CN101967209B - N-acetylethylenediamine chelate resin and preparation method thereof - Google Patents
N-acetylethylenediamine chelate resin and preparation method thereof Download PDFInfo
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- CN101967209B CN101967209B CN201010512734XA CN201010512734A CN101967209B CN 101967209 B CN101967209 B CN 101967209B CN 201010512734X A CN201010512734X A CN 201010512734XA CN 201010512734 A CN201010512734 A CN 201010512734A CN 101967209 B CN101967209 B CN 101967209B
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- 239000011347 resin Substances 0.000 title claims abstract description 96
- 229920005989 resin Polymers 0.000 title claims abstract description 96
- DAKZISABEDGGSV-UHFFFAOYSA-N n-(2-aminoethyl)acetamide Chemical compound CC(=O)NCCN DAKZISABEDGGSV-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000013522 chelant Substances 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000460 chlorine Substances 0.000 claims abstract description 13
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 125000000524 functional group Chemical group 0.000 claims abstract description 6
- 239000010413 mother solution Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims abstract description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- 238000004132 cross linking Methods 0.000 claims description 24
- 241001566735 Archon Species 0.000 claims description 17
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000007265 chloromethylation reaction Methods 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 12
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 230000008961 swelling Effects 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 108010010803 Gelatin Proteins 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 239000008273 gelatin Substances 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 4
- 235000019322 gelatine Nutrition 0.000 claims description 4
- 235000011852 gelatine desserts Nutrition 0.000 claims description 4
- 238000000638 solvent extraction Methods 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 3
- 229960001708 magnesium carbonate Drugs 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 2
- 238000001256 steam distillation Methods 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 11
- -1 Cu<2+> and the like Chemical class 0.000 abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000003891 environmental analysis Methods 0.000 abstract description 2
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 238000005065 mining Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000000605 extraction Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- 238000010792 warming Methods 0.000 description 10
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000011181 potassium carbonates Nutrition 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004094 preconcentration Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012609 strong anion exchange resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
Abstract
The invention discloses an N-acetylethylenediamine chelate resin and a preparation method thereof, belonging to the field of chelate resin. The constructional unit is shown in the specification, wherein the functional group is N-acetylethylenediamine; and the content of the functional group is 0.71-1.39mmol/g. The preparation method of the resin comprises the following steps: preparing a white ball; preparing a chlorine ball; extracting the chlorine ball through a soxhletextractor; then taking N,N-dimethylformamide as sweller, adding 2-aminothiazole-4-ethyl acetate potassium carbonate, and stirring for reaction to obtain faint yellow 2-aminothiazole-4-ethyl acetate based resin; washing the obtained resin; adding ethylenediamine solution; condensing and reacting; and filtering and drying to obtain the N-acetylethylenediamine chelate resin. The resin provided by the invention can selectively adsorb and separate heavy metal ions, such as Cu<2+> and the like, has wide applications in the fields of mining and metallurgy production mother solution extraction, production waste water management, heavy metal separation and preenrichment in the environmental analysis and the like.
Description
Technical field
The present invention relates to a kind of resin and compound method thereof, specifically, be meant a kind of N-acetylethylenediamine resin and preparation method thereof.
Background technology
Polyethylene polyamine class resin is one type of nitrogen-atoms coordinate superpolymer; Through lone-pair electron on the nitrogen and metals ion effect; Can form complex compound with contents of many kinds of heavy metal ion, especially the transition group heavy metal ion had excellent adsorption performance and adsorption selectivity.The polyethylene polyamine resinoid of report is bigger to the loading capacity of metals ion at present, but not enough for special metal ionic adsorption selectivity in the polycomponent solution.Employing epoxy chloropropane such as domestic grandson Xiang Rong carry out the back crosslinking reaction to the triethylene tetramine crosslinked polystyrene, and the gained resin obviously improves the selectivity of cupric ion.Bibliographical information is that to be superior to polyethyene diamine be unitary aminoresin for the quadrol resin absorption performance of chain unit with the polyoxyethylene glycol; Increase oxyethyl chain joint number amount and Sauerstoffatom is replaced with sulphur atom, resin significantly improves the loading capacity of gold.It is thus clear that; For polyethylene polyamine class resin; Zip length between substituting group and parent and chain link kind have a significant effect for the absorption property of resin; Therefore can improve the absorption property of heavy metal through the classification of regulating chain length and chain unit, enrichment target heavy metal, the adsorption selectivity of raising resin.
Literature search shows, is matrix with the chlorine ball, and the compound method of the resin through the ester group bonding quadrol on the thiazole ring is not appeared in the newspapers.
Summary of the invention
The purpose of this invention is to provide a kind of N-acetylethylenediamine resin and preparation method thereof, can synthesize the resin that has N-acetylethylenediamine structure, cupric ion is had special adsorption selectivity through the present invention.
Technical scheme of the present invention is following:
A kind of N-acetylethylenediamine resin, its structural unit is following:
From structural unit, can find out and contain functional group in the resin: N-acetylethylenediamine and thiazole ring, and the sequestering action Adsorption of Heavy Metal Ions through nitrogen, Sauerstoffatom.This resin possibly form the ring-type chelate structure through nitrogen-atoms on the group and Sauerstoffatom:
Said N-acetylethylenediamine resin chemical functional group content is 0.71~1.39mmol/g.
A kind of preparation method of N-acetylethylenediamine resin comprises following step:
(a) utilize vinylbenzene to make monomer, divinylbenzene is made linking agent, utilizes one or both the mixed pore-creating agents of doing in liquid wax or No. 200 solvent oils; With one or more the mixed dispersion agents of doing in magnesiumcarbonate, gelatin, the Z 150PH; Make initiator with Lucidol, adopt suspension polymerization, preparation low crosslinking degree macropore styrene-divinylbenzene copolymer; Select for use steam distillation or ethanol, acetone, industrial spirit, low boiling point solvent gasoline to make solvent extraction; Remove residual pore-creating agent in the resin duct, obtain low cross-linking macroporous polystyrene-divinylbenzene resin through air stream drying again, hereinafter to be referred as Archon;
(b) Archon is soaked in the chloromethyl ether of 4~7 times of its weight; 20~50% the zinc chloride that adds Archon weight is made catalyzer, under 25~55 ℃ of temperature, carries out chloromethylation, reaches 10% above stopped reaction up to cl content; Leach the resin spheroid; Water or ethanol, acetone are washed chlorination mother solution remaining in the most resin, and air stream drying obtains chloromethylation low cross-linking macroporous polystyrene-divinylbenzene resin, hereinafter to be referred as the chlorine ball;
(c) after the step (b), generally through Soxhlet extractor extracting 4~8 hours, then with N; Dinethylformamide is a swelling agent, under 85 ℃, adds the reaction of thiazolamine-4-ETHYLE ACETATE and salt of wormwood; Go into thiazolamine-4-ETHYLE ACETATE consumption and be 2~5 times of weight resin; The salt of wormwood consumption is 1~2 times of weight resin, and stirring reaction 6~24h can get faint yellow resin.
(d) with after the resin washing and drying that obtains in the step (c), add the ethylenediamine solution of 15~30 times of weight resins, at 125 ℃ of reaction 24~30h, suction filtration also washs the dry N-acetylethylenediamine resin that gets.
Among the preparation method of said resin, it is characterized in that step (c) reaction times temperature of reaction is controlled at 85 ℃ of steps, (d) reaction times at 24~30h, temperature of reaction is controlled at 125 ℃.Through adding the consumption and the reaction times of reagent in the control reaction, can make serial resin.Usually confirm other conditions, the reaction times is longer, and then the surface group number is bigger; The consumption of reagent is bigger, and the surface group of the resin of gained the more.
Beneficial effect
The invention discloses a kind of N-acetylethylenediamine resin and preparation method thereof, resin provided by the invention can carry out selectivity property fractionation by adsorption to heavy metal ion such as Cu2+.Atom pairs heavy metals such as contained N, O performance chelating coordination.The present invention adopts thiazolamine-4-ETHYLE ACETATE and the ethylene diamine-modified N-acetylethylenediamine resin that obtains; Contained group can form the higher complex compound of stability constant with some heavy metal; Have higher adsorption selectivity, fields such as the separation of heavy metal and pre-concentration have extensive use in mining and metallurgy production mother liquor purification and factory effluent improvement and environmental analysis.
Embodiment
Below further specify the present invention through embodiment.
Embodiment 1
(a) suspension polymerization
Styrene monomer adds a certain amount of diluted sodium hydroxide solution or monomer is directly filtered to remove stopper through the resin column that strong anion-exchange resin is housed.
In the 1000mL beaker, add 210g vinylbenzene, the 26g divinylbenzene, the 140g whiteruss, the back that stirs is subsequent use.
In the 1000mL there-necked flask, add 600g zero(ppm) water and be warming up to 40 ℃, add the 6g gelatin again; Be stirred to dissolving fully, be warming up to 50 ℃ simultaneously, add the 2mL methylene blue; Stir, add the mixed liquid of above-mentioned vinylbenzene, divinylbenzene and liquid wax, add initiator Lucidol 4.0g; Adjust suitable stirring velocity and make the oil droplet size to fit, progressively be warming up to 80 ℃ with the speed of 1 ℃/6min, and insulation 4h, progressively be warming up to 85 ℃ of insulation 3h again; 90 ℃ of insulation 2h, 95 ℃ of insulation 4h, reaction finishes, and leaches resin; Earlier use hot wash, leach resin, dry the Soxhlet extractor of packing into; Clean with the acetone extracting, air stream drying sieves, and the resin of getting suitable particle size is subsequent use.
(b) chloromethylation
In the 2000mL there-necked flask, add the 300g Archon, the 1200g chloromethyl ether soaks more than the 2h down in 20~25 ℃; Stir down, add the 150g zinc chloride, controlled temperature is not higher than 25 ℃, behind the stirring 1h; Be warming up to 38 ℃, insulation 8~12h, the control cl content can finish reaction more than 10%.
Reaction leaches the resin spheroid after finishing, washing back extracting resin, and water is washed till neutrality again, and air stream drying obtains the chlorine ball.
(c) nucleophilic substitution reaction
In the 250mL there-necked flask, add the prepared chloromethyl resin 8g of step (b), with the DMF swelling 4h of 150ml; Add thiazolamine-4-ETHYLE ACETATE 20g, Anhydrous potassium carbonate 10g is warming up to 65 ℃ then, stirs, and reaction 20h leaches resin, water, acetone, water washing successively, and oven dry can make the resin that contains the ester group structure.
(d) nucleophilic substitution reaction
In the 250mL there-necked flask, add the prepared resin 8g of step (c), quadrol 150mL, condensing reflux reaction 30h under 115 ℃ of conditions, suction filtration and washing, washing with acetone, washing get N-acetylethylenediamine resin after the drying.
Embodiment 2
The synthesis step of another embodiment of the present invention is following:
(a) suspension polymerization
Utilize vinylbenzene to make monomer, divinylbenzene is made linking agent, utilizes No. 200 solvent oils to make pore-creating agent; Make dispersion agent with gelatin, make initiator, adopt suspension polymerization with Lucidol; Synthetic low crosslinking degree macroporous polystyrene-divinylbenzene copolymer selects for use ethanol (or acetone, industrial spirit, low boiling point solvent gasoline) to make solvent extraction, removes residual pore-creating agent in the resin duct; Obtain low cross-linking macroporous polystyrene-divinylbenzene resin, i.e. Archon through air stream drying again.
Wherein dosage of crosslinking agent is 7% of monomer and a linking agent total amount, and the pore-creating agent consumption is 100% of a monomer weight, and the degree of crosslinking of low cross-linking macroporous polystyrene is 10%.
(b) chloromethylation
Archon is soaked in the chloromethyl ether of 4 times of its weight; 20% the zinc chloride that adds Archon weight is made catalyzer, when 35 ℃ of temperature, carries out chloromethylation, reaches 10% above stopped reaction up to cl content; Leach the resin spheroid; With remaining chlorination mother solution in the most resin of washing, air stream drying obtains chloromethylation low cross-linking macroporous polystyrene-divinylbenzene resin, i.e. chlorine ball.
(c) nucleophilic substitution reaction
With the prepared chlorine ball 15g of the DMF swelling step (b) of 300ml; Add 42g thiazolamine-4-ETHYLE ACETATE behind the 4h, the 15g Anhydrous potassium carbonate is warming up to 85 ℃, stirs, and reaction 8h leaches resin, successively water, acetone, water washing.
(d) nucleophilic substitution reaction
In the 500mL there-necked flask, add the prepared resin 15g of step (c), ethylenediamine solution 300mL, be warming up to 125 ℃ and condensing reflux 24h then, suction filtration, washing, washing with acetone, washing get N-acetylethylenediamine resin after the drying.
Embodiment 3:
The synthesis step of another embodiment of the present invention is following:
(a) suspension polymerization
Utilize vinylbenzene to make monomer, divinylbenzene is made linking agent, utilizes No. 200 solvent oils to make pore-creating agent; Make dispersion agent with magnesiumcarbonate, make initiator, adopt suspension polymerization with Lucidol; Synthetic low crosslinking degree macroporous polystyrene-divinylbenzene copolymer is selected wet distillation for use, removes residual pore-creating agent in the resin duct; Obtain low cross-linking macroporous polystyrene-divinylbenzene resin, i.e. Archon through air stream drying again.
Wherein dosage of crosslinking agent is 8% of monomer and a linking agent total amount, and the pore-creating agent consumption is 40% of a monomer weight, and the degree of crosslinking of low cross-linking macroporous polystyrene is 2%.
(b) chloromethylation
Archon is soaked in the chloromethyl ether of 7 times of its weight; 50% the zinc chloride that adds Archon weight is made catalyzer, in 40 ℃ of temperature, carries out chloromethylation, reaches 10% above stopped reaction up to cl content; Leach the resin spheroid; Wash chlorination mother solution remaining in the most resin with acetone, air stream drying obtains chloromethylation low cross-linking macroporous polystyrene-divinylbenzene resin, i.e. chlorine ball.
(c) nucleophilic substitution reaction
In the 500mL there-necked flask, add chlorine ball 10g, and with 250mlDMF swelling 4h; Add thiazolamine-4-ETHYLE ACETATE 20g, Anhydrous potassium carbonate 12g is warming up to 80 ℃ then, stirs, and reaction 6h leaches resin, successively water, acetone, water washing.
(d) nucleophilic substitution reaction
In the 250mL there-necked flask, add the prepared resin 10g of step (c), quadrol 200mL, condensing reflux reaction 30h under 120 ℃ of conditions, suction filtration, washing, washing with acetone, washing get N-acetylethylenediamine resin after the drying.
The constitutional features such as the following table of this technology synthetic N-acetylethylenediamine resin:
The key technical indexes is following: (Resin A, B and C be corresponding case study on implementation 1,2,3 prepared resins respectively)
Embodiment 4:
The synthesis step of another embodiment of the present invention is following:
(b) suspension polymerization
Utilize vinylbenzene to make monomer, divinylbenzene is made linking agent, utilizes liquid wax to make pore-creating agent; Make dispersion agent with Z 150PH, make initiator, adopt suspension polymerization with Lucidol; Synthetic low crosslinking degree macroporous polystyrene-divinylbenzene copolymer selects for use ethanol to do solvent extraction, removes residual pore-creating agent in the resin duct; Obtain low cross-linking macroporous polystyrene-divinylbenzene resin, i.e. Archon through air stream drying again.
Wherein dosage of crosslinking agent is 4% of monomer and a linking agent total amount, and the pore-creating agent consumption is 40% of a monomer weight, and the degree of crosslinking of low cross-linking macroporous polystyrene is 2%.
(b) chloromethylation
Archon is soaked in the chloromethyl ether of 4 times of its weight; 20% the zinc chloride that adds Archon weight is made catalyzer, in 35 ℃ of temperature, carries out chloromethylation, reaches 10% above stopped reaction up to cl content; Leach the resin spheroid; Wash chlorination mother solution remaining in the most resin with ethanol, air stream drying obtains chloromethylation low cross-linking macroporous polystyrene-divinylbenzene resin, i.e. chlorine ball.
(c) nucleophilic substitution reaction
In the there-necked flask that 25g chlorine ball is housed, add 600ml swelling agent DMF, add reagent thiazolamine-4-ETHYLE ACETATE behind the 6h, consumption is 2 times of weight resin; Anhydrous potassium carbonate 25g; Stirring reaction 12h under 70 ℃ of conditions leaches resin, successively water, acetone, water washing.
(d) nucleophilic substitution reaction
In the 1000mL there-necked flask, add the prepared resin 20g of step (c), quadrol 700mL is warming up to 110 ℃ and condensing reflux 20h, and suction filtration, washing, washing with acetone, washing get N-acetylethylenediamine resin after the drying.
Claims (6)
2. a kind of N-acetylethylenediamine resin according to claim 1 is characterized in that functional group is the N-acetylethylenediamine, and functional group content is 0.71~1.39mmol/g.
3. the preparation method of a N-acetylethylenediamine resin is characterized in that comprising following step:
(a) utilize vinylbenzene to make monomer, divinylbenzene is made linking agent, utilizes one or both the mixed pore-creating agents of doing in liquid wax or the 200# solvent oil; With one or more the mixed dispersion agents of doing in magnesiumcarbonate, gelatin, the Z 150PH; Make initiator with Lucidol, adopt suspension polymerization, preparation low crosslinking degree macropore vinylbenzene-divinylbenzene copolymer; Select for use steam distillation or ethanol, acetone, industrial spirit, low boiling point solvent gasoline to make solvent extraction; Remove residual pore-creating agent in the resin duct, obtain low cross-linking macroporous polystyrene-divinylbenzene resin through air stream drying again, hereinafter to be referred as Archon;
(b) Archon is soaked in the chloromethyl ether of 4~7 times of its weight; 20~50% the zinc chloride that adds Archon weight is made catalyzer, under 25~55 ℃ of temperature, carries out chloromethylation, reaches 10% above stopped reaction up to cl content; Leach the resin spheroid; Water or ethanol, acetone are washed chlorination mother solution remaining in the most resin, and air stream drying obtains chloromethylation low cross-linking macroporous polystyrene-divinylbenzene resin, hereinafter to be referred as the chlorine ball;
(c) after the step (b); Through Soxhlet extractor extracting 4~8 hours; Then with N; Dinethylformamide is a swelling agent, and thiazolamine-4-ETHYLE ACETATE that the adding weight resin is 2~5 times and 1~5 times salt of wormwood can get faint yellow thiazolamine-4-ethyl acetate base resin at 40~100 ℃ of following stirring reaction 6~24h;
(d) with after the resin washing that obtains in the step (c), add ethylenediamine solution, consumption is 20~50 times of weight resin, and in 105~125 ℃ of condensing reflux reaction 20~30h, suction filtration also washs the dry N-acetylethylenediamine resin that gets.
4. according to the preparation method of a kind of N-acetylethylenediamine resin described in the claim 3; It is characterized in that in the step (a); Dosage of crosslinking agent is 4~12% of monomer and a linking agent total amount during preparation Archon; The pore-creating agent consumption is 40~100% of a monomer weight, and the degree of crosslinking of the low cross-linking macroporous polystyrene that makes is 2~10%.
5. according to the preparation method of a kind of N-acetylethylenediamine resin described in claim 3 or 4, it is characterized in that controlling reaction time is 8~18h in the step (b), obtain the chlorine ball of different cl contenies.
6. according to the preparation method of a kind of N-acetylethylenediamine resin described in claim 3 or 4, it is characterized in that in the step (c), control reaction temperature is 40~85 ℃.
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