CN105688740A - Novel cationic gemini surfactant and preparation method thereof - Google Patents
Novel cationic gemini surfactant and preparation method thereof Download PDFInfo
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- CN105688740A CN105688740A CN201610137143.6A CN201610137143A CN105688740A CN 105688740 A CN105688740 A CN 105688740A CN 201610137143 A CN201610137143 A CN 201610137143A CN 105688740 A CN105688740 A CN 105688740A
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Abstract
The invention discloses a novel cationic gemini surfactant with the chemical name of 1,3-propane diamine N,N'-bis(myristyl N,N' dimethyl)-disalicylate. The yield of the synthesized quaternary ammonium salt cationic surfactant is higher and the highest yield is 96.2% after purification, synthesis steps are simple and efficient, reaction conditions are easier to control, a product is easy to purify, and the surfactant has higher surface activity and dispersity and can be applied to the fields of oilfield development, domestic care products and the like.
Description
Technical field
The invention belongs to the preparation field of surfactant in Colloid and interface chemistry, the preparation method particularly relating to a kind of new symmetrical Gemini quaternary ammonium salt cationic surfactant。
Background technology
Anionic Gemini Surfactant, also referred to as Gemini surface active agent, gemini surfactants or dimeric surfactant, is be formed by connecting by chemical bond by a linking group at its hydrophilic head Ji Chu or close hydrophilic head Ji Chu by two or more amphiphile, amphiphilic molecules。The extensive concern of domestic and international researcher is received just because of the special construction of such surfactant。Compare with single linked list surface-active agent, the head base in orderly accumulation process is inhibited to separate owing to two head bases are connected such special construction by a linking group, its " monomer " close-packed arrays in interface or molecule aggregate can be promoted preferably, low 1-2 the order of magnitude shows good composite cooperative effect with other surfactants when mixing than conventional surfactant to make system cmc value, and therefore twin type surfactant can be widely applied to prepare the fields such as new material, antibacterial, suppression metal erosion, fabric finishing, cosmetics research and development and oil exploitation。
The type surfactant is typically expressed as m-s-m', and wherein m, m' and s represent on the hydrophobic chain of both sides and the middle carbon atom number connected on base respectively。If m=m', then it it is symmetric form Gemini surface active agent;If m ≠ m', it it is asymmetric Gemini surface active agent。Exactly because the kind that Anionic Gemini Surfactant connection base and the multiformity of hydrophobic chain make Anionic Gemini Surfactant is abundanter, thus having attracted large quantities of researcher to remove research and synthesizing new Shuangzi activating agent and for different field。There is now anionic, cationic, non-ionic and amphoteric Anionic Gemini Surfactant are synthesized out。Bis-quaternary Ammonium Surfactants in its cationic quickly grows because of its superior physicochemical property, and pluralistic theory and applied research also focus on this。But Anionic Gemini Surfactant synthesis, separation and purification are relatively difficult, expensive, most products are also in laboratory synthesis phase, do not realize industrialized production, which limits the popularization in the fields such as industry and daily life of this type of surfactant and use, also hinder researcher such surfactant carries out further investigation and extensively explores simultaneously。Having two for the problems referred to above solution: one, composite with conventional surfactants, finding some cooperative effects is well interaction parameter (β) low-down system;Its two, from synthesis angle, apply cheap raw material, adopt eco-friendly process route。Both compare, and the former needs to carry out substantial amounts of experiment and finds suitable proportioning, cumbersome and time consuming；As long as and the latter's synthesis condition is gentle, cheaper starting materials is easy to get, synthesis technique is simple and environmentally-friendly just can help to the Anionic Gemini Surfactant promotion and application in China。Therefore attempt different chain length and the synthesis of the different Gemini surface active agent connecting base, utilize the raw material that is easy to get, explore simple synthetic route, more sample can be provided for the research of such Anionic Gemini Surfactant and application, thus promoting its research and application。
For the quaternary Anionic Gemini Surfactant of major part synthesis, counter ion part is generally inorganic anion, such as Cl-, Br-, this is because cation group is active group, the attention rate of people is higher。But experimentation shows: counter ion not only affects the surface activity of surfactant, also play a crucial role in some property, in forming ability and the rheology of solution energy etc. of intelligence aggregated structure, these functions are all extremely important to the practical application of Gemini quaternary ammonium salt surfactant。For these reasons, novel kind important in inhibiting is researched and developed。Through retrieval, 1,3-propane diamine N, N '-two (myristyl N, N ' dimethyl) the existing research of synthetic method of-dihalide, but with 1,3-propane diamine N that organic salicylate is anion, N '-two (myristyl N, N ' dimethyl)-two salicylate-type twin cationic surfactants synthesis and performance measurement have not been reported。
Summary of the invention
For existing problem, it is an object of the present invention to provide the preparation method about Gemini quaternary ammonium salt cationic surfactant 1,3-propane diamine N, N '-two (myristyl N, N ' dimethyl)-two Salicylates。
The present invention, using dodecyldimethylamine base tertiary amine, hydrochloric acid, epoxychloropropane and sodium salicylate as raw material, synthesizes this new Gemini quaternary ammonium salt cationic surfactant with phase transfer method。With synthesis in the past 1,3-propane diamine N, raw material based on N '-two (myristyl N, N ' dimethyl)-dihalide, at specific temperature and ratio, sodium salicylate is added in raw material, it is sufficiently mixed after uniformly, 1,3-propane diamine N can be synthesized by progressively falling temperature method, N '-two (myristyl N, N ' dimethyl)-two Salicylates。Newly synthesized this Gemini surface active agent has higher surface activity, and the kind for cationic Anionic Gemini Surfactant adds newcomer。
The present invention program is, Gemini quaternary ammonium salt type cationic surfactant, and chemical name is 1,3-propane diamine N, N '-two (myristyl N, N ' dimethyl)-two Salicylates, and structural formula is as follows:
。
The preparation method that present invention also offers Gemini quaternary ammonium salt cationic surfactant, is using dodecyldimethylamine base tertiary amine, hydrochloric acid, epoxychloropropane, sodium salicylate as raw material, with the Gemini quaternary ammonium salt cationic surfactant of phase transfer method synthesis。
Described preparation method, step is:
(1) 1, 3-propane diamine N, N '-two (myristyl N, N ' dimethyl) synthesis of-dichloride: in four-hole boiling flask, add normal propyl alcohol solvent and dodecyldimethylamine base tertiary amine, dropping concentrated hydrochloric acid, stir, after 5-6 minute, continue dropping normal propyl alcohol, cold water cools down, until reactant liquor clear, colorless, solution acid alkalinity weakly acidic pH is recorded with pH reagent paper, after white smoke in bottle disappears, dropping epoxychloropropane, connect cooling water, when heating flask by solvent refluxing 10 minutes with electric jacket, dropping dodecyldimethylamine base tertiary amine (dropping duration 20 minutes), drip normal propyl alcohol again, control temperature 94-102 DEG C, maintain the reflux for, voltage 120 volts, react 4-5 hour, question response liquid is dark brown, stop heating, cooling, solvent is evaporated with Rotary Evaporators, not dripping solvent to Rotary Evaporators, obtain thick white shape material and do purification process, products therefrom is transferred to vacuum drying oven, dry 24 hours, namely 1 is obtained, 3-propane diamine N, N '-two (myristyl N, N ' dimethyl) the thick product of-dichloride。
(2) 1,3-propane diamine N, N '-two (myristyl N, N ' dimethyl) synthesis of-two Salicylates: by 1,3-propane diamine N, N '-two (myristyl N, N ' dimethyl) the thick transferred product of-dichloride is to four-hole bottle, add dehydrated alcohol, stirring and dissolving, adds sodium salicylate, stirring, and in the tepidarium of 75-85 DEG C, reaction backflow 3-4 hour；After completion of the reaction, cooling stands, and by precipitation filtration, takes supernatant and moves in pears type bottle, evaporating solvent with Rotary Evaporators, namely obtaining the thick product of 1,3-propane diamine N, N '-two (myristyl N, N ' dimethyl)-two Salicylates；
(3) 1, 3-propane diamine N, N '-two (myristyl N, N ' dimethyl) purification of-two Salicylates: by step (2) gained 1, 3-propane diamine N, N '-two (myristyl N, N ' dimethyl) the thick transferred product of-two Salicylates is to four-hole bottle, add the ethyl acetate/acetone mixed solvent of its volume 5-10 times, heated and stirred refluxes, temperature is maintained at 85 ± 2 DEG C, precipitation occurs bottom mixed solution, filter this precipitation and take supernatant, transfer in pears type bottle, by Rotary Evaporators evaporation of acetic acid ethyl ester/acetone mixed solvent, obtain white solid, gained white solid solubilizer again, recrystallization, through vacuum drying, obtain sterling 1, 3-propane diamine N, N '-two (myristyl N, N ' dimethyl)-two Salicylates。
The preparation method of described novel cation Anionic Gemini Surfactant, step (1) dodecyldimethylamine base tertiary amine: epoxychloropropane: hydrochloric acid is preferred with molar ratio computing for 0.10: 0.04:0.04-0.05(, dodecyldimethylamine base tertiary amine: epoxychloropropane: hydrochloric acid is with molar ratio computing for 0.10: 0.04:0.045)。
The preparation method of described novel cation Anionic Gemini Surfactant, it is 96-100 DEG C (preferred, to control temperature at 98 DEG C) that step (1) controls temperature。
The preparation method of described novel cation Anionic Gemini Surfactant, the operation of step (1) purification process is by thick white shape substance transfer to another there-necked flask for purification process operation, add acetone, after being heated to reflux 5-15 minute, first carry out hot sucking filtration, treat that filtrate cooling precipitates out white solid, carry out cold sucking filtration again, and then recrystallization, acetone is added through decompression sucking filtration or in the pear shape bottle fill thick white object after, stand 12 hours, again liquid is transferred in four-hole bottle, heating is to boiling, carry out heat filtering, mother solution is transferred in beaker, it is cooled to room temperature, obtain white solid precipitation, reduce pressure sucking filtration again。
The preparation method of described novel cation Anionic Gemini Surfactant, step (2) 1,3-propane diamine N, N '-two (myristyl N, N ' dimethyl)-dichloride: sodium salicylate is with molar ratio computing for 1: 2.0-2.1。
The preparation method of described novel cation Anionic Gemini Surfactant, step (2) tepidarium temperature is 77-83 DEG C (preferred, tepidarium temperature is 80 DEG C)。
The preparation method of described novel cation Anionic Gemini Surfactant, in step (3) ethyl acetate/acetone mixed solvent, ethyl acetate and acetone ratio are 2:1。
The preparation method of described novel cation Anionic Gemini Surfactant, the solvent that step (3) adds is the one in acetone or ethyl acetate/alcohol mixeding liquid。
The preparation method of described novel cation Anionic Gemini Surfactant, step (3) adds 4-8 times (preferred, to add 6 times that amount is white solid volume of solvent) that amount is white solid volume of solvent。
The preparation method that the invention discloses a kind of novel quaternary ammonium salt twin cationic surfactant 1,3-propane diamine N, N '-two (myristyl N, N ' dimethyl)-two Salicylates。Its synthetic route is by dodecyldimethylamine base tertiary amine and epoxychloropropane when pH value is neutral, using normal propyl alcohol as solvent, reacts 4h-5h at 98 DEG C ± 1 DEG C, obtains 1,3-propane diamine N, N '-two (myristyl N, N ' dimethyl)-dichloride；Then with dehydrated alcohol by 1,3-propane diamine N, N '-two (myristyl N, N ' dimethyl) dissolving of-dichloride, add sodium salicylate, in 80 DEG C ± 2 DEG C water-baths, react 3-4h, filter precipitation, with the mixed solvent (volume ratio is 2:1) of ethyl acetate and dehydrated alcohol, supernatant is carried out recrystallization operation, obtain 1,3-propane diamine N, N '-two (myristyl N, N ' dimethyl)-two Salicylates。The inventive method step is simple and direct, easily-controlled reaction conditions, and the productivity of target Gemini quaternary ammonium salt cationic surfactant is higher, and product is prone to purify。
Advantage for present invention is as follows:
1. use the common dodecyldimethylamine base tertiary amine easily purchased and inexpensive epoxychloropropane and concentrated hydrochloric acid as raw material, first synthesis counter ion is the Gemini quaternary ammonium salt cationic surfactant of chlorine, again this activating agent and sodium salicylate are reacted with 1:1 mol ratio, obtain the novel Gemini quaternary ammonium salt cationic surfactant that counter ion is salicylate, owing to the structure of salicylate self is easily formed hydrogen bond, it is thus possible to improve the surface activity of surfactant。Concrete surface activity parameter is in Table 2。In order to conveniently compare, the surface activity data of 1,3-propane diamine N, N '-two (myristyl N, N ' dimethyl)-dichloride are also listed in the lump。
2. the productivity of the quaternary cationics synthesized by the present invention is higher, is up to 96.2% after purification。
3. the synthesis step of the present invention is simple and direct efficiently, and reaction condition is relatively easy to control。
4. product is prone to purification。
5. the cheaper starting materials of the quaternary twin cationic surfactant of present invention research be easy to get, synthetic route simply efficient。Owing to the connection base of this surfactant containing a hydroxyl, in aqueous, this hydroxyl can form hydrogen bond in the middle of each other and with hydrone so that the distance between the ion head base of hydroxyl molecule is more tight, thus improve the dispersibility of surfactant。Additionally, this activating agent can also form vermiculate glues, therefore can be used for the field such as oil field development, household care product。
Detailed description of the invention
Below in conjunction with embodiment, present invention is described in further detail, but is not limited only to this。
Raw materials used and the reagent of the present invention:
Dodecyldimethylamine base tertiary amine (CP)；Epoxychloropropane (AR)；Hydrochloric acid (AR)；Normal propyl alcohol (AR)；Ethyl acetate (AR)；Acetone (AR)；Dehydrated alcohol (AR)。
Synthetic route is as follows:
(1)
(2)
(3)
Embodiment 1
The preparation method of 1,3-propane diamine N, N '-two (myristyl N, N ' dimethyl) two Salicylates, comprises the steps of:
(1) 1, the synthesis of 3-propane diamine N, N '-two (myristyl N, N ' dimethyl) dichloride
20ml normal propyl alcohol and 0.04mol (9.64g is added in 250ml four-hole boiling flask, about 13.1ml) dodecyldimethylamine base tertiary amine, stir, then dropping concentrated hydrochloric acid 0.045mol(is about 3.8ml), stir, after 5-6 minute, after white smoke disappears, drip the stirring of 20ml normal propyl alcohol again, cool down with cold water, until solution clear, colorless, record solution acid alkalinity value with pH reagent paper and be about 6, dropping 0.04mol(be about 3.2ml) epoxychloropropane, electric jacket heating flask refluxes to reactant liquor, after reaction 10 minutes, drip 0.06mol(again and be about 19.75ml) excessive dodecyldimethylamine base tertiary amine, note to drip in 20 minutes, then 10ml normal propyl alcohol is dripped again, for keeping reactant liquor backflow, heating-up temperature should be controlled at 98 DEG C, heating voltage is kept to be about 120V, react 4.5 hours, tea color is presented to reactant liquor, when temperature rises to nearly 100 DEG C, stop heating。With Rotary Evaporators by solvent rotary evaporation in reactant liquor out, and reclaim normal propyl alcohol, obtain the solid of thick white, continue rotation and steam to having foam generation solvent to be no longer evaporated, notice that during rotary evaporation, voltage is not so high。
Then in the pear shape bottle fill thick white solid, add 60ml acetone, stand 12 hours, being transferred in four-hole bottle by liquid again, heating, to boiling, carries out heat filtering, mother solution is transferred in beaker, it is cooled to room temperature, obtains white solid precipitation, after decompression sucking filtration, obtain colourless thick product 14-3 (OH)-14 (2Cl), obtaining product 20.82g, yield is 90.5%。
(2) 1, the synthesis of 3-propane diamine N, N '-two (myristyl N, N ' dimethyl) two Salicylates
The 20.82g of above-mentioned synthesis is transferred in the four-hole bottle of 500ml, add dehydrated alcohol 100ml, heated and stirred makes it dissolve, then according to 1, the ratio that 3-propane diamine N, N '-two (myristyl N, N ' dimethyl)-dichloride and sodium salicylate mol ratio are 1:2 adds sodium salicylate (about 11.59g), and in 80 DEG C of tepidarium constant temperature and agitating solution so that it is reaction backflow 3.5 hours；After question response, solution is moved in pears type bottle, stand 1 hour, filter precipitation, take supernatant and with Rotary Evaporators, dehydrated alcohol steamed, namely obtaining 1 with a small amount of NaCl, the thick product of 3-propane diamine N, N '-two (myristyl N, N ' dimethyl)-two Salicylates。
(3) 1, the purification of 3-propane diamine N, N '-two (myristyl N, N ' dimethyl) two Salicylates
1 is obtained by above-mentioned, 3-propane diamine N, N '-two (myristyl N, N ' dimethyl) the thick transferred product of-two Salicylates is to four-hole bottle, add the ethyl acetate/acetone mixture (ethyl acetate/acetone volume ratio is 2:1) of its volume 7.5 times, heated and stirred, temperature is allowed to be maintained at (85 ± 2) DEG C, solution is made to reflux, precipitation occurs bottom mixed solution, filter this precipitation and take supernatant, transfer in pears type bottle, by Rotary Evaporators evaporation of acetic acid ethyl ester/acetone mixed solvent, obtain white solid, gained white solid adds the ethyl acetate/dehydrated alcohol mixed liquor (ethyl acetate/dehydrated alcohol volume ratio is 2:1) of 6 times of its volume again, recrystallization 3-4 time, product is after vacuum drying, obtain 14-3 (OH)-14 (2Sal) sterling of 20.02g。
Embodiment 2
The preparation method of 1,3-propane diamine N, N '-two (myristyl N, N ' dimethyl) two Salicylates, comprises the steps:
(1) 1, the synthesis of 3-propane diamine N, N '-two (myristyl N, N ' dimethyl) dichloride
In 250mL four-hole bottle, add 25mL normal propyl alcohol and 0.04mol (about 13.5mL) dodecyldimethylamine base tertiary amine, magnetic stirrer is stirred (rotating speed is unsuitable too fast), there is white smoke in dropping 0.045mol concentrated hydrochloric acid (about 3.8ml), after 5-6 minute, 25mL normal propyl alcohol is dripped again with separatory funnel, and it is cooled to reactant liquor clear, colorless with cold water, survey its pH value weakly acidic pH (pH value is about 6 or 7), after white smoke in bottle disappears, dropping 0.04mol (about 3.1mL) epoxychloropropane, load onto condensing tube, electric jacket heated solution makes it reflux, after 10 minutes, first dropping dodecyldimethylamine base tertiary amine 0.06mol (about 20mL, within about 20 minutes, drip), drip 10mL normal propyl alcohol again, control temperature (98 ± 1) DEG C, voltage 120 volts, 4.5 hours response time, reactant liquor is dark brown, stop heating immediately, solution is slightly cooled down, rotary evaporation normal propyl alcohol is not until Rotary Evaporators drips solvent, more thick white shape material is now had to occur。By thick white shape substance transfer to another there-necked flask, add 60mL acetone, be heated to reflux 10 minutes, carry out hot sucking filtration, after filtrate cooling precipitates out white solid, carry out cold sucking filtration again, then recrystallization 3 times again, obtain white solid by decompression sucking filtration and be 1,3-propane diamine N, N '-two (myristyl N, N ' dimethyl)-dichloride, productivity 90.7%。Product is transferred to vacuum drying oven, dry 24 hours。
(2) 1, the synthesis of 3-propane diamine N, N '-two (myristyl N, N ' dimethyl)-two Salicylates
By above-mentioned 1,3-dry propane diamine N, N '-two (myristyl N, N ' dimethyl)-dichloride is transferred in four-hole bottle, adding dehydrated alcohol, stirring and dissolving, according to 1,3-propane diamine N, N '-two (myristyl N, N ' dimethyl)-dichloride adds sodium salicylate, stirring with the ratio that sodium salicylate mol ratio is 1:2, and in the tepidarium of (80 ± 2) DEG C, react 3.5 hours；After completion of the reaction, cooling stands, and filters precipitation, obtains supernatant and move in pears type bottle, steam solvent with Rotary Evaporators and reclaim, and namely obtains the thick product of 1,3-propane diamine N, N '-two (myristyl N, N ' dimethyl)-two Salicylates；
(3) 1, the purification of 3-propane diamine N, N '-two (myristyl N, N ' dimethyl)-two Salicylates
By step (2) gained 1, 3-propane diamine N, N '-two (myristyl N, N ' dimethyl) the thick transferred product of-two Salicylates is to four-hole bottle, add the ethyl acetate/acetone mixed solvent (ratio is 2:1) of its volume 7.5 times, continue heated and stirred backflow, temperature is maintained at (85 ± 2) DEG C, obtain the mixed solution containing a small amount of precipitation, filter and the supernatant obtained be transferred in pears type bottle, evaporation of acetic acid ethyl ester/acetone mixed solvent is continued with Rotary Evaporators, obtain white solid, gained white solid adds the acetone of its volume 6 times again, stir, recrystallization again, products obtained therefrom is through vacuum drying, obtain sterling 1, 3-propane diamine N, N '-two (myristyl N, N ' dimethyl) two Salicylates。
The product obtained carried out elementary analysis and1HNMR spectroscopic assay。Result is in Table 1
The nuclear-magnetism of table 1.14-3 (OH)-14 (2Sal) and Elemental analysis data
Table 2: the comparison of some surface activity parameters is (in order to conveniently compare, by 1,3-propane diamine N, N '-two (myristyl N, N ' dimethyl) dichloride is abbreviated as 14-3 (OH)-14 (2Cl), 1,3-propane diamine N, N '-two (myristyl N, N ' dimethyl) two Salicylates are abbreviated as 14-3 (OH)-14 (2Sal)。
Table 2. surface activity parameter (25oC)
cmc1With By Means of Electrical Conductivity, cmc2Use tensammetric determination。
By table 1,2 it can be seen that contrast the 14-3 (OH)-14 (2Cl) that counter ion is chlorine, newly synthesized surfactant is owing to introducing Organic counter-ion salicylate, making surface activity improve nearly 1 order of magnitude, namely cmc is by 0.316mmol L-1It is reduced to 0.0475 or 0.0482mmol L-1。The fusing point of compound reduces to 83-84 DEG C from 87-88 DEG C。Surface tension γ cmc during critical micelle concentration is reduced to 39.32mN mL-1。Saturated extent of adsorption also increases about 1.6 times。
Finally it should be noted that, embodiment is the detailed description of the invention that the present invention is optimum, it is not limited to the present invention, although the present invention being described in detail with reference to previous embodiment, for a person skilled in the art, technical scheme described in foregoing embodiments still can be modified by it, or wherein portion of techniques feature carries out equivalent replacement。All within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention。
The present invention has been subsidized by state natural sciences fund (No:21473084,21073081) and Liaocheng University's emphasis science fund (318011402), the teaching and research problem of emphasis (311161518)。
Claims (10)
1. novel cation Anionic Gemini Surfactant, it is characterised in that chemical name is 1,3-propane diamine N, N '-two (myristyl N, N ' dimethyl)-two Salicylates, and structural formula is as follows:
。
2. the preparation method of novel cation Anionic Gemini Surfactant as claimed in claim 1, it is characterised in that step is:
(1) 1, 3-propane diamine N, N '-two (myristyl N, N ' dimethyl) synthesis of-dichloride: in four-hole boiling flask, add normal propyl alcohol solvent and dodecyldimethylamine base tertiary amine, dropping concentrated hydrochloric acid, stir, after 5-6 minute, continue dropping normal propyl alcohol, cold water cools down, until reactant liquor clear, colorless, solution acid alkalinity weakly acidic pH is recorded with pH reagent paper, after white smoke in bottle disappears, dropping epoxychloropropane, connect cooling water, when heating flask by solvent refluxing 10 minutes with electric jacket, dropping dodecyldimethylamine base tertiary amine (dropping duration 20 minutes), drip normal propyl alcohol again, control temperature 94-102 DEG C, maintain the reflux for, voltage 120 volts, react 4-5 hour, question response liquid is dark brown, stop heating, cooling, solvent is evaporated with Rotary Evaporators, not dripping solvent to Rotary Evaporators, obtain thick white shape material and do purification process, products therefrom is transferred to vacuum drying oven, dry 24 hours, namely 1 is obtained, 3-propane diamine N, N '-two (myristyl N, N ' dimethyl) the thick product of-dichloride；
(2) 1,3-propane diamine N, N '-two (myristyl N, N ' dimethyl) synthesis of-two Salicylates: by 1,3-propane diamine N, N '-two (myristyl N, N ' dimethyl) the thick transferred product of-dichloride is to four-hole bottle, add dehydrated alcohol, stirring and dissolving, adds sodium salicylate, stirring, and in the tepidarium of 75-85 DEG C, reaction backflow 3-4 hour；After completion of the reaction, cooling stands, and by precipitation filtration, takes supernatant and moves in pears type bottle, evaporating solvent with Rotary Evaporators, namely obtaining the thick product of 1,3-propane diamine N, N '-two (myristyl N, N ' dimethyl)-two Salicylates；
(3) 1, 3-propane diamine N, N '-two (myristyl N, N ' dimethyl) purification of-two Salicylates: by step (2) gained 1, 3-propane diamine N, N '-two (myristyl N, N ' dimethyl) the thick transferred product of-two Salicylates is to four-hole bottle, add the ethyl acetate/acetone mixed solvent of its volume 5-10 times, heated and stirred refluxes, temperature is maintained at 85 ± 2 DEG C, precipitation occurs bottom mixed solution, filter this precipitation and take supernatant, transfer in pears type bottle, by Rotary Evaporators evaporation of acetic acid ethyl ester/acetone mixed solvent, obtain white solid, gained white solid solubilizer again, recrystallization, through vacuum drying, obtain sterling 1, 3-propane diamine N, N '-two (myristyl N, N ' dimethyl)-two Salicylates。
3. the preparation method of novel cation Anionic Gemini Surfactant as claimed in claim 2, it is characterized in that, step (1) dodecyldimethylamine base tertiary amine: epoxychloropropane: concentrated hydrochloric acid is preferred with molar ratio computing for 0.10: 0.04:0.04-0.05(, dodecyldimethylamine base tertiary amine: epoxychloropropane: concentrated hydrochloric acid: acetone is with molar ratio computing for 0.10: 0.04:0.045)。
4. the preparation method of novel cation Anionic Gemini Surfactant as claimed in claim 2, it is characterised in that it is 96-100 DEG C (preferred, to control temperature at 98 DEG C) that step (1) controls temperature。
5. the preparation method of novel cation Anionic Gemini Surfactant as claimed in claim 2, it is characterized in that, the operation of step (1) purification process is for by thick white shape substance transfer to another there-necked flask, add acetone, after being heated to reflux 5-15 minute, first carry out hot sucking filtration, treat that filtrate cooling precipitates out white solid, carry out cold sucking filtration again, and then recrystallization, acetone is added through decompression sucking filtration or in the pear shape bottle fill thick white object after, stand 12 hours, again liquid is transferred in four-hole bottle, heating is to boiling, carry out heat filtering, mother solution is transferred in beaker, it is cooled to room temperature, obtain white solid precipitation, reduce pressure sucking filtration again。
6. the preparation method of novel cation Anionic Gemini Surfactant as claimed in claim 2, it is characterised in that step (2) 1, and 3-propane diamine N, N '-two (myristyl N, N ' dimethyl)-dichloride: sodium salicylate is with molar ratio computing for 1: 2-2.1。
7. the preparation method of novel cation Anionic Gemini Surfactant as claimed in claim 2, it is characterised in that step (2) tepidarium temperature is 77-83 DEG C (preferred, tepidarium temperature is 80 DEG C)。
8. the preparation method of novel cation Anionic Gemini Surfactant as claimed in claim 2, it is characterised in that in step (3) ethyl acetate/acetone mixed solvent, ethyl acetate and acetone ratio are 2:1。
9. the preparation method of novel cation Anionic Gemini Surfactant as claimed in claim 2, it is characterised in that the solvent that step (3) adds is the one in acetone or ethyl acetate/dehydrated alcohol mixed liquor。
10. the preparation method of novel cation Anionic Gemini Surfactant as claimed in claim 2, it is characterised in that step (3) adds 4-8 times (preferred, to add 6 times that amount is white solid volume of solvent) that amount is white solid volume of solvent。
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| US5093448A (en) * | 1987-12-21 | 1992-03-03 | Exxon Research And Engineering Company | Polymerizable cationic visco-elastic monomer fluids |
| CN102453481A (en) * | 2011-01-21 | 2012-05-16 | 中国石油大学(北京) | Acidic visco-elastic fluid, its preparation method and application thereof |
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| US5093448A (en) * | 1987-12-21 | 1992-03-03 | Exxon Research And Engineering Company | Polymerizable cationic visco-elastic monomer fluids |
| CN102453481A (en) * | 2011-01-21 | 2012-05-16 | 中国石油大学(北京) | Acidic visco-elastic fluid, its preparation method and application thereof |
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| 陈萍等: "双十二烷基γ-双季铵盐杀菌剂的制备及其性能", 《过程工程学报》 * |
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