CN104119495A - Preparation method of biological oil-based polyhydric alcohol - Google Patents
Preparation method of biological oil-based polyhydric alcohol Download PDFInfo
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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
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4288—Polycondensates having carboxylic or carbonic ester groups in the main chain modified by higher fatty oils or their acids or by resin 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
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4891—Polyethers modified with higher fatty oils or their acids or by resin 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
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
Abstract
The invention discloses a preparation method of biological oil-based polyhydric alcohol. The preparation method comprises the following steps: first, adding an initiator into biological oil for heating and stirring for the first time, wherein the initiator accounts for 0.5-2% of the total weight of the biological oil and the initiator; then, after uniformly heating and stirring for the first time, respectively adding a poly-reactive hydrogen compound and a solid base catalyst for heating and stirring for the second time, wherein the weight ratio of the poly-reactive hydrogen compound to the biological oil is 1: 5 to 1: 20 and the solid base catalyst accounts for 0.5-2% of the total weight of the biological oil and the initiator; and finally, after uniformly heating and stirring for the second time, cooling to room temperature and filtering and separating to obtain the biological oil-based polyhydric alcohol. According to the preparation method of the biological oil-based polyhydric alcohol disclosed by the invention, the biological oil-based polyhydric alcohol obtained can be regenerated and is available in raw materials for preparation, regenerable, good in biodegradability, simple to prepare, adjustable in hydroxyl value and free from environmental pollution.
Description
Technical field
The present invention relates to a kind of preparation method of bio oil polylol.
Background technology
Along with the progress of polyurethane chemistry research, product manufacture and application art technology, polyurethane products kind, Application Areas, industry size expand rapidly, and urethane has become one of high molecular synthetic material with fastest developing speed over nearly 20 years.But in urethane, polyvalent alcohol used is oil derived product mostly at present, oil is as Nonrenewable resources, scarcity causes the continuous rise of its price, and also when the river rises the boat goes up to cause polyvalent alcohol production main raw material to comprise the prices such as PO, EO, ethylene glycol, propylene glycol, thanomin, makes the development of polyvalent alcohol industry be affected and limit.The reproducible biomass of forest ecosystem have important strategic importance; facing under the background of Mineral resources exhaustion; the whole world all seeking to take recycling economy, the ecological economy is guidance; adhere to the strategy of sustainable development; from to protect mankind natural resources, ecotope, fully effectively utilize reproducible, huge biomass resource.In bio oil polylol, owing to having ester bond, biological degradability is good, and water tolerance and thermotolerance all increase.American National Standard and technological associations (MST) have completed an investigation work of the environmental influence about novel biomass polyvalent alcohol recently, find the level that affects of the environment of bio oil polyvalent alcohol, be only petroleum base polyvalent alcohol show 1/4th, can obviously alleviate the hazard rating to environment such as Global warming, smog formation, ecological degeneration.In bio oil, chief component is fatty acid triglyceride, and except Viscotrol C hydroxyl, other are hydroxyl not all, so exploitation vegetable oil polyol need to be introduced hydroxyl on the molecular chain of vegetables oil.Mainly by alcoholysis, alkoxylate, ozone oxidation, epoxidation and hydroxylation, hydroformylation etc. at present.Vegetable oil polyol cost prepared by alcoholysis method is relatively low, but the polyvalent alcohol molecular weight being made by this method is lower, and the scope of adjustment is less, and range of application is narrower.Polyvalent alcohol molecular weight prepared by alkoxylation process is adjustable, but need to use the Viscotrol C that price is more expensive, and the epoxy compounds using still need to obtain from petroleum.The hydroxyl of the vegetable oil polyol that Ozonation makes is all primary hydroxyl, has greater activity, but because its molecular weight is very little and its functionality is subject to double key number quantitative limitation in vegetables oil, so its application range of products is very limited.Hydroformylation be take precious metal as catalyzer, and expensive, economy is unreasonable, and this technological reaction condition is harsh, is not suitable for large industrialized.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of bio oil polylol, the bio oil polylol of its acquisition is renewable, and raw materials is easy to get, and renewable, biological degradability is good, and preparation is simple, and hydroxyl value is adjustable, environmentally safe.
In order to achieve the above object, technical scheme of the present invention is:
A kind of preparation method of bio oil polylol, comprise the steps: first initiator to be joined and in bio oil, carry out heated and stirred for the first time, the quality that adds initiator is 0.5%-2% of bio oil and initiator total mass, heated and stirred temperature is 30-120 ℃ for the first time, and the heated and stirred time is 1-12 hours for the first time; Then when adding respectively containing many active hydrogen compoundss, solid base catalyst after evenly, heated and stirred for the first time carries out heated and stirred for the second time, adding the mass ratio containing many active hydrogen compoundss and bio oil is 1:5-1:20, the quality that adds solid base catalyst is 0.5%-2% of bio oil and initiator total mass, heated and stirred temperature is 60-200 ℃ for the second time, and the heated and stirred time is 2-24 hours for the second time; Finally when heated and stirred is for the second time cooled to room temperature after all and thereby filtering separation obtains bio oil polylol.
First initiator is joined in bio oil and carry out heated and stirred for the first time, the quality that adds initiator is 1% of bio oil and initiator total mass, and heated and stirred temperature is 80 ℃ for the first time, and the heated and stirred time is 6 hours for the first time; Then when adding respectively containing many active hydrogen compoundss, solid base catalyst after evenly, heated and stirred for the first time carries out heated and stirred for the second time, adding the mass ratio containing many active hydrogen compoundss and bio oil is 1:12, the quality that adds solid base catalyst is 1% of bio oil and initiator total mass, heated and stirred temperature is 130 ℃ for the second time, and the heated and stirred time is 12 hours for the second time; Finally when heated and stirred is for the second time cooled to room temperature after all and thereby filtering separation obtains bio oil polylol.
Described bio oil adopts a kind of in Vegetable oil lipoprotein, animal grease, waste grease.
Described Vegetable oil lipoprotein comprises soybean oil, rapeseed oil, peanut oil, sunflower seed oil, plam oil, Semen Maydis oil, sesame oil, sweet oil, Rice pollard oil, Oleum Cocois, wheatgerm oil, Oleum Gossypii semen, walnut oil, safflower oil, linseed oil, raisin seed oil, Semen Cucurbitae oil, Semen setariae oil, described animal grease comprises lard, butter, sheep oil, and described waste grease comprises sewer oil.
Described initiator is Diisopropyl azodicarboxylate.
Describedly containing many active hydrogen compoundss, adopt a kind of in the active hydrogen compounds that contains hydroxyl, amino, carboxyl, saccharide compound, high molecular weight material.
The described active hydrogen compounds that contains hydroxyl, amino, carboxyl comprises glycerol, ethylene glycol, quadrol, thanomin, diethanolamine, trolamine, propylene glycol, tetramethylolmethane, TriMethylolPropane(TMP), 2,2-dimethylol propionic acid, described saccharide compound comprises glucose, starch, sucrose, described high molecular weight material comprises polyester polyol, polyether glycol.
Described solid base catalyst adopts a kind of in magnesium oxide, calcium oxide, salt of wormwood supported magnesium oxide, salt of wormwood Supported alumina, Potassium monofluoride Supported alumina, Potassium monofluoride supported magnesium oxide, hydrotalcite, hydroxide radical exchanged water talcum, alkoxyl group exchanged water talcum.
The invention has the beneficial effects as follows: (1) raw material is easy to get, take reproducible bio oil as matrix; (2) environmental protection, biological degradability is good, can be degraded rapidly; (3) preparation process is simple, and employing solid alkali is catalyzer, and three industrial wastes discharge is little; (4) molecular structure is adjustable, can be according to selecting suitable feedstock and feed ratio, and the performances such as smooth Molecular regulator amount and hydroxyl value; (5) of many uses, can be used for the fields such as polyurethane foam, sizing agent, polyurethane coating, tensio-active agent; (6) environment to affect level low, carbon emissions etc. are far below petroleum base polyvalent alcohol.
Embodiment
embodiment 1
The preparation method of a kind of bio oil polylol described in the present embodiment, comprises the steps:
First initiator Diisopropyl azodicarboxylate is joined and in rapeseed oil, carry out heated and stirred for the first time, the quality that adds initiator Diisopropyl azodicarboxylate is 0.5% of rapeseed oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 80 ℃ for the first time, and the heated and stirred time is 6 hours for the first time; Then when heated and stirred for the first time adds respectively glycerol, calcium oxide solid base catalyst to carry out heated and stirred for the second time after evenly, the mass ratio that adds glycerol and rapeseed oil is 1:15, the quality that adds calcium oxide solid base catalyst is 0.5% of rapeseed oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 170 ℃ for the second time, and the heated and stirred time is 6 hours for the second time; Finally, when heated and stirred is for the second time cooled to room temperature after all and thereby filtering separation obtains rapeseed oil glyceryl polyvalent alcohol, hydroxyl value is 354mgKOH/g.
The preparation method of a kind of bio oil polylol of the present embodiment, the bio oil polylol of its acquisition is renewable, and raw materials is easy to get, and renewable, biological degradability is good, and preparation is simple, and hydroxyl value is adjustable, environmentally safe.
embodiment 2
The preparation method of a kind of bio oil polylol described in the present embodiment, comprises the steps:
First initiator Diisopropyl azodicarboxylate is joined and in peanut oil, carry out heated and stirred for the first time, the quality that adds initiator Diisopropyl azodicarboxylate is 0.7% of peanut oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 60 ℃ for the first time, and the heated and stirred time is 4 hours for the first time; Then when heated and stirred for the first time adds respectively tetramethylolmethane, magnesium oxide solid base catalyst to carry out heated and stirred for the second time after evenly, the mass ratio that adds tetramethylolmethane and peanut oil is 1:10, the quality that adds magnesium oxide solid base catalyst is 1% of peanut oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 180 ℃ for the second time, and the heated and stirred time is 8 hours for the second time; Finally, when heated and stirred is for the second time cooled to room temperature after all and thereby filtering separation obtains peanut oil tetramethylolmethane polylol, hydroxyl value is 425mgKOH/g.
The preparation method of a kind of bio oil polylol of the present embodiment, the bio oil polylol of its acquisition is renewable, and raw materials is easy to get, and renewable, biological degradability is good, and preparation is simple, and hydroxyl value is adjustable, environmentally safe.
The preparation method of a kind of bio oil polylol of the present embodiment, the bio oil polylol of its acquisition is renewable, and raw materials is easy to get, and renewable, biological degradability is good, and preparation is simple, and hydroxyl value is adjustable, environmentally safe.
embodiment 3
The preparation method of a kind of bio oil polylol described in the present embodiment, comprises the steps:
First initiator Diisopropyl azodicarboxylate is joined and in plam oil, carry out heated and stirred for the first time, the quality that adds initiator Diisopropyl azodicarboxylate is 1% of plam oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 80 ℃ for the first time, and the heated and stirred time is 2 hours for the first time; Then when heated and stirred for the first time adds respectively diethanolamine, salt of wormwood Supported alumina solid base catalyst to carry out heated and stirred for the second time after evenly, adding diethanolamine and palmitic mass ratio is 1:12, the quality that adds salt of wormwood Supported alumina solid base catalyst is 0.5% of plam oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 160 ℃ for the second time, and the heated and stirred time is 6 hours for the second time; Finally, when heated and stirred is for the second time cooled to room temperature after all and thereby filtering separation obtains plam oil diethanolamine polylol, hydroxyl value is 315mgKOH/g.
The preparation method of a kind of bio oil polylol of the present embodiment, the bio oil polylol of its acquisition is renewable, and raw materials is easy to get, and renewable, biological degradability is good, and preparation is simple, and hydroxyl value is adjustable, environmentally safe.
embodiment 4
The preparation method of a kind of bio oil polylol described in the present embodiment, comprises the steps:
First initiator Diisopropyl azodicarboxylate is joined and in Oleum Gossypii semen, carry out heated and stirred for the first time, the quality that adds initiator Diisopropyl azodicarboxylate is 0.5% of Oleum Gossypii semen and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 60 ℃ for the first time, and the heated and stirred time is 3 hours for the first time; Then when heated and stirred for the first time adds respectively 2 after evenly, 2-dimethylol propionic acid, magnesium oxide solid base catalyst carry out heated and stirred for the second time, add 2, the mass ratio of 2-dimethylol propionic acid and Oleum Gossypii semen is 1:14, the quality that adds magnesium oxide solid base catalyst is 1% of Oleum Gossypii semen and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 120 ℃ for the second time, and the heated and stirred time is 6 hours for the second time; Finally, when heated and stirred is for the second time cooled to room temperature after all and thereby filtering separation obtains plam oil diethanolamine polylol, hydroxyl value is 235mgKOH/g.
The preparation method of a kind of bio oil polylol of the present embodiment, the bio oil polylol of its acquisition is renewable, and raw materials is easy to get, and renewable, biological degradability is good, and preparation is simple, and hydroxyl value is adjustable, environmentally safe.
embodiment 5
The preparation method of a kind of bio oil polylol described in the present embodiment, comprises the steps:
First initiator Diisopropyl azodicarboxylate is joined and in linseed oil, carry out heated and stirred for the first time, the quality that adds initiator Diisopropyl azodicarboxylate is 0.8% of linseed oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 70 ℃ for the first time, and the heated and stirred time is 4 hours for the first time; Then when heated and stirred for the first time adds respectively starch, alkoxyl group exchange hydrotalcite solid base catalyst to carry out heated and stirred for the second time after evenly, the mass ratio that adds starch and linseed oil is 1:18, adding the quality of alkoxyl group exchange hydrotalcite solid base catalyst is 1% of linseed oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 140 ℃ for the second time, and the heated and stirred time is 12 hours for the second time; Finally, when heated and stirred is for the second time cooled to room temperature after all and thereby filtering separation obtains linseed oil starch base polyvalent alcohol, hydroxyl value is 453mgKOH/g.
The preparation method of a kind of bio oil polylol of the present embodiment, the bio oil polylol of its acquisition is renewable, and raw materials is easy to get, and renewable, biological degradability is good, and preparation is simple, and hydroxyl value is adjustable, environmentally safe.
embodiment 6
The preparation method of a kind of bio oil polylol described in the present embodiment, comprises the steps:
First initiator Diisopropyl azodicarboxylate is joined and in lard, carry out heated and stirred for the first time, the quality that adds initiator Diisopropyl azodicarboxylate is 0.8% of lard and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 60 ℃ for the first time, and the heated and stirred time is 4 hours for the first time; Then when heated and stirred for the first time adds respectively TriMethylolPropane(TMP), Potassium monofluoride Supported alumina solid base catalyst to carry out heated and stirred for the second time after evenly, the mass ratio that adds TriMethylolPropane(TMP) and lard is 1:10, the quality that adds Potassium monofluoride Supported alumina solid base catalyst is 1% of lard and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 180 ℃ for the second time, and the heated and stirred time is 10 hours for the second time; Finally, when heated and stirred is for the second time cooled to room temperature after all and thereby filtering separation obtains lard TriMethylolPropane(TMP) polylol, hydroxyl value is 212mgKOH/g.
The preparation method of a kind of bio oil polylol of the present embodiment, the bio oil polylol of its acquisition is renewable, and raw materials is easy to get, and renewable, biological degradability is good, and preparation is simple, and hydroxyl value is adjustable, environmentally safe.
embodiment 7
The preparation method of a kind of bio oil polylol described in the present embodiment, comprises the steps:
First initiator Diisopropyl azodicarboxylate is joined and in sewer oil, carry out heated and stirred for the first time, the quality that adds initiator Diisopropyl azodicarboxylate is 1% of sewer oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 60 ℃ for the first time, and the heated and stirred time is 2 hours for the first time; Then when heated and stirred for the first time adds respectively polyether glycol, hydrotalcite solid base catalyst to carry out heated and stirred for the second time after evenly, the hydroxyl value 238mgKOH/g of described polyether glycol, the mass ratio that adds polyether glycol and lard is 1:10, the quality that adds Potassium monofluoride Supported alumina solid base catalyst is 1% of sewer oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 120 ℃ for the second time, and the heated and stirred time is 8 hours for the second time; Finally, when heated and stirred is for the second time cooled to room temperature after all and thereby filtering separation obtains sewer oil polyether glycol polylol, hydroxyl value is 139mgKOH/g.
The preparation method of a kind of bio oil polylol of the present embodiment, the bio oil polylol of its acquisition is renewable, and raw materials is easy to get, and renewable, biological degradability is good, and preparation is simple, and hydroxyl value is adjustable, environmentally safe.
embodiment 8
The preparation method of a kind of bio oil polylol described in the present embodiment, comprises the steps:
First initiator Diisopropyl azodicarboxylate is joined and in sunflower seed oil, carry out heated and stirred for the first time, the quality that adds initiator Diisopropyl azodicarboxylate is 1.5% of sunflower seed oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 110 ℃ for the first time, and the heated and stirred time is 2 hours for the first time; Then when heated and stirred for the first time adds respectively ethylene glycol, salt of wormwood supported magnesium oxide solid base catalyst to carry out heated and stirred for the second time after evenly, the mass ratio that adds ethylene glycol and sunflower seed oil is 1:6, the quality that adds salt of wormwood supported magnesium oxide solid base catalyst is 1.2% of sunflower seed oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 120 ℃ for the second time, and the heated and stirred time is 8 hours for the second time; Finally when heated and stirred is for the second time cooled to room temperature after all and thereby filtering separation obtains sunflower seed oil ethylene glycol polyvalent alcohol.
The preparation method of a kind of bio oil polylol of the present embodiment, the bio oil polylol of its acquisition is renewable, and raw materials is easy to get, and renewable, biological degradability is good, and preparation is simple, and hydroxyl value is adjustable, environmentally safe.
embodiment 9
The preparation method of a kind of bio oil polylol described in the present embodiment, comprises the steps:
First initiator Diisopropyl azodicarboxylate is joined and in soybean oil, carry out heated and stirred for the first time, the quality that adds initiator Diisopropyl azodicarboxylate is 1.9% of soybean oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 40 ℃ for the first time, and the heated and stirred time is 11 hours for the first time; Then when heated and stirred for the first time adds respectively quadrol, Potassium monofluoride supported magnesium oxide solid base catalyst to carry out heated and stirred for the second time after evenly, the mass ratio that adds quadrol and soybean oil is 1:19, the quality that adds Potassium monofluoride supported magnesium oxide solid base catalyst is 1.8% of soybean oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 70 ℃ for the second time, and the heated and stirred time is 22 hours for the second time; Finally when heated and stirred is for the second time cooled to room temperature after all and thereby filtering separation obtains soybean oil quadrol polylol.
The preparation method of a kind of bio oil polylol of the present embodiment, the bio oil polylol of its acquisition is renewable, and raw materials is easy to get, and renewable, biological degradability is good, and preparation is simple, and hydroxyl value is adjustable, environmentally safe.
embodiment 10
The preparation method of a kind of bio oil polylol described in the present embodiment, comprise the steps: first initiator Diisopropyl azodicarboxylate to be joined and in Semen Maydis oil, carry out heated and stirred for the first time, the quality that adds initiator Diisopropyl azodicarboxylate is 0.5% of Semen Maydis oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 120 ℃ for the first time, and the heated and stirred time is 1 hour for the first time; Then when heated and stirred for the first time adds respectively thanomin, hydroxide radical exchange hydrotalcite solid base catalyst to carry out heated and stirred for the second time after evenly, the mass ratio that adds thanomin and Semen Maydis oil is 1:5, the quality of hydroxide radical exchange hydrotalcite solid base catalyst is 0.5% of Semen Maydis oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 200 ℃ for the second time, and the heated and stirred time is 2 hours for the second time; Finally when heated and stirred is for the second time cooled to room temperature after all and thereby filtering separation obtains Semen Maydis oil thanomin polylol.
The preparation method of a kind of bio oil polylol of the present embodiment, the bio oil polylol of its acquisition is renewable, and raw materials is easy to get, and renewable, biological degradability is good, and preparation is simple, and hydroxyl value is adjustable, environmentally safe.
embodiment 11
The preparation method of a kind of bio oil polylol described in the present embodiment, comprise the steps: first initiator Diisopropyl azodicarboxylate to be joined and in sesame oil, carry out heated and stirred for the first time, the quality that adds initiator Diisopropyl azodicarboxylate is 1.7% of sesame oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 30 ℃ for the first time, and the heated and stirred time is 12 hours for the first time; Then when heated and stirred for the first time adds respectively trolamine, magnesium oxide solid base catalyst to carry out heated and stirred for the second time after evenly, the mass ratio that adds trolamine and sesame oil is 1:7, the quality of magnesium oxide solid base catalyst is 0.6% of sesame oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 190 ℃ for the second time, and the heated and stirred time is 4 hours for the second time; Finally when heated and stirred is for the second time cooled to room temperature after all and thereby filtering separation obtains sesame oil trolamine polylol.
The preparation method of a kind of bio oil polylol of the present embodiment, the bio oil polylol of its acquisition is renewable, and raw materials is easy to get, and renewable, biological degradability is good, and preparation is simple, and hydroxyl value is adjustable, environmentally safe.
embodiment 12
The preparation method of a kind of bio oil polylol described in the present embodiment, comprise the steps: first initiator Diisopropyl azodicarboxylate to be joined and in sweet oil, carry out heated and stirred for the first time, the quality that adds initiator Diisopropyl azodicarboxylate is 1.5% of sweet oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 100 ℃ for the first time, and the heated and stirred time is 4 hours for the first time; Then when heated and stirred for the first time adds respectively propylene glycol, calcium oxide solid base catalyst to carry out heated and stirred for the second time after evenly, the mass ratio that adds propylene glycol and sweet oil is 1:8, the quality of calcium oxide solid base catalyst is 0.8% of sweet oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 80 ℃ for the second time, and the heated and stirred time is 20 hours for the second time; Finally when heated and stirred is for the second time cooled to room temperature after all and thereby filtering separation obtains sweet oil propylene-glycol-based polyvalent alcohol.
The preparation method of a kind of bio oil polylol of the present embodiment, the bio oil polylol of its acquisition is renewable, and raw materials is easy to get, and renewable, biological degradability is good, and preparation is simple, and hydroxyl value is adjustable, environmentally safe.
embodiment 13
The preparation method of a kind of bio oil polylol described in the present embodiment, comprise the steps: first initiator Diisopropyl azodicarboxylate to be joined and in Rice pollard oil, carry out heated and stirred for the first time, the quality that adds initiator Diisopropyl azodicarboxylate is 1.5% of Rice pollard oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 100 ℃ for the first time, and the heated and stirred time is 4 hours for the first time; Then when heated and stirred for the first time adds respectively glucose, salt of wormwood supported magnesium oxide solid base catalyst to carry out heated and stirred for the second time after evenly, the mass ratio that adds glucose and Rice pollard oil is 1:13, the quality of salt of wormwood supported magnesium oxide solid base catalyst is 1.5% of Rice pollard oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 130 ℃ for the second time, and the heated and stirred time is 13 hours for the second time; Finally when heated and stirred is for the second time cooled to room temperature after all and thereby filtering separation obtains Rice pollard oil glucosyl group polyvalent alcohol.
The preparation method of a kind of bio oil polylol of the present embodiment, the bio oil polylol of its acquisition is renewable, and raw materials is easy to get, and renewable, biological degradability is good, and preparation is simple, and hydroxyl value is adjustable, environmentally safe.
embodiment 14
The preparation method of a kind of bio oil polylol described in the present embodiment, comprise the steps: first initiator Diisopropyl azodicarboxylate to be joined and in Oleum Cocois, carry out heated and stirred for the first time, the quality that adds initiator Diisopropyl azodicarboxylate is 1.4% of Oleum Cocois and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 85 ℃ for the first time, and the heated and stirred time is 2.5 hours for the first time; Then when heated and stirred for the first time adds respectively sucrose, salt of wormwood Supported alumina solid base catalyst to carry out heated and stirred for the second time after evenly, the mass ratio that adds sucrose and Oleum Cocois is 1:14, the quality of salt of wormwood Supported alumina solid base catalyst is 1.4% of Oleum Cocois and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 135 ℃ for the second time, and the heated and stirred time is 11.5 hours for the second time; Finally when heated and stirred is for the second time cooled to room temperature after all and thereby filtering separation obtains Oleum Cocois sucrose polylol.
The preparation method of a kind of bio oil polylol of the present embodiment, the bio oil polylol of its acquisition is renewable, and raw materials is easy to get, and renewable, biological degradability is good, and preparation is simple, and hydroxyl value is adjustable, environmentally safe.
embodiment 15
The preparation method of a kind of bio oil polylol described in the present embodiment, comprise the steps: first initiator Diisopropyl azodicarboxylate to be joined and in wheatgerm oil, carry out heated and stirred for the first time, the quality that adds initiator Diisopropyl azodicarboxylate is 1.2% of wheatgerm oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 65 ℃ for the first time, and the heated and stirred time is 8 hours for the first time; Then when heated and stirred for the first time adds respectively polyester polyol, Potassium monofluoride Supported alumina solid base catalyst to carry out heated and stirred for the second time after evenly, the mass ratio that adds polyester polyol and wheatgerm oil is 1:7, the quality of Potassium monofluoride Supported alumina solid base catalyst is 1.2% of wheatgerm oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 115 ℃ for the second time, and the heated and stirred time is 10 hours for the second time; Finally when heated and stirred is for the second time cooled to room temperature after all and thereby filtering separation obtains wheatgerm oil polyester polyol polylol.
The preparation method of a kind of bio oil polylol of the present embodiment, the bio oil polylol of its acquisition is renewable, and raw materials is easy to get, and renewable, biological degradability is good, and preparation is simple, and hydroxyl value is adjustable, environmentally safe.
embodiment 16
The preparation method of a kind of bio oil polylol described in the present embodiment, comprise the steps: first initiator Diisopropyl azodicarboxylate to be joined and in walnut oil, carry out heated and stirred for the first time, the quality that adds initiator Diisopropyl azodicarboxylate is 1.3% of walnut oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 45 ℃ for the first time, and the heated and stirred time is 10 hours for the first time; Then when heated and stirred for the first time adds respectively glycerol, Potassium monofluoride supported magnesium oxide solid base catalyst to carry out heated and stirred for the second time after evenly, the mass ratio that adds glycerol and walnut oil is 1:9, the quality of Potassium monofluoride supported magnesium oxide solid base catalyst is 1.3% of walnut oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 120 ℃ for the second time, and the heated and stirred time is 11 hours for the second time; Finally when heated and stirred is for the second time cooled to room temperature after all and thereby filtering separation obtains walnut oil glycerol polylol.
The preparation method of a kind of bio oil polylol of the present embodiment, the bio oil polylol of its acquisition is renewable, and raw materials is easy to get, and renewable, biological degradability is good, and preparation is simple, and hydroxyl value is adjustable, environmentally safe.
embodiment 17
The preparation method of a kind of bio oil polylol described in the present embodiment, comprise the steps: first initiator Diisopropyl azodicarboxylate to be joined and in safflower oil, carry out heated and stirred for the first time, the quality that adds initiator Diisopropyl azodicarboxylate is 1.6% of safflower oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 65 ℃ for the first time, and the heated and stirred time is 7.5 hours for the first time; Then when heated and stirred for the first time adds respectively ethylene glycol, hydrotalcite solid base catalyst to carry out heated and stirred for the second time after evenly, the mass ratio that adds ethylene glycol and safflower oil is 1:11, the quality of hydrotalcite solid base catalyst is 1.6% of safflower oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 130 ℃ for the second time, and the heated and stirred time is 10 hours for the second time; Finally when heated and stirred is for the second time cooled to room temperature after all and thereby filtering separation obtains safflower oil ethylene glycol polyvalent alcohol.
The preparation method of a kind of bio oil polylol of the present embodiment, the bio oil polylol of its acquisition is renewable, and raw materials is easy to get, and renewable, biological degradability is good, and preparation is simple, and hydroxyl value is adjustable, environmentally safe.
embodiment 18
The preparation method of a kind of bio oil polylol described in the present embodiment, comprise the steps: first initiator Diisopropyl azodicarboxylate to be joined and in raisin seed oil, carry out heated and stirred for the first time, the quality that adds initiator Diisopropyl azodicarboxylate is 1.8% of raisin seed oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 105 ℃ for the first time, and the heated and stirred time is 5.5 hours for the first time; Then when heated and stirred for the first time adds respectively diethanolamine, hydroxide radical exchange hydrotalcite solid base catalyst to carry out heated and stirred for the second time after evenly, the mass ratio that adds diethanolamine and raisin seed oil is 1:13, the quality of hydroxide radical exchange hydrotalcite solid base catalyst is 1.8% of raisin seed oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 150 ℃ for the second time, and the heated and stirred time is 8 hours for the second time; Finally when heated and stirred is for the second time cooled to room temperature after all and thereby filtering separation obtains raisin seed oil diethanolamine polylol.
The preparation method of a kind of bio oil polylol of the present embodiment, the bio oil polylol of its acquisition is renewable, and raw materials is easy to get, and renewable, biological degradability is good, and preparation is simple, and hydroxyl value is adjustable, environmentally safe.
embodiment 19
The preparation method of a kind of bio oil polylol described in the present embodiment, comprise the steps: first initiator Diisopropyl azodicarboxylate to be joined and in Semen Cucurbitae oil, carry out heated and stirred for the first time, the quality that adds initiator Diisopropyl azodicarboxylate is 1.9% of Semen Cucurbitae oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 115 ℃ for the first time, and the heated and stirred time is 2 hours for the first time; Then when heated and stirred for the first time adds respectively trolamine, alkoxyl group exchange hydrotalcite solid base catalyst to carry out heated and stirred for the second time after evenly, the mass ratio that adds trolamine and Semen Cucurbitae oil is 1:15, the quality of alkoxyl group exchange hydrotalcite solid base catalyst is 1.9% of Semen Cucurbitae oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 170 ℃ for the second time, and the heated and stirred time is 5 hours for the second time; Finally when heated and stirred is for the second time cooled to room temperature after all and thereby filtering separation obtains Semen Cucurbitae oil trolamine polylol.
The preparation method of a kind of bio oil polylol of the present embodiment, the bio oil polylol of its acquisition is renewable, and raw materials is easy to get, and renewable, biological degradability is good, and preparation is simple, and hydroxyl value is adjustable, environmentally safe.
embodiment 20
The preparation method of a kind of bio oil polylol described in the present embodiment, comprise the steps: first initiator Diisopropyl azodicarboxylate to be joined and in Semen setariae oil, carry out heated and stirred for the first time, the quality that adds initiator Diisopropyl azodicarboxylate is 1.7% of Semen setariae oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 95 ℃ for the first time, and the heated and stirred time is 3.5 hours for the first time; Then when heated and stirred for the first time adds respectively TriMethylolPropane(TMP), salt of wormwood Supported alumina solid base catalyst to carry out heated and stirred for the second time after evenly, the mass ratio that adds TriMethylolPropane(TMP) and Semen setariae oil is 1:17, the quality of salt of wormwood Supported alumina solid base catalyst is 1.7% of Semen setariae oil and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 190 ℃ for the second time, and the heated and stirred time is 3 hours for the second time; Finally when heated and stirred is for the second time cooled to room temperature after all and thereby filtering separation obtains Semen setariae oil TriMethylolPropane(TMP) polylol.
The preparation method of a kind of bio oil polylol of the present embodiment, the bio oil polylol of its acquisition is renewable, and raw materials is easy to get, and renewable, biological degradability is good, and preparation is simple, and hydroxyl value is adjustable, environmentally safe.
embodiment 21
The preparation method of a kind of bio oil polylol described in the present embodiment, comprise the steps: first initiator Diisopropyl azodicarboxylate to be joined and in butter, carry out heated and stirred for the first time, the quality that adds initiator Diisopropyl azodicarboxylate is 1.5% of butter and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 65 ℃ for the first time, and the heated and stirred time is 7 hours for the first time; Then when heated and stirred for the first time adds respectively 2 after evenly, 2-dimethylol propionic acid, magnesium oxide solid base catalyst carry out heated and stirred for the second time, add 2, the mass ratio of 2-dimethylol propionic acid and butter is 1:14, the quality of magnesium oxide solid base catalyst is 1.5% of butter and initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 170 ℃ for the second time, and the heated and stirred time is 6 hours for the second time; Finally when heated and stirred is for the second time cooled to room temperature after all and thereby filtering separation obtains butter 2,2-dimethylol propionic acid polylol.
The preparation method of a kind of bio oil polylol of the present embodiment, the bio oil polylol of its acquisition is renewable, and raw materials is easy to get, and renewable, biological degradability is good, and preparation is simple, and hydroxyl value is adjustable, environmentally safe.
embodiment 22
The preparation method of a kind of bio oil polylol described in the present embodiment, comprise the steps: that first initiator Diisopropyl azodicarboxylate being joined to Yang Youzhong carries out heated and stirred for the first time, the quality that adds initiator Diisopropyl azodicarboxylate is sheep oil and 1.3% of initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 80 ℃ for the first time, and the heated and stirred time is 9 hours for the first time; Then when heated and stirred for the first time adds respectively starch, magnesium oxide solid base catalyst to carry out heated and stirred for the second time after evenly, the mass ratio that adds starch and sheep oil is 1:14, the quality of magnesium oxide solid base catalyst is sheep oil and 1.3% of initiator Diisopropyl azodicarboxylate total mass, heated and stirred temperature is 170 ℃ for the second time, and the heated and stirred time is 6 hours for the second time; Finally when heated and stirred is for the second time cooled to room temperature after all and thereby filtering separation obtains sheep oil starch base polyvalent alcohol.
The preparation method of a kind of bio oil polylol of the present embodiment, the bio oil polylol of its acquisition is renewable, and raw materials is easy to get, and renewable, biological degradability is good, and preparation is simple, and hydroxyl value is adjustable, environmentally safe.
Claims (8)
1. the preparation method of a bio oil polylol, it is characterized in that comprising the steps: first initiator being joined and in bio oil, carry out heated and stirred for the first time, the quality that adds initiator is 0.5%-2% of bio oil and initiator total mass, heated and stirred temperature is 30-120 ℃ for the first time, and the heated and stirred time is 1-12 hours for the first time; Then when adding respectively containing many active hydrogen compoundss, solid base catalyst after evenly, heated and stirred for the first time carries out heated and stirred for the second time, adding the mass ratio containing many active hydrogen compoundss and bio oil is 1:5-1:20, the quality that adds solid base catalyst is 0.5%-2% of bio oil and initiator total mass, heated and stirred temperature is 60-200 ℃ for the second time, and the heated and stirred time is 2-24 hours for the second time; Finally when heated and stirred is for the second time cooled to room temperature after all and thereby filtering separation obtains bio oil polylol.
2. the preparation method of a kind of bio oil polylol according to claim 1, it is characterized in that: first initiator is joined and in bio oil, carry out heated and stirred for the first time, the quality that adds initiator is 1% of bio oil and initiator total mass, heated and stirred temperature is 80 ℃ for the first time, and the heated and stirred time is 6 hours for the first time; Then when adding respectively containing many active hydrogen compoundss, solid base catalyst after evenly, heated and stirred for the first time carries out heated and stirred for the second time, adding the mass ratio containing many active hydrogen compoundss and bio oil is 1:12, the quality that adds solid base catalyst is 1% of bio oil and initiator total mass, heated and stirred temperature is 130 ℃ for the second time, and the heated and stirred time is 12 hours for the second time; Finally when heated and stirred is for the second time cooled to room temperature after all and thereby filtering separation obtains bio oil polylol.
3. the preparation method of a kind of bio oil polylol according to claim 1 and 2, is characterized in that: described bio oil adopts a kind of in Vegetable oil lipoprotein, animal grease, waste grease.
4. the preparation method of a kind of bio oil polylol according to claim 3, it is characterized in that: described Vegetable oil lipoprotein comprises soybean oil, rapeseed oil, peanut oil, sunflower seed oil, plam oil, Semen Maydis oil, sesame oil, sweet oil, Rice pollard oil, Oleum Cocois, wheatgerm oil, Oleum Gossypii semen, walnut oil, safflower oil, linseed oil, raisin seed oil, Semen Cucurbitae oil, Semen setariae oil, described animal grease comprises lard, butter, sheep oil, and described waste grease comprises sewer oil.
5. the preparation method of a kind of bio oil polylol according to claim 1 and 2, is characterized in that: described initiator is Diisopropyl azodicarboxylate.
6. the preparation method of a kind of bio oil polylol according to claim 1 and 2, is characterized in that: describedly containing many active hydrogen compoundss, adopt a kind of in the active hydrogen compounds that contains hydroxyl, amino, carboxyl, saccharide compound, high molecular weight material.
7. the preparation method of a kind of bio oil polylol according to claim 6, it is characterized in that: described in contain hydroxyl, amino, carboxyl active hydrogen compounds comprise glycerol, ethylene glycol, quadrol, thanomin, diethanolamine, trolamine, propylene glycol, tetramethylolmethane, TriMethylolPropane(TMP), 2,2-dimethylol propionic acid, described saccharide compound comprises glucose, starch, sucrose, described high molecular weight material comprises polyester polyol, polyether glycol.
8. the preparation method of a kind of bio oil polylol according to claim 1 and 2, is characterized in that: described solid base catalyst adopts a kind of in magnesium oxide, calcium oxide, salt of wormwood supported magnesium oxide, salt of wormwood Supported alumina, Potassium monofluoride Supported alumina, Potassium monofluoride supported magnesium oxide, hydrotalcite, hydroxide radical exchanged water talcum, alkoxyl group exchanged water talcum.
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