CN109134260A - A kind of bio-based polyol and its preparation method and application - Google Patents
A kind of bio-based polyol and its preparation method and application Download PDFInfo
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- CN109134260A CN109134260A CN201811201272.2A CN201811201272A CN109134260A CN 109134260 A CN109134260 A CN 109134260A CN 201811201272 A CN201811201272 A CN 201811201272A CN 109134260 A CN109134260 A CN 109134260A
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- micro
- microreactor
- oil
- reaction
- oxabicyclo
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- 229920005862 polyol Polymers 0.000 title claims abstract description 23
- 150000003077 polyols Chemical class 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 120
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 54
- WFVNGCRJBMMCGB-UHFFFAOYSA-N 5,6-dimethyl-7-oxabicyclo[4.1.0]heptane Chemical compound CC1CCCC2OC12C WFVNGCRJBMMCGB-UHFFFAOYSA-N 0.000 claims abstract description 41
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 24
- 239000008158 vegetable oil Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 60
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 33
- 239000003549 soybean oil Substances 0.000 claims description 30
- 235000012424 soybean oil Nutrition 0.000 claims description 30
- 239000004593 Epoxy Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 4
- 239000002285 corn oil Substances 0.000 claims description 3
- 235000005687 corn oil Nutrition 0.000 claims description 3
- 235000012343 cottonseed oil Nutrition 0.000 claims description 3
- 235000019482 Palm oil Nutrition 0.000 claims description 2
- 235000019483 Peanut oil Nutrition 0.000 claims description 2
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 2
- 235000019486 Sunflower oil Nutrition 0.000 claims description 2
- 239000003240 coconut oil Substances 0.000 claims description 2
- 235000019864 coconut oil Nutrition 0.000 claims description 2
- 239000002385 cottonseed oil Substances 0.000 claims description 2
- 239000004006 olive oil Substances 0.000 claims description 2
- 235000008390 olive oil Nutrition 0.000 claims description 2
- 239000002540 palm oil Substances 0.000 claims description 2
- 239000000312 peanut oil Substances 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011496 polyurethane foam Substances 0.000 claims description 2
- 239000008159 sesame oil Substances 0.000 claims description 2
- 235000011803 sesame oil Nutrition 0.000 claims description 2
- 239000002600 sunflower oil Substances 0.000 claims description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims 1
- -1 ethylene glycol Diol Chemical class 0.000 claims 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims 1
- 235000013772 propylene glycol Nutrition 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000010924 continuous production Methods 0.000 abstract description 2
- 238000005086 pumping Methods 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 59
- 238000007599 discharging Methods 0.000 description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 235000011187 glycerol Nutrition 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
- 239000003921 oil Substances 0.000 description 13
- 235000019198 oils Nutrition 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 10
- 150000002924 oxiranes Chemical class 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 229920002635 polyurethane Polymers 0.000 description 8
- 239000004814 polyurethane Substances 0.000 description 8
- RBVDRKDVTKRIEC-UHFFFAOYSA-M potassium;propane-1,2,3-triol;hydroxide Chemical compound [OH-].[K+].OCC(O)CO RBVDRKDVTKRIEC-UHFFFAOYSA-M 0.000 description 7
- 150000005846 sugar alcohols Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000006735 epoxidation reaction Methods 0.000 description 6
- 238000007142 ring opening reaction Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 244000068988 Glycine max Species 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- WNEUNPWLVWPBGB-UHFFFAOYSA-N 1,6-dimethyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCCC2(C)OC21C WNEUNPWLVWPBGB-UHFFFAOYSA-N 0.000 description 1
- GODZNYBQGNSJJN-UHFFFAOYSA-N 1-aminoethane-1,2-diol Chemical compound NC(O)CO GODZNYBQGNSJJN-UHFFFAOYSA-N 0.000 description 1
- FIEKVYPYFQSFTP-UHFFFAOYSA-N 6-methyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCCC2OC21C FIEKVYPYFQSFTP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 241000221089 Jatropha Species 0.000 description 1
- 241001048891 Jatropha curcas Species 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 238000004617 QSAR study Methods 0.000 description 1
- 229920000263 Rubber seed oil Polymers 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000011938 amidation process Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical group CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Compounds (AREA)
- Fats And Perfumes (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 chemical materials and its production technical fields, and in particular to a kind of biopolyol and its preparation side
Method and application, and the biopolyol that the present invention synthesizes is suitable for preparing polyurethane material.
Background technique
Polyurethane rigid foam material is a kind of important functional material, has good thermal insulation property and structural strength, extensively
It is all applied to building heat preservation, pipeline heat insulation, household electrical appliances heat preservation, fitting-up, light weight board, automobile manufacture, electronic components fabrication etc.
Conglomerate, the Chinese market demand is more than 2,500,000 tons/year, and nearly 30,000,000,000 yuan/year of the output value, application industry scale is more reachable downstream
Hundreds billion of member/years, and keep 11.6% average annual demand increase rate (being shown in Table 1).
The Chinese polyurethane product production status (unit: ten thousand tons) of table 1
For conventional urethane hard bubble polyalcohol based on petrochemical industry polyether polyol, the generally existing following is insufficient: 1) all kinds of
Polyether product kind is mixed and disorderly, and quality is irregular；2) production process is dangerous, is related to the application of a large amount of propylene oxide；3) resource according to
Rely property too strong, product lacks environment friendly.Therefore, it is hard that high-performance, environmental-friendly, process safety bio-based polyurethane are developed
Bubble polyalcohol has become the research hotspot of global industrial circle, and China's proposition will be disposed in advance, the cutting edge technology of primary study
With major fields.
Currently, many esbablished corporations have put into a large amount of research and development strengths progress bio-based polyurethane hard bubble polyalcohols in the world
Exploitation, such as BASF, Royal DSM, company of Du Pont.But the area research still belongs to the starting stage, and institute's development, which faces, to be difficult to pair
Petrochemical industry polyether polyol realizes that full substitution (substitution rate is only 20-50%) and foam exist on heating conduction and mechanical property
The international headache of notable defect, and any document is had no to the quantitative structure activity relationship between polyol molecule structure and foamed material
It is reported.It is probed by mechanism, the research of bio-based polyurethane polyalcohol is primarily present structure component complexity, material component at present
Various and molecular structure is difficult to the international common problem effectively constructed, greatly hinders the industry hair of bio-based polyurethane material
Exhibition.
CN1837180A and CN101139252A is respectively using rapeseed oil and Jatropha curcas oil as raw material, and through alcoholysis ,/epoxidation/is opened
Vegetable oil polyol is prepared in ring three-step reaction.CN1837181A and CN10118803A is respectively with rapeseed oil and Jatropha curcus
Oil is raw material, and vegetable oil polyol is prepared through epoxidation/open loop/alcoholysis three-step reaction.CN101906016A is with rubber seed
Oil is primary raw material, and vegetable oil polyol is prepared through the reaction of two step of epoxidation/open loop.Pass through epoxy in CN101659627A
Ring-opening reaction and ester group amidation process between vegetable oil and glycol amine, are prepared vegetable oil polyol.
CN101747184A and CN101230020A is reacted in acid condition using epoxidation reaction and ring-opening reaction, one-step method system
It is standby to obtain vegetable oil polyol.In the above patent, the preparation of vegetable oil polyol is based on open loop again, open loop after double bond epoxidation
Reagent is mainly small molecular alcohol, hydramine or carboxylic acid, and there are problems, such as product quality is not high, post-processing is cumbersome, in reaction
Easily there is crosslinking side reaction etc..In addition, the vegetable oil polyol being prepared still needs to compound a certain proportion of petrochemical industry polyalcohol.
Potassium permanganate alkaline solution and vegetable oil are pumped into microchannel module reaction unit by CN104673501A simultaneously,
The biopolyol with pinacol structure is prepared after reacting post-treated.CN103274930A is in microchannel module
Epoxidation reaction and ring-opening reaction are realized simultaneously in reaction unit, so that vegetable oil polyol be prepared.CN103288642A
The organic solution of epoxidized vegetable oil and catalyst aqueous solution are pumped into microchannel module reaction unit, by ring-opening reaction system
It is standby to obtain vegetable oil polyol.In above-mentioned patent, pass through using so that integrated artistic process for microchannel module reaction unit
The degree of automation be significantly improved, shorten the reaction time, reduce energy consumption, weaken side reaction.But institute in this 3 patents
The Ring Opening Reagent used causes the product quality of final vegetable oil polyol poor for water, is applied to when prepared by polyurethane still
It need to be used in compounding with petrochemical industry polyalcohol.
Summary of the invention
It is existing to solve the object of the present invention is to provide a kind of method for preparing biopolyol using micro-reaction device
Batch process prepares vegetable oil polyol, and the existing reaction time is long in the process, energy consumption is high, product quality is not high, cannot continuous metaplasia
The problems such as production and the degree of automation are low.
It is a further object to provide a kind of biopolyols being prepared using the method.
Final object of the present invention is to provide the application of the biopolyol.
To achieve the above object, The technical solution adopted by the invention is as follows:
A method of biopolyol is prepared, is included the following steps:
(1) by the alcoholic solution of the ethyl acetate solution of 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane and potassium hydroxide
It is pumped into the first microreactor of micro-reaction device and is reacted simultaneously, obtain reaction efflux；
(2) the reaction efflux that step (1) obtains is pumped into micro- react with the ethyl acetate solution of epoxidized vegetable oil simultaneously
It is reacted in second microreactor of device, obtains biopolyol.
Reaction equation of the present invention is as follows:
Preferably, the method for preparing biopolyol, includes the following steps:
(1) by the alcoholic solution of the ethyl acetate solution of 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane and potassium hydroxide
It is pumped into the first micro-mixer of micro-reaction device simultaneously respectively, is flowed into after being sufficiently mixed in the first microreactor of micro-reaction device
It is reacted, obtains reaction efflux；
(2) ethyl acetate solution of reaction efflux and epoxidized vegetable oil that step (1) obtains is pumped into simultaneously respectively micro-
Second micro-mixer of reaction unit, after being sufficiently mixed flow into micro-reaction device the second microreactor in reacted to get
Biopolyol.
In step (1), the alcohol is methanol, ethyl alcohol, 1,2-PD, 1,3-PD, diethylene glycol (DEG), ethylene glycol or third
Triol, preferably 1,2-PD, 1,3-PD, pentaerythrite, diethylene glycol (DEG), ethylene glycol or glycerine, more preferably the third three
Alcohol.
In step (1), 1,2- in the ethyl acetate solution of described 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane
The mass fraction of dimethyl -7- oxabicyclo [4.1.0] heptane is 10wt%-20wt%.
In step (1), the mass fraction of potassium hydroxide is 0.1wt%-1wt% in the alcoholic solution of potassium hydroxide.
In step (1), in the first microreactor, reaction temperature is 100-200 DEG C, preferably 120-170 DEG C；Reaction stops
Time is 10-30min, preferably 15-25min, and the volume of the first microreactor is 5-50mL, 1,2- dimethyl -7- oxabicyclo
The flow velocity that the ethyl acetate solution of [4.1.0] heptane is pumped into micro-reaction device is 0-1mL/min, and the alcoholic solution of potassium hydroxide is pumped into
The flow velocity of micro-reaction device is 0-1mL/min.
In step (1), the molar ratio of 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane and alcohol is 1:(1-10).
In step (2), the epoxidized vegetable oil is epoxy olive oil, epoxy peanut oil, epoxy rapeseed oil, epoxy cottonseed
In oil, epoxidized soybean oil, epoxy coconut oil, epoxy palm oil, epoxy sesame oil, epoxy corn oil or epoxy sunflower oil
Any one or a few, preferably epoxidized soybean oil (ESO), epoxidized vegetable oil in the ethyl acetate solution of epoxidized vegetable oil
Mass fraction 10wt%-20wt%.
In step (2), in the second microreactor, reaction temperature is 120-200 DEG C, preferably 150-180 DEG C；Reaction stops
Time is 20-30min, preferably 20-25min, and the volume of the second microreactor is 10-40mL, the reaction outflow that step (1) obtains
The flow velocity that liquid pump enters micro-reaction device is 0.2-1mL/min, and the ethyl acetate solution of epoxidized soybean oil is pumped into micro-reaction device
Flow velocity is 0.2-1mL/min.
In step (2), the molar ratio of 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane and epoxidized soybean oil is (1-
10):1。
In step (2), by the reaction efflux water-oil separation in the second microreactor, organic phase is taken, organic phase is washed,
To get biopolyol after drying.The washing, which refers to, is washed to pH6.5~7.5 for organic phase, and drying means is to use
Anhydrous sodium sulfate or anhydrous magnesium sulfate etc. are dried.
The micro-reaction device includes the first micro-mixer being successively linked in sequence by connecting tube, first micro- reaction
Device, the second micro-mixer and the second microreactor.Reaction raw materials by accurate and low pulse pump input micro-mixer and its it
In equipment afterwards.
First micro-mixer, the second micro-mixer are slit plate mixer LH25 each independently
(Hastelloy C), Y type mixer or T-type mixer.
First microreactor, the second microreactor be each independently meander reactor HC,
Sandwich reactor HC, fixed bed meander reactor HC or capillary (internal diameter 0.1-2mm).
The biopolyol that method of the present invention is prepared.
Biopolyol of the present invention is preparing the application in hard polyurethane foam.
The present invention is basic raw material with epoxidized soybean oil, on the basis of structure activity study and Molecular Design, fortune
With micro-reaction device, is continuously synthesized by multistep, novel Ring Opening Reagent is prepared.The preparation method is continuous operation, system
Standby technique easy operation control, the reaction time is short, and low energy consumption, and side reaction is obviously weakened, and the controllable hydroxyl value range of product is larger.This
On the one hand invention can increase hydroxyl value using 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane, on the other hand pass through 1,2- bis-
Being introduced into so that introduce rigid structure in the structure of biopolyol for methyl -7- oxabicyclo [4.1.0] heptane, improves hard bubble
Compressive strength and thermodynamic property, mitigate suspention chain bring adverse effect.
The utility model has the advantages that compared with prior art, the present invention has the advantage that
1, the preparation method of biopolyol provided by the present invention be continuous process, preparation process easy operation control,
Highly-safe, reaction condition is mild, and reaction time is short, stable product quality, high income.It is simple with process units, easily
Dismounting, feature easy to carry and mobile.It can easily be adjusted by simply increasing and decreasing microchannel quantity, class is not present
Like industrial " enlarge-effect ".
2, it can overcome the problems, such as that existing production exists using biopolyol preparation method of the present invention, avoid
The use of complicated catalyst, production cost is low, and technique serialization degree is high, increases substantially the safety of production process, improves
The quality of product.
Detailed description of the invention
Fig. 1 is the schematic diagram of micro-reaction device.
Specific embodiment
Micro-reaction device described in following embodiment, as shown in Figure 1, include be sequentially connected in series by connecting tube it is first micro- mixed
Clutch, the first microreactor, the second micro-mixer and the second microreactor；Wherein, the feed inlet of the first micro-mixer and first
Feed liquid storage tank (the alcoholic solution storage tank of potassium hydroxide) is connected by pump A, the feed inlet of the first micro-mixer and the second feed liquid storage tank
(the ethyl acetate solution storage tank of 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane) is connected by pump B, the second micro-mixer
Feed inlet be connected with the discharge port of the first microreactor, (epoxy is big for the feed inlet and third feed liquid storage tank of the second micro-mixer
The ethyl acetate solution storage tank of soya-bean oil) it is connected by pump C.
First micro-mixer, the second micro-mixer are each independently slit plate mixer LH25
One of (Hastelloy C), Y type mixer, T-type mixer.
First microreactor, the second microreactor are each independently meander reactor HC, sandwich
One of reactor HC, fixed bed meander reactor HC, capillary (internal diameter 0.1-2mm).
Hydroxyl value calculation method is calculated referring to GB/T 12008.3-2009, epoxide number referring to GB/T 1677-2008.
Embodiment 1:
By the ethyl acetate solution (10wt%) of 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane and potassium hydroxide
Glycerin solution (0.1wt%) is with the molar ratio of 1:1 (with 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane and glycerine
Molar ratio computing) it is pumped into the first micro-mixer simultaneously respectively, the acetic acid second of 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane
The flow velocity of ester solution is 0.95mL/min, and the flow velocity of the glycerin solution of potassium hydroxide is 0.05mL/min, is led to after being sufficiently mixed
Enter and is reacted in the first microreactor in micro-reaction device；The volume of first microreactor is 10mL.Mixed system is micro- first
10min is stopped at 100 DEG C in reactor.Again by the ethyl acetate solution of epoxidized soybean oil (10wt%) and the first microreactor
Discharging is pumped into the second micro-mixer respectively simultaneously, and the flow velocity of the ethyl acetate solution of epoxidized soybean oil is 1.65mL/min, the
The flow velocity of the discharging of one microreactor is 1mL/min, is passed through in the second microreactor in micro-reaction device after being sufficiently mixed, the
The volume of two microreactors is 26.5mL.Wherein, 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane and epoxidized soybean oil
Molar ratio is 1:1.After material stops 10min at 120 DEG C in the second microreactor, discharging is imported in oil water separator, it is quiet
Layering is set, the aqueous solution of lower layer is removed, upper organic phase is washed to pH 6.5~7.5, after anhydrous sodium sulfate drying, is obtained
Biopolyol, hydroxyl value 120mgKOH/g, epoxide number 0.
Embodiment 2:
By the ethyl acetate solution (10wt%) of 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane and potassium hydroxide
Glycerin solution (0.5wt%) is with the molar ratio of 1:5 (with 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane and glycerine
Molar ratio computing) it is pumped into the first micro-mixer simultaneously respectively, the acetic acid second of 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane
The flow velocity of ester solution is 0.8mL/min, and the flow velocity of the glycerin solution of potassium hydroxide is 0.2mL/min, is passed through after being sufficiently mixed
It is reacted in the first microreactor in micro-reaction device；The volume of first microreactor is 20mL.Mixed system is micro- anti-first
It answers in device and stops 20min at 150 DEG C.Going out the ethyl acetate solution of epoxidized soybean oil (20wt%) and the first microreactor again
Material is pumped into the second micro-mixer respectively simultaneously, and the flow velocity of the ethyl acetate solution of epoxidized soybean oil is 0.66mL/min, and first
The flow velocity of the discharging of microreactor is 1mL/min, is passed through in the second microreactor in micro-reaction device after being sufficiently mixed, second
The volume of microreactor is 33.2mL.Wherein, 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane and epoxidized soybean oil rub
You are than being 5:1.After material stops 20min at 160 DEG C in the second microreactor, discharging is imported in oil water separator, is stood
Layering, removes the aqueous solution of lower layer, upper organic phase is washed to pH6.5~7.5, after anhydrous sodium sulfate drying, is given birth to
Object polylol, hydroxyl value 320mgKOH/g, epoxide number 0.
Embodiment 3:
By the ethyl acetate solution (20wt%) of 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane and potassium hydroxide
Glycerin solution (1wt%) is with the molar ratio of 1:10 (with 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane and glycerine
Molar ratio computing) it is pumped into the first micro-mixer simultaneously respectively, the acetic acid second of 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane
The flow velocity of ester solution is 0.49mL/min, and the flow velocity of the glycerin solution of potassium hydroxide is 0.51mL/min, is led to after being sufficiently mixed
Enter and is reacted in the first microreactor in micro-reaction device；The volume of first microreactor is 30mL.Mixed system is micro- first
30min is stopped at 200 DEG C in reactor.Again by the ethyl acetate solution of epoxidized soybean oil (15wt%) and the first microreactor
Discharging is pumped into the second micro-mixer respectively simultaneously, and the flow velocity of the ethyl acetate solution of epoxidized soybean oil is 1.13mL/min, the
The flow velocity of the discharging of one microreactor is 1mL/min, is passed through in the second microreactor in micro-reaction device after being sufficiently mixed, the
The volume of two microreactors is 33.5mL.Wherein, 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane and epoxidized soybean oil
Molar ratio is 10:1.After material stops 15min at 200 DEG C in the second microreactor, discharging is imported in oil water separator, it is quiet
Layering is set, the aqueous solution of lower layer is removed, upper organic phase is washed to pH6.5~7.5, after anhydrous sodium sulfate drying, is obtained
Biopolyol, hydroxyl value 280mgKOH/g, epoxide number 0.
Embodiment 4:
By the ethyl acetate solution (20wt%) of 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane and potassium hydroxide
Glycerin solution (1wt%) is with the molar ratio of 1:10 (with 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane and glycerine
Molar ratio computing) it is pumped into the first micro-mixer simultaneously respectively, the acetic acid second of 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane
The flow velocity of ester solution is 0.49mL/min, and the flow velocity of the glycerin solution of potassium hydroxide is 0.51mL/min, is led to after being sufficiently mixed
Enter and is reacted in the first microreactor in micro-reaction device；The volume of first microreactor is 25mL.Mixed system is micro- first
25min is stopped at 120 DEG C in reactor.Again by the ethyl acetate solution of epoxidized soybean oil (20wt%) and the first microreactor
Discharging is pumped into the second micro-mixer respectively simultaneously, and the flow velocity of the ethyl acetate solution of epoxidized soybean oil is 0.84mL/min, the
The flow velocity of the discharging of one microreactor is 1mL/min, is passed through in the second microreactor in micro-reaction device after being sufficiently mixed, the
The volume of two microreactors is 37mL.Wherein, 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane and epoxidized soybean oil rub
You are than being 10:1.After material stops 20min at 180 DEG C in the second microreactor, discharging is imported in oil water separator, is stood
Layering, removes the aqueous solution of lower layer, upper organic phase is washed to pH6.5~7.5, after anhydrous sodium sulfate drying, is given birth to
Object polylol, hydroxyl value 480mgKOH/g, epoxide number 0.
Embodiment 5:
By the ethyl acetate solution (20wt%) of 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane and potassium hydroxide
Glycerin solution (1wt%) is with the molar ratio of 1:10 (with 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane and glycerine
Molar ratio computing) it is pumped into the first micro-mixer simultaneously respectively, the acetic acid second of 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane
The flow velocity of ester solution is 0.49mL/min, and the flow velocity of the glycerin solution of potassium hydroxide is 0.51mL/min, is led to after being sufficiently mixed
Enter and is reacted in the first microreactor in micro-reaction device；The volume of first microreactor is 15mL.Mixed system is micro- first
15min is stopped at 170 DEG C in reactor.Again by the ethyl acetate solution of epoxidized soybean oil (20wt%) and the first microreactor
Discharging is pumped into the second micro-mixer respectively simultaneously, and the flow velocity of the ethyl acetate solution of epoxidized soybean oil is 0.84mL/min, the
The flow velocity of the discharging of one microreactor is 1mL/min, is passed through in the second microreactor in micro-reaction device after being sufficiently mixed, the
The volume of two microreactors is 37mL.Wherein, 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane and epoxidized soybean oil rub
You are than being 10:1.After material stops 20min at 150 DEG C in the second microreactor, discharging is imported in oil water separator, is stood
Layering, removes the aqueous solution of lower layer, upper organic phase is washed to pH6.5~7.5, after anhydrous sodium sulfate drying, is given birth to
Object polylol, hydroxyl value 450mgKOH/g, epoxide number 0.
Embodiment 6:
By the ethyl acetate solution (15wt%) of 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane and potassium hydroxide
Glycerin solution (1wt%) is with the molar ratio of 1:10 (with 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane and glycerine
Molar ratio computing) respectively import simultaneously be pumped into the first micro-mixer, the second of 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane
The flow velocity of acetate solution is 0.56mL/min, and the flow velocity of the glycerin solution of potassium hydroxide is 0.44mL/min, is sufficiently mixed
It is reacted in the first microreactor being passed through in micro-reaction device afterwards；The volume of first microreactor is 25mL.Mixed system is
25min is stopped at 170 DEG C in one microreactor.The ethyl acetate solution of epoxidized soybean oil (15wt%) micro- is reacted with first again
The discharging of device is pumped into the second micro-mixer respectively simultaneously, and the flow velocity of the ethyl acetate solution of epoxidized soybean oil is 0.97mL/
Min, the flow velocity of the discharging of the first microreactor are 1mL/min, the micro- reaction of second be passed through in micro-reaction device after being sufficiently mixed
In device, the volume of the second microreactor is 39.4mL.Wherein, 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane and epoxy are big
The molar ratio of soya-bean oil is 10:1.After material stops 20min at 180 DEG C in the second microreactor, discharging is imported into water-oil separating
In device, stratification removes the aqueous solution of lower layer, and upper organic phase is washed to pH 6.5~7.5, dry with anhydrous sodium sulfate
Afterwards, biopolyol, hydroxyl value 440mgKOH/g, epoxide number 0 are obtained.
Embodiment 7:
By the ethyl acetate solution (20wt%) of 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane and potassium hydroxide
Glycerin solution (1wt%) is with the molar ratio of 1:5 (with rubbing for 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane and glycerine
You are than meter) it is pumped into the first micro-mixer simultaneously respectively, the ethyl acetate of 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane
The flow velocity of solution is 0.66mL/min, and the flow velocity of the glycerin solution of potassium hydroxide is 0.34mL/min, is passed through after being sufficiently mixed
It is reacted in the first microreactor in micro-reaction device；The volume of first microreactor is 25mL.Mixed system is micro- anti-first
It answers in device and stops 25min at 170 DEG C.Going out the ethyl acetate solution of epoxidized soybean oil (20wt%) and the first microreactor again
Material is pumped into the second micro-mixer respectively simultaneously, and the flow velocity of the ethyl acetate solution of epoxidized soybean oil is 1.12mL/min, and first
The flow velocity of the discharging of microreactor is 1mL/min, is passed through in the second microreactor in micro-reaction device after being sufficiently mixed, second
The volume of microreactor is 40mL.Wherein, mole of 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane and epoxidized soybean oil
Than for 5:1.After material stops 19min at 180 DEG C in the second microreactor, discharging is imported in oil water separator, stands and divides
Layer, removes the aqueous solution of lower layer, upper organic phase is washed to pH6.5~7.5, after anhydrous sodium sulfate drying, obtains biology
Polylol, hydroxyl value 500mgKOH/g, epoxide number 0.The hydroxyl value of petrochemical industry based polyether polyol 4110 is 420 ± 20mgKOH/
G, viscosity 2800-3500cp, the foam thermal conductivity obtained that foams is 24-28mW/mK；Bio-based polyhydric in this patent
Alcohol hydroxyl value is 500mgKOH/g, and viscosity is 3800 ± 300cp, and the foam thermal conductivity obtained that foams is 24-28mW/mK.
Embodiment 8:
Same as Example 7, difference is only that the type of alcohol is different, obtains biopolyol, hydroxyl value and epoxide number
It is shown in Table 2.
Table 2
| The type of alcohol | Hydroxyl value/(mgKOH/g) | Epoxide number |
| Methanol | 150 | 0 |
| Ethyl alcohol | 140 | 0 |
| 1,2-PD | 300 | 0 |
| 1,3-PD | 350 | 0 |
| Diethylene glycol (DEG) | 360 | 0 |
| Ethylene glycol | 380 | 0 |
Embodiment 9
The hard bubble thermal coefficient of biopolyol that the present invention obtains preparation is incompressible strong in 21.2mW/mK or so
Degree is in 289KPa or so；Hard bubble thermal coefficient 24-28mW/mK prepared by widely used polyether polyol 4110 on the market,
Incompressible intensity 200-250KPa.
Embodiment 10
Same as Example 7, difference is only that: epoxidized soybean oil being replaced with epoxy cotton seed oil, it is more to obtain biology base
First alcohol.
Embodiment 11
Same as Example 7, difference is only that: epoxidized soybean oil being replaced with epoxy corn oil, obtains bio-based polyhydric
Alcohol.
Claims (10)
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