CN109134260A - A kind of biopolyol and its preparation method and application - Google Patents
A kind of biopolyol 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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- 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
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- 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
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- 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
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- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- 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
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Abstract
The invention discloses a kind of biopolyols and its preparation method and application, described method includes following steps: (1) by 1, the ethyl acetate solution of 2- dimethyl -7- oxabicyclo [4.1.0] heptane, which is pumped into simultaneously in the first microreactor of micro-reaction device with the alcoholic solution of potassium hydroxide, to be reacted, and reaction efflux is obtained；(2) the reaction efflux that step (1) obtains is pumped into the second microreactor of micro-reaction device simultaneously with the ethyl acetate solution of epoxidized vegetable oil and is reacted, obtain biopolyol.The advantages of preparation method of the invention is simple and efficient, and has selectivity height, highly-safe, can be with continuous production and without using new 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)
1. a kind of method for preparing biopolyol, which comprises the steps of:
(1) simultaneously 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, obtain reaction efflux；
(2) ethyl acetate solution of reaction efflux and epoxidized vegetable oil that step (1) obtains is pumped into micro-reaction device simultaneously
The second microreactor in reacted, obtain biopolyol.
2. preparation method according to claim 1, which is characterized in that in step (1), the alcohol be methanol, ethyl alcohol, 1,
2- propylene glycol, 1,3-PD, pentaerythrite, diethylene glycol (DEG), ethylene glycol or glycerine, 1, the 2- dimethyl -7- oxa- are double
The mass fraction of 1,2- dimethyl -7- oxabicyclo [4.1.0] heptane is in the ethyl acetate solution of ring [4.1.0] heptane
10wt%-20wt%, the mass fraction of potassium hydroxide is 0.1wt%-1wt% in the alcoholic solution of potassium hydroxide.
3. preparation method according to claim 1, which is characterized in that in step (1), in the first microreactor, reaction
Temperature is 100-200 DEG C, reaction time 10-30min, and the volume of the first microreactor is 5-50mL, 1,2- dimethyl-
The flow velocity that the ethyl acetate solution of 7- oxabicyclo [4.1.0] heptane is pumped into micro-reaction device is 0.1-1mL/min, potassium hydroxide
Alcoholic solution be pumped into micro-reaction device flow velocity be 0.1-1mL/min.
4. preparation method according to claim 1, which is characterized in that in step (1), 1,2- dimethyl -7- oxabicyclo
The molar ratio of [4.1.0] heptane and alcohol is 1:(1-10).
5. preparation method according to claim 1, which is characterized in that in step (2), the epoxidized vegetable oil is epoxy olive
Olive oil, epoxy peanut oil, epoxy rapeseed oil, epoxy cottonseed oil, epoxidized soybean oil, epoxy coconut oil, epoxy palm oil, epoxy sesame
Any one or a few in sesame oil, epoxy corn oil or epoxy sunflower oil, in the ethyl acetate solution of epoxidized vegetable oil
Epoxidized vegetable oil mass fraction 10wt%-20wt%.
6. preparation method according to claim 1, which is characterized in that in step (2), in the second microreactor, reaction
Temperature is 120-200 DEG C, reaction time 20-30min, and the volume of the second microreactor is 10-40mL, epoxidized soybean oil
Ethyl acetate solution be pumped into micro-reaction device flow velocity be 0.2-1mL/min.
7. preparation method according to claim 1, which is characterized in that in step (2), 1,2- dimethyl -7- oxabicyclo
The molar ratio of [4.1.0] heptane and epoxidized soybean oil is (1-10): 1.
8. preparation method according to claim 1, which is characterized in that the micro-reaction device include by connecting tube according to
The first micro-mixer, the first microreactor, the second micro-mixer and the second microreactor of secondary sequential connection.
9. the biopolyol that method described in claim 1~8 any one is prepared.
10. biopolyol as claimed in claim 9 is preparing the application in hard polyurethane foam.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110372841A (en) * | 2019-07-24 | 2019-10-25 | 张家港市飞航科技有限公司 | A kind of Polyurethane Thermal Insulation Building Materials and preparation method thereof |
| CN112321429A (en) * | 2020-11-03 | 2021-02-05 | 南京工业大学 | Method for continuously preparing bio-based polyol by using micro-channel and multi-stage reaction kettle |
| CN112898160A (en) * | 2021-01-25 | 2021-06-04 | 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 |
|---|
| 杨宁宁等: "环氧环己烷基聚氨酯透明材料的制备", 《聚氨酯工业》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110372841A (en) * | 2019-07-24 | 2019-10-25 | 张家港市飞航科技有限公司 | A kind of Polyurethane Thermal Insulation Building Materials and preparation method thereof |
| CN112321429A (en) * | 2020-11-03 | 2021-02-05 | 南京工业大学 | Method for continuously preparing bio-based polyol by using micro-channel and multi-stage reaction kettle |
| CN112898160A (en) * | 2021-01-25 | 2021-06-04 | 南京工业大学 | Vegetable oil polyalcohol, preparation method and application thereof in polyurethane material |
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