A bio-based plasticizer and its preparation method and application

Abstract

The invention discloses a bio-based plasticizer and a preparation method and application thereof, and relates to the technical field of plasticizers. A bio-based plasticizer, in terms of mass percentage, comprises the following components: 35-65 parts of a bio-based dibasic acid, 30-60 parts of a bio-based diol, 5-7 parts of a terminator, 0.3-0.9 parts of an antioxidant, 0.004-0.006 parts of a catalyst, and 0.04-0.08 parts of an auxiliary agent; the bio-based dibasic acid is prepared by the following method: vegetable oleic acid, anhydride and a catalyst are added to a reactor, wherein the molar ratio of the vegetable oleic acid to the anhydride is 1:(2-4), the amount of the catalyst added is 0.6-0.9 parts of the total mass of the vegetable oleic acid and the anhydride, the temperature is controlled at 120-140°C, the reaction is completed when the acid value no longer decreases, and the reaction is cooled to room temperature to obtain the bio-based dibasic acid. The present invention uses dibasic acids, diols and bio-based long-chain acids extracted from oil plants to generate products, replacing products produced from petroleum-based basic materials, achieving environmental protection, zero pollution and reduced carbon pollution.

Description

Technical Field

[0001] The present invention relates to the technical field of plasticizers, and in particular to a bio-based plasticizer and a preparation method and application thereof. Background Art

[0002] Bio-based polymers are a type of polymer synthesized through biological or chemical processes using bio-renewable resources as raw materials. Plastics, rubbers, fibers, adhesives and coatings obtained with bio-based polymers as matrix resins are collectively referred to as bio-based polymer materials. Bio-based polymer materials avoid dependence on petrochemical resources and have the advantages of low carbon and environmental protection. They are a potential substitute for petrochemical polymer materials. However, the current use of bio-based polymer materials is less than 1 part of polymer materials. Therefore, bio-based polymer materials will be one of the important directions for future development in the polymer field. Plasticizers are additives that will be inserted between polymer molecules when used, weakening the forces between macromolecules and increasing the activity of polymer molecules, thereby improving the processability of polymers and the flexibility of products. At present, petroleum-based plasticizers are more commonly used. How to develop bio-based plasticizers and improve the application performance of bio-based plasticizers is an urgent problem to be solved. Summary of the invention

[0003] In view of the above problems, the present invention provides a bio-based plasticizer and a preparation method and application thereof to solve the problems of the background technology.

[0004] In order to achieve the above-mentioned purpose, the present invention provides the following technical solutions:

[0005] A bio-based plasticizer, the components are as follows, in terms of mass percentage:

[0006]

[0007] In some of the embodiments, the mass ratio of the bio-based diacid to the bio-based diol is (40-50):(50-60).

[0008] In some embodiments, the catalyst is selected from at least one of sodium methoxide, p-toluenesulfonic acid, tetrabutyl titanate, stannous chloride, dibutyltin oxide, antimony glycol, antimony trioxide, trifluoromethanesulfonic acid, and scandium trifluoromethanesulfonate.

[0009] In some of the embodiments, the catalyst is a mixture of tetra-n-butyl titanate and dibutyl tin oxide, and the mass ratio of the tetra-n-butyl titanate to dibutyl tin oxide is 3:2.

[0010] In some embodiments, the terminator is one of lauryl alcohol / acid, dodecanoic acid and long-chain fatty acids.

[0011] In some embodiments, the antioxidant is BHT, DBHQ or 1010 antioxidant. By adding the antioxidant, the discoloration caused by light and heat can be reduced.

[0012] In some of the embodiments, the auxiliary agent is a mixture of an anti-wear agent and an inhibitor, and the mass ratio of the anti-wear agent to the inhibitor is (1-3): (3-5).

[0013] The polymerization inhibitor is at least one of p-hydroxyanisole, hydroquinone, 2,6-di-tert-butyl-p-cresol, FIRSTCURE ST-1 and FIRSTCURE ST-2. The polymerization inhibition efficiency and thermal stability can be improved by adding the polymerization inhibitor. The anti-wear agent is AF-29 or AF-30. The wear resistance and toughness of the bio-based plasticizer can be improved by adding the anti-wear agent.

[0014] In some of the embodiments, the bio-based dibasic acid is prepared by the following method: adding vegetable oleic acid, anhydride and a catalyst into a reactor, wherein the molar ratio of vegetable oleic acid to anhydride is 1:(2-4), the amount of the catalyst added is 0.6-0.9 parts of the total mass of the vegetable oleic acid and the anhydride, the temperature is controlled at 120°C-140°C, the reaction is completed when the acid value no longer decreases, and the reaction is cooled to room temperature to obtain the bio-based dibasic acid.

[0015] In some of the embodiments, the vegetable oleic acid is a mixture of soybean oleic acid and cottonseed oleic acid, and the mass ratio of the soybean oleic acid to the cottonseed oleic acid is (1-5):1; the acid anhydride is at least one of methylhexahydrophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, suberic anhydride, azelaic anhydride and sebacic anhydride; in the method for preparing bio-based dibasic acid, the catalyst is stannous chloride.

[0016] In some of the embodiments, the bio-based diol is prepared by the following method: vegetable oil and dihydroxy secondary amine are mixed, and the bio-based diol is obtained by condensation reaction under the action of an alkaline catalyst.

[0017] In some embodiments, the vegetable oil is a mixture of palm kernel oil, linseed oil and coconut oil, and the mass ratio of the palm kernel oil, linseed oil and coconut oil is (1-2): (3-5): (1-3).

[0018] In some of the embodiments, the dihydroxy secondary amine is a mixture of dimethanolamine and diethanolamine, and the mass ratio of the dimethanolamine to diethanolamine is 1:(3-5).

[0019] In some embodiments, the alkaline catalyst is sodium hydroxide, sodium amide or potassium hydroxide.

[0020] The present invention also provides a method for preparing the bio-based plasticizer as described above, comprising the following steps: weighing a bio-based dibasic acid, a bio-based diol, an antioxidant, a catalyst and an auxiliary agent and adding them into a reaction tank, heating the temperature to 120-170°C to start the reaction, then heating the temperature to 210°C, starting to evacuate when the acid value is lower than 30, evacuating the entire area when the acid value is less than 1, breaking the vacuum with nitrogen and adding a terminator when the hydroxyl value reaches 125-160, and reacting for 1 hour until the acid value is less than 1, thereby obtaining the bio-based plasticizer.

[0021] The present invention also provides the use of the above-mentioned bio-based plasticizer in the preparation of polyurethane, PVC, and polyester products. In specific applications, the amount of the bio-based plasticizer added to the polyurethane, PVC, and polyester products is 5-20 parts.

[0022] Compared with the prior art, the bio-based plasticizer and its preparation method and application of the present invention have the following beneficial effects:

[0023] The present invention uses dibasic acids, diols and bio-based long-chain acids extracted from oil plants to generate products, replacing products produced from petroleum-based basic materials, achieving environmental protection, zero pollution and reduced carbon pollution. Through the mutual coordination between the components, the bio-based plasticizer can improve the strength and flexibility of the product. DETAILED DESCRIPTION

[0024] The present invention is described in detail below in conjunction with specific embodiments.

[0025] Example 1

[0026] A bio-based plasticizer, the components are as follows, in terms of mass percentage:

[0027]

[0028] The bio-based dibasic acid is prepared by the following method: 60.5 g of soybean oleic acid (0.2 mol), 60.5 g of cottonseed oleic acid (0.15 mol), 40.6 g of itaconic anhydride (0.7 mol) and 0.96 g of stannous chloride are added into a reactor, the temperature is controlled at 140° C., the reaction is completed when the acid value no longer decreases, and the reaction is cooled to room temperature to obtain the bio-based dibasic acid.

[0029] The bio-based diol is prepared by the following method: 50 g of palm kernel oil, 150 g of linseed oil and 50 g of coconut oil are added into a reactor and mixed, nitrogen is introduced and heated to 50° C., a mixture of 20 g of dimethanolamine and 60 g of diethanolamine is added dropwise and stirred for 35 minutes, 2.8 g of sodium hydroxide solution (concentration 35 wt parts) is added dropwise, the mixture is stirred and reacted for 3 hours, the mixture is dissolved with dichloromethane and then washed with saturated brine to remove the catalyst, anhydrous magnesium sulfate is added to dry, dichloromethane is removed by rotary evaporation after separation, and the bio-based diol is obtained.

[0030] The preparation method of the bio-based plasticizer in this embodiment 1 includes the following steps: weighing bio-based dibasic acid, bio-based diol, BHT, sodium methoxide, p-hydroxyanisole and AF-29 and adding them into a reaction tank, heating to 170°C to start the reaction, and then heating to 210°C. When the acid value is lower than 30, vacuuming is started, and when the acid value is less than 1, full vacuuming is performed. When the hydroxyl value reaches 125, the vacuum is broken with nitrogen and lauryl alcohol / acid is added. After 1 hour of reaction, the reaction can be stopped when the acid value is less than 1 to obtain the bio-based plasticizer.

[0031] Example 2

[0032] A bio-based plasticizer, the components are as follows, in terms of mass percentage:

[0033]

[0034]

[0035] The bio-based dibasic acid is prepared by the following method: 200.5 g of soybean oleic acid (0.1 mol), 40.1 g of cottonseed oleic acid (0.1 mol), 32.58 g of methylhexahydrophthalic anhydride (0.8 mol) and 1.2 g of stannous chloride are added into a reactor, the temperature is controlled at 120° C., the reaction is completed when the acid value no longer decreases, and the reaction is cooled to room temperature to obtain the bio-based dibasic acid.

[0036] The bio-based diol is prepared by the following method: 10 g of palm kernel oil, 50 g of linseed oil and 30 g of coconut oil are added into a reactor and mixed, nitrogen is introduced and heated to 50° C., a mixture of 10 g of dimethylolamine and 50 g of diethanolamine is added dropwise and stirred for 35 minutes, 2.5 g of potassium hydroxide solution (concentration 35 wt parts) is added dropwise, the mixture is stirred for reaction for 10 hours, the mixture is dissolved with dichloromethane and then washed with saturated brine to remove the catalyst, anhydrous magnesium sulfate is added for drying, dichloromethane is removed by rotary evaporation after separation, and the bio-based diol is obtained.

[0037] The preparation method of the bio-based plasticizer in this embodiment 2 includes the following steps: weighing bio-based dibasic acid, bio-based diol, DBHQ, p-toluenesulfonic acid, hydroquinone, 2,6-di-tert-butyl-p-cresol and AF-30 and adding them into a reaction tank, heating to 120°C to start the reaction, and then heating to 210°C. When the acid value is lower than 30, vacuuming is started, and when the acid value is less than 1, full vacuuming is performed. When the hydroxyl value reaches 160, the vacuum is broken with nitrogen and dodecanoic acid is added. After 1 hour of reaction, the reaction can be stopped when the acid value is less than 1 to obtain the bio-based plasticizer.

[0038] Example 3

[0039] A bio-based plasticizer, the components are as follows, in terms of mass percentage:

[0040]

[0041]

[0042] The bio-based dibasic acid is prepared by the following method: 70.46 g of soybean oleic acid (0.2 mol), 23.52 g of cottonseed oleic acid (0.1 mol), 15.48 g of succinic anhydride (0.3 mol), 24.27 g of maleic anhydride (0.6 mol) and 0.93 g of stannous chloride are added into a reactor, the temperature is controlled at 130° C., the reaction is completed when the acid value no longer decreases, and the reaction is cooled to room temperature to obtain the bio-based dibasic acid.

[0043] The bio-based diol is prepared by the following method: 15 g of palm kernel oil, 40 g of linseed oil and 20 g of coconut oil are added into a reactor and mixed, nitrogen is introduced and heated to 50° C., a mixture of 5 g of dimethylolamine and 20 g of diethanolamine is added dropwise and stirred for 35 minutes, 2.5 g of sodium hydroxide solution (concentration 35 wt parts) is added dropwise, the mixture is stirred and reacted for 3 hours, the mixture is dissolved with dichloromethane and then washed with saturated brine to remove the catalyst, anhydrous magnesium sulfate is added to dry, dichloromethane is removed by rotary evaporation after separation, and the bio-based diol is obtained.

[0044] The preparation method of the bio-based plasticizer in this embodiment 3 includes the following steps: weighing a bio-based dibasic acid, a bio-based diol, BHT, tetra-n-butyl titanate, dibutyltin oxide, p-hydroxyanisole and AF-30, adding them into a reaction tank, heating to 140°C to start the reaction, and then heating to 210°C. When the acid value is lower than 30, vacuuming is started, and when the acid value is less than 1, full vacuuming is performed. When the hydroxyl value reaches 140, the vacuum is broken with nitrogen and dodecanoic acid is added. After 1 hour of reaction, the reaction can be stopped when the acid value is less than 1 to obtain the bio-based plasticizer.

[0045] Example 4

[0046] A bio-based plasticizer, the components are as follows, in terms of mass percentage:

[0047]

[0048]

[0049] The bio-based dibasic acid is prepared by the following method: 34.67 g of soybean oleic acid (0.1 mol), 63.25 g of cottonseed oleic acid (0.2 mol), 25.23 g of suberic anhydride (0.3 mol), 12.38 g of azelaic anhydride (0.3 mol) and 0.94 g of stannous chloride are added into a reactor, the temperature is controlled at 120° C., the reaction is completed when the acid value no longer decreases, and the reactor is cooled to room temperature to obtain the bio-based dibasic acid.

[0050] The bio-based diol is prepared by the following method: 20 g of palm kernel oil, 40 g of linseed oil and 20 g of coconut oil are added into a reactor and mixed, nitrogen is introduced and heated to 50° C., a mixture of 10 g of dimethylolamine and 30 g of diethanolamine is added dropwise and stirred for 35 minutes, 3.0 g of sodium amide solution (concentration 35 wt parts) is added dropwise, the mixture is stirred for reaction for 3 hours, the mixture is dissolved with dichloromethane and then washed with saturated brine to remove the catalyst, anhydrous magnesium sulfate is added to dry, dichloromethane is removed by rotary evaporation after separation, and the bio-based diol is obtained.

[0051] The preparation method of the bio-based plasticizer of this embodiment 4 includes the following steps: weighing bio-based dibasic acid, bio-based diol, 1010 antioxidant, dibutyltin oxide, 2,6-di-tert-butyl-p-cresol and AF-29, adding them into a reaction tank, heating to 150°C to start the reaction, and then heating to 210°C. When the acid value is lower than 30, vacuuming is started, and when the acid value is less than 1, full vacuuming is performed. When the hydroxyl value reaches 150, the vacuum is broken with nitrogen and dodecanol / acid is added. After 1 hour of reaction, the reaction can be stopped when the acid value is less than 1 to obtain the bio-based plasticizer.

[0052] Example 5

[0053] A bio-based plasticizer, the components are as follows, in terms of mass percentage:

[0054]

[0055]

[0056] The bio-based dibasic acid is prepared by the following method: 56.32 g of soybean oleic acid (0.2 mol), 42.18 g of cottonseed oleic acid (0.2 mol), 14.37 g of methylhexahydrophthalic anhydride (0.2 mol), 18.25 g of suberic anhydride (0.4 mol) and 1.04 g of stannous chloride are added into a reactor, the temperature is controlled at 130° C., the reaction is completed when the acid value no longer decreases, and the reactor is cooled to room temperature to obtain the bio-based dibasic acid.

[0057] The bio-based diol is prepared by the following method: 30 g of palm kernel oil, 90 g of linseed oil and 30 g of coconut oil are added into a reactor and mixed, nitrogen is introduced and heated to 50° C., a mixture of 20 g of dimethanolamine and 60 g of diethanolamine is added dropwise and stirred for 30 minutes, 2.7 g of potassium hydroxide solution (concentration 35 wt parts) is added dropwise, the mixture is stirred and reacted for 6 hours, the mixture is dissolved with dichloromethane and then washed with saturated brine to remove the catalyst, anhydrous magnesium sulfate is added to dry, dichloromethane is removed by rotary evaporation after separation, and the bio-based diol is obtained.

[0058] The preparation method of the bio-based plasticizer in this embodiment 5 includes the following steps: weighing bio-based dibasic acid, bio-based diol, DBHQ, tetra-n-butyl titanate, FIRSTCURE ST-2 and AF-29 into a reaction tank, heating to 130° C. to start the reaction, then heating to 210° C., starting to evacuate when the acid value is lower than 30, evacuating to a full vacuum when the acid value is less than 1, breaking the vacuum with nitrogen when the hydroxyl value reaches 130 and adding dodecyl alcohol / acid, reacting for 1 hour, stopping when the acid value is less than 1, and obtaining the bio-based plasticizer.

[0059] Comparative Example 1

[0060] The difference from Example 3 is that the bio-based dibasic acid in Comparative Example 1 is prepared by the following method: 70.46 g of soybean oleic acid (0.2 mol), 23.52 g of cottonseed oleic acid (0.1 mol), 15.48 g of succinic anhydride (0.2 mol), 24.27 g of maleic anhydride (0.1 mol) and 0.93 g of stannous chloride are added into a reactor, the temperature is controlled at 130° C., the reaction is completed when the acid value no longer decreases, and the reaction is cooled to room temperature to obtain the bio-based dibasic acid.

[0061] Comparative Example 2

[0062] The difference from Example 3 is that the bio-based dibasic acid in Comparative Example 2 is prepared by the following method: 70.46 g of soybean oleic acid (0.2 mol), 23.52 g of cottonseed oleic acid (0.1 mol), 15.48 g of succinic anhydride (0.3 mol), 24.27 g of maleic anhydride (0.6 mol) and 0.66 g of stannous chloride are added into a reactor, the temperature is controlled at 130° C., the reaction is completed when the acid value no longer decreases, and the reaction is cooled to room temperature to obtain the bio-based dibasic acid.

[0063] Comparative Example 3

[0064] The difference from Example 3 is that the bio-based dibasic acid in Comparative Example 3 is prepared by the following method: 93.98 g of ricinoleic acid (0.3 mol), 15.48 g of succinic anhydride (0.3 mol), 24.27 g of maleic anhydride (0.6 mol) and 0.93 g of stannous chloride are added into a reactor, the temperature is controlled at 130° C., the reaction is completed when the acid value no longer decreases, and the reaction is cooled to room temperature to obtain the bio-based dibasic acid.

[0065] Comparative Example 4

[0066] The difference from Example 3 is that the bio-based diol in Comparative Example 3 is prepared by the following method: 75 g of palm kernel oil is added to the reactor and mixed, nitrogen is introduced and heated to 50° C., a mixture of 5 g of dimethanolamine and 20 g of diethanolamine is added dropwise and stirred for 35 minutes, 2.5 g of sodium hydroxide solution (concentration 35 wt parts) is added dropwise, the reaction is stirred for 3 hours, the mixture is dissolved with dichloromethane and then washed with saturated brine to remove the catalyst, anhydrous magnesium sulfate is added to dry, dichloromethane is removed by rotary evaporation after separation, and bio-based diol is obtained.

[0067] Comparative Example 4

[0068] The difference from Example 3 is that the bio-based diol in Comparative Example 4 is prepared by the following method: 55 g of palm kernel oil and 20 g of coconut oil are added to a reactor and mixed, nitrogen is introduced and heated to 50° C., and then a mixture of 5 g of dimethanolamine and 20 g of diethanolamine is added dropwise and stirred for 35 minutes, 2.5 g of sodium hydroxide solution (concentration 35 wt parts) is added dropwise, and the reaction is stirred for 3 hours, dissolved with dichloromethane and then washed with saturated brine to remove the catalyst, and then anhydrous magnesium sulfate is added to dry, and dichloromethane is removed by rotary evaporation after separation to obtain bio-based diol.

[0069] Comparative Example 5

[0070] The difference from Example 3 is that the bio-based diol in Comparative Example 5 is prepared by the following method: 15 g of palm kernel oil, 40 g of linseed oil, and 20 g of coconut oil are added to a reactor and mixed, nitrogen is introduced and heated to 50° C., 25 g of diethanolamine is added dropwise to the mixture and stirred for 35 minutes, 2.5 g of sodium hydroxide solution (concentration 35 wt parts) is added dropwise, the reaction is stirred for 3 hours, the mixture is dissolved with dichloromethane and then washed with saturated brine to remove the catalyst, anhydrous magnesium sulfate is added to dry, dichloromethane is removed by rotary evaporation after separation, and bio-based diol is obtained.

[0071] Comparative Example 6

[0072] The difference from Example 3 is that the bio-based diol in Comparative Example 6 is prepared by the following method: 15 g of castor oil, 40 g of linseed oil, and 20 g of coconut oil are added to a reactor and mixed, nitrogen is introduced and heated to 50° C., and then a mixture of 5 g of dimethylolamine and 20 g of diethanolamine is added dropwise and stirred for 35 minutes, 2.5 g of sodium hydroxide solution (concentration 35 wt parts) is added dropwise, and the reaction is stirred for 3 hours, dissolved with dichloromethane and then washed with saturated brine to remove the catalyst, and then anhydrous magnesium sulfate is added to dry, and dichloromethane is removed by rotary evaporation after separation to obtain bio-based diol.

[0073] Comparative Example 7

[0074] The difference from Example 3 is that the bio-based diol in Comparative Example 7 is prepared by the following method: 15 g of palm kernel oil, 40 g of linseed oil, and 20 g of coconut oil are added to a reactor and mixed, nitrogen is introduced and heated to 50° C., and then a mixture of 5 g of dibutanolamine and 20 g of diethanolamine is added dropwise and stirred for 35 minutes, 2.5 g of sodium hydroxide solution (concentration 35 wt parts) is added dropwise, and the reaction is stirred for 3 hours, dissolved with dichloromethane and then washed with saturated brine to remove the catalyst, and then anhydrous magnesium sulfate is added to dry, and dichloromethane is removed by rotary evaporation after separation to obtain bio-based diol.

[0075] Comparative Example 8

[0076] The difference from Example 3 is that the bio-based diol in Comparative Example 8 is prepared by the following method: 15 g of palm kernel oil, 15 g of linseed oil, and 15 g of coconut oil are added to a reactor and mixed, nitrogen is introduced and heated to 50° C., and then a mixture of 5 g of dimethylolamine and 20 g of diethanolamine is added dropwise and stirred for 35 minutes, 2.5 g of sodium hydroxide solution (concentration 35 wt parts) is added dropwise, and the reaction is stirred for 3 hours, dissolved with dichloromethane and then washed with saturated brine to remove the catalyst, and then anhydrous magnesium sulfate is added to dry, and dichloromethane is removed by rotary evaporation after separation to obtain bio-based diol.

[0077] Comparative Example 9

[0078] The difference from Example 3 is that the bio-based diol in Comparative Example 9 is prepared by the following method: 15 g of palm kernel oil, 15 g of linseed oil, and 15 g of coconut oil are added to a reactor and mixed, nitrogen is introduced and heated to 50° C., and then a mixture of 5 g of dimethanolamine and 5 g of diethanolamine is added dropwise and stirred for 35 minutes, 2.5 g of sodium hydroxide solution (concentration 35 wt parts) is added dropwise, and the reaction is stirred for 3 hours, dissolved with dichloromethane and then washed with saturated brine to remove the catalyst, and then anhydrous magnesium sulfate is added to dry, and dichloromethane is removed by rotary evaporation after separation to obtain bio-based diol.

[0079] Comparative Example 9 The mass ratio of dimethanolamine to diethanolamine is outside the range

[0080] Comparative Example 10

[0081] The difference from Example 3 is that the bio-based diol in Comparative Example 10 is prepared by the following method: 30 g of palm kernel oil, 10 g of linseed oil, and 40 g of coconut oil are added to a reactor and mixed, nitrogen is introduced and heated to 50° C., and then a mixture of 10 g of dimethanolamine and 20 g of diethanolamine is added dropwise and stirred for 35 minutes, 2.5 g of sodium hydroxide solution (concentration 35 wt parts) is added dropwise, and the reaction is stirred for 3 hours, dissolved with dichloromethane and then washed with saturated brine to remove the catalyst, and then anhydrous magnesium sulfate is added to dry, and dichloromethane is removed by rotary evaporation after separation to obtain bio-based diol.

[0082] In Comparative Example 10, the mass ratio of palm kernel oil, linseed oil and coconut oil and the mass ratio of dimethylolamine to diethanolamine were all outside the range.

[0083] Experimental example

[0084] The performance of the bio-based plasticizers of Examples 1-5 and Comparative Examples 1-10 was tested and evaluated, and the results are shown in Table 1.

[0085] Preparation of the experiment:

[0086] 15 parts by weight of the bio-based plasticizers of Examples 1-5 and Comparative Examples 1-10 and 85 parts by weight of PVC were added to a high-speed mixer according to the formula, and after being evenly mixed, they were melt-blended in a twin-screw extruder and extruded into granules. The obtained granules were dried at a temperature of 80° C. for 6 hours, and injection-molded into standard specimens for testing by an injection molding machine, with a thickness of 3.5 mm.

[0087] Test method: 1. The tensile strength (MPa) and elongation at break (%) of the sample are tested according to GB / T 1040-2006, and the tensile speed is 50 mm / min.

[0088] Table 1

[0089] Tensile strength(MPa) Elongation at break (%) Example 1 32.7 463.7 Example 2 32.5 469.4 Example 3 35.7 485.8 Example 4 34.4 477.5 Example 5 33.6 475.6 Comparative Example 1 27.4 283.8 Comparative Example 2 28.3 332.5 Comparative Example 3 27.6 226.7 Comparative Example 4 29.2 223.3 Comparative Example 5 30.1 230.4 Comparative Example 6 32.6 267.2 Comparative Example 7 29.1 243.1 Comparative Example 8 29.6 237.8 Comparative Example 9 31.3 242.3 Comparative Example 10 27.1 231.6 PVC 26.4 186.4

[0090] As shown in Table 1, the results of the samples of Examples 1-5 are compared with the performance of Comparative Examples 1-10 and PVC, indicating that the bio-based plasticizer of the present invention has excellent performance and can improve the strength and flexibility of PVC.

[0091] By comparing the results of Examples 1-3 with Comparative Example 1, the effect of the molar ratio of vegetable oleic acid to acid anhydride of 1:(2-4) in the preparation of bio-based dibasic acid is better than the effect of the molar ratio of vegetable oleic acid to acid anhydride of 1:1.

[0092] By comparing the results of Examples 1-3 with Comparative Example 2, the effect of adding a catalyst in an amount of 0.6-0.9 parts of the total mass of vegetable oleic acid and anhydride in the preparation of bio-based dibasic acid is better than that of adding a catalyst in an amount of 0.5 parts of the total mass of vegetable oleic acid and anhydride.

[0093] By comparing the results of Example 3 with those of Comparative Example 3, it can be seen that in the preparation of bio-based dibasic acids, the effect of mixing soybean oleic acid and cottonseed oleic acid is better than that of ricinoleic acid.

[0094] By comparing the results of Examples 1-3 with Comparative Example 4, the effect of the mixture of palm kernel oil, linseed oil and coconut oil in the preparation of bio-based diols is better than the effect of the mixture of palm kernel oil, linseed oil and coconut oil in the preparation of bio-based diols.

[0095] By comparing the results of Examples 1-3 with Comparative Example 4, the effect of the mixture of palm kernel oil, linseed oil and coconut oil in the preparation of bio-based diols is better than the effect of the vegetable oil lacking linseed oil.

[0096] Based on Comparative Examples 3 and 4, it is shown that the mixing effect of palm kernel oil, linseed oil and coconut oil in the preparation of bio-based diols is better.

[0097] By comparing the results of Examples 1-3 with Comparative Example 5, the mixed effect of diethanolamine and diethanolamine in the preparation of bio-based diols is better than that of diethanolamine alone, which indicates that the mixed effect of diethanolamine and diethanolamine is better than that of single use.

[0098] By comparing the results of Examples 1-3 with Comparative Example 6, the mixed effect of palm kernel oil, linseed oil and coconut oil in the preparation of bio-based diols is better than the mixed effect of castor oil, linseed oil and coconut oil. This shows that the plant oils in the preparation of bio-based diols need to be specifically compounded with palm kernel oil, linseed oil and coconut oil, and even if similar plant oils are used instead, the effect is greatly reduced.

[0099] By comparing the results of Examples 1-3 with Comparative Example 7, the mixed effect of dihydroxy secondary amines of dimethanolamine and diethanolamine in the preparation of bio-based diols is better than the mixed effect of dihydroxy secondary amines of dibutanolamine and diethanolamine. This shows that the dihydroxy secondary amines in the preparation of bio-based diols require a specific compound of dimethanolamine and diethanolamine, and even if similar dihydroxy secondary amine components are used instead, the effect is greatly reduced.

[0100] By comparing the results of Examples 1-3 with Comparative Example 8, the mass ratio of palm kernel oil, linseed oil and coconut oil in the preparation of bio-based diols is (1-2): (3-5): (1-3) with better effects than those outside the ratio range, indicating that palm kernel oil, linseed oil and coconut oil can only play a better effect within a specific ratio range.

[0101] By comparing the results of Examples 1-3 with Comparative Example 9, the effect of the mass ratio of dimethanolamine to diethanolamine in the preparation of bio-based diols is better than that outside the ratio range, which indicates that dimethanolamine and diethanolamine can only play a better effect within a specific range.

[0102] By comparing the results of Examples 1-3 with Comparative Example 10, the mass ratios of palm kernel oil, linseed oil and coconut oil in the preparation of bio-based diols are (1-2): (3-5): (1-3) and the mass ratio of dimethylolamine to diethanolamine is 1: (3-5), which is better than the effect outside the ratio range. This shows that the compounding effect of vegetable oil and dihydroxy secondary amine is better only when compounded within the specific ratio range of the present invention.

[0103] Compared with the results of Examples 1-5, Examples 3-5 have better effects, indicating that when the mass ratio of the bio-based dibasic acid to the bio-based diol is (40-50): (50-60), the effect is better.

[0104] In the absence of conflict, the above-mentioned embodiments and features thereof may be combined with each other.

[0105] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention, rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A bio-based plasticizer, characterized in that: In terms of mass percentage, the components are as follows: 35-65 parts of bio-based dibasic acid 30-60 parts of bio-based glycol 5-7 parts of terminator Antioxidant 0.3-0.9 parts Catalyst 0.004-0.006 parts Additives 0.04-0.08 parts; The bio-based dibasic acid is prepared by the following method: adding vegetable oleic acid, anhydride and a catalyst into a reactor, wherein the molar ratio of the vegetable oleic acid to the anhydride is 1:(2-4), the amount of the catalyst added is 0.6-0.9 parts of the total mass of the vegetable oleic acid and the anhydride, the temperature is controlled at 120°C-140°C, the reaction is completed when the acid value no longer decreases, and the reaction is cooled to room temperature to obtain the bio-based dibasic acid; the vegetable oleic acid is a mixture of soybean oleic acid and cottonseed oleic acid, and the mass ratio of the soybean oleic acid to the cottonseed oleic acid is (1-5):1; The bio-based diol is prepared by the following method: vegetable oil and dihydroxy secondary amine are mixed, and the bio-based diol is obtained by condensation reaction under the action of an alkaline catalyst; The vegetable oil is a mixture of palm kernel oil, linseed oil and coconut oil, and the mass ratio of the palm kernel oil, linseed oil and coconut oil is (1-2): (3-5): (1-3); The dihydroxy secondary amine is a mixture of dimethylolamine and diethanolamine, and the mass ratio of the dimethylolamine to diethanolamine is 1: (3-5).

2. The bio-based plasticizer according to claim 1, characterized in that The mass ratio of the bio-based dibasic acid to the bio-based diol is (40-50):(50-60).

3. The bio-based plasticizer according to claim 1, characterized in that The acid anhydride is at least one of methylhexahydrophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, suberic anhydride, azelaic anhydride and sebacic anhydride.

4. The bio-based plasticizer according to claim 1, characterized in that The alkaline catalyst is sodium hydroxide, sodium amide or potassium hydroxide.

5. A method for preparing a bio-based plasticizer according to any one of claims 1 to 4, characterized in that: The method comprises the following steps: weighing bio-based dibasic acid, bio-based diol, antioxidant, catalyst and auxiliary agent and adding them into a reaction tank, heating to 120-170°C to start reaction, then heating to 210°C, starting vacuuming when the acid value is lower than 30, and fully vacuuming when the acid value is lower than 1, breaking the vacuum with nitrogen and adding a terminator when the hydroxyl value reaches 125-160, and stopping the reaction when the acid value is lower than 1 after one hour of reaction to obtain a bio-based plasticizer.

6. Use of the bio-based plasticizer according to any one of claims 1 to 4 in the preparation of polyurethane, PVC, and polyester products, wherein the amount of the bio-based plasticizer added to the polyurethane, PVC, and polyester products is 5 to 20 parts.

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