CN105646225B - A kind of tung oil polylol and preparation method - Google Patents
A kind of tung oil polylol and preparation method Download PDFInfo
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Abstract
The invention discloses a kind of tung oil polylol and preparation methods, tung oil, organometallic complex catalyst, hydroxylating agent are mixed in proportion, and be warming up to 50 ~ 70 DEG C;Under intense agitation, hydrogenperoxide steam generator is added dropwise, control rate of addition makes reaction temperature maintain 70 ~ 90 DEG C, after being added dropwise, and maintaining reaction temperature 3 ~ 5 hours, reaction was completed;Reaction system filters to isolate solid catalyst successively, and stratification isolates water phase, and vacuum distillation obtains tung oil polylol.Tung oil polylol yield prepared by the present invention is higher than 92%, and product hydroxyl value is 120 ~ 270mgKOH/g, and acid value is less than 1.0mgKOH/g, and moisture is less than 0.1wt%, can be used for preparing polyurethane material.
Description
Technical field
The invention belongs to polyurethane material fields, and in particular to a kind of tung oil polylol and preparation method.
Background technology
Polyurethane material due to have the characteristics that good mechanical performance and be easy to molding, have been widely used for industry and
In daily life.Main raw material(s) for producing polyurethane includes isocyanates, polyalcohol and other additives,
The ratio of middle polyalcohol accounts for 50% or more.In industrial processes, polyalcohol is mainly used in polyurethane field, therefore poly-
The influence factor of urethane industry is also the major influence factors in polyalcohol market.Polyalcohol can be divided into polyether polyols by molecular structure
Alcohol and polyester polyol, wherein polyether polyol is occupied an leading position in the market, occupy the 70% of entire polyalcohol demand with
On.
In general, polyalcohol is to extract to prepare from oil.And oil, as non-renewable resources, scarcity causes its valence
The continuous rise of lattice, and the price for the primary raw material of polynary alcohol production such as lead to downstream product propylene oxide, ethylene oxide continues
Go up, and according to current depletion rate, petroleum resources want depleted eventually.Therefore, from sustainable development and competition among enterprises
The angle of power is set out, and finding the new material that can substitute petroleum base polyethers and new process becomes strategic development task.
The U.S. is the major producing country of soybean oil in the world, and in addition to edible, the scientific research institution in the U.S. is also actively working to out
Hair is using soybean oil as the various chemical products of raw material, to substitute petroleum-based chemicals.It concentrates on utilizing soybean oil strand recently
In unsaturated bond make vegetable oil that epoxidation, hydroxylating occur by the modification to double bond, it is more to prepare soybean oil
First alcohol.The advantages of the method is that reaction temperature is relatively low(40-70℃), product qualities, color and luster are good, so obtained extensive pass
Note.
Peroxy acid and the soybean oil such as the Z.S. Petrovic in kansas, U.S.A (Kansas) polymer research center
Reaction, is prepared for epoxidized soybean oil, double bond is changed into epoxy group;Then epoxidized soybean oil urging in effective catalyst tetrafluoro boric acid
Change effect is lower to occur ring-opening reaction with water and alcohol, prepares the vegetable oil polyol containing hydroxyl, the hydroxyl value of polyalcohol for 110 ~
213mgKOH/g, viscosity are 1000 ~ 7000mPas, and conversion ratio is up to 85% ~ 95%.
US20070123725 provides a kind of method preparing soybean oil polyol, includes the epoxy of polyunsaturated vegetable oil
Change and hydroxylation procedures form vegetable oil-based polyether polyol.First, by the polyunsaturated vegetable oils such as soybean oil or rapeseed oil with have
Machine acid and hydroperoxidation, form epoxidized vegetable oil, then open the mixed solution of epoxidized vegetable oil and first alcohol and water
Ring reaction generates vegetable oil polyol.
US20060041157 describes the method for preparing soybean oil polyol, including the vegetable oil of PART EPOXY is made to exist
It is reacted with Ring Opening Reagent under catalysts conditions, forms oligomeric vegetable oil polylol, Ring Opening Reagent includes small molecule polyol, plants
Object oil polyalcohol or other polyols.The degree of functionality of oligomeric vegetable oil polyalcohol is 1 ~ 6, and hydroxyl value is 20 ~ 300mgKOH/
g。
Tung oil is the specialty in China, is also important the raw material of industry and traditional exporting.Currently, China's tung oil is produced per year
Amount accounts for 35% or so of world's tung oil yield up to 100,000 tons or more.Therefore, China studies tung oil and makes more related with tung oil
Product industrialization has special significance.But high-quality vegetable oil polyol is prepared using tung oil, not due to tung oil
Saturation degree is higher, and is the polyunsaturated vegetable oil uniquely in nature with conjugated double bond, and iodine number reaches 170 or more, wherein 85%
Above unsaturated bond be carbon carbon conjugated triene key, so tung oil prepare polyalcohol it is epoxidised during due to conjugated double bond
Presence keep epoxy group reactivity higher, side reaction easily occurs for poor selectivity, to generate macromolecules cross-linking product, leads
Induced viscosity sharply increases, normally solid at room temperature, can not be used for further synthesis of polyurethane material.Research Literature(Such as
Epoxidation of Natural Triglycerides with Ethylmethyldioxirane,《Journal of
the American Oil Chemists' Society》, 1996,73:461-464)Different vegetable oil, such as corn are investigated
The epoxidation process of the polyunsaturated vegetable oils such as oil, soybean oil, sunflower oil, cottonseed oil, tung oil, it is again seen that only having conjugation double
Cross-linking reaction has occurred during epoxidised in the tung oil of key, and viscosity is caused to increased dramatically.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of tung oil polylol and preparation methods.The present invention utilizes
The conjugated double bond of tung oil can improve the characteristics of epoxy group reactivity, in epoxidised while hydroxylating agent is added, energy
It is enough effectively prevented from the generation of crosslinking side reaction, and forms tung oil polylol product.
The preparation method of tung oil polylol of the present invention, including following content:Tung oil, organometallic complex are catalyzed
Agent, hydroxylating agent mix in proportion, and are warming up to 50 ~ 70 DEG C;Under intense agitation, hydrogenperoxide steam generator, control is added dropwise
Rate of addition processed makes reaction temperature maintain 70 ~ 90 DEG C, after being added dropwise, and maintaining reaction temperature 3 ~ 5 hours, reaction was completed;Instead
System is answered to filter to isolate solid catalyst successively, stratification isolates water phase, and vacuum distillation obtains tung oil Quito
First alcohol.
The organometallic complex catalyst has following general formula:
Wherein, M can be transition metal molybdenum, vanadium, titanium, manganese, cobalt, copper, nickel etc..The transition metal source in:Acetyl
Acetone molybdenum, vanadium acetylacetonate, titanium acetylacetone, manganese acetylacetonate, acetylacetone cobalt, acetylacetone copper, nickel acetylacetonate, acetic acid
Manganese, cobalt acetate, copper acetate, nickel acetate, copper chloride or nickel chloride etc..Means known in the art may be used and prepare organometallic ligand
Object is closed, document First Dioxomolybdenum (VI) Complexes Containing Chiral such as may be used
Oxazoline Ligands: Synthesis, Characterization and Catalytic Activity
(《European Journal of Inorganic Chemistry》, 2001,4:1071-1076)The method prepares organic
Metal complex.It is had the following advantages using organometallic complex as catalyst:Realize the epoxy under the conditions of no carboxylic acid
Change, avoids the etching problem of reaction kettle;Reaction product easy post-processing, need not wash and etc., avoid discharge of wastewater etc.
Problem;Anacidity reaction system can reduce the degree of crosslinking side reaction;Catalyst recycling is easy and can reuse, and is a kind of
Environmentally protective novel solid organometallic complex catalyst.The catalyst amount be tung oil quality 0.01% ~
2.0%。
The hydroxylating agent can be alcohols or alcamines, and dosage is 0.5 ~ 2 times of tung oil quality.Wherein alcohols hydroxyl
Base reagent is selected from methanol, ethyl alcohol, ethylene glycol, propyl alcohol, isopropanol, glycerine, butanol, 1,4- butanediols, pentaerythrite, xylose
One or more of alcohol, sorbierite etc., preferably butanol;Alcamines hydroxylating agent is selected from monoisopropanolamine, diisopropanol
One or more of amine, triisopropanolamine, ethanol amine, diethanol amine, triethanolamine etc., preferably triethanolamine.
The hydrogenperoxide steam generator plays the role of oxidant, can under the action of organometallic complex catalyst
Unsaturated double-bond directly and in vegetable oil carries out epoxidation reaction.The concentration of hydrogen peroxide is higher, and reaction is more violent, and system is put
It is hot serious, side reaction easily occurs, so a concentration of 20wt% ~ 60wt% of selection hydrogenperoxide steam generator, the use of hydrogenperoxide steam generator
Amount is 1.0 ~ 2.0 times of tung oil quality.
The vacuum distillation is the hydroxylating in removing system under the conditions of 1000 ~ 3000Pa of pressure, 60 ~ 120 DEG C of temperature
Reagent and residual moisture make product moisture content be less than 0.1wt%.
Tung oil polylol of the present invention is prepared by aforementioned present invention method.Prepared tung oil polylol
Yield is higher than 92%, and product hydroxyl value is 120 ~ 270mgKOH/g, and acid value is less than 1.0mgKOH/g, and moisture is less than 0.1wt%, is suitable for
Prepare polyurethane material.
China is the country of origin and big producer of tung oil in the world, and raw material rich reserves are studied using tung oil as raw material chemical industry
Product has a very important significance, especially the huge polyol product of industrial consumption amount.But due in tung oil molecule 85% with
On unsaturated bond be carbon carbon conjugated triene key, since the presence of conjugated double bond keeps epoxy group anti-during preparing polyalcohol
Answer activity higher, side reaction easily occurs for poor selectivity, to generate macromolecules cross-linking product, viscosity is caused to sharply increase, can not
For further synthesis of polyurethane material.
The characteristics of present invention can improve epoxy group reactivity using the conjugated double bond of tung oil, it is epoxidised simultaneously
Hydroxylating agent is added, the generation of crosslinking side reaction can be effectively prevented from, the tung oil polyol product of acquisition is suitable for poly- ammonia
The preparation of ester material.Prepared tung oil polylol compared with petroleum-based polyols, have raw material it is renewable, it is non-toxic and
The good advantage of biological degradability, belongs to environmental-friendly biopolyol.
Specific implementation mode
With reference to embodiment, the invention will be further described.In the present invention, wt% indicates mass fraction.It is prepared more
The hydroxyl value of first alcohol product is measured according to the phthalic anhydride esterification method in GB/T12008.3-2009, and acid value is according to GB/T
12008.5-2010 methods measure, and viscosity is measured according to the rotational viscometer method in GB/T 12008.7-2010.
Embodiment 1
500g tung oil, 0.5g Organic Molybdenum Metals complex, 300g butanol are added in 2000mL three-necked flasks, is warming up to 60
It DEG C stirs evenly.Then 30wt% aqueous hydrogen peroxide solution 750g are slowly added dropwise under intense agitation, control drop rate makes
Reaction temperature maintains 80 DEG C or so, after being added dropwise, at 80 DEG C constant temperature 4h, reaction terminate.Solid is isolated by filtration out
Organic Molybdenum Metal composition catalyst removes water phase, by oil phase in 2000Pa, 80 DEG C of conditions then after reaction system layering
Lower distillation 2h is 241mgKOH/g, viscosity 7900mPa to get tung oil polylol product, yield 93.5%, product hydroxyl value
S, acid value 0.47mgKOH/g, moisture are less than 0.1wt%, can be used for preparing hard polyurethane foam product.
Embodiment 2
500g tung oil, 0.5g Organic Molybdenum Metals complex, 300g butanol are added in 2000mL three-necked flasks, is warming up to 70
It DEG C stirs evenly.Then 30wt% aqueous hydrogen peroxide solution 750g are slowly added dropwise under intense agitation, control drop rate makes
Reaction temperature maintains 90 DEG C or so, after being added dropwise, at 90 DEG C constant temperature 5h, reaction terminate.Solid is isolated by filtration out
Organic Molybdenum Metal composition catalyst removes water phase, by oil phase in 2000Pa, 80 DEG C of conditions then after reaction system layering
Lower distillation 2h is 232mgKOH/g, viscosity 8600mPa to get tung oil polylol product, yield 93.3%, product hydroxyl value
S, acid value 0.48mgKOH/g, moisture are less than 0.1wt%, can be used for preparing hard polyurethane foam product.
Embodiment 3
500g tung oil, 0.5g Organic Molybdenum Metals complex, 300g butanol are added in 2000mL three-necked flasks, is warming up to 50
It DEG C stirs evenly.Then 30wt% aqueous hydrogen peroxide solution 750g are slowly added dropwise under intense agitation, control drop rate makes
Reaction temperature maintains 70 DEG C or so, after being added dropwise, at 70 DEG C constant temperature 4h, reaction terminate.Solid is isolated by filtration out
Organic Molybdenum Metal composition catalyst removes water phase, by oil phase in 2000Pa, 80 DEG C of conditions then after reaction system layering
Lower distillation 2h is 176mgKOH/g, viscosity 6900mPa to get tung oil polylol product, yield 92.6%, product hydroxyl value
S, acid value 0.42mgKOH/g, moisture are less than 0.1wt%, can be used for preparing hard polyurethane foam product.
Embodiment 4
500g tung oil, 0.5g Organic Molybdenum Metals complex, 300g ethyl alcohol are added in 2000mL three-necked flasks, is warming up to 60
It DEG C stirs evenly.Then 30wt% aqueous hydrogen peroxide solution 750g are slowly added dropwise under intense agitation, control drop rate makes
Reaction temperature maintains 80 DEG C or so, after being added dropwise, at 80 DEG C constant temperature 4h, reaction terminate.Solid is isolated by filtration out
Organic Molybdenum Metal composition catalyst removes water phase, by oil phase in 2000Pa, 80 DEG C of conditions then after reaction system layering
Lower distillation 2h is 227mgKOH/g, viscosity 11200mPa to get tung oil polylol product, yield 93.2%, product hydroxyl value
S, acid value 0.44mgKOH/g, moisture are less than 0.1wt%, can be used for preparing hard polyurethane foam product.
Embodiment 5
500g tung oil, 0.5g Organic Molybdenum Metals complex, 300g triethanolamines, heating are added in 2000mL three-necked flasks
It is stirred evenly to 60 DEG C.Then 30wt% aqueous hydrogen peroxide solution 750g are slowly added dropwise under intense agitation, speed is added dropwise in control
Rate makes reaction temperature maintain 80 DEG C or so, after being added dropwise, at 80 DEG C constant temperature 4h, reaction terminate.It is isolated by filtration out
SOLID ORGANIC molybdenum composition catalyst, then after reaction system layering after, remove water phase, by oil phase 2000Pa, 80 DEG C
Under the conditions of distillation 2h to get tung oil polylol product, yield 93.2%, product hydroxyl value is 224mgKOH/g, viscosity
10900mPas, acid value 0.44mgKOH/g, moisture are less than 0.1wt%, can be used for preparing hard polyurethane foam product.
Embodiment 6
500g tung oil, 4g Organic Molybdenum Metals complex, 250g butanol are added in 2000mL three-necked flasks, is warming up to 60 DEG C
It stirs evenly.Then 30wt% aqueous hydrogen peroxide solution 750g are slowly added dropwise under intense agitation, control drop rate makes instead
Answer temperature to maintain 80 DEG C or so, after being added dropwise, at 80 DEG C constant temperature 4h, reaction terminate.Solid, which is isolated by filtration out, to be had
Machine molybdenum composition catalyst removes water phase, by oil phase under the conditions of 2000Pa, 80 DEG C then after reaction system layering
Distilling 2h to get tung oil polylol product, yield 93.3%, product hydroxyl value is 244mgKOH/g, viscosity 12200mPas,
Acid value 0.49mgKOH/g, moisture are less than 0.1wt%, can be used for preparing hard polyurethane foam product.
Embodiment 7
500g tung oil, 0.5g Organic Molybdenum Metals complex, 500g butanol are added in 2000mL three-necked flasks, is warming up to 60
It DEG C stirs evenly.Then 30wt% aqueous hydrogen peroxide solution 900g are slowly added dropwise under intense agitation, control drop rate makes
Reaction temperature maintains 80 DEG C or so, after being added dropwise, at 80 DEG C constant temperature 4h, reaction terminate.Solid is isolated by filtration out
Organic Molybdenum Metal composition catalyst removes water phase, by oil phase in 2000Pa, 80 DEG C of conditions then after reaction system layering
Lower distillation 2h is 258mgKOH/g, viscosity 7450mPa to get tung oil polylol product, yield 93.8%, product hydroxyl value
S, acid value 0.45mgKOH/g, moisture are less than 0.1wt%, can be used for preparing hard polyurethane foam product.
Embodiment 8
Using treatment process condition same as Example 1, the difference is that 0.5g organic vanadium metal complexs are added
Catalyst.The yield of tung oil polylol is 93.4%, and product hydroxyl value is 224mgKOH/g, viscosity 7150mPas, acid value
0.42mgKOH/g, moisture are less than 0.1wt%, can be used for preparing hard polyurethane foam product.
Comparative example 1
Using treatment process condition same as Example 1, the difference is that being added without hydroxylating agent.Product glues
Spend 195000 mPas, since product viscosity is excessive and can not dissolve, can not further carry out hydroxylating, thus product without
Method is used to prepare polyurethane products.
Comparative example 2
Using treatment process condition same as Example 1, the difference is that being added without hydroxylating agent, oil is added
Ether 300g(Play the role of diluent).173000 mPas of product viscosity can not since product viscosity is excessive and can not dissolve
Hydroxylating is further carried out, therefore product is not used to prepare polyurethane products.
Comparative example 3
Using treatment process condition same as Example 1, the difference is that preparing polyalcohol using soybean oil.Product
Hydroxyl value is 5.9mgKOH/g, and since not occur hydroxylating, hydroxyl value too low for product, therefore product is not used to prepare polyurethane
Product.
Claims (10)
1. a kind of preparation method of tung oil polylol, it is characterised in that including following content:By tung oil, organometallic complex
Catalyst, hydroxylating agent mix in proportion, and are warming up to 50 ~ 70 DEG C;Under intense agitation, it is molten that hydrogen peroxide is added dropwise
Liquid, control rate of addition make reaction temperature maintain 70 ~ 90 DEG C, after being added dropwise, and maintaining reaction temperature 3 ~ 5 hours terminates anti-
It answers;Reaction system filters to isolate solid catalyst successively, and stratification isolates water phase, and vacuum distillation obtains tung oil
Polylol.
2. according to the method for claim 1, it is characterised in that:The organometallic complex catalyst has following logical
Formula:
Wherein, M is transition metal molybdenum, vanadium, titanium, manganese, cobalt, copper or nickel.
3. according to the method for claim 2, which is characterized in that the transition metal source is in acetyl acetone, levulinic
Ketone vanadium, titanium acetylacetone, manganese acetylacetonate, acetylacetone cobalt, acetylacetone copper, nickel acetylacetonate, manganese acetate, cobalt acetate, second
Sour copper, nickel acetate, copper chloride or nickel chloride.
4. according to method as claimed in claim 1,2 or 3, it is characterised in that:Catalyst amount be tung oil quality 0.01% ~
2.0%。
5. according to the method for claim 1, it is characterised in that:The hydroxylating agent is alcohols or alcamines, dosage
It is 0.5 ~ 2 times of tung oil quality.
6. according to the method for claim 5, it is characterised in that:The alcohols hydroxylating agent is selected from methanol, ethyl alcohol, second two
One or more of alcohol, propyl alcohol, isopropanol, glycerine, butanol, 1,4- butanediols, pentaerythrite, xylitol, sorbierite;Institute
The alcamines hydroxylating agent stated is selected from monoisopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, ethanol amine, diethanol amine, three second
One or more of hydramine.
7. according to the method described in claim 1 or 6, it is characterised in that:The hydroxylating agent is butanol.
8. according to the method for claim 1, it is characterised in that:A concentration of 20wt% ~ 60wt% of the hydrogenperoxide steam generator,
Dosage is 1.0 ~ 2.0 times of tung oil quality.
9. according to the method for claim 1, it is characterised in that:Vacuum distillation be in 1000 ~ 3000Pa of pressure, temperature 60 ~
Hydroxylating agent and residual moisture under the conditions of 120 DEG C in removing system make product moisture content be less than 0.1wt%.
10. tung oil polylol prepared by any the method for claim 1~9, it is characterised in that:Tung oil polylol product
Hydroxyl value is 120 ~ 270mgKOH/g, and acid value is less than 1.0mgKOH/g, and moisture is less than 0.1wt%, can be used for preparing polyurethane material.
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CN106957227B (en) * | 2016-01-11 | 2020-01-10 | 中国石油化工股份有限公司 | Method for producing tung oil polyalcohol and byproduct glycerol |
CN107151209B (en) * | 2016-03-03 | 2020-01-10 | 中国石油化工股份有限公司 | Method for synthesizing tung oil polyol by using ionic liquid |
CN106076424A (en) * | 2016-07-05 | 2016-11-09 | 南京林业大学 | A kind of preparation method and application of straight chain corn starch loaded catalyst |
CN107602843B (en) * | 2017-09-08 | 2022-04-15 | 浙江皇马科技股份有限公司 | Low-unsaturation-degree isomeric alcohol polyoxyethylene polyoxypropylene ether and preparation method thereof |
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