CN1394897A - Superbranched polyquaternary ammonium salt and its preparation method - Google Patents
Superbranched polyquaternary ammonium salt and its preparation method Download PDFInfo
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Abstract
The present invention relates to a superbranched polyquaternary ammonium salt and its preparation method. Said method includes the following steps: firstly, using tertiary amine with dihydroxyl group or trihydroxy group as raw material to synthesize halogenated monoquaternary ammonium halate with two functionalities or three functionalities, then using dichloromethane as tracting agent of synthesize halogenated tertiary amine self-body with two functionalities or three functionalities, finally adding zeolite, heating and making reflux reaction so as to synthesize the invented superbranched polyquaternary ammonium salt. It can be directly used in the various places of phase transfer catalysis, nano-grade catalysis, reactor, immunodiagnosis reagent, medicine and gene vector, etc. or after having been modified it can be used in the above-mentioned various places.
Description
Technical field
The present invention relates to a kind of superbranched polyquaternary ammonium salt and preparation method thereof, belong to technical field of polymer materials.
Background technology
Branch type polymer is a kind of highly branched structure that has, and the chain backbone periphery has the novel polymeric of a large amount of end groups.Branch type polymer is divided into dendrimer, dendritic polymer and hyper-branched polymer two classes again.Dendrimer, dendritic polymer adopts disperses method or convergence method, synthetic by reaction purification step repeatedly.Dendrimer, dendritic polymer has definite algebraically, molecular structure height symmetry, the end group uniform distribution of molecule periphery.The said structure feature makes it have low melt and soltion viscosity, high dissolving and characteristics such as miscibility, hyperergy.Hyper-branched polymer is usually by AB
2Or AB
3Monomer, synthetic by single stage method.Though hyper-branched polymer does not have the ordered structure of dendrimer, dendritic polymer, show a lot of characteristics of similar dendrimer, dendritic polymer.Because its preparation method is simple relatively, has a good application prospects industrial.The main application of hyper-branched polymer comprises the carrier of nm-class catalyst, reactor, immune diagnostic reagent, medicine and gene, and can be used as the synthetic more complicated macromolecular substance of tectonic element.
Superbranched polyquaternary ammonium salt be a kind of with the nitrogen positive ion as branch point, in structure, contain the highly-branched polymers of a large amount of positive charges.This base polymer not only has the high molecular essential characteristic of branch type, and a large amount of positive charges in its structure make it have the characteristic feature of polycation.The combination of above-mentioned two kinds of features makes this base polymer show make new advances functional.The polycation with highly branched structure as a class novelty will have good application prospects in a lot of fields.
At present seldom about the report of dendroid polyquaternium family macromolecule.J.L.Kreider etc. (JOURNAL OFPOLYMER SCIENCE PART A-POLYMER CHEMISTRY 39 (6): 821-832 2001) have reported that utilizing hyperbranched one poly-(trimethylene imines) (poly (propylene imine)) of different number-average molecular weights be support, utilize HCOOH/HCHO and-NH
2Reaction with the amino tertiary amineization at edge, then with CH
3I is that quaternizing agent has synthesized a series of dendroid polyquaterniums.Synthetic dendroid polyquaternium comprises that to have only fringe node quaternized and the branch node is not quaternized or have only the branch node quaternized and fringe node is not quaternized, or all nodes are all by quaternised superbranched polyquaternary ammonium salt.
But this method need be carried out polystep reaction to polymkeric substance, therefore has shortcomings such as building-up process is loaded down with trivial details, severe reaction conditions.
Summary of the invention
The objective of the invention is to propose a kind of superbranched polyquaternary ammonium salt and preparation method thereof, overcome the shortcoming of prior art, make building-up process simple, reduce production cost of products.
The superbranched polyquaternary ammonium salt that the present invention proposes has following structure:
X＝Cl、Br；R
1、R
2、R
3＝-C
nH
2n+1(n＝1、2、3、4)
In the following formula, R
1, R
2, R
3Can be identical, also can be different.
The preparation method of the superbranched polyquaternary ammonium salt that the present invention proposes comprises the steps:
1, synthetic two functionality or three-functionality-degree halo single cropping ammonium halate:
In two hydroxyls or triatomic tertiary amine (N-methyl di-alcohol, the N-ethyldiethanolamine, N-tertiary butyl base diethanolamine, trolamine, three Virahols) in, add solvent (benzene, methylene dichloride or tetrahydrofuran (THF)), cool off with ice-water bath, under condition of stirring, with halide reagent (thionyl chloride, phosphorus tribromide, phosphorus trichloride phosphorus oxychloride or tribromo oxygen phosphorus) splash in two hydroxyls or the triatomic ertiary amine solution, the molar ratio of tertiary amine and halide reagent is 1: 0.5～5, in the reaction solvent by volume consumption be 1.5～2.5 times of both reactive material volume summations.Halide reagent removes ice-water bath after dripping off fully, reheat back flow reaction five hours.After reaction finishes, reaction mixture is poured in the beaker, allow its slow cool to room temperature, can observe and begin to separate out white crystal in the solution, leave standstill 1 hour, then suction filtration, after the gained crystal washs with dry solvent, place baking oven (40 ℃) drying, if the crystal of gained is not a white and slightly have a yellow, with dry again behind the dehydrated alcohol recrystallization.
2, the dichloromethane solution of synthetic two functionality or three-functionality-degree halo tertiary amine:
Above-mentioned the first step synthetic halo single cropping ammonium halate is dissolved in 0 ℃ the deionized water, adds methylene dichloride as extraction agent, wherein the amount of water is to dissolve halo single cropping ammonium halate fully, and the volume ratio of water and methylene dichloride is 1.5～2.5: 1; Under agitation slowly add mass percent then and be 10～15% NaOH or KOH solution to water layer and white emulsion no longer occurs; Isolate dichloromethane layer immediately, water layer extracts for several times with the each 5～10ml of methylene dichloride, and combined dichloromethane layer and extracting solution promptly obtain the dichloromethane solution of halo tertiary amine.
3, synthesis of super branched polyquaternium:
In the solution of above-mentioned second two functionality that go on foot or three-functionality-degree halo tertiary amine monomers, add zeolite, heating reflux reaction 6～8 hours adds deionized water then, and water and volume of organic solvent ratio are 1～3: 1, the rising Heating temperature continues to keep back flow reaction; Back flow reaction termination reaction after 30～50 hours again; The mixing solutions separatory is obtained aqueous layer,, place vacuum drying oven following dry 12 hours again in 30 ℃ with its oven dry; Make solvent with acetone at last, extracting 10～12 hours gets superbranched polyquaternary ammonium salt to the end after dry 12 hours.
The preparation method of the superbranched polyquaternary ammonium salt that the present invention proposes, its building-up process is simple, and reacts and carry out at normal temperatures and pressures, so the synthetic cost of product is low, and the productive rate of product is higher in addition.Institute's synthetic superbranched polyquaternary ammonium salt with the nitrogen positive ion as branch point, in structure, contain a large amount of positive charges, can be directly or again through being used for the various uses such as carrier of phase-transfer catalysis, nano level catalysis, reactor, immune diagnostic reagent, medicine and gene after the modification.Embodiment
In the concrete preparation process of the present invention, two functionality or three-functionality-degree halo single cropping ammonium halate synthetic be by different halide reagents with contain two hydroxyls or triatomic tertiary amine and react and obtain.Concrete reaction process is that two hydroxyls or triatomic tertiary amine are joined in the there-necked flask, add a certain amount of solvent then, cool off with ice-water bath, under condition of stirring, halide reagent is splashed in two hydroxyls or the triatomic ertiary amine solution, halide reagent removes ice-water bath after dripping off fully, reheat back flow reaction five hours.After reaction finishes, reaction mixture is poured in the beaker, allow its slow cool to room temperature, can observe and begin to separate out white crystal in the solution, leave standstill 1 hour, then suction filtration, after the gained crystal washs with dry solvent, place baking oven dry, if the crystal of gained is not a white and slightly have yellow, with dry again behind the dehydrated alcohol recrystallization.The ratio of tertiary amine monomers and halide reagent is decided according to different reaction monomers and halide reagent in this step reaction: wherein the tertiary amine of pair hydroxyls and the molar ratio scope of thionyl chloride are 1: 2.5～4; The molar ratio scope that the tertiary amine of two hydroxyls and three halogen (chlorine, bromine) are changed phosphorus or three halogen (chlorine, bromine) oxygen phosphorus is 1: 0.7～1; The molar ratio scope of triatomic tertiary amine and thionyl chloride is 1: 3.5～5; The molar ratio scope that triatomic tertiary amine and three halogen (chlorine, bromine) are changed phosphorus or three halogen (chlorine, bromine) oxygen phosphorus is 1: 1.1～1.25.Solvent load in the reaction (by volume) is 1.5～2.5 times of both reactive material volume summations.
Below introduce embodiments of the invention:
Embodiment 1
1, the hydrochloride of N-methyl two (2-chloro ethyl) amine is synthetic: the raw material molar ratio is a N methyldiethanol amine: thionyl chloride=1: 3.N methyldiethanol amine with 14.4ml joins in the exsiccant there-necked flask earlier, adds solvent seasoning benzene 80ml then.Cool off with ice-water bath.Under condition of stirring, with constant pressure funnel with 36.6ml thionyl chloride SOCl
2Slowly splash in the cold N methyldiethanol amine, for the SO in preventing to react
2Too violent the effusion taken thionyl chloride out of, must keep the cooling of continuous effective.As thionyl chloride SOCl
2Drip off fully, remove ice-water bath, reheat back flow reaction five hours can be observed reaction solution and become gradually and be yellow in heat-processed, layering occurs.After reaction finishes, reaction mixture is poured in the beaker, allowed its slow cool to room temperature, can observe and begin to separate out white crystal in the solution, left standstill then 1 hour.Suction filtration, gained crystal place baking oven dry (40 ℃) with after the dry benzene washing, if the crystal of gained is not a white and slightly have yellow, with dry again behind the dehydrated alcohol recrystallization.
2, N-methyl two (2-chloro ethyl) amine is synthetic: the hydrochloride of previous step synthetic N-methyl two (2-chloro ethyl) amine is dissolved in the 80ml frozen water, add the 40ml methylene dichloride as extraction agent, under agitation slowly add mass percent and be 15% NaOH solution to water layer and white emulsion no longer occurs.Isolate dichloromethane layer immediately, water layer extracts three times with the each 5ml of methylene dichloride, and combined dichloromethane layer and extracting solution promptly obtain the dichloromethane solution of product.
3, poly-(N-methyl two (the 2-chloro ethyl) amine) quaternary ammonium salt of dendroid is synthetic: the dichloromethane solution of N-methyl two (the 2-chloro ethyl) amine that will obtain above joins in the single port bottle, add zeolite, heating reflux reaction six hours, can observe a spot of white solid matter is arranged in methylene dichloride, at this time in the single port bottle, add proper amount of deionized water (volume ratio of water and methylene dichloride is 2: 1), the rising Heating temperature allows it continue to keep back flow reaction.Back flow reaction is termination reaction after 35 hours.The mixing solutions separatory is obtained aqueous layer, pour in the watch-glass, oven dry to the thick substances that can observe white occurs naturally, places vacuum drying oven (30 ℃) drying.Make solvent with acetone then, extracting 12 hours, drying can obtain that little the heavy-gravity white solid matter is arranged is poly-(N-methyl two (the 2-chloro ethyl) amine) quaternary ammonium salt of dendroid, and productive rate is 84.5%.
Embodiment 2:
1, the hydrochloride of N-methyl two (2-bromoethyl) amine is synthetic: the raw material molar ratio is a N methyldiethanol amine: phosphorus tribromide=1: 0.83.N methyldiethanol amine with 20ml joins in the exsiccant there-necked flask earlier, adds solvent seasoning benzene 70ml then.Cool off with ice-water bath.Under condition of stirring, with constant pressure funnel the 13.8ml phosphorus tribromide is slowly splashed in the cold N methyldiethanol amine, must keep the cooling of continuous effective in the dropping process.When phosphorus tribromide drips off fully, remove ice-water bath, reheat back flow reaction seven hours can be observed reaction solution and become gradually and be yellow in heat-processed, layering occurs.After reaction finishes, reaction mixture is poured in the beaker, allowed its slow cool to room temperature, can observe and begin to separate out white crystal in the solution, left standstill then 1 hour.Suction filtration, gained crystal place baking oven dry with after the dry benzene washing, if the crystal of gained is not a white and slightly have yellow, with dry again behind the dehydrated alcohol recrystallization.
2, N-methyl two (2-bromoethyl) amine is synthetic: the hydrochloride of previous step synthetic N-methyl two (2-bromoethyl) amine is dissolved in the 80ml frozen water, add the 40ml methylene dichloride as extraction agent, under agitation slowly add mass percent and be 15% KOH solution to water layer and white emulsion no longer occurs.Isolate dichloromethane layer immediately, water layer extracts three times with the each 5ml of methylene dichloride, and combined dichloromethane layer and extracting solution promptly obtain the dichloromethane solution of product.
3, poly-(N-methyl two (2-bromoethyl) amine) quaternary ammonium salt of dendroid is synthetic: the dichloromethane solution of N-methyl two (2-bromoethyl) amine that will obtain above joins in the single port bottle, add zeolite, heating reflux reaction eight hours, can observe a spot of white solid matter is arranged in methylene dichloride, at this time in the single port bottle, add proper amount of deionized water (volume ratio of water and methylene dichloride is 1.8: 1), the rising Heating temperature allows it continue to keep back flow reaction.Back flow reaction is termination reaction after 35 hours.The mixing solutions separatory is obtained aqueous layer, pour in the watch-glass, oven dry to the thick substances that can observe white occurs naturally, places vacuum drying oven (30 ℃) drying.Make solvent with acetone then, extracting 12 hours, drying can obtain that little the heavy-gravity white solid matter is arranged is poly-(N-methyl two (2-bromoethyl) amine) quaternary ammonium salt of dendroid, and productive rate is 82.3%.
Embodiment 3:
1, the hydrochloride of N-three (2-chloro ethyl) amine is synthetic: the raw material molar ratio is a trolamine: thionyl chloride=1: 4.N methyldiethanol amine with 15ml joins in the exsiccant there-necked flask earlier, adds solvent seasoning benzene 90ml then.Cool off with ice-water bath.Under condition of stirring, with constant pressure funnel with 33ml thionyl chloride SOCl
2Slowly splash in the cold trolamine, for the SO in preventing to react
2Too violent the effusion taken thionyl chloride out of, must keep the cooling of continuous effective.As thionyl chloride SOCl
2Drip off fully, remove ice-water bath, reheat back flow reaction six hours can be observed reaction solution and become gradually and be yellow in heat-processed, layering occurs.After reaction finishes, reaction mixture is poured in the beaker, allowed its slow cool to room temperature, can observe and begin to separate out white crystal in the solution, left standstill then 1 hour.Suction filtration, gained crystal place baking oven dry (40 ℃) with after the dry benzene washing, if the crystal of gained is not a white and slightly have yellow, with dry again behind the dehydrated alcohol recrystallization.
2, N-three (2-chloro ethyl) amine is synthetic: the hydrochloride of previous step synthetic N-three (2-chloro ethyl) amine is dissolved in the 80ml frozen water, add the 40ml methylene dichloride as extraction agent, under agitation slowly add mass percent and be 15% NaOH solution to water layer and white emulsion no longer occurs.Isolate dichloromethane layer immediately, water layer extracts three times with the each 5ml of methylene dichloride, and combined dichloromethane layer and extracting solution promptly obtain the dichloromethane solution of product.
3, poly-(N-three (the 2-chloro ethyl) amine) quaternary ammonium salt of dendroid is synthetic: the dichloromethane solution of N-three (the 2-chloro ethyl) amine that will obtain above joins in the single port bottle, add zeolite, heating reflux reaction seven hours, in the single port bottle, add proper amount of deionized water (volume ratio of water and methylene dichloride is 2.5: 1) then, the rising Heating temperature allows it continue to keep back flow reaction.Back flow reaction is termination reaction after 42 hours.The mixing solutions separatory is obtained aqueous layer, pour in the watch-glass, according to occurring, place vacuum drying oven (30 ℃) drying to the thick substances that can observe white with common infrared lamp baking.Make solvent with acetone then, extracting 12 hours, drying can obtain that little the heavy-gravity white solid matter is arranged is poly-(N-three (the 2-chloro ethyl) amine) quaternary ammonium salt of dendroid, and productive rate is 83.8%.
Embodiment 4:
1, the bromate of N-three (2-bromoethyl) amine is synthetic: the raw material molar ratio is a trolamine: phosphorus tribromide=1: 1.25.Trolamine with 20ml joins in the exsiccant there-necked flask earlier, adds solvent seasoning benzene 70ml then.Cool off with ice-water bath.Under condition of stirring, with constant pressure funnel the 27ml phosphorus tribromide is slowly splashed in the cold trolamine, the dropping process must keep the cooling of continuous effective.When phosphorus tribromide drips off fully, remove ice-water bath, reheat back flow reaction five hours.After reaction finishes, reaction mixture is poured in the beaker, allowed its slow cool to room temperature, can observe and begin to separate out white crystal in the solution, left standstill again 1 hour.Suction filtration, then with the gained crystal with after the dry benzene washing, place baking oven dry (40 ℃), if the crystal of gained is not a white and slightly have yellow, with dry again behind the dehydrated alcohol recrystallization.
2, N-three (2-bromoethyl) amine is synthetic: the hydrochloride of previous step synthetic N-three (2-bromoethyl) amine is dissolved in the 80ml frozen water, add the 40ml methylene dichloride as extraction agent, under agitation slowly add mass percent and be 12% NaOH solution to water layer and white emulsion no longer occurs.Isolate dichloromethane layer immediately, water layer extracts twice with the each 8ml of methylene dichloride, and combined dichloromethane layer and extracting solution promptly obtain the dichloromethane solution of product.
3, poly-(N-three (2-bromoethyl) amine) quaternary ammonium salt of dendroid is synthetic: the dichloromethane solution of three (2-bromoethyl) amine that will obtain above joins in the single port bottle, add zeolite, heating reflux reaction seven hours, in the single port bottle, add proper amount of deionized water (volume ratio of water and methylene dichloride is 1.5: 1) then, the rising Heating temperature allows it continue to keep back flow reaction.Back flow reaction is termination reaction after 40 hours.The mixing solutions separatory is obtained aqueous layer, pour in the watch-glass, common infrared lamp baking places vacuum drying oven (30 ℃) drying according to occurring to the thick substances that can observe white.Make solvent with acetone then, extracting 12 hours, drying can obtain little heavy-gravity white solid matter that has, and promptly dendroid is gathered (N-three (2-bromoethyl) amine) quaternary ammonium salt, and productive rate is 82.1%.
Embodiment 5:
1, the hydrochloride of N-ethyl two (2-chloro ethyl) amine is synthetic: the raw material molar ratio is the N-ethyldiethanolamine: phosphorus trichloride=1: 0.8.N-ethyldiethanolamine with 0.2mol joins in the exsiccant there-necked flask earlier, adds methylene chloride 80ml then.Cool off with ice-water bath.Under condition of stirring, with constant pressure funnel the 0.16mol phosphorus trichloride is slowly splashed in the cold N-ethyldiethanolamine, must keep the cooling of continuous effective in the dropping process.When phosphorus trichloride drips off fully, remove ice-water bath, reheat back flow reaction eight hours.After reaction finishes, reaction mixture is poured in the beaker, allowed its slow cool to room temperature, can observe and begin to separate out white crystal in the solution, left standstill then 1 hour.Suction filtration, gained crystal place baking oven dry (40 ℃) with after the dry methylene chloride washing, if the crystal of gained is not a white and slightly have yellow, with dry again behind the dehydrated alcohol recrystallization.
2, N-ethyl two (2-chloro ethyl) amine is synthetic: the hydrochloride of previous step synthetic N-ethyl two (2-chloro ethyl) amine is dissolved in the 80ml frozen water, add the 40ml methylene dichloride as extraction agent, under agitation slowly add mass percent and be 15% NaOH solution to water layer and white emulsion no longer occurs.Isolate dichloromethane layer immediately, water layer extracts twice with the each 10ml of methylene dichloride, and combined dichloromethane layer and extracting solution promptly obtain the dichloromethane solution of product.
3, poly-(N-ethyl two (the 2-chloro ethyl) amine) quaternary ammonium salt of dendroid is synthetic: the dichloromethane solution of N-ethyl two (the 2-chloro ethyl) amine that will obtain above joins in the single port bottle, add zeolite, heating reflux reaction eight hours, in the single port bottle, add proper amount of deionized water (volume ratio of water and methylene dichloride is 2: 1) then, the rising Heating temperature allows it continue to keep back flow reaction.Back flow reaction is termination reaction after 50 hours.The mixing solutions separatory is obtained aqueous layer, pour in the watch-glass, common infrared lamp baking was shone after 12 hours, and the thick substances that can observe white occurs, and places vacuum drying oven (30 ℃) drying.Make solvent with acetone then, extracting 12 hours, drying can obtain little heavy-gravity white solid matter that has, and promptly dendroid is gathered (N-ethyl two (2-chloro ethyl) amine) quaternary ammonium salt, and productive rate is 78.5%.
Embodiment 6:
1, the hydrochloride of the N-tertiary butyl two (2-chloro ethyl) amine is synthetic: the raw material molar ratio is a N-tertiary butyl diethanolamine: phosphorus oxychloride=1: 0.9.N-tertiary butyl diethanolamine with 0.2mol joins in the exsiccant there-necked flask earlier, adds solvents tetrahydrofurane 90ml then.Cool off with ice-water bath.Under condition of stirring, with constant pressure funnel the 0.18mol phosphorus trichloride is slowly splashed in the cold N-tertiary butyl diethanolamine, must keep the cooling of continuous effective in the dropping process.When phosphorus oxychloride drips off fully, remove ice-water bath, reheat back flow reaction eight hours.After reaction finishes, reaction mixture is poured in the beaker, allowed its slow cool to room temperature, can observe and begin to separate out white crystal in the solution, left standstill then 1 hour.Suction filtration, gained crystal place baking oven dry (40 ℃) with after the tetrahydrofuran (THF) washing, if the crystal of gained is not a white and slightly have yellow, with dry again behind the dehydrated alcohol recrystallization.
2, the N-tertiary butyl two (2-chloro ethyl) amine is synthetic: the hydrochloride of the previous step synthetic N-tertiary butyl two (2-chloro ethyl) amine is dissolved in the 80ml frozen water, add the 40ml methylene dichloride as extraction agent, under agitation slowly add mass percent and be 15% NaOH solution to water layer and white emulsion no longer occurs.Isolate dichloromethane layer immediately, water layer extracts three times with the each 5ml of methylene dichloride, and combined dichloromethane layer and extracting solution promptly obtain the dichloromethane solution of product.
3, poly-(the N-tertiary butyl two (the 2-chloro ethyl) amine) quaternary ammonium salt of dendroid is synthetic: the dichloromethane solution of the N-tertiary butyl two (the 2-chloro ethyl) amine that will obtain above joins in the single port bottle, add zeolite, heating reflux reaction eight hours, in the single port bottle, add proper amount of deionized water (volume ratio of water and methylene dichloride is 1.5: 1) then, the rising Heating temperature allows it continue to keep back flow reaction.Back flow reaction is termination reaction after 50 hours.The mixing solutions separatory is obtained aqueous layer, pour in the watch-glass, common infrared lamp baking places vacuum drying oven (30 ℃) drying again according to occurring to the thick substances that can observe white.Make solvent with acetone then, extracting 12 hours, drying can obtain little heavy-gravity white solid matter that has, and promptly dendroid is gathered (the N-tertiary butyl two (2-chloro ethyl) amine) quaternary ammonium salt, and productive rate is 75.8%.Embodiment 7:
1, the hydrochloride of N-three (2-bromo sec.-propyl) amine is synthetic: the raw material molar ratio is a tri-isopropanolamine: tribromo oxygen phosphorus=1: 1.15.N-tertiary butyl diethanolamine with 0.2mol joins in the exsiccant there-necked flask earlier, adds solvent benzol 90ml then.Cool off with ice-water bath.Under condition of stirring, with constant pressure funnel 0.23mol tribromo oxygen phosphorus is slowly splashed in the cold tri-isopropanolamine, must keep the cooling of continuous effective in the dropping process.When tribromo oxygen phosphorus drips off fully, remove ice-water bath, reheat back flow reaction eight hours.After reaction finishes, reaction mixture is poured in the beaker, allowed its slow cool to room temperature, can observe and begin to separate out white crystal in the solution, left standstill then 1 hour.Suction filtration, gained crystal place baking oven dry (40 ℃) with after the benzene washing, if the crystal of gained is not a white and slightly have yellow, with dry again behind the dehydrated alcohol recrystallization.
2, N-three (2-bromo sec.-propyl) amine is synthetic: the hydrochloride of previous step synthetic N-three (2-bromo sec.-propyl) amine is dissolved in the 80ml frozen water, add the 40ml methylene dichloride as extraction agent, under agitation slowly add mass percent and be 15% NaOH solution to water layer and white emulsion no longer occurs.Isolate dichloromethane layer immediately, water layer extracts three times with the each 5ml of methylene dichloride, and combined dichloromethane layer and extracting solution promptly obtain the dichloromethane solution of product.
3, poly-(N-three (the 2-bromo sec.-propyl) amine) quaternary ammonium salt of dendroid is synthetic: the dichloromethane solution of N-three (the 2-bromo sec.-propyl) amine that will obtain above joins in the single port bottle, add zeolite, heating reflux reaction eight hours, in the single port bottle, add proper amount of deionized water (volume ratio of water and methylene dichloride is 1.8: 2) then, the rising Heating temperature allows it continue to keep back flow reaction.Back flow reaction is termination reaction after 50 hours.The mixing solutions separatory is obtained aqueous layer, pour in the watch-glass, common infrared lamp baking places vacuum drying oven (30 ℃) drying again according to occurring to the thick substances that can observe white.Make solvent with acetone then, extracting 12 hours, drying can obtain little heavy-gravity white solid matter that has, and promptly dendroid is gathered (N-three (2-bromo sec.-propyl) amine) quaternary ammonium salt, and productive rate is 75.2%.
Claims (5)
1, a kind of superbranched polyquaternary ammonium salt is characterized in that having following structure:
X＝Cl、Br；R
1、R
2、R
3＝-CnH
2n+1(n＝1、2、3、4)
In the following formula, R
1, R
2, R
3Identical or inequality.
2, a kind of preparation method of superbranched polyquaternary ammonium salt is characterized in that this preparation method comprises the steps:
(1) synthetic two functionality or three-functionality-degree halo single cropping ammonium halate:
In two hydroxyls or triatomic tertiary amine, add solvent, cool off with ice-water bath, under condition of stirring, halide reagent is splashed in two hydroxyls or the triatomic ertiary amine solution, and the molar ratio of tertiary amine and halide reagent is 1: 0.5～5, in the reaction solvent by volume consumption be 1.5～2.5 times of both reactive material volume summations, heating reflux reaction five hours,, slow cool to room temperature, suction filtration, gained crystal place 40 ℃ in baking oven dry down;
(2) dichloromethane solution of synthetic two functionality or three-functionality-degree halo tertiary amine:
Above-mentioned the first step synthetic halo single cropping ammonium halate is dissolved in 0 ℃ the deionized water, add methylene dichloride as extraction agent, wherein the amount of water is to dissolve halo single cropping ammonium halate fully, the volume ratio of water and methylene dichloride is 1.5～2.5: 1, under agitation slowly add mass percent then and be 10～15% NaOH or KOH solution to water layer and white emulsion no longer occurs, isolate dichloromethane layer, water layer extracts for several times with methylene dichloride 5～10ml, combined dichloromethane layer and extracting solution promptly obtain the dichloromethane solution of halo tertiary amine;
(3) synthesis of super branched polyquaternium:
In the solution of above-mentioned second two functionality that go on foot or three-functionality-degree halo tertiary amine monomers, add zeolite, heating reflux reaction 6～8 hours adds deionized water then, and water and volume of organic solvent ratio are 1～3: 1, the rising Heating temperature continues to keep back flow reaction; Back flow reaction termination reaction after 30～50 hours obtains aqueous layer with the mixing solutions separatory again, with its oven dry, place again vacuum drying oven in 30 ℃～40 ℃ dry 10～12 hours down; Make solvent with acetone at last, extracting 10～12 hours obtains superbranched polyquaternary ammonium salt after dry 12 hours.
3, method as claimed in claim 2 is characterized in that wherein two hydroxyls in (1) step or triatomic tertiary amine are any in N-methyl di-alcohol, N-ethyldiethanolamine, N-tertiary butyl base diethanolamine, trolamine or three Virahols.
4, method as claimed in claim 2, the solvent that it is characterized in that wherein for (1) step are any in benzene, methylene dichloride or the tetrahydrofuran (THF).
5, method as claimed in claim 2, the halide reagent that it is characterized in that wherein for (1) step are any in thionyl chloride, phosphorus tribromide, phosphorus trichloride phosphorus oxychloride or the tribromo oxygen phosphorus.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012784A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Preparation method of polyquaternary ammonium salt, product obtained with method, and application thereof |
| CN103012783A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Preparation method of polyquaternary ammonium salt, product obtained with method, and application thereof |
| CN105860040A (en) * | 2016-05-12 | 2016-08-17 | 江南大学 | Hyperbranched polyether ester preparation method |
| CN107344914A (en) * | 2017-07-06 | 2017-11-14 | 陕西科技大学 | A kind of synthesis technique of antibacterial debonding agent, antibacterial debonding agent and purposes |
-
2002
- 2002-08-21 CN CNB021289050A patent/CN1169863C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012784A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Preparation method of polyquaternary ammonium salt, product obtained with method, and application thereof |
| CN103012783A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Preparation method of polyquaternary ammonium salt, product obtained with method, and application thereof |
| CN103012783B (en) * | 2011-09-22 | 2015-01-14 | 中国石油化工股份有限公司 | Preparation method of polyquaternary ammonium salt, product obtained with method, and application thereof |
| CN103012784B (en) * | 2011-09-22 | 2015-01-14 | 中国石油化工股份有限公司 | Preparation method of polyquaternary ammonium salt, product obtained with method, and application thereof |
| CN105860040A (en) * | 2016-05-12 | 2016-08-17 | 江南大学 | Hyperbranched polyether ester preparation method |
| CN105860040B (en) * | 2016-05-12 | 2017-10-13 | 江南大学 | A kind of preparation method of ultra-branching polyether ester |
| CN107344914A (en) * | 2017-07-06 | 2017-11-14 | 陕西科技大学 | A kind of synthesis technique of antibacterial debonding agent, antibacterial debonding agent and purposes |
| CN107344914B (en) * | 2017-07-06 | 2019-07-12 | 陕西科技大学 | A kind of synthesis technology of antibacterial debonding agent, antibacterial debonding agent and purposes |
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| CN1169863C (en) | 2004-10-06 |
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