CN104689799A - Method for preparing flexible arm phenylalkylamine-modified macroporous resin - Google Patents
Method for preparing flexible arm phenylalkylamine-modified macroporous resin Download PDFInfo
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Abstract
The invention discloses a method for preparing flexible arm phenylalkylamine-modified macroporous resin, and particularly relates to a method for modifying D113 cation exchange resin by adopting phenylalkylamine. With commercially available phenylalkylamine, dicyclohexylcarbodiimide and D113 cation exchange resin as raw materials, the flexible arm phenylalkylamine-modified macroporous resin is prepared by simple processes of preparing a mixed liquid, preparing hydrogen-form D113 cation exchange resin, preparing a hydrogen-form D113 cation exchange resin glycerinum dispersion liquid, grafting, and recovering glycerinum and ethyl alcohol. The method is high in specifity, simple and convenient to operate, simple in production equipment, and mild in reaction condition; energy sources are saved; material resources are recycled; emission of three wastes is avoided; the method is environmentally friendly; and the flexible arm phenylalkylamine-modified macroporous resin prepared by the method disclosed by the invention can be widely applied to the fields of separation of bioengineering products and medicines and the like.
Description
One, technical field
The present invention relates to macroreticular resin preparation field, be specifically related to a kind of method preparing flexible arm phenylalkylamine modification macroreticular resin.
Two, background technology
The reactive polymer that macroporous absorbent resin is is skeleton with polystyrene or polyacrylate etc., with the adsorbing separation of the realize target such as hydrogen bond, hydrophobic interaction thing, extensive use in medicine preparation, medical analysis, compound purifying, wastewater treatment etc.
Existing macroporous absorbent resin is almost all using its skeleton as adsorption functional group, and such as polystyrene type polymeric adsorbent take phenyl as adsorption functional group, and polyacrylate polymeric adsorbent is its adsorption functional group with ester bond ketonic oxygen.Be that the polymeric adsorbent of adsorption functional group exists following defect with skeleton: 1. adsorption functional group is positioned on resin matrix, the impact by adjacent group is large, adsorbate near time resistance large, cause adsorption capacity little; 2. can only adsorbate near adsorption and diffusion to skeleton, action space is narrow; And the diffusional resistance that adsorbate diffuses near resin matrix is very big, thus adsorption capacity is low; 3. adsorption functional group is single and kind is few, and be difficult to meet the adsorbate of various structures and form with it single-minded absorption, be separated selectivity poor, separative efficiency is low.Therefore, be necessary the thinking innovated, research and development new macroporous polymeric adsorbent.
With existing macroreticular resin for inert carrier, introduce specific adsorption functional group by chemical reaction, preparation modification type macroporous absorbent resin is one of main method researching and developing new macroporous polymeric adsorbent now.Such as application number is 201110410753.6, name is called the patent of invention of " a kind of method preparing polylysine modification both sexes macroporous ion exchange resin ", disclosed in this patent, method is: join in lysine solution by macropore acidulous acrylic acid cationic ion-exchange resin, stirring and adsorbing is after 3 hours, add dicyclohexylcarbodiimide ethanolic solution again and carry out graft reaction 1-2 hour, collect grafting reactant, be carry out suction filtration after ethanol and the distilled water washing of 95% to be separated by volumetric concentration, collect trapped substance and be the polylysine modification both sexes macroporous ion exchange resin prepared.The subject matter that the method exists is: the both sexes macroporous ion exchange resin 1. prepared exists yin, yang two kinds of cation exchange groups simultaneously, both can exchange cation when being separated, and also can exchange anion, inferior separating effect simultaneously; 2. carry out dehydration condensation in aqueous, meet water due to dicyclohexylcarbodiimide and be namely hydrolyzed, generate water-insoluble isourea, grafting efficiency is poor.Master's thesis " synthesis characterization of cross-linked chitosan-L-phenylalanine resin and application " disclosed in September, 2009 University Of Chongqing, disclosed in this paper, method is: shitosan is used 1% dissolving with hydrochloric acid, obtains shitosan colloidal sol; Add the last atoleine of Paris white and Tween 80 dispersion, obtain shitosan emulsion; Crosslinked chitosan resin is obtained again through glutaraldehyde cross-linking, adjustment pH, drilling and washing step; Crosslinked chitosan resin to be scattered in 50% ethanolic solution containing phenylalanine stirring and adsorbing after 3 hours, then to add dicyclohexylcarbodiimide ethanol solution and carry out dehydration condensation.Question response completely after, by volumetric concentration be 95% ethanol with carry out suction filtration after distilled water washing and be separated, collect trapped substance and obtain cross-linked chitosan-L-phenylalanine resin.The subject matter that the method exists is: the cross-linked chitosan-L-phenylalanine resin 1. prepared is subject to microorganism or glycosidases, generates soluble small molecular, poor stability; 2. the method only make use of amino and carries out cross-linking reaction, and form Schiff key and amido link respectively, percent grafting is low; And make a large amount of chitosan hydroxyl existed be in idle state, though the reactivity of chitosan hydroxyl is lower than amino, but the good hydrogen donor of hydrogen bond and hydrogen acceptor, thus this method had both wasted active group, significantly reduced again absorption selectivity; 3. existing phenyl on cross-linked chitosan-L-phenylalanine resin that this legal system is standby, the amino of lotus positive electricity is had again, also has a large amount of free hydroxyl group, the hydrophobic interaction of existing phenyl when being therefore separated, there is again amino electrostatic interaction, also have interaction of hydrogen bond, thus it is separated selectivity and effect inequality.
Three, summary of the invention
The object of the invention is to: provide a kind of and prepare the method that flexible arm phenylalkylamine modifies macroreticular resin, there is reaction condition gentleness, simple to operate, cost is lower, easy to utilize, the absorption selectivity of environmental protection and modified resins is strong, separative efficiency high.
Principle of the present invention is: 1. the functional group of D113 cationic ion-exchange resin is free carboxy, under the catalysis of condensing agent dicyclohexylcarbodiimide, this carboxyl and phenylalkylamine generation condensation reaction, the amino generation dehydration condensation of such as this carboxyl and phenylethylamine or phenylpropylamine or phenyibutylamine, generates amido link.2. the resin after modifying is only adsorption functional group with phenyl ring, phenyl ring is the flat annular structure of electron cloud mean allocation, when " closing on " with the adsorbate containing phenyl ring or ring-like structure, selectivity absorption is formed between the two by π-π hydrophobic interaction, both structures are more similar, and the selectivity adsorption area of formation is larger, absorption is more firm, separating effect is better.Owing to forming amido link with the carboxyl dehydration of the amino of phenylalkylamine and D113 cationic ion-exchange resin, the alkyl connected between phenyl and resin amido link is strand, can different angles rotate or " stretching ", likeness in form flexible arm, so just prepare the macroporous absorbent resin of flexible arm phenylalkylamine modification.
Realize technical scheme of the present invention: a kind of method preparing flexible arm phenylalkylamine modification macroreticular resin, with commercially available phenylalkylamine, dicyclohexylcarbodiimide and D113 cationic ion-exchange resin for raw material, through preparing mixed liquor, preparing Hydrogen D113 cationic ion-exchange resin, prepare D113 cationic ion-exchange resin glycerine dispersion liquid, preparing the step that phenylalkylamine modifies macroporous absorbent resin and recovery glycerine and ethanol, prepare the macroporous absorbent resin modified through phenylalkylamine.Its concrete method step is as follows:
1. phenylalkylamine-carbodiimide alcohol mixeding liquid is prepared
It is first the ratio of 1: 1 ~ 3 (mmol: mmol) according to the mol ratio of phenylalkylamine and dicyclohexylcarbodiimide, under agitation successively phenylalkylamine and dicyclohexylcarbodiimide are dissolved in absolute ethyl alcohol, make ethanolic solution that phenylalkylamine concentration is 0.2 ~ 0.5mmol/L and dicyclohexylcarbodiimide concentration is the ethanolic solution of 0.2 ~ 1.5mmol/L, then both equal proportions are mixed, namely make phenylalkylamine-carbodiimide alcohol mixeding liquid, wherein phenylalkylamine comprises phenylethylamine, phenylpropylamine, phenyibutylamine.
2. Hydrogen D113 cationic ion-exchange resin is prepared
Newly purchase D113 cationic ion-exchange resin and first use purified rinse water, refilter, collect filtrate and trapped substance respectively.To the filtrate of collecting, pump into clarifier-tank process rear discharge up to standard; To the trapped substance collected, the volume ratio being the hydrochloric acid solution of 2 ~ 6% according to the quality of trapped substance and volumetric concentration is the ratio of 1: 4 ~ 8 (g: mL), trapped substance being scattered in volumetric concentration is process 30 ~ 60min in the hydrochloric acid solution of 2 ~ 6%, then filters.Collect trapped substance and filtrate respectively, to the filtrate of collecting, can again for the preparation of Hydrogen D113 cationic ion-exchange resin when supplementary hydrochloric acid to volumetric concentration is 2 ~ 6%; The trapped substance pure water collected repeatedly is rinsed, filtered, until again filter and collect trapped substance when pH reaches 5, namely prepare Hydrogen D113 cationic ion-exchange resin, for repeatedly rinsing with pure water, filtering and the filtrate of collecting, pump into clarifier-tank process rear discharge up to standard.
3. Hydrogen D113 cationic ion-exchange resin glycerine dispersion liquid is prepared
2. walked after, according to the ratio that the quality of Hydrogen D113 cationic ion-exchange resin and the volume ratio of glycerine are 1: 3 ~ 6 (g: mL), first glycerine is pumped in reactor, under agitation add again and 2. walk the Hydrogen D113 cationic ion-exchange resin prepared, continue stirring 30 ~ 60min, namely prepare D113 cationic ion-exchange resin glycerine dispersion liquid, prepare phenylalkylamine for lower step and modify macroreticular resin.
4. prepare phenylalkylamine and modify macroreticular resin
3. walked after, according to the ratio that the volume ratio of Hydrogen D113 cationic ion-exchange resin glycerine dispersion liquid and phenylalkylamine-carbodiimide alcohol mixeding liquid is 1: 3 ~ 6 (mL: mL), add phenylalkylamine-carbodiimide alcohol mixeding liquid that 1. walk preparation, stirring reaction 60 ~ 90min.Carry out centrifugation after having reacted, collect sediment and the supernatant liquor of centrifugation respectively, to the supernatant liquor collected, for reclaiming glycerine and ethanol; To the sediment collected, according to the ratio that the volume ratio of sedimentary quality and 50 ~ 80% ethanolic solutions is 1: 4 ~ 8 (g: mL), stir condition under, add in sediment concentration be 50 ~ 80% ethanolic solution wash, the time is 3060min.Agitator treating filters after completing, and collects trapped substance and filtrate respectively, to the trapped substance collected, repeats three times wash and filter according to identical condition, collects trapped substance and filtrate.For the filtrate of collecting, for reclaiming ethanol; For the trapped substance collected, according to the ratio that the quality of trapped substance and pure water volume ratio are 1: 5 ~ 8 (g: mL), in trapped substance, add pure water carry out agitator treating 30 ~ 60min, filter after agitator treating completes, collect trapped substance and filtrate respectively.For the trapped substance collected, be phenylalkylamine and modify macroreticular resin; For the filtrate of collecting, pump into clarifier-tank and process, rear discharge up to standard.
5. glycerine and ethanol is reclaimed
The 4. walked after, the supernatant liquor 4. walking collection by the is sent in distillation still, and controlling vapo(u)rizing temperature is 65 ~ 85 DEG C, distillation ethanol, until stop distillation without during ethanol taste.Blowing also carries out vacuum filtration, collects vacuum filtration filtrate and trapped substance respectively, to the trapped substance collected, is dicyclohexylisourea, as the raw material of synthetic chemistry reagent, fine chemicals, medicine intermediate, material intermediate.To the filtrate of collecting, send in decompression distillation still, control temperature is 85 ~ 95 DEG C, and vacuum is that 0.08 ~ 0.1MPa carries out decompression distillation, until distillation moisture lower than 1% time only.The distillation collected, is recovery glycerine, can again for the preparation of D113 cationic ion-exchange resin glycerine dispersion liquid.
After the present invention adopts technique scheme, mainly contain following effect:
1. the present invention prepares the macroreticular resin that phenylalkylamine is modified, because the alkyl in phenylalkylamine is strand, rotatable and " stretching ", in addition chain length is different, be equivalent to the flexible arm connecting different length between adsorption functional group phenyl and resin carrier amido link, expand the sphere of action of adsorption functional group phenyl.
2. the adsorption functional group of macroreticular resin that the inventive method is prepared is only phenyl, adsorbate by means of only π-π hydrophobic interaction and similar forms selectivity and adsorbs, both structures are more similar, and the selectivity adsorption area of formation is larger, absorption is more firm, separating effect is better.Therefore, this polymeric adsorbent can be used for the benzene series adsorbates such as efficient separating aromatic amino acid, flavones.Experimental result is pointed out, this polymeric adsorbent is applied to separation of phenylalanine, and obtaining its adsorbance is 0.623mmol/g, and be better than the cross-linked chitosan-L-phenylalanine resin described in technical background, this resin is to the adsorbance 0.471mmol/g of phenylalanine.
3. this preparation technology reaction condition is gentle, economize energy, without obviously " three wastes " generation, and environmental protection.
Four, detailed description of the invention
Below in conjunction with detailed description of the invention, further illustrate the present invention.
Embodiment 1
Prepare the method that flexible arm phenylalkylamine modifies macroreticular resin, concrete grammar step is as follows:
1. phenylalkylamine-carbodiimide alcohol mixeding liquid is prepared
It is first the ratio of 1: 1 (mmol: mmol) according to the mol ratio of phenylalkylamine and dicyclohexylcarbodiimide, under agitation successively phenylalkylamine and dicyclohexylcarbodiimide are dissolved in absolute ethyl alcohol, make ethanolic solution that phenylalkylamine concentration is 0.2mmol/L and dicyclohexylcarbodiimide concentration is the ethanolic solution of 0.2mmol/L, then both equal proportions are mixed, namely make phenylalkylamine-carbodiimide alcohol mixeding liquid, wherein phenylalkylamine comprises phenylethylamine, phenylpropylamine, phenyibutylamine.
2. Hydrogen D113 cationic ion-exchange resin is prepared
Newly purchase D113 cationic ion-exchange resin and first use purified rinse water, refilter, collect filtrate and trapped substance respectively.To the filtrate of collecting, pump into clarifier-tank process rear discharge up to standard; To the trapped substance collected, the volume ratio being the hydrochloric acid solution of 2% according to the quality of trapped substance and volumetric concentration is the ratio of 1: 4 (g: mL), under agitation trapped substance being scattered in volumetric concentration is process 30min in the hydrochloric acid solution of 2%, then filters.Collect trapped substance and filtrate respectively, to the filtrate of collecting, can again for the preparation of Hydrogen D113 cationic ion-exchange resin when supplementary hydrochloric acid to volumetric concentration is 2%; The trapped substance pure water collected repeatedly is rinsed, filtered, until again filter and collect trapped substance when pH reaches 5, namely prepare Hydrogen D113 cationic ion-exchange resin, for repeatedly rinsing with pure water, filtering and the filtrate of collecting, pump into clarifier-tank process rear discharge up to standard.
3. Hydrogen D113 cationic ion-exchange resin glycerine dispersion liquid is prepared
2. walked after, according to the ratio that the quality of Hydrogen D113 cationic ion-exchange resin and the volume ratio of glycerine are 1: 3 (g: mL), first glycerine is pumped in reactor, under agitation add again and 2. walk the Hydrogen D113 cationic ion-exchange resin prepared, continue to stir 30min, namely prepare D113 cationic ion-exchange resin glycerine dispersion liquid, prepare phenylalkylamine for lower step and modify macroreticular resin.
4. prepare phenylalkylamine and modify macroreticular resin
3. walked after, according to the ratio that the volume ratio of Hydrogen D113 cationic ion-exchange resin glycerine dispersion liquid and phenylalkylamine-carbodiimide alcohol mixeding liquid is 1: 3 (mL: mL), add phenylalkylamine-carbodiimide alcohol mixeding liquid that 1. walk preparation, stirring reaction 60min.Carry out centrifugation after having reacted, collect sediment and the supernatant liquor of centrifugation respectively, to the supernatant liquor collected, for reclaiming glycerine and ethanol; To the sediment collected, be the ratio of 1: 4 (g: mL) according to the volume ratio of sedimentary quality and 50% ethanolic solution, under the condition of stirring, add in sediment concentration be 50% ethanolic solution wash, the time is 30min.Agitator treating filters after completing, and collects trapped substance and filtrate respectively, to the trapped substance collected, repeats three times wash and filter according to identical condition, collects trapped substance and filtrate.For the filtrate of collecting, for reclaiming ethanol; For the trapped substance collected, be the ratio of 1: 5 (g: mL) according to quality and the pure water volume ratio of trapped substance, in trapped substance, add pure water carry out agitator treating 30min, filter after agitator treating completes, respectively collection trapped substance and filtrate.For the trapped substance collected, be phenylalkylamine and modify macroreticular resin; For the filtrate of collecting, pump into clarifier-tank and process, rear discharge up to standard.
5. glycerine and ethanol is reclaimed
The 4. walked after, the supernatant liquor 4. walking collection by the is sent in distillation still, and controlling vapo(u)rizing temperature is 65 DEG C, distillation ethanol, until stop distillation without during ethanol taste.Blowing also carries out vacuum filtration, collects vacuum filtration filtrate and trapped substance respectively, to the trapped substance collected, is dicyclohexylisourea, as the raw material of synthetic chemistry reagent, fine chemicals, medicine intermediate, material intermediate.To the filtrate of collecting, send in decompression distillation still, control temperature is 85 DEG C, and vacuum is that 0.08MPa carries out decompression distillation, until distillation moisture lower than 1% time only.The distillation collected, is recovery glycerine, can again for the preparation of D113 cationic ion-exchange resin glycerine dispersion liquid.
Embodiment 2
Prepare the method that flexible arm phenylalkylamine modifies macroreticular resin, concrete grammar step is as follows:
1. phenylalkylamine-carbodiimide alcohol mixeding liquid is prepared
It is first the ratio of 1: 2 (mmol: mmol) according to the mol ratio of phenylalkylamine and dicyclohexylcarbodiimide, under agitation successively phenylalkylamine and dicyclohexylcarbodiimide are dissolved in absolute ethyl alcohol, make ethanolic solution that phenylalkylamine concentration is 0.4mmol/L and dicyclohexylcarbodiimide concentration is the ethanolic solution of 0.8mmol/L, then both equal proportions are mixed, namely make phenylalkylamine-carbodiimide alcohol mixeding liquid, wherein phenylalkylamine comprises phenylethylamine, phenylpropylamine, phenyibutylamine.
2. Hydrogen D113 cationic ion-exchange resin is prepared
Newly purchase D113 cationic ion-exchange resin and first use purified rinse water, refilter, collect filtrate and trapped substance respectively.To the filtrate of collecting, pump into clarifier-tank process rear discharge up to standard; To the trapped substance collected, the volume ratio being the hydrochloric acid solution of 4% according to the quality of trapped substance and volumetric concentration is the ratio of 1: 6 (g: mL), under agitation trapped substance being scattered in volumetric concentration is process 50min in the hydrochloric acid solution of 4%, then filters.Collect trapped substance and filtrate respectively, to the filtrate of collecting, can again for the preparation of Hydrogen D113 cationic ion-exchange resin when supplementary hydrochloric acid to volumetric concentration is 4%; The trapped substance pure water collected repeatedly is rinsed, filtered, until again filter and collect trapped substance when pH reaches 5, namely prepare Hydrogen D113 cationic ion-exchange resin, for repeatedly rinsing with pure water, filtering and the filtrate of collecting, pump into clarifier-tank process rear discharge up to standard.
3. Hydrogen D113 cationic ion-exchange resin glycerine dispersion liquid is prepared
2. walked after, according to the ratio that the quality of Hydrogen D113 cationic ion-exchange resin and the volume ratio of glycerine are 1: 5 (g: mL), first glycerine is pumped in reactor, under agitation add again and 2. walk the Hydrogen D113 cationic ion-exchange resin prepared, continue to stir 50min, namely prepare D113 cationic ion-exchange resin glycerine dispersion liquid, prepare phenylalkylamine for lower step and modify macroreticular resin.
4. prepare phenylalkylamine and modify macroreticular resin
3. walked after, according to the ratio that the volume ratio of Hydrogen D113 cationic ion-exchange resin glycerine dispersion liquid and phenylalkylamine-carbodiimide alcohol mixeding liquid is 1: 5 (mL: mL), add phenylalkylamine-carbodiimide alcohol mixeding liquid that 1. walk preparation, stirring reaction 80min.Carry out centrifugation after having reacted, collect sediment and the supernatant liquor of centrifugation respectively, to the supernatant liquor collected, for reclaiming glycerine and ethanol; To the sediment collected, be the ratio of 1: 6 (g: mL) according to the volume ratio of sedimentary quality and 70% ethanolic solution, under the condition of stirring, add in sediment concentration be 70% ethanolic solution wash, the time is 50min.Agitator treating filters after completing, and collects trapped substance and filtrate respectively, to the trapped substance collected, repeats three times wash and filter according to identical condition, collects trapped substance and filtrate.For the filtrate of collecting, for reclaiming ethanol; For the trapped substance collected, be the ratio of 1: 6 (g: mL) according to quality and the pure water volume ratio of trapped substance, in trapped substance, add pure water carry out agitator treating 50min, filter after agitator treating completes, respectively collection trapped substance and filtrate.For the trapped substance collected, be phenylalkylamine and modify macroreticular resin; For the filtrate of collecting, pump into clarifier-tank and process, rear discharge up to standard.
5. glycerine and ethanol is reclaimed
The 4. walked after, the supernatant liquor 4. walking collection by the is sent in distillation still, and controlling vapo(u)rizing temperature is 75 DEG C, distillation ethanol, until stop distillation without during ethanol taste.Blowing also carries out vacuum filtration, collects vacuum filtration filtrate and trapped substance respectively, to the trapped substance collected, is dicyclohexylisourea, as the raw material of synthetic chemistry reagent, fine chemicals, medicine intermediate, material intermediate.To the filtrate of collecting, send in decompression distillation still, control temperature is 90 DEG C, and vacuum is that 0.09MPa carries out decompression distillation, until distillation moisture lower than 1% time only.The distillation collected, is recovery glycerine, can again for the preparation of D113 cationic ion-exchange resin glycerine dispersion liquid.
Embodiment 3
Prepare the method that flexible arm phenylalkylamine modifies macroreticular resin, concrete grammar step is as follows:
1. phenylalkylamine-carbodiimide alcohol mixeding liquid is prepared
It is first the ratio of 1: 3 (mmol: mmol) according to the mol ratio of phenylalkylamine and dicyclohexylcarbodiimide, under agitation successively phenylalkylamine and dicyclohexylcarbodiimide are dissolved in absolute ethyl alcohol, make ethanolic solution that phenylalkylamine concentration is 0.5mmol/L and dicyclohexylcarbodiimide concentration is the ethanolic solution of 1.5mmol/L, then both equal proportions are mixed, namely make phenylalkylamine-carbodiimide alcohol mixeding liquid, wherein phenylalkylamine comprises phenylethylamine, phenylpropylamine, phenyibutylamine.
2. Hydrogen D113 cationic ion-exchange resin is prepared
Newly purchase D113 cationic ion-exchange resin and first use purified rinse water, refilter, collect filtrate and trapped substance respectively.To the filtrate of collecting, pump into clarifier-tank process rear discharge up to standard; To the trapped substance collected, the volume ratio being the hydrochloric acid solution of 6% according to the quality of trapped substance and volumetric concentration is the ratio of 1: 8 (g: mL), under agitation trapped substance being scattered in volumetric concentration is process 60min in the hydrochloric acid solution of 6%, then filters.Collect trapped substance and filtrate respectively, to the filtrate of collecting, can again for the preparation of Hydrogen D113 cationic ion-exchange resin when supplementary hydrochloric acid to volumetric concentration is 6%; The trapped substance pure water collected repeatedly is rinsed, filtered, until again filter and collect trapped substance when pH reaches 5, namely prepare Hydrogen D113 cationic ion-exchange resin, for repeatedly rinsing with pure water, filtering and the filtrate of collecting, pump into clarifier-tank process rear discharge up to standard.
3. Hydrogen D113 cationic ion-exchange resin glycerine dispersion liquid is prepared
2. walked after, according to the ratio that the quality of Hydrogen D113 cationic ion-exchange resin and the volume ratio of glycerine are 1: 6 (g: mL), first glycerine is pumped in reactor, under agitation add again and 2. walk the Hydrogen D113 cationic ion-exchange resin prepared, continue to stir 60min, namely prepare D113 cationic ion-exchange resin glycerine dispersion liquid, prepare phenylalkylamine for lower step and modify macroreticular resin.
4. prepare phenylalkylamine and modify macroreticular resin
3. walked after, according to the ratio that the volume ratio of Hydrogen D113 cationic ion-exchange resin glycerine dispersion liquid and phenylalkylamine-carbodiimide alcohol mixeding liquid is 1: 6 (mL: mL), add phenylalkylamine-carbodiimide alcohol mixeding liquid that 1. walk preparation, stirring reaction 90min.Carry out centrifugation after having reacted, collect sediment and the supernatant liquor of centrifugation respectively, to the supernatant liquor collected, for reclaiming glycerine and ethanol; To the sediment collected, be the ratio of 1: 8 (g: mL) according to the volume ratio of sedimentary quality and 80% ethanolic solution, under the condition of stirring, add in sediment concentration be 80% ethanolic solution wash, the time is 60min.Agitator treating filters after completing, and collects trapped substance and filtrate respectively, to the trapped substance collected, repeats three times wash and filter according to identical condition, collects trapped substance and filtrate.For the filtrate of collecting, for reclaiming ethanol; For the trapped substance collected, according to the ratio that the quality of trapped substance and pure water volume ratio are 1: 8 (g: mL), in trapped substance, add pure water carry out agitator treating 60min, filter after agitator treating completes, collect trapped substance and filtrate respectively.For the trapped substance collected, be phenylalkylamine and modify macroreticular resin; For the filtrate of collecting, pump into clarifier-tank and process, rear discharge up to standard.
5. glycerine and ethanol is reclaimed
The 4. walked after, the supernatant liquor 4. walking collection by the is sent in distillation still, and controlling vapo(u)rizing temperature is 85 DEG C, distillation ethanol, until stop distillation without during ethanol taste.Blowing also carries out vacuum filtration, collects vacuum filtration filtrate and trapped substance respectively, to the trapped substance collected, is dicyclohexylisourea, as the raw material of synthetic chemistry reagent, fine chemicals, medicine intermediate, material intermediate.To the filtrate of collecting, send in decompression distillation still, control temperature is 95 DEG C, and vacuum is that 0.1MPa carries out decompression distillation, until distillation moisture lower than 1% time only.The distillation collected, is recovery glycerine, can again for the preparation of D113 cationic ion-exchange resin glycerine dispersion liquid.
Claims (1)
1. prepare the method that flexible arm phenylalkylamine modifies macroreticular resin, it is characterized in that concrete processing step is as follows:
1. phenylalkylamine-carbodiimide alcohol mixeding liquid is prepared
Be first the ratio of 1mmol: 1 ~ 3mmol according to phenylethylamine or the phenylalkylamine of phenylpropylamine or phenyibutylamine class and the mol ratio of dicyclohexylcarbodiimide, under agitation successively phenylalkylamine and dicyclohexylcarbodiimide are dissolved in absolute ethyl alcohol, make ethanolic solution that phenylalkylamine concentration is 0.2 ~ 0.5mmol/L and dicyclohexylcarbodiimide concentration is the ethanolic solution of 0.2 ~ 1.5mmol/L, then both equal proportions are mixed, make phenylalkylamine-carbodiimide alcohol mixeding liquid;
2. Hydrogen D113 cationic ion-exchange resin is prepared
Newly purchase D113 cationic ion-exchange resin and first use purified rinse water, refilter, collect filtrate and trapped substance respectively, the filtrate of collection pumps into clarifier-tank process rear discharge up to standard; The volume ratio being the hydrochloric acid solution of 2 ~ 6% according to the quality of trapped substance and volumetric concentration is the ratio of 1g: 4 ~ 8mL, trapped substance being scattered in volumetric concentration is process 30 ~ 60min in the hydrochloric acid solution of 2 ~ 6%, then filter, collect trapped substance and filtrate respectively, the trapped substance pure water collected repeatedly rinses, filters, until again filter and collect trapped substance when pH reaches 5, prepare Hydrogen D113 cationic ion-exchange resin;
3. D113 cationic ion-exchange resin glycerine dispersion liquid is prepared
2. walked after, be the ratio of 1g: 3 ~ 6mL according to the quality of Hydrogen D113 cationic ion-exchange resin and the volume ratio of glycerine, first glycerine is pumped in reactor, under agitation add again and 2. walk the Hydrogen D113 cationic ion-exchange resin prepared, continue stirring 30 ~ 60min, prepare D113 cationic ion-exchange resin glycerine dispersion liquid;
4. prepare phenylalkylamine and modify macroreticular resin
3. walked after, be the ratio of 1mL: 3 ~ 6mL according to the volume ratio of Hydrogen D113 cationic ion-exchange resin glycerine dispersion liquid and phenylalkylamine-carbodiimide alcohol mixeding liquid, add phenylalkylamine-carbodiimide alcohol mixeding liquid that 1. walk preparation, stirring reaction 60 ~ 90min; Carry out centrifugation after having reacted, collect sediment and the supernatant liquor of centrifugation respectively, to the supernatant liquor collected, for reclaiming glycerine, ethanol respectively; To the sediment collected, be the ratio of 1g: 4 ~ 8mL according to the volume ratio of sedimentary quality and 50 ~ 80% ethanolic solutions, under the condition stirred, add in sediment concentration be 50 ~ 80% ethanolic solution wash, time is 30 ~ 60min, agitator treating filters after completing, and collects trapped substance and filtrate respectively, to the trapped substance collected, repeat three times according to identical condition wash and filter, collect trapped substance and filtrate, for the filtrate of collecting, for reclaiming ethanol; For the trapped substance collected, be the ratio of 1g: 5 ~ 8mL according to the quality of trapped substance and pure water volume ratio, in trapped substance, add pure water carry out agitator treating 30 ~ 60min, agitator treating filters after completing, collect trapped substance and filtrate respectively, for the trapped substance collected, be phenylalkylamine and modify macroreticular resin; For the filtrate of collecting, pump into clarifier-tank and process, rear discharge up to standard;
5. glycerine and ethanol is reclaimed
4. walked after, 4. the supernatant liquor walking collection by the is sent in distillation still, controlling vapo(u)rizing temperature is 65 ~ 85 DEG C, distillation ethanol, until stop distillation without during ethanol taste, blowing also carries out vacuum filtration, collects vacuum filtration filtrate and trapped substance respectively, to the trapped substance collected, be dicyclohexylisourea, to the filtrate of collecting, send in decompression distillation still, control temperature is 85 ~ 95 DEG C, vacuum is that 0.08 ~ 0.1MPa carries out decompression distillation, until distillation moisture lower than 1% time only, the distillation of collection, is recovery glycerine.
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| CN112062219A (en) * | 2020-09-03 | 2020-12-11 | 四川佳士特环境检测有限公司 | Purifying mixing column for determination of perchlorate in water and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3536669A (en) * | 1966-11-30 | 1970-10-27 | Henkel & Cie Gmbh | Process for the preparation of modified glycidyl isocyanurate resin |
| CN101824117A (en) * | 2010-02-04 | 2010-09-08 | 中南大学 | Chelate resin immobilized with dendrimer and preparation method thereof |
-
2015
- 2015-01-26 CN CN201510044800.8A patent/CN104689799B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3536669A (en) * | 1966-11-30 | 1970-10-27 | Henkel & Cie Gmbh | Process for the preparation of modified glycidyl isocyanurate resin |
| CN101824117A (en) * | 2010-02-04 | 2010-09-08 | 中南大学 | Chelate resin immobilized with dendrimer and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112062219A (en) * | 2020-09-03 | 2020-12-11 | 四川佳士特环境检测有限公司 | Purifying mixing column for determination of perchlorate in water and preparation method |
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| CN104689799B (en) | 2017-02-22 |
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