CN109574842B - Vegetable oil polyalcohol and preparation method and application thereof - Google Patents
Vegetable oil polyalcohol and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses vegetable oil polyalcohol and a preparation method and application thereof, wherein mixed liquid prepared from hydrogen peroxide, organic acid, a catalyst and a stabilizer and vegetable oil are respectively pumped into a first microstructure reactor of a microchannel modular reaction device for reaction to obtain epoxy vegetable oil with an iodine value of 15-20; preparing mixed solution of glycerol and tetra-n-butylammonium acetate, and pumping the mixed solution and benzoyl chloride into a second microstructure reactor of the microchannel modular reaction device to react to obtain the polyhydroxy compound shown in the formula III; and finally, simultaneously pumping the epoxy vegetable oil and the polyhydroxy compound shown in the formula III into a third microstructure reactor of the microchannel modular reaction device respectively for reaction to obtain the vegetable oil polyol. The vegetable oil polyol prepared by adopting the novel ring-opening reagent has the advantages of novel structure, high hydroxyl value, uniform distribution and lower viscosity, and can completely replace the traditional petrochemical polyol to be applied to the preparation of polyurethane foam materials.
Description
Technical Field
The invention belongs to the technical field of chemical materials and production thereof, and particularly relates to vegetable oil polyol and a preparation method and application thereof.
Background
Polyurethane is a polyurethane with a repeating unit structure of urethane chain segment prepared by the reaction of isocyanate and polyol, and is widely used in the fields of foam plastics, surface coatings, adhesives, sealants, composite materials and the like. The polyurethane material has excellent performance and wide application, and the polyurethane foam plastic has the most wide application. Currently, the depletion of petrochemical fuel resources and the growing concern for environmental issues are forcing researchers around the world to use vegetable oils to make polyurethanes.
The vegetable oil polyalcohol is mainly applied to the field of polyurethane preparation, and the prepared vegetable oil-based polyurethane material completely meets the requirement of environmental protection; and because of the hydrophobicity of the fatty glyceride serving as the main component of the vegetable oil, the vegetable oil-based polyurethane material has excellent physical and chemical properties, and particularly has better hydrophobicity and thermal stability. Thus, vegetable oil polyols and their polyurethane materials have been rapidly developed.
The vegetable oil polyalcohol is an important renewable resource, can react with isocyanate compounds to generate polyurethane, and is a good substitute raw material of petroleum-based polyalcohol. In recent years, the main methods for synthesizing vegetable oil polyols include: 1) carrying out alcoholysis reaction on vegetable oil and polyol to generate a polyhydroxy compound; 2) oxidizing unsaturated double bonds in the vegetable oil by using ozone to generate a polyhydroxy compound with terminal hydroxyl; 3) vegetable oils are oxidized to epoxidized vegetable oils and then treated by hydrolysis, hydrogenation, methyl esterification or halogenation to produce polyols.
Among the above-mentioned methods for synthesizing vegetable oil polyols, the methods 1) and 3) are employed in many cases. CN1837180A and CN101139252A respectively use rapeseed oil and jatropha curcas oil as main raw materials to prepare vegetable oil polyol through three reactions of alcoholysis/epoxidation/ring opening. CN10106016A is prepared by using rubber seed oil as a main raw material and performing epoxidation/ring opening two-step reaction. CN1907944A directly takes epoxy rapeseed oil as a main raw material to prepare vegetable oil polyol through two-step reaction of ring opening/alcoholysis. CN101659627A is prepared by epoxy vegetable oil and diol amine simultaneously undergoing epoxy group ring opening reaction and ester amidation reaction.
The vegetable oil polyalcohol prepared by the above patents is mainly based on epoxy open loop and is reacted by an intermittent reaction kettle, and the following defects are mainly existed: 1) the reaction time is long; 2) the energy consumption is high; 3) the automatic control level of the equipment is low; 4) the crosslinking side reaction results in low hydroxyl value and high viscosity of the product.
In addition, the epoxidized vegetable oil prepared by the traditional method has lower iodine value and higher epoxy value, so that the vegetable oil polyol prepared by the traditional method has higher viscosity and is not beneficial to subsequent foaming.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the problems of high hydroxyl value and high viscosity of a generated polyol product caused by low iodine value and high epoxy value of the existing epoxidized vegetable oil, the invention provides a preparation method of vegetable oil polyol, and the prepared vegetable oil polyol has a novel structure, an iodine value of 15-20, a moderate hydroxyl value and low viscosity, and can completely replace petrochemical polyol and be applied to vegetable oil polyol in the field of polyurethane foam materials. It is another object of the present invention to provide the use of the vegetable oil polyols.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of vegetable oil polyalcohol comprises the following steps:
(1) respectively pumping mixed liquid prepared from hydrogen peroxide, organic acid, a catalyst and a stabilizer and vegetable oil into a first microstructure reactor of a microchannel modular reaction device for reaction to obtain epoxy vegetable oil with an iodine value of 15-20;
(2) preparing mixed solution of glycerol and tetra-n-butylammonium acetate, and pumping the mixed solution and benzoyl chloride into a second microstructure reactor of the microchannel modular reaction device to react to obtain the polyhydroxy compound shown in the formula III;
(3) and (3) respectively and simultaneously pumping the epoxidized vegetable oil obtained in the step (1) and the polyhydroxy compound of the formula III obtained in the step (2) into a third microstructure reactor of the microchannel modular reaction device for reaction to obtain vegetable oil polyol.
In the step (1), the organic acid is formic acid or acetic acid, the catalyst is sulfuric acid or phosphoric acid, the stabilizer is ethylenediamine tetraacetic acid, the vegetable oil is at least one of olive oil, peanut oil, rapeseed oil, cottonseed oil, soybean oil, palm oil, sesame oil, sunflower oil, linseed oil, tung oil, safflower oil, rice bran oil, corn oil and tea oil, and the molar ratio of the vegetable oil double bonds, hydrogen peroxide, the organic acid, the catalyst and the stabilizer is 1 (15-18) to (0.1-0.2) to (0.02-0.05).
Preferably, the reaction temperature in the first microstructure reactor is 80-120 ℃, the reaction residence time is 10-15 minutes, the volume of the first microstructure reactor is 25-75 mL, the flow rate of a mixed liquid prepared from hydrogen peroxide, organic acid, a catalyst and a stabilizer pumped into the microchannel modular reaction device is 2.0-4.0 mL/min, and the flow rate of a vegetable oil pumped into the microchannel modular reaction device is 0.5-1.0 mL/min.
In the step (2), the benzoyl chloride is one of p-ethylbenzoyl chloride, p-n-butylbenzoyl chloride, p-hexylbenzoyl chloride and p-octylbenzoyl chloride, the molar ratio of glycerol to benzoyl chloride is 1 (1.9-2.2), and the molar ratio of glycerol to tetra-n-butylammonium acetate is 1 (0.5-0.7).
Preferably, the reaction temperature in the second microstructure reactor is 20-30 ℃, the reaction residence time is 10-15 minutes, the volume of the second microstructure reactor is 99-518 mL, the flow rate of the mixed liquid prepared from glycerol and tetra-n-butylammonium acetate pumped into the microchannel modular reaction device is 2.0-4.0 mL/min, and the flow rate of the benzoyl chloride pumped into the microchannel modular reaction device is 7.91-30.53 mL/min.
In the step (3), the reaction temperature in the third microstructure reactor is 80-120 ℃, the reaction residence time is 12-16 minutes, and the volume of the third microstructure reactor is 149-632 mL.
The microchannel modular reaction device comprises a first micro mixer, a first microstructure reactor, an oil-water separator, a second micro mixer, a second microstructure reactor, a third micro mixer and a third microstructure reactor; the first micro mixer, the first micro-structure reactor and the oil-water separator are connected in sequence; the discharge hole of the second micro-structure reactor and the discharge hole of the oil-water separator are connected in parallel to the feed inlet of the third micro-mixer; the third micro mixer and the third micro-structure reactor are connected in sequence through a pipeline; the reaction raw materials are input into the micromixer and the subsequent equipment through a low-pulsation pump.
The model of the first micro mixer, the second micro mixer and the third micro mixer is slit plate mixer LH 25.
The first microstructure reactor, the second microstructure reactor and the third microstructure reactor are of the models of a meaanderator HC, a sandwich bioreactor HC, a fixed bed meanger bioreactor HC or a Hastelloy microchannel reactor.
The vegetable oil polyol prepared by the method is also in the protection scope of the invention.
The invention also claims the application of the vegetable oil polyalcohol prepared by the method in preparing polyurethane foam.
According to the preparation method, vegetable oil is subjected to epoxidation reaction to prepare epoxy vegetable oil with an iodine value of 15-20, glycerin is reacted with benzoyl chloride to prepare a polyhydroxy compound in a formula III, and finally the epoxy vegetable oil is reacted with the polyhydroxy compound in the formula III to obtain vegetable oil polyol which is applied to polyurethane foaming; aromatic acid chlorides have rigidity compared to aliphatic acid chlorides. The vegetable oil contains unsaturated carbon-carbon double bonds, epoxy groups are generated through Prileshajev epoxidation reaction, then hydroxyl groups are introduced into the epoxy groups through ring opening reaction, commonly used ring opening reagents mainly comprise micromolecular alcohol, alcohol amine or carboxylic acid, wherein for the ring opening reagent with single functionality, the hydroxyl value of a product is lower, for the ring opening reagent with multiple functions, because all the hydroxyl groups are adjacent, the condition that the epoxy groups in a plurality of grease molecules are opened by the ring opening reagent with single molecule in the reaction exists, and the newly generated hydroxyl groups also participate in the ring opening reaction, so that grease molecules are polymerized together, the viscosity of the product is overlarge, and the hydroxyl value is lower. According to the invention, the polyhydroxy compound in the formula III is used as a ring-opening reagent, and aliphatic hydrocarbon is introduced into the structure of the polyhydroxy compound, so that the water resistance of the product can be effectively improved; the vegetable oil polyalcohol product prepared by ring opening can be ensured to have higher hydroxyl value, the crosslinking side reaction can be reduced, the product viscosity is reduced, and the polyurethane foam material based on the vegetable oil polyalcohol has excellent performance. In addition, the catalyst used in the method is very small in dosage, the use of the polyhydric alcohol is not influenced by trace residues, the product does not need to be further refined, and the process is simple.
Has the advantages that:
compared with the prior art, the invention adopts a novel ring-opening reagent, introduces aliphatic hydrocarbon into the structure and effectively improves the water resistance of the polyurethane product; the functionality of the ring-opening reagent is moderate, so that the hydroxyl value of a polyol product can be ensured, the cross-linking side reaction can be reduced, the product viscosity can be reduced, and the conventional petrochemical polyol can be completely replaced and applied to the preparation of polyurethane foam materials. Meanwhile, the method has the advantages of simple process, convenient operation, low energy consumption, less side reaction and high reaction efficiency, and the obtained product does not need further treatment and is very suitable for industrial production. Particularly, the micro-channel modular reaction device can effectively improve the reaction efficiency, control the occurrence of side reactions and reduce the energy consumption.
Drawings
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 is a schematic view of a microchannel modular reactor apparatus.
FIG. 2 is a scheme showing the synthesis of the polyhydroxy compound of formula III.
Detailed Description
The invention will be better understood from the following examples.
The related determination method of the prepared vegetable oil polyol and polyurethane foam material comprises the following steps:
measuring the hydroxyl value according to GB/T12008.3-2009;
measuring the viscosity according to GB/T12008.7-2010;
measuring the iodine value according to GB/T5532-;
determining the apparent density of the foam according to GB/T6343-2009;
the impact strength of the rigid foam is determined according to GB/T11548-1989, and the impact strength is used for representing the toughness or the resistance to fracture of the material in a high-speed impact state;
the dimensional stability of the rigid foams was determined according to GB/T8811-2008.
As shown in fig. 1, the microchannel modular reaction apparatus for sampling according to the present invention includes a first micromixer 1, a first microstructure reactor 3, an oil-water separator 5, a second micromixer 2, a second microstructure reactor 4, a third micromixer 6, and a third microstructure reactor 7; the first micro mixer 1, the first micro-structure reactor 3 and the oil-water separator 5 are connected in sequence; the discharge hole of the second micro-structure reactor 4 and the discharge hole of the oil-water separator 5 are connected in parallel to the feed inlet of the third micro-mixer 6; the third micromixer 6 and the third microstructure reactor 7 are connected in sequence through pipelines; the reaction feed is fed into the micromixer by a low-pulsation pump (A, B, C, D).
As shown in FIG. 2, in the present invention, glycerol (I) and benzoyl chloride (II) were synthesized into polyol (III) according to the illustrated synthetic route.
Example 1
200g of soybean oil (containing 0.99mol of double bonds) is taken as a component a, 1813.9g of 30 wt% hydrogen peroxide (16mol, counted by hydrogen peroxide) is mixed with 751.5g of formic acid (16mol), and 15.02g of sulfuric acid (0.15mol, counted by H) is added2SO4Metering) and EDTA13.14g (0.03mol) are used as a component b, the component a and the component b are respectively pumped into a first micro mixer of a micro-channel modular reaction device at the sampling rates of 0.7mL/min and 3.5mL/min at the same time, the components are fully mixed and then flow into a first micro-structure reactor, the volume of the first micro-structure reactor is 42mL, the reaction residence time is kept for 10 minutes, and the components are reacted at the normal pressure and 80 ℃; 1686.2g (10mol) of p-ethylbenzoyl chloride is taken as a component c, 921g (10mol) of glycerol and 1507g (5mol) of tetra-n-butylammonium acetate are taken to be mixed into a component d, the component c and the component d are simultaneously pumped into a second micro mixer of a micro-channel modular reaction device at the sampling rates of 8.92mL/min and 3.5mL/min respectively, the fully mixed components flow into a second micro-structure reactor, the volume of the second micro-structure reactor is 124.2mL, the reaction residence time is kept for 10 minutes, and the reaction is carried out at the normal pressure and the temperature of 25 ℃; pumping the epoxy vegetable oil output from the discharge port of the oil-water separator and the polyhydroxy compound output from the discharge port of the second microreactor into a third micromixer of the microchannel modular reaction device at the same time, fully mixing, then flowing into a third microstructure reactor, keeping the volume of the third microstructure reactor to be 249.3mL, keeping the reaction for 15 minutes, reacting at 90 ℃, collecting the product to obtain the soybean oil polyol, wherein the hydroxyl value of the soybean oil polyol is 309mg KOH/g, the viscosity of the soybean oil polyol is 2099 mPas, and the iodine value of the soybean oil polyol is 18.7.
Example 2
200g of cottonseed oil (containing 0.812mol of double bonds) is taken as a component a, 1473.8g of 30 wt% hydrogen peroxide (13mol calculated by hydrogen peroxide) is mixed with 610.6g of formic acid (13mol), and 15.02g of sulfuric acid (0.15mol calculated by H) is added2SO4Metering) and EDTA13.14g (0.03mol) are used as a component b, the component a and the component b are respectively pumped into a first micro mixer of a micro-channel modular reaction device at the sampling rates of 0.7mL/min and 3.5mL/min at the same time, the components are fully mixed and then flow into a first micro-structure reactor, the volume of the first micro-structure reactor is 42mL, the reaction residence time is kept for 10 minutes, and the components are reacted at the normal pressure and the temperature of 100 ℃; taking 785g (10mol) of n-butyl benzoyl chloride as a component c, taking 921g (10mol) of glycerol and 1507g (5mol) of tetra-n-butylammonium acetate to mix the glycerol and the component d into a component d, simultaneously pumping the component c and the component d into a second micro mixer of a micro-channel modular reaction device at the sampling rates of 8.92mL/min and 3.5mL/min, fully mixing the components, then flowing the mixture into a second micro-structure reactor, keeping the volume of the second micro-structure reactor at 124.2mL for reaction for 10 minutes, and reacting at the normal pressure and 25 ℃; pumping the epoxidized vegetable oil output from the discharge port of the oil-water separator and the polyhydroxy compound output from the discharge port of the second microreactor into a third micromixer of the microchannel modular reaction device at the same time, fully mixing, then flowing into a third microstructure reactor, keeping the volume of the third microstructure reactor to be 249.3mL, keeping the reaction for 15 minutes, reacting at 90 ℃, collecting the product to obtain the soybean oil polyol, wherein the hydroxyl value of the soybean oil polyol is 305mg KOH/g, the viscosity of the soybean oil polyol is 2056 mPas, and the iodine value of the soybean oil polyol is 17.4.
Example 3
200g of rapeseed oil (containing 0.785mol of double bonds) is taken as a component a, 1423.9g of 30 wt% hydrogen peroxide (12.56mol, calculated by hydrogen peroxide) is taken to be mixed with 589.9g of formic acid (12.56mol), and 15.02g of sulfuric acid (0.15mol, calculated by H) is added2SO4Calculated) and EDTA13.14g (0.03mol) are taken as a component b, the component a and the component b are respectively pumped into a first micro mixer of a micro-channel modular reaction device at the same time at the injection rate of 0.7mL/min and at the injection rate of 3.5mL/min, the components are fully mixed and then flow into a first micro-structure reactor, the volume of the first micro-structure reactor is 42mL, the reaction residence time is kept for 10 minutes, and the reaction is carried out at normal pressure and at normal pressureReacting at 120 ℃; taking 785g (10mol) of p-hexylbenzoyl chloride as a component c, taking 921g (10mol) of glycerol and 1507g (5mol) of tetra-n-butylammonium acetate to mix as a component d, simultaneously pumping the component c and the component d into a second micro mixer of a micro-channel modular reaction device at the sampling rates of 8.92mL/min and 3.5mL/min, fully mixing, flowing into a second micro-structure reactor, keeping the reaction residence time for 10 minutes, and reacting at the normal pressure and 25 ℃; pumping the epoxidized vegetable oil output from the discharge port of the oil-water separator and the polyhydroxy compound output from the discharge port of the second microreactor into a third micromixer of the microchannel modular reaction device at the same time, fully mixing, then flowing into a third microstructure reactor, keeping the volume of the third microstructure reactor to be 249.3mL, keeping the reaction for 15 minutes, reacting at 90 ℃, collecting the product to obtain the soybean oil polyol, wherein the hydroxyl value of the soybean oil polyol is 301mg KOH/g, the viscosity of the soybean oil polyol is 2022 mPas, and the iodine value of the soybean oil polyol is 16.7.
Examples 4 to 14
The procedure was the same as in example 1, but the specific reaction conditions and product properties are shown in Table 1:
TABLE 1
Example 15
The soybean oil polyol prepared in the example 1 is taken, and a one-step free foaming process is adopted to be mixed with foam stabilizers AK-8803 (Nanjing Maisted), cyclohexylamine (Jiangdu Dajiang chemical industry) and isocyanate
PM-200 (Rituwanhua) and a foaming agent cyclopentane (Foshan Meilong) react to foam, and the hard polyurethane foam can be prepared, and has the apparent density of 405kPa and the impact strength of 0.101kJ/m2And the dimensional stability is lower than 0.75%.
The present invention provides a vegetable oil polyol, a preparation method and application thereof, and a plurality of methods and ways for implementing the technical scheme, and the above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, a plurality of modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (9)
1. The preparation method of the vegetable oil polyol is characterized by comprising the following steps:
(1) respectively pumping mixed liquid prepared from hydrogen peroxide, organic acid, a catalyst and a stabilizer and vegetable oil into a first microstructure reactor of a microchannel modular reaction device for reaction to obtain epoxy vegetable oil with an iodine value of 15-20;
(2) preparing mixed solution of glycerol and tetra-n-butylammonium acetate, and pumping the mixed solution and benzoyl chloride into a second microstructure reactor of the microchannel modular reaction device to react to obtain the polyhydroxy compound shown in the formula III;
(3) respectively and simultaneously pumping the epoxidized vegetable oil obtained in the step (1) and the polyhydroxy compound shown in the formula III obtained in the step (2) into a third microstructure reactor of the microchannel modular reaction device for reaction to obtain vegetable oil polyol;
in step (2), the polyol of formula III has the following molecular formula:
2. The method for preparing the vegetable oil polyol according to claim 1, wherein in the step (1), the organic acid is formic acid or acetic acid, the catalyst is sulfuric acid or phosphoric acid, the stabilizer is ethylenediamine tetraacetic acid, the vegetable oil is at least one of olive oil, peanut oil, rapeseed oil, cottonseed oil, soybean oil, palm oil, sesame oil, sunflower oil, linseed oil, tung oil, safflower oil, rice bran oil, corn oil and tea oil, and the molar ratio of the vegetable oil double bonds, hydrogen peroxide, the organic acid, the catalyst and the stabilizer is 1 (15-18): 15-18) (0.1-0.2): 0.02-0.05).
3. The preparation method of the vegetable oil polyol as claimed in claim 1, wherein in the step (1), the reaction temperature in the first microstructure reactor is 80-120 ℃, the reaction residence time is 10-15 minutes, the volume of the first microstructure reactor is 25-75 mL, the flow rate of the mixed liquid prepared from hydrogen peroxide, the organic acid, the catalyst and the stabilizer pumped into the microchannel modular reaction device is 2.0-4.0 mL/min, and the flow rate of the vegetable oil pumped into the microchannel modular reaction device is 0.5-1.0 mL/min.
4. The method for preparing the vegetable oil polyol as claimed in claim 1, wherein in the step (2), the benzoyl chloride is one of p-ethylbenzoyl chloride, p-n-butylbenzoyl chloride, p-hexylbenzoyl chloride and p-octylbenzoyl chloride, the molar ratio of glycerol to benzoyl chloride is 1 (1.9-2.2), and the molar ratio of glycerol to tetra-n-butylammonium acetate is 1 (0.5-0.7).
5. The preparation method of the vegetable oil polyol as claimed in claim 1, wherein in the step (2), the reaction temperature in the second micro-structure reactor is 20-30 ℃, the reaction residence time is 10-15 minutes, the volume of the second micro-structure reactor is 99-518 mL, the flow rate of the mixed liquid of the glycerol and the tetra-n-butylammonium acetate pumped into the micro-channel modular reaction device is 2.0-4.0 mL/min, and the flow rate of the benzoyl chloride pumped into the micro-channel modular reaction device is 7.91-30.53 mL/min.
6. The preparation method of the vegetable oil polyol as claimed in claim 1, wherein in the step (3), the reaction temperature in the third microstructure reactor is 80-120 ℃, the reaction residence time is 12-16 minutes, and the volume of the third microstructure reactor is 149-632 mL.
7. The method of claim 1, wherein the microchannel modular reaction apparatus comprises a first micromixer, a first microstructure reactor, an oil-water separator, a second micromixer, a second microstructure reactor, a third micromixer, and a third microstructure reactor; the first micro mixer, the first micro-structure reactor and the oil-water separator are connected in sequence; the discharge hole of the second micro-structure reactor and the discharge hole of the oil-water separator are connected in parallel to the feed inlet of the third micro-mixer; the third micro mixer and the third micro-structure reactor are connected in sequence through a pipeline; the reaction raw materials are input into the micromixer through a low-pulsation pump.
8. A vegetable oil polyol prepared by the process of any one of claims 1 to 7.
9. Use of the vegetable oil polyol of claim 8 in the preparation of a polyurethane foam.
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