CN102786679A - Preparation method for polyoxyethylene mono-caprylic-capric acid glyceride - Google Patents
Preparation method for polyoxyethylene mono-caprylic-capric acid glyceride Download PDFInfo
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- CN102786679A CN102786679A CN2012102831496A CN201210283149A CN102786679A CN 102786679 A CN102786679 A CN 102786679A CN 2012102831496 A CN2012102831496 A CN 2012102831496A CN 201210283149 A CN201210283149 A CN 201210283149A CN 102786679 A CN102786679 A CN 102786679A
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Abstract
The invention discloses a preparation method for polyoxyethylene mono-caprylic-capric acid glyceride. The preparation method comprises the following steps of: 1) esterification reaction: glycerol and caprylic-capric acid are taken as raw materials, a solid catalyst is added, water is separated from the mixture under nitrogen flow, a temperature is increased to 150 DEG C to 180 DEG C, heat is preserved for 3-6 hours, and the temperature is decreased at 50 DEG C to 70 DEG C; 2) purification of mono-caprylic-capric acid ester; and 3) condensation reaction of ethylene oxide: mono-caprylic-capric acid ester after purification is taken as the raw material, an alkaline catalyst is added, nitrogen is substituted, the temperature is increased to 100 DEG C to 120 DEG C, after 20-40 minutes, ethylene oxide is slowly led into for 3-5 hours, after the addition is finished, processes of aging, pressure reduction, temperature lowering and degassing are carried out, and the product is obtained after the discharging. The preparation method has the characteristics of reasonable process, high product purity and good use performance.
Description
Technical field
The present invention relates to a kind of preparation method of T 46155 list Glycerin, mixed triester with caprylic acid capric acid, belong to the synthesis technical field of nonionogenic tenside in the organic chemistry.
Background technology
T 46155 list Glycerin, mixed triester with caprylic acid capric acid belongs to polyol-based non-ionic surfactant, is a kind of high-quality and efficient emulsifying agent, and good emulsification, dispersion and stabilization are arranged.Glycerine has good softness, emulsification, lubricated, anti-mist, antistatic and add dissolubility, and toxicity is low, and is little to skin irritation, is prone to characteristics such as degraded, has purposes widely in food, medicine, makeup and metal processing and other fields.Particularly this product is the food emulsifier of a kind of colourless (or little yellow) tasteless high-hydrophilic, its existing good hydrophilic and oleophilic performance, again acidproof ability is arranged, and along with the raising of oxyethaneization, the HLB value can reach higher level.Owing to its middle carbon structure, more can embody the consistency and the emulsifying stability of this product and other products, so the application of this product must be up-and-coming, have purposes widely in food, medicine, makeup and metal processing and other fields.This product can replace the tween series product in food-processing, be a kind of New-type emulsifier.The condensation number of oxyethane can not be greater than 20, and too high words oleophilicity can not embody.
Have report to do the bullion of the hot decylate of Catalyst Production glycerine list with alkali, it is very dark that alkali is done the esterified prod color of Catalyst Production; With the hot decylate of the method purification glycerine list of solvent recrystallization, technology is pretty troublesome, and environmental pollution is big.
The content of invention
The object of the present invention is to provide a kind of preparation method of T 46155 list Glycerin, mixed triester with caprylic acid capric acid, technology is reasonable, and product purity is high, has the characteristics of better use properties.
For achieving the above object, technical scheme of the present invention is:
A kind of preparation method of T 46155 list Glycerin, mixed triester with caprylic acid capric acid comprises the steps: 1) esterification: with glycerine and hot capric acid is raw material, adds solid catalyst; Tell the water that esterification generates under the condition of nitrogen gas stream; Be warming up to 150 ℃-180 ℃, insulation 3-6h reduces to 50-70 ℃; 2) the single hot decylate of purification; 3) ethylene oxide condensation reaction: the single Glycerin, mixed triester with caprylic acid capric acid that obtains with purification is a raw material, adds basic catalyst, nitrogen replacement; Be warmed up to 100 ℃-120 ℃, behind the 20-40min, slowly feed oxyethane 3-5h; Add slaking, step-down cooling degassing discharging gets product.
The weight ratio of said glycerine and hot capric acid is 1:1.60-1.85.
Solid catalyst add-on in the said esterification is the 0.01%-0.08% of glycerine and hot capric acid gross weight.
Described solid catalyst adopts a kind of in tin protochloride, the tin protoxide.
The single hot decylate of described purification is to use the rotor segment thin-film evaporator, and the collection temperature of single Glycerin, mixed triester with caprylic acid capric acid is 130-140 ℃, and pressure is 8-12Pa.
The weight ratio of hot decylate of said glycerine list and oxyethane is 1:1-3.0; Basic catalyst in the said ethylene oxide condensation reaction is the 0.1%-0.5% of single hot decylate and oxyethane gross weight.
Basic catalyst in the reaction of said ethylene oxide condensation is for adopting a kind of in Pottasium Hydroxide, the sodium hydroxide.
The invention has the beneficial effects as follows: the preparation method of a kind of T 46155 list Glycerin, mixed triester with caprylic acid capric acid that the application of the invention obtains has the following advantages: 1, adopt the esterification under the solid catalyst effect, conversion unit is simple.2, the present invention adopts the rotor segment thin-film evaporator to obtain the higher product of purity than other separation methods, and is easy to operate.3, the T 46155 list Glycerin, mixed triester with caprylic acid capric acid that is made by the present invention has the hydrophilic and oleophilic base, has excellent emulsifying property, with other products good consistency and emulsifying stability is arranged.4, the present invention does not almost pollute environment.
Embodiment
Embodiment 1
1) esterification: in the flask of 2L, add 644 gram glycerine by weight, the hot capric acid of 1036 grams stirs the 0.336 gram solid catalyst tin protochloride of adding down; Slowly heat up, in time tell the water that esterification generates under the condition of nitrogen gas stream, be warming up under 180 ℃ the reaction conditions; Be incubated 3.0 hours; After be cooled to 60 ℃, blowing, acid transformation efficiency be 99.9%.
2) the single hot decylate of purification: use the rotor segment thin-film evaporator, collecting temperature is 130 ℃, single Glycerin, mixed triester with caprylic acid capric acid about lighting end 700 grams of pressure 8Pa, and another cut is two Glycerin, mixed triester with caprylic acid capric acid by products.
3) ethylene oxide condensation reaction: in the addition still of 2L, add the single Glycerin, mixed triester with caprylic acid capric acid of 400 grams, stir and add Pottasium Hydroxide 7.6 grams, heat up behind the nitrogen replacement three times; Temperature to 100 ℃, behind the dehydration 30min, temperature is transferred to 100 ℃ and is slowly fed oxyethane 1153 grams; 5 hours time added slaking, and equipressure drops to reduce to and ends; Cooling degassing discharging gets product T 46155 list Glycerin, mixed triester with caprylic acid capric acid 1555 grams.
Preparing method through using a kind of T 46155 list Glycerin, mixed triester with caprylic acid capric acid that present embodiment obtains has the following advantages: 1, adopt the esterification under the solid catalyst effect, conversion unit is simple.2, present embodiment adopts the rotor segment thin-film evaporator to obtain the higher product of purity than other separation methods, and is easy to operate.3, the T 46155 list Glycerin, mixed triester with caprylic acid capric acid that is made by present embodiment has the hydrophilic and oleophilic base, has excellent emulsifying property, with other products good consistency and emulsifying stability is arranged.4, present embodiment does not almost pollute environment.
Embodiment 2
1) esterification: in the flask of 2L, add 644 gram glycerine by weight, the hot capric acid of 1085 grams stirs the 0.5187 gram solid catalyst tin protoxide of adding down; Slowly heat up, in time tell the water that esterification generates under the condition of nitrogen gas stream, be warming up under 150 ℃ the reaction conditions; Be incubated 6.0 hours; After be cooled to 50 ℃, blowing, acid transformation efficiency be 99.8%.
2) the single hot decylate of purification: use the rotor segment thin-film evaporator, collecting temperature is 140 ℃, single Glycerin, mixed triester with caprylic acid capric acid about lighting end 750 grams of pressure 10Pa, and another cut is two Glycerin, mixed triester with caprylic acid capric acid by products.
3) ethylene oxide condensation reaction: in the addition still of 2L, add the single Glycerin, mixed triester with caprylic acid capric acid of 400 grams, stir and add sodium hydroxide 3.6 grams, heat up behind the nitrogen replacement three times; Temperature to 120 ℃, behind the dehydration 40min, temperature is transferred to 120 ℃ and is slowly fed oxyethane 776 grams; 4.5 hours time added slaking, and equipressure drops to reduce to and ends; Cooling degassing discharging gets product T 46155 list Glycerin, mixed triester with caprylic acid capric acid 1175 grams.
Preparing method through using a kind of T 46155 list Glycerin, mixed triester with caprylic acid capric acid that present embodiment obtains has the following advantages: 1, adopt the esterification under the solid catalyst effect, conversion unit is simple.2, present embodiment adopts the rotor segment thin-film evaporator to obtain the higher product of purity than other separation methods, and is easy to operate.3, the T 46155 list Glycerin, mixed triester with caprylic acid capric acid that is made by present embodiment has the hydrophilic and oleophilic base, has excellent emulsifying property, with other products good consistency and emulsifying stability is arranged.4, present embodiment does not almost pollute environment.
Embodiment 3
1) esterification: in the flask of 2L, add 644 gram glycerine by weight, the hot capric acid of 1141 grams stirs the 0.7140 gram solid catalyst tin protochloride of adding down; Slowly heat up, in time tell the water that esterification generates under the condition of nitrogen gas stream, be warming up under 160 ℃ the reaction conditions; Be incubated 5.0 hours; After be cooled to 70 ℃, blowing, acid transformation efficiency be 99.99%.
2) the single hot decylate of purification: use the rotor segment thin-film evaporator, collecting temperature is 135 ℃, single Glycerin, mixed triester with caprylic acid capric acid about lighting end 790 grams of pressure 12Pa, and another cut is two Glycerin, mixed triester with caprylic acid capric acid by products.
3) ethylene oxide condensation reaction: in the addition still of 2L, add the single Glycerin, mixed triester with caprylic acid capric acid of 400 grams, stir and add sodium hydroxide 2.4 grams, heat up behind the nitrogen replacement three times; Temperature to 110 ℃, behind the dehydration 20min, temperature is transferred to 110 ℃ and is slowly fed oxyethane 400 grams; 3 hours time added slaking, and equipressure drops to reduce to and ends; Cooling degassing discharging gets product T 46155 list Glycerin, mixed triester with caprylic acid capric acid 795 grams.
Preparing method through using a kind of T 46155 list Glycerin, mixed triester with caprylic acid capric acid that present embodiment obtains has the following advantages: 1, adopt the esterification under the solid catalyst effect, conversion unit is simple.2, present embodiment adopts the rotor segment thin-film evaporator to obtain the higher product of purity than other separation methods, and is easy to operate.3, the T 46155 list Glycerin, mixed triester with caprylic acid capric acid that is made by present embodiment has the hydrophilic and oleophilic base, has excellent emulsifying property, with other products good consistency and emulsifying stability is arranged.4, present embodiment does not almost pollute environment.
Embodiment 4
1) esterification: in the flask of 2L, add 644 gram glycerine by weight, the hot capric acid of 1190 grams stirs the 0.9170 gram solid catalyst tin protoxide of adding down; Slowly heat up, in time tell the water that esterification generates under the condition of nitrogen gas stream, be warming up under 170 ℃ the reaction conditions; Be incubated 4.0 hours; After be cooled to 60 ℃, blowing, acid transformation efficiency be 99.8%.
2) the single hot decylate of purification: use the rotor segment thin-film evaporator, collecting temperature is 130 ℃, single Glycerin, mixed triester with caprylic acid capric acid about lighting end 780 grams of pressure 10Pa, and another cut is two Glycerin, mixed triester with caprylic acid capric acid by products.
3) ethylene oxide condensation reaction: in the addition still of 2L, add the single Glycerin, mixed triester with caprylic acid capric acid of 400 grams, stir and add Pottasium Hydroxide 3.1 grams, heat up behind the nitrogen replacement three times; Temperature to 100 ℃, behind the dehydration 30min, temperature is transferred to 100 ℃ and is slowly fed oxyethane 620 grams; 4 hours time added slaking, and equipressure drops to reduce to and ends; Cooling degassing discharging gets product T 46155 list Glycerin, mixed triester with caprylic acid capric acid 1015 grams.
Preparing method through using a kind of T 46155 list Glycerin, mixed triester with caprylic acid capric acid that present embodiment obtains has the following advantages: 1, adopt the esterification under the solid catalyst effect, conversion unit is simple.2, present embodiment adopts the rotor segment thin-film evaporator to obtain the higher product of purity than other separation methods, and is easy to operate.3, the T 46155 list Glycerin, mixed triester with caprylic acid capric acid that is made by present embodiment has the hydrophilic and oleophilic base, has excellent emulsifying property, with other products good consistency and emulsifying stability is arranged.4, present embodiment does not almost pollute environment.
Its esterification equation is in the foregoing description:
R is:
(CH
2)
6CH
3Or (CH
2)
8CH
3
Its ethylene oxide condensation reaction equation is in the foregoing description:
R is:
(CH
2)
6CH
3Or (CH
2)
8CH
3M+n=5～15.
Claims (7)
1. the preparation method of a T 46155 list Glycerin, mixed triester with caprylic acid capric acid; It is characterized in that comprising the steps: 1) esterification: with glycerine and hot capric acid is raw material; Add solid catalyst, tell the water that esterification generates under the condition of nitrogen gas stream, be warming up to 150 ℃-180 ℃; Insulation 3-6h reduces to 50-70 ℃; 2) the single hot decylate of purification; 3) ethylene oxide condensation reaction: the single Glycerin, mixed triester with caprylic acid capric acid that obtains with purification is a raw material, adds basic catalyst, nitrogen replacement; Be warmed up to 100 ℃-120 ℃, behind the 20-40min, slowly feed oxyethane 3-5h; Add slaking, step-down, cooling degassing discharging get product.
2. the preparation method of a kind of T 46155 list Glycerin, mixed triester with caprylic acid capric acid according to claim 1 is characterized in that: the weight ratio of said glycerine and hot capric acid is 1:1.60-1.85.
3. the preparation method of a kind of T 46155 list Glycerin, mixed triester with caprylic acid capric acid according to claim 1 is characterized in that: the solid catalyst add-on in the said esterification is the 0.01%-0.08% of glycerine and hot capric acid gross weight.
4. according to the preparation method of claim 1 or the described a kind of T 46155 list Glycerin, mixed triester with caprylic acid capric acid of claim 3, it is characterized in that: described solid catalyst adopts a kind of in tin protochloride, the tin protoxide.
5. the preparation method of a kind of T 46155 list Glycerin, mixed triester with caprylic acid capric acid according to claim 1; It is characterized in that: the single hot decylate of described purification is to use the rotor segment thin-film evaporator; The collection temperature of single Glycerin, mixed triester with caprylic acid capric acid is 130-140 ℃, and pressure is 8-12Pa.
6. the preparation method of a kind of T 46155 list Glycerin, mixed triester with caprylic acid capric acid according to claim 1 is characterized in that: the weight ratio of hot decylate of said glycerine list and oxyethane is 1:1-3.0; Basic catalyst in the said ethylene oxide condensation reaction is the 0.1%-0.5% of single hot decylate and oxyethane gross weight.
7. according to the preparation method of claim 1 or the described a kind of T 46155 list Glycerin, mixed triester with caprylic acid capric acid of claim 6, it is characterized in that: the basic catalyst in the reaction of said ethylene oxide condensation is for adopting a kind of in Pottasium Hydroxide, the sodium hydroxide.
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| CN201210283149.6A CN102786679B (en) | 2012-08-10 | 2012-08-10 | Preparation method for polyoxyethylene mono-caprylic-capric acid glyceride |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102963577A (en) * | 2012-11-28 | 2013-03-13 | 广州嘉德乐生化科技有限公司 | Method for packaging glycerin monostearate |
| CN103145554A (en) * | 2013-02-22 | 2013-06-12 | 玛耀生物医药（上海）有限公司 | Preparation method of 1-decanoyl-rac-glycerol compound |
| CN104974340A (en) * | 2015-06-25 | 2015-10-14 | 淄博德信联邦化学工业有限公司 | Preparation method of highly active polyether polyol containing ester bonds in main chain |
| CN105399941A (en) * | 2015-12-10 | 2016-03-16 | 浙江皇马科技股份有限公司 | A preparing method of polyether polyol aliphatic esters |
| CN108299638A (en) * | 2017-12-29 | 2018-07-20 | 浙江皇马科技股份有限公司 | A kind of synthetic method of allyl alcohol polyethenoxy ether carboxylic acid ethylene oxidic ester |
| CN108822289A (en) * | 2018-07-12 | 2018-11-16 | 广州汇科精细化工有限公司 | Composite catalyst and its application and the method for preparing water-soluble aliphatic ester |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102963577A (en) * | 2012-11-28 | 2013-03-13 | 广州嘉德乐生化科技有限公司 | Method for packaging glycerin monostearate |
| CN102963577B (en) * | 2012-11-28 | 2015-01-07 | 广州嘉德乐生化科技有限公司 | Method for packaging glycerin monostearate |
| CN103145554A (en) * | 2013-02-22 | 2013-06-12 | 玛耀生物医药（上海）有限公司 | Preparation method of 1-decanoyl-rac-glycerol compound |
| CN104974340A (en) * | 2015-06-25 | 2015-10-14 | 淄博德信联邦化学工业有限公司 | Preparation method of highly active polyether polyol containing ester bonds in main chain |
| CN104974340B (en) * | 2015-06-25 | 2017-03-29 | 淄博德信联邦化学工业有限公司 | The preparation method of the polyether polyol with high activity containing ester bond in main chain |
| CN105399941A (en) * | 2015-12-10 | 2016-03-16 | 浙江皇马科技股份有限公司 | A preparing method of polyether polyol aliphatic esters |
| CN108299638A (en) * | 2017-12-29 | 2018-07-20 | 浙江皇马科技股份有限公司 | A kind of synthetic method of allyl alcohol polyethenoxy ether carboxylic acid ethylene oxidic ester |
| CN108299638B (en) * | 2017-12-29 | 2020-04-28 | 浙江皇马科技股份有限公司 | Synthesis method of allyl alcohol polyoxyethylene ether carboxylic glycidyl ester |
| CN108822289A (en) * | 2018-07-12 | 2018-11-16 | 广州汇科精细化工有限公司 | Composite catalyst and its application and the method for preparing water-soluble aliphatic ester |
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Effective date of registration: 20150706 Address after: 312363 Shangyu City, Zhejiang Province Zhang Town Industrial Zone Patentee after: Zhejiang Huangma Technology Co., Ltd. Address before: 312363, Zhejiang, Shangyu, Shaoxing Province town industrial zone, Zhejiang Real Madrid Chemical Group Co., Ltd. Patentee before: Huangma Chemical Group Co., Zhejiang |