:

[0039] 1) The method of the present invention uses carbonic acid diester and isosorbide as raw materials for preparing isosorbide carbonate, and the raw material selection range is wide. The transesterification method has mild reaction conditions, the reaction process does not cause environmental pollution, and the reaction product does not contain toxic substances. It is an efficient, green and low-cost preparation method.

[0040] 2) The preparation method of the present invention uses a solid base as a catalyst, and by balancing the activity of the internal and external hydroxyl groups in isosorbide, the nucleophilicity of the oxygen atoms of the internal and external hydroxyl groups in isosorbide and the electrophilicity of the carbonyl carbon of the carbonic acid diester are improved, thereby suppressing the occurrence of the methylation side reaction, promoting the forward transesterification reaction, and improving the yield of isosorbide carbonate. This catalyst not only has excellent thermal stability and catalytic activity, but also can be easily separated as a heterogeneous catalyst, effectively avoiding the influence of catalyst residue on isosorbide carbonate.

[0041] 3) The isosorbide carbonate prepared by the present invention is a bio-based intermediate. When used as a plasticizer, it can weaken the intermolecular forces of the material, reduce the melting temperature and melt viscosity, improve the plasticity of the material, increase the elongation at break of the material, and enhance the optical transmittance of the material. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 This is the 1H-NMR graph of the isosorbide carbonate plasticizer prepared in Example 3 of the present invention after being purified by column chromatography;

[0043] Figure 2 The isosorbide carbonate plasticizer prepared in Example 3 of the present invention was purified by column chromatography. 14 C-NMR spectrum;

[0044] Figure 3 This is a mass spectrum of the isosorbide carbonate plasticizer prepared in Example 3 of the present invention after purification by column chromatography.

[0045] 1 HNMR (400MHz, CDCl3): d=5.09–5.04(m,2H),4.87(t,1H),4.53(d,1H),4.08–4.00(m,2H),3.93–3.85(m,2H),3.80(s,3H),3.78ppm(s,3H);

[0046] 13 C NMR (400MHz, CDCl3): d=155.14,154.82,85.88,81.25,80.90,76.81,73.26,70.52,55.18,55.14ppm;

[0047] HRMS (ESI) m / z: 262.07

[0048] Combination Figure 1 The hydrogen spectrum of Figure 2 The carbon spectrum and Figure 3 The mass spectrum of isosorbide carbonate was proved to be synthesized, and its molecular formula is: 10 H 14 O8. DETAILED DESCRIPTION

[0049] The present invention is described in detail below in conjunction with specific drawings and embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by those skilled in the art based on the content of the present invention still fall within the scope of protection of the present invention.

[0050] The raw materials used in the examples of the present invention are all commercially available products, and their specific information is shown in Table 1 below.

[0051] Table 1

[0052] raw material source Dimethyl carbonate Chengdu Longke Chemicals Co., Ltd. Isosorbide Jinan Yuteng Pharmaceutical Co., Ltd. Potassium fluoride Shanghai Adamas Reagent Co., Ltd. Nano magnesium oxide Shanghai Dibai Biotechnology Co., Ltd. Diphenyl carbonate Chongqing Changan Chemical Co., Ltd. Diethyl carbonate Chengdu Longke Chemicals Co., Ltd. Lithium carbonate Shanghai MacLean Biochemical Technology Co., Ltd. Titanium Dioxide Shanghai Yuanye Biotechnology Co., Ltd. Aluminum oxide Shanghai Dibai Biotechnology Co., Ltd. Potassium carbonate Shanghai MacLean Biochemical Technology Co., Ltd. Di-n-butyl carbonate Chengdu Longke Chemicals Co., Ltd. PET Beijing Huarui Xincheng Technology Co., Ltd. PVC powder Dongguan Zhangmutou Tesulang Chemical Co., Ltd. Calcium zinc stabilizer Beijing Qisong Biotechnology Co., Ltd.

[0053] Example 1

[0054] The preparation method of the supported solid base catalyst in this embodiment is as follows: 1g of KF is added to 9g of MgO, and 10g of deionized water is added. After magnetic stirring for three hours, the mixture is placed in a 100°C oven and dried for 12 hours to obtain a solid. After grinding, the solid powder is placed in a muffle furnace and calcined at a temperature set at 500°C for 5 hours to obtain a catalyst 10%-KF / MgO-500°C.

[0055] Under nitrogen atmosphere, 5g of isosorbide, 30g of dimethyl carbonate (the molar ratio of isosorbide to dimethyl carbonate is 1:10) and 0.01g of the above-prepared catalyst 10%-KF / MgO-500°C are added to a three-necked flask equipped with a magnetic stirrer, and the reaction is carried out for 6 hours at an ester exchange temperature of 120 degrees Celsius, and the stirring speed is 20rpm. The ester exchange reaction liquid is successively filtered and distilled under reduced pressure to obtain an isosorbide carbonate plasticizer (structural formula is as follows). The product is a light yellow oily liquid, and the isosorbide conversion rate is 25.12% by gas chromatography analysis; the yield of methanol is 18.9%; and the yield of isosorbide carbonate is 13.46%.

[0056]

[0057] Example 2

[0058] The preparation method of the supported solid base catalyst in this embodiment is as follows: 2 g of KF is added to 8 g of MgO, and 10 g of deionized water is added. After magnetic stirring for three hours, the mixture is placed in a 100°C oven and dried for 12 hours to obtain a solid. After grinding, the solid powder is placed in a muffle furnace and calcined at a temperature set at 500°C for 5 hours to obtain a catalyst 20%-KF / MgO-500°C.

[0059] The preparation method of this embodiment is the same as that of Example 1, except that the loading amount of the catalyst 20%-KF / MgO-500°C is increased, and the isosorbide conversion rate analyzed by gas chromatography is 71.12%; the yield of methanol is 45.82%; and the yield of isosorbide carbonate is 46.53%.

[0060] Example 3

[0061] The preparation method of the supported solid base catalyst in this embodiment is as follows: 4 g of KF is added to 6 g of MgO, and 10 g of deionized water is added. After magnetic stirring for three hours, the mixture is placed in a 100°C oven and dried for 12 hours to obtain a solid. After grinding, the solid powder is placed in a muffle furnace and calcined at a temperature set at 500°C for 5 hours to obtain a catalyst 40%-KF / MgO-500°C.

[0062] The preparation method of this embodiment is the same as that of Example 1, except that: the loading amount of the catalyst 40%-KF / MgO-500°C is increased, and the isosorbide conversion rate analyzed by gas chromatography is 99.99%; the yield of methanol is 99.96%; and the yield of isosorbide carbonate is 92.63%.

[0063] Example 4

[0064] The preparation method of the supported solid base catalyst in this embodiment is as follows: 5 g of KF is added to 5 g of MgO, and 10 g of deionized water is added. After magnetic stirring for three hours, the mixture is placed in a 100°C oven and dried for 12 hours to obtain a solid. After grinding, the solid powder is placed in a muffle furnace and calcined at a temperature set at 500°C for 5 hours to obtain a catalyst 50%-KF / MgO-500°C.

[0065] The preparation method of this embodiment is the same as that of embodiment 1, except that: the loading amount of the catalyst 50%-KF / MgO-500°C is increased, and the isosorbide conversion rate analyzed by gas chromatography is 33.18%; the yield of methanol is 19.12%; and the yield of isosorbide carbonate is 3.46%.

[0066] Example 5

[0067] The preparation method of the supported solid base catalyst in this embodiment is as follows: 4 g of KF is added to 6 g of MgO, and 10 g of deionized water is added. After magnetic stirring for three hours, the solid is placed in a 100°C oven and dried for 12 hours to obtain a solid. After grinding, the solid powder is placed in a muffle furnace and calcined at a temperature set at 200°C for 5 hours to obtain a catalyst 40%-KF / MgO-200°C.

[0068] The preparation method of this embodiment is the same as that of embodiment 4, except that the calcination temperature of the catalyst 40%-KF / MgO-200°C is lowered, and the isosorbide conversion rate analyzed by gas chromatography is 96.95%; the yield of methanol is 70.61%; and the yield of isosorbide carbonate is 76.53%.

[0069] Example 6

[0070] The preparation method of the supported solid base catalyst in this embodiment is as follows: 4 g of KF is added to 6 g of MgO, and 10 g of deionized water is added. After magnetic stirring for three hours, the mixture is placed in a 100°C oven and dried for 12 hours to obtain a solid. After grinding, the solid powder is placed in a muffle furnace and calcined at a temperature set at 800°C for 5 hours to obtain a catalyst 40%-KF / MgO-800°C.

[0071] The preparation method of this embodiment is the same as that of Example 4, except that the calcination temperature of the catalyst 40%-KF / MgO-800°C is increased, and the isosorbide conversion rate analyzed by gas chromatography is 99.99%; the yield of methanol is 34.06%; and the yield of isosorbide carbonate is 46.21%.

[0072] Example 7

[0073] The preparation method of the supported solid base catalyst in this embodiment is as follows: 1g of K2CO3 is added to 9g of Al2O3, and 10g of deionized water is added. After magnetic stirring for three hours, the solid is placed in a 100°C oven and dried for 12 hours to obtain a solid. After grinding, the solid powder is placed in a muffle furnace and calcined at a temperature set at 500°C for 5 hours to obtain a catalyst 10%-K2CO3 / Al2O3-500°C.

[0074] Under nitrogen atmosphere, 5g of isosorbide, 40g of diethyl carbonate (the molar ratio of isosorbide to diethyl carbonate is 1:10) and 0.01g of catalyst 10%-K2CO3 / Al2O3-500°C were added into a three-necked flask equipped with magnetic stirring, and the reaction was carried out at an ester exchange temperature of 120°C for 6 hours, and the stirring speed was 20rpm. The ester exchange reaction liquid was filtered and vacuum distilled in sequence to obtain an isosorbide carbonate plasticizer (structural formula is as follows). The isosorbide conversion rate was 64.75% by gas chromatography analysis; the ethanol yield was 34.06%; and the yield of isosorbide carbonate was 9.07%.

[0075]

[0076] Example 8

[0077] The preparation method of the supported solid base catalyst in this embodiment is as follows: 1g of KF is added to 9g of Al2O3, and 10g of deionized water is added. After magnetic stirring for three hours, the mixture is placed in a 100°C oven and dried for 12 hours to obtain a solid. After grinding, the solid powder is placed in a muffle furnace and calcined at a temperature set at 500°C for 5 hours to obtain a catalyst 10%-KF / Al2O3-500°C.

[0078] Under nitrogen atmosphere, 5g of isosorbide, 23.6g of di-n-butyl carbonate (the molar ratio of isosorbide to n-butyl carbonate is 1:4) and 0.01g of catalyst 10%-KF / Al2O3-500°C were added into a three-necked flask equipped with magnetic stirring, and the reaction was carried out at an ester exchange temperature of 120°C for 6 hours, and the stirring speed was 20rpm. The ester exchange reaction liquid was filtered and vacuum distilled in sequence to obtain an isosorbide carbonate plasticizer (structural formula is as follows). The isosorbide conversion rate was 86.32% by gas chromatography analysis; the yield of n-butanol was 67.83%; and the yield of isosorbide carbonate was 23.3%.

[0079]

[0080] Example 9

[0081] The preparation method of the supported solid base catalyst in this embodiment is as follows: 1g of KF is added to 9g of TiO2, and 10g of deionized water is added. After magnetic stirring for three hours, the solid is placed in a 100°C oven and dried for 12 hours to obtain a solid. After grinding, the solid powder is placed in a muffle furnace and calcined at a temperature set at 500°C for 5 hours to obtain a catalyst 10%-KF / TiO2-500°C.

[0082] Under nitrogen atmosphere, 5g of isosorbide, 7.33g of diphenyl carbonate (the molar ratio of isosorbide to diphenyl carbonate is 1:1) and 0.01g of catalyst 10%-KF / TiO2-500°C were added into a three-necked flask equipped with magnetic stirring, and the reaction was carried out at an ester exchange temperature of 200°C for 6 hours, and the stirring speed was 20rpm. The ester exchange reaction liquid was filtered and vacuum distilled in sequence to obtain an isosorbide carbonate plasticizer (structural formula is as follows). The isosorbide conversion rate was 39.99% by gas chromatography analysis; the phenol yield was 17.73%; and the isosorbide carbonate yield was 13.12%.

[0083]

[0084] Example 10

[0085] The preparation method of the supported solid base catalyst in this embodiment is as follows: 1g of Li2CO3 is added to 9g of TiO2, and 10g of deionized water is added. After magnetic stirring for three hours, the solid is placed in a 100°C oven and dried for 12 hours to obtain a solid. After grinding, the solid powder is placed in a muffle furnace and calcined at a temperature set at 500°C for 5 hours to obtain a catalyst 10%-Li2CO3 / TiO2-500°C.

[0086] Under nitrogen atmosphere, 5g of isosorbide, 7.33g of diphenyl carbonate (the molar ratio of isosorbide to diphenyl carbonate is 1:1) and 0.01g of catalyst 10%-Li2CO3 / TiO2-500℃ were added into a three-necked flask equipped with magnetic stirring, and the reaction was carried out at an ester exchange temperature of 200℃ for 6 hours, and the stirring speed was 20rpm. The ester exchange reaction liquid was filtered and vacuum distilled in sequence to obtain an isosorbide carbonate plasticizer. The isosorbide conversion rate was 19.76% by gas chromatography analysis; the yield of phenol was 10.63%; and the yield of isosorbide carbonate was 9.73%.

[0087] It can be seen from the experimental results of the above Examples 1-4 that, as the loading amount of the alkali metal in the supported solid base catalyst increases, the yield of isosorbide carbonate first increases and then decreases, and the optimal loading amount is about 40%; it can be seen from the experimental results of Examples 3, 5 and 6 that, as the calcination temperature of the carrier in the supported solid base catalyst increases, the yield of isosorbide carbonate also shows a trend of first increasing and then decreasing.

[0088] 100g PET powder and different proportions of isosorbide carbonate plasticizer (DC in the table) prepared in Example 3 were mixed evenly and put into an oven for drying. Dumbbell-shaped modified PET strips with a width of 2mm and a thickness of 1mm were obtained by hot pressing using a screw extruder in accordance with ISO 527-2:1993. The elongation at break and tensile strength of the material before and after modification were measured using an electronic universal testing machine (NKK 3010D). The results are shown in Table 2.

[0089] Table 2

[0090] Material Tensile strength MPa Elongation at break % PET 41.85±20.63 2.5±1 PET+5%DC 46.72±27.41 10.88±5.15 PET+15%DC 25.4±14.36 8.14±0.87 PET+25%DC 23.22±15.72 4.38±1.96

[0091] As can be seen from Table 2, the bio-based isosorbide carbonate plasticizer prepared by the present invention is added to the material as an external plasticizer to weaken the interaction between polymer molecules, while improving the flexibility of the material to a certain extent and improving the brittleness of the material.

[0092] The sample weighing more than 4 mg was placed in a crucible under the protection of N2 flow (flow rate of 50 mL / min), first cooled to -70 ° C, then heated to 200 ° C at a rate of 10 ° C / min for the first scan; kept at 200 ° C for 5 min, then cooled to -70 ° C at a rate of 10 ° C / min for the second scan; finally heated to 200 ° C at a rate of 10 ° C / min for the third scan. The PET material before and after plasticization was thermodynamically characterized using a differential scanning calorimeter (Mettler Toledo, USA) with ASTD D3418-2003 as the standard, and the results are shown in Table 3.

[0093] Table 3

[0094] Material Glass transition temperature (Tg) PET 78℃ PET+5%DC 61℃ PET+15%DC Below 30℃

[0095] From the test results in Table 3, it can be seen that the addition of plasticizer reduces the melting temperature and melt viscosity of the material, improves the processing performance, and increases the fluidity during molding.

[0096] The weight loss rate of PVC powder modified by isosorbide plasticizer was tested with reference to the patent with publication number CN108658998A, entitled A kind of isosorbide plasticizer and its preparation method and application. Test method: 500g PVC powder and 15g calcium zinc stabilizer were mixed with different contents of isosorbide carbonate plasticizer prepared in Example 3 to obtain a mixture, and the mixture was placed on a hot press at 160°C for 10 minutes, and the modified PVC was obtained by hot pressing. The modified PVC was dried at 25°C for 48h, weighed to obtain m1, and then the sample was dried at 70°C for 24h, and weighed again to obtain the mass m2. The weight loss rate of the modified PVC was obtained by the formula (m1-m2) / m1, and the test results are shown in Table 4 (wherein, the data of PVC+isosorbide carbonate is the data of Application Example 1 in Table 2 of the specific implementation method of the reference patent).

[0097] Table 4

[0098] Material Weight loss rate (%) PVC 0.00％ PVC+5%DC 0.01％ PVC+15%DC 0.21％ PVC+isosorbide carboxylate 0.35％

[0099] The weight loss rate data can reflect the ability of the plasticizer to volatilize and dissipate into the air or decompose under heat to a certain extent during the processing process. The smaller the weight loss rate of the plasticizer, the better the durability and stability of the plasticizer. From the data comparison in Table 4, it can be seen that the weight loss rate of isosorbide carbonate as a plasticizer is relatively small, and its durability and stability are better than the current isosorbide carboxylate, and it has better commercial effects.

[0100] It can be seen from the above test results that the isosorbide ester plasticizer provided by the present invention has good plasticizing durability and stability. At the same time, as a bio-based plasticizer, its preparation method is more convenient than the preparation method of carboxylic acid isosorbide plasticizer in the prior art, and can be obtained without complicated post-processing, which protects the environment and saves costs.

[0101] The embodiments and product examples described above are only descriptions of the preferred modes of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field shall fall within the scope of protection determined by the claims of the present invention.

Claims

1. A bio-based isosorbide carbonate plasticizer, characterized in that The isosorbide carbonate plasticizer structural formula is: wherein R1 and R2 are independently selected from -CH3, -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3, -(CH2)4CH3, -(CH2)5CH3, -(CH2)6CH3, -(CH2)7CH3, -(CH2)2OH, -(CH2)3OH, -CH2CH(CH3)OH, -C(CH3)3, R1 and R2 may be the same or different.

2. A method for preparing the bio-based isosorbide carbonate plasticizer according to claim 1, characterized in that The method comprises: In a protective gas atmosphere, carbonic acid diester and isosorbide are used as raw materials and a catalyst to carry out an ester exchange reaction; after the reaction is completed, post-treatment is performed to obtain the isosorbide carbonate plasticizer.

3. The method for preparing the bio-based isosorbide carbonate plasticizer according to claim 2, characterized in that: The molar ratio of isosorbide to carbonic acid diester is 1:(0.5-14), preferably 1:(1-8); The mass ratio of isosorbide to catalyst is 100:(0.001-1), preferably 100:(0.01-0.1).

4. The method for preparing the bio-based isosorbide carbonate plasticizer according to claim 2, characterized in that: The carbonic acid diester is at least one of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, di-n-butyl carbonate, dipentyl carbonate, dihexyl carbonate, diheptyl carbonate, dioctyl carbonate, diethyl oxalate, di-tert-butyl dicarbonate, ethylene carbonate, propylene carbonate, trimethylene carbonate, and diphenyl carbonate.

5. The method for preparing the bio-based isosorbide carbonate plasticizer according to claim 2, characterized in that: The catalyst is a supported solid base catalyst; Preferably, The loading amount of the alkali metal compound of the supported solid base catalyst on the surface of the carrier is 1%-80%, preferably 20%-60%; The calcination temperature of the carrier of the supported solid base catalyst is 100°C-800°C, preferably 200°C-600°C.

6. The method for preparing the bio-based isosorbide carbonate plasticizer according to claim 5, characterized in that: The carrier of the supported solid base catalyst is at least one of magnesium oxide, calcium oxide, zinc oxide, aluminum oxide, lanthanum oxide, titanium dioxide and tin dioxide; and / or, The alkali metal compound supported on the surface of the carrier of the supported solid base catalyst is at least one or more of alkali metal hydroxides, alkali metal bicarbonates, alkali metal carbonates, alkali metal halides, alkali metal bisulfites, alkali metal sulfites, and alkali metal acetates, preferably at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, lithium fluoride, sodium fluoride, potassium fluoride, lithium bisulfite, sodium bisulfite, potassium bisulfite, lithium sulfite, sodium sulfite, potassium sulfite, lithium acetate, sodium acetate, potassium acetate, cesium acetate, lithium acetylacetonate, and sodium acetylacetonate.

7. The method for preparing the bio-based isosorbide carbonate plasticizer according to claim 2, characterized in that: The temperature of the transesterification reaction is 90-150°C, preferably 90-120°C; The transesterification reaction time is 1-15h, preferably 6-8h; The stirring speed of the transesterification reaction is 10-60 rpm, preferably 15-30 rpm.

8. The method for preparing the bio-based isosorbide carbonate plasticizer according to claim 2, characterized in that: The post-treatment includes suction filtration and reduced pressure distillation of the reaction solution after the reaction is completed.

9. A bio-based isosorbide carbonate plasticizer prepared by the preparation method according to any one of claims 2 to 9.

10. Use of the bio-based isosorbide carbonate plasticizer as claimed in claim 1 as a plastic processing aid.

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