Methods for producing and using bio-based polyols

Abstract

The present invention discloses a method for preparing and using bio-based polyol, which relates to the technical field of polyol preparation. The present invention uses tartaric acid ester as the first ring-opening reagent to carry out the first ring-opening reaction of epoxy, then uses a second ring-opening reagent containing a secondary alcohol to carry out the second ring-opening reaction, and finally uses a primary alcohol to carry out the third ring-opening reaction of the remaining epoxy to obtain a bio-based polyol product with an epoxy value of about 0. The bio-based polyol prepared by the present invention has a proper and uniform distribution and low viscosity, and can replace traditional petrochemical-derived polyols, and the polyurethane coating prepared by using the bio-based polyol prepared by the method of the present invention has significantly improved performance.

Description

[Technical field]

[0001] The present invention relates to the technical field of polyol production, and in particular to the production and use of bio-based polyols. [Background technology]

[0002] Polyurethane is a polymer with repeating structural units of urethane segments, produced by the reaction of polyols and isocyanates. Polyurethane products are divided into two categories: foamed products and non-foamed products. Foamed products include flexible, rigid, and semi-rigid polyurethane foams, while non-foamed products include paints, binders, synthetic leather, elastomers, and elastic fibers. Of the two types of monomers used in the synthesis of polyurethane, the isocyanate products are few in number, mainly including MDI and TDI. The other monomer, alcohol, has many types, various qualities, and diverse downstream applications, so further research is needed.

[0003] The development of vegetable oil polyol is considered to be an effective method for developing bio-based materials. As an important monomer of bio-based polyurethane materials, vegetable oil polyol is derived from the molecular structure chemically modified using vegetable oil as a raw material, which is an important renewable resource, and can react with isocyanate compounds to produce polyurethane, making it suitable as an alternative raw material to petroleum-based polyol.

[0004] At present, in the field of bio-based polyurethane foam products, there are many brands on the market. However, in the field of paints, the development of bio-based polyols derived from vegetable oils is relatively slow. Especially in anti-corrosion paints, polyurethane paints developed using bio-based polyols currently have difficulty in achieving a balance in terms of hardness, toughness, and corrosion resistance.

[0005] Scientific researchers have done a lot of research in this field. The main methods for synthesizing vegetable oil polyols are as follows: 1) Using the basic core of triglyceride to carry out alcoholysis reaction between vegetable oil and polyol to produce polyhydroxy compounds. This method can obtain high-functionality polyol monomers, but the hydroxy group distribution is uneven and uncontrollable, which limits its application. 2) Using ozone to oxidize the unsaturated double bonds in vegetable oil to produce polyhydroxy compounds with terminal hydroxy groups. This method can obtain highly reactive terminal hydroxy groups, but the atom economy is low and the functionality is low, which also greatly limits downstream applications. 3) Oxidizing vegetable oil to epoxidized vegetable oil, and producing polyhydroxy compounds through ring-opening reaction, etc. This method has the advantages of high atom economy, flexibility, structure controllability, and molecular diversity, and is currently the main method used to develop bio-based polyols.

[0006] The long-chain group in the structure of vegetable oil replaces the polyether or polyester repeating unit of traditional petrochemical polyol, and the basic core of triglyceride in its structure has a star-shaped spatial structure, which gives downstream polyurethane more functional properties and application possibilities, but vegetable oil polyol often has performance deficiencies, the main reason is that the reaction process is difficult to control, and in the functional group conversion process, multiple epoxy groups and ester groups are often involved in multiple side reactions, so it is difficult to construct a designed molecular structure by traditional chemical methods, and the quality of polyol is greatly limited, and it is often necessary to mix with traditional petrochemical polyol to achieve a certain application effect. Analysis of the reaction mechanism has found that the main reasons are as follows: Oil esters often have low miscibility with reaction reagents, low reactivity, and require long and high-intensity reactions, but due to the influence of multiple functional groups in the structure, it is difficult to balance reaction selectivity and conversion rate, and the process controllability is poor, resulting in poor molecular uniformity, high viscosity, and large difference between macroscopic index and microscopic index of a single molecule. Therefore, even though the price of vegetable oil is often cheaper than petrochemical repeat unit monomers, it is difficult to obtain vegetable oil polyol products that are advantageous in both cost and quality. Product quality control by controlling the chemical process is necessary, and in this reaction system, the use of micro reaction technology that intensifies and continuously and accurately controls the chemical reaction process is an effective solution.

[0007] In general, polyurethane products formed with polyester polyols have better mechanical strength than polyurethane products formed with polyether polyols. This is thought to be due to the potential effect of hydrogen bonds formed by the ester groups of the polyol and the ammonia of the isocyanate. Therefore, it is possible to carry out a ring-opening reaction between epoxidized vegetable oil and a ring-opening reagent with an ester group, and adjust the hydroxyl value according to the structure of the ring-opening reagent to give it a certain functionality. Of course, a higher hydroxyl value helps to improve strength and hardness, but it may lead to an increase in the viscosity of the polyol and a decrease in toughness. Previous studies have also shown that residual epoxy improves corrosion resistance performance but may reduce functionality. As mentioned above, the adjustment of functionality in the structure, the proportion of residual epoxy, the number and spatial arrangement of ester groups, the hydroxyl value and the spatial arrangement of hydroxyl groups all have a significant impact on the results. These parameters also affect each other, but a complete structure-activity relationship is lacking, which is the main reason why development in this field is limited.

[0008] Since vegetable oils are not composed of a single component and the structure-activity relationship is not clear, the quality of polyol products can only be controlled through reaction process and macroscopic index control. Therefore, controlling the uniformity of products as much as possible through process control plays an important role in the development and downstream applications of new polyol products. Summary of the Invention [Problem to be solved by the invention]

[0009] In response to the deficiencies of the prior art, the present invention provides methods for making and using bio-based polyols. [Means for solving the problem]

[0010] In order to achieve the above objectives, the present invention is achieved by the following technical solutions. In one aspect, the present invention provides a method for producing a method for treating a cancer cell comprising: Step 1: mixing an epoxidized vegetable oil with a catalyst to obtain a first mixed solution; dissolving at least one of a first ring-opening reagent, dimethyl tartrate, diethyl tartrate, and diisopropyl tartrate, in an organic solvent to obtain a second mixed solution; and simultaneously pumping the first mixed solution and the second mixed solution into a first microreactor of a microchannel modular reactor to carry out a first ring-opening reaction and obtain a first reaction effluent; Step 2: dissolving a second ring-opening reagent, 1,2-propylene glycol, in an organic solvent to obtain a third mixture; and simultaneously pumping the third mixture and the first reaction effluent into a second microreactor of a microchannel modular reactor to carry out a second ring-opening reaction and obtain a second reaction effluent; Step 3: dissolving at least one of methanol and ethanol, which is a third ring-opening reagent, in an organic solvent to obtain a fourth mixture; and simultaneously pumping the fourth mixture and the second reaction effluent into a third microreactor of a microchannel modular reactor to carry out a third ring-opening reaction and obtain a third reaction effluent; and step 4 of concentrating the third reaction effluent to a predetermined volume, adding a predetermined volume of ethyl acetate, washing with sodium bicarbonate solution and water in turn, separating the layers, drying the organic phase, suction filtering and concentrating to obtain a bio-based polyol.

[0011] Preferably, the epoxidized vegetable oil is at least one of epoxidized olive oil, epoxidized peanut oil, epoxidized rapeseed oil, epoxidized cottonseed oil, epoxidized soybean oil, epoxidized coconut oil, epoxidized palm oil, epoxidized sesame oil, epoxidized corn oil, epoxidized sunflower oil.

[0012] Preferably, the organic solvent is at least one of ethyl acetate, dichloromethane, dichloroethane, chloroform, n-hexane, tetrahydrofuran, 1,4-dioxane, carbon tetrachloride, toluene, xylene, and the catalyst is at least one of fluoroboric acid, phosphoric acid, phosphotungstic acid, and lipase CALB.

[0013] Preferably, the mass volume ratio (g / ml) of the first ring-opening reagent to the organic solvent is 1:0.5-2, the mass ratio of the epoxidized vegetable oil to the catalyst is 1:0.02-0.1, and the volume of the first microreactor in the epoxidized vegetable oil is 5-20 ml.

[0014] Preferably, in the first ring-opening reaction, the reaction temperature is 80 to 120° C. and the reaction time is 3 to 15 minutes.

[0015] Preferably, the molar ratio of epoxy in the epoxidized vegetable oil to the second ring-opening reagent is 1:0.1-0.2, and the mass volume ratio (g / ml) of the second ring-opening reagent to the organic solvent is 1:1-4.

[0016] Preferably, in the second ring-opening reaction, the reaction temperature is 80 to 120° C. and the reaction time is 3 to 15 minutes.

[0017] Preferably, the molar ratio of epoxy in the epoxidized vegetable oil to the third ring-opening reagent is 1:0.4-0.6, and the mass volume ratio (g / ml) of the third ring-opening reagent to the organic solvent is 1:4-8.

[0018] Preferably, in the third ring-opening reaction, the reaction temperature is 80 to 120° C. and the reaction time is 3 to 15 minutes.

[0019] Preferably, the microchannel modular reactor includes a first feed pump, a second feed pump, a third feed pump, a fourth feed pump, a first micro mixer, a second micro mixer, a third micro mixer, a micro reaction pipeline, a tubular temperature control module, a first micro reactor, a second micro reactor, a third micro reactor, and a collection vessel, wherein the first feed pump and the second feed pump are connected in parallel to the first micro mixer, the first micro mixer and the first micro reactor are connected through a micro reaction pipeline, the first micro reactor and the third feed pump are connected in parallel to the second micro mixer, the second micro mixer and the second micro reactor are connected through a micro reaction pipeline, the second micro reactor and the fourth feed pump are connected in parallel to the third micro mixer, and the third micro mixer, the third micro reactor, and a collection vessel are connected in series through a micro reaction pipeline.

[0020] The first micro mixer, the second micro mixer, and the third micro mixer are preferably model slit plate mixer LH25. The first micro reactor, the second micro reactor, and the third micro reactor are preferably model Vapotech. The first micro reactor, the second micro reactor, and the third micro reactor all have a volume of 5 to 20 ml. The reaction temperatures of the first micro reactor, the second micro reactor, and the third micro reactor are all controlled by heating with an oil bath.

[0021] In another aspect, the present invention also provides the use of a bio-based polyol produced by the process described above in the manufacture of a polyurethane coating. Effect of the Invention

[0022] Compared with the prior art, the present invention has the following beneficial effects: 1. In order to improve the mechanical properties of the downstream product of polyester polyol, the present invention uses tartaric acid ester as the first ring-opening reagent to carry out the first ring-opening reaction of epoxy, then uses the second ring-opening reagent containing secondary alcohol to carry out the second ring-opening reaction, and finally uses primary alcohol to carry out the third ring-opening reaction of the remaining epoxy to obtain a vegetable oil polyol product with an epoxy value of about 0. In order to avoid non-selective ring-opening in the ring-opening reaction causing crosslinking side reactions, the present invention utilizes micro-reaction technology to further control the ring-opening group by using a microchannel modular reactor as the reaction device.

[0023] 2. In the present invention, the bio-based polyol prepared by using the new ring-opening reagent contains an ester group structure, which has a certain effect on improving the structural performance of the product; and since the selected ring-opening reagent contains secondary alcohol, the toughness of the bio-based polyol can be improved.

[0024] 3. In the present invention, the bio-based polyol produced by using the new ring-opening reagent has a new structure, and this polyol has a proper and uniform distribution and low viscosity, which can replace the traditional polyol derived from petrochemical materials. The polyurethane coating made by using the bio-based polyol produced by the method of the present invention has significantly improved performance. [Brief description of the drawings]

[0025] In order to more clearly describe the embodiments of the present invention or the technical solutions in the prior art, the drawings necessary for the description of the embodiments or the prior art will be briefly described below. However, the drawings in the following description are only some embodiments of the present invention, and it is obvious to those skilled in the art that they can obtain other drawings based on these drawings without any creative efforts.

[0026] [Figure 1] 1 is a flowchart of a method for producing a bio-based polyol in an embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] In order to make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely, but it is clear that the described embodiments are only a part of the embodiments of the present invention, and are not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative labor belong to the protection scope of the present invention.

[0028] The relevant measurement methods for the bio-based polyol and polyurethane coating prepared in the present invention are as follows: (1) Determine the hydroxyl value according to GB / T 12008.3-2009. (2) Measure the viscosity according to GB / T 12008.7-2010. (3) Measure the drying time of the paint according to GB / T 1728-1979(1989). (4) Determine the pencil hardness of the paint according to GB / T 6739-2006. (5)Measure the impact resistance of the coating according to GB / T 1732-1993. (6) Measure the flexibility of the paint according to GB / T 1731-1993.

[0029] Referring to FIG. 1, the microchannel reactions in the following examples and comparative examples are all realized based on a microchannel modular reactor, including a first feed pump, a second feed pump, a third feed pump, a fourth feed pump, a first micromixer, a second micromixer, a third micromixer, a micro reaction pipeline, a tubular temperature control module, a first microreactor, a second microreactor, a third microreactor, and a collection vessel, the first feed pump and the second feed pump are connected in parallel to the first micromixer, the first micromixer and the first microreactor are connected through a micro reaction pipeline, the first microreactor and the third feed pump are connected in parallel to the second micromixer, the second micromixer and the second microreactor are connected through a micro reaction pipeline, the second microreactor and the fourth feed pump are connected in parallel to the third micromixer, and the third micromixer, the third microreactor, and the collection vessel are connected in series through a micro reaction pipeline.

[0030] The first micro mixer, the second micro mixer, and the third micro mixer are slit plate mixer LH25 models, and the first micro reactor, the second micro reactor, and the third micro reactor are all Vapotech models. The reaction temperatures of the first micro reactor, the second micro reactor, and the third micro reactor are all controlled by heating with an oil bath. The first supply pump, the second supply pump, the third supply pump, and the fourth supply pump are all high-precision and low-pulsation supply pumps, and the first supply pump is responsible for pumping the first mixed liquid, the second supply pump is responsible for pumping the second mixed liquid, the third supply pump is responsible for pumping the third mixed liquid, and the fourth supply pump is responsible for pumping the fourth mixed liquid.

[0031] Example 1: Preparation of bio-based polyol Step 1: 100g of epoxidized soybean oil (epoxy value 6.5%) and 0.2g of fluoroboric acid (20mg, 50%) were mixed to obtain a first mixed liquid, and 28.55g of diisopropyl tartrate and 29ml of 1,4-dioxane were mixed to obtain a second mixed liquid. The temperature of the first microreactor was adjusted to 100°C, and the first mixed liquid and the second mixed liquid were simultaneously pumped into the 10ml first microreactor at rates of 1ml / min and 0.56ml / min, respectively, to carry out the first ring-opening reaction, and a first reaction effluent was obtained. Step 2: 4.64 g of 1,2-propylene glycol and 14 ml of 1,4-dioxane were mixed to obtain a third mixed liquid. The temperature of the second microreactor was adjusted to 100°C. The third mixed liquid and the first reaction effluent were separately and simultaneously pumped into a 15 ml second microreactor at a rate of 0.18 ml / min to carry out a second ring-opening reaction, and a second reaction effluent was obtained. Step 3: 7.16 g of methanol and 29 ml of 1,4-dioxane were mixed to obtain a fourth mixed solution, the temperature of the third microreactor was adjusted to 100°C, and the fourth mixed solution was pumped at a rate of 0.35 ml / min together with the second reaction effluent into a third 20 ml microreactor to carry out a third ring-opening reaction and obtain a third reaction effluent. Step 4: After the reaction was completed, the third reaction effluent was concentrated to 200 ml, 200 ml of ethyl acetate was added, and the mixture was washed with 50 ml of 5% sodium bicarbonate solution, then washed twice with 50 ml of water. The layers were separated, and the organic phase was dried, suction filtered and concentrated to obtain a bio-based polyol with a hydroxyl value of 226 mg KOH / g and a viscosity of 796 mPa s.

[0032] Preparation of bio-based polyurethane paint: The bio-based polyol obtained in this example was mixed with isocyanate so that the molar ratio of NCO functional groups to OH functional groups was 1.25:1, and then a catalyst was added in an amount of 3‰ relative to the mass of the polyol, and reacted for 2 hours to obtain a prepolymer mixture. A predetermined amount of hydrophilic chain extender was added to the prepolymer mixture, and the mixture was reacted for 3 hours to obtain a polymer mixture. An appropriate amount of neutralizing agent was added to neutralize the polymer mixture, and a diluent was added to emulsify by shearing at high speed to form a polyurethane emulsion. The polyurethane emulsion was sprayed onto a steel plate substrate, and the thickness of the dried film by one spray was 60 μm. After leaving it in a laboratory environment for 168 hours, it was tested.

[0033] Example 2: Preparation of bio-based polyol Step 1: 100g of epoxidized soybean oil (epoxy value 6%) and 0.2g of fluoroboric acid (20mg, 50%) were mixed to obtain a first mixed solution, and 27.06g of diethyl tartrate and 27ml of 1,4-dioxane were mixed to obtain a second mixed solution. The temperature of the first microreactor was adjusted to 100°C, and the first mixed solution and the second mixed solution were simultaneously pumped into the 10ml first microreactor at rates of 1ml / min and 0.53ml / min, respectively, to carry out the first ring-opening reaction, and a first reaction effluent was obtained. Step 2: 4.28 g of 1,2-propylene glycol and 13 ml of 1,4-dioxane were mixed to obtain a third mixed liquid. The temperature of the second microreactor was adjusted to 100° C., and the third mixed liquid was pumped simultaneously with the first reaction effluent at a rate of 0.17 ml / min into a 15 ml second microreactor to carry out a second ring-opening reaction and obtain a second reaction effluent. Step 3: 6.01 g of methanol and 24 ml of 1,4-dioxane were mixed to obtain a fourth mixed liquid. The temperature of the third microreactor was adjusted to 100°C. The fourth mixed liquid was pumped simultaneously with the second reaction effluent at a rate of 0.29 ml / min into a third 20 ml microreactor to carry out a third ring-opening reaction and obtain a third reaction effluent. Step 4: After the reaction was completed, the third reaction effluent was concentrated to 200 ml, 200 ml of ethyl acetate was added, and the mixture was washed with 50 ml of 5% sodium bicarbonate solution, then washed twice with 50 ml of water. The layers were separated, and the organic phase was dried, suction filtered and concentrated to obtain a bio-based polyol with a hydroxyl value of 217 mg KOH / g and a viscosity of 759 mPa s.

[0034] Preparation of bio-based polyurethane paint: The bio-based polyol obtained in this example was mixed with isocyanate so that the molar ratio of NCO functional groups to OH functional groups was 1.25:1.05, and then a catalyst was added in an amount of 3‰ relative to the mass of the polyol, and reacted for 2 hours to obtain a prepolymer mixture. A predetermined amount of hydrophilic chain extender was added to the prepolymer mixture, and the mixture was reacted for 3 hours to obtain a polymer mixture. An appropriate amount of neutralizing agent was added to neutralize the polymer mixture, and a diluent was added to emulsify by shearing at high speed to form a polyurethane emulsion. The polyurethane emulsion was sprayed onto a steel plate substrate, and the thickness of the dried film by one spray was 80 μm. After leaving it in a laboratory environment for 168 hours, it was tested.

[0035] Example 3: Preparation of Bio-Based Polyol Step 1: 100g of epoxidized soybean oil (epoxy value 6.5%) and 0.2g of fluoroboric acid (20mg, 50%) were mixed to obtain a first mixed solution, and 24.61g of dimethyl tartrate and 25ml of 1,4-dioxane were mixed to obtain a second mixed solution. The temperature of the first microreactor was adjusted to 100°C, and the first mixed solution and the second mixed solution were simultaneously pumped into the 10ml first microreactor at rates of 1ml / min and 0.48ml / min, respectively, to carry out the first ring-opening reaction, and a first reaction effluent was obtained. Step 2: 4.95 g of 1,2-propylene glycol and 15 ml of 1,4-dioxane were mixed to obtain a third mixed liquid. The temperature of the second microreactor was adjusted to 100° C., and the third mixed liquid was pumped at a rate of 0.19 ml / min separately from the first reaction effluent into a 15 ml second microreactor to carry out a second ring-opening reaction and obtain a second reaction effluent. Step 3: 6.51 g of methanol and 26 ml of 1,4-dioxane were mixed to obtain a fourth mixed liquid. The temperature of the third microreactor was adjusted to 100°C. The fourth mixed liquid was pumped simultaneously with the second reaction effluent at a rate of 0.31 ml / min into a third 20 ml microreactor to carry out a third ring-opening reaction and obtain a third reaction effluent. Step 4: After the reaction was completed, the third reaction effluent was concentrated to 200 ml, 200 ml of ethyl acetate was added, and the mixture was washed with 50 ml of 5% sodium bicarbonate solution, then washed twice with 50 ml of water. The layers were separated, and the organic phase was dried, suction filtered and concentrated to obtain a bio-based polyol with a hydroxyl value of 241 mg KOH / g and a viscosity of 864 mPa s.

[0036] Preparation of bio-based polyurethane paint: The bio-based polyol obtained in this example was mixed with isocyanate so that the molar ratio of NCO functional groups to OH functional groups was 1.25:1, and then a catalyst was added in an amount of 3‰ relative to the mass of the polyol, and reacted for 2 hours to obtain a prepolymer mixture. A predetermined amount of hydrophilic chain extender was added to the prepolymer mixture, and the mixture was reacted for 3 hours to obtain a polymer mixture. An appropriate amount of neutralizing agent was added to neutralize the polymer mixture, and a diluent was added to emulsify by shearing at high speed to form a polyurethane emulsion. The polyurethane emulsion was sprayed onto a steel plate substrate, and the thickness of the dried film by one spray was 60 μm. After leaving it in a laboratory environment for 168 hours, it was tested.

[0037] Example 4: Preparation of Bio-Based Polyol Step 1: 100g of epoxidized soybean oil (epoxy value 6%) and 0.2g of fluoroboric acid (20mg, 50%) were mixed to obtain a first mixed solution, and 28.99g of diisopropyl tartrate and 29ml of 1,4-dioxane were mixed to obtain a second mixed solution. The temperature of the first microreactor was adjusted to 100°C, and the first mixed solution and the second mixed solution were simultaneously pumped into the 10ml first microreactor at rates of 1ml / min and 0.57ml / min, respectively, to carry out the first ring-opening reaction, and a first reaction effluent was obtained. Step 2: 4.85 g of 1,2-propylene glycol and 15 ml of 1,4-dioxane were mixed to obtain a third mixed liquid. The temperature of the second microreactor was adjusted to 100° C., and the third mixed liquid was pumped simultaneously with the first reaction effluent at a rate of 0.19 ml / min into a 15 ml second microreactor to carry out a second ring-opening reaction and obtain a second reaction effluent. Step 3: 8.64 g of ethanol and 35 ml of 1,4-dioxane were mixed to obtain a fourth mixed solution, the temperature of the third microreactor was adjusted to 100°C, and the fourth mixed solution was pumped simultaneously with the second reaction effluent at a rate of 0.42 ml / min into a third 20 ml microreactor to carry out a third ring-opening reaction and obtain a third reaction effluent. Step 4: After the reaction was completed, the third reaction effluent was concentrated to 200 ml, 200 ml of ethyl acetate was added, and the mixture was washed with 50 ml of 5% sodium bicarbonate solution, then washed twice with 50 ml of water. The layers were separated, and the organic phase was dried, suction filtered and concentrated to obtain a bio-based polyol with a hydroxyl value of 203 mg KOH / g and a viscosity of 768 mPa s.

[0038] Preparation of bio-based polyurethane paint: The bio-based polyol obtained in this example was mixed with isocyanate so that the molar ratio of NCO functional groups to OH functional groups was 1.25:1, and then a catalyst was added in an amount of 3‰ relative to the mass of the polyol, and reacted for 2 hours to obtain a prepolymer mixture. A predetermined amount of hydrophilic chain extender was added to the prepolymer mixture, and the mixture was reacted for 3 hours to obtain a polymer mixture. An appropriate amount of neutralizing agent was added to neutralize the polymer mixture, and a diluent was added to emulsify by shearing at high speed to form a polyurethane emulsion. The polyurethane emulsion was sprayed onto a steel plate substrate, and the thickness of the dried film by one spray was 60 μm. After leaving it in a laboratory environment for 168 hours, it was tested.

[0039] Example 5: Preparation of Bio-Based Polyol Step 1: 100g of epoxidized soybean oil (epoxy value 6.5%) and 0.2g of fluoroboric acid (20mg, 50%) were mixed to obtain a first mixed solution, and 33.51g of diisopropyl tartrate and 34ml of 1,4-dioxane were mixed to obtain a second mixed solution. The temperature of the first microreactor was adjusted to 100°C, and the first mixed solution and the second mixed solution were simultaneously pumped into the 10ml first microreactor at rates of 1ml / min and 0.66ml / min, respectively, to carry out the first ring-opening reaction, and a first reaction effluent was obtained. Step 2: 4.64 g of 1,2-propylene glycol and 14 ml of 1,4-dioxane were mixed to obtain a third mixed liquid. The temperature of the second microreactor was adjusted to 100° C., and the third mixed liquid was pumped at a rate of 0.18 ml / min separately from the first reaction effluent into a 15 ml second microreactor to carry out a second ring-opening reaction and obtain a second reaction effluent. Step 3: 8.42 g of ethanol and 34 ml of 1,4-dioxane were mixed to obtain a fourth mixed liquid. The temperature of the third microreactor was adjusted to 100° C., and the fourth mixed liquid was pumped simultaneously with the second reaction effluent at a rate of 0.41 ml / min into a third 20 ml microreactor to carry out a third ring-opening reaction and obtain a third reaction effluent. Step 4: After the reaction was completed, the third reaction effluent was concentrated to 200 ml, 200 ml of ethyl acetate was added, and the mixture was washed with 50 ml of 5% sodium bicarbonate solution, then washed twice with 50 ml of water. The layers were separated, and the organic phase was dried, suction filtered and concentrated to obtain a bio-based polyol with a hydroxyl value of 228 mg KOH / g and a viscosity of 807 mPa s.

[0040] Preparation of bio-based polyurethane paint: The bio-based polyol obtained in this example was mixed with isocyanate so that the molar ratio of NCO functional groups to OH functional groups was 1.25:1, and then a catalyst was added in an amount of 3‰ relative to the mass of the polyol, and reacted for 2 hours to obtain a prepolymer mixture. A predetermined amount of hydrophilic chain extender was added to the prepolymer mixture, and the mixture was reacted for 3 hours to obtain a polymer mixture. An appropriate amount of neutralizing agent was added to neutralize the polymer mixture, and a diluent was added to emulsify by shearing at high speed to form a polyurethane emulsion. The polyurethane emulsion was sprayed onto a steel plate substrate, and the thickness of the dried film by one spray was 60 μm. After leaving it in a laboratory environment for 168 hours, it was tested.

[0041] Example 6: Preparation of Bio-Based Polyol Step 1: 100g of epoxidized soybean oil (epoxy value 6%) and 0.2g of fluoroboric acid (20mg, 50%) were mixed to obtain a first mixed solution, and 26.72g of dimethyl tartrate and 27ml of 1,4-dioxane were mixed to obtain a second mixed solution. The temperature of the first microreactor was adjusted to 100°C, and the first mixed solution and the second mixed solution were simultaneously pumped into the 10ml first microreactor at rates of 1ml / min and 0.52ml / min, respectively, to carry out the first ring-opening reaction, and a first reaction effluent was obtained. Step 2: 5.71 g of 1,2-propylene glycol and 17 ml of 1,4-dioxane were mixed to obtain a third mixed liquid. The temperature of the second microreactor was adjusted to 100° C., and the third mixed liquid was pumped at a rate of 0.22 ml / min separately from the first reaction effluent into a 15 ml second microreactor to carry out a second ring-opening reaction and obtain a second reaction effluent. Step 3: 6.91 g of ethanol and 28 ml of 1,4-dioxane were mixed to obtain a fourth mixed liquid. The temperature of the third microreactor was adjusted to 100° C., and the fourth mixed liquid was pumped simultaneously with the second reaction effluent at a rate of 0.34 ml / min into a third 20 ml microreactor to carry out a third ring-opening reaction and obtain a third reaction effluent. Step 4: After the reaction was completed, the third reaction effluent was concentrated to 200 ml, 200 ml of ethyl acetate was added, and the mixture was washed with 50 ml of 5% sodium bicarbonate solution, then washed twice with 50 ml of water. The layers were separated, and the organic phase was dried, suction filtered and concentrated to obtain a bio-based polyol with a hydroxyl value of 229 mg KOH / g and a viscosity of 772 mPa s.

[0042] Preparation of bio-based polyurethane paint: The bio-based polyol obtained in this example was mixed with isocyanate so that the molar ratio of NCO functional groups to OH functional groups was 1.25:1, and then a catalyst was added in an amount of 3‰ relative to the mass of the polyol, and reacted for 2 hours to obtain a prepolymer mixture. A predetermined amount of hydrophilic chain extender was added to the prepolymer mixture, and the mixture was reacted for 3 hours to obtain a polymer mixture. An appropriate amount of neutralizing agent was added to neutralize the polymer mixture, and a diluent was added to emulsify by shearing at high speed to form a polyurethane emulsion. The polyurethane emulsion was sprayed onto a steel plate substrate, and the thickness of the dried film by one spray was 60 μm. After leaving it in a laboratory environment for 168 hours, it was tested.

[0043] Comparative Example 1: Production of Bio-Based Polyol Step 1: 100 g of epoxidized soybean oil (epoxy value 6.5%) and 0.2 g of fluoroboric acid (20 mg, 50%) were mixed to obtain a first mixed liquid, and 28.55 g of diisopropyl tartrate and 29 ml of 1,4-dioxane were mixed to obtain a second mixed liquid. The first and second mixed liquids were added to a reactor to carry out a ring-opening reaction at 100°C and reacted for 2 hours. Step 2: 10.82 g of 1,2-propylene glycol and 32 ml of 1,4-dioxane were mixed to obtain a third mixture, and the third mixture was added to the reactor to continue the ring-opening reaction at 100° C. for 2 h. Step 3: 4.56 g of methanol and 18 ml of 1,4-dioxane were mixed to obtain a fourth mixture, and the fourth mixture was added to the reactor, and the ring-opening reaction was continued at 100° C. for 2 h. Step 4: After the reaction was completed, the reaction solution was concentrated to 200 ml, 200 ml of ethyl acetate was added, and the mixture was washed with 50 ml of 5% sodium bicarbonate solution, then washed twice with 50 ml of water. The layers were separated, and the organic phase was dried, suction filtered and concentrated to obtain a bio-based polyol with a hydroxyl value of 147 mg KOH / g and a viscosity of 1049 mPa s.

[0044] Preparation of bio-based polyurethane paint: The bio-based polyol and isocyanate obtained in this comparative example were mixed so that the molar ratio of NCO functional groups to OH functional groups was 1.25:1, and a catalyst was added in an amount of 3‰ relative to the mass of the polyol, and reacted for 2 hours to obtain a prepolymer mixture. A predetermined amount of hydrophilic chain extender was added to the prepolymer mixture, and the mixture was reacted for 3 hours to obtain a polymer mixture. An appropriate amount of neutralizing agent was added to neutralize the polymer mixture, and a diluent was added and emulsified by shearing at high speed to form a polyurethane emulsion. The polyurethane emulsion was sprayed onto a steel plate substrate, and the thickness of the dried film from one spray was 60 μm. After leaving it in a laboratory environment for 168 hours, it was tested.

[0045] Comparative Example 2: Production of Bio-Based Polyol Step 1: 100g of epoxidized soybean oil (epoxy value 6%) and 0.2g of fluoroboric acid (20mg, 50%) were mixed to obtain a first mixed liquid, and 14.27g of 1,2-propylene glycol and 14ml of 1,4-dioxane were mixed to obtain a second mixed liquid. The temperature of the first microreactor was adjusted to 100°C, and the first mixed liquid and the second mixed liquid were simultaneously pumped into the 10ml first microreactor at a rate of 1ml / min and 0.28ml / min, respectively, to carry out a first ring-opening reaction, and a first reaction effluent was obtained. Step 2: 6.01 g of methanol and 18 ml of 1,4-dioxane were mixed to obtain a third mixed liquid. The temperature of the second microreactor was adjusted to 100° C., and the third mixed liquid was pumped simultaneously with the first reaction effluent at a rate of 0.23 ml / min into a 15 ml second microreactor to carry out a second ring-opening reaction and obtain a second reaction effluent. Step 3: After the reaction was completed, the second reaction effluent was concentrated to 200 ml, 200 ml of ethyl acetate was added, and the mixture was washed with 50 ml of 5% sodium bicarbonate solution, then washed twice with 50 ml of water. The layers were separated, and the organic phase was dried, suction filtered and concentrated to obtain a bio-based polyol with a hydroxyl value of 252 mg KOH / g and a viscosity of 652 mPa s.

[0046] Preparation of bio-based polyurethane paint: The bio-based polyol and isocyanate obtained in this comparative example were mixed so that the molar ratio of NCO functional groups to OH functional groups was 1.25:1, and a catalyst was added in an amount of 3‰ relative to the mass of the polyol, and reacted for 2 hours to obtain a prepolymer mixture. A predetermined amount of hydrophilic chain extender was added to the prepolymer mixture, and the mixture was reacted for 3 hours to obtain a polymer mixture. An appropriate amount of neutralizing agent was added to neutralize the polymer mixture, and a diluent was added and emulsified by shearing at high speed to form a polyurethane emulsion. The polyurethane emulsion was sprayed onto a steel plate substrate, and the thickness of the dried film from one spray was 60 μm. After leaving it in a laboratory environment for 168 hours, it was tested.

[0047] Comparative Example 3: Production of Bio-Based Polyol Step 1: 100g of epoxidized soybean oil (epoxy value 6.5%) and 0.2g of fluoroboric acid (20mg, 50%) were mixed to obtain a first mixed liquid, and 47.58g of diisopropyl tartrate and 48ml of 1,4-dioxane were mixed to obtain a second mixed liquid. The temperature of the first microreactor was adjusted to 100°C, and the first mixed liquid and the second mixed liquid were simultaneously pumped into the 10ml first microreactor at a rate of 1ml / min and 0.93ml / min, respectively, to carry out the first ring-opening reaction, and a first reaction effluent was obtained. Step 2: 6.51 g of methanol and 20 ml of 1,4-dioxane were mixed to obtain a third mixed liquid. The temperature of the second microreactor was adjusted to 100° C., and the third mixed liquid was pumped simultaneously with the first reaction effluent at a rate of 0.26 ml / min into a 15 ml second microreactor to carry out a second ring-opening reaction and obtain a second reaction effluent. Step 3: After the reaction was completed, the second reaction effluent was concentrated to 200 ml, 200 ml of ethyl acetate was added, and the mixture was washed with 50 ml of 5% sodium bicarbonate solution, then washed twice with 50 ml of water. The layers were separated, and the organic phase was dried, suction filtered and concentrated to obtain a bio-based polyol with a hydroxyl value of 213 mg KOH / g and a viscosity of 825 mPa s.

[0048] Preparation of bio-based polyurethane paint: The bio-based polyol and isocyanate obtained in this comparative example were mixed so that the molar ratio of NCO functional groups to OH functional groups was 1.25:1, and a catalyst was added in an amount of 3‰ relative to the mass of the polyol, and reacted for 2 hours to obtain a prepolymer mixture. A predetermined amount of hydrophilic chain extender was added to the prepolymer mixture, and the mixture was reacted for 3 hours to obtain a polymer mixture. An appropriate amount of neutralizing agent was added to neutralize the polymer mixture, and a diluent was added and emulsified by shearing at high speed to form a polyurethane emulsion. The polyurethane emulsion was sprayed onto a steel plate substrate, and the thickness of the dried film from one spray was 60 μm. After leaving it in a laboratory environment for 168 hours, it was tested.

[0049] Comparative Example 4: Production of Bio-Based Polyol Step 1: 100g of epoxidized soybean oil (epoxy value 6%) and 0.2g of fluoroboric acid (20mg, 50%) were mixed to obtain a first mixed liquid, and 43.92g of diisopropyl tartrate and 44ml of 1,4-dioxane were mixed to obtain a second mixed liquid. The temperature of the first microreactor was adjusted to 100°C, and the first mixed liquid and the second mixed liquid were simultaneously pumped into the 10ml first microreactor at a rate of 1ml / min and 0.86ml / min, respectively, to carry out the first ring-opening reaction, and a first reaction effluent was obtained. Step 2: 14.27 g of 1,2-propylene glycol and 43 ml of 1,4-dioxane were mixed to obtain a third mixed liquid. The temperature of the second microreactor was adjusted to 100° C., and the third mixed liquid was pumped at a rate of 0.55 ml / min separately from the first reaction effluent into a 15 ml second microreactor to carry out a second ring-opening reaction and obtain a second reaction effluent. Step 3: After the reaction was completed, the second reaction effluent was concentrated to 200 ml, 200 ml of ethyl acetate was added, and the mixture was washed with 50 ml of 5% sodium bicarbonate solution, then washed twice with 50 ml of water. The layers were separated, and the organic phase was dried, suction filtered and concentrated to obtain a bio-based polyol with a hydroxyl value of 249 mg KOH / g and a viscosity of 727 mPa s.

[0050] Preparation of bio-based polyurethane paint: The bio-based polyol and isocyanate obtained in this comparative example were mixed so that the molar ratio of NCO functional groups to OH functional groups was 1.25:1, and a catalyst was added in an amount of 3‰ relative to the mass of the polyol, and reacted for 2 hours to obtain a prepolymer mixture. A predetermined amount of hydrophilic chain extender was added to the prepolymer mixture, and the mixture was reacted for 3 hours to obtain a polymer mixture. An appropriate amount of neutralizing agent was added to neutralize the polymer mixture, and a diluent was added and emulsified by shearing at high speed to form a polyurethane emulsion. The polyurethane emulsion was sprayed onto a steel plate substrate, and the thickness of the dried film from one spray was 60 μm. After leaving it in a laboratory environment for 168 hours, it was tested.

[0051] Table 1 shows the performance indexes of the bio-based polyols produced in Examples 1 to 6 and Comparative Examples 1 to 4, and Table 2 shows the performance indexes of the produced bio-based polyurethane coating materials.

[0052] Performance indexes of bio-based polyols produced in Examples 1 to 6 and Comparative Examples 1 to 4 JPEG0007659288000002.jpg80170

[0053] Performance indexes of bio-based polyurethane paints produced in Examples 1 to 6 and Comparative Examples 1 to 4 JPEG0007659288000003.jpg78170

[0054] From the data in Tables 1 and 2, it is clear that the bio-based polyol produced in a conventional reactor has a low hydroxyl value, serious attenuation, and many crosslinking side reactions, resulting in large molecular weight, high viscosity, and uncontrollable reactions in the reactor.

[0055] The basic principles and main features of the present invention, as well as the advantages of the present invention, have been shown and described above. Those skilled in the art should understand that the present invention is not limited to the above examples, and that the above examples and the description in the specification are merely illustrative of the principles of the present invention, and that the present invention can be modified and improved in various ways without departing from the spirit and scope of the present invention, and all such modifications and improvements are included in the scope of the present invention as claimed. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. 1. A method for producing a bio-based polyol, comprising: Step 1: mixing an epoxidized vegetable oil with a catalyst to obtain a first mixed solution; dissolving at least one of a first ring-opening reagent, dimethyl tartrate, diethyl tartrate, and diisopropyl tartrate, in an organic solvent to obtain a second mixed solution; simultaneously pumping the first mixed solution and the second mixed solution into a first microreactor of a microchannel modular reactor to carry out a first ring-opening reaction; and obtaining a first reaction effluent; Step 2: dissolving a second ring-opening reagent, 1,2-propylene glycol, in an organic solvent to obtain a third mixture; and simultaneously pumping the third mixture and the first reaction effluent into a second microreactor of a microchannel modular reactor to carry out a second ring-opening reaction and obtain a second reaction effluent; Step 3: dissolving at least one of methanol and ethanol, which is a third ring-opening reagent, in an organic solvent to obtain a fourth mixture; and simultaneously pumping the fourth mixture and the second reaction effluent into a third microreactor of a microchannel modular reactor to carry out a third ring-opening reaction and obtain a third reaction effluent; and step 4 of concentrating the third reaction effluent to a predetermined volume, adding a predetermined volume of ethyl acetate, washing with sodium bicarbonate solution and water in turn, separating the layers, drying the organic phase, suction filtering and concentrating to obtain a bio-based polyol.

2. 2. The method of claim 1, wherein the epoxidized vegetable oil is at least one of epoxidized olive oil, epoxidized peanut oil, epoxidized rapeseed oil, epoxidized cottonseed oil, epoxidized soybean oil, epoxidized coconut oil, epoxidized palm oil, epoxidized sesame oil, epoxidized corn oil, and epoxidized sunflower oil.

3. 2. The method according to claim 1, wherein the organic solvent is at least one of ethyl acetate, dichloromethane, dichloroethane, chloroform, n-hexane, tetrahydrofuran, 1,4-dioxane, carbon tetrachloride, toluene, and xylene, and the catalyst is at least one of fluoroboric acid, phosphoric acid, phosphotungstic acid, and lipase CALB.

4. 2. The method according to claim 1, wherein a mass / volume ratio (g / ml) of the first ring-opening reagent to the organic solvent is 1:0.5-2, a mass ratio of the epoxidized vegetable oil to the catalyst is 1:0.02-0.1, and a molar ratio of the epoxy in the epoxidized vegetable oil to the first ring-opening reagent is 1:0.3-0.

4.

5. 2. The method according to claim 1, wherein the first ring-opening reaction is carried out at a reaction temperature of 80 to 120° C. for a reaction time of 3 to 15 min.

6. 2. The method according to claim 1, wherein a molar ratio of the epoxy in the epoxidized vegetable oil to the second ring-opening reagent is 1:0.1-0.2, and a mass volume ratio (g / ml) of the second ring-opening reagent to the organic solvent is 1:1-4.

7. 2. The method according to claim 1, wherein the second ring-opening reaction is carried out at a reaction temperature of 80 to 120° C. for a reaction time of 3 to 15 min.

8. 2. The method according to claim 1, wherein a molar ratio of the epoxy in the epoxidized vegetable oil to the third ring-opening reagent is 1:0.4-0.6, and a mass volume ratio (g / ml) of the third ring-opening reagent to the organic solvent is 1:4-8.

9. 2. The method according to claim 1, wherein the third ring-opening reaction is carried out at a reaction temperature of 80 to 120° C. for a reaction time of 3 to 15 min.

10. 10. Use of a bio-based polyol produced by the process according to any one of claims 1 to 9 in the production of a polyurethane coating.

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