CN102911012B - Bio-based polyalcohol and one-step synthetic method and application thereof - Google Patents
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Abstract
The invention discloses bio-based polyalcohol and a one-step synthetic method and an application thereof. The bio-based polyalcohol with a pinacol structure is prepared by performing an oxidizing reaction on unsaturated double bonds of animal grease or plant grease and potassium permanganate in a mixed system of an alkaline organic solvent and water under the action of a catalyst; and the hydroxyl value of the bio-based polyalcohol is 200-600mgKOH/g. The bio-based polyalcohol has the advantages of simple preparation process, environment-friendly raw materials, rich raw material source, low cost, mild and controllable reaction conditions, recycling of waste water and organic solvents, low pollution, low energy consumption, large controllable hydroxyl value range of a product, higher physicochemical property and biodegradability than petrochemicals, and high suitability for industrial production.
Description
Technical field
The present invention relates to biopolyol, particularly relate to a kind of high hydroxyl value bio-base polyol adopting biological grease to prepare through one-step synthesis, and the biopolyol 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.
The polyvalent alcohol for the preparation of polyurethane material common at present divides three classes: one generates polymkeric substance for starting raw material by oxyethane and propylene oxide with polyvalent alcohol or organic amine, is often called polyether glycol; The second is modify and graft polyether glycol, and then obtaining through bulk polymerization in polyvalent alcohol with vinyl monomer, is polymer polyatomic alcohol; The third is the polyvalent alcohol of tetrahydrofuran ring opening polymerization.These polyvalent alcohols mostly need petrochemical industry base product to be raw material, and therefore the source of raw material and cost are subject to larger restriction.
Along with consumption of petroleum amount increases, the minimizing day by day of fossil resources reserves, petroleum chemicals price continuous rise, more and more causes the attention of people, utilizes renewable resources to enjoy people to pay close attention to as the raw material of Chemicals with renewable resources production material and fuel.
The type of polyvalent alcohol plays a part abnormal important in polyurethane foam, also has material impact to the performance of product after foaming, and therefore, people expect to find novel cheap, eco-friendly biopolyol to substitute petrochemical industry polyvalent alcohol.
CN1837180A and CN101139252A individually discloses " a kind of biopolyol utilizing rapeseed oil to prepare " and " utilizing biopolyol prepared by Jatropha curcas oil ", respectively with rapeseed oil and Jatropha curcas oil for main raw material, obtain biopolyol through alcoholysis/epoxidation/open loop three-step reaction.CN1837181A and CN101108803A discloses " a kind of biopolyol adopting rapeseed oil to prepare " and " a kind of biopolyol adopting Jatropha curcas oil to prepare ", respectively with rapeseed oil and Jatropha curcas oil for main raw material, obtain biopolyol through epoxidation/open loop/alcoholysis three-step reaction.CN1907944A discloses " a kind of biopolyol adopting epoxy rapeseed oil to prepare ", is directly main raw material with epoxy rapeseed oil, through the obtained biopolyol of open loop/alcoholysis two step reaction.CN101906016A discloses " a kind of rubber seed oil polyalcohol and preparation method thereof ", take rubber seed oil as main raw material, through the obtained biopolyol of epoxidation/open loop two step reaction.In above patent, the preparation of biopolyol all adopts polystep reaction technique, and not only complex steps, also wastes energy, and production efficiency is low.
CN101659627A discloses " adopting high hydroxyl value bio-base polyol prepared by epoxidized vegetable oil through one-step reaction ", there is epoxy group(ing) ring-opening reaction and ester group amidate action by epoxidized vegetable oil and glycol amine simultaneously, prepare biopolyol, but it is raw material with epoxidized vegetable oil that the method needs direct, non-natural grease.
CN101747184A and CN101230020A individually discloses " single stage method is prepared the method for polyvalent alcohol by soybean oil " and " method of synthesizing macromonomer for polymer polyol by plant oil and uses thereof ", utilize epoxidation and open loop to react all in acid condition, single stage method prepares hydroxylated vegetable oil.CN101218272A discloses " adopting the novel polyols that method for oxidation derives from vegetables oil ", with tetraamido macrocyclic ligand for catalyzer, obtains biopolyol with hydrogen peroxide oxidation vegetables oil.In above patent, prepare polyvalent alcohol although claim by single stage method, still include epoxidation and this two-step reaction of open loop in essence, there is the problems such as long reaction time, temperature of reaction is high, technique is loaded down with trivial details.
In addition, the open loop that the above patent adopts alcohol, hydramine mostly, epoxy is carried out in acid, the biopolyol of preparation does not have pinacol structure.
Based on above problem, special invention one-step synthesis, shortens reaction process, reduces energy consumption, improve productive rate, prepare the biopolyol possessing pinacol structure.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of new bio polylol with pinacol structure adopting natural fats and oils to prepare through single step reaction is provided.
The technical problem that the present invention also will solve is to provide above-mentioned biopolyol and is preparing the application in polyurethane foaming products.
For solving the problems of the technologies described above, thinking of the present invention is as follows:
Vegetables oil is as a kind of renewable resources, and using more has Viscotrol C, soybean oil, plam oil, rapeseed oil, Oleum Gossypii semen, peanut wet goods.Containing a large amount of Unsaturatcd fatty acid glycerides in the middle of vegetables oil, these Unsaturatcd fatty acid glycerides are the natural compoundss be combined into by the unsaturated acid such as oleic acid, linoleic acid plus linolenic acid and glycerine, are distributed widely in occurring in nature.Animal oil is the structure of the ester that lipid acid and glycerine are formed equally, and the lipid acid in some animal oil belongs to saturated fatty acid, but also has containing unsaturated group in some animal oil, as lard, butter, fish oil etc.Its structure is as follows.
R
1, R
2or R
3linear chain structure in there is one or more unsaturated double-bond
This kind of animal-plant oil is cheap, and functionality is high, and is renewable resources; Have unsaturated double-bond in structure simultaneously, can utilize this kind of unsaturated double-bond, change into pinacol structure, thus introducing hydroxyl obtains polyol compound in the structure, concrete reaction formula is as follows.
Urethane prepared by this kind of biopolyol and isocyanic ester, the urethane ratio obtained compared with petrochemical industry polyvalent alcohol, has many advantages, mainly comprises with low cost, environmental protection, stable in properties, water-tolerant etc.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
An one-step synthesis for biopolyol, it is the unsaturated double-bond utilizing animal grease or Vegetable oil lipoprotein, in the organic solvent of alkalescence and the mixed system of water, is obtained by reacting has pinacol structure by catalyst action and potassium permanganate oxidation
biopolyol, its hydroxyl value is 200 ~ 600mgKOH/g.
Wherein, described animal grease is at least one in whale oil, fish oil, silkworm chrysalis oil, suet and lard; Described Vegetable oil lipoprotein is at least one in soybean oil, Viscotrol C, oleum lini, sunflower seed oil, Semen Maydis oil, Thistle oil, sesame oil, sweet oil, rapeseed oil, Oleum Gossypii semen, plam oil, peanut oil, Oleum Cocois, Rice pollard oil and tung oil, is preferably soybean oil or Viscotrol C.
Wherein, described alkalescence is pH 9-11.
Wherein, described organic solvent is mibk, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, tetrahydrofuran (THF), methyl acetate, ethyl acetate, propyl acetate or methylene dichloride; Described water and the volume ratio of organic solvent are 1:2 ~ 6.
Wherein, described catalyzer be benzyltriethylammonium chloride, hydrogen sulfate TBuA, halogenated phosphates, tetradecyl trimethyl ammonium chloride, Lvization Si Ben Phosphonium, iodate tetramethyl phosphonium, bicyclohexane also-hexaoxacyclooctadecane-6-6 or [2.2.2]-cave ether.
Wherein, described catalyzer accounts for 0.5 ~ 6% of oil quality.
Wherein, described grease and the mass ratio of potassium permanganate are 1:0.5 ~ 1.5.
Wherein, described oxidation reaction condition is at 5 DEG C ~ 50 DEG C, reaction 3 ~ 12h.
The biopolyol prepared by above-mentioned one-step synthesis is also within protection scope of the present invention.
The biopolyol prepared by above-mentioned one-step synthesis is preparing the application in polyurethane foaming products.New bio polylol functionality of the present invention is large, hydroxyl value is higher, as renewable resources organism-based raw material, can be applicable to prepare polyurethane foamed material, good with other component mutual solubilities such as isocyanic ester, speed of reaction is large, and reactive strong, obtained porous plastics hardness is large, mechanical and physical performance is good, good heat insulating.
Beneficial effect: the invention has the advantages that preparation technology is simple, raw material environmental protection, abundance, cost is low, reaction conditions gentleness is controlled, and waste water and organic solvent reusable edible, pollute little, energy consumption is low, the controlled hydroxyl value scope of product is comparatively large, has better physico-chemical property and biodegradability, be very suitable for suitability for industrialized production compared with petroleum chemicals.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
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 measuring method of the present invention to prepared novel polyols acid number and hydroxyl value is as follows:
(1) mensuration of acid number: survey acid number by GB/T 12008.5-2010;
(2) mensuration of hydroxyl value: survey hydroxyl value by GB/T 12008.3-2009.
Embodiment 1:
By 20g soybean oil, 5g water, 20mL ethyl acetate, 0.4g halogenated phosphates mixes, and regulate mixed solution to be 10 to pH with sodium hydroxide, temperature is set as 25 DEG C, adds potassium permanganate 24g, reacts 6h in stirring.The hydroxylation grease separating funnel obtained is isolated oil phase, is 7 through water washing to pH, concentratedly obtains biopolyol, and its hydroxyl value is 515mgKOH/g.
Embodiment 2:
By 20g Viscotrol C, 6g water, 22mL methyl acetate, 0.3g tetradecyl trimethyl ammonium chloride mixes, and regulate mixed solution to be 10 to pH with sodium hydroxide, temperature is set as 30 DEG C, adds potassium permanganate 14g, reacts 8h in stirring.The hydroxylation grease separating funnel obtained is isolated oil phase, is 7 through water washing to pH, concentratedly obtains biopolyol, and its hydroxyl value is 305mgKOH/g.
Embodiment 3:
By 20g oleum lini, 8g water, 16mL methylene dichloride, 1.2g benzyltriethylammonium chloride mixes, and regulate mixed solution to be 11 to pH with sodium hydroxide, temperature is set as 25 DEG C, adds potassium permanganate 30g, reacts 7h in stirring.The hydroxylation grease separating funnel obtained is isolated oil phase, is 7 through water washing to pH, concentratedly obtains biopolyol, and its hydroxyl value is 580mgKOH/g.
Embodiment 4:
By 20g sunflower seed oil, 7g water, 28mL tetrahydrofuran (THF), 0.4g benzyltriethylammonium chloride mixes, and regulate mixed solution to be 11 to pH with sodium hydroxide, temperature is set as 20 DEG C, adds potassium permanganate 22g, reacts 10h in stirring.The hydroxylation grease obtained first being revolved steaming, remove portion tetrahydrofuran (THF), then isolate oil phase with separating funnel, is 7 through water washing to pH, concentratedly obtains biopolyol, and its hydroxyl value is 510mgKOH/g.
Embodiment 5:
By 20g Semen Maydis oil, 7g water, 14mL propyl acetate, 0.4g hydrogen sulfate TBuA mixes, and regulate mixed solution to be 9 to pH with sodium hydroxide, temperature is set as 10 DEG C, adds potassium permanganate 20g, reacts 8h in stirring.The hydroxylation grease separating funnel obtained is isolated oil phase, is 7 through water washing to pH, concentratedly obtains biopolyol, and its hydroxyl value is 472mgKOH/g.
Embodiment 6:
By 20g Thistle oil, 4g water, 20mL methyl acetate, 0.4g halogenated phosphates mixes, and regulate mixed solution to be 11 to pH with sodium hydroxide, temperature is set as 15 DEG C, adds potassium permanganate 26g, reacts 3h in stirring.The hydroxylation grease separating funnel obtained is isolated oil phase, is 7 through water washing to pH, concentratedly obtains biopolyol, and its hydroxyl value is 550mgKOH/g.
Embodiment 7:
By 20g sesame oil, 5g water, 28mL methylene dichloride, 0.4g tetradecyl trimethyl ammonium chloride mixes, and regulate mixed solution to be 10 to pH with sodium hydroxide, temperature is set as 40 DEG C, adds potassium permanganate 20g, reacts 9h in stirring.The hydroxylation grease separating funnel obtained is isolated oil phase, is 7 through water washing to pH, concentratedly obtains biopolyol, and its hydroxyl value is 430mgKOH/g.
Embodiment 8:
By 20g sweet oil, 5g water, 23mL ethyl acetate, 0.8g hydrogen sulfate TBuA mixes, and regulate mixed solution to be 9 to pH with sodium hydroxide, temperature is set as 45 DEG C, adds potassium permanganate 14g, reacts 4h in stirring.The hydroxylation grease separating funnel obtained is isolated oil phase, is 7 through water washing to pH, concentratedly obtains biopolyol, and its hydroxyl value is 292mgKOH/g.
Embodiment 9:
By 20g rapeseed oil, 7g water, 17mL ethylene glycol monoethyl ether, 0.8g tetradecyl trimethyl ammonium chloride mixes, and regulate mixed solution to be 10 to pH with sodium hydroxide, temperature is set as 25 DEG C, adds potassium permanganate 18g, reacts 7h in stirring.The hydroxylation grease separating funnel obtained is isolated oil phase, is 7 through water washing to pH, concentratedly obtains biopolyol, and its hydroxyl value is 389mgKOH/g.
Embodiment 10:
By 20g Oleum Gossypii semen, 6g water, 12mL propyl acetate, 0.7g Lvization Si Ben Phosphonium mixes, and regulate mixed solution to be 10 to pH with sodium hydroxide, temperature is set as 30 DEG C, adds potassium permanganate 18g, reacts 9h in stirring.The hydroxylation grease separating funnel obtained is isolated oil phase, is 7 through water washing to pH, concentratedly obtains biopolyol, and its hydroxyl value is 413mgKOH/g.
Embodiment 11:
By 20g plam oil, 9g water, 30mL mibk, 0.4g bicyclohexane also-hexaoxacyclooctadecane-6-6 mixes, regulate mixed solution to be 9 to pH with sodium hydroxide, temperature is set as 35 DEG C, adds potassium permanganate 14g, reacts 12h in stirring.The hydroxylation grease separating funnel obtained is isolated oil phase, is 7 through water washing to pH, concentratedly obtains biopolyol, and its hydroxyl value is 261mgKOH/g.
Embodiment 12:
By 20g peanut oil, 8g water, 18mL methylene dichloride, 0.1g benzyltriethylammonium chloride mixes, and regulate mixed solution to be 11 to pH with sodium hydroxide, temperature is set as 15 DEG C, adds potassium permanganate 16g, reacts 6h in stirring.The hydroxylation grease separating funnel obtained is isolated oil phase, is 7 through water washing to pH, concentratedly obtains biopolyol, and its hydroxyl value is 336mgKOH/g.
Embodiment 13:
By 20g Oleum Cocois, 8g water, 34mL methyl acetate, 0.9g hydrogen sulfate TBuA mixes, and regulate mixed solution to be 11 to pH with sodium hydroxide, temperature is set as 40 DEG C, adds potassium permanganate 12g, reacts 5h in stirring.The hydroxylation grease separating funnel obtained is isolated oil phase, is 7 through water washing to pH, concentratedly obtains biopolyol, and its hydroxyl value is 226mgKOH/g.
Embodiment 14:
By 20g Rice pollard oil, 7g water, 27mL ethylene glycol monomethyl ether, 1.0g iodate tetramethyl phosphonium mixes, and regulate mixed solution to be 9 to pH with sodium hydroxide, temperature is set as 20 DEG C, adds potassium permanganate 16g, reacts 8h in stirring.The hydroxylation grease separating funnel obtained is isolated oil phase, is 7 through water washing to pH, concentratedly obtains biopolyol, and its hydroxyl value is 355mgKOH/g.
Embodiment 15:
By 20g tung oil, 8g water, 26mL mibk, 0.7g benzyltriethylammonium chloride mixes, and regulate mixed solution to be 10 to pH with sodium hydroxide, temperature is set as 20 DEG C, adds potassium permanganate 28g, reacts 6h in stirring.The hydroxylation grease separating funnel obtained is isolated oil phase, is 7 through water washing to pH, concentratedly obtains biopolyol, and its hydroxyl value is 556mgKOH/g.
Embodiment 16:
By 20g suet, 10g water, 25mL tetrahydrofuran (THF), 0.5g [2.2.2]-cave ether mixing, regulate mixed solution to be 11 to pH with sodium hydroxide, temperature is set as 50 DEG C, adds potassium permanganate 18g, reacts 8h in stirring.The hydroxylation grease obtained first being revolved steaming, remove portion tetrahydrofuran (THF), then isolate oil phase with separating funnel, is 7 through water washing to pH, concentratedly obtains biopolyol, and its hydroxyl value is 265mgKOH/g.
Embodiment 17:
By 20g lard, 10g water, 24mL methylene dichloride, 0.4g tetradecyl trimethyl ammonium chloride mixes, and regulate mixed solution to be 10 to pH with sodium hydroxide, temperature is set as 5 DEG C, adds potassium permanganate 14g, reacts 11h in stirring.The hydroxylation grease separating funnel obtained is isolated oil phase, is 7 through water washing to pH, concentratedly obtains biopolyol, and its hydroxyl value is 280mgKOH/g.
Embodiment 18:
By 20g fish oil, 10g water, 22mL propyl acetate, 0.7g halogenated phosphates mixes, and regulate mixed solution to be 9 to pH with sodium hydroxide, temperature is set as 35 DEG C, adds potassium permanganate 14g, reacts 6h in stirring.The hydroxylation grease separating funnel obtained is isolated oil phase, is 7 through water washing to pH, concentratedly obtains biopolyol, and its hydroxyl value is 302mgKOH/g.
Embodiment 19: the performance test of hard polyurethane foam prepared by new bio polylol.
Get at least one biopolyol prepared in above-described embodiment, with polyether glycol 635(hydroxyl value 490mgKOH/g, the red Pola in Nanjing), suds-stabilizing agent AK8803(Nanjing Mei Side), hexahydroaniline (great river, Jiangdu chemical industry), isocyanic ester PM200(Yantai ten thousand China), blowing agent H CFC-141b(Changshu three likes rich fluorine chemical) reaction foams, and can prepare hard polyurethane foams.
The measuring method of the present invention to hard polyurethane foam prepared by new bio polylol is as follows:
(1) apparent density of porous plastics is measured according to GB/T 6343-1995;
(2) measure the compressive strength of rigid foam according to GB/T 8813-88, 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.
The results are shown in Table 1.
Table 1
| The oil source of biological multielement alcohol | Density/(kg/m 3) | Vertical compressive strength/kPa |
| Soybean oil | 45.2 | 149 |
| Viscotrol C | 49.7 | 155 |
| Oleum lini | 38.9 | 134 |
| Sunflower seed oil | 36.3 | 130 |
| Semen Maydis oil | 48.2 | 153 |
| Thistle oil | 44.3 | 146 |
| Sesame oil | 35.1 | 127 |
| Sweet oil | 50.2 | 159 |
| Rapeseed oil | 38.8 | 131 |
| Oleum Gossypii semen | 35.5 | 125 |
| Plam oil | 37.3 | 132 |
| Peanut oil | 46.5 | 149 |
| Oleum Cocois | 43.2 | 143 |
| Rice pollard oil | 33.2 | 122 |
| Tung oil | 46.2 | 134 |
| Suet | 53.3 | 119 |
| Lard | 56.5 | 123 |
| Fish oil | 49.9 | 130 |
Claims (2)
1. the one-step synthesis of a biopolyol, it is characterized in that, it is the unsaturated double-bond utilizing animal grease or Vegetable oil lipoprotein, in the organic solvent of alkalescence and the mixed system of water, be obtained by reacting the biopolyol with pinacol structure by catalyst action and potassium permanganate oxidation, its hydroxyl value is 226 ~ 600mgKOH/g;
Described alkalescence is pH 9-11;
Described organic solvent is mibk, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, tetrahydrofuran (THF), methyl acetate, ethyl acetate, propyl acetate or methylene dichloride; Described water and the volume ratio of organic solvent are 1:2 ~ 6;
Described catalyzer be benzyltriethylammonium chloride, hydrogen sulfate TBuA, halogenated phosphates, tetradecyl trimethyl ammonium chloride, Lvization Si Ben Phosphonium, iodate tetramethyl phosphonium, bicyclohexane also-hexaoxacyclooctadecane-6-6 or [2.2.2]-cave ether;
Described catalyzer accounts for 0.5 ~ 6% of oil quality;
Described grease and the mass ratio of potassium permanganate are 1:0.5 ~ 1:1.5;
Described oxidation reaction condition is at 5 DEG C ~ 50 DEG C, reaction 3 ~ 12h.
2. the one-step synthesis of biopolyol according to claim 1, is characterized in that, described animal grease is at least one in whale oil, fish oil, silkworm chrysalis oil, suet and lard; Described Vegetable oil lipoprotein is at least one in soybean oil, Viscotrol C, oleum lini, sunflower seed oil, Semen Maydis oil, Thistle oil, sesame oil, sweet oil, rapeseed oil, Oleum Gossypii semen, plam oil, peanut oil, Oleum Cocois, Rice pollard oil and tung oil.
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| CN105712882B (en) * | 2014-12-05 | 2017-10-27 | 中国石油化工股份有限公司 | A kind of tung oil polyalcohol and synthetic method |
| CN105712880B (en) * | 2014-12-05 | 2017-10-27 | 中国石油化工股份有限公司 | A kind of tung oil polyalcohol and its synthetic method |
| CN104673501A (en) * | 2015-02-05 | 2015-06-03 | 南京工业大学 | Method for continuously synthesizing bio-based polyol |
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| CN101108803A (en) * | 2007-08-02 | 2008-01-23 | 南京红宝丽股份有限公司 | Bio-surfactant polylol manufactured with jatropha curcas oil |
| CN101218272A (en) * | 2005-03-03 | 2008-07-09 | 南达科他大豆处理机有限公司 | Novel polyols derived from a vegetable oil using an oxidation process |
| CN101747184A (en) * | 2008-12-01 | 2010-06-23 | 天津工业大学 | One-step preparation method of polyol with soybean oil |
| CN101139252B (en) * | 2007-08-23 | 2010-12-01 | 南京红宝丽股份有限公司 | Biological radical polyatomic alcohol prepared by Jatropha curcas oil |
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| CN101218272A (en) * | 2005-03-03 | 2008-07-09 | 南达科他大豆处理机有限公司 | Novel polyols derived from a vegetable oil using an oxidation process |
| CN101108803A (en) * | 2007-08-02 | 2008-01-23 | 南京红宝丽股份有限公司 | Bio-surfactant polylol manufactured with jatropha curcas oil |
| CN101139252B (en) * | 2007-08-23 | 2010-12-01 | 南京红宝丽股份有限公司 | Biological radical polyatomic alcohol prepared by Jatropha curcas oil |
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