CN108745198A - Castor oil-base quaternary ammonium salt emulsifier and preparation method thereof - Google Patents
Castor oil-base quaternary ammonium salt emulsifier and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of castor oil-base quaternary ammonium salt emulsifiers and preparation method thereof, it is related to emulsifier industrial technical field, castor oil-base quaternary ammonium salt emulsifier provided by the invention is mainly by castor oil and N, and N- dimethylethanolamines are in ionic-liquid catalyst [Hmim] HSO4Under the action of carry out ester exchange reaction obtain castor oil-base amide first, gained castor oil-base amide is then carried out quaternization reaction again is made.Castor oil-base quaternary ammonium salt emulsifier of the present invention with it is existing it is traditional using chemical organic compounds compared with quaternary ammonium salt emulsifier made from raw material, application of the present invention can regenerated castor-oil plants be largely raw material, castor oil-base quaternary ammonium salt emulsifier is obtained by chemical modification method, it has been effectively relieved in existing conventional quaternary ammonium salts synthetic method and has often related to a large amount of harmful organic matters and organic solvent, the problem of being easy to pollute the environment.
Description
Technical field
The present invention relates to emulsifier industrial technical fields, more particularly, to a kind of castor oil-base quaternary ammonium salt emulsifier and its system
Preparation Method.
Background technology
Quaternary ammonium salt emulsifier is in cationic emulsifier using most a kind of extensively.The property of quaternary emulsifier with it is inorganic
Ammonia salt is similar, no matter exists in the form of quaternary ammonium ion in acid, neutral, alkaline solution, therefore application range is most wide.It with
Other types emulsifier has good compatibility, can have excellent anti-microbial property with the compounding of anion emulsifier.This
Outside, quaternary ammonium salt emulsifier may be constructed letting out for charge by the ionic adsorption of ionogen or polar group in the surface of solids
Channel is leaked, anlistatig purpose is reached.One kind breast that quaternary ammonium salt cationic emulsifier is maximum as current production rate, purposes is most wide
Agent, new structural exploitation and its research of application performance always are hot spot of people's attention.
Castor oil is important industrial chemicals, is widely used in production senior lubricant, paint, coating, soap, ink, helps
Stain, plasticizer, polyurethane and emulsifier etc..With the appearance of energy crisis, plant oil base emulsifier is prepared using vegetable oil
It has been be widely popularized that, in the selection of each vegetable oil, castor oil receives favor because of its unique chemical constitution.Therefore, by
Have been widely used and higher economic value in castor oil tool, occupies an important position in national economy, especially working as
When this life boundary stone pasta faces depleted crisis, the castor-oil plant as plant source oil plant is since it is with the important of sustainable production
Value, is just being increasingly subject to the attention of countries in the world, industrial prospect is boundless.
Synthesis quaternary ammonium salt uses first amidation, rear quaternized process route mostly both at home and abroad at present.Wherein synthesize quaternary ammonium
The committed step of salt is amidation process, and rough technique is first synthctic fat isoxazolecarboxylic acid, then carries out amidation process with amine；Or
First synthesizing fatty acid methyl ester, then carry out amidation process with amine.But the catalytic efficiency that the above method has catalyst is relatively low,
Need to consume that a large amount of organic reagent, complex process are cumbersome, and the reaction time is longer and product yield is more low in reaction process
Problem is unfavorable for realizing the industrialization large-scale production of castor oil-base quaternary ammonium salt emulsifier.
Therefore, it using renewable resource is that raw material is prepared to research and develop a kind of, has simple production process, at
The quaternary ammonium salt emulsifier for the advantages that this is cheap, and reaction required time is short, and then the method for alleviating existing conventional synthesis quaternary ammonium salt
Middle catalytic efficiency is low, while a large amount of harmful organic solvents involved in preparation process, the problem of being easy to pollute the environment, becomes
It obtains very necessary and urgent.
In view of this, special propose the present invention.
Invention content
The first object of the present invention is to provide a kind of castor oil-base quaternary ammonium salt emulsifier, the castor oil-base quaternary ammonium salt breast
Agent with it is existing it is traditional using chemical organic compounds compared with quaternary ammonium salt emulsifier made from raw material, the present invention is with can be a large amount of regenerated
Castor-oil plant is raw material, and castor oil-base quaternary ammonium salt emulsifier is obtained by chemical modification method, and existing synthesis quaternary ammonium salt has been effectively relieved
Conventional method involved in a large amount of harmful organic matters and organic solvent, be easy the defect polluted the environment.
The second object of the present invention is to provide a kind of preparation method of castor oil-base quaternary ammonium salt emulsifier, this method production
Simple process and low cost is honest and clean, the time required to reaction than in the prior art using first amidation again quaternized required time shorten 4~
For 24 hours, the reaction time is highly shortened, has saved production cost, and the yield of product is higher (up to 90.44%), carries
The high economic benefit of castor-oil plant industry, is advantageously implemented the industrialization large-scale production of castor oil-base quaternary ammonium salt emulsifier.
A kind of castor oil-base quaternary ammonium salt emulsifier provided by the invention, the castor oil-base quaternary ammonium salt emulsifier is mainly by castor
Sesame oil and N, N- dimethylethanolamines are in ionic-liquid catalyst [Hmim] HSO4Under the action of carry out ester exchange reaction first
To castor oil-base amide, gained castor oil-base amide is then subjected to quaternization reaction again and is made.
Further, the molal weight of the N, N- dimethylethanolamine and castor oil ratio is 2~8:1.
Further, ionic-liquid catalyst [Hmim] HSO4Addition be castor-oil plant weight of oil 5~20%.
Further, the ester exchange reaction is to be stirred to react 2~10h under conditions of 60~80 DEG C.
Further, the quaternizing agent of the quaternization reaction is epoxychloropropane.
Further, the molal weight ratio of the epoxychloropropane and castor oil-base amide is 1~4:1.
Further, the quaternization reaction is that castor oil-base amide is first heated to 45~50 DEG C, and epoxy chlorine is added
Propane is then stirred to react 1~2h at 40~60 DEG C, obtains castor oil-base quaternary ammonium salt emulsifier.
A kind of preparation method of castor oil-base quaternary ammonium salt emulsifier provided by the invention includes the following steps：
(a) first, by castor oil and N, N- dimethylethanolamines are with 2~8:1 molal weight ratio is mixed, and is added
Account for ionic-liquid catalyst [Hmim] HSO of castor-oil plant weight of oil 5~20%4, then 2 are stirred to react under conditions of 60~80 DEG C
~10h, separation and recovery obtain castor oil-base amide；
(b) the castor oil-base amide that separation and recovery obtains is heated to 45~50 DEG C, epoxychloropropane is added, then 40
It is stirred to react 1~2h at~60 DEG C, obtains castor oil-base quaternary ammonium salt emulsifier.
Further, the method for step (a) the castor oil-base amide separation and recovery is：It stands and divides after being stirred to react
Layer, and castor oil-base quaternary ammonium salt is dried to obtain after supernatant is washed.
Further, the preparation method further includes dividing the castor oil-base quaternary ammonium salt emulsifier that step (b) obtains
The step of from purifying；
Preferably, described the step of being isolated and purified to castor oil-base quaternary ammonium salt emulsifier, is：It is anti-in step (b) stirring
Should after stratification, take the faint yellow turbid in upper layer, n-hexane be used in combination to remove excess epoxy chloropropane in the turbid of upper layer, dry castor
Sesame oil based quaternary ammonium salt emulsifier.
Compared with prior art, beneficial effects of the present invention are：
Castor oil-base quaternary ammonium salt emulsifier provided by the invention is mainly by castor oil and N, and N- dimethylethanolamines are in ion
Liquid catalyst [Hmim] HSO4Under the action of carry out ester exchange reaction obtain castor oil-base amide first, then by gained castor-oil plant
Oil base amide carries out quaternization reaction and is made again.Castor oil-base quaternary ammonium salt emulsifier of the present invention with it is existing it is traditional with chemistry it is organic
Object is that quaternary ammonium salt emulsifier made from raw material is compared, the present invention using can a large amount of regenerated castor-oil plants as raw material, by chemical modification side
Method obtains castor oil-base quaternary ammonium salt emulsifier, has been effectively relieved involved in the conventional method of existing synthesis quaternary ammonium salt to a large amount of harmful
Organic matter and organic solvent, be easy the defect polluted the environment.
The preparation method simple production process of castor oil-base quaternary ammonium salt emulsifier provided by the invention, of low cost, reaction
Required time than in the prior art using first amidation again quaternized required time shorten 4~for 24 hours, when highly shortened reaction
Between, production cost is saved, and the yield of product is higher (up to 90.44%), improves the economic benefit of castor-oil plant industry,
It is advantageously implemented the industrialization large-scale production of castor oil-base quaternary ammonium salt emulsifier.
Description of the drawings
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art are briefly described, it should be apparent that, in being described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, other drawings may also be obtained based on these drawings.
Fig. 1 is the production technological process of castor oil-base quaternary ammonium salt emulsifier provided by the invention；
Fig. 2 is the liquid chromatography mass combination figure for the castor oil-base amide that the embodiment of the present invention 4 provides；
Fig. 3 is the mass spectrogram for the castor oil-base amide that the embodiment of the present invention 4 provides；
Fig. 4 is the infrared spectrogram for the castor oil-base amide that the embodiment of the present invention 4 provides；
Fig. 5 is the liquid chromatography mass combination figure for the castor oil-base quaternary ammonium salt that the embodiment of the present invention 9 provides；
Fig. 6 is the mass spectrogram for the castor oil-base quaternary ammonium salt that the embodiment of the present invention 9 provides；
Fig. 7 is the infrared spectrogram for the castor oil-base quaternary ammonium salt that the embodiment of the present invention 9 provides；
Fig. 8 is the surface tension for the castor oil-base quaternary ammonium salt that the embodiment of the present invention 9 provides.
Specific implementation mode
Technical scheme of the present invention is clearly and completely described below in conjunction with attached drawing, it is clear that described implementation
Example is a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill
The every other embodiment that personnel are obtained without making creative work, shall fall within the protection scope of the present invention.
As shown in Figure 1, according to an aspect of the present invention, a kind of castor oil-base quaternary ammonium salt emulsifier, the castor oil-base
Quaternary ammonium salt emulsifier is mainly by castor oil and N, and N- dimethylethanolamines are in ionic-liquid catalyst [Hmim] HSO4Under the action of
It carries out ester exchange reaction and obtains castor oil-base amide first, gained castor oil-base amide is then subjected to quaternization reaction system again
?.
Preferably, ionic-liquid catalyst [Hmim] HSO4It is made by the concentrated sulfuric acid and N- methylimidazoles.
Castor oil-base quaternary ammonium salt emulsifier provided by the invention is mainly by castor oil and N, and N- dimethylethanolamines are in ion
Liquid catalyst [Hmim] HSO4Under the action of carry out ester exchange reaction obtain castor oil-base amide first, then by gained castor-oil plant
Oil base amide carries out quaternization reaction and is made again.Castor oil-base quaternary ammonium salt emulsifier of the present invention with it is existing it is traditional with chemistry it is organic
Object is that quaternary ammonium salt emulsifier made from raw material is compared, the present invention using can a large amount of regenerated castor-oil plants as raw material, by chemical modification side
Method obtains castor oil-base quaternary ammonium salt emulsifier, has been effectively relieved involved in the conventional method of existing synthesis quaternary ammonium salt to a large amount of harmful
Organic matter and organic solvent, be easy the defect polluted the environment.
In the preferred embodiment of the present invention, the molal weight of the N, N- dimethylethanolamine and castor oil ratio
It is 2~8:1.
Preferably, the molal weight of above-mentioned N, N- dimethylethanolamine and castor oil ratio is 4~8：1.
It is furthermore preferred that the molal weight of above-mentioned N, N- dimethylethanolamine and castor oil ratio is 6:1.
In the preferred embodiment of the present invention, ionic-liquid catalyst [Hmim] HSO4Addition be castor
The 5~20% of sesame oil weight.
Preferably, above-mentioned ionic-liquid catalyst [Hmim] HSO4Addition be castor-oil plant weight of oil 10~20%.
It is furthermore preferred that above-mentioned ionic-liquid catalyst [Hmim] HSO4Addition be castor-oil plant weight of oil 8%.
In the preferred embodiment of the present invention, the ester exchange reaction is to be stirred anti-under conditions of 60~80 DEG C
Answer 2~10h.
In the present invention, the temperature of above-mentioned ester exchange reaction it is typical but it is non-limiting for 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C and
80℃。
In the preferred embodiment of the present invention, the quaternizing agent of the quaternization reaction is epoxychloropropane.
In above-mentioned preferred embodiment, the molal weight ratio of the epoxychloropropane and castor oil-base amide is 1~4:
1。
Preferably, the molal weight ratio of above-mentioned epoxychloropropane and castor oil-base amide is 2~3：1.
In above-mentioned preferred embodiment, the quaternization reaction is that castor oil-base amide is first heated to 45~50 DEG C,
Epoxychloropropane is added, is then stirred to react 1~2h at 40~60 DEG C, obtains castor oil-base quaternary ammonium salt emulsifier.
Preferably, the quaternization reaction is that castor oil-base amide is first heated to 45 DEG C, epoxychloropropane is added, then
It is stirred to react 1h at 50 DEG C, obtains castor oil-base quaternary ammonium salt emulsifier.
According to an aspect of the present invention, a kind of preparation method of castor oil-base quaternary ammonium salt emulsifier includes the following steps：
(a) first, by castor oil and N, N- dimethylethanolamines are with 2~8:1 molal weight ratio is mixed, and is added
Ionic-liquid catalyst [Hmim] HSO4 for accounting for castor-oil plant weight of oil 5~20%, is then stirred to react 2 under conditions of 60~80 DEG C
~10h, separation and recovery obtain castor oil-base amide；
(b) the castor oil-base amide that separation and recovery obtains is heated to 45~50 DEG C, epoxychloropropane is added, then 40
It is stirred to react 1~2h at~60 DEG C, obtains castor oil-base quaternary ammonium salt emulsifier；
The molal weight ratio of the epoxychloropropane and castor oil-base amide is 1~4:1.
The preparation method simple production process of castor oil-base quaternary ammonium salt emulsifier provided by the invention, of low cost, reaction
Required time than in the prior art using first amidation again quaternized required time shorten 4~for 24 hours, when highly shortened reaction
Between, production cost is saved, and the yield of product is higher (up to 90.44%), improves the economic benefit of castor-oil plant industry,
It is advantageously implemented the industrialization large-scale production of castor oil-base quaternary ammonium salt emulsifier.
In the preferred embodiment of the present invention, the method for step (a) the castor oil-base amide separation and recovery is：
The stratification after being stirred to react, and dry 10~15h after supernatant is washed and obtain castor oil-base quaternary ammonium salt.
In the preferred embodiment of the present invention, the preparation method further includes the castor oil obtained to step (b)
The step of based quaternary ammonium salt emulsifier is isolated and purified；
Preferably, described the step of being isolated and purified to castor oil-base quaternary ammonium salt emulsifier, is：It is anti-in step (b) stirring
Should after stratification, take the faint yellow turbid in upper layer, n-hexane be used in combination to remove excess epoxy chloropropane in the turbid of upper layer, dry castor
Sesame oil based quaternary ammonium salt emulsifier.
Preferably, drying of the present invention is vacuum drying.
In the preferred embodiment of the present invention, before the step (a), castor oil is purified, is removed
Water in castor oil and other solvents.
In the preferred embodiment of the present invention, the specific system of castor oil-base quaternary ammonium salt emulsifier provided by the invention
Preparation Method includes：
By castor oil by being evaporated under reduced pressure, the water in castor oil and other solvents are removed, then by processed castor-oil plant
Oil is added in the four-hole boiling flask with mechanical stirring device, and N, N- dimethylethanolamines and ionic-liquid catalyst is added
[Hmim]HSO4, reacted 2-10 hours at 60-80 DEG C, be then allowed to stand layering, the ionic-liquid catalyst of lower layer can carry out
It recycles and reuses, takes supernatant, and hereafter supernatant is mostly dried in vacuo using water washing, obtain castor oil-base amide,
The molal weight of middle N, N- dimethylethanolamine and castor oil ratio is 2~8:1, the dosage of catalyst is the 5- of castor-oil plant weight of oil
20%；
Obtained castor oil-base amide is added in the four-hole boiling flask with agitating device again, after being heated to 48 DEG C, is added
Enter epoxychloropropane, reacted 1-2 hours at 40-55 DEG C, stratification takes supernatant, takes the faint yellow turbid in upper layer, upper layer light
Yellow turbid n-hexane removes excess epoxy chloropropane, and vacuum drying obtains castor oil-base quaternary ammonium salt.
Experimental method in following embodiments is unless otherwise specified conventional method.Examination as used in the following examples
Agent material etc. is commercially available products unless otherwise specified.
Embodiment 1
10g castor oil is evaporated under reduced pressure, the water in castor oil and other solvents are removed, then by processed castor
Sesame oil is added in the four-hole boiling flask with mechanical stirring device, and N, N- dimethylethanolamines and ionic-liquid catalyst is added
[Hmim]HSO4, reacted 2 hours at 60 DEG C and under conditions of stirring, obtain castor oil acid acid amides；Wherein, N, N- dimethyl ethanol
The molal weight of amine and castor oil ratio is 2:1；The dosage of catalyst is the 5% of reactant castor-oil plant weight of oil；
After testing, the yield of the present embodiment castor oil-base amide is 59.43%.
Embodiment 2
10g castor oil is evaporated under reduced pressure, the water in castor oil and other solvents are removed, then by processed castor
Sesame oil is added in the four-hole boiling flask with mechanical stirring device, and N, N- dimethylethanolamines and ionic-liquid catalyst is added
[Hmim]HSO4, reacted 3 hours at 70 DEG C and under conditions of stirring, obtain castor oil acid acid amides；Wherein, N, N- dimethyl ethanol
The molal weight of amine and castor oil ratio is 4:1；The dosage of catalyst is the 10% of reactant castor-oil plant weight of oil；
After testing, the yield of the present embodiment castor oil-base amide is 63.53%.
Embodiment 3
10g castor oil is evaporated under reduced pressure, the water in castor oil and other solvents are removed, then by processed castor
Sesame oil is added in the four-hole boiling flask with mechanical stirring device, and N, N- dimethylethanolamines and ionic-liquid catalyst is added
[Hmim]HSO4, reacted 5 hours at 75 DEG C and under conditions of stirring, obtain castor oil acid acid amides；Wherein, N, N- dimethyl ethanol
The molal weight of amine and castor oil ratio is 6:1；The dosage of catalyst is the 15% of reactant castor-oil plant weight of oil；
After testing, the yield of the present embodiment castor oil-base amide is 73.53%.
Embodiment 4
10g castor oil is evaporated under reduced pressure, the water in castor oil and other solvents are removed, then by processed castor
Sesame oil is added in the four-hole boiling flask with mechanical stirring device, and N, N- dimethylethanolamines and ionic-liquid catalyst is added
[Hmim]HSO4, reacted 8 hours at 80 DEG C and under conditions of stirring, obtain castor oil acid acid amides；Wherein, N, N- dimethyl ethanol
The molal weight of amine and castor oil ratio is 6:1；The dosage of catalyst is the 8% of reactant castor-oil plant weight of oil；
After testing, the yield of the present embodiment castor oil-base amide is 91.56%.Fig. 2~4 respectively illustrate the present embodiment system
Liquid chromatography mass combination figure, mass spectrogram and the infrared spectrogram of standby castor oil-base amide.As shown in Fig. 2, in liquid chromatogram
A main peak is only existed in mass spectrometry figure, illustrates that the purity of castor oil acid acid amides in final product is very high.Meanwhile intermediate product
The relative molecular weight of castor oil acid acid amides is 369.6, by known to Fig. 3 mass spectrograms 370.3319 for ([C22H43NO3]+H)+, i.e.,
Castor oil acid acid amides.
Embodiment 5
10g castor oil is evaporated under reduced pressure, the water in castor oil and other solvents are removed, then by processed castor
Sesame oil is added in the four-hole boiling flask with mechanical stirring device, and N, N- dimethylethanolamines and ionic-liquid catalyst is added
[Hmim]HSO4, reacted 8 hours at 80 DEG C and under conditions of stirring, obtain castor oil acid acid amides；Wherein, N, N- dimethyl ethanol
The molal weight of amine and castor oil ratio is 8:1；The dosage of catalyst is the 20% of reactant castor-oil plant weight of oil；
After testing, the yield of the present embodiment castor oil-base amide is 88.24%；
By the product yield value of 1~5 castor oil-base amide of above-described embodiment it is found that ricinoleic acid first prepared by embodiment 4
Ester has best yield (91.56%), that is, works as N, and the molal weight ratio of N- dimethylethanolamines and castor oil is 6:1, catalysis
Agent dosage is the 8% of reactant castor-oil plant weight of oil, and reaction temperature is 80 DEG C, when the reaction time is 8h, product castor oil-base amide
With optimal yield.
Embodiment 6
The castor oil-base amide that the method for taking 10g embodiments 4 is prepared is added to the four-hole boiling flask with agitating device
In, after being heated to 48 DEG C, epoxychloropropane is added, is reacted 1 hour at 50 DEG C, stratification takes supernatant, takes upper layer yellowish
Color cloud liquid, the faint yellow turbid in upper layer remove excess epoxy chloropropane with n-hexane, are dried in vacuo to obtain castor oil-base quaternary ammonium emulsifying salt
Agent；
The molal weight ratio of above-mentioned epoxychloropropane and castor oil-base amide is 1:1；
After testing, the yield of the present embodiment castor oil-base quaternary ammonium salt emulsifier is 64.42%.
Embodiment 7
The castor oil-base amide that the method for taking 10g embodiments 4 is prepared is added to the four-hole boiling flask with agitating device
In, after being heated to 48 DEG C, epoxychloropropane is added, is reacted 1 hour at 50 DEG C, stratification takes supernatant, takes upper layer yellowish
Color cloud liquid, the faint yellow turbid in upper layer remove excess epoxy chloropropane with n-hexane, are dried in vacuo to obtain castor oil-base quaternary ammonium emulsifying salt
Agent；
The molal weight ratio of above-mentioned epoxychloropropane and castor oil-base amide is 1:2；
After testing, the yield of the present embodiment castor oil-base quaternary ammonium salt emulsifier is 78.75%.
Embodiment 8
The castor oil-base amide that the method for taking 10g embodiments 4 is prepared is added to the four-hole boiling flask with agitating device
In, after being heated to 48 DEG C, epoxychloropropane is added, is reacted 2 hours at 50 DEG C, stratification takes supernatant, takes upper layer yellowish
Color cloud liquid, the faint yellow turbid in upper layer remove excess epoxy chloropropane with n-hexane, are dried in vacuo to obtain castor oil-base quaternary ammonium emulsifying salt
Agent；
The molal weight ratio of above-mentioned epoxychloropropane and castor oil-base amide is 1:3；
After testing, the yield of the present embodiment castor oil-base quaternary ammonium salt emulsifier is 85.39%.
Embodiment 9
The castor oil-base amide that the method for taking 10g embodiments 4 is prepared is added to the four-hole boiling flask with agitating device
In, after being heated to 48 DEG C, epoxychloropropane is added, is reacted 1 hour at 50 DEG C, stratification takes supernatant, takes upper layer yellowish
Color cloud liquid, the faint yellow turbid in upper layer remove excess epoxy chloropropane with n-hexane, are dried in vacuo to obtain castor oil-base quaternary ammonium emulsifying salt
Agent；
The molal weight ratio of above-mentioned epoxychloropropane and castor oil-base amide is 1:3；
After testing, the yield of the present embodiment castor oil-base quaternary ammonium salt emulsifier is 90.44%.Fig. 5~8 respectively illustrate this
Liquid chromatography mass combination figure, mass spectrogram, infrared spectrogram and the surface of castor oil-base quaternary ammonium salt emulsifier prepared by embodiment
Tonogram.As shown in Figure 5, a main peak is only existed in liquid chromatography mass combination figure, illustrates castor oil-base in final product
The purity of quaternary ammonium salt is very high.The relative molecular weight of target product castor oil-base quaternary ammonium salt be 462, by Fig. 6 mass spectrograms it is found that
462.3348 for ([C25H48ClNO4]+H)+, i.e. castor oil-base quaternary ammonium salt, 426.3579 for castor oil-base quaternary ammonium salt sun from
Subbase group [C25H48NO4]+, 464.3330 should be the by-product of quaternization reaction.
Embodiment 10
The castor oil-base amide that the method for taking 10g embodiments 4 is prepared is added to the four-hole boiling flask with agitating device
In, after being heated to 48 DEG C, epoxychloropropane is added, is reacted 1 hour at 50 DEG C, stratification takes supernatant, takes upper layer yellowish
Color cloud liquid, the faint yellow turbid in upper layer remove excess epoxy chloropropane with n-hexane, are dried in vacuo to obtain castor oil-base quaternary ammonium emulsifying salt
Agent；
The molal weight ratio of above-mentioned epoxychloropropane and castor oil-base amide is 1:4；
After testing, the yield of the present embodiment castor oil-base quaternary ammonium salt emulsifier is 87.32%.
Embodiment 11
The castor oil-base amide that the method for taking 10g embodiments 4 is prepared is added to the four-hole boiling flask with agitating device
In, after being heated to 48 DEG C, epoxychloropropane is added, is reacted 1 hour at 55 DEG C, stratification takes supernatant, takes upper layer yellowish
Color cloud liquid, the faint yellow turbid in upper layer remove excess epoxy chloropropane with n-hexane, are dried in vacuo to obtain castor oil-base quaternary ammonium emulsifying salt
Agent；
The molal weight ratio of above-mentioned epoxychloropropane and castor oil-base amide is 1:5；
After testing, the yield of the present embodiment castor oil-base quaternary ammonium salt emulsifier is 80.32%.
Embodiment 12
The castor oil-base amide that the method for taking 10g embodiments 4 is prepared is added to the four-hole boiling flask with agitating device
In, after being heated to 48 DEG C, epoxychloropropane is added, is reacted 2 hours at 50 DEG C, stratification takes supernatant, takes upper layer yellowish
Color cloud liquid, the faint yellow turbid in upper layer remove excess epoxy chloropropane with n-hexane, are dried in vacuo to obtain castor oil-base quaternary ammonium emulsifying salt
Agent；
The molal weight ratio of above-mentioned epoxychloropropane and castor oil-base amide is 1:6；
After testing, the yield of the present embodiment castor oil-base quaternary ammonium salt emulsifier is 82.15%.
By the yield value of 6~12 castor oil-base quaternary ammonium salt emulsifier of above-described embodiment it is found that castor oil prepared by embodiment 9
Based quaternary ammonium salt emulsifier has best yield (90.44%), i.e. mole matter when epoxychloropropane and castor oil-base quaternary ammonium salt
Amount is than being 1:3, reaction temperature is 50 DEG C, and the reaction time is 1 hour, and product castor oil-base quaternary ammonium salt has optimal yield.
In conclusion castor oil-base quaternary ammonium salt emulsifier provided by the invention is mainly by castor oil and N, N- dimethyl ethanols
Amine is in ionic-liquid catalyst [Hmim] HSO4Under the action of carry out ester exchange reaction obtain castor oil-base amide first, then will
Gained castor oil-base amide carries out quaternization reaction and is made again.Castor oil-base quaternary ammonium salt emulsifier of the present invention with it is existing it is traditional with
Chemical organic compounds are that quaternary ammonium salt emulsifier made from raw material is compared, the present invention using can a large amount of regenerated castor-oil plants as raw material, passing through
It learns method of modifying and obtains castor oil-base quaternary ammonium salt emulsifier, arrived involved in the conventional method that existing synthesis quaternary ammonium salt has been effectively relieved
A large amount of harmful organic matters and organic solvent, are easy the defect polluted the environment.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that：Its according to
So can with technical scheme described in the above embodiments is modified, either to which part or all technical features into
Row equivalent replacement；And these modifications or replacements, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of castor oil-base quaternary ammonium salt emulsifier, which is characterized in that the castor oil-base quaternary ammonium salt emulsifier is mainly by castor-oil plant
Oil and N, N- dimethylethanolamine are in ionic-liquid catalyst [Hmim] HSO4Under the action of carry out ester exchange reaction obtain first
Then gained castor oil-base amide is carried out quaternization reaction and is made by castor oil-base amide again.
2. castor oil-base quaternary ammonium salt emulsifier according to claim 1, which is characterized in that the N, N- dimethylethanolamine
Molal weight ratio with castor oil is 2~8:1.
3. castor oil-base quaternary ammonium salt emulsifier according to claim 1, which is characterized in that the ionic-liquid catalyst
[Hmim]HSO4Addition be castor-oil plant weight of oil 5~20%.
4. castor oil-base quaternary ammonium salt emulsifier according to claim 1, which is characterized in that the ester exchange reaction is 60
It is stirred to react 2~10h under conditions of~80 DEG C.
5. castor oil-base quaternary ammonium salt emulsifier according to claim 1, which is characterized in that the quaternary ammonium of the quaternization reaction
Change reagent is epoxychloropropane.
6. castor oil-base quaternary ammonium salt emulsifier according to claim 5, which is characterized in that the epoxychloropropane and castor-oil plant
The molal weight ratio of oil base amide is 1~4:1.
7. castor oil-base quaternary ammonium salt emulsifier according to claim 5, which is characterized in that the quaternization reaction is first will
Castor oil-base amide is heated to 45~50 DEG C of addition epoxychloropropane, is then stirred to react 1~2h at 40~60 DEG C, obtains castor
Sesame oil based quaternary ammonium salt emulsifier.
8. a kind of preparation method according to claim 1~7 any one of them castor oil-base quaternary ammonium salt emulsifier, feature exists
In the described method comprises the following steps：
(a) first, by castor oil and N, N- dimethylethanolamines are with 2~8:1 molal weight ratio is mixed, and is added and is accounted for castor
Ionic-liquid catalyst [Hmim] HSO of sesame oil weight 5~20%4, then it is stirred to react 2 under conditions of 60~80 DEG C~
10h, separation and recovery obtain castor oil-base amide；
(b) the castor oil-base amide that separation and recovery obtains is heated to 45~50 DEG C of addition epoxychloropropane, then 40~60
It is stirred to react 1~2h at DEG C, obtains castor oil-base quaternary ammonium salt emulsifier.
9. the preparation method of castor oil-base quaternary ammonium salt emulsifier according to claim 8, which is characterized in that the step
(a) method of castor oil-base amide separation and recovery is：The stratification after being stirred to react, and be dried to obtain after supernatant is washed
Castor oil-base quaternary ammonium salt.
10. the preparation method of castor oil-base quaternary ammonium salt emulsifier according to claim 8, which is characterized in that the preparation
Method further includes the steps that being isolated and purified to the castor oil-base quaternary ammonium salt emulsifier that step (b) obtains；
Preferably, described the step of being isolated and purified to castor oil-base quaternary ammonium salt emulsifier, is：After step (b) is stirred to react
Stratification takes the faint yellow turbid in upper layer, and n-hexane is used in combination to remove excess epoxy chloropropane in the turbid of upper layer, dry castor oil
Based quaternary ammonium salt emulsifier.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110627746A (en) * | 2019-09-27 | 2019-12-31 | 盐城工学院 | Castor oil-based quaternary ammonium salt anti-mud agent and preparation method thereof |
| CN111760334A (en) * | 2020-07-21 | 2020-10-13 | 滨州市广友化工有限公司 | Organic silicone oil defoaming agent and preparation method thereof |
| CN113854320A (en) * | 2021-10-18 | 2021-12-31 | 阜南县猛发工艺品有限公司 | Insect-proof mildew-proof agent for bamboo rattan woven product and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284794A (en) * | 2008-05-27 | 2008-10-15 | 中国林业科学研究院林产化学工业研究所 | Rosinyl quaternary ammonium salt type gemini surfactant and method for preparing same |
| CN101745340A (en) * | 2008-12-08 | 2010-06-23 | 中国石油天然气股份有限公司 | Cationic asphalt emulsifier and preparation method and application thereof |
| CN102336675A (en) * | 2010-07-21 | 2012-02-01 | 博兴华润油脂化学有限公司 | Production method of esterquats |
| CN102671576A (en) * | 2012-05-08 | 2012-09-19 | 中国石油化工股份有限公司 | Quaternary ammonium cationic surfactant and synthetic method thereof |
| CN103071423A (en) * | 2013-02-19 | 2013-05-01 | 齐齐哈尔大学 | Pyridine carbamyl quaternary ammonium surfactant and preparation method thereof |
| CN103992223A (en) * | 2014-04-25 | 2014-08-20 | 盐城工学院 | Preparation method of methyl acetylricinolate |
| CN105061233A (en) * | 2015-08-11 | 2015-11-18 | 西京学院 | Preparation method for gemini waste oil cationic surfactant of paper softening agent |
| US20170137740A1 (en) * | 2010-11-23 | 2017-05-18 | The Lubrizol Corporation | Functionalised Copolymers and Lubricating Compositions Thereof |
-
2018
- 2018-07-12 CN CN201810768217.5A patent/CN108745198B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284794A (en) * | 2008-05-27 | 2008-10-15 | 中国林业科学研究院林产化学工业研究所 | Rosinyl quaternary ammonium salt type gemini surfactant and method for preparing same |
| CN101745340A (en) * | 2008-12-08 | 2010-06-23 | 中国石油天然气股份有限公司 | Cationic asphalt emulsifier and preparation method and application thereof |
| CN102336675A (en) * | 2010-07-21 | 2012-02-01 | 博兴华润油脂化学有限公司 | Production method of esterquats |
| US20170137740A1 (en) * | 2010-11-23 | 2017-05-18 | The Lubrizol Corporation | Functionalised Copolymers and Lubricating Compositions Thereof |
| CN102671576A (en) * | 2012-05-08 | 2012-09-19 | 中国石油化工股份有限公司 | Quaternary ammonium cationic surfactant and synthetic method thereof |
| CN103071423A (en) * | 2013-02-19 | 2013-05-01 | 齐齐哈尔大学 | Pyridine carbamyl quaternary ammonium surfactant and preparation method thereof |
| CN103992223A (en) * | 2014-04-25 | 2014-08-20 | 盐城工学院 | Preparation method of methyl acetylricinolate |
| CN105061233A (en) * | 2015-08-11 | 2015-11-18 | 西京学院 | Preparation method for gemini waste oil cationic surfactant of paper softening agent |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110627746A (en) * | 2019-09-27 | 2019-12-31 | 盐城工学院 | Castor oil-based quaternary ammonium salt anti-mud agent and preparation method thereof |
| CN111760334A (en) * | 2020-07-21 | 2020-10-13 | 滨州市广友化工有限公司 | Organic silicone oil defoaming agent and preparation method thereof |
| CN113854320A (en) * | 2021-10-18 | 2021-12-31 | 阜南县猛发工艺品有限公司 | Insect-proof mildew-proof agent for bamboo rattan woven product and preparation method thereof |
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