Totally bio-based vegetable oil polyol and preparation method and use thereof

Abstract

A method comprises enabling epoxy vegetable oil to react with a compound of a formula III in a second microstructured reactor to obtain the vegetable oil polyol. Compared with the existing technology, the present invention adopts a novel, environment-friendly ring-opening agent, the obtained polyol is novel in structure, high in hydroxyl value, even in distribution and low in viscosity, and can completely replace traditional petrochemical polyol to be applied to the preparation of polyurethane foam materials.

Claims

1. A preparation method of a totally bio-based vegetable oil polyol, comprising enabling epoxy vegetable oil to react with a compound of a formula III in a second microstructured reactor to obtain the vegetable oil polyol ##STR00005##

2. The method according to claim 1, comprising the following steps: (1) simultaneously pumping a mixed solution of hydrogen peroxide, an organic acid, a catalyst and a stabilizer as well as the vegetable oil into a first microstructured reactor of a micro-channel modular reaction device for reacting to obtain a reaction solution containing the epoxy vegetable oil; (2) simultaneously pumping the reaction solution containing the epoxy vegetable oil obtained from the step (1) and the compound of the formula III into the second microstructured reactor of the micro-channel modular reaction device for reacting to obtain the vegetable oil polyol ##STR00006##

3. The method according to claim 2, 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 selected from 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 teaseed oil, and the mole ratio of double bonds in the vegetable oil to the hydrogen peroxide to the organic acid to the catalyst to the stabilizer is 1:(6-20):(6-20):(0.02-0.4):(0.006-0.2).

4. The method according to claim 2, wherein, in the step (1), the first microstructured reactor has a reaction temperature of 60-130 C., a reaction residence time of 5-10 min and a volume of 20-60 mL, the vegetable oil is pumped into the micro-channel modular reaction device at a flow rate of 0.5-1.0 mL/min and the mixed solution is pumped into the micro-channel modular reaction device at a flow rate of 3.5-5.0 mL/min.

5. The method according to claim 2, wherein, in the step (2), the mole ratio of epoxy groups in the epoxy vegetable oil to the compound of the formula III is 1:(1.5-4.5), the second microstructured reactor has a reaction temperature of 70-100 C., a reaction residence time of 6-10 min and a volume of 96-240 mL, the compound of the formula III is pumped into the micro-channel modular reaction device at a flow rate of 12.0-18.0 mL/min.

6. The method according to claim 2, wherein the micro-channel modular reaction device comprises a first micro-mixer, a first microstructured heat exchanger, a first tubular temperature control module, the first microstructured reactor, a second micro-mixer, a second microstructured heat exchanger, a second tubular temperature control module and the second microstructured reactor which are sequentially connected through pipelines.

7. The method according to claim 1, wherein, in the step (2), the compound of the formula III is prepared by the following process, comprising: (a) dissolving furfuryl alcohol in a reaction solvent, dropwise adding thionyl chloride into the solution at 10 C. to 10 C., continuing stirring and reacting for 0.5-2 h, adding water to quench the reaction, collecting an organic phase, and spin drying the reaction solvent to obtain colorless liquid; (b) then adding glycerol and sodium into the colorless liquid, continuing stirring and reacting for 3-6 h at 30-50 C. to obtain the compound of the formula III.

8. The method according to claim 7, wherein, in the step (a), the reaction solvent is one or more of dichloromethane, dichloroethane, chloroform and benzene, and the mole ratio of furfuryl alcohol to thionyl chloride to glycerol to sodium is 1:(1.0-2.0):(1.0-2.0):(1.0-2.0).

9. A totally bio-based vegetable oil polyol wherein the totally bio-based vegetable oil polyol is prepared by a method according to claim 1.

10. A process for using a totally bio-based vegetable oil polyol of claim 9, wherein the process for using the totally bio-based vegetable oil polyol for preparing a polyurethane foam.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0044] FIG. 1 shows a schematic diagram of a micro-channel modular reaction device. VO=Vegetable oil; HOCS=Hydrogen peroxide Organic acid Catalyst Stabilizer; MM=micro-mixer; MHE=microstructured heat exchanger; MR=microstructured reactor; TTCM=tubular temperature control module; AL=Aqueous Layer; OWS=oil-water separator.

DETAILED DESCRIPTION OF THE INVENTION

[0045] The present invention will be better understood according to the following Examples.

[0046] The vegetable oil polyol and the polyurethane foam material prepared according to the present invention are analyzed with following methods:

[0047] (1) The hydroxyl value is measured according to GB/T 12008.3-2009;

[0048] (2) The viscosity is measured according to GB/T 12008.7-2010;

[0049] (3) The apparent density of foam plastics is measured according to GB/T 6343-2009;

[0050] (4) The compressive strength of rigid foam plastic is measured according to GB/T 8813-2008 with the cross section in the direction perpendicular to the foaming as the compression face, the compression rate of 5 mm/min and the measurement value at 10% deformation of a sample as the compressive strength of the material;

[0051] (5) The impact strength of rigid foam plastic is measured according to GB/T 11548-1989. The impact strength is used for characterizing the toughness under high speed impact or the resistance to fracture of the materials;

[0052] (6) The dimensional stability of rigid foam plastic is measured according to GB/T 8811-2008.

[0053] As shown in FIG. 1, a micro-channel modular reaction device described in the following examples includes a first micro-mixer, a first microstructured heat exchanger, a first tubular temperature control module, a first microstructured reactor, a second micro-mixer, a second microstructured heat exchanger, a second tubular temperature control module, a second microstructured reactor, an oil-water separator and a receiver which are sequentially connected through pipelines. The feeding inlet of the first micro-mixer is connected with a first liquid storage tank (a vegetable oil storage tank) through a pump A. The feeding inlet of the first micro-mixer is connected with a second liquid storage tank (a storage tank for a mixed solution of hydrogen peroxide, organic acid, catalyst and stabilizer) through a pump B. The feeding inlet of the second micro-mixer is connected with the discharging outlet of the first micro-reactor. The feeding inlet of the second micro-mixer is connected with a third liquid storage tank (a storage tank of a compound of a formula III) through a pump C.

[0054] The types of the first micro-mixer and the second micro-mixer are both plate mixer LH25.

[0055] The types of the first microstructured heat exchanger and the second microstructured heat exchanger are both coaxial heat exchanger.

[0056] The types of the first microstructured reactor and the second microstructured reactor are meander reactor HC, sandwich reactor HC, fixed bed meander reactor HC or Hastelloy micro-channel reactor, respectively.

Example 1

[0057] (1) Preparation of the Compound of the Formula III

[0058] 196.2 g (2 mol) furfuryl alcohol (a compound of a formula I) was dissolved in 4 L dichloromethane, thionyl chloride (145.26 mL, 2 mol) was dropwise added into the solution at 0 C. slowly, stirring and reacting were performed at 0 C. for 1 h, and 4 L water was added to quench the reaction. An organic layer was collected and an aqueous layer was washed for three times with dichloromethane. The organic layer was combined and the solvent was spin-dried, so as to obtain colorless liquid. 184.18 g glycerol (2 mol) and 46 g sodium (2 mol) were added into the liquid and stirring and reacting were continued for 4 h at 40 C. 500 mL water was added. The organic layer was separated. The aqueous layer was extracted with toluene (250 mL*3) and the organic layer was combined. The combined organic layer was dried with anhydrous sodium sulfate and the toluene was recovered by distillation. Atmospheric distillation was carried out to obtain 292.46 g of the compound of the formula III (purity: 99.8%; yield: 85%).

[0059] (2) Preparation of the Vegetable Oil Polyol

[0060] 200 g soybean oil (containing 0.99 mol of double bonds) was taken as a component I and 1360.4 g 30 wt % hydrogen peroxide (12 mol) was mixed with 563.63 g formic acid (12 mol), then 20.02 g sulfuric acid (0.2 mol, counted by H.sub.2SO.sub.4) and 4.38 g EDTA (0.01 mol) were added as a component II, the component I and the component II were simultaneously pumped into the first micro-mixer of the micro-channel modular reaction device at the feeding rates of 0.8 ml/min and 4.7 ml/min respectively and mixed. Then the resulted mixed solution was flowed into the first microstructured reactor and reacted. The first microstructured reactor had a volume of 44 mL and a reaction residence time of 8 min. The reaction was performed at normal pressure and 90 C., thus obtaining a reaction solution containing the epoxy vegetable oil. Next, 258 g of the compound of the formula III (1.5 mol) and the reaction solution containing the epoxy vegetable oil output by the first microstructured reactor were simultaneously pumped into the second micro-mixer of the micro-channel modular reaction device at the feeding rates of 16.6 mL/min and 5.5 mL/min respectively and mixed. Then the resulted mixed solution was flowed into the second microstructured reactor and reacted. The second microstructured reactor had a volume of 176.8 mL, a reaction residence time of 8 min and a reaction temperature of 85 C. The crude reaction product was introduced into the oil-water separator to remove the aqueous phase. Then the oil phase product was collected, thus obtaining a soybean oil polyol with the hydroxyl value of 299 mg KOH/g and the viscosity of 4736 mPa.Math.s.

Example 2

[0061] (1) Preparation of the Compound of the Formula III

[0062] 196.2 g (2 mol) furfuryl alcohol (the compound of the formula I) was dissolved in 4 L dichloromethane, thionyl chloride (217.89 mL, 3 mol) was dropwise added into the solution at 0 C. slowly, stirring and reacting were performed at 0 C. for 2 h, and 4 L water was added to quench the reaction. An organic layer was collected and an aqueous layer was washed for three times with dichloromethane. The organic layer was combined and the solvent was spin-dried, so as to obtain colorless liquid. 184.18 g glycerol (2 mol) and 46 g sodium (2 mol) were added into the liquid and stirring and reacting were continued for 4 h at 40 C. 500 mL water was added. The organic layer was separated. The aqueous layer was extracted with toluene (250 mL*3) and the organic layer was combined. The combined organic layer was dried with anhydrous sodium sulfate and the toluene was recovered by distillation. Atmospheric distillation was carried out to obtain 309.67 g of the compound of the formula III (purity: 99.6%; yield: 90%).

[0063] (2) Preparation of the Vegetable Oil Polyol

[0064] 200 g soybean oil (containing 0.99 mol of double bonds) was taken as a component I and a mixture of 1700 g 30 wt % hydrogen peroxide (15 mol) was mixed with 704.54 g formic acid (15 mol), then 30.03 g sulfuric acid (0.3 mol, counted by H.sub.2SO.sub.4) and 2.92 g EDTA (0.015 mol) were added as a component II, the component I and the component II were simultaneously pumped into the first micro-mixer of the micro-channel modular reaction device at the feeding rates of 0.8 ml/min and 4.7 ml/min respectively and mixed. Then the resulted mixed solution was flowed into the first microstructured reactor and reacted. The first microstructured reactor had a volume of 44 mL and a reaction residence time of 8 min. The reaction was performed at normal pressure and 90 C., thus obtaining a reaction solution containing the epoxy vegetable oil. Next, 258 g of the compound of the formula III (1.5 mol) and the reaction solution containing the epoxy vegetable oil output by the first microstructured reactor were simultaneously pumped into the second micro-mixer of the micro-channel modular reaction device at the feeding rates of 15.0 mL/min and 5.5 mL/min respectively and mixed. Then the resulted mixed solution was flowed into the second microstructured reactor and reacted. The second microstructured reactor had a volume of 164 mL, a reaction residence time of 8 min and a reaction temperature of 85 C. The crude reaction product was introduced into the oil-water separator to remove the aqueous phase. Then the oil phase product was collected, thus obtaining a soybean oil polyol with the hydroxyl value of 312 mg KOH/g and the viscosity of 4658 mPa.Math.s.

Example 3

[0065] (1) Preparation of the Compound of the Formula III

[0066] 196.2 g (2 mol) furfuryl alcohol (the compound of the formula I) was dissolved in 4 L dichloromethane, thionyl chloride (217.89 mL, 3 mol) was dropwise added into the solution at 5 C. slowly, stirring and reacting were performed at 0 C. for 2 h, and 4 L water was added to quench the reaction. An organic layer was collected and an aqueous layer was washed for three times with dichloromethane. The organic layer was combined and the solvent was spin-dried, so as to obtain colorless liquid. 276.27 g glycerol (3 mol) and 69 g sodium (3 mol) were added into the liquid and stirring and reacting were continued for 4 h at 35 C. 500 mL water was added. The organic layer was separated. The aqueous layer was extracted with toluene (250 mL*3) and the organic layer was combined. The combined organic layer was dried with anhydrous sodium sulfate and the toluene was recovered by distillation. Atmospheric distillation was carried out to obtain 302.79 g of the compound of the formula III (purity: 99.9%; yield: 88%).

[0067] (2) Preparation of the Vegetable Oil Polyol

[0068] 200 g soybean oil (containing 0.99 mol of double bonds) was taken as a component I and 1700 g 30 wt % hydrogen peroxide (15 mol) was mixed with 900.75 g acetic acid (15 mol), then 30.03 g sulfuric acid (0.3 mol, counted by H.sub.2SO.sub.4) and 2.92 g EDTA (0.015 mol) were added as a component II, the component I and the component II were simultaneously pumped into the first micro-mixer of the micro-channel modular reaction device at the feeding rates of 0.8 ml/min and 4.7 ml/min respectively and mixed. Then the resulted mixed solution was flowed into the first microstructured reactor and reacted. The first microstructured reactor had a volume of 44 mL and a reaction residence time of 8 min. The reaction was performed at normal pressure and 90 C., thus obtaining a reaction solution containing the epoxy vegetable oil. Next, 292 g of the compound of the formula III (1.7 mol) and the reaction solution containing the epoxy vegetable oil output by the first microstructured reactor were simultaneously pumped into the second micro-mixer of the micro-channel modular reaction device at the feeding rates of 22 mL/min and 5.5 mL/min respectively and mixed. Then the resulted mixed solution was flowed into the second microstructured reactor and reacted. The second microstructured reactor had a volume of 220 mL, a reaction residence time of 8 min and a reaction temperature of 85 C. The crude reaction product was introduced into the oil-water separator to remove the aqueous phase. Then the oil phase product was collected, thus obtaining a soybean oil polyol with the hydroxyl value of 304 mg KOH/g and the viscosity of 4895 mPa.Math.s.

Example 4

[0069] (1) Preparation of the Compound of the Formula III

[0070] 196.2 g (2 mol) furfuryl alcohol (the compound of the formula I) was dissolved in 4 L dichloroethane, thionyl chloride (217.89 mL, 3 mol) was dropwise added into the solution at 5 C. slowly, stirring and reacting were performed at 0 C. for 2 h and 4 L water was added to quench the reaction. An organic layer was collected and an aqueous layer was washed for three times with dichloroethane. The organic layer was combined and the solvent was spin-dried, so as to obtain colorless liquid. 276.27 g glycerol (3 mol) and 69 g sodium (3 mol) were added into the liquid and stirring and reacting were continued for 4 h at 35 C. 500 mL water was added. The organic layer was separated. The aqueous layer was extracted with toluene (250 mL*3) and the organic layer was combined. The combined organic layer was dried with anhydrous sodium sulfate and the toluene was recovered by distillation. Atmospheric distillation was carried out to obtain 289.02 g of the compound of the formula III (purity: 99.5%; yield: 84%).

[0071] (2) Preparation of the Vegetable Oil Polyol

[0072] 200 g grapeseed oil (containing 0.785 mol of double bonds) was taken as a component I and 1700 g 30 wt % hydrogen peroxide (15 mol) was mixed with 900.75 g acetic acid (15 mol), then 30.03 g sulfuric acid (0.3 mol, by H.sub.2SO.sub.4) and 2.92 g EDTA (0.015 mol) were added as a component II, the component I and the component II were simultaneously pumped into the first micro-mixer of the micro-channel modular reaction device at the feeding rates of 0.8 ml/min and 4.7 ml/min respectively and mixed. Then the resulted mixed solution was flowed into the first microstructured reactor and reacted. The first microstructured reactor had a volume of 44 mL and a reaction residence time of 8 min. The reaction was performed at normal pressure and 90 C., thus obtaining a reaction solution containing the epoxy vegetable oil. Next, 292 g of the compound of the formula III (1.7 mol) and the reaction solution containing the epoxy vegetable oil output by the first microstructured reactor were simultaneously pumped into the second micro-mixer of the micro-channel modular reaction device at the feeding rates of 19.2 mL/min and 5.5 mL/min respectively and mixed. Then the resulted mixed solution was flowed into the second microstructured reactor and reacted. The second microstructured reactor had a volume of 197.6 mL, a reaction residence time of 8 min and a reaction temperature of 85 C. The crude reaction product was introduced into the oil-water separator to remove the aqueous phase. Then the oil phase product was collected, thus obtaining a grapeseed oil polyol with the hydroxyl value of 291 mg KOH/g and the viscosity of 4959 mPa.Math.s.

Example 5: Performance Test of the Rigid Polyurethane Foam Prepared from the Vegetable Oil Polyol

[0073] The soybean oil polyol prepared from Example 1 was enabled to react with a foam stabilizer AK-8803 (Maysta, Nanjing), cyclohexylamine (Dajiang Chemical, Jiangdu), isocyanate WANNATE PM-200 (Wanhua Chemical, Yantai) and a cyclopentane foaming agent (Meilong Chemical, Foshan) for foaming by a one-step free foaming process, thus preparing the rigid polyurethane foam with the apparent density of 211 kPa, the impact strength of 0.069 kJ/m.sup.2 and the dimensional stability lower than 0.8%.

Example 6

[0074] This example has the same process as Example 1, except that the mole ratio of furfuryl alcohol to thionyl chloride to glycerol to sodium is 1:1.0:1.0:1.0. Upon detection, the resulted vegetable oil polyol had similar performance with the vegetable oil polyol prepared in Example 1.

Example 7

[0075] This example has the same process as Example 1, except that the mole ratio of furfuryl alcohol to thionyl chloride to glycerol to sodium is 1:2.0:2.0:2.0. Upon detection, the resulted vegetable oil polyol had similar performance with the vegetable oil polyol prepared in Example 1.

Example 8

[0076] This example has the same process as Example 1, except that the catalyst was phosphoric acid, the vegetable oil was olive oil, and the mole ratio of the double bonds in the vegetable oil to hydrogen peroxide to organic acid to catalyst to stabilizer is 1:6:6:0.02:0.006. Upon detection, the resulted vegetable oil polyol had similar performance with the vegetable oil polyol prepared in Example 1.

Example 9

[0077] This example has the same process as Example 1, except that the catalyst was phosphoric acid, the vegetable oil was peanut oil, and the mole ratio of the double bonds in the vegetable oil to hydrogen peroxide to organic acid to catalyst to stabilizer is 1:20:20:0.4:0.2. Upon detection, the resulted vegetable oil polyol had similar performance with the vegetable oil polyol prepared in Example 1.

Example 10

[0078] This example has the same process as Example 1, except that the catalyst was phosphoric acid, and the vegetable oil was palm oil. The first microstructured reactor has a reaction temperature of 60 C., a reaction residence time of 10 min and a volume of 20 mL. The mole ratio of the epoxy groups in the epoxy vegetable oil to the compound of the formula III is 1:1.5. The second microstructured reactor has a reaction temperature of 70 C., a reaction residence time of 10 min and a volume of 96 mL. Upon detection, the resulted vegetable oil polyol had similar performance with the vegetable oil polyol prepared in Example 1.

Example 11

[0079] This example has the same process as Example 1, except that the catalyst was phosphoric acid, and the vegetable oil was sunflower oil. The first microstructured reactor has a reaction temperature of 130 C., a reaction residence time of 5 min and a volume of 60 mL. The mole ratio of the epoxy groups in the epoxy vegetable oil to the compound of the formula III is 1:4.5. The second microstructured reactor has a reaction temperature of 100 C., a reaction residence time of 10 min and a volume of 240 mL. Upon detection, the resulted vegetable oil polyol had similar performance with the vegetable oil polyol prepared in Example 1.