CN109134260B - Bio-based polyol and preparation method and application thereof - Google Patents
Bio-based polyol and preparation method and application thereof Download PDFInfo
- Publication number
- CN109134260B CN109134260B CN201811201272.2A CN201811201272A CN109134260B CN 109134260 B CN109134260 B CN 109134260B CN 201811201272 A CN201811201272 A CN 201811201272A CN 109134260 B CN109134260 B CN 109134260B
- Authority
- CN
- China
- Prior art keywords
- epoxidized
- oil
- microreactor
- reaction
- micro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Fats And Perfumes (AREA)
- Epoxy Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a bio-based polyol and a preparation method and application thereof, wherein the method comprises the following steps: (1) simultaneously pumping an ethyl acetate solution of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane and an alcoholic solution of potassium hydroxide into a first microreactor of a micro-reaction device for reaction to obtain a reaction effluent; (2) and (2) pumping the reaction effluent obtained in the step (1) and an ethyl acetate solution of the epoxidized vegetable oil into a second microreactor of the microreactor at the same time for reaction to obtain the bio-based polyol. The preparation method disclosed by the invention is simple and efficient, and has the advantages of high selectivity, high safety, continuous production and no need of using a novel catalyst.
Description
Technical Field
The invention belongs to the technical field of chemical materials and production thereof, and particularly relates to a bio-based polyol, a preparation method and application thereof.
Background
The polyurethane rigid foam material is an important functional material, has good heat preservation performance and structural strength, is widely applied to various industries such as building heat preservation, pipeline heat preservation, household appliance heat preservation, decoration and finishing, light board material, automobile manufacturing, electronic component manufacturing and the like, wherein the national market demand exceeds 250 million tons/year, the output value is nearly 300 million yuan/year, the downstream application industry scale can reach several hundred million yuan/year, and the annual average market demand growth rate is kept to be 11.6% (see table 1).
TABLE 1 production of Chinese polyurethane products (Unit: ten thousand tons)
The traditional polyurethane rigid foam polyol mainly comprises petrochemical polyether polyol, and has the following defects: 1) various polyether products are disordered in variety and have different qualities; 2) the production process is dangerous and involves the application of a large amount of propylene oxide; 3) the resource dependence is too strong, and the product is not environment-friendly. Therefore, the development of high-performance, environment-friendly and safe-process bio-based polyurethane rigid foam polyol has become a research hotspot in the global industrial industry, and is also a leading-edge technology and a key field for advanced deployment and key research in China.
At present, many international known enterprises have put a lot of research and development efforts into the development of biobased polyurethane rigid foam polyols, such as basf, imperial, dupont, etc. However, the research in the field still belongs to the starting stage, the developed product faces the international problems that the full replacement of the petrochemical polyether polyol is difficult to realize (the replacement rate is only 20-50 percent) and the foam has obvious defects in the heat-conducting property and the mechanical property, and no document reports the quantitative structure-activity relationship between the molecular structure of the polyol and the foam material. Through mechanism exploration, the research on the bio-based polyurethane polyol mainly has the international common problems that the structural components are complex, the raw material components are various and the molecular structure is difficult to effectively construct at present, and the industrial development of the bio-based polyurethane material is greatly hindered.
CN1837180A and CN101139252A respectively use rapeseed oil and jatropha curcas oil as raw materials to prepare vegetable oil polyol through three steps of alcoholysis/epoxidation/ring opening reaction. CN1837181A and CN10118803A respectively take rapeseed oil and jatropha curcas oil as raw materials, and the vegetable oil polyol is prepared by three steps of reaction of epoxidation/ring opening/alcoholysis. CN101906016A is prepared from rubber seed oil as main raw material by epoxidation/ring opening two-step reaction to obtain vegetable oil polyol. In CN101659627A, vegetable oil polyol is prepared through ring-opening reaction and ester amidation reaction between epoxidized vegetable oil and glycol amine. CN101747184A and CN101230020A react under an acidic condition by virtue of epoxidation reaction and ring-opening reaction, and the vegetable oil polyol is prepared by a one-step method. In the above patents, the preparation of vegetable oil polyols is based on ring opening after double bond epoxidation, and the ring opening reagent is mainly small molecular alcohol, alcohol amine or carboxylic acid, which has many problems, such as low product quality, complicated post-treatment, and easy occurrence of cross-linking side reaction in the reaction. In addition, the prepared vegetable oil polyol still needs to be compounded with a certain proportion of petrochemical polyol.
CN104673501A pumps potassium permanganate alkaline solution and vegetable oil into the micro-channel modular reaction device simultaneously, and biological base polyol with a pinacol structure is prepared after reaction and post-treatment. CN103274930A realizes epoxidation reaction and ring-opening reaction simultaneously in a microchannel modular reaction device, thereby preparing the vegetable oil polyol. CN103288642A pumps the organic solution of the epoxy vegetable oil and the catalyst water solution into a micro-channel modular reaction device, and prepares the vegetable oil polyol through ring-opening reaction. In the patent, the automation degree of the whole process flow is obviously improved by using the micro-channel modular reaction device, the reaction time is shortened, the energy consumption is reduced, and the side reaction is weakened. However, the ring-opening reagent used in these 3 patents is water, which results in poor product quality of the final vegetable oil polyol, and the final vegetable oil polyol is still required to be compounded with petrochemical polyol for use in polyurethane preparation.
Disclosure of Invention
The invention aims to provide a method for preparing bio-based polyol by using a micro-reaction device, which aims to solve the problems of long reaction time, high energy consumption, low product quality, incapability of continuous production, low automation degree and the like in the conventional batch method for preparing vegetable oil polyol.
Another object of the present invention is to provide a bio-based polyol prepared by the method.
It is a final object of the invention to provide the use of said bio-based polyols.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method of preparing a bio-based polyol, comprising the steps of:
(1) simultaneously pumping an ethyl acetate solution of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane and an alcoholic solution of potassium hydroxide into a first microreactor of a micro-reaction device for reaction to obtain a reaction effluent;
(2) and (2) pumping the reaction effluent obtained in the step (1) and an ethyl acetate solution of the epoxidized vegetable oil into a second microreactor of the microreactor at the same time for reaction to obtain the bio-based polyol.
The reaction formula of the invention is as follows:
preferably, the method for preparing the bio-based polyol comprises the following steps:
(1) respectively and simultaneously pumping an ethyl acetate solution of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane and an alcoholic solution of potassium hydroxide into a first micro mixer of a micro-reaction device, fully mixing, and flowing into a first microreactor of the micro-reaction device for reaction to obtain a reaction effluent;
(2) and (2) respectively and simultaneously pumping the reaction effluent obtained in the step (1) and an ethyl acetate solution of the epoxidized vegetable oil into a second micro mixer of the micro reaction device, fully mixing, and then flowing into a second micro reactor of the micro reaction device for reaction to obtain the bio-based polyol.
In the step (1), the alcohol is methanol, ethanol, 1, 2-propylene glycol, 1, 3-propylene glycol, diethylene glycol, ethylene glycol or glycerol, preferably 1, 2-propylene glycol, 1, 3-propylene glycol, pentaerythritol, diethylene glycol, ethylene glycol or glycerol, and more preferably glycerol.
In the step (1), the mass fraction of the 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane in the ethyl acetate solution of the 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane is 10wt% -20 wt%.
In the step (1), the mass fraction of potassium hydroxide in the alcoholic solution of potassium hydroxide is 0.1wt% -1 wt%.
In the step (1), in the first microreactor, the reaction temperature is 100-; the reaction residence time is 10-30min, preferably 15-25min, the volume of the first microreactor is 5-50mL, the flow rate of the ethyl acetate solution of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane pumped into the micro-reaction device is 0-1mL/min, and the flow rate of the alcoholic solution of potassium hydroxide pumped into the micro-reaction device is 0-1 mL/min.
In the step (1), the molar ratio of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane to alcohol is 1 (1-10).
In the step (2), the epoxidized vegetable oil is one or more 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 or epoxidized sunflower seed oil, preferably Epoxidized Soybean Oil (ESO), and the mass fraction of the epoxidized vegetable oil in the ethyl acetate solution of the epoxidized vegetable oil is 10-20 wt%.
In the step (2), in the second microreactor, the reaction temperature is 120-; the reaction residence time is 20-30min, preferably 20-25min, the volume of the second microreactor is 10-40mL, the flow rate of the reaction effluent obtained in the step (1) pumped into the micro-reaction device is 0.2-1mL/min, and the flow rate of the ethyl acetate solution of epoxidized soybean oil pumped into the micro-reaction device is 0.2-1 mL/min.
In the step (2), the molar ratio of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane to epoxidized soybean oil is (1-10): 1.
And (2) separating water oil from the reaction effluent in the second microreactor, taking an organic phase, washing the organic phase with water, and drying to obtain the bio-based polyol. The washing refers to washing the organic phase to pH 6.5-7.5, and the drying method is drying by adopting anhydrous sodium sulfate or anhydrous magnesium sulfate and the like.
The micro-reaction device comprises a first micro-mixer, a first micro-reactor, a second micro-mixer and a second micro-reactor which are sequentially connected through a connecting pipe. The reaction raw materials are fed into the micromixer and the subsequent equipment by means of a precise and low-pulsation pump.
The first micromixer and the second micromixer are respectively and independently a slit plate mixer LH25(Hastelloy C), a Y-type mixer or a T-type mixer.
The first micro-reactor and the second micro-reactor are respectively and independently a meander reactivor HC, a sandwich reactivor HC, a fixed bed meander reactivor HC or a capillary (the inner diameter is 0.1-2 mm).
The bio-based polyol prepared by the method is provided.
The invention relates to application of bio-based polyol in preparation of rigid polyurethane foam.
According to the invention, epoxidized soybean oil is used as a basic raw material, and a novel ring-opening reagent is prepared by a multi-step continuous synthesis by using a micro-reaction device on the basis of structure-activity relationship research and molecular structure design. The preparation method is continuous operation, the preparation process is easy to operate and control, the reaction time is short, the energy consumption is low, the side reaction is obviously weakened, and the controllable hydroxyl value range of the product is larger. According to the invention, 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane is adopted, on one hand, the hydroxyl value can be increased, on the other hand, a rigid structure is introduced into the structure of the bio-based polyol by introducing 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane, the compression strength and the thermodynamic property of a hard bubble are improved, and the adverse effect brought by a suspension chain is alleviated.
Has the advantages that: compared with the prior art, the invention has the following advantages:
1. the preparation method of the bio-based polyol provided by the invention is a continuous process, the preparation process is easy to operate and control, the safety is high, the reaction condition is mild, the reaction residence time is short, the product quality is stable, and the yield is high. The production device has the characteristics of simplicity, easy disassembly and assembly, and convenient carrying and movement. Can be conveniently adjusted by simply increasing or decreasing the number of the micro-channels, and has no amplification effect similar to industrial production.
2. The preparation method of the bio-based polyol can overcome the problems in the existing production, avoids the use of complex catalysts, has low production cost and high process continuity, greatly improves the safety of the production process and improves the product quality.
Drawings
FIG. 1 is a schematic view of a micro-reaction device.
Detailed Description
The micro-reaction device described in the following embodiment, as shown in fig. 1, includes a first micro-mixer, a first micro-reactor, a second micro-mixer and a second micro-reactor connected in series in sequence through connecting pipes; wherein, the feed inlet of the first micro mixer is connected with a first feed liquid storage tank (a storage tank for alcoholic solution of potassium hydroxide) through a pump A, the feed inlet of the first micro mixer is connected with a second feed liquid storage tank (a storage tank for ethyl acetate solution of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane) through a pump B, the feed inlet of the second micro mixer is connected with the discharge port of the first microreactor, and the feed inlet of the second micro mixer is connected with a third feed liquid storage tank (a storage tank for ethyl acetate solution of epoxidized soybean oil) through a pump C.
The first micromixer and the second micromixer are respectively and independently one of slit plate mixer LH25(Hastelloy C), a Y-type mixer and a T-type mixer.
The first micro-reactor and the second micro-reactor are respectively and independently one of a meander reactivor HC, a sandwich reactivor HC, a fixed bed meander reactivor HC and a capillary (the inner diameter is 0.1-2 mm).
The hydroxyl value calculation method refers to GB/T12008.3-2009, and the epoxy value calculation refers to GB/T1677-2008.
Example 1:
an ethyl acetate solution (10 wt%) of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane and a glycerol solution (0.1 wt%) of potassium hydroxide were mixed in a ratio of 1:1 (in terms of the molar ratio of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane to glycerol) is respectively and simultaneously pumped into a first micro mixer, the flow rate of the ethyl acetate solution of the 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane is 0.95mL/min, the flow rate of the glycerol solution of potassium hydroxide is 0.05mL/min, and the mixture is fully mixed and then introduced into a first microreactor in a micro reaction device for reaction; the volume of the first microreactor was 10 mL. The mixed system stays in the first micro-reactor for 10min at 100 ℃. And then, simultaneously and respectively pumping the ethyl acetate solution (10 wt%) of the epoxidized soybean oil and the discharged material of the first microreactor into a second micromixer, wherein the flow rate of the ethyl acetate solution of the epoxidized soybean oil is 1.65mL/min, the flow rate of the discharged material of the first microreactor is 1mL/min, fully mixing the materials, and then introducing the materials into a second microreactor in a microreactor, wherein the volume of the second microreactor is 26.5 mL. Wherein the molar ratio of the 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane to the epoxidized soybean oil is 1: 1. And (3) after the material stays in a second microreactor for 10min at 120 ℃, introducing the discharged material into an oil-water separator, standing and layering, removing the aqueous solution of the lower layer, washing the organic phase of the upper layer to pH 6.5-7.5, and drying with anhydrous sodium sulfate to obtain the bio-based polyol, wherein the hydroxyl value is 120mgKOH/g, and the epoxy value is 0.
Example 2:
an ethyl acetate solution (10 wt%) of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane and a glycerol solution (0.5 wt%) of potassium hydroxide were mixed in a ratio of 1: 5 (calculated by the molar ratio of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane to glycerol) are respectively and simultaneously pumped into a first micro mixer, the flow rate of the ethyl acetate solution of the 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane is 0.8mL/min, the flow rate of the glycerol solution of potassium hydroxide is 0.2mL/min, and the mixture is fully mixed and then introduced into a first microreactor in a micro reaction device for reaction; the volume of the first microreactor was 20 mL. The mixed system stays in the first micro-reactor for 20min at 150 ℃. And respectively pumping the ethyl acetate solution (20 wt%) of the epoxidized soybean oil and the discharged material of the first microreactor into a second micromixer at the same time, wherein the flow rate of the ethyl acetate solution of the epoxidized soybean oil is 0.66mL/min, the flow rate of the discharged material of the first microreactor is 1mL/min, fully mixing, and introducing into a second microreactor in the microreactor, wherein the volume of the second microreactor is 33.2 mL. Wherein the molar ratio of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane to epoxidized soybean oil is 5: 1. And (3) after the material stays in a second microreactor for 20min at 160 ℃, introducing the discharged material into an oil-water separator, standing and layering, removing the aqueous solution of the lower layer, washing the organic phase of the upper layer to pH 6.5-7.5, and drying with anhydrous sodium sulfate to obtain the bio-based polyol with the hydroxyl value of 320mgKOH/g and the epoxy value of 0.
Example 3:
an ethyl acetate solution (20 wt%) of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane and a glycerol solution (1 wt%) of potassium hydroxide were mixed in a ratio of 1: 10 (in terms of the molar ratio of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane to glycerol) are respectively and simultaneously pumped into a first micro mixer, the flow rate of the ethyl acetate solution of the 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane is 0.49mL/min, the flow rate of the glycerol solution of potassium hydroxide is 0.51mL/min, and the mixture is fully mixed and then introduced into a first microreactor in a micro reaction device for reaction; the volume of the first microreactor was 30 mL. The mixed system stays in the first micro-reactor for 30min at 200 ℃. And respectively pumping the ethyl acetate solution (15 wt%) of the epoxidized soybean oil and the discharged material of the first microreactor into a second micromixer at the same time, wherein the flow rate of the ethyl acetate solution of the epoxidized soybean oil is 1.13mL/min, the flow rate of the discharged material of the first microreactor is 1mL/min, fully mixing, and then introducing into a second microreactor in the microreactor, wherein the volume of the second microreactor is 33.5 mL. Wherein the molar ratio of the 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane to the epoxidized soybean oil is 10: 1. And (3) after the material stays in a second microreactor for 15min at 200 ℃, introducing the discharged material into an oil-water separator, standing and layering, removing the aqueous solution of the lower layer, washing the organic phase of the upper layer to pH 6.5-7.5, and drying with anhydrous sodium sulfate to obtain the bio-based polyol with the hydroxyl value of 280mgKOH/g and the epoxy value of 0.
Example 4:
an ethyl acetate solution (20 wt%) of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane and a glycerol solution (1 wt%) of potassium hydroxide were mixed in a ratio of 1: 10 (in terms of the molar ratio of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane to glycerol) are respectively and simultaneously pumped into a first micro mixer, the flow rate of the ethyl acetate solution of the 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane is 0.49mL/min, the flow rate of the glycerol solution of potassium hydroxide is 0.51mL/min, and the mixture is fully mixed and then introduced into a first microreactor in a micro reaction device for reaction; the volume of the first microreactor was 25 mL. The mixed system stays in the first micro-reactor for 25min at 120 ℃. And respectively pumping the ethyl acetate solution (20 wt%) of the epoxidized soybean oil and the discharged material of the first microreactor into a second micromixer at the same time, wherein the flow rate of the ethyl acetate solution of the epoxidized soybean oil is 0.84mL/min, the flow rate of the discharged material of the first microreactor is 1mL/min, fully mixing, and then introducing into the second microreactor in the microreactor, and the volume of the second microreactor is 37 mL. Wherein the molar ratio of the 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane to the epoxidized soybean oil is 10: 1. And (3) after the material stays in a second microreactor for 20min at 180 ℃, introducing the discharged material into an oil-water separator, standing and layering, removing the aqueous solution of the lower layer, washing the organic phase of the upper layer to pH 6.5-7.5, and drying with anhydrous sodium sulfate to obtain the bio-based polyol, wherein the hydroxyl value is 480mgKOH/g, and the epoxy value is 0.
Example 5:
an ethyl acetate solution (20 wt%) of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane and a glycerol solution (1 wt%) of potassium hydroxide were mixed in a ratio of 1: 10 (in terms of the molar ratio of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane to glycerol) are respectively and simultaneously pumped into a first micro mixer, the flow rate of the ethyl acetate solution of the 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane is 0.49mL/min, the flow rate of the glycerol solution of potassium hydroxide is 0.51mL/min, and the mixture is fully mixed and then introduced into a first microreactor in a micro reaction device for reaction; the volume of the first microreactor was 15 mL. The mixed system stays in the first micro-reactor for 15min at 170 ℃. And respectively pumping the ethyl acetate solution (20 wt%) of the epoxidized soybean oil and the discharged material of the first microreactor into a second micromixer at the same time, wherein the flow rate of the ethyl acetate solution of the epoxidized soybean oil is 0.84mL/min, the flow rate of the discharged material of the first microreactor is 1mL/min, fully mixing, and then introducing into the second microreactor in the microreactor, and the volume of the second microreactor is 37 mL. Wherein the molar ratio of the 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane to the epoxidized soybean oil is 10: 1. And (3) after the material stays in a second microreactor for 20min at the temperature of 150 ℃, introducing the discharged material into an oil-water separator, standing and layering, removing the aqueous solution of the lower layer, washing the organic phase of the upper layer to the pH value of 6.5-7.5, and drying with anhydrous sodium sulfate to obtain the bio-based polyol, wherein the hydroxyl value is 450mgKOH/g, and the epoxy value is 0.
Example 6:
an ethyl acetate solution (15 wt%) of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane and a glycerol solution (1 wt%) of potassium hydroxide were mixed in a ratio of 1: 10 (calculated by the molar ratio of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane to glycerol) are respectively imported and simultaneously pumped into a first micro mixer, the flow rate of the ethyl acetate solution of the 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane is 0.56mL/min, the flow rate of the glycerol solution of potassium hydroxide is 0.44mL/min, and the mixture is fully mixed and then is introduced into a first microreactor in a micro reaction device for reaction; the volume of the first microreactor was 25 mL. The mixed system stays in the first micro-reactor for 25min at 170 ℃. And respectively pumping the ethyl acetate solution (15 wt%) of the epoxidized soybean oil and the discharged material of the first microreactor into a second micromixer at the same time, wherein the flow rate of the ethyl acetate solution of the epoxidized soybean oil is 0.97mL/min, the flow rate of the discharged material of the first microreactor is 1mL/min, fully mixing, and then introducing into a second microreactor in the microreactor, wherein the volume of the second microreactor is 39.4 mL. Wherein the molar ratio of the 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane to the epoxidized soybean oil is 10: 1. And (3) after the material stays in a second microreactor for 20min at 180 ℃, introducing the discharged material into an oil-water separator, standing and layering, removing the aqueous solution of the lower layer, washing the organic phase of the upper layer to pH 6.5-7.5, and drying with anhydrous sodium sulfate to obtain the bio-based polyol with the hydroxyl value of 440mgKOH/g and the epoxy value of 0.
Example 7:
an ethyl acetate solution (20 wt%) of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane and a glycerol solution (1 wt%) of potassium hydroxide were mixed in a ratio of 1: 5 (calculated by the molar ratio of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane to glycerol) are respectively and simultaneously pumped into a first micro mixer, the flow rate of the ethyl acetate solution of the 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane is 0.66mL/min, the flow rate of the glycerol solution of potassium hydroxide is 0.34mL/min, and the mixture is fully mixed and then introduced into a first microreactor in a micro reaction device for reaction; the volume of the first microreactor was 25 mL. The mixed system stays in the first micro-reactor for 25min at 170 ℃. And respectively pumping the ethyl acetate solution (20 wt%) of the epoxidized soybean oil and the discharged material of the first microreactor into a second micromixer at the same time, wherein the flow rate of the ethyl acetate solution of the epoxidized soybean oil is 1.12mL/min, the flow rate of the discharged material of the first microreactor is 1mL/min, fully mixing, and then introducing into a second microreactor in the microreactor, and the volume of the second microreactor is 40 mL. Wherein the molar ratio of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane to epoxidized soybean oil is 5: 1. And (3) after the material stays in a second microreactor for 19min at 180 ℃, introducing the discharged material into an oil-water separator, standing and layering, removing the aqueous solution of the lower layer, washing the organic phase of the upper layer to pH 6.5-7.5, and drying with anhydrous sodium sulfate to obtain the bio-based polyol with the hydroxyl value of 500mgKOH/g and the epoxy value of 0. The hydroxyl value of petrochemical polyether polyol 4110 is 420 +/-20 mgKOH/g, the viscosity is 2800-; the hydroxyl value of the bio-based polyol in the patent is 500mgKOH/g, the viscosity is 3800 +/-300 cp, and the thermal conductivity coefficient of foam prepared by foaming is 24-28 mW/m.K.
Example 8:
bio-based polyols were obtained in the same manner as in example 7, except that the alcohol type was changed, and the hydroxyl value and epoxy value were as shown in Table 2.
TABLE 2
| Kind of alcohol | Hydroxyl value/(mgKOH/g) | Epoxy value |
| Methanol | 150 | 0 |
| Ethanol | 140 | 0 |
| 1, 2-propanediol | 300 | 0 |
| 1, 3-propanediol | 350 | 0 |
| Diethylene glycol | 360 | 0 |
| Ethylene glycol | 380 | 0 |
Example 9
The hard foam prepared from the bio-based polyol has the thermal conductivity of about 21.2 mW/m.K and the compressive strength of about 289 KPa; the heat conductivity coefficient of the hard foam prepared by polyether polyol 4110 widely used in the market is 24-28 mW/m.K, and the compressive strength is 200-250 KPa.
Example 10
The same as example 7, except that: replacing the epoxidized soybean oil with epoxidized cottonseed oil to obtain the bio-based polyol.
Example 11
The same as example 7, except that: replacing the epoxidized soybean oil with an epoxidized corn oil to obtain a bio-based polyol.
Claims (10)
1. A method of preparing a bio-based polyol, comprising the steps of:
(1) simultaneously pumping an ethyl acetate solution of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane and an alcoholic solution of potassium hydroxide into a first microreactor of a micro-reaction device for reaction to obtain a reaction effluent;
(2) and (2) pumping the reaction effluent obtained in the step (1) and an ethyl acetate solution of the epoxidized vegetable oil into a second microreactor of the microreactor at the same time for reaction to obtain the bio-based polyol.
2. The method according to claim 1, wherein in the step (1), the alcohol is methanol, ethanol, 1, 2-propanediol, 1, 3-propanediol, pentaerythritol, diethylene glycol, ethylene glycol or glycerol, the mass fraction of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane in the ethyl acetate solution of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane is 10wt% to 20wt%, and the mass fraction of potassium hydroxide in the alcoholic solution of potassium hydroxide is 0.1wt% to 1 wt%.
3. The preparation method according to claim 1, wherein in the step (1), the reaction temperature is 100-200 ℃, the reaction residence time is 10-30min, the volume of the first microreactor is 5-50mL, the flow rate of the ethyl acetate solution of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane pumped into the micro-reaction device is 0.1-1 mL/min, and the flow rate of the alcoholic solution of potassium hydroxide pumped into the micro-reaction device is 0.1-1 mL/min.
4. The process according to claim 1, wherein the molar ratio of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane to the alcohol in the step (1) is 1 (1-10).
5. The preparation method according to claim 1, wherein in the step (2), the epoxidized vegetable oil is any one or more 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 or epoxidized sunflower oil, and the mass fraction of the epoxidized vegetable oil in the ethyl acetate solution of the epoxidized vegetable oil is 10wt% to 20 wt%.
6. The preparation method according to claim 1, wherein in the step (2), the epoxidized vegetable oil is epoxidized soybean oil, the reaction temperature in the second microreactor is 120-200 ℃, the reaction residence time is 20-30min, the volume of the second microreactor is 10-40mL, and the flow rate of the ethyl acetate solution of epoxidized soybean oil pumped into the microreactor is 0.2-1 mL/min.
7. The method according to claim 1, wherein in the step (2), the epoxidized vegetable oil is epoxidized soybean oil, and the molar ratio of 1, 2-dimethyl-7-oxabicyclo [4.1.0] heptane to epoxidized soybean oil is (1-10): 1.
8. The method of claim 1, wherein the micro-reaction device comprises a first micro-mixer, a first micro-reactor, a second micro-mixer and a second micro-reactor sequentially connected through a connecting pipe.
9. A biobased polyol prepared by the process of any of claims 1 to 8.
10. Use of the bio-based polyol of claim 9 in the preparation of rigid polyurethane foam.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811201272.2A CN109134260B (en) | 2018-10-16 | 2018-10-16 | Bio-based polyol and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811201272.2A CN109134260B (en) | 2018-10-16 | 2018-10-16 | Bio-based polyol and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109134260A CN109134260A (en) | 2019-01-04 |
| CN109134260B true CN109134260B (en) | 2021-03-16 |
Family
ID=64811961
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811201272.2A Active CN109134260B (en) | 2018-10-16 | 2018-10-16 | Bio-based polyol and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109134260B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110372841B (en) * | 2019-07-24 | 2022-02-11 | 张家港市飞航科技有限公司 | Polyurethane hard foam heat-insulating material and preparation method thereof |
| CN112321429B (en) * | 2020-11-03 | 2021-09-17 | 南京工业大学 | Method for continuously preparing bio-based polyol by using micro-channel and multi-stage reaction kettle |
| CN112898160B (en) * | 2021-01-25 | 2021-09-24 | 南京工业大学 | Vegetable oil polyalcohol, preparation method and application thereof in polyurethane material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610060A (en) * | 2015-02-05 | 2015-05-13 | 南京工业大学 | High hydroxyl value vegetable oil polyol and preparation method and application thereof |
| CN104744222A (en) * | 2013-12-31 | 2015-07-01 | 岳阳昌德化工实业有限公司 | Method for preparing 2-alkoxy cyclohexanol |
| CN104829824A (en) * | 2015-05-18 | 2015-08-12 | 南京工业大学 | Method for synthesizing polyether polyol in microstructure reactor |
| CN105541621A (en) * | 2015-03-17 | 2016-05-04 | 南京工业大学 | Vegetable oil polyalcohol and preparation method and application thereof |
| WO2017204509A1 (en) * | 2016-05-23 | 2017-11-30 | Mitsui Chemicals & Skc Polyurethanes Inc. | Bio-based polyol for preparing polyurethane |
| CN108033875A (en) * | 2017-12-14 | 2018-05-15 | 中国科学院过程工程研究所 | A kind of system and method for continuous production glycol ether |
-
2018
- 2018-10-16 CN CN201811201272.2A patent/CN109134260B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104744222A (en) * | 2013-12-31 | 2015-07-01 | 岳阳昌德化工实业有限公司 | Method for preparing 2-alkoxy cyclohexanol |
| CN104610060A (en) * | 2015-02-05 | 2015-05-13 | 南京工业大学 | High hydroxyl value vegetable oil polyol and preparation method and application thereof |
| CN105541621A (en) * | 2015-03-17 | 2016-05-04 | 南京工业大学 | Vegetable oil polyalcohol and preparation method and application thereof |
| CN104829824A (en) * | 2015-05-18 | 2015-08-12 | 南京工业大学 | Method for synthesizing polyether polyol in microstructure reactor |
| WO2017204509A1 (en) * | 2016-05-23 | 2017-11-30 | Mitsui Chemicals & Skc Polyurethanes Inc. | Bio-based polyol for preparing polyurethane |
| CN108033875A (en) * | 2017-12-14 | 2018-05-15 | 中国科学院过程工程研究所 | A kind of system and method for continuous production glycol ether |
Non-Patent Citations (1)
| Title |
|---|
| 环氧环己烷基聚氨酯透明材料的制备;杨宁宁等;《聚氨酯工业》;20161231;第31卷(第2期);第9-11页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109134260A (en) | 2019-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109134260B (en) | Bio-based polyol and preparation method and application thereof | |
| CN103288642B (en) | Method for preparing vegetable oil polyalcohol by using continuous method | |
| CN105541621A (en) | Vegetable oil polyalcohol and preparation method and application thereof | |
| CN105669450A (en) | High hydroxyl value vegetable oil polyol and preparation method and application thereof | |
| CN104725229B (en) | The method for preparing polymethoxy dimethyl ether carbonyl compound and methoxy menthyl acetate | |
| CN112321429B (en) | Method for continuously preparing bio-based polyol by using micro-channel and multi-stage reaction kettle | |
| US10259771B2 (en) | Vegetable oil polyol and the preparation method and the application thereof | |
| CN104557478A (en) | Method for preparing tert-butyl ether | |
| US20190119493A1 (en) | Vegetable Oil Polyol for Flexible Polyurethane Foam and Preparation Method and Application Thereof | |
| CN106220481A (en) | A kind of technique of continuous production polyoxymethylene dimethyl ether | |
| CN108102683B (en) | Preparation method of branched alkane in range of renewable dodecyl alcohol and aviation kerosene | |
| CN104045516B (en) | The method improving quality of ethylene glycol product | |
| CN106349019A (en) | Method for producing cyclohexanol | |
| CN107602358B (en) | Method for preparing methoxy acetone by using micro-reaction device | |
| CN101863738A (en) | Method for preparing neopentyl glycol | |
| CN104130107A (en) | Preparation method for synthesizing 3-methyl-3-butene-1-ol by using formaldehyde hemiacetal | |
| CN110950760B (en) | Process for synthesizing tert-butyl acrylate | |
| CN102603500A (en) | Method for preparing glutaraldehyde by utilizing microchannel reactor | |
| CN109134259B (en) | Bio-based polyol and preparation method and application thereof | |
| CN106831661B (en) | Method for preparing epoxypropane by using micro-reaction device | |
| CN102391070B (en) | Method for producing trimethylolpropane by utilizing formaldehyde | |
| CN105503610A (en) | Method for preparing o-nitro anisole by using micro-channel reaction apparatus | |
| CN101380576B (en) | Catalyst for hydrogenolysis of rare glycerol to produce diatomic alcohol and preparation method thereof | |
| CN102260170B (en) | Method for microwave pipeline production of butyl acetate | |
| CN108727159B (en) | Method and device for preparing dichloropropanol by micro-channel chlorination reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |