CN102389744B - First class s-triazine amphoteric betaine surfactant and synthesizing method thereof - Google Patents
First class s-triazine amphoteric betaine surfactant and synthesizing method thereof Download PDFInfo
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- CN102389744B CN102389744B CN201110266673.8A CN201110266673A CN102389744B CN 102389744 B CN102389744 B CN 102389744B CN 201110266673 A CN201110266673 A CN 201110266673A CN 102389744 B CN102389744 B CN 102389744B
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Abstract
The invention belongs to the field of surfactant synthetic chemistry. The first class s-triazine amphoteric betaine surfactant is characterized in that: the long alkyl carbon chains on a triazine ring are symmetrical, and the chemical name is N-(4,6-double fatty amino-1,3,5-s-triazine-2-radical)-N',N'-dimethyl-N'-carboxymethyl alkyl diamine amphoteric betaine surfactant. In addition, the invention further provides a synthesizing method of the amphoteric betaine surfactant, which takes cyanuric chloride, fatty amine, N,N-dimethyl alkyl diamine and sodium chloroacetate as main raw materials for preparation, and the amphoteric betaine surfactant is prepared through three steps. In the N-(4,6-double fatty amino-1,3,5-s-triazine-2-radical)-N',N'-dimethyl-N'-carboxymethyl alkyl diamine amphoteric betaine surfactant of the invention, compared with the sulfonate surfactant, the carboxylate amphoteric betaine surfactant has good tenderness, is not easy to settle, can be used with different surfactants in media of various pH, and has great superiority.
Description
Technical field
The invention belongs to tensio-active agent synthetic chemistry field, particularly a class s-triazine both sexes beet alkali surface activator also relates to its synthetic method in addition.
Background technology
Cyanuric chloride is important industrial raw material, and it is significant that the amine that itself and amine reaction form replaces s-triazine derivative.Three chlorine atoms on the s-triazine ring can be by stages by-OH ,-NH
2,-SH ,-displacement of functional groups such as NHR, thus the s-triazine derivative of formation different properties and purposes, for example reactive dyestuffs, agricultural chemicals and tensio-active agent etc.The s-triazine tensio-active agent demonstrates good prospects for application with characteristics such as its excellent performance and environmental friendliness.
S-triazine type tensio-active agent is to be raw material with the cyanuric chloride, prepares by amine replacement cyanuric chloride chlorine in ring atom.The hydrophobic chain of s-triazine tensio-active agent is introduced by aliphatic amide, and hydrophilic group can be introduced by the chlorine direct reaction on water-soluble organic amine and the s-triazine, perhaps introduces hydrophilic group by quaterisation.
Nitrogen-atoms in the aliphatic amide and the formed key of s-triazine ring are more firm, are not easy hydrolysis.One substituent of cyanuric chloride and aliphatic amide reaction generally just can carry out at 0～5 ℃, amido replaces s-triazine chlorine in ring atom makes the passivation of remaining two chlorine atoms, therefore, second chlorine atom of amido one replacement s-triazine replaced and will just can carry out at 30～50 ℃ by amine.In like manner, the 3rd the chlorine atom that amido two replaces on the s-triazine then will just can carry out more than 80 ℃, and the reaction complexity will determine according to activity and the reaction environment of amine nucleophilic reagent.It is loaded down with trivial details to replace s-triazine chlorine in ring atomic operation successively, and by product is more, the aftertreatment trouble, and productive rate is lower.Especially single substitution product be prepared as thermopositive reaction, the local condition of 0～5 ℃ of reaction is difficult to control, generates two easily and replaces even trisubstitution products, the aftertreatment trouble of purifying also.Solvent method is generally adopted in three substitution reactions on the s-triazine ring, has long reaction time, aftertreatment difficulty, the not high shortcoming of column chromatography for separation purification productive rate.Chen L etc. are raw material with single sodium salt of cyanuric chloride, aliphatic amide and H-acid, and sodium hydroxide is acid binding agent, by two step substitution reactions, but have synthesized the scission of link alkyl s-triazine sulfonate anionic surfactant of serial dibasic different carbon chain lengths.Xue changes to eat to wait and utilizes similar approach to synthesize fatty amido-4-(the 2-sulfo group ethyl) amido-6-chloro-1,3 of 2-, 5-s-triazine long alkyl chain tensio-active agent.Xue C L etc. with s-triazine and aliphatic amide be raw material synthesized Kraft point and micelle-forming concentration low, the serial alkyl betaine-type Gemini surface active agent that surfactivity is higher.In the building-up process of this three classes tensio-active agent, in the first step reaction, all be to have used toluene to make solvent, human body is had certain injury.Qiao Weihong etc. synthesize a class N-methyl-N-, and (synthetic method is fairly simple for 4,6-, two fatty amidos-1,3,5-guanamine-yl)-2-aminoethyl sulfonic acid sodium amphoterics.Gabriele Candiani etc. utilizes cyanuric chloride, aliphatic amide etc. to synthesize the cationic-liposome of serial cyanuro as genophore.
Summary of the invention
The purpose of this invention is to provide a class s-triazine both sexes beet alkali surface activator, mildness is good, is difficult for producing precipitation, in the medium of various pH, can be used with the tensio-active agent of any kind, and tool has an enormous advantage.
Another object of the present invention provides the synthetic method of this tensio-active agent, the reaction conditions gentleness, and aftertreatment is simple, and transformation efficiency is higher.
Technical scheme of the present invention: a class s-triazine both sexes beet alkali surface activator, long alkyl carbon chain on the triazine ring is symmetrical, chemical name: N-(4, the two fatty amidos-1 of 6-, 3, the 5-guanamine-yl)-N ', N '-dimethyl-N '-carboxymethyl alkyl diamine both sexes beet alkali surface activator, its structural formula is:
Wherein, n=8,10,12,14, the corresponding fatty octylame of difference, decyl amine, amino dodecane and tetradecy lamine, alkyl carbon atoms adds up to 16～28; M=1,2, the corresponding N of difference, N-dimethyl 1 and N, N-dimethyl-1,3-propylene diamine.
The synthetic method of the present invention's one class s-triazine both sexes beet alkali surface activator, with cyanuric chloride, aliphatic amide, N, N-dimethyl alkyl diamine and sodium chloroacetate are that main raw material divides three-step reaction:
The first step reaction: cyanuric chloride is dissolved in the chloroform, drips the aliphatic amide reaction under the room temperature, and with alkaline solution as acid binding agent; After finishing, reaction obtains intermediate 2 with chloroform/methanol (volume ratio 1/8～1/1) recrystallization, the two fatty amidos of 4--6-chloro-1,3,5-s-triazine;
The reaction of second step: under 85～95 ℃, intermediate 2, the two fatty amidos of 4--6-chloro-1,3,5-s-triazine and N, N-dimethyl alkyl diamine reaction 5～6h, reaction is finished, and adds deionized water and separates out white solid, suction filtration, be 8～9 with deionized water wash white solid to pH value, the white solid chloroform extraction, chloroform layer is with anhydrous sodium sulfate drying, filtration, desolventizing obtains intermediate N (the two fatty amidos-1 of 4,6-, 3,5-guanamine-yl)-N ', N '-dimethyl alkyl diamine;
Three-step reaction: with intermediate N (4, the two fatty amidos-1 of 6-, 3,5-guanamine-yl)-N ', ethanolic soln and the sodium chloroacetate of N '-dimethyl alkyl diamine, quaterisation 12～18h under refluxad, generate N-(the two fatty amidos-1,3 of 4,6-, the 5-guanamine-yl)-N ', N '-dimethyl-N '-carboxymethyl alkyl diamine both sexes beet alkali surface activator.
Described the first step reaction: the alkaline solution with mass concentration 5%～10% is regulated pH to 7～10, reacts 12h under the room temperature, and reaction finishes.
Used alkaline solution is a kind of in sodium hydroxide solution, potassium hydroxide solution or the sodium carbonate solution in the reaction of the described the first step.
Described second step reaction: with intermediate 2, the two fatty amidos of 4--6-chloro-1,3, the 5-s-triazine stirs and slowly is warming up to 30～40 ℃, drips N, and N-dimethyl alkyl diamine continues to be warming up to 85～95 ℃ of reaction 5～6h.
Used N in the described second step reaction, N-dimethyl alkyl diamine is N, N-dimethyl-1 or N, N-dimethyl-1, a kind of in the 3-propylene diamine.
Described three-step reaction: in intermediate N (4, the two fatty amidos-1,3 of 6-, the 5-guanamine-yl)-N ', in N '-dimethyl alkyl diamine ethanolic soln, drip the sodium chloroacetate aqueous solution and be warming up to 85～90 ℃, back flow reaction 12～18h is after reaction finishes, desolventizing obtains white solid, white solid is dissolved in ethanol, the centrifugal sodium chloroacetate of removing, desolventizing gets the white solid crude product again.
The crude product of described three-step reaction is the eluent separation and purification with chloroform/methanol mixing solutions (volume ratio is 1/6～1/1), obtain target product N-(4, the two fatty amidos-1 of 6-, 3, the 5-guanamine-yl)-N ', N '-dimethyl-N '-carboxymethyl alkyl diamine both sexes beet alkali surface activator.
The charging capacity of described the first step reaction is that the molar ratio of mol ratio 1:2～2.05, the second steps and three-step reaction is 1:1.20.
And the present invention replaces the chlorine atoms by the while two, and three replace and quaternized preparation s-triazine both sexes beet alkali surface activators then.At room temperature prepared in reaction two replaces intermediate, and the reaction conditions gentleness is simple with the recrystallization purification operations, the transformation efficiency height.With N, N-dimethyl alkyl diamine makes reactant and solvent directly carries out three substitution reactions, shortens for three substitution reaction times greatly, and recrystallization obtains three substituents simultaneously, and is simple to operate, the productive rate height.The present invention can overcome above-mentioned replacement successively well and cause by product many, and productive rate is low, shortcomings such as aftertreatment complexity.
Beneficial effect of the present invention: N-(4 of the present invention, the two fatty amidos-1 of 6-, 3,5-guanamine-yl)-N ', N '-dimethyl-N '-carboxymethyl alkyl diamine both sexes beet alkali surface activator, compare with sulfosalt surfactant, carboxylate salt both sexes beet alkali surface activator mildness among the present invention is good, is difficult for producing precipitation, in the medium of various pH, can be used with the tensio-active agent of any kind, tool has an enormous advantage.
And synthetic method of the present invention, the reaction conditions gentleness, aftertreatment is simple, and transformation efficiency is higher.Make through three-step reaction, react under the first step reaction room temperature, mild condition, the transformation efficiency height, chloroform/methanol (volume ratio 1/8～1/1) recrystallization, simple to operate; N in the second step reaction, N-dimethyl alkyl diamine is not only made reactant but also make reaction solvent, and is simple to operate, and aftertreatment is 93.1～96.3% for using deionized water recrystallization, transformation efficiency, obviously improves than 70～85% transformation efficiencys of bibliographical information in the early time.
Description of drawings
With N-(the two amino dodecane bases-1,3 of 4,6-, 5-guanamine-yl)-N ', N '-dimethyl-N '-carboxymethyl-1,3-propylene diamine both sexes beet alkali surface activator be characterized by example explanation.
Fig. 1 is N-(the two amino dodecane bases-1,3 of 4,6-, 5-guanamine-yl)-N ', N '-dimethyl-N '-carboxymethyl-1, the mass spectrum of 3-propylene diamine.Wherein,
M/z606.0044 be target product [M+H]
+The peak,
M/z909.0181 be target product [3M+2H]
+/ 2 peaks,
M/z1211.0342 be [2M+H]
+The peak.
Fig. 2 is N-(the two amino dodecane bases-1,3 of 4,6-, 5-guanamine-yl)-N ', N '-dimethyl-N '-carboxymethyl-1, the 3-propylene diamine
1HNMR schemes (400MHz, CDCl
3, 25 ℃, TMS).Wherein, 0.86-0.90 (t, 6H, 2C
H 3 CH
2), 1.25-1.28[d, 36H, 2CH
3(C
H 2 ) 9 CH
2], 1.51[s, 4H, 2CH
3(CH2)
9C
H 2 CH
2], 1.99-2.03[d, 2H, 2 (CH
3)
2NCH
2C
H 2 CH
2NH], 2.50[s, 6H, (C
H 3 )
2N (CH
2)
3NH], 3.22-3.84[m, 10H, (CH
3)
2NC
H 2 (CH
2)
2NH, OOCC
H 2 (CH
3)
2NH
2, (CH
3)
2NCH
2CH
2C
H 2 NH, 2CH
3(CH
2)
8C
H 2 NH].
Fig. 3 is N-(the two amino dodecane bases-1,3 of 4,6-, 5-guanamine-yl)-N ', N '-dimethyl-N '-carboxymethyl-1, the 3-propylene diamine
13C NMR schemes (400MHz, CDCl
3, 25 ℃, TMS).Wherein, δ=165.96,51.07,40.76,31.93,29.72,29.69,29.51,29.38,27.10,22.68,14.09.
Fig. 4 is N-(the two amino dodecane bases-1,3 of 4,6-, 5-guanamine-yl)-N ', N '-dimethyl-N '-carboxymethyl-1, the infrared spectrum of 3-propylene diamine.Wherein, 3287.32cm
-1(s) be δ
N-H, 2916.40cm
-1(s), 2848.91cm
-1(s) be δ
C-H, 1533.51cm
-1(s) be δ
C=N, 1625.66cm
-1(s) be δ
C=O, 1576.86 cm
-1(s) be δ
N-H1366.58 cm
-1Be δ
C-O, 721.23cm
-1(m) be δ
CH2(n 〉=4).
Embodiment
Below in conjunction with specific embodiment the present invention is described in further detail, but the present invention is not limited to specific embodiment.
Embodiment 1: and preparation N-(the two octylame bases-1,3 of 4,6-, the 5-guanamine-yl)-and N ', N '-dimethyl-N '-carboxymethyl-1 both sexes beet alkali surface activator
The first step reaction: intermediate 2, the two octylame bases of 4--6-chloro-1,3,5-s-triazine synthetic
In reaction flask, 1.84g (0.01mol) cyanuric chloride is dissolved in the 30mL chloroform, drips the chloroformic solution of 2.58g (0.02mol) octylame under the room temperature, regulate pH to 7～10 with 5～8% potassium hydroxide solutions, react 12h under the room temperature.Reaction finishes, and desolventizing obtains white solid.White solid obtains intermediate 2 with chloroform/methanol (volume ratio is 1/8～1/1) recrystallization, the two octylame bases of 4--6-chloro-1,3, and 5-s-triazine 2.89g, productive rate are 78.3%.
The second step reaction: intermediate N (the two octylame bases-1,3 of 4,6-, 5-guanamine-yl)-N ', N '-dimethyl-1 synthetic
With 2.89g (0.00783mol) 2, the two octylame bases of 4--6-chloro-1,3, the 5-s-triazine stirs and slowly is warming up to 30～40 ℃.Drip 20mL N, N-dimethyl-1 continues to be warming up to 85～95 ℃, reaction 5～6h.After reaction finishes, pour reaction solution into beaker, add the 200mL deionized water, the adularescent solid is separated out.White solid is 7～8 with deionized water wash until the pH value.Use the chloroform extraction white solid, the chloroform layer anhydrous sodium sulfate drying filters, and desolventizing, vacuum-drying obtain intermediate product N-(N '-dimethyl-1 3.17g, productive rate are 96.1% for the two octylame bases-1,3 of 4,6-, 5-guanamine-yl)-N '.
Three-step reaction: N-(the two octylame bases-1,3 of 4,6-, 5-guanamine-yl)-N ', N '-dimethyl-N '-carboxymethyl-1 both sexes beet alkali surface activator synthetic
At 3.17g (0.0075mol) N-(the two octylame bases-1,3 of 4,6-, the 5-guanamine-yl)-N ', in N '-dimethyl-1 ethanol, drip the aqueous solution of 1.05g (0.009mol) sodium chloroacetate and be warming up to 85～90 ℃, back flow reaction 12～18h.After reaction finishes, concentrate desolventizing, get white solid.White solid is dissolved in 30mL ethanol, the centrifugal sodium chloroacetate of removing, desolventizing again, vacuum-drying.Obtain white solid.White solid eluent chloroform: methyl alcohol=1:4(V/V) separation and purification obtains end product N-(the two octylame bases-1 of 4,6-, 3,5-guanamine-yl)-N ', N '-dimethyl-N '-carboxymethyl-1,2-quadrol both sexes beet alkali surface activator 3.02g, yield 84.1%.
Embodiment 2: and preparation N-(the two decyl amine bases-1,3 of 4,6-, the 5-guanamine-yl)-and N ', N '-dimethyl-N '-carboxymethyl-1 both sexes beet alkali surface activator
The first step reaction: intermediate 2, the two decyl amine bases of 4--6-chloro-1,3,5-s-triazine synthetic
In reaction flask, 1.84g (0.01mol) cyanuric chloride is dissolved in the 30mL chloroform, drips the chloroformic solution of 3.14g (0.02mol) decyl amine under the room temperature, regulate pH to 7～10 with 5～8% sodium hydroxide solutions, react 12h under the room temperature.Reaction finishes, and desolventizing obtains white solid.White solid obtains intermediate 2 with chloroform/methanol (volume ratio is 1/8～1/1) recrystallization, the two decyl amine bases of 4--6-chloro-1,3, and 5-s-triazine 3.31g, productive rate are 77.8%.
The second step reaction: intermediate N (the two decyl amine bases-1,3 of 4,6-, 5-guanamine-yl)-N ', N '-dimethyl-1 synthetic
With 3.31g (0.0078mol) 2, the two decyl amine bases of 4--6-chloro-1,3, the 5-s-triazine stirs and slowly is warming up to 30～40 ℃.Drip 20mL N, N-dimethyl-1 continues to be warming up to 85～95 ℃, reaction 5～6h.After reaction finishes, pour reaction solution into beaker, add the 200mL deionized water, the adularescent solid is separated out.White solid is 7～8 with deionized water wash until the pH value.Use the chloroform extraction white solid, the chloroform layer anhydrous sodium sulfate drying filters, and desolventizing, vacuum-drying obtain intermediate product N-(N '-dimethyl-1 3.52g, productive rate are 94.5% for the two decyl amine bases-1,3 of 4,6-, 5-guanamine-yl)-N '.
Three-step reaction: N-(the two decyl amine bases-1,3 of 4,6-, 5-guanamine-yl)-N ', N '-dimethyl-N '-carboxymethyl-1 both sexes beet alkali surface activator synthetic
At 3.52g (0.0074 mol) N-(the two decyl amine bases-1,3 of 4,6-, the 5-guanamine-yl)-N ', in the ethanolic soln of N '-dimethyl-1, drip the aqueous solution of 1.03g (0.0088mol) sodium chloroacetate and be warming up to 85～90 ℃, back flow reaction 12～18h.After reaction finishes, concentrate desolventizing, get white solid.White solid is dissolved in 30mL ethanol, the centrifugal sodium chloroacetate of removing, desolventizing again, vacuum-drying.Obtain white solid.White solid eluent chloroform: methyl alcohol=1:6(V/V) separation and purification obtains end product N-(the two decyl amine bases-1 of 4,6-, 3,5-guanamine-yl)-N ', N '-dimethyl-N '-carboxymethyl-1,2-quadrol both sexes beet alkali surface activator 3.43g, yield 86.7%.
Embodiment 3: and preparation N-(the two amino dodecane bases-1,3 of 4,6-, the 5-guanamine-yl)-and N ', N '-dimethyl-N '-carboxymethyl-1,2-propylene diamine amphoterics
The first step reaction: intermediate 2, the two amino dodecane bases of 4--6-chloro-1,3,5-s-triazine synthetic
In reaction flask, 1.84g (0.01mol) cyanuric chloride is dissolved in the 30mL chloroform, drips the chloroformic solution of 3.71g (0.02mol) amino dodecane under the room temperature, regulate pH to 7～10 with 5～8% sodium hydroxide solutions, react 12h under the room temperature.Reaction finishes, and desolventizing obtains white solid.White solid obtains intermediate 2 with chloroform/methanol (volume ratio is 1/8～1/1) recrystallization, the two amino dodecane bases of 4--6-chloro-1,3, and 5-s-triazine 4.24g, productive rate are 88.1%.
The second step reaction: intermediate N (the two amino dodecane bases-1,3 of 4,6-, 5-guanamine-yl)-N ', N '-dimethyl-1,3-propylene diamine synthetic
With 4.24g (0.0088mol) 2, the two amino dodecane bases of 4--6-chloro-1,3, the 5-s-triazine stirs and slowly is warming up to 30～40 ℃, drip 20mL N, N-dimethyl-1,3-propylene diamine, continue to be warming up to 85～95 ℃, reaction 5～6h after reaction finishes, pours reaction solution into beaker, add the 200mL deionized water, the adularescent solid is separated out.White solid is 8～9 with deionized water wash until the pH value.Use the chloroform extraction white solid, the chloroform layer anhydrous sodium sulfate drying filters, desolventizing, vacuum-drying obtain intermediate product N-(the two amino dodecane bases-1,3 of 4,6-, 5-guanamine-yl)-N ', N '-dimethyl-1,3-propylene diamine 4.48g, productive rate are 93.1%.
Three-step reaction: N-(the two amino dodecane bases-1,3 of 4,6-, 5-guanamine-yl)-N ', N '-dimethyl-N '-carboxymethyl-1,2-propylene diamine both sexes beet alkali surface activator synthetic
At 4.48g (0.0082mol) N-(the two amino dodecane bases-1,3 of 4,6-, the 5-guanamine-yl)-N ', N '-dimethyl-1 is in the ethanolic soln of 2-propylene diamine, drip the aqueous solution of 1.14g (0.0098mol) sodium chloroacetate and be warming up to 85～90 ℃, back flow reaction 12～18h.After reaction finishes, concentrate desolventizing, get white solid.White solid is dissolved in 30mL ethanol, the centrifugal sodium chloroacetate of removing, desolventizing again, vacuum-drying obtains white solid.White solid eluent chloroform: methyl alcohol=1:1(V/V) separation and purification obtains end product N-(the two amino dodecane bases-1 of 4,6-, 3,5-guanamine-yl)-N ', N '-dimethyl-N '-carboxymethyl-1,2-propylene diamine amphoterics 4.14g, yield 85.5%.
Embodiment 4: and preparation N-(the two tetradecy lamine bases-1,3 of 4,6-, the 5-guanamine-yl)-and N ', N '-dimethyl-N '-carboxymethyl-1,3-propylene diamine amphoterics
The first step reaction: intermediate 2, the two tetradecy lamine bases of 4--6-chloro-1,3,5-s-triazine synthetic
In reaction flask, 1.84g (0.01mol) cyanuric chloride is dissolved in the 30mL chloroform, drips the chloroformic solution of 4.26g (0.02mol) tetradecy lamine under the room temperature, regulate pH to 7～10 with 5～8% sodium carbonate solutions, react 12h under the room temperature.Reaction finishes, and desolventizing obtains white solid.White solid obtains intermediate 2 with chloroform/methanol (volume ratio is 1/8～1/1) recrystallization, the two tetradecy lamine bases of 4--6-chloro-1,3, and 5-Strinoline .05g, productive rate are 94.0%.
The second step reaction: intermediate N (the two tetradecy lamine bases-1,3 of 4,6-, 5-guanamine-yl)-N ', N '-dimethyl-1,3-propylene diamine synthetic
With 5.05g (0.0094mol) 2, the two tetradecy lamine bases of 4--6-chloro-1,3, the 5-s-triazine stirs and slowly is warming up to 30～40 ℃.Drip 20mL N, N-dimethyl-1, the 3-propylene diamine continues to be warming up to 89～90 ℃, reaction 5～6h.After reaction finishes, pour reaction solution into beaker, add the 200mL deionized water, the adularescent solid is separated out.White solid is 8～9 with deionized water wash until the pH value.Use the chloroform extraction white solid, the chloroform layer anhydrous sodium sulfate drying filters desolventizing, vacuum-drying obtains intermediate product N-(the two tetradecy lamine bases-1,3 of 4,6-, 5-guanamine-yl)-N ', N '-dimethyl-1,3-propylene diamine 5.46g, productive rate are 96.3%.
Three-step reaction: N-(the two tetradecy lamine bases-1,3 of 4,6-, 5-guanamine-yl)-N ', N '-dimethyl-N '-carboxymethyl-1,3-propylene diamine both sexes beet alkali surface activator synthetic
At 5.46g (0.0091mol) N-(the two tetradecy lamine bases-1,3 of 4,6-, the 5-guanamine-yl)-N ', N '-dimethyl-1,3-propylene diamine ethanolic soln, drip the aqueous solution of 1.26g (0.011mol) sodium chloroacetate and be warming up to 85～90 ℃, back flow reaction 12～18h.After reaction finishes, concentrate desolventizing, get white solid.White solid is dissolved in 30mL ethanol, the centrifugal sodium chloroacetate of removing, desolventizing again, vacuum-drying.Obtain white solid.White solid eluent chloroform: methyl alcohol=1:3(V/V) separation and purification obtains end product N-(the two tetradecy lamine bases-1 of 4,6-, 3,5-guanamine-yl)-N ', N '-dimethyl-N '-carboxymethyl-1,3-propylene diamine amphoterics 5.07g, yield 84.3%.
Claims (9)
1. a class s-triazine both sexes beet alkali surface activator, it is characterized in that: the long alkyl carbon chain on the triazine ring is symmetrical, chemical name: N-(4, the two fatty amidos-1 of 6-, 3, the 5-guanamine-yl)-N ', N '-dimethyl-N '-carboxymethyl alkyl diamine both sexes beet alkali surface activator, its structural formula is:
Wherein, n=8,10,12,14; M=1,2.
2. the synthetic method of a class s-triazine both sexes beet alkali surface activator, it is characterized in that: it is with cyanuric chloride, aliphatic amide, N, and N-dimethyl alkyl diamine and sodium chloroacetate are that main raw material divides three-step reaction:
The first step reaction: cyanuric chloride is dissolved in the chloroform, drips the aliphatic amide reaction under the room temperature, and with alkaline solution as acid binding agent; The reaction back that finishes is that 1/8～1/1 chloroform and recrystallizing methanol obtain intermediate 2 with volume ratio, 4-pair of fatty amidos-6-chloro-1,3,5-s-triazine;
The reaction of second step: under 85～95 ℃, intermediate 2, the two fatty amidos of 4--6-chloro-1,3,5-s-triazine and N, N-dimethyl alkyl diamine reaction 5～6h, reaction is finished, and adds deionized water and separates out white solid, suction filtration, be 8～9 with deionized water wash white solid to pH value, the white solid chloroform extraction, chloroform layer is with anhydrous sodium sulfate drying, filtration, desolventizing obtains intermediate N (the two fatty amidos-1 of 4,6-, 3,5-guanamine-yl)-N ', N '-dimethyl alkyl diamine;
Three-step reaction: with intermediate N (4, the two fatty amidos-1 of 6-, 3,5-guanamine-yl)-N ', ethanolic soln and the sodium chloroacetate of N '-dimethyl alkyl diamine, quaterisation 12～18h under refluxad, generate N-(the two fatty amidos-1,3 of 4,6-, the 5-guanamine-yl)-N ', N '-dimethyl-N '-carboxymethyl alkyl diamine both sexes beet alkali surface activator.
3. the synthetic method of a class s-triazine both sexes beet alkali surface activator according to claim 2 is characterized in that: described the first step reaction: with alkaline solution adjusting pH to 7～10 of mass concentration 5%～10%, react 12h under the room temperature, the reaction end.
4. the synthetic method of a class s-triazine both sexes beet alkali surface activator according to claim 2 is characterized in that: used alkaline solution is a kind of in sodium hydroxide solution, potassium hydroxide solution or the sodium carbonate solution in the described the first step reaction.
5. the synthetic method of a class s-triazine both sexes beet alkali surface activator according to claim 2, it is characterized in that: described second step reaction: with intermediate 2, the two fatty amidos of 4--6-chloro-1,3, the 5-s-triazine stirs and slowly is warming up to 30～40 ℃, drip N, N-dimethyl alkyl diamine continues to be warming up to 85～95 ℃ of reaction 5～6h.
6. the synthetic method of a class s-triazine both sexes beet alkali surface activator according to claim 2 is characterized in that: used N in described second step reaction, and N-dimethyl alkyl diamine is N, N-dimethyl-1,2-quadrol or N, N-dimethyl-1, a kind of in the 3-propylene diamine.
7. the synthetic method of a class s-triazine both sexes beet alkali surface activator according to claim 2 is characterized in that: the charging capacity of described the first step reaction is that the molar ratio of mol ratio 1:2～2.05, the second steps and three-step reaction is 1:1.20.
8. according to the synthetic method of the arbitrary described class s-triazine both sexes beet alkali surface activator of claim 2-7, it is characterized in that: described three-step reaction: in intermediate N (4, the two fatty amidos-1 of 6-, 3, the 5-guanamine-yl)-N ', in N '-dimethyl alkyl diamine ethanolic soln, drip the sodium chloroacetate aqueous solution and be warming up to 85～90 ℃, back flow reaction 12～18h, after reaction finished, desolventizing obtained white solid, and white solid is dissolved in ethanol, the centrifugal sodium chloroacetate of removing, desolventizing gets the white solid crude product again.
9. the synthetic method of a class s-triazine both sexes beet alkali surface activator according to claim 8, it is characterized in that: the crude product of described three-step reaction is that 1/6～1/1 chloroform and methanol mixed solution are the eluent separation and purification with volume ratio, obtain target product N-(4, the two fatty amidos-1 of 6-, 3, the 5-guanamine-yl)-N ', N '-dimethyl-N '-carboxymethyl alkyl diamine both sexes beet alkali surface activator.
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