CN108467354A - 3,3 '-dithiodipropionic acids are double（Isooctanol ester）Preparation method and applications - Google Patents
3,3 '-dithiodipropionic acids are double（Isooctanol ester）Preparation method and applications Download PDFInfo
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- CN108467354A CN108467354A CN201810308754.1A CN201810308754A CN108467354A CN 108467354 A CN108467354 A CN 108467354A CN 201810308754 A CN201810308754 A CN 201810308754A CN 108467354 A CN108467354 A CN 108467354A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
Abstract
The present invention provides 1 ' dithiodipropionic acid pair（Isooctanol ester）Preparation method and applications, wherein the preparation method includes the following steps：Under the conditions of acidic catalyst, 3,3 ' dithiodipropionic acids and isooctanol reaction are bis- (isooctanol ester) to generate 3,3 ' dithiodipropionic acids.
Description
Technical field
The present invention relates to the field of chemical synthesis, are related to the preparation method of one 3,3'- dithiodipropionic acids bis- (isooctanol esters)
And its application.
Background technology
Antioxidant can effectively inhibit or reduce the speed of oxidation reaction, it will be apparent that improve product such as plastics
The service life of product.
Thioesters antioxidant is one kind in antioxidant, anti-by being used as auxiliary antioxidant and Hinered phenols
Oxidant is used cooperatively, and generates good synergistic effect, is had the effect of preferably preventing oxidation for a long time, is widely used in poly-
In alkene, polystyrene, ABS resin and rubber.
Thioesters antioxidant is environmentally friendly, and existing overwhelming majority thioesters are with natural oil derivative high-carbon
Alcohol is raw material, such as lauryl alcohol (laruyl alcohol), octadecyl alcolol (stearyl alcohol), tetradecyl alchohol (myristyl alcohol) etc..Therefore, thioesters are anti-
80% or so the carbon composition of oxidant derives from renewable resource, develops thio alcohols antioxidant, more meets circular economy
With the theory of sustainable development.
It is noted that the biological safety of thioesters antioxidant is also higher, such as thioesters antioxidant
DLTP can be used as vegetable fat antioxidant, can also be used as antioxidant and makes an addition to and facilitates based food.The prosperities such as Europe, the United States, day
Country allows anti-oxidant DLTP, DSPP to add use in the plastic food packaging materials such as PE, PP, PS, PET, PVC.
The one kind of 3,3 '-dithiodipropionic acids bis- (isooctanol esters) as thioesters antioxidant, works as in industrial production
In can directly as antioxidant use, can also be used as raw material and prepare other thioesters class antioxidants, there is important answer
Use foreground.
Invention content
The present invention's one is designed to provide 1 ' it the preparation method of-dithiodipropionic acid bis- (isooctanol esters) and its answers
With by the preparation method, 3,3 '-dithiodipropionic acids bis- (isooctanol esters) are simple and easy to get.
Another object of the present invention is to provide 1 ' preparation method of-dithiodipropionic acid bis- (isooctanol esters) and its
Using the preparation method has a higher yield, to save cost.
Another object of the present invention is to provide 1 '-dithiodipropionic acid is bis- (isooctanol ester)
It is another object of the present invention to provide 1 ' preparation method of-dithiodipropionic acid bis- (isooctanol esters) and
It is applied, and the preparation method reaction condition is mild, is suitable for large-scale industrial production.
Another object of the present invention is to provide 1 ' preparation method of-dithiodipropionic acid bis- (isooctanol esters) and its
Using the preparation method member easy to operate is easy to spread.
Another object of the present invention is to provide 1 ' preparation method of-dithiodipropionic acid bis- (isooctanol esters) and its
Using the preparation method directly uses raw material as solvent, need not use additional organic solvent.
Another object of the present invention is to provide 1 ' preparation method of-dithiodipropionic acid bis- (isooctanol esters) and its
Using as the raw material of solvent in the preparation method, remaining raw material can be recycled after having reacted.
Another object of the present invention is to provide 1 ' preparation method of-dithiodipropionic acid bis- (isooctanol esters)
According to an aspect of the present invention, in order to reach at least one of foregoing invention purpose, one 3,3 '-two sulphur are provided
For the preparation method of dipropionic acid bis- (isooctanol esters), include the following steps：
Under the conditions of acidic catalyst, 3,3 '-dithiodipropionic acids and isooctanol reaction are to generate 3,3 '-dithio dipropyls
Sour bis- (isooctanol esters).
An embodiment according to the present invention, the acidic catalyst are liquid acidic catalysts.
An embodiment according to the present invention, the acidic catalyst is in the combination concentrated sulfuric acid, phosphoric acid and p-methyl benzenesulfonic acid
It is one or more.
An embodiment according to the present invention, the acidic catalyst are solid catalysts.
An embodiment according to the present invention, the solid catalyst are selected from the acid ion exchange resin of combination, acid particles carclazyte
With it is one or more in zeolite molecular sieve solid.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Molar equivalent ratio=1 of the isooctanol：
1.8~3.0.
An embodiment according to the present invention, the preparation method further comprise following steps：
(a) described 3,3 '-dithiodipropionic acids, the isooctanol and the acidic catalyst are added in a reaction vessel
Agent；With
(b) temperature to reaction is increased to terminate.
An embodiment according to the present invention, the reaction temperature are 80 DEG C~190 DEG C.
An embodiment according to the present invention, further comprises following steps：
(c) aqueous solution that antalkali is added after reaction neutralizes；
(d) water layer is detached after standing；And
(e) the remaining isooctanol is recovered under reduced pressure and show that product 3,3'- dithiodipropionic acids are bis- (isooctanol ester).
An embodiment according to the present invention, in the step (c), the antalkali is selected from combination sodium hydroxide, carbon
Sour sodium, it is one or more in sodium bicarbonate.
Alkaline aqueous solution neutralization is added after being implemented as cooling in an embodiment according to the present invention, the step (c).
An embodiment according to the present invention, addition alkalinity is water-soluble after the step (c) is implemented as 60 DEG C to 70 DEG C of cooling
Liquid neutralizes.
An embodiment according to the present invention, further comprises a step (f), wherein the step (f) includes：
Water is rejoined for the organic layer after separation water layer；With
Organic layer and water layer are detached after stirring in a manner of standing, then detaches water layer, the step (f) is located at the step
Suddenly between (d) and the step (e).
According to another aspect of the present invention, it is bis- (isooctanol ester) that one 3,3 '-dithiodipropionic acids are provided, wherein described 3,
3 '-dithiodipropionic acids are bis- (isooctanol ester), are prepared by any preparation method of the claims.
Specific implementation mode
It is described below for disclosing the present invention so that those skilled in the art can realize the present invention.It is excellent in being described below
Embodiment is selected to be only used as illustrating, it may occur to persons skilled in the art that other obvious modifications.It defines in the following description
The present invention basic principle can be applied to other embodiments, deformation scheme, improvement project, equivalent program and do not carry on the back
Other technologies scheme from the spirit and scope of the present invention.
As used herein, term "comprising", " comprising ", " having " or their any other modification are intended to and cover non-row
His property includes.For example, composition, step, method, product or equipment comprising series of elements are not necessarily limited to those members
Element, and may include other not expressly listed elements or such composition, step, method, product or the intrinsic member of equipment
Element.In addition, unless expressly stated to the contrary, "or" refers to the "or" of inclusive, without referring to exclusive "or".For example,
Following any type situation is satisfied by condition A or B：A is true (or existing) and B is false (or being not present), and A is
False (or be not present) and B is true (or existing) and A and B is true (or existing).Equally, it relates to
And indefinite article of the number of element or component example (things occurred) before element of the present invention or component "one" or " one
Kind " be intended to be non-limiting.Therefore, "one" or "an" should be interpreted as including one or at least one, and element
Or the singulative of component also includes plural number, unless there are digital apparent expression odd number.
Ratio general expression herein is the single number relative to numerical value 1；Such as it refers to 4: 1 that ratio, which is 4,.Term
" equivalent ratio " refers to a kind of equivalents of component (such as alkali) relative to another component being added in reaction mixture, is recognized
Know, certain every mole of compounds can provide two equivalents or more equivalent.The present invention provides a 3,3'- dithiodipropionic acids are double
The preparation method of (isooctanol ester), wherein the preparation method utilizes 3,3 '-dithiodipropionic acids and isooctanol in acidic catalyst
It is bis- (isooctanol ester) that reaction generation product 3,3'- dithiodipropionic acids are carried out under the action of agent.
The preparation method of an embodiment according to the present invention, 3, the 3'- dithiodipropionic acids bis- (isooctanol esters) includes
Following steps：
Under the conditions of acidic catalyst, 3,3 '-dithiodipropionic acids and isooctanol reaction are to generate 3,3 '-dithio dipropyls
Sour bis- (isooctanol esters).
An embodiment according to the present invention, the acidic catalyst are liquid acidic catalysts.
An embodiment according to the present invention, the liquid acidic catalyst are selected from combination sulfuric acid, phosphoric acid and p-methyl benzenesulfonic acid
In it is one or more.
An embodiment according to the present invention, the acidic catalyst are solid catalysts.
An embodiment according to the present invention, the solid catalyst are selected from the acid ion exchange resin of combination, acid particles carclazyte
With it is one or more in zeolite molecular sieve solid.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Molar equivalent ratio=1 of the isooctanol：
1.8~3.0.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The isooctanol：The acidic catalyst
Molar equivalent ratio=1：1.8~3.0：0.04~0.1.
An embodiment according to the present invention, the preparation method further comprise following steps：
(a) described 3,3 '-dithiodipropionic acids, the isooctanol and the acidic catalyst are added in a reaction vessel
Agent；With
(b) temperature to reaction is increased to terminate.
An embodiment according to the present invention, the reaction temperature are 80 DEG C~190 DEG C.
An embodiment according to the present invention, further comprises following steps：
(c) aqueous solution that antalkali is added after reaction neutralizes；
(d) water phase is detached after standing；And
(e) the remaining isooctanol is recovered under reduced pressure and show that product 3,3'- dithiodipropionic acids are bis- (isooctanol ester).
An embodiment according to the present invention, in the step (c), the antalkali is selected from combination sodium hydroxide, carbon
Sour sodium, it is one or more in sodium bicarbonate.
An embodiment according to the present invention is added alkaline aqueous solution in the step (c), after cooling and neutralizes.
An embodiment according to the present invention is added after being cooled to 60 DEG C to 70 DEG C in alkaline aqueous solution in the step (c)
With.
An embodiment according to the present invention, in the step (c), the acidic catalyst：The antalkali is worked as
Measure ratio=1:1~1.2.
An embodiment according to the present invention, further comprises a step (f), wherein the step (f) includes：
Water is rejoined for the organic layer after separation water phase；With
Organic layer and water layer are detached after stirring in a manner of standing, then detaches water layer.The step (f) is located at the step
Suddenly between (d) and the step (e).
In order to preferably illustrate, the present invention provides an embodiment 1A, wherein the embodiment 1A includes the following steps：
Under the conditions of existing for the acidic catalyst concentrated sulfuric acid, 3,3 '-dithiodipropionic acids and isooctanol are reacted to generate 3,
3 '-dithiodipropionic acids are bis- (isooctanol ester).
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Molar equivalent ratio=1 of the isooctanol：
1.8。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Molar equivalent ratio=1 of the isooctanol：
3.0。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Molar equivalent ratio=1 of the isooctanol：
2.0。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Molar equivalent ratio=1 of the isooctanol：
1.8~3.0.
An embodiment according to the present invention, the acidic catalyst are 98% concentrated sulfuric acids.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The isooctanol：Mole of the sulfuric acid
Equivalent proportion=1：1.8：0.04.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The isooctanol：Mole of the sulfuric acid
Equivalent proportion=1：3.0：0.04.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The isooctanol：Mole of the sulfuric acid
Equivalent proportion=1：2.0：0.04.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The isooctanol：Mole of the sulfuric acid
Equivalent proportion=1：1.8：0.1.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The isooctanol：Mole of the sulfuric acid
Equivalent proportion=1：3.0：0.1.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The isooctanol：Mole of the sulfuric acid
Equivalent proportion=1：2.0：0.1.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The isooctanol：Mole of the sulfuric acid
Equivalent proportion=1：1.8~3.0：0.04~0.1.
An embodiment according to the present invention, the preparation method further comprise following steps：
(a) described 3,3 '-dithiodipropionic acids, the isooctanol and the concentrated sulfuric acid are added in a reaction vessel；With
(b) temperature to reaction is increased to terminate.
An embodiment according to the present invention, the reaction temperature are 80 DEG C.
An embodiment according to the present invention, the reaction temperature are 100 DEG C.
An embodiment according to the present invention, the reaction temperature are 190 DEG C.
An embodiment according to the present invention, the reaction temperature are 80~190 DEG C.
An embodiment according to the present invention, further comprises following steps：
(c) aqueous solution that antalkali is added after reaction neutralizes；
(d) water phase is detached after standing；And
(e) the remaining isooctanol is recovered under reduced pressure and show that product 3,3'- dithiodipropionic acids are bis- (isooctanol ester).
An embodiment according to the present invention, in the step (c), the antalkali is selected from combination sodium hydroxide, carbon
Sour sodium, it is one or more in sodium bicarbonate.
An embodiment according to the present invention is added alkaline aqueous solution in the step (c), after cooling and neutralizes.
An embodiment according to the present invention is added alkaline aqueous solution in the step (c), after being cooled to 60 DEG C and neutralizes.
An embodiment according to the present invention is added alkaline aqueous solution in the step (c), after being cooled to 70 DEG C and neutralizes.
An embodiment according to the present invention is added alkaline aqueous solution in the step (c), after being cooled to 65 DEG C and neutralizes.
An embodiment according to the present invention is added after being cooled to 60 DEG C to 70 DEG C in alkaline aqueous solution in the step (c)
With.
An embodiment according to the present invention, in the step (c), the concentrated sulfuric acid：The equivalent proportion of the antalkali
=1:1.
An embodiment according to the present invention, in the step (c), the concentrated sulfuric acid：The equivalent proportion of the antalkali
=2:2.1.
An embodiment according to the present invention, in the step (c), the concentrated sulfuric acid：The equivalent proportion of the antalkali
=1:1.2.
An embodiment according to the present invention, in the step (c), the concentrated sulfuric acid：The equivalent proportion of the antalkali
=1:1~1.2.
An embodiment according to the present invention, further comprises a step (f), wherein the step (f) includes：
Water is rejoined for the organic layer after separation water phase；With
Organic layer and water layer are detached after stirring in a manner of standing, then detaches water layer.The step (f) is located at the step
Suddenly between (d) and the step (e).
Embodiment 1B
Be added 3,3 '-dithiodipropionic acid 60g (0.285mol) into reaction vessel, isooctanol 100g (0.768mol) and
98% concentrated sulfuric acid 2g (0.02mol) of catalyst, wherein 3,3 '-dithiodipropionic acids：Isooctanol：Molar ratio=1 of sulfuric acid:1.8:
0.4.It stirs and is warming up to raw material and be completely dissolved, temperature is kept to terminate to 120 DEG C to reaction.Temperature is reduced to 60 DEG C, is added
10% sodium hydrate aqueous solution of 10g adjusts pH, is stood after being stirred to react.Separation lower layer water phase obtains upper organic phase.Add
Enter deionized water 10g (0.56mol), and stirs 10 minutes.It stands, upper organic phase is obtained after separation lower layer water phase, by subtracting
It pushes back and receives remaining raw material isooctanol, obtain product 3, bis- (isooctanol ester) 112g (0.258mol) of 3'- dithiodipropionic acids, production
Rate 90.3%.
In order to preferably illustrate, the present invention provides an embodiment 2A, wherein the embodiment 2A includes the following steps：
Under the conditions of existing for acidic catalyst phosphoric acid, 3,3 '-dithiodipropionic acids and isooctanol reaction are to generate 3,3 '-
Dithiodipropionic acid is bis- (isooctanol ester).
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Molar equivalent ratio=1 of the isooctanol：
1.8。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Molar equivalent ratio=1 of the isooctanol：
3.0。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Molar equivalent ratio=1 of the isooctanol：
2.0。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Molar equivalent ratio=1 of the isooctanol：
1.8~3.0.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The isooctanol：Mole of the phosphoric acid
Equivalent proportion=1：1.8：0.04.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The isooctanol：Mole of the phosphoric acid
Equivalent proportion=1：3.0：0.04.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The isooctanol：Mole of the phosphoric acid
Equivalent proportion=1：2.0：0.04.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The isooctanol：Mole of the phosphoric acid
Equivalent proportion=1：1.8：0.1.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The isooctanol：Mole of the phosphoric acid
Equivalent proportion=1：3.0：0.1.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The isooctanol：Mole of the phosphoric acid
Equivalent proportion=1：2.0：0.1.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The isooctanol：Mole of the phosphoric acid
Equivalent proportion=1：1.8~3.0：0.04~0.1.
An embodiment according to the present invention, the preparation method further comprise following steps：
(a) described 3,3 '-dithiodipropionic acids, the isooctanol and the phosphoric acid are added in a reaction vessel；With
(b) temperature to reaction is increased to terminate.
An embodiment according to the present invention, the reaction temperature are 80 DEG C.
An embodiment according to the present invention, the reaction temperature are 100 DEG C.
An embodiment according to the present invention, the reaction temperature are 190 DEG C.
An embodiment according to the present invention, the reaction temperature are 80~190 DEG C.
An embodiment according to the present invention, further comprises following steps：
(c) aqueous solution that antalkali is added after reaction neutralizes；
(d) water phase is detached after standing；And
(e) the remaining isooctanol is recovered under reduced pressure and show that product 3,3'- dithiodipropionic acids are bis- (isooctanol ester).
An embodiment according to the present invention, in the step (c), the antalkali is selected from combination sodium hydroxide, carbon
Sour sodium, it is one or more in sodium bicarbonate.
An embodiment according to the present invention is added alkaline aqueous solution in the step (c), after cooling and neutralizes.
An embodiment according to the present invention is added alkaline aqueous solution in the step (c), after being cooled to 60 DEG C and neutralizes.
An embodiment according to the present invention is added alkaline aqueous solution in the step (c), after being cooled to 70 DEG C and neutralizes.
An embodiment according to the present invention is added alkaline aqueous solution in the step (c), after being cooled to 65 DEG C and neutralizes.
An embodiment according to the present invention is added after being cooled to 60 DEG C to 70 DEG C in alkaline aqueous solution in the step (c)
With.
An embodiment according to the present invention, in the step (c), the phosphoric acid：The equivalent proportion of the antalkali=
1:1。
An embodiment according to the present invention, in the step (c), the phosphoric acid：The equivalent proportion of the antalkali=
2:2.1。
An embodiment according to the present invention, in the step (c), the phosphoric acid：The equivalent proportion of the antalkali=
1:1.2。
An embodiment according to the present invention, in the step (c), the phosphoric acid：The equivalent proportion of the antalkali=
1:1~1.2.
An embodiment according to the present invention, further comprises a step (f), wherein the step (f) includes：
Water is rejoined for the organic layer after separation water phase；With
Organic layer and water layer are detached after stirring in a manner of standing, then detaches water layer.The step (f) is located at the step
Suddenly between (d) and the step (e).
Embodiment 1B
Be added 3,3 '-dithiodipropionic acid 60g (0.285mol) into reaction vessel, isooctanol 100g (0.768mol) and
Catalyst phosphoric acid 2g (0.02mol).It stirs and is warming up to raw material and be completely dissolved, temperature is kept to terminate to 120 DEG C to reaction.Drop
For low temperature to 60 DEG C, 10% sodium hydrate aqueous solution that 10g is added adjusts pH, is stood after being stirred to react.Detach lower layer's water phase
Obtain upper organic phase.Deionized water 10g (0.56mol) is added, and stirs 10 minutes.It stands, is obtained after separation lower layer water phase
Upper organic phase obtains product 3,3'- dithiodipropionic acids are bis- (isooctanol ester) by the way that remaining raw material isooctanol is recovered under reduced pressure
112g (0.258mol), yield 90.3%.
In order to preferably illustrate, the present invention provides an embodiment 3A, wherein the embodiment 3A includes the following steps：
Under the conditions of existing for acidic catalyst p-methyl benzenesulfonic acid, 3,3 '-dithiodipropionic acids and isooctanol reaction are with life
It is bis- (isooctanol ester) at 3,3 '-dithiodipropionic acids.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Molar equivalent ratio=1 of the isooctanol：
1.8。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Molar equivalent ratio=1 of the isooctanol：
3.0。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Molar equivalent ratio=1 of the isooctanol：
2.0。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Molar equivalent ratio=1 of the isooctanol：
1.8~3.0.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The isooctanol：The p-methyl benzenesulfonic acid
Molar equivalent ratio=1：1.8：0.04.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The isooctanol：The p-methyl benzenesulfonic acid
Molar equivalent ratio=1：3.0：0.04.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The isooctanol：The p-methyl benzenesulfonic acid
Molar equivalent ratio=1：2.0：0.04.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The isooctanol：The p-methyl benzenesulfonic acid
Molar equivalent ratio=1：1.8：0.1.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The isooctanol：The p-methyl benzenesulfonic acid
Molar equivalent ratio=1：3.0：0.1.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The isooctanol：The p-methyl benzenesulfonic acid
Molar equivalent ratio=1：2.0：0.1.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The isooctanol：The p-methyl benzenesulfonic acid
Molar equivalent ratio=1：1.8~3.0：0.04~0.1.
An embodiment according to the present invention, the preparation method further comprise following steps：
(a) described 3,3 '-dithiodipropionic acids are added in a reaction vessel, the isooctanol and described to toluene sulphur
Acid；With
(b) temperature to reaction is increased to terminate.
An embodiment according to the present invention, the reaction temperature are 80 DEG C.
An embodiment according to the present invention, the reaction temperature are 100 DEG C.
An embodiment according to the present invention, the reaction temperature are 190 DEG C.
An embodiment according to the present invention, the reaction temperature are 80~190 DEG C.
An embodiment according to the present invention, further comprises following steps：
(c) aqueous solution that antalkali is added after reaction neutralizes；
(d) water phase is detached after standing；And
(e) the remaining isooctanol is recovered under reduced pressure and show that product 3,3'- dithiodipropionic acids are bis- (isooctanol ester).
An embodiment according to the present invention, in the step (c), the antalkali is selected from combination sodium hydroxide, carbon
Sour sodium, it is one or more in sodium bicarbonate.
An embodiment according to the present invention is added alkaline aqueous solution in the step (c), after cooling and neutralizes.
An embodiment according to the present invention is added alkaline aqueous solution in the step (c), after being cooled to 60 DEG C and neutralizes.
An embodiment according to the present invention is added alkaline aqueous solution in the step (c), after being cooled to 70 DEG C and neutralizes.
An embodiment according to the present invention is added alkaline aqueous solution in the step (c), after being cooled to 65 DEG C and neutralizes.
An embodiment according to the present invention is added after being cooled to 60 DEG C to 70 DEG C in alkaline aqueous solution in the step (c)
With.
An embodiment according to the present invention, in the step (c), the p-methyl benzenesulfonic acid：The antalkali is worked as
Measure ratio=1:1.
An embodiment according to the present invention, in the step (c), the p-methyl benzenesulfonic acid：The antalkali is worked as
Measure ratio=2:2.1.
An embodiment according to the present invention, in the step (c), the p-methyl benzenesulfonic acid：The antalkali is worked as
Measure ratio=1:1.2.
An embodiment according to the present invention, in the step (c), the p-methyl benzenesulfonic acid：The antalkali is worked as
Measure ratio=1:1~1.2.
An embodiment according to the present invention, further comprises a step (f), wherein the step (f) includes：
Water is rejoined for the organic layer after separation water phase；With
Organic layer and water layer are detached after stirring in a manner of standing, then detaches water layer.The step (f) is located at the step
Suddenly between (d) and the step (e).
Embodiment 3B
Be added 3,3 '-dithiodipropionic acid 60g (0.285mol) into reaction vessel, isooctanol 100g (0.768mol) and
Catalyst p-methyl benzenesulfonic acid 2g (0.012mol).It stirs and is warming up to raw material and be completely dissolved, temperature is kept extremely to be reacted to 130 DEG C
Terminate.Temperature is reduced to 50 DEG C, 10% sodium hydrate aqueous solution that 10g is added adjusts pH, is stood after being stirred to react.Under separation
Layer water phase obtains upper organic phase.Deionized water 10g (0.56mol) is added, and stirs 10 minutes.It stands, separation lower layer water phase
After obtain upper organic phase, by the way that remaining raw material isooctanol is recovered under reduced pressure, obtain product 3,3'- dithiodipropionic acids are bis- (different
Octanol ester) 112g (0.258mol), yield 90.3%.
In order to preferably illustrate, the present invention provides an embodiment 4A, wherein the embodiment 4A includes the following steps：
Under the conditions of existing for acid ion resin, 3,3 '-dithiodipropionic acids and isooctanol reaction are to generate 3,3 '-two
Thio-2 acid is bis- (isooctanol ester).
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Molar equivalent ratio=1 of the isooctanol：
1.8。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Molar equivalent ratio=1 of the isooctanol：
3.0。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Molar equivalent ratio=1 of the isooctanol：
2.0。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Molar equivalent ratio=1 of the isooctanol：
1.8~3.0.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The mass ratio of the acid ion resin=
1:0.1。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The mass ratio of the acid ion resin=
1:0.2。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The mass ratio of the acid ion resin=
1:0.3。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The mass ratio of the acid ion resin=
1:0.5。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The mass ratio of the acid ion resin=
1:0.1~0.5.
An embodiment according to the present invention, the acid ion resin are selected from combination strong-acid ion exchange resin DH, 732
With it is one or more in large hole cation exchanger resin Amberlystl5, D72.
Using acid ion resin as catalyst, equipment will not be caused to corrode, and catalyst can also repeat to make
With.
An embodiment according to the present invention, the preparation method further comprise following steps：
(a) described 3,3 '-dithiodipropionic acids, the isooctanol and the acid ion tree are added in a reaction vessel
Fat；With
(b) temperature to reaction is increased to terminate.
An embodiment according to the present invention, the reaction temperature are 80 DEG C.
An embodiment according to the present invention, the reaction temperature are 100 DEG C.
An embodiment according to the present invention, the reaction temperature are 190 DEG C.
An embodiment according to the present invention, the reaction temperature are 80~190 DEG C.
An embodiment according to the present invention, further comprises following steps：
(c) aqueous solution that antalkali is added after reaction neutralizes；
(d) water phase is detached after standing；And
(e) the remaining isooctanol is recovered under reduced pressure and show that product 3,3'- dithiodipropionic acids are bis- (isooctanol ester).
An embodiment according to the present invention, the step (c) are implemented as：
Cooled and filtered acidity of catalyst ion exchange resin；With
Antalkali is added in filtrate.
An embodiment according to the present invention, in the step (c), the antalkali is selected from combination sodium hydroxide, carbon
Sour sodium, it is one or more in sodium bicarbonate.
An embodiment according to the present invention is added alkaline aqueous solution in the step (c), after cooling and neutralizes.
An embodiment according to the present invention is added alkaline aqueous solution in the step (c), after being cooled to 60 DEG C and neutralizes.
An embodiment according to the present invention is added alkaline aqueous solution in the step (c), after being cooled to 70 DEG C and neutralizes.
An embodiment according to the present invention is added alkaline aqueous solution in the step (c), after being cooled to 65 DEG C and neutralizes.
An embodiment according to the present invention is added after being cooled to 60 DEG C to 70 DEG C in alkaline aqueous solution in the step (c)
With.
An embodiment according to the present invention, further comprises a step (f), wherein the step (f) includes：
Water is rejoined for the organic layer after separation water phase；With
Organic layer and water layer are detached after stirring in a manner of standing, then detaches water layer.The step (f) is located at the step
Suddenly between (d) and the step (e).
Embodiment 4B
Be added 3,3 '-dithiodipropionic acid 60g (0.285mol) into reaction vessel, isooctanol 100g (0.768mol) and
Acidity of catalyst ion exchange resin 18g.It stirs and is warming up to raw material and be completely dissolved, temperature is kept to terminate to 120 DEG C to reaction.Drop
The 10% sodium hydrate aqueous solution tune of 10g is added to 60 DEG C in low temperature in filtrate after filtration catalytic agent acid ion resin
PH is saved, is stood after being stirred to react.Separation lower layer water phase obtains upper organic phase.Deionized water 10g (0.56mol) is added, and stirs
It mixes 10 minutes.It stands, obtains upper organic phase after separation lower layer water phase, by the way that remaining raw material isooctanol is recovered under reduced pressure, obtain
Product 3, bis- (isooctanol ester) 100g (0.230mol) of 3'- dithiodipropionic acids, yield 80.6%.
In order to preferably illustrate, the present invention provides an embodiment 5A, wherein the embodiment 5A includes the following steps：
Under the conditions of existing for acidic molecular sieve, 3,3 '-dithiodipropionic acids and isooctanol reaction are to generate 3,3 '-two sulphur
It is bis- (isooctanol ester) for dipropionic acid.
An embodiment according to the present invention, the acidic molecular screened from combination HZSM-5, Hbeta, HM in one kind or
It is a variety of.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Molar equivalent ratio=1 of the isooctanol：
1.8。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Molar equivalent ratio=1 of the isooctanol：
3.0。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Molar equivalent ratio=1 of the isooctanol：
2.0。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Molar equivalent ratio=1 of the isooctanol：
1.8~3.0.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Mass ratio=1 of the acidic molecular sieve:
0.1。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Mass ratio=1 of the acidic molecular sieve:
0.02。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Mass ratio=1 of the acidic molecular sieve:
0.03。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Mass ratio=1 of the acidic molecular sieve:
0.05。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Mass ratio=1 of the acidic molecular sieve:
0.05~0.1.
An embodiment according to the present invention, the preparation method further comprise following steps：
(a) described 3,3 '-dithiodipropionic acids, the isooctanol and the acidic molecular are added in a reaction vessel
Sieve；With
(b) temperature to reaction is increased to terminate.
An embodiment according to the present invention, the reaction temperature are 110 DEG C.
An embodiment according to the present invention, the reaction temperature are 190 DEG C.
An embodiment according to the present invention, the reaction temperature are 110~190 DEG C.
An embodiment according to the present invention, further comprises following steps：
(c) aqueous solution that antalkali is added after reaction neutralizes；
(d) water phase is detached after standing；And
(e) the remaining isooctanol is recovered under reduced pressure and show that product 3,3'- dithiodipropionic acids are bis- (isooctanol ester).
An embodiment according to the present invention, the step (c) are implemented as：
Cooled and filtered acidity of catalyst molecular sieve；With
Antalkali is added in filtrate.
An embodiment according to the present invention, in the step (c), the antalkali is selected from combination sodium hydroxide, carbon
Sour sodium, it is one or more in sodium bicarbonate.
An embodiment according to the present invention is added alkaline aqueous solution in the step (c), after cooling and neutralizes.
An embodiment according to the present invention is added alkaline aqueous solution in the step (c), after being cooled to 60 DEG C and neutralizes.
An embodiment according to the present invention is added alkaline aqueous solution in the step (c), after being cooled to 70 DEG C and neutralizes.
An embodiment according to the present invention is added alkaline aqueous solution in the step (c), after being cooled to 65 DEG C and neutralizes.
An embodiment according to the present invention is added after being cooled to 60 DEG C to 70 DEG C in alkaline aqueous solution in the step (c)
With.
An embodiment according to the present invention, further comprises a step (f), wherein the step (f) includes：
Water is rejoined for the organic layer after separation water phase；With
Organic layer and water layer are detached after stirring in a manner of standing, then detaches water layer.The step (f) is located at the step
Suddenly between (d) and the step (e).
According to embodiment 5B provided by the invention, wherein the embodiment 5B is implemented as：
Be added 3,3 '-dithiodipropionic acid 60g (0.285mol) into reaction vessel, isooctanol 100g (0.768mol) and
Acidity of catalyst molecular sieve 6g.It stirs and is warming up to raw material and be completely dissolved, temperature is kept to terminate to 120 DEG C to reaction.It reduces
For temperature to 60 DEG C, 10% sodium bicarbonate aqueous solution that 10g is added adjusts pH, is stood after being stirred to react.Separation lower layer water phase obtains
Go out upper organic phase.Deionized water 10g (0.56mol) is added, and stirs 10 minutes.It stands, is obtained after separation lower layer water phase
Layer organic phase obtains product 3,3'- dithiodipropionic acids are bis- (isooctanol ester) by the way that remaining raw material isooctanol is recovered under reduced pressure
115g (0.265mol), yield 92.7%.
In order to preferably illustrate, the present invention provides an embodiment 6A, wherein the embodiment 6A includes the following steps：
Under the conditions of existing for acid particles carclazyte, 3,3 '-dithiodipropionic acids and isooctanol reaction are to generate 3,3 '-two
Thio-2 acid is bis- (isooctanol ester).
An embodiment according to the present invention, the acid particles carclazyte are the catalyst that load has phosphotungstic acid.
An embodiment according to the present invention, the acid particles carclazyte are the catalyst that load has Lewis acid.
An embodiment according to the present invention, the acid particles carclazyte, which is load, Zn2+, H+, Ni+, Fe2+, Al3+, Mg2+
Solid acid catalyst.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Molar equivalent ratio=1 of the isooctanol：
1.8。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Molar equivalent ratio=1 of the isooctanol：
3.0。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Molar equivalent ratio=1 of the isooctanol：
2.0。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Molar equivalent ratio=1 of the isooctanol：
1.8~3.0.
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The mass ratio of the acid particles carclazyte=
1:0.1。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The mass ratio of the acid particles carclazyte=
1:0.02。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The mass ratio of the acid particles carclazyte=
1:0.03。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：The mass ratio of the acid particles carclazyte=
1:0.05。
An embodiment according to the present invention, described 3,3 '-dithiodipropionic acids：Mass ratio=1 of the acidic molecular sieve:
0.05~0.1.
An embodiment according to the present invention, the preparation method further comprise following steps：
(a) described 3,3 '-dithiodipropionic acids are added in a reaction vessel, the isooctanol and the acid particles are white
Soil；With
(b) temperature to reaction is increased to terminate.
An embodiment according to the present invention, the reaction temperature are 80 DEG C.
An embodiment according to the present invention, the reaction temperature are 100 DEG C.
An embodiment according to the present invention, the reaction temperature are 190 DEG C.
An embodiment according to the present invention, the reaction temperature are 80~190 DEG C.
An embodiment according to the present invention, further comprises following steps：
(c) aqueous solution that antalkali is added after reaction neutralizes；
(d) water phase is detached after standing；And
(e) the remaining isooctanol is recovered under reduced pressure and show that product 3,3'- dithiodipropionic acids are bis- (isooctanol ester).
An embodiment according to the present invention, the step (c) are implemented as：
Cooled and filtered acidity of catalyst granular carclazyte；With
Antalkali is added in filtrate.
An embodiment according to the present invention, in the step (c), the antalkali is selected from combination sodium hydroxide, carbon
Sour sodium, it is one or more in sodium bicarbonate.
An embodiment according to the present invention is added alkaline aqueous solution in the step (c), after cooling and neutralizes.
An embodiment according to the present invention is added alkaline aqueous solution in the step (c), after being cooled to 60 DEG C and neutralizes.
An embodiment according to the present invention is added alkaline aqueous solution in the step (c), after being cooled to 70 DEG C and neutralizes.
An embodiment according to the present invention is added alkaline aqueous solution in the step (c), after being cooled to 65 DEG C and neutralizes.
An embodiment according to the present invention is added after being cooled to 60 DEG C to 70 DEG C in alkaline aqueous solution in the step (c)
With.
An embodiment according to the present invention, further comprises a step (f), wherein the step (f) includes：
Water is rejoined for the organic layer after separation water phase；With
Organic layer and water layer are detached after stirring in a manner of standing, then detaches water layer.The step (f) is located at the step
Suddenly between (d) and the step (e).
For example, the present invention provides an embodiment 6B.
Be added 3,3 '-dithiodipropionic acid 60g (0.285mol) into reaction vessel, isooctanol 100g (0.768mol) and
Acidity of catalyst granular carclazyte 3g.It stirs and is warming up to raw material and be completely dissolved, temperature is kept to terminate to 120 DEG C to reaction.Drop
10% aqueous sodium carbonate of 15g is added to 60 DEG C in low temperature in filtrate after filtration residue acidity of catalyst granular carclazyte
PH is adjusted, is stood after being stirred to react.Separation lower layer water phase obtains upper organic phase.Deionized water 10g (0.56mol) is added, and
Stirring 10 minutes.It stands, obtains upper organic phase after separation lower layer water phase, by the way that remaining raw material isooctanol is recovered under reduced pressure, obtain
To product 3, bis- (isooctanol ester) 109g (0.251mol) of 3'- dithiodipropionic acids, yield 87.9%.
It should be understood by those skilled in the art that the embodiment of the present invention shown in foregoing description be only used as citing and and it is unlimited
The system present invention.The purpose of the present invention has been fully and effectively achieved.The function and structural principle of the present invention is in embodiment
Displaying and explanation, under without departing from the principle, embodiments of the present invention can have any deformation or modification.
Claims (14)
1. the preparation method of one 3,3 '-dithiodipropionic acids bis- (isooctanol esters), which is characterized in that include the following steps：
Under the conditions of acidic catalyst, 3,3 '-dithiodipropionic acids and isooctanol reaction are double to generate 3,3 '-dithiodipropionic acids
(isooctanol ester).
2. preparation method according to claim 1, wherein the acidic catalyst is liquid acidic catalyst.
3. preparation method according to claim 2, wherein the acidic catalyst is selected from the combination concentrated sulfuric acid, phosphoric acid and to first
It is one or more in benzene sulfonic acid.
4. preparation method according to claim 1, wherein the acidic catalyst is solid catalyst.
5. preparation method according to claim 4, wherein the solid catalyst is selected from the acid ion exchange resin of combination, acidity
It is one or more in granular carclazyte and zeolite molecular sieve solid.
6. preparation method according to claim 1, wherein described 3,3 '-dithiodipropionic acids：Mole of the isooctanol
Equivalent proportion=1：1.8~3.0.
7. preparation method according to claim 1, wherein the preparation method further comprises following steps：
(a) described 3,3 '-dithiodipropionic acids, the isooctanol and the acidic catalyst are added in a reaction vessel；With
(b) temperature to reaction is increased to terminate.
8. preparation method according to claim 7, wherein the reaction temperature is 80 DEG C~190 DEG C.
9. preparation method according to claim 7, further comprises following steps：
(c) aqueous solution that antalkali is added after reaction neutralizes；
(d) water layer is detached after standing；And
(e) the remaining isooctanol is recovered under reduced pressure and show that product 3,3'- dithiodipropionic acids are bis- (isooctanol ester).
10. preparation method according to claim 9, wherein in the step (c), the antalkali is selected from combination hydrogen
Sodium oxide molybdena, sodium carbonate are one or more in sodium bicarbonate.
11. preparation method according to claim 9, wherein addition alkalinity is water-soluble after the step (c) is implemented as cooling
Liquid neutralizes.
12. preparation method according to claim 9, wherein the step (c) adds after being implemented as 60 DEG C to 70 DEG C of cooling
Enter alkaline aqueous solution neutralization.
13. preparation method according to claim 9 further comprises a step (f), wherein the step (f) includes：
Water is rejoined for the organic layer after separation water layer；With
Organic layer and water layer are detached after stirring in a manner of standing, then detaches water layer, the step (f) is located at the step
(d) between the step (e).
14. one 3,3 '-dithiodipropionic acids are bis- (isooctanol ester), which is characterized in that any described by claim 1 to 13
Preparation method is prepared.
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| CN1651411A (en) * | 2004-11-23 | 2005-08-10 | 中国海洋大学 | Ester derivative of indole, its preparation method and application |
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| US4707440A (en) * | 1984-01-30 | 1987-11-17 | Enzo Biochem, Inc. | Nucleic acid hybridization assay and detectable molecules useful in such assay |
| CN1651411A (en) * | 2004-11-23 | 2005-08-10 | 中国海洋大学 | Ester derivative of indole, its preparation method and application |
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