A kind of betaine type amphoteric surfac-tant and preparation method thereof
Technical field
The present invention relates to a kind of betaine type amphoteric surfac-tants and preparation method thereof.
Background technology
Amphoteric surfactant refers to being existed simultaneously in same molecular structure by bridge chain (hydrocarbon chain, carbon fluorine chain etc.) even
The surfactant of the positive and negative charge-site (or dipole center) of one or more connect, biodegradability are good, less toxic, anti-
Electrostatic.Amphoteric surfactant is appeared in earliest in the 1930s, being gradually developed application later, and China is in both sexes table
Research and development in terms of the activating agent of face are started late, and there is a big difference compared with other developed countries for kind and yield.
Domestic surfactant is based on anionic surfactant and nonionic surfactant, this two classes surface
Activating agent pollutes the environment, it is difficult to biodegradable.Alkylamide propyl-betaine is a kind of new and effective amphoteric surface's work
Property agent there is performance is mild, decontamination is strong, frothing capacity is good, conditioning performance is superior etc. containing amide group and quaternary amines
Advantage is widely used in articles for washing, especially shampoo, hair cream etc. in recent years.Currently, personal care articles industry alkane
The annual consumption of base amide betaine amphoteric surfactant is about ten tens of thousands of tons, wide market.
The preparation process of alkylamide propyl-betaine is broadly divided into following two step:1) amidation process:With aliphatic acid and
3- dimethylamine propylamines are that raw material prepares alkylamide propyl dimethyl tertiary amine;2) quaternary ammonium reaction:With alkylamide propyl two
Methyl tertiary amine and sodium chloroacetate are raw material, water and isopropanol as reaction dissolvent, prepare alkylamide propyl-betaine.Mainly deposit
In problems with:1) acid value of amidation process is difficult to decrease, and to which yield is relatively low, production cost is higher;2) mostly with mixing
Fatty acid is raw materials for production, but this kind of fatty acid contains more impurity, and property is unstable, and it is production also to have with fatty acid methyl esters
Raw material, but further increase production cost;3) purifying technique is fairly simple, and obtained Product Activity content of material is low.
Invention content
The purpose of the present invention is to provide a kind of betaine type amphoteric surfac-tants and preparation method thereof.
The technical solution used in the present invention is:
A kind of betaine type amphoteric surfac-tant, structural formula are:
Wherein n is 12 or 14 or 16.
The preparation method of above-mentioned betaine type amphoteric surfac-tant includes the following steps:
1) amidation process:Natural oil resin acid is melted, 3- dimethylamine propylamines are added, mix well, catalyst is added
Amidation process is carried out, 4A molecular sieves are added after reacting 5~7h, the reaction was continued, removes unreacted 3- diformazans after completion of the reaction
Amido propylamine and natural oil resin acid, obtain alkylamide propyl dimethyl tertiary amine;
2) quaternary ammonium reaction:Reactor is added in alkylamide propyl dimethyl tertiary amine and sodium chloroacetate, adds water to chloroethene
The dissolving of sour sodium is complete, adds isopropanol, adjusts pH value to 7~8, carries out quaternary ammonium reaction, remove after completion of the reaction isopropanol,
Water and unreacted sodium chloroacetate, obtain betaine type amphoteric surfac-tant.
The structural formula of natural oil resin acid described in step 1) is:Wherein n be 12 or 14 or
16。
Catalyst described in step 1) is KOH, NaOH, NaF, CH3One kind in ONa, additive amount are natural oil resin acid matter
The 0.3%~0.7% of amount.
The molar ratio of natural oil resin acid, 3- dimethylamine propylamines described in step 1) is 1:(1.05~1.08).
The mass ratio of natural oil resin acid, 4A molecular sieves described in step 1) is 1:(0.33~0.46).
The reaction temperature of amidation process described in step 1) is 160~180 DEG C, and the reaction time is 9~11 hours.
The molar ratio of alkylamide propyl dimethyl tertiary amine, sodium chloroacetate described in step 2) is 1:(1.05~1.15).
The volume ratio of water, isopropanol described in step 2) is (1.5~2):1.
The reaction temperature of quaternary ammonium reaction described in step 2) is 80~95 DEG C, and the reaction time is 4~6 hours.
The present invention relates to reaction it is as follows:
1) amidation process:
2) quaternary ammonium reaction:
The beneficial effects of the invention are as follows:
1) contain amido bond in amphoteric surfactant group of the invention, change the performance of molecule, have better
Foam stability, performance is mild, and emulsifiability is substantially better than empgen BB surfactant;
2) preparation method of the invention is simple for process, and production cost is low, and selected reaction raw materials are natural oil resin acid,
Source is wide, green safe, degradable, and absorbs the water generated during amidation process by 4A molecular sieves, can be effective
Promote reaction to be carried out to positive direction, improves yield.
Description of the drawings
Fig. 1 is the infrared spectrogram of betaine type amphoteric surfac-tant prepared by embodiment 1.
Fig. 2 is the nuclear magnetic resonance spectroscopy of betaine type amphoteric surfac-tant prepared by embodiment 1.
Fig. 3 is the surface tension test result figure of betaine type amphoteric surfac-tant prepared by embodiment 1.
Fig. 4 is solubilising test result figure of the betaine type amphoteric surfac-tant to benzene of the preparation of embodiment 1.
Fig. 5 is influence test result figure of the 4A molecular sieves to amidation process conversion ratio.
Specific implementation mode
A kind of betaine type amphoteric surfac-tant, structural formula are:
Wherein n is 12 or 14 or 16.
The preparation method of above-mentioned betaine type amphoteric surfac-tant includes the following steps:
1) amidation process:Natural oil resin acid is melted, 3- dimethylamine propylamines are added, mix well, catalyst is added
It carries out
4A molecular sieves are added after reacting 5~7h in amidation process, and the reaction was continued, removes after completion of the reaction unreacted
3- dimethylamine propylamines and natural oil resin acid, obtain alkylamide propyl dimethyl tertiary amine;
2) quaternary ammonium reaction:Reactor is added in alkylamide propyl dimethyl tertiary amine and sodium chloroacetate, adds water to chloroethene
Sour sodium is molten
Solution is complete, adds isopropanol, adjusts pH value to 7~8, carries out quaternary ammonium reaction, remove after completion of the reaction different
Propyl alcohol, water and unreacted sodium chloroacetate, obtain betaine type amphoteric surfac-tant.
Preferably, the structural formula of the natural oil resin acid described in step 1) is:Wherein n is
12 or 14 or 16.
Preferably, the catalyst described in step 1) is KOH, NaOH, NaF, CH3One kind in ONa, additive amount are natural oil
The 0.3%~0.7% of resin acid quality.
Preferably, the natural oil resin acid described in step 1), 3- dimethylamine propylamines molar ratio be 1:(1.05~1.08).
Preferably, the natural oil resin acid described in step 1), 4A molecular sieves mass ratio be 1:(0.33~0.46).
Preferably, the reaction temperature of the amidation process described in step 1) is 160~180 DEG C, and the reaction time is 9~11 small
When.
Preferably, the alkylamide propyl dimethyl tertiary amine described in step 2), sodium chloroacetate molar ratio be 1:(1.05~
1.15)。
Preferably, the water described in step 2), isopropanol volume ratio be (1.5~2):1.
Preferably, the reaction temperature of the quaternary ammonium reaction described in step 2) is 80~95 DEG C, and the reaction time is 4~6 hours.
The present invention is made further explanation and description with reference to specific embodiment.
Embodiment 1:
A kind of preparation method of betaine type amphoteric surfac-tant includes the following steps:
1) amidation process:The palmitic acid of 25.6475g is added in the three-necked flask equipped with reflux condenser, is warming up to
80 DEG C so that palmitic acid slowly melts, then 3- dimethylamine propylamines (palmitic acid and the 3- dimethylamine of 10.728g are added dropwise while stirring
The molar ratio of base propylamine is 1:1.05), 30min is dripped off, and is added the KOH of 0.177g as catalyst, is warming up to 160 DEG C, into
Row amidation process, reacts the 4A molecular sieves that 10g is added after 6h, the reaction was continued 5h, and first vacuum distillation after completion of the reaction removes thick
Unreacted 3- dimethylamine propylamines and by-product water in product, then the Na with mass fraction 1%2CO3Solution washing removes not anti-
The palmitic acid answered obtains palmitamide propyl-dimethyl tertiary amine, yield 93.42%;
2) quaternary ammonium reaction:The palmitamide dimethylamine of 34.06g is added in the three-necked flask equipped with reflux condenser
(molar ratio of palmitamide propyl-dimethyl tertiary amine and sodium chloroacetate is 1 to the sodium chloroacetate of base tertiary amine and 13.40g:1.15), then
The water of 30.5g, which is added, makes sodium chloroacetate dissolve just completely, adds the isopropanol of 15.25g, adjusts pH between 7~8, rises
Temperature measures once free amine value to 80 DEG C of progress quaternary ammonium reactions, every a hour, and after reacting 6h, conversion ratio is not further added by,
Stop reaction, obtain crude product, rotary evaporation removes the isopropyl alcohol and water in crude product, and the isopropanol for adding 3 times of volumes is molten
Solution filtering, removes unreacted sodium chloroacetate, and last rotary evaporation recycles isopropanol, obtains palmitamide propyl betaine, i.e.,
The betaine type amphoteric surfac-tant of the present invention, yield 95.32%.
The infrared spectrogram of palmitamide propyl betaine manufactured in the present embodiment is as shown in Figure 1, its nuclear magnetic resonance spectroscopy
(500MHz, DMSO) as shown in Figure 2.
As shown in Figure 1:3311.58cm-1Place is the stretching vibration absworption peak of hydrogen bound to nitrogen N-H;2918.13cm-1、
2850.62cm-1And 1467.74cm-1Place is the stretching vibration absworption peak of C-H bond C-H;1641.33cm-1Place is amido bond-
The characteristic absorption peak of CONH-;1552.61cm-1Place is the antisymmetric stretching vibration absorption peak of carboxylate, and 1398.31cm-1Place
For its symmetrical stretching vibration absorption peak;1232.44cm-1Place is the vibration absorption peak of carbonnitrogen bond-C-N-;721.33cm-1Place for-
(CH2)nRocking vibration absorption peak.
As shown in Figure 2:δ=7.75-7.72 (s, 1H ,-CONH-), δ=4.43-4.09 (s, 2H, N+-CH2COO-), δ=
3.37-3.34 (s, 6H, CH3-N+-CH3), δ=3.11-2.94 (s, 4H ,-NH-CH2-CH2-CH2-N+), δ=2.17-2.12
(s, 2H ,-CH2-CO-), δ=2.09-2.08 (m, 2H ,-CH2-CH2-CH2-N+), δ=1.47-1.44 (s, 2H ,-CH2-CH2-
CONH-), δ=1.24-1.19 (s, 22H ,-(CH2)11), δ=1.12-1.03 (s, 2H ,-CH2-CH3), δ=0.85 (s, 3H ,-
CH3)。
Complex chart 1 and Fig. 2 are understood:Palmitamide propyl betaine product impurity prepared by above-mentioned technological process is few, purity
It is higher.
Embodiment 2:
A kind of preparation method of betaine type amphoteric surfac-tant includes the following steps:
1) amidation process:The myristic acid of 22.84g is added in the three-necked flask equipped with reflux condenser, is warming up to
80 DEG C so that myristic acid slowly melts, then 3- dimethylamine propylamines (myristic acid and the 3- bis- of 10.73g are added dropwise while stirring
The molar ratio of methylamino propylamine is 1:1.05), 30min is dripped off, and is added the NaOH of 0.17g as catalyst, is warming up to 160
DEG C, amidation process is carried out, reacts the 4A molecular sieves that 10g is added after 6h, the reaction was continued 5h, first vacuum distillation removes after completion of the reaction
Go unreacted 3- dimethylamine propylamines and by-product water in crude product, then the Na with mass fraction 1%2CO3Solution washing removes
Unreacted myristic acid obtains myristamide propyl-dimethyl tertiary amine, yield 92.31%;
2) quaternary ammonium reaction:The myristamide propyl two of 31.26g is added in the three-necked flask equipped with reflux condenser
(molar ratio of myristamide propyl-dimethyl tertiary amine and sodium chloroacetate is 1 to the sodium chloroacetate of methyl tertiary amine and 13.40g:
1.15), adding the water of 30.50g makes sodium chloroacetate dissolve just completely, adds the isopropanol of 15.25g, adjust pH 7~
Between 8,80 DEG C of progress quaternary ammonium reactions are warming up to, measure once free amine value every a hour, after reacting 6h, conversion ratio is not
It is further added by, stops reaction, obtain crude product, rotary evaporation removes the isopropyl alcohol and water in crude product, adds the different of 3 times of volumes
Propyl alcohol dissolution filter, removes unreacted sodium chloroacetate, and last rotary evaporation recycles isopropanol, obtains myristamide propyl sweet tea
Dish alkali, i.e. betaine type amphoteric surfac-tant of the invention, yield 94.86%.
Embodiment 3:
A kind of preparation method of betaine type amphoteric surfac-tant includes the following steps:
1) amidation process:The palmitic acid of 25.64g is added in the three-necked flask equipped with reflux condenser, is warming up to 80
DEG C so that palmitic acid slowly melts, then 3- dimethylamine propylamines (palmitic acid and the 3- dimethylamine of 11.1169g are added dropwise while stirring
The molar ratio of base propylamine is 1:1.08), 30min is dripped off, and is added the NaF of 0.18g as catalyst, is warming up to 160 DEG C, carries out
Amidation process reacts the 4A molecular sieves of addition 10g after 6h, the reaction was continued 5h, the after completion of the reaction thick production of first vacuum distillation removing
Unreacted 3- dimethylamine propylamines and by-product water in object, then the Na with mass fraction 1%2CO3Solution washing removes unreacted
Palmitic acid, obtain palmitamide propyl-dimethyl tertiary amine, yield 89.46%;
2) quaternary ammonium reaction:The palmitamide dimethylamine of 34.16g is added in the three-necked flask equipped with reflux condenser
(molar ratio of palmitamide propyl-dimethyl tertiary amine and sodium chloroacetate is 1 to the sodium chloroacetate of base tertiary amine and 12.40g:1.06), then
The water of 31g, which is added, makes sodium chloroacetate dissolve just completely, adds the isopropanol of 15.25g, adjusts pH between 7~8, heating
To 80 DEG C of progress quaternary ammonium reactions, free amine value being measured once every a hour, reacts and continues 6h, conversion ratio is not further added by,
Stop reaction, obtain crude product, rotary evaporation removes the isopropyl alcohol and water in crude product, and the isopropanol for adding 3 times of volumes is molten
Solution filtering, removes unreacted sodium chloroacetate, and last rotary evaporation recycles isopropanol, obtains palmitamide propyl betaine, i.e.,
The betaine type amphoteric surfac-tant of the present invention, yield 76.22%.
Embodiment 4:
A kind of preparation method of betaine type amphoteric surfac-tant includes the following steps:
1) amidation process:The palmitic acid of 25.67g is added in the three-necked flask equipped with reflux condenser, is warming up to 80
DEG C so that palmitic acid slowly melts, then 3- dimethylamine propylamines (palmitic acid and the 3- dimethylamino of 11.43g are added dropwise while stirring
The molar ratio of propylamine is 1:1.06), 30min is dripped off, and adds the CH of 0.190g3ONa is warming up to 160 DEG C as catalyst, into
Row amidation process, reacts the 4A molecular sieves that 10g is added after 6h, the reaction was continued 5h, and first vacuum distillation after completion of the reaction removes thick
Unreacted 3- dimethylamine propylamines and by-product water in product, then the Na with mass fraction 1%2CO3Solution washing removes not anti-
The palmitic acid answered obtains palmitamide propyl-dimethyl tertiary amine, yield 89.60%;
2) quaternary ammonium reaction:The palmitamide dimethylamine of 34.01g is added in the three-necked flask equipped with reflux condenser
(molar ratio of palmitamide propyl-dimethyl tertiary amine and sodium chloroacetate is 1 to the sodium chloroacetate of base tertiary amine and 12.2g:1.05), then
The water of 30g, which is added, makes sodium chloroacetate dissolve just completely, adds the isopropanol of 11.80g, adjusts pH between 7~8, heating
To 95 DEG C of progress quaternary ammonium reactions, free amine value is measured once every a hour, after reacting 6h, conversion ratio is not further added by, and is stopped
It only reacts, obtains crude product, rotary evaporation removes the isopropyl alcohol and water in crude product, adds the isopropanol dissolving of 3 times of volumes
Filtering removes unreacted sodium chloroacetate, and last rotary evaporation recycles isopropanol, obtains palmitamide propyl betaine, i.e., originally
The betaine type amphoteric surfac-tant of invention, yield 84.31%.
Embodiment 5:
A kind of preparation method of betaine type amphoteric surfac-tant includes the following steps:
1) amidation process:The palmitic acid of 25.63g is added in the three-necked flask equipped with reflux condenser, is warming up to 80
DEG C so that palmitic acid slowly melts, then 3- dimethylamine propylamines (palmitic acid and the 3- dimethylamino of 10.78g are added dropwise while stirring
The molar ratio of propylamine is 1:1.05), 30min is dripped off, and is added the NaOH of 0.190g as catalyst, is warming up to 160 DEG C, carries out
Amidation process reacts the 4A molecular sieves of addition 10g after 6h, the reaction was continued 5h, the after completion of the reaction thick production of first vacuum distillation removing
Unreacted 3- dimethylamine propylamines and by-product water in object, then the Na with mass fraction 1%2CO3Solution washing removes unreacted
Palmitic acid, obtain palmitamide propyl-dimethyl tertiary amine, yield 89.31%;
2) quaternary ammonium reaction:The palmitamide dimethylamine of 34.39g is added in the three-necked flask equipped with reflux condenser
(molar ratio of palmitamide propyl-dimethyl tertiary amine and sodium chloroacetate is 1 to the sodium chloroacetate of base tertiary amine and 13.08g:1.11), then
The water of 27g, which is added, makes sodium chloroacetate dissolve just completely, adds the isopropanol of 16.12g, adjusts pH between 7~8, heating
To 85 DEG C of progress quaternary ammonium reactions, free amine value is measured once every a hour, after reacting 6h, conversion ratio is not further added by, and is stopped
It only reacts, obtains crude product, rotary evaporation removes the isopropyl alcohol and water in crude product, adds the isopropanol dissolving of 3 times of volumes
Filtering removes unreacted sodium chloroacetate, and last rotary evaporation recycles isopropanol, obtains palmitamide propyl betaine, i.e., originally
The betaine type amphoteric surfac-tant of invention, yield 88.28%.
Embodiment 6:
A kind of preparation method of betaine type amphoteric surfac-tant includes the following steps:
1) amidation process:The palmitic acid of 25.65g is added in the three-necked flask equipped with reflux condenser, is warming up to 80
DEG C so that palmitic acid slowly melts, then 3- dimethylamine propylamines (palmitic acid and the 3- dimethylamino of 10.83g are added dropwise while stirring
The molar ratio of propylamine is 1:1.06), 30min is dripped off, and is added the KOH of 0.19g as catalyst, is warming up to 160 DEG C, carries out acyl
Aminating reaction reacts the 4A molecular sieves that 10g is added after 6h, and the reaction was continued 5h, first vacuum distillation removes crude product after completion of the reaction
In unreacted 3- dimethylamine propylamines and by-product water, then the Na with mass fraction 1%2CO3Solution washing removes unreacted
Palmitic acid obtains palmitamide propyl-dimethyl tertiary amine, yield 89.31%;
2) quaternary ammonium reaction:The palmitamide dimethylamine of 34.39g is added in the three-necked flask equipped with reflux condenser
(molar ratio of palmitamide propyl-dimethyl tertiary amine and sodium chloroacetate is 1 to the sodium chloroacetate of base tertiary amine and 12.71g:1.10), then
The water of 27g, which is added, makes sodium chloroacetate dissolve just completely, adds the isopropanol of 16.12g, adjusts pH between 7~8, heating
To 85 DEG C of progress quaternary ammonium reactions, free amine value is measured once every a hour, after reacting 6h, conversion ratio is not further added by, and is stopped
It only reacts, obtains crude product, rotary evaporation removes the isopropyl alcohol and water in crude product, adds the isopropanol dissolving of 3 times of volumes
Filtering removes unreacted sodium chloroacetate, and last rotary evaporation recycles isopropanol, obtains palmitamide propyl betaine, i.e., originally
The betaine type amphoteric surfac-tant of invention, yield 84.62%.
Test case:
1) surface tension is tested
Surface tension test is carried out to palmitamide propyl betaine prepared by embodiment 1 at 24 DEG C, test result is such as
Shown in Fig. 3.
As shown in Figure 3:With being continuously increased for surfactant concentration, the surface tension of solution continuously decreases, until going out
The variation of existing inflection point rear surface tension tends towards stability, and the critical micelle concentration cmc for thus obtaining palmitamide propyl betaine is
1.12×10-4Mol/L, corresponding γcmcFor 31.63mN/m, there is the performance of the preferable surface tension for reducing water, this benefit
In the chain hydrophobic alkyl that palmitamide propyl betaine possesses.
2) solubilising of benzene is tested
Solubilising test to benzene, test result such as Fig. 4 institutes are carried out to palmitamide propyl betaine prepared by embodiment 1
Show.
As shown in Figure 4:The solubilized limit A of palmitamide propyl betainePAPB=0.498ml, is calculated palmitamide
The solubilising power X=4980ml/mol of propyl betaine, because the palmitamide propyl betaine of synthesis has chain hydrophobic end,
So the aggregation number of the surfactant is bigger, so that the solubilizing amount for being solubilized into the non-polar hydrocarbon of micelle inner core increases
Add, there is preferable characteristic of solubilizing.
3) emulsifiability is tested
The palmitamide propyl betaine and empgen BB prepared to embodiment 1 carries out emulsifiability test, surveys
Test result is as shown in table 1:
The emulsifiability of 1 palmitamide propyl betaine of table and empgen BB in different oil phases
As shown in Table 1:Palmitamide propyl betaine prepared by embodiment 1 is suitable to the emulsifying capacity sizes of different oil phases
Sequence is as follows:Benzene > turpentine oil > atoleine > tetrafluoroethene, and it is bright to the emulsifiability of benzene, turpentine oil and tetrafluoroethene
It is aobvious to be better than empgen BB.It is primarily due to draw in the alkylamide propyl-betaine type surfactant group of the present invention
Enter amide group, changed the performance of molecule, made it have better foam stability, mildness, plays increasing in formula
Add the effect of viscosity, compatibility and solubility property can be substantially improved, expands its application range, and contain in the long-chain of synthetic product
16 atomicities and the ability with the surface tension for reducing water well so that its emulsion process median surface film strength increases
By force, emulsibility also improves therewith.
4) influence of the 4A molecular sieves to amidation process conversion ratio
At 160 DEG C, acid is 1 with amine molar ratio:1.05 ω(KOH)Under conditions of=0.5%, amidation process process is compared
Middle to add and do not add 4A molecular sieves, reaction conversion ratio changes with time, and test results are shown in figure 5.
As shown in Figure 5:Before 5h, addition and not add 4A molecular sieves reaction conversion ratio be all rapid growth at any time
, the reaction conversion ratio for not adding that group of 4A molecular sieves after 5h is basicly stable, increases unobvious, but adds 4A molecular sieves
That group reaction conversion ratio continue to increase, final reaction conversion ratio is apparently higher than that group for not adding 4A molecular sieves, reaction
What is carried out is more thorough, and the water of amidation process generation can be absorbed by being primarily due to 4A molecular sieves, to promote reaction forward
It carries out, reaction conversion ratio also improves therewith.Therefore, selection is added 4A molecular sieves after amidation process carries out 5~7h and more closes
It is suitable.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.