CN105713170B - A kind of tung oil polylol and preparation method thereof - Google Patents
A kind of tung oil polylol and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of tung oil polylols and preparation method thereof, and tung oil, hydroxylating agent are mixed in proportion, and are warming up to 35 ~ 45 DEG C；Under intense agitation, peroxy acid solution is added dropwise, control rate of addition makes reaction temperature maintain 40 ~ 65 DEG C, after being added dropwise, and maintaining reaction temperature 3 ~ 5 hours, reaction was completed；Reaction system successively passes through stratification, isolates water phase, neutralized, washes, 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 ~ 270 mgKOH/g, and acid value is lower than 1.0mgKOH/g, and moisture is lower than 0.1wt%, can be used for preparing polyurethane material, particularly useful for making polyurethane rigid foam material.
Description
Technical field
The invention belongs to polyurethane material fields, and in particular to a kind of tung oil polylol and preparation method thereof.
Background technique
Polyurethane material due to having the characteristics that good mechanical performance and easy to form, 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
Pure and mild 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 preparation from petroleum.And petroleum, 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, so that it is more to prepare soybean oil by the modification to double bond
First alcohol.The advantages of the method is that reaction temperature is lower (40-70 DEG C), and product qualities, color 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 for preparing soybean oil polyol, the epoxy including polyunsaturated vegetable oil
Change and hydroxylation procedures form vegetable oil-based polyether polyol.Firstly, 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.
The method that US20060041157 describes preparation soybean oil polyol, including making the vegetable oil of PART EPOXY exist
It is reacted under catalysts conditions with Ring Opening Reagent, 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 uniquely with the polyunsaturated vegetable oil of conjugated double bond in nature, 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, poor selectivity, easily generation side reaction led to generate macromolecules cross-linking product
Induced viscosity sharply increases, normally solid at room temperature, can not be used to further synthesis of polyurethane material.Research Literature is (such as
Epoxidation of Natural Triglycerides with Ethylmethyldioxirane, " Journal of
The American Oil Chemists'Society ", 1996,73:461-464) investigate different vegetable oil, such as corn
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.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of tung oil polylol and preparation method thereof.The present invention utilizes
The conjugated double bond of tung oil can be improved 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, hydroxylating agent are mixed in proportion
It closes, and is warming up to 35 ~ 45 DEG C；Under intense agitation, peroxy acid solution is added dropwise, control rate of addition maintains reaction temperature
At 40 ~ 65 DEG C, after being added dropwise, maintaining reaction temperature 3 ~ 5 hours, reaction was completed；Reaction system successively passes through stratification, point
Water phase is separated out, it is neutralized, it washes, vacuum distillation obtains tung oil polylol.
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- butanediol, 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 peroxy acid solution is peroxyformic acid, Peracetic acid, Perpropionic Acid, Perbutyric Acid, peroxide isovaleric acid, peroxide benzene
One or more of formic acid, metachloroperbenzoic acid, nitroperoxybenzoic, preferably Peracetic acid.Use peroxy acid solution
The advantages of making oxidant is that strong acid catalyst is not needed in epoxidation process, substantially reduces acid concentration in reaction system, subtracts
Lack the generation of side reaction, and peroxide acid reactivity is high, can reduce the reaction time, improves production efficiency.The peroxy acid is molten
The concentration of liquid is, 15wt% ~ 50wt%, and dosage is 0.5 ~ 1.5 times of tung oil quality.
The neutralization reaction can be with ammonium hydroxide, sodium carbonate or sodium bicarbonate, it is preferable to use concentration is 5wt% ~ 20wt%'s
Sodium bicarbonate solution neutralizes.The washing temperature is 50 ~ 80 DEG C, to prevent system from emulsion occur.The decompression is steamed
Evaporating is hydroxylating agent and residual moisture under the conditions of 1000 ~ 3000Pa of pressure, 60 ~ 120 DEG C of temperature in removing system, makes to produce
Product moisture content is 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 lower than 1.0mgKOH/g, and moisture is lower than 0.1wt%, can be used for
Polyurethane material is prepared, particularly useful for making polyurethane rigid foam 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, presence during preparing polyalcohol due to conjugated double bond keeps epoxy group anti-
Active higher, poor selectivity is answered, easily generation side reaction causes viscosity to sharply increase to generate macromolecules cross-linking product, can not
For further synthesis of polyurethane material.
The characteristics of present invention can be improved 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 polylol product of acquisition is suitable for poly-
The preparation of urethane material.Prepared tung oil polylol compared with petroleum-based polyols, have raw material it is renewable, it is non-toxic,
And the advantage that biological degradability is good, belong to environmental-friendly biopolyol.
Specific embodiment
Below 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
The measurement of 12008.5-2010 method, viscosity are measured according to the rotational viscometer method in GB/T 12008.7-2010.
Embodiment 1
500g tung oil, 300g butanol are added in 2000mL three-necked flask, is warming up to 40 DEG C and stirs evenly.Then violent
35wt% peracetic acid soln 500g is slowly added dropwise under stirring condition, control drop rate makes reaction temperature maintain 50 DEG C or so,
After being added dropwise, constant temperature 4h, reaction terminate at 50 DEG C.After reaction system layering, water phase is removed, mutually uses 10wt% carbon for oily
Sour hydrogen sodium water solution is washed to neutrality, then with 70 DEG C hot water washed product 3 times.By the product after washing in 2000Pa, 80 DEG C
Under the conditions of distillation 2h to get tung oil polylol product, yield 94.7%, product hydroxyl value is 252mgKOH/g, viscosity
8340mPas, acid value 0.79mgKOH/g, moisture are lower than 0.1wt%, can be used for preparing hard polyurethane foam product.
Embodiment 2
500g tung oil, 300g butanol are added in 2000mL three-necked flask, is warming up to 45 DEG C and stirs evenly.Then violent
35wt% peracetic acid soln 500g is slowly added dropwise under stirring condition, control drop rate makes reaction temperature maintain 65 DEG C or so,
After being added dropwise, constant temperature 5h, reaction terminate at 65 DEG C.After reaction system layering, water phase is removed, mutually uses 10wt% carbon for oily
Sour hydrogen sodium water solution is washed to neutrality, then with 70 DEG C hot water washed product 3 times.By the product after washing in 2000Pa, 80 DEG C
Under the conditions of distillation 2h to get tung oil polylol product, yield 94.3%, product hydroxyl value is 236mgKOH/g, viscosity
11070mPas, acid value 0.94mgKOH/g, moisture are lower than 0.1wt%, can be used for preparing hard polyurethane foam product.
Embodiment 3
500g tung oil, 300g butanol are added in 2000mL three-necked flask, is warming up to 35 DEG C and stirs evenly.Then violent
35wt% peracetic acid soln 500g is slowly added dropwise under stirring condition, control drop rate makes reaction temperature maintain 40 DEG C or so,
After being added dropwise, constant temperature 4h, reaction terminate at 40 DEG C.After reaction system layering, water phase is removed, mutually uses 10wt% carbon for oily
Sour hydrogen sodium water solution is washed to neutrality, then with 70 DEG C hot water washed product 3 times.By the product after washing in 2000Pa, 80 DEG C
Under the conditions of distillation 2h to get tung oil polylol product, yield 93.8%, product hydroxyl value is 192mgKOH/g, viscosity
7400mPas, acid value 0.76mgKOH/g, moisture are lower than 0.1wt%, can be used for preparing hard polyurethane foam product.
Embodiment 4
500g tung oil, 300g ethyl alcohol are added in 2000mL three-necked flask, is warming up to 40 DEG C and stirs evenly.Then violent
35wt% peracetic acid soln 500g is slowly added dropwise under stirring condition, control drop rate makes reaction temperature maintain 50 DEG C or so,
After being added dropwise, constant temperature 4h, reaction terminate at 50 DEG C.After reaction system layering, water phase is removed, mutually uses 10wt% carbon for oily
Sour hydrogen sodium water solution is washed to neutrality, then with 70 DEG C hot water washed product 3 times.By the product after washing in 2000Pa, 80 DEG C
Under the conditions of distillation 2h to get tung oil polylol product, yield 94.3%, product hydroxyl value is 226mgKOH/g, viscosity
12200mPas, acid value 0.88mgKOH/g, moisture are lower than 0.1wt%, can be used for preparing hard polyurethane foam product.
Embodiment 5
500g tung oil, 300g triethanolamine are added in 2000mL three-necked flask, is warming up to 40 DEG C and stirs evenly.Then exist
35wt% peracetic acid soln 500g is slowly added dropwise under intense agitation, control drop rate makes reaction temperature maintain 50 DEG C
Left and right, after being added dropwise, constant temperature 4h, reaction terminate at 50 DEG C.After reaction system layering, water phase is removed, is mutually used oily
10wt% sodium bicarbonate aqueous solution is washed to neutrality, then with 70 DEG C hot water washed product 3 times.Product after washing is existed
2000Pa, distillation 2h is to get tung oil polylol product under the conditions of 80 DEG C, and yield 94.1%, product hydroxyl value is 227mgKOH/
G, viscosity 12300mPas, acid value 0.84mgKOH/g, moisture are lower than 0.1wt%, can be used for preparing hard polyurethane foam product.
Embodiment 6
500g tung oil, 300g butanol are added in 2000mL three-necked flask, is warming up to 40 DEG C and stirs evenly.Then violent
35wt% peracetic acid soln 400g is slowly added dropwise under stirring condition, control drop rate makes reaction temperature maintain 50 DEG C or so,
After being added dropwise, constant temperature 4h, reaction terminate at 50 DEG C.After reaction system layering, water phase is removed, mutually uses 10wt% carbon for oily
Sour hydrogen sodium water solution is washed to neutrality, then with 70 DEG C hot water washed product 3 times.By the product after washing in 2000Pa, 80 DEG C
Under the conditions of distillation 2h to get tung oil polylol product, yield 93.5%, product hydroxyl value is 184mgKOH/g, viscosity
7200mPas, acid value 0.73mgKOH/g, moisture are lower than 0.1wt%, can be used for preparing hard polyurethane foam product.
Embodiment 7
500g tung oil, 300g butanol are added in 2000mL three-necked flask, is warming up to 40 DEG C and stirs evenly.Then violent
35wt% benzoyl hydroperoxide solution 500g is slowly added dropwise under stirring condition, control drop rate makes reaction temperature maintain 50 DEG C of left sides
The right side, after being added dropwise, constant temperature 4h, reaction terminate at 50 DEG C.After reaction system layering, water phase is removed, oil is mutually used into 10wt%
Sodium bicarbonate aqueous solution is washed to neutrality, then with 70 DEG C hot water washed product 3 times.By the product after washing in 2000Pa, 80
2h is distilled under the conditions of DEG C to get tung oil polylol product, yield 94.5%, product hydroxyl value is 221mgKOH/g, viscosity
8190mPas, acid value 0.78mgKOH/g, moisture are lower than 0.1wt%, can be used for preparing hard polyurethane foam product.
Embodiment 8
500g tung oil, 300g butanol are added in 2000mL three-necked flask, is warming up to 40 DEG C and stirs evenly.Then violent
35wt% metachloroperbenzoic acid solution 500g is slowly added dropwise under stirring condition, control drop rate makes reaction temperature maintain 50
DEG C or so, after being added dropwise, constant temperature 4h, reaction terminate at 50 DEG C.After reaction system layering, water phase is removed, is mutually used oily
10wt% sodium bicarbonate aqueous solution is washed to neutrality, then with 70 DEG C hot water washed product 3 times.Product after washing is existed
2000Pa, distillation 2h is to get tung oil polylol product under the conditions of 80 DEG C, and yield 94.0%, product hydroxyl value is 217mgKOH/
G, viscosity 8020mPas, acid value 0.77mgKOH/g, moisture are lower 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 546000 mPas, since product viscosity is excessive and can not dissolve, can not further progress hydroxylating, therefore product without
Method is used to prepare hard polyurethane foam product.
Comparative example 2
Using treatment process condition same as Example 1, the difference is that being added without hydroxylating agent, petroleum is added
Ether 300g(plays the role of diluent).463000 mPas of product viscosity can not since product viscosity is excessive and can not dissolve
Further progress hydroxylating, therefore product is not used to prepare hard polyurethane foam product.
Comparative example 3
Using treatment process condition same as Example 1, the difference is that preparing polyalcohol using soybean oil.Product
Hydroxyl value is 5.2mgKOH/g, and since product is there is no hydroxylating, hydroxyl value are too low, therefore product is not used to prepare polyurethane
Product.
Claims (8)
1. a kind of preparation method of tung oil polylol, it is characterised in that including following content: by tung oil, hydroxylating agent press than
Example mixing, and it is warming up to 35 ~ 45 DEG C；Under intense agitation, peroxy acid solution is added dropwise, control rate of addition makes reaction temperature
40 ~ 65 DEG C, after being added dropwise are maintained, maintaining reaction temperature 3 ~ 5 hours, reaction was completed；Reaction system is successively divided by standing
Layer, isolates water phase, neutralized, washes, and vacuum distillation obtains tung oil polylol；The hydroxylating agent be alcohols or
Alcamines, the alcohols hydroxylating agent are selected from methanol, ethyl alcohol, ethylene glycol, propyl alcohol, isopropanol, glycerine, butanol, Isosorbide-5-Nitrae-fourth
One or more of glycol, pentaerythrite, xylitol, sorbierite；The alcamines hydroxylating agent is selected from an isopropanol
One or more of amine, diisopropanolamine (DIPA), triisopropanolamine, ethanol amine, diethanol amine, triethanolamine.
2. according to the method for claim 1, it is characterised in that: the dosage of the hydroxylating agent is tung oil quality
0.5 ~ 2 times.
3. according to the method for claim 1, it is characterised in that: the hydroxylating agent is butanol.
4. according to the method for claim 1, it is characterised in that: the peroxy acid is peroxyformic acid, Peracetic acid, peroxide third
One of acid, Perbutyric Acid, peroxide isovaleric acid, benzoyl hydroperoxide, metachloroperbenzoic acid, nitroperoxybenzoic are several
Kind.
5. according to the method for claim 4, it is characterised in that: the peroxy acid is Peracetic acid.
6. according to method described in claim 1,4 or 5, it is characterised in that: the concentration of the peroxy acid solution be 15wt % ~
50wt%, dosage are 0.5 ~ 1.5 times of tung oil quality.
7. according to the method for claim 1, it is characterised in that: the carbon that the neutralization reaction is 5wt% ~ 20wt% using concentration
Sour hydrogen sodium solution；Washing temperature is 50 ~ 80 DEG C；Vacuum distillation is removed under the conditions of 1000 ~ 3000Pa of pressure, 60 ~ 120 DEG C of temperature
The hydroxylating agent and residual moisture in system are removed, product moisture content is made to be less than 0.1wt%.
8. the tung oil polylol of any the method preparation of claim 1~7, it is characterised in that: the production of tung oil polylol
Rate is higher than 92%, and product hydroxyl value is 120 ~ 270mgKOH/g, and acid value is lower than 1.0mgKOH/g, and moisture is lower than 0.1wt%, can be used for making
Standby polyurethane rigid foam material.
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| CN101535235A (en) * | 2006-11-16 | 2009-09-16 | 嘉吉公司 | Viscoelastic polyurethane foams comprising oligomeric natural oil polyols |
| CN101125912A (en) * | 2007-08-13 | 2008-02-20 | 南京红宝丽股份有限公司 | Polyurethane foam plastic prepared from barbadosnut oil |
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