CN101085943A - Method for preparing vegetable oil based polyatomic alcohol for hard bubble polyurethane - Google Patents
Method for preparing vegetable oil based polyatomic alcohol for hard bubble polyurethane Download PDFInfo
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- CN101085943A CN101085943A CN 200610027353 CN200610027353A CN101085943A CN 101085943 A CN101085943 A CN 101085943A CN 200610027353 CN200610027353 CN 200610027353 CN 200610027353 A CN200610027353 A CN 200610027353A CN 101085943 A CN101085943 A CN 101085943A
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Abstract
The invention relates to a method for preparing rigid polyurethane plant oil- based polyhydric alcohol. It comprises following steps: esterifying soybean oil with sulfate, hydrolyzing with water, carrying out amidation reaction with amine which contains three or more than three active hydrogen atoms, and ester exchanging with glycerin, triethanolamine or normosterol. It mainly to solve problems of high raw material price, dangerous reaction, difficult treatment for side product, large consumption of solvent in one material feed time, low productivity and narrow hydroxyl value for product in current method.
Description
Technical field
The present invention relates to the preparation method of urethane with the preparation field, particularly a kind of vegetable oil based polyatomic alcohol for hard bubble polyurethane of polyvalent alcohol.
Background technology
Rigid urethane foam is called for short hard polyurethane foam, and its consumption in polyurethane product is only second to flexible PU foam.Hard polyurethane foam mostly is unicellular structure, have good characteristics such as insulation effect is good, in light weight, specific tenacity big, easy construction, also have characteristics such as sound insulation, shockproof, electrical isolation, heat-resisting, cold-resistant, anti-solvent simultaneously, can be applicable to be used for industries such as refrigerator, refrigerator, thermal container.Account for 51.9% of the total amount of hard bubbling at American Architecture with hard bubbling, so China's market potential of hard bubbling for building is also very big.In addition, also to use a large amount of rigid foam materials that get in industries such as adiabatic, the imitative wooden imitation stone material of industry, packing, communications and transportation.At present, China's polyvalent alcohol market demand of hard bubbling is approximately 250,000 tons/year, and annual with 17% the ratio rapid growth.
Usually the urethane polyvalent alcohol extracts preparation from oil.
Oil is a kind of non-renewable resource, and present global prospective oil has more than 800 hundred million tons approximately, and the consumption of petroleum amount in whole world every year is above 3,000,000,000 tons; According to present spending rate, petroleum resources will approach exhaustion; Therefore, the new forms of energy that replace oil are all being sought by each state.Crude oil price is all the time in high position concussion in recent years, causes the cost of the downstream manufacturer of oil related products to become and more and more is difficult to accept.Certainly will to seek now novel material and progressively replace dependence oil.
Vegetables oil is a kind of reproducible resource.
Common vegetables oil all can be used for preparing polyvalent alcohol, these vegetables oil comprise soybean oil, one or more in Rice pollard oil, Semen Maydis oil, sesame oil, peanut oil, sweet oil, Oleum Gossypii semen, Thistle oil, rapeseed oil, plam oil, palm kernel oil, oleum lini, the sunflower seed oil.
The technology of document introduction mainly is that unsaturated link(age) in the soybean oil is carried out chemical treatment.These documents comprise US6107433, US6686435, CN1583828A, Journal of PolymerScience (Part A) Vol.38, No.22,4062-4069 (2000) etc.Usually the treatment process of document introduction has: 1. hydrogenating reduction; 2. oxidation; 3. epoxidation; 4. addition; 5. hydroformylation.And then further reaction becomes product.For example, earlier soybean oil is carried out epoxidation, then by following reaction formula reaction:
where?Y＝-OCH
3，-Cl，-Br，or-H
In these methods, cost of material is higher, and reaction has certain danger, and by product is handled trouble, uses than multi-solvent in feeding intake, cause single batch of yield efficiency not high, and the hydroxyl value scope of product is narrower, has limited its purposes for single batch.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of vegetable oil based polyatomic alcohol for hard bubble polyurethane, it is higher mainly to solve existing method cost of material, reaction has certain danger, by product is handled trouble, use than multi-solvent in feeding intake for single batch, cause single batch of yield efficiency not high, and the narrower technical problem of hydroxyl value scope of product.
For solving the problems of the technologies described above, the present invention is achieved in that
A kind of preparation method of vegetable oil based polyatomic alcohol for hard bubble polyurethane, it is characterized in that: soybean oil is carried out esterification with sulfuric acid, be hydrolyzed with water again, carry out amidate action with the amine that contains the reactive hydrogen atom more than three or three then, carry out transesterification reaction with polyvalent alcohols such as glycerine, trolamine or tetramethylolmethanes more at last.
The preparation method of described vegetable oil based polyatomic alcohol for hard bubble polyurethane is characterized in that:
The sulfuric acid that the used vitriol oil concentration of this esterification is 95%-98%, its consumption is the 15-40% of soybean oil consumption; Temperature of reaction is 70-150 ℃, and the reaction times is 2-10 hour;
During hydrolysis reaction, the consumption of water is the 15-45% of soybean oil consumption, and temperature of reaction is 50-110 ℃, and the reaction times is 2-10 hour; The product of esterification is directly added in the entry, and heat up then hydrolysis, cooling, layering are told organic layer and are got final product;
In this amidate action, the consumption of these amine substances is 10-40 part of soybean oil consumption; Temperature of reaction is 120-250 ℃, and the reaction times is 2-10 hour.
In this transesterification reaction, the consumption of polyol is 10-45 part of soybean oil consumption, and temperature of reaction is 120-250 ℃, and the reaction times is 2-10 hour;
Add SODIUM PHOSPHATE, MONOBASIC, trisodium phosphate, atlapulgite or hexa-magnesium silicate in this refinement treatment process, its consumption is the 0.1-1.0 ‰ of total inventory, and treatment temp is 40-120 ℃, suitably filters to get product.
The preparation method of described vegetable oil based polyatomic alcohol for hard bubble polyurethane is characterized in that: the amine in this amidate action comprises monoethanolamine, diethanolamine or propylene diamine etc.
The preparation method of described vegetable oil based polyatomic alcohol for hard bubble polyurethane is characterized in that: can add a little auxiliary in this amidate action, this auxiliary agent is sodium borohydride or potassium hydroxide, and its consumption is the 0-0.3 ‰ of total inventory.
The preparation method of described vegetable oil based polyatomic alcohol for hard bubble polyurethane is characterized in that: available rare gas element is protected in this amidate action.
The preparation method of described vegetable oil based polyatomic alcohol for hard bubble polyurethane is characterized in that: can react under the state of vacuumizing in this amidate action, vacuum tightness is 2-300mmHg.
The preparation method of described vegetable oil based polyatomic alcohol for hard bubble polyurethane is characterized in that: can add a spot of salt of wormwood auxiliary agent in this transesterification reaction, its consumption is the 0.1-0.8 ‰ of total inventory.
The preparation method of described vegetable oil based polyatomic alcohol for hard bubble polyurethane is characterized in that: available rare gas element is protected in this transesterification reaction.
The preparation method of described vegetable oil based polyatomic alcohol for hard bubble polyurethane is characterized in that: can react under the state of vacuumizing in this transesterification reaction, vacuum tightness is 2-300mmHg.
By technique scheme, technique effect of the present invention is:
1, owing to the soybean oil abundant raw material in the vegetables oil, and price is lower, is example so select soybean oil for use, prepares vegetable oil polyol.
2, with the soybean oil of the inventive method preparation, the hydroxyl value scope of its product is 200-700mgKOH/g, can carry out product design according to customer requirements in this scope, satisfies user's needs; In the finished product soybean oil polyvalent alcohol, soybean oil accounts for 45-85% weight.
3, the vegetable oil polyol preparation method is simple among the present invention, and raw material sources are abundant, and the controlled hydroxyl scope of product is bigger, can satisfy all hydroxyl area requirements of hard-foam polyurethane.
Embodiment
The invention provides a kind of preparation method of vegetable oil based polyatomic alcohol for hard bubble polyurethane.Owing to consider the soybean oil abundant raw material in the vegetables oil, and price is lower, so select soybean oil for use.
Method may further comprise the steps among the present invention:
1, esterification; 2, hydrolysis; 3, amidate action; 4, transesterification reaction; 5, refinement treatment.
Major technique comprises: with sulfuric acid soybean oil is carried out esterification, be hydrolyzed with water, carry out amidate action with amines such as diethanolamine then, carry out transesterification reaction with polyvalent alcohols such as glycerine, trolamine or tetramethylolmethanes more at last.
Below each step of the inventive method is elaborated:
1, esterification
Promptly two keys in the soybean oil are reacted, generate sulfuric ester with the vitriol oil.
The sulfuric acid that to react used vitriol oil concentration be 95%-98%, its consumption is the 15-40% of soybean oil consumption; Temperature of reaction is 70-150 ℃, and the reaction times is 2-10 hour.
2, hydrolysis
During hydrolysis reaction, the consumption of water is the 15-45% of soybean oil consumption, and temperature of reaction is 50-110 ℃, and the reaction times is 2-10 hour.
The product of esterification is directly added in the entry, and heat up then hydrolysis, cooling, layering are told organic layer and are got final product.
3, amidate action
Among the present invention, amidate action is the organic product and the reaction that contains the amine of the reactive hydrogen atom more than three or three after the hydrolysis.
These amines comprise monoethanolamine, diethanolamine, propylene diamine etc.
In the reaction, the consumption of these amine substances is 10-40 part of soybean oil consumption; Temperature of reaction is 120-250 ℃, and the reaction times is 2-10 hour.Can add a little auxiliary such as sodium borohydride, potassium hydroxide etc., its consumption is the 0-0.3 ‰ of total inventory.
During reaction, available rare gas element such as nitrogen are protected; Also can react under the state of vacuumizing, vacuum tightness is 2-300mmHg.
4, transesterification reaction
In the transesterification reaction, promptly be, react with polyols such as glycerine, tetramethylolmethane, trihydroxy-propane, sucrose, ethylene glycol, trolamines with the intermediates after the amidation.
In the reaction, the consumption of polyol is 10-45 part of soybean oil consumption; Temperature of reaction is 120-250 ℃, and the reaction times is 2-10 hour.
Can add a spot of auxiliary agent such as salt of wormwood etc., its consumption is the 0.1-0.8 ‰ of total inventory.
During reaction, available rare gas element such as nitrogen are protected, and also can react under the state of vacuumizing, and vacuum tightness is 2-300mmHg.
5, refinement treatment
In amidation and transesterify, added a little auxiliary respectively, to promote the carrying out of reaction, guarantee product quality.These compounds remain in the vegetable oil polyol, may be influential to polyurethane foam, so need carry out aftertreatment, removed.
Refinement treatment generally adds SODIUM PHOSPHATE, MONOBASIC, trisodium phosphate, atlapulgite or hexa-magnesium silicate etc.Its consumption is the 0.1-1.0 ‰ of total inventory, and treatment temp is 40-120 ℃, suitably filters to get product.
In the finished product vegetable oil polyol (is example with the soybean oil polyvalent alcohol), vegetables oil accounts for 45-85% weight.
The hydroxyl value scope of series product is 200-700mgKOH/g, can design hydroxyl value as requested in this scope, to satisfy the demand.
Embodiment 1:
The 700g soybean oil is mixed with the 140g vitriol oil, be warming up to 100 ℃, be incubated 4 hours, then material is added in the 130g pure water, be warming up to 90 ℃, be incubated 4 hours.Standing demix is told organic layer.Organic layer and 145g diethanolamine and 0.15g sodium borohydride are reacted, be evacuated to 10mmHg, be warming up to 180 ℃, be incubated 6 hours.Cooling adds glycerine 200g, tetramethylolmethane 35g, trolamine 56g and potassium hydroxide 0.2g then slightly, is evacuated to 10mmHg, is warming up to 180 ℃, is incubated 6 hours.Be chilled to 80 ℃, add trisodium phosphate 0.5g and atlapulgite 0.5g, stir half an hour, cooling is filtered, and gets the about 1100g of product SD-630, and its hydroxyl value is 640mgKOH/g, and viscosity is 2200mPas, and pH value is 9.1.
Embodiment 2:
The 600g soybean oil is mixed with the 120g vitriol oil, be warming up to 100 ℃, be incubated 4 hours, then material is added in the 120g pure water, be warming up to 90 ℃, be incubated 4 hours.Standing demix is told organic layer.Organic layer and 100g diethanolamine and 0.15g sodium borohydride are reacted, be evacuated to 10mmHg, be warming up to 180 ℃, be incubated 6 hours.Cooling adds glycerine 90g, tetramethylolmethane 18g, trolamine 30g and potassium hydroxide 0.15g then slightly, is evacuated to 10mmHg, is warming up to 1 80 ℃, is incubated 6 hours.Be chilled to 80 ℃, add trisodium phosphate 0.4g and atlapulgite 0.4g, stir half an hour, cooling is filtered, and gets the about 810g of product SD-430, and its hydroxyl value is 420mgKOH/g, and viscosity is 1100mPas, and pH value is 9.2.
Embodiment 3:
The 800g soybean oil is mixed with the 170g vitriol oil, be warming up to 100 ℃, be incubated 4 hours, then material is added in the 160g pure water, be warming up to 90 ℃, be incubated 4 hours.Standing demix is told organic layer.Organic layer and 100g diethanolamine and 0.2g sodium borohydride are reacted, be evacuated to 10mmHg, be warming up to 180 ℃, be incubated 6 hours.Cooling adds glycerine 38g, trolamine 45g and potassium hydroxide 0.2g then slightly, is evacuated to 10mmHg, is warming up to 180 ℃, is incubated 6 hours.Be chilled to 80 ℃, add SODIUM PHOSPHATE, MONOBASIC 0.5g and atlapulgite 0.5g, stir half an hour, cooling is filtered, and gets the about 950g of product SD-250, and its hydroxyl value is 245mgKOH/g, and viscosity is 360mPas, and pH value is 9.2.
Being preferred embodiment of the present invention only in sum, is not to be used for limiting practical range of the present invention.Be that all equivalences of doing according to the content of the present patent application claim change and modification, all should be technology category of the present invention.
Claims (9)
1, a kind of preparation method of vegetable oil based polyatomic alcohol for hard bubble polyurethane, it is characterized in that: soybean oil is carried out esterification with sulfuric acid, be hydrolyzed with water again, carry out amidate action with the amine that contains the reactive hydrogen atom more than three or three then, carry out transesterification reaction with polyvalent alcohols such as glycerine, trolamine or tetramethylolmethanes more at last.
2, the preparation method of vegetable oil based polyatomic alcohol for hard bubble polyurethane according to claim 1 is characterized in that:
The sulfuric acid that the used vitriol oil concentration of this esterification is 95%-98%, its consumption is the 15-40% of soybean oil consumption; Temperature of reaction is 70-150 ℃, and the reaction times is 2-10 hour;
During hydrolysis reaction, the consumption of water is the 15-45% of soybean oil consumption, and temperature of reaction is 50-110 ℃, and the reaction times is 2-10 hour; The product of esterification is directly added in the entry, and heat up then hydrolysis, cooling, layering are told organic layer and are got final product;
In this amidate action, the consumption of these amine substances is 10-40 part of soybean oil consumption; Temperature of reaction is 120-250 ℃, and the reaction times is 2-10 hour.
In this transesterification reaction, the consumption of polyol is 10-45 part of soybean oil consumption, and temperature of reaction is 120-250 ℃, and the reaction times is 2-10 hour;
Add SODIUM PHOSPHATE, MONOBASIC, trisodium phosphate, atlapulgite or hexa-magnesium silicate in this refinement treatment process, its consumption is the 0.1-1.0 ‰ of total inventory, and treatment temp is 40-120 ℃, suitably filters to get product.
3, the preparation method of vegetable oil based polyatomic alcohol for hard bubble polyurethane according to claim 2 is characterized in that: the amine in this amidate action comprises monoethanolamine, diethanolamine or propylene diamine etc.
4, according to the preparation method of claim 2 or 3 described vegetable oil based polyatomic alcohol for hard bubble polyurethane, it is characterized in that: can add a little auxiliary in this amidate action, this auxiliary agent is sodium borohydride or potassium hydroxide, and its consumption is the 0-0.3 ‰ of total inventory.
5, according to the preparation method of claim 2 or 3 described vegetable oil based polyatomic alcohol for hard bubble polyurethane, it is characterized in that: available rare gas element is protected in this amidate action.
6, according to the preparation method of claim 2 or 3 described vegetable oil based polyatomic alcohol for hard bubble polyurethane, it is characterized in that: can react under the state of vacuumizing in this amidate action, vacuum tightness is 2-300mmHg.
7, the preparation method of vegetable oil based polyatomic alcohol for hard bubble polyurethane according to claim 2 is characterized in that: can add a spot of salt of wormwood auxiliary agent in this transesterification reaction, its consumption is the 0.1-0.8 ‰ of total inventory.
8, according to the preparation method of claim 2 or 7 described vegetable oil based polyatomic alcohol for hard bubble polyurethane, it is characterized in that: available rare gas element is protected in this transesterification reaction.
9, according to the preparation method of claim 2 or 7 described vegetable oil based polyatomic alcohol for hard bubble polyurethane, it is characterized in that: can react under the state of vacuumizing in this transesterification reaction, vacuum tightness is 2-300mmHg.
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| CN 200610027353 CN101085943A (en) | 2006-06-07 | 2006-06-07 | Method for preparing vegetable oil based polyatomic alcohol for hard bubble polyurethane |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113553A (en) * | 2013-01-30 | 2013-05-22 | 上海市医药保健品进出口有限公司 | Pure vegetable oil based polyalcohol and preparation method thereof |
| CN103709415A (en) * | 2013-12-24 | 2014-04-09 | 武汉理工大学 | Preparation method of composite slow-breaking slow-curing asphalt emulsifier |
-
2006
- 2006-06-07 CN CN 200610027353 patent/CN101085943A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113553A (en) * | 2013-01-30 | 2013-05-22 | 上海市医药保健品进出口有限公司 | Pure vegetable oil based polyalcohol and preparation method thereof |
| CN103709415A (en) * | 2013-12-24 | 2014-04-09 | 武汉理工大学 | Preparation method of composite slow-breaking slow-curing asphalt emulsifier |
| CN103709415B (en) * | 2013-12-24 | 2015-07-22 | 武汉理工大学 | Preparation method of composite slow-breaking slow-curing asphalt emulsifier |
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