CN101942085B - Synthetic method of sorbierite polyoxyethylene ether tall-oil acid ester - Google Patents
Synthetic method of sorbierite polyoxyethylene ether tall-oil acid ester Download PDFInfo
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- CN101942085B CN101942085B CN2010102643197A CN201010264319A CN101942085B CN 101942085 B CN101942085 B CN 101942085B CN 2010102643197 A CN2010102643197 A CN 2010102643197A CN 201010264319 A CN201010264319 A CN 201010264319A CN 101942085 B CN101942085 B CN 101942085B
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- polyoxyethylene ether
- sorbitol polyoxyethylene
- tallate
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Abstract
The invention discloses a synthetic method of sorbierite polyoxyethylene ether tall-oil acid ester, the method takes sorbierite and ethylene oxide as raw materials, which are polymerized at certain temperature and under base catalyst, thus preparing sorbierite polyoxyethylene ether, then the sorbierite polyoxyethylene ether and tall-oil acid ester are used as the raw materials, under the function of organic acid catalyst, dehydration condensation reaction is carried out at low temperature, hydroxyl of high activity reacts with carboxyl completely, and then heating reaction is carried out, thus preparing the orbierite polyoxyethylene ether tall-oil acid ester. The synthetic method has the characteristics of simple operation and good using performance.
Description
Technical field
The present invention relates to a kind of compound method of sorbitol polyoxyethylene ether tallate, belong to technical field of synthesis of ester compounds in the organic chemistry, also relate to the ethylene oxide polymerization reaction.
Background technology
The sorbitol polyoxyethylene ether tallate is the nonionogenic tenside of a kind of high-hydrophilic (HLB); Main emulsifying agent, aqueous dispersant, the oily emulsification assistant agent that is used as (O/W) of oil-in-water-type is applied to industrial coating, decorative paint, Synolac and metal processing and other fields.The compound method report of sorbitan fatty acid ester is more, and CN1228774A has introduced a kind of with sorbyl alcohol and the directly synthetic sorbitan fatty acid ester of lipid acid, prepares the verivate Span with alkylene oxide reaction again.Patent CN1420877A has introduced with alkali and has made catalyzer, and the direct esterification technology of SYNTHETIC OPTICAL WHITNER or organic solvent is produced Span in a large number.Sorbitol polyoxyethylene ether tallate report is then less.
Summary of the invention
Main purpose of the present invention is to provide a kind of compound method of sorbitol polyoxyethylene ether tallate, have simple to operate, the characteristics that use properties is good.
The present invention is a kind of compound method of sorbitol polyoxyethylene ether tallate, and said raw material sorbyl alcohol, oxyethane, tall oil acid are commercially available common raw material, and sorbyl alcohol is the sorbitol aqueous solution of commercially available Neosorb or 70%.Said sorbitol polyoxyethylene ether has following general formula:
Annotate: a+b+c+d+e+f=n n is 20～50
Said sorbitol polyoxyethylene ether tallate is a yellow liquid.Have following general formula:
Annotate: a+b+c+d+e+f=20～50, M=H or RCO
In order to reach above-mentioned purpose, solution of the present invention is:
A kind of compound method of sorbitol polyoxyethylene ether tallate is a raw material with sorbyl alcohol, oxyethane, and sorbitol polyoxyethylene ether is polymerized under certain temperature and alkaline catalysts; And then be raw material with sorbitol polyoxyethylene ether, tall oil acid; Under the effect of organic acid catalyst, carry out dehydration condensation at low temperatures earlier, make active high hydroxyl complete with carboxyl reaction earlier; Temperature reaction again makes the sorbitol polyoxyethylene ether tallate.
The mol ratio of described sorbyl alcohol and oxyethane is 1: 20～50.
Described alkaline catalysts is a kind of in sodium methylate, sodium hydroxide, the Pottasium Hydroxide.
The add-on of described alkaline catalysts is 0.1～1.0% of a sorbyl alcohol weight.
The temperature of described polyreaction is 130～180 ℃.
The mol ratio of said sorbitol polyoxyethylene ether and tall oil acid can be 1: 3.0～and 5.0.
Described organic acid catalyst is mixture or the mixture of tosic acid and Hypophosporous Acid, 50 or the mixture of Witco 1298 Soft Acid and Hypophosporous Acid, 50 of Witco 1298 Soft Acid and tosic acid.
The add-on of described organic acid catalyst is 0.2～1.0% of sorbitol polyoxyethylene ether and a tall oil acid gross weight.
The reaction times of described dehydration condensation is 1～5 hour.
The temperature of reaction of described low temperature dewatering condensation reaction is 70～100 ℃, and temperature reaction temperature again is 130～160 ℃.
Beneficial effect of the present invention is: 1, the production process reaction conditions is gentle, and equipment used is simple, thereby facility investment and energy consumption are more saved.2, the dehydration condensation under the effect of employing organic acid catalyst, technology is simple, and side reaction is few, can effectively reduce cost, and improves yield.3, the sorbitol polyoxyethylene ether tallate that is made by the present invention is the nonionogenic tenside of a kind of high-hydrophilic (HLB); Main emulsifying agent, aqueous dispersant, the oily emulsification assistant agent that is used as (O/W) of oil-in-water-type is applied to industrial coating, decorative paint, Synolac and metal processing and other fields.
Embodiment
Following embodiment polyreaction all adopts the autoclave of 2 liters stirring-type, and esterification adopts 1 liter four-hole boiling flask, vacuum diaphragm pump.Sorbyl alcohol is 70% the aqueous solution, and the tall oil acid staple is an octadecenic acid, molecular weight 289.
Embodiment 1
Sorbitol polyoxyethylene ether in the present embodiment (the oxyethane adduct number is 20) is 1: 3 with the mol ratio of tall oil acid.
In reaction kettle, add sorbyl alcohol and the 0.4g catalyst solid Pottasium Hydroxide of 370g70% by weight, be warming up to 120 ℃ of vacuum hydro-extractions, collect water; Finish dehydration when the water yield reaches 111.0g, be warmed up to 160 ℃, slowly feed oxyethane 1252.2g; After polyreaction finishes; Be cooled to 80 ℃, add the neutralization of 0.4g acetic acid, blowing.In 1 liter of four-hole boiling flask, add the above-mentioned sorbitol polyoxyethylene ether of 400g (20), add the 327g tall oil acid, stir the mixed catalyst that adds 2.0g tosic acid and Hypophosporous Acid, 50 down, heat up gradually; Under 80 ℃ of vacuum states, reacted 2 hours, heat up again; Insulation is 3 hours under the reaction conditions of 150 ℃ of temperature, is cooled to 60 ℃ of blowings, No. 4, color and luster (Gardner); Acid number 5.0mgKOH/g, hydroxyl value 95.2mgKOH/g
Embodiment 2
Sorbitol polyoxyethylene ether in the present embodiment (the oxyethane adduct number is 20) is 1: 5 with the mol ratio of tall oil acid.
By the sorbitol polyoxyethylene ether (20) of quality adding 300g embodiment 1, the 408g tall oil acid stirs adding 3.5g dodecylbenzene sulfonic acid catalyst down, heats up gradually in reaction kettle; Under 90 ℃ of vacuum states, reacted 2 hours, heat up again; Under the vacuum outgas state, be insulation 4 hours under 150 ℃ the reaction conditions in temperature, be cooled to 60 ℃ of blowings; No. 5, color and luster (Gardner), acid number 8.2mgKOH/g, hydroxyl value 33.1mgKOH/g.
Embodiment 3
Sorbitol polyoxyethylene ether in the present embodiment (the oxyethane adduct number is 50) is 1: 4 with the mol ratio of tall oil acid.
In reaction kettle, add sorbyl alcohol and the 0.5g catalyst solid Pottasium Hydroxide of 155.7g70% by weight, be warming up to 120 ℃ of vacuum hydro-extractions, collect water; Finish dehydration when the water yield reaches 46.7g, be warmed up to 160 ℃, slowly feed oxyethane 1320g; After polyreaction finishes; Be cooled to 80 ℃, add the neutralization of 0.5g acetic acid, blowing.In 1 liter of four-hole boiling flask, add the above-mentioned sorbitol polyoxyethylene ether of 500g (50), add the 241g tall oil acid, stir adding 2.0g tosic acid down; Heat up again, under 80 ℃ of vacuum states, reacted 2 hours; Heat up gradually, insulation is 4 hours under the reaction conditions of 150 ℃ of temperature, is cooled to 60 ℃ of blowings; No. 5, color and luster (Gardner), acid number 6.6mgKOH/g, hydroxyl value 39.6mgKOH/g.
Embodiment 4
Sorbitol polyoxyethylene ether in the present embodiment (the oxyethane adduct number is 50) is 1: 3 with the mol ratio of tall oil acid.
In reaction kettle,, stir the mixed catalyst that adds 2.7g Witco 1298 Soft Acid and Hypophosporous Acid, 50 down, heat up gradually by sorbitol polyoxyethylene ether (50) and the 145.6g tall oil acid of quality adding 400g embodiment 3; Under 90 ℃ of vacuum outgas states, reacted 2 hours, heat up again; Be insulation 4 hours under 160 ℃ the reaction conditions in temperature, be cooled to 60 ℃ of blowings, No. 6, color and luster (Gardner); Acid number 8.5mgKOH/g, hydroxyl value 27.3mgKOH/g.
The polyreaction equation is in the foregoing description:
Annotate: a+b+c+d+e+f=n n is 20～50
Its dehydration condensation equation is in the foregoing description:
Annotate: a+b+c+d+e+f=20～50, X=3～5, M=H or RCO.
Claims (8)
1. the compound method of a sorbitol polyoxyethylene ether tallate; It is characterized in that: with sorbyl alcohol, oxyethane is raw material; The sorbitol polyoxyethylene ether that under 130～180 ℃, alkaline catalysts, is polymerized, and then be raw material with sorbitol polyoxyethylene ether, tall oil acid, under the effect of organic acid catalyst; Earlier under 70～100 ℃ of low temperature, carry out dehydration condensation; Make active high hydroxyl complete with carboxyl reaction earlier, 130～160 ℃ of temperature reactions make the sorbitol polyoxyethylene ether tallate again.
2. the compound method of a kind of sorbitol polyoxyethylene ether tallate as claimed in claim 1 is characterized in that: the mol ratio of described sorbyl alcohol and oxyethane is 1: 20～50.
3. the compound method of a kind of sorbitol polyoxyethylene ether tallate as claimed in claim 1 is characterized in that: described alkaline catalysts is a kind of in sodium methylate, sodium hydroxide, the Pottasium Hydroxide.
4. the compound method of a kind of sorbitol polyoxyethylene ether tallate as claimed in claim 1 is characterized in that: the add-on of described alkaline catalysts is 0.1～1.0% of a sorbyl alcohol weight.
5. the compound method of a kind of sorbitol polyoxyethylene ether tallate as claimed in claim 1 is characterized in that: the mol ratio of said sorbitol polyoxyethylene ether and tall oil acid can be 1: 3.0～and 5.0.
6. the compound method of a kind of sorbitol polyoxyethylene ether tallate as claimed in claim 1 is characterized in that: described organic acid catalyst is mixture or the mixture of tosic acid and Hypophosporous Acid, 50 or the mixture of Witco 1298 Soft Acid and Hypophosporous Acid, 50 of Witco 1298 Soft Acid and tosic acid.
7. the compound method of a kind of sorbitol polyoxyethylene ether tallate as claimed in claim 1 is characterized in that: the add-on of described organic acid catalyst is 0.2～1.0% of sorbitol polyoxyethylene ether and a tall oil acid gross weight.
8. the compound method of a kind of sorbitol polyoxyethylene ether tallate as claimed in claim 1 is characterized in that: the reaction times of described dehydration condensation is 1～5 hour.
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