CN105712882B - A kind of tung oil polyalcohol and synthetic method - Google Patents
A kind of tung oil polyalcohol and synthetic method Download PDFInfo
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Abstract
The invention discloses a kind of tung oil polyalcohol and synthetic method, tung oil, carboxylic acid, metal ion support type cation exchange resin catalyst, hydroxylating agent, deionized water are mixed, and be warming up to 35 ~ 45 DEG C in proportion；Under intense agitation, hydrogenperoxide steam generator is added dropwise, control rate of addition makes reaction temperature maintain 40 ~ 65 DEG C, after completion of dropping, and maintenance reaction temperature 3 ~ 5 hours terminates reaction；Reaction system, which is sequentially passed through, filters to isolate solid catalyst, and stratification isolates aqueous phase, neutralized, and washing, vacuum distillation obtains tung oil polyalcohol.Tung oil polyalcohol yield prepared by the present invention is higher than 92%, and product hydroxyl value is 120 ~ 270mgKOH/g, and acid number is less than 1.0mgKOH/g, and moisture is less than 0.1wt%, available for preparing polyurethane material.
Description
Technical field
The invention belongs to polyurethane material field, and in particular to a kind of tung oil polyalcohol and synthetic method.
Background technology
Polyurethane material due to good mechanical performance and be easy to shaping the characteristics of, have been widely used for industry and
In daily life.Main raw material(s) for producing polyurethane includes isocyanates, polyalcohol and other additives, its
The ratio of middle polyalcohol account for more than 50%.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 PEPA, wherein, PPG is occupied an leading position in the market, occupy the 70% of whole polyalcohol demand with
On.
Generally, polyalcohol is to extract to prepare from oil.And oil, as non-renewable resources, scarcity causes its valency
The continuous rise of lattice, and cause the price of the primary raw material of the polynary alcohol production such as downstream product expoxy propane, oxirane to continue
Go up, and according to current depletion rate, petroleum resources are depleted eventually.Therefore, from sustainable development and competition among enterprises
The angle of power is set out, and finds the new material and new technology that can substitute petroleum base polyethers as 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
The various chemical products by raw material of soybean oil are sent out, to substitute petroleum-based chemicals.Concentrate on recently and utilize soybean oil strand
In unsaturated bond, by the modification to double bond, make vegetable oil occur epoxidation, hydroxylating so that it is more to prepare soybean oil
First alcohol.The advantage 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 radicals；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, and the hydroxyl value of polyalcohol is 110 ~
213mgKOH/g, viscosity is 1000 ~ 7000mPas, and conversion ratio is up to 85% ~ 95%.
US20070123725 provides a kind of method for preparing soybean oil polyol, includes the epoxy of polyunsaturated vegetable oil
Change and hydroxylation procedures, form vegetable oil-based polyether polyol.First, by polyunsaturated vegetable oils such as soybean oil or rapeseed oils with having
Machine acid and hydroperoxidation, form epoxidized vegetable oil, are then opened the mixed solution of epoxidized vegetable oil and first alcohol and water
Ring reaction generation vegetable oil polyol.
US20060041157 describes the method for preparing soybean oil polyol, including the vegetable oil of PART EPOXY is existed
Reacted under catalysts conditions with Ring Opening Reagent, form oligomeric vegetable oil polylol, Ring Opening Reagent includes small molecule polyol, planted
Thing 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 special product of China, is also the important raw material of industry and traditional exporting.At present, China's tung oil is produced per year
Amount accounts for 35% or so of world's tung oil yield up to more than 100,000 tons.Therefore, China studies tung oil and made more relevant with tung oil
Product industrialization has special significance.But, high-quality vegetable oil polyol is prepared using tung oil, due to tung oil not
Saturation degree is higher, and is unique polyunsaturated vegetable oil with conjugated double bond in nature, and iodine number reaches more than 170, wherein 85%
More than unsaturated bond be carbon carbon conjugated triene key, so tung oil prepare polyalcohol it is epoxidised during due to conjugated double bond
Presence make epoxide group reactivity higher, side reaction easily occurs for poor selectivity, so as to generate macromolecules cross-linking product, leads
Induced viscosity is sharply increased, normally solid at room temperature, it is impossible to 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
The tung oil of key there occurs cross-linking reaction during epoxidised, cause viscosity increased dramatically.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of tung oil polyalcohol and synthetic method.The present invention utilizes paulownia
The conjugated double bond of oil be the characteristics of can improve epoxide group reactivity, can epoxidised while add hydroxylating agent
The generation of crosslinking side reaction is effectively prevented from, and forms tung oil polyol product.
The synthetic method of tung oil polyalcohol of the present invention, including following content：By tung oil, carboxylic acid, metal ion support type sun
Ion-exchange resin catalyst, hydroxylating agent, deionized water are mixed in proportion, and are warming up to 35 ~ 45 DEG C；It is being stirred vigorously bar
Under part, hydrogenperoxide steam generator is added dropwise, control rate of addition makes reaction temperature maintain 40 ~ 65 DEG C, after completion of dropping, maintenance reaction
Temperature 3 ~ 5 hours, terminates reaction；Reaction system, which is sequentially passed through, filters to isolate solid catalyst, stratification, separates water outlet
Phase, neutralized, washing, vacuum distillation obtains tung oil polyalcohol.
Described carboxylic acid can be one kind or several in formic acid, acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, phenylacetic acid etc.
Plant, preferably formic acid.Carboxylic acid can make the conjugation in tung oil double with hydrogenperoxide steam generator reaction generation peroxycarboxylic acid, peroxycarboxylic acid
Key is converted into epoxy bond, while carboxylic acid is discharged, therefore while epoxy bond is generated, carboxylic acid is not consumed, but very few
Carboxylic acid content will cause system reaction rate slack-off, so the mass ratio for controlling carboxylic acid and tung oil is 0.05:1~0.5:1.
In described metal ion support type cationic ion-exchange resin, matrix cationic ion-exchange resin is macroporous type highly acid
Styrene type cation exchange resin, the metal ion of load is selected from Al3+、Fe3+、Fe2+、Cu2+、Zn2+、Sn4+、Ni2+、Co3+In
One or more, preferably Al3+, metal ion load capacity accounts for the 0.5% ~ 3% of catalyst quality.The catalyst amount is paulownia
The 5% ~ 15% of oil quality.The catalyst can be prepared using means known in the art, can such as use document " metal load type
Catalyzing cation exchange resin synthesizing n-butyl acetate "（Li Yunshan, Zhang Wenwen, a yellow ripple etc., Chemical Engineering Technology and exploitation, 2011,
40（1）：9~12）Described in prepare the method for metal ion support type cationic ion-exchange resin, and according to the metal to be loaded
Element selects suitable metal salt, you can obtain loading the metal ion support type cationic ion-exchange resin of different metal element.
It is pointed out that the general technology path used using sulfuric acid as catalyst of the preparation of peroxy acid in epoxidation reaction, due to sulphur
Acid is strong acid, and the corrosivity to equipment is larger.The present invention uses metal ion support type cationic ion-exchange resin to have for catalyst
Have the advantage that：（1）Excellent catalytic effect, can effectively reduce the consumption of carboxylic acid；（2）The acidity of reaction system is reduced, is conducive to
The shortcoming that the corrosion and reaction product for preventing equipment crosslinking side reaction occur and cause product viscosity to increase；（3）Catalyst can
Easily realize and reclaim and recycling.
Described hydroxylating agent can be alcohols or alcamines, and consumption is 0.5 ~ 2 times of tung oil quality.Wherein alcohols hydroxyl
Base reagent is selected from methanol, ethanol, ethylene glycol, propyl alcohol, isopropanol, glycerine, butanol, 1,4- butanediols, pentaerythrite, xylose
One or more in alcohol, sorbierite etc., preferably butanol；Alcamines hydroxylating agent is selected from monoisopropanolamine, diisopropanol
One or more in amine, triisopropanolamine, monoethanolamine, diethanol amine, triethanolamine etc., preferably triethanolamine.
The consumption of the deionized water is 0.01 ~ 0.2 times of tung oil quality, and the addition of deionized water can prevent reaction just
The esterification of phase carboxylic acid and hydroxylating agent, it is to avoid the consumption of carboxylic acid, increases double bond conversion rate.
The hydrogenperoxide steam generator plays a part of oxidant, carboxylic acid is oxidized to peroxy acid.The concentration of hydrogen peroxide
It is higher, react more violent, system heat release is serious, easily occurs side reaction, so the concentration of selection hydrogenperoxide steam generator for 20wt % ~
60wt%, the consumption of hydrogenperoxide steam generator is 0.6 ~ 1.2 times of tung oil quality.
Described neutralization reaction can use ammoniacal liquor, sodium carbonate or sodium acid carbonate, and it is 5wt% ~ 20wt%'s to preferably use concentration
Sodium bicarbonate solution is neutralized.Described washing temperature is 50 ~ 80 DEG C, to prevent system from emulsion occur.Described decompression is steamed
Evaporate is that, in 1000 ~ 3000Pa of pressure, residual moisture in removing system, is less than product moisture content under the conditions of 60 ~ 120 DEG C of temperature
0.1wt%。
Tung oil polyalcohol of the present invention is prepared by the invention described above method.Prepared tung oil polyalcohol yield
Higher than 92%, product hydroxyl value is 120 ~ 270mgKOH/g, and acid number is less than 1.0mgKOH/g, and moisture is less than 0.1wt%, available for preparing
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 tool is of great 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, the presence due to conjugated double bond during polyalcohol is prepared makes epoxide group anti-
Active higher, poor selectivity is answered, easily occurs side reaction, so as to generate macromolecules cross-linking product, causes viscosity to sharply increase, it is impossible to
For further synthesis of polyurethane material.
The characteristics of present invention can improve epoxide 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 applied to poly- ammonia
The preparation of ester material.Prepared tung oil polyalcohol is renewable, non-toxic and raw with raw material compared with petroleum-based polyols
The good advantage of thing degradability, belongs to environment-friendly biopolyol.
Embodiment
With reference to embodiment, the invention will be further described.In the present invention, wt% represents mass fraction.It is prepared many
The hydroxyl value of first alcohol product is determined according to the phthalic anhydride esterification method in GB/T12008.3-2009, and acid number is according to GB/T
12008.5-2010 methods are determined, and viscosity is determined according to the rotation viscometer method in GB/T 12008.7-2010.
Embodiment 1
500g tung oil, 115g formic acid are added in 2000mL three-necked flasks（85wt% solution）、50g Al3+Support type sun from
Sub-exchange resin catalyst（Wherein Al3+Load capacity accounts for the 2% of catalyst quality, similarly hereinafter）, 300g butanol, 50g deionized waters, rise
Warm to 40 DEG C stir.Then 30wt% aqueous hydrogen peroxide solution 450g are slowly added dropwise under intense agitation, control is added dropwise
Speed makes reaction temperature maintain 50 DEG C or so, after completion of dropping, and the constant temperature 4h at 50 DEG C, reaction terminates.Question response system point
After layer, aqueous phase is removed, oil phase is washed with 10wt% sodium bicarbonate aqueous solutions to neutrality, then with 70 DEG C of hot wash products 3
It is secondary.Product after washing is distilled into 2h under the conditions of 2000Pa, 80 DEG C, tung oil polyol product is produced, yield is 93.8%, produced
Product hydroxyl value is 250mgKOH/g, viscosity 8200mPas, acid number 0.80mgKOH/g, and moisture is less than 0.1wt%, poly- available for preparing
Urethane is hard bubbled product.
Embodiment 2
500g tung oil, 115g formic acid are added in 2000mL three-necked flasks（85wt% solution）、50g Al3+Support type sun from
Sub-exchange resin catalyst, 300g butanol, 50g deionized waters, are warming up to 45 DEG C and stir.Then under intense agitation
30wt% aqueous hydrogen peroxide solution 450g are slowly added dropwise, control drop rate makes reaction temperature maintain 65 DEG C or so, completion of dropping
Afterwards, the constant temperature 5h at 65 DEG C, reaction terminates.After question response system layering, aqueous phase is removed, by oil phase 10wt% sodium bicarbonate waters
Solution is washed to neutrality, then with 70 DEG C of hot wash products 3 times.Product after washing is steamed under the conditions of 2000Pa, 80 DEG C
2h is evaporated, tung oil polyol product is produced, yield is 93.5%, product hydroxyl value is 232mgKOH/g, viscosity 10400mPas, acid number
0.92mgKOH/g, moisture is less than 0.1wt%, available for preparing hard polyurethane foam product.
Embodiment 3
500g tung oil, 115g formic acid are added in 2000mL three-necked flasks（85wt% solution）、50g Al3+Support type sun from
Sub-exchange resin catalyst, 300g butanol, 50g deionized waters, are warming up to 35 DEG C and stir.Then under intense agitation
30wt% aqueous hydrogen peroxide solution 450g are slowly added dropwise, control drop rate makes reaction temperature maintain 40 DEG C or so, completion of dropping
Afterwards, the constant temperature 4h at 40 DEG C, reaction terminates.After question response system layering, aqueous phase is removed, by oil phase 10wt% sodium bicarbonate waters
Solution is washed to neutrality, then with 70 DEG C of hot wash products 3 times.Product after washing is steamed under the conditions of 2000Pa, 80 DEG C
2h is evaporated, tung oil polyol product is produced, yield is 92.6%, product hydroxyl value is 172mgKOH/g, viscosity 3290mPas, acid number
0.68mgKOH/g, moisture is less than 0.1wt%, available for preparing polyurethane products.
Embodiment 4
500g tung oil, 115g formic acid are added in 2000mL three-necked flasks（85wt% solution）、50g Al3+Support type sun from
Sub-exchange resin catalyst, 300g ethanol, 50g deionized waters, are warming up to 40 DEG C and stir.Then under intense agitation
30wt% aqueous hydrogen peroxide solution 450g are slowly added dropwise, control drop rate makes reaction temperature maintain 50 DEG C or so, completion of dropping
Afterwards, the constant temperature 4h at 50 DEG C, reaction terminates.After question response system layering, aqueous phase is removed, by oil phase 10wt% sodium bicarbonate waters
Solution is washed to neutrality, then with 70 DEG C of hot wash products 3 times.Product after washing is steamed under the conditions of 2000Pa, 80 DEG C
2h is evaporated, tung oil polyol product is produced, yield is 93.1%, product hydroxyl value is 228mgKOH/g, viscosity 11900mPas, acid number
0.84mgKOH/g, moisture is less than 0.1wt%, available for preparing hard polyurethane foam product.
Embodiment 5
500g tung oil, 115g formic acid are added in 2000mL three-necked flasks（85wt% solution）、50g Al3+Support type sun from
Sub-exchange resin catalyst, 300g triethanolamines, 50g deionized waters, are warming up to 40 DEG C and stir.Then it is being stirred vigorously bar
30wt% aqueous hydrogen peroxide solution 450g are slowly added dropwise under part, control drop rate makes reaction temperature maintain 50 DEG C or so, dropwise addition
After finishing, the constant temperature 4h at 50 DEG C, reaction terminates.After question response system layering, aqueous phase is removed, by oil phase 10wt% bicarbonates
Sodium water solution is washed to neutrality, then with 70 DEG C of hot wash products 3 times.By the product after washing in 2000Pa, 80 DEG C of conditions
Lower distillation 2h, produces tung oil polyol product, and yield is 93.0%, product hydroxyl value be 225mgKOH/g, viscosity 11400mPas,
Acid number 0.82mgKOH/g, moisture is less than 0.1wt%, available for preparing hard polyurethane foam product.
Embodiment 6
500g tung oil, 100g formic acid are added in 2000mL three-necked flasks（85wt% solution）、75g Al3+Support type sun from
Sub-exchange resin catalyst, 300g butanol, 50g deionized waters, are warming up to 40 DEG C and stir.Then under intense agitation
30wt% aqueous hydrogen peroxide solution 350g are slowly added dropwise, control drop rate makes reaction temperature maintain 50 DEG C or so, completion of dropping
Afterwards, the constant temperature 4h at 50 DEG C, reaction terminates.After question response system layering, aqueous phase is removed, by oil phase 10wt% sodium bicarbonate waters
Solution is washed to neutrality, then with 70 DEG C of hot wash products 3 times.Product after washing is steamed under the conditions of 2000Pa, 80 DEG C
2h is evaporated, tung oil polyol product is produced, yield is 92.6%, product hydroxyl value is 176mgKOH/g, viscosity 7100mPas, acid number
0.73mgKOH/g, moisture is less than 0.1wt%, available for preparing hard polyurethane foam product.
Embodiment 7
500g tung oil, 150g formic acid are added in 2000mL three-necked flasks（85wt% solution）、25g Al3+Support type sun from
Sub-exchange resin catalyst, 300g butanol, 50g deionized waters, are warming up to 40 DEG C and stir.Then under intense agitation
30wt% aqueous hydrogen peroxide solution 500g are slowly added dropwise, control drop rate makes reaction temperature maintain 50 DEG C or so, completion of dropping
Afterwards, the constant temperature 4h at 50 DEG C, reaction terminates.After question response system layering, aqueous phase is removed, by oil phase 10wt% sodium bicarbonate waters
Solution is washed to neutrality, then with 70 DEG C of hot wash products 3 times.Product after washing is steamed under the conditions of 2000Pa, 80 DEG C
2h is evaporated, tung oil polyol product is produced, yield is 93.7%, product hydroxyl value is 258mgKOH/g, viscosity 8200mPas, acid number
0.81mgKOH/g, moisture is less than 0.1wt%, available for preparing hard polyurethane foam product.
Embodiment 8
Using treatment process condition same as Example 1, difference is the butanol for adding 500g.Tung oil polyalcohol
Yield is 93.5%, and product hydroxyl value is 245mgKOH/g, and viscosity 7150mPas, acid number 0.68mgKOH/g, moisture is less than
0.1wt%, available for preparing hard polyurethane foam product.
Embodiment 9
Using treatment process condition same as Example 1, difference is that catalyst uses 50g Fe3+Support type sun
Ion-exchange resin catalyst（Wherein Fe3+Load capacity accounts for the 2% of catalyst quality）.Tung oil polyalcohol yield is 93.3%, product
Hydroxyl value is 232mgKOH/g, viscosity 7850mPas, acid number 0.76mgKOH/g, and moisture is less than 0.1wt%, available for preparing poly- ammonia
Ester hard bubbles product.
Embodiment 10
Using treatment process condition same as Example 1, difference is that organic carboxyl acid uses 115g glacial acetic acids.Paulownia
Oil polyalcohol yield is 92.2%, and product hydroxyl value is 141mgKOH/g, viscosity 2570mPas, acid number 0.52mgKOH/g, moisture
Less than 0.1wt%, available for preparing polyurethane products.
Comparative example 1
Using treatment process condition same as Example 1, difference is to be added without hydroxylating agent.Product it is viscous
384000 mPas are spent, because product viscosity is excessive and can not dissolve, it is impossible to further carry out hydroxylating, thus product without
Method is used to prepare hard polyurethane foam product.
Comparative example 2
Using treatment process condition same as Example 1, difference is to be added without hydroxylating agent, adds oil
Ether 300g（Play diluent effect）.The mPas of product viscosity 349200, because product viscosity is excessive and can not dissolve, it is impossible to
Hydroxylating is further carried out, therefore product is not used to prepare hard polyurethane foam product.
Comparative example 3
Using treatment process condition same as Example 1, difference is to prepare polyalcohol using soybean oil.Product
Hydroxyl value is 4.5mgKOH/g, and due to product, not occur hydroxylating, hydroxyl value too low, therefore product is not used to prepare polyurethane
Product.
Claims (10)
1. a kind of synthetic method of tung oil polyalcohol, it is characterised in that including following content：Tung oil, carboxylic acid, metal ion are born
Load type cation exchange resin catalyst, hydroxylating agent, deionized water are mixed in proportion, and are warming up to 35 ~ 45 DEG C；Violent
Under stirring condition, hydrogenperoxide steam generator is added dropwise, control rate of addition makes reaction temperature maintain 40 ~ 65 DEG C, after completion of dropping, dimension
Hold reaction temperature 3 ~ 5 hours, terminate reaction；In described metal ion support type cationic ion-exchange resin, matrix cation is handed over
Resin is changed for macroporous type strongly acidic styrene type cation exchange resin, the metal ion of load is selected from Al3+、Fe3+、Fe2+、Cu2 +、Zn2+、Sn4+、Ni2+、Co3+In one or more；Reaction system, which is sequentially passed through, filters to isolate solid catalyst, stands and divides
Layer, isolates aqueous phase, neutralized, and washing, vacuum distillation obtains tung oil polyalcohol.
2. in accordance with the method for claim 1, it is characterised in that：Described carboxylic acid is formic acid, acetic acid, propionic acid, butyric acid, penta
One or more in acid, benzoic acid, phenylacetic acid；The mass ratio for controlling carboxylic acid and tung oil is 0.05:1~0.5:1.
3. in accordance with the method for claim 1, it is characterised in that：Described metal ion support type cationic ion-exchange resin
In, metal ion load capacity accounts for the 0.5% ~ 3% of catalyst quality.
4. according to the method described in claim 1 or 3, it is characterised in that：The catalyst amount is the 5% ~ 15% of tung oil quality.
5. in accordance with the method for claim 1, it is characterised in that：Described hydroxylating agent is alcohols or alcamines, consumption
For 0.5 ~ 2 times of tung oil quality.
6. in accordance with the method for claim 5, it is characterised in that：The alcohols hydroxylating agent is selected from methanol, ethanol, second two
One or more in 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, monoethanolamine, diethanol amine, three second
One or more in hydramine.
7. according to the method described in claim 1 or 6, it is characterised in that：The hydroxylating agent is butanol.
8. in accordance with the method for claim 1, it is characterised in that：The consumption of the deionized water for tung oil quality 0.01 ~
0.2 times.
9. in accordance with the method for claim 1, it is characterised in that：The concentration of the hydrogenperoxide steam generator be 20wt % ~
60wt%, consumption is 0.6 ~ 1.2 times of tung oil quality.
10. in accordance with the method for claim 1, it is characterised in that：The neutralization reaction concentration is 5wt% ~ 20wt%'s
Sodium bicarbonate solution；Washing temperature is 50 ~ 80 DEG C；Vacuum distillation is in 1000 ~ 3000Pa of pressure, under the conditions of 60 ~ 120 DEG C of temperature
Hydroxylating agent and residual moisture in removing system, make product moisture content be less than 0.1wt%.
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