CN105541621A - Vegetable oil polyhydric alcohol as well as preparation method and application of vegetable oil polyhydric alcohol - Google Patents
Vegetable oil polyhydric alcohol as well as preparation method and application of vegetable oil polyhydric alcohol Download PDFInfo
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- CN105541621A CN105541621A CN201610060812.4A CN201610060812A CN105541621A CN 105541621 A CN105541621 A CN 105541621A CN 201610060812 A CN201610060812 A CN 201610060812A CN 105541621 A CN105541621 A CN 105541621A
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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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/708—Ethers
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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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- 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
Abstract
The invention discloses vegetable oil polyhydric alcohol as well as a preparation method and application of the vegetable oil polyhydric alcohol. The vegetable oil polyhydric alcohol is prepared by a ring-opening reaction of epoxy vegetable oil and a polyhydroxy compound. Compared with the prior art, the vegetable oil polyhydric alcohol prepared by adopting a novel ring opening agent has a novel structure, a high hydroxyl value and low viscosity, and can be used for completely replacing traditional petrochemical polyhydric alcohol to be applied to preparation of a polyurethane foam material. Meanwhile, the method is simple in process and the obtained product does not need to be subjected to post treatment and is very suitable for industrialized production; particularly, after a tubular reactor is selected, the reaction efficiency can be improved, a side reaction is controlled and the energy consumption is reduced.
Description
Technical field
The invention belongs to chemical materials and production technical field thereof, relate to a kind of vegetable oil polyol and preparation method thereof and application, and the vegetable oil polyol of the present invention's synthesis is applicable to prepare polyurethane material.
Background technology
Urethane is a kind of polymkeric substance with carbamate segment repeated structural unit be made up of isocyanic ester and polyol reaction.Polyurethane product is divided into foaming product and the large class of non-foamed goods two, and foaming product has soft, hard, semi-hard polyurethane foam plastic; Non-foamed goods comprise coating, tackiness agent, synthetic leather, elastomerics and spandex fiber etc.Polyurethane material excellent performance, of many uses, goods kind is many, wherein especially extensive with the purposes of urethane foam.
Polyvalent alcohol used in urethane mainly contains three classes, a kind of be with polyvalent alcohol or organic amine for initiator is by being polymerized with oxyethane, propylene oxide or butylene oxide ring the polymkeric substance obtained, be called polyether glycol; Another kind of modify and graft polyether glycol is based on polyether glycol, then obtain through bulk polymerization in polyvalent alcohol with vinyl monomer, is called polymer polyatomic alcohol, often and polyether glycol with the use of; The third is by the polyvalent alcohol of tetrahydrofuran ring opening polymerization.Along with fossil resources reserves reduce day by day, petroleum chemicals price continuous rise, the throughput of domestic olefin oxide is limited in addition, needs import, buys inconvenience, directly has influence on the production of product.
Vegetable oil polyol is important renewable resources, can react produce urethane with isocyanate ester compound, is the good alternative materials of petroleum-based polyols.The method of synthesizing vegetable oil polyol in recent years mainly contains: 1) vegetables oil and polyvalent alcohol are carried out alcoholysis reaction, generates polyol; 2) utilize the unsaturated double-bond in ozone oxidation vegetables oil, generate the polyol with end position hydroxyl; 3) be epoxidized vegetable oil by vegetable oil being oxygenized, then by process generation polyols such as hydrolysis, hydrogenation, esterification or halogenations.
In the method for above-mentioned synthesis vegetable oil polyol, method 1) and 3) employing is more usually.CN1837180A and CN101139252A respectively with rapeseed oil and Jatropha curcas oil for main raw material, obtain vegetable oil polyol through alcoholysis/epoxidation/open loop three-step reaction.CN1837181A and CN101108803A respectively with rapeseed oil and Jatropha curcas oil for main raw material, obtain vegetable oil polyol through epoxidation/open loop/alcoholysis three-step reaction.CN101906016A take rubber seed oil as main raw material, through the obtained vegetable oil polyol of epoxidation/open loop two step reaction.CN1907944A is directly main raw material with epoxy rapeseed oil, through the obtained vegetable oil polyol of open loop/alcoholysis two step reaction.
In above patent, the synthesis of vegetable oil polyol is all based on open loop again after double bond epoxy, Ring Opening Reagent mainly selects micromolecular alcohol, hydramine or carboxylic acid, but have that product qualities is not high, aftertreatment is loaded down with trivial details, easily occur the problems such as crosslinking side reaction in reaction, and when being applied to polyurethane material, still need composite a certain proportion of petrochemical industry polyvalent alcohol.Based on above problem, the present invention overcomes the deficiencies in the prior art part, synthesizes novel structure, and hydroxyl value is high, and viscosity is low, and technique is simple, and product, without the need to aftertreatment, can substitute the vegetable oil polyol that traditional petrochemical industry polyvalent alcohol is applied to polyurethane foamed material completely.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of novel structure, hydroxyl value is high, and viscosity is low, and technique is simple, and product, without the need to aftertreatment, can substitute the vegetable oil polyol that traditional petrochemical industry polyvalent alcohol is applied to polyurethane foamed material completely.
The technical problem that the present invention also will solve is to provide above-mentioned vegetable oil polyol and is preparing the application in polyurethane foamed material.
For solving the problems of the technologies described above, thinking of the present invention is as follows:
Containing unsaturated carbon-carbon double bond in vegetables oil, epoxy group(ing) is become through Prileshajev epoxidation reaction, epoxy group(ing) introduces hydroxyl through ring-opening reaction subsequently, conventional Ring Opening Reagent mainly contains micromolecular alcohol, hydramine or carboxylic acid, wherein for the Ring Opening Reagent of single functionality, product hydroxyl value is on the low side, for the Ring Opening Reagent of polyfunctionality, because each hydroxyl adjoins closely, deposit the situation of the multiple grease molecules epoxy group of unit molecule Ring Opening Reagent open loop in the reaction (for tetramethylolmethane open loop epoxidized vegetable oil, see Fig. 1), in addition newly-generated hydroxyl also participates in ring-opening reaction, grease molecules is caused to be aggregated to together, and then cause product viscosity large, hydroxyl value is low.Even if polyfunctionality small molecules Ring Opening Reagent only consumes single hydroxyl in reaction process, but generate vegetable oil polyol due to each hydroxyl too concentrate (for tetramethylolmethane open loop epoxidized vegetable oil, see Fig. 2, in figure, the hydroxyl spacing at i, ii, iii, iv place is nearer), polyurethane foam performance can be caused not good.In addition, existing operate in open loop state selects an acidic catalyst mostly, and the polyvalent alcohol of high acid value is unfavorable for the use in urethane, therefore product needs washing refining, and technique is loaded down with trivial details.
The present invention selects specific polyol as Ring Opening Reagent, this polyol is with 1,2-propylene glycol, 1, ammediol, glycol ether, ethylene glycol, TriMethylolPropane(TMP), glycerol, 1,2,6-hexanetriol, tetramethylolmethane, Xylitol, N.F,USP MANNITOL, sorbyl alcohol are initiator, and with the product of propylene oxide generation addition reaction, initiator and propylene oxide have rational mol ratio.Take tetramethylolmethane as initiator, react to obtain polyol (see Fig. 3) with waiting mol propylenoxy, this polyol open loop epoxidized vegetable oil can obtain vegetable oil polyol (see Fig. 4).The present invention use polyol due to its chain length, functionality moderate, can ensure that vegetable oil polyol prepared by its open loop has lower viscosity and higher hydroxyl value, and the reasonable layout of hydroxyl makes the polyurethane foam performance based on this vegetable oil polyol excellent.In addition, the catalyst levels that the present invention selects is few, and micro residue does not affect the use of polyvalent alcohol, and product need not wash refining, simple process.
The present invention, in reactive mode, except selecting conventional tank reactor, also adopts tubular reactor, mainly micro passage reaction.Microchannel reaction is as a new synthesis technology, and at medicine, field of fine chemical has certain application, is also the study hotspot of current international technical field of fine.Compared with popular response system, microchannel reaction has that reaction preference is high, mass-and heat-transfer efficiency is high makes that reactive behavior is high, the reaction times is short, transformation efficiency is high, security is good and is easy to the advantages such as control.Select microchannel reaction technology to be applied to polyol open loop epoxidized vegetable oil, can reaction efficiency be improved, control the generation of side reaction, reduce energy consumption.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A preparation method for vegetable oil polyol, polyol and epoxidized vegetable oil are obtained by reacting vegetable oil polyol by it under catalyst action;
Wherein, described reaction is the ring-opening reaction that the hydroxyl of polyol and the epoxide group of epoxidized vegetable oil occur.
Wherein, described polyol refers to the product of initiator and propylene oxide generation addition reaction;
Wherein, initiator is 1,2-PD, 1,3-PD, glycol ether, ethylene glycol, TriMethylolPropane(TMP), glycerol, 1,2,6-hexanetriol, tetramethylolmethane, Xylitol, N.F,USP MANNITOL or sorbyl alcohol;
Wherein, for any one initiator above-mentioned, if functionality is n, then the mol ratio of itself and propylene oxide is 1: 1 ~ n;
Wherein, the condition of addition reaction: small molecular alcohol, propylene oxide and potassium hydroxide (consumption is 1% of small molecular alcohol quality) are mixed; pass into nitrogen protection; mechanic whirl-nett reaction 5h at 30 DEG C; then through phosphoric acid neutralization, dehydration, adsorption of magnesium silicate and filtration, polyol is obtained.
Wherein, described epoxidized vegetable oil is any one or a few the combination in epoxy sweet oil, epoxy peanut oil, epoxy rapeseed oil, epoxy cottonseed oil, epoxy soybean oil, epoxy coconut oil, epoxy palm oil, epoxy sesame oil, epoxy sunflower seed oil, epoxidized linseed oil, epoxy castor oil, epoxy tung oil, nontoxic plasticizer and epoxy Semen Maydis oil.
Wherein, described catalyzer is sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, sodium isopropylate, propyl carbinol sodium, sodium tert-butoxide, potassium methylate, potassium ethylate, potassium isopropoxide or potassium tert.-butoxide; Wherein, the mass ratio of catalyzer and epoxidized vegetable oil is 0.02 ~ 0.06%.
Wherein, described epoxidized vegetable oil epoxy group group is 1:0.8 ~ 1:1 with the mol ratio of polyol.
Wherein, epoxidized vegetable oil and polyol react in tank reactor or tubular reactor.
Wherein, described tubular reactor is microchannel module reaction unit, comprise the micro mixer, microstructure heat exchanger, tubulose temperature control modules and the micro-structured reactor that are linked in sequence successively by pipeline, reaction raw materials passes through accurately and the pump of low pulse inputs in micro mixer and equipment afterwards thereof; Preferably, described micro mixer is slitplatemixerLH25; Microstructure heat exchanger is coaxialheatexchanger; Micro-structured reactor is meanderreactorHC, sandwichreactorHC, fixedbedmeanderreactorHC or Hastelloy micro passage reaction.
Wherein, epoxidized vegetable oil and the polyol temperature of reaction in tank reactor is 120 ~ 165 DEG C, and the reaction times is 1 ~ 6h, needs nitrogen protection during reaction; Epoxidized vegetable oil and the polyol temperature of reaction in tubular reactor is 100 ~ 140 DEG C, reaction retention time is 5 ~ 15min, wherein the sample rate of epoxidized vegetable oil is 1.0 ~ 3.5mL/min, and the sample rate of polyol is 0.6 ~ 2.4mL/min.
The vegetable oil polyol that above-mentioned preparation method obtains is also within protection scope of the present invention.
The application of the vegetable oil polyol that above-mentioned preparation method obtains in the preparation of polyurethane foamed material is also within protection scope of the present invention.
Beneficial effect: compared with prior art, the present invention adopts novel Ring Opening Reagent, the vegetable oil polyol novel structure prepared, and hydroxyl value is high, and viscosity is low, can substitute the preparation that traditional petrochemical industry polyvalent alcohol is applied to polyurethane foamed material completely.Meanwhile, the inventive method technique is simple, and products therefrom, without the need to aftertreatment, is very suitable for suitability for industrialized production, especially can improve reaction efficiency after selecting tubular reactor, controls the generation of side reaction, reduces energy consumption.
Accompanying drawing explanation
Oligomerization when Fig. 1 is tetramethylolmethane open loop epoxidized vegetable oil.
Fig. 2 is the reaction formula of tetramethylolmethane open loop epoxidized vegetable oil.
Fig. 3 is the structural formula of tetramethylolmethane based polyols.
Fig. 4 is the reaction formula of the inventive method.
Embodiment
According to following embodiment, the present invention may be better understood.But those skilled in the art will readily understand, the content described by embodiment only for illustration of the present invention, and should can not limit the present invention described in detail in claims yet.
The related assays method of the present invention to prepared vegetable oil polyol and polyurethane foamed material is as follows:
(1) hydroxyl value is surveyed according to GB/T12008.3-2009;
(2) according to GB/T12008.7-2010 viscosimetric;
(3) apparent density of porous plastics is measured according to GB/T6343-2009;
(4) measure the compressive strength of rigid foam according to GB/T8813-2008, getting foaming vertical direction cross section is compressing surface, and compression speed is 5mm/min, and test value during sample thief 10% deflection is as the compressive strength of material;
(5) measure the shock strength of rigid foam according to GB/T11548-1989, shock strength is used for the toughness of exosyndrome material under high speed impact state or the resistivity to fracture.
Embodiment 1:
100g epoxy soybean oil, 75g polyol (tetramethylolmethane with etc. the product that reacts of mol propylenoxy), 0.03g sodium methylate are mixed; be placed in conventional still reaction still; pass into nitrogen protection; mechanical stirring; be warming up to 130 DEG C, stopped reaction after reaction 3h, obtains soybean oil polyol; its hydroxyl value is 561mgKOH/g, and viscosity is 2950mPas.
Embodiment 2:
Getting 100g epoxy rapeseed oil is component A, separately getting 0.02g propyl carbinol sodium is dissolved in 55g polyol (product that ethylene glycol and twice mol propylenoxy react), for B component, by in A, B component simultaneous pumping in a subtle way path modular reaction unit, react in sandwichreactorHC at normal pressure and 130 DEG C, the sample rate of A, B component is respectively 3.0mL/min, 1.6mL/min, keep reaction time 8min, namely collecting reaction product obtains rapeseed oil polyvalent alcohol, its hydroxyl value is 380mgKOH/g, and viscosity is 3050mPas.
Embodiment 3:
Getting 100g epoxy tung oil is component A, separately get 0.02g sodium tert-butoxide and be dissolved in 67g polyol (1,2-propylene glycol and the product waiting mol propylenoxy to react) in, for B component, by in A, B component simultaneous pumping in a subtle way path modular reaction unit, react in Hastelloy micro passage reaction at normal pressure and 140 DEG C, the sample rate of A, B component is respectively 1.2mL/min, 0.8mL/min, keep reaction time 10min, namely collecting reaction product obtains tung oil polyvalent alcohol, its hydroxyl value is 485mgKOH/g, and viscosity is 2850mPas.
Embodiment 4: polyol and tetramethylolmethane are as the controlled trial of Ring Opening Reagent
With reference to embodiment 1,75g polyol (tetramethylolmethane and the product waiting mol propylenoxy to react) etc. mole is replaced with 52.6g tetramethylolmethane, and all the other are consistent, and product hydroxyl value is 215mgKOH/g, and viscosity is 13350mPas; Compared to polyvalent alcohol prepared by embodiment 1, polyvalent alcohol hydroxyl value prepared by the present embodiment is on the low side, and viscosity is bigger than normal.
Embodiment 5: the controlled trial that material reacts in tank reactor and tubular reactor
With reference to embodiment 1, getting 100g epoxy soybean oil is component A, separately getting 0.03g sodium methylate is dissolved in 75g polyol (tetramethylolmethane and the product waiting mol propylenoxy to react), for B component, by A, B component simultaneous pumping is in a subtle way in path modular reaction unit, react in sandwichreactorHC at normal pressure and 130 DEG C, A, the sample rate of B component is respectively 2.9mL/min, 1.7mL/min, keep reaction time 8min, namely collecting reaction product obtains soybean oil polyol, its hydroxyl value is 613mgKOH/g, viscosity is 2580mPas, compared to polyvalent alcohol prepared by embodiment 1, polyvalent alcohol hydroxyl value prepared by the present embodiment is higher, and viscosity is lower.
Embodiment 6: the performance test of hard polyurethane foam prepared by vegetable oil polyol
The soybean oil polyol of preparation in Example 1, adopts single stage method free foaming technique, with suds-stabilizing agent AK-8803 (Nanjing Mei Side), hexahydroaniline (great river, Jiangdu chemical industry), isocyanic ester
pM-200 (Yantai ten thousand China), whipping agent pentamethylene (the U.S. dragon in Foshan) reaction are foamed, and can prepare hard polyurethane foams, its apparent density is 30.3kg/m
3, vertical compressive strength is 179kPa, and shock strength is 0.083kJ/m
2.
Claims (10)
1. a preparation method for vegetable oil polyol, is characterized in that, polyol and epoxidized vegetable oil are obtained by reacting vegetable oil polyol by it under catalyst action;
Wherein, described reaction is the ring-opening reaction that the hydroxyl of polyol and the epoxide group of epoxidized vegetable oil occur.
2. preparation method according to claim 1, is characterized in that, described polyol refers to the product of initiator and propylene oxide generation addition reaction;
Wherein, initiator is 1,2-PD, 1,3-PD, glycol ether, ethylene glycol, TriMethylolPropane(TMP), glycerol, 1,2,6-hexanetriol, tetramethylolmethane, Xylitol, N.F,USP MANNITOL or sorbyl alcohol;
Wherein, for any one initiator above-mentioned, if functionality is n, then the mol ratio of itself and propylene oxide is 1:1 ~ n;
Wherein, the condition of addition reaction passes into nitrogen protection, mechanic whirl-nett reaction 5h at 30 DEG C after small molecular alcohol, propylene oxide and potassium hydroxide being mixed, and then through phosphoric acid neutralization, dehydration, adsorption of magnesium silicate and filtration, obtains polyol; Wherein, the mass percent of potassium hydroxide and small molecular alcohol is 1%.
3. preparation method according to claim 1, it is characterized in that, described epoxidized vegetable oil is any one or a few the combination in epoxy sweet oil, epoxy peanut oil, epoxy rapeseed oil, epoxy cottonseed oil, epoxy soybean oil, epoxy coconut oil, epoxy palm oil, epoxy sesame oil, epoxy sunflower seed oil, epoxidized linseed oil, epoxy castor oil, epoxy tung oil, nontoxic plasticizer and epoxy Semen Maydis oil.
4. preparation method according to claim 1, is characterized in that, described catalyzer is sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, sodium isopropylate, propyl carbinol sodium, sodium tert-butoxide, potassium methylate, potassium ethylate, potassium isopropoxide or potassium tert.-butoxide; Wherein, the mass ratio of catalyzer and epoxidized vegetable oil is 0.02 ~ 0.06%.
5. preparation method according to claim 1, is characterized in that, described epoxidized vegetable oil epoxy group group is 1:0.8 ~ 1:1 with the mol ratio of polyol.
6. preparation method according to claim 1, is characterized in that, epoxidized vegetable oil and polyol react in tank reactor or tubular reactor.
7. preparation method according to claim 6, it is characterized in that, described tubular reactor is microchannel module reaction unit, comprise the micro mixer, microstructure heat exchanger, tubulose temperature control modules and the micro-structured reactor that are linked in sequence successively by pipeline, reaction raw materials passes through accurately and the pump of low pulse inputs in micro mixer and equipment afterwards thereof.
8. preparation method according to claim 6, is characterized in that, epoxidized vegetable oil and the polyol temperature of reaction in tank reactor is 120 ~ 165 DEG C, and the reaction times is 1 ~ 6h, needs nitrogen protection during reaction; Epoxidized vegetable oil and the polyol temperature of reaction in tubular reactor is 100 ~ 140 DEG C, and reaction retention time is 5 ~ 15min.
9. the vegetable oil polyol that in claim 1 ~ 8, any one prepares.
10. vegetable oil polyol according to claim 9 is preparing the application in polyurethane foamed material.
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| CN201510062170.7A CN104610540A (en) | 2015-03-17 | 2015-03-17 | Vegetable oil polyalcohol as well as preparation method and application of vegetable oil polyalcohol |
| CN201610060812.4A CN105541621A (en) | 2015-03-17 | 2016-01-28 | Vegetable oil polyhydric alcohol as well as preparation method and application of vegetable oil polyhydric alcohol |
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| CN109134259A (en) * | 2018-10-15 | 2019-01-04 | 南京工业大学 | A kind of biopolyol and its preparation method and application |
| CN109134260A (en) * | 2018-10-16 | 2019-01-04 | 张家港市飞航科技有限公司 | A kind of biopolyol and its preparation method and application |
| CN109651590A (en) * | 2019-01-07 | 2019-04-19 | 江南大学 | A kind of preparation method of glucose soybean oil base crosslinking one-step synthesis polyurethane |
| CN110922578A (en) * | 2019-10-24 | 2020-03-27 | 南京先进生物材料与过程装备研究院有限公司 | High-selectivity preparation of polyol by microwave heating in microreactor and method |
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| CN109369871B (en) * | 2018-10-11 | 2020-11-27 | 南京工业大学 | Polyurethane polyol and preparation method and application thereof |
| CN109180482A (en) * | 2018-10-15 | 2019-01-11 | 南京工业大学 | A kind of vegetable oil polyol and its preparation method and application |
| CN113717374A (en) * | 2021-09-24 | 2021-11-30 | 长春工业大学 | Preparation method and application of bio-based flame-retardant polyether polyol |
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