CN1075521C - Polystyrene sulfonyl hydrazino dithio formate resin - Google Patents
Polystyrene sulfonyl hydrazino dithio formate resin Download PDFInfo
- Publication number
- CN1075521C CN1075521C CN97122185A CN97122185A CN1075521C CN 1075521 C CN1075521 C CN 1075521C CN 97122185 A CN97122185 A CN 97122185A CN 97122185 A CN97122185 A CN 97122185A CN 1075521 C CN1075521 C CN 1075521C
- Authority
- CN
- China
- Prior art keywords
- resin
- polystyrene
- reaction
- sulfonyl
- dithio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The present invention relates to polystyrene sulfonyl hydrazino dithio formate resin and a preparing method and the application thereof. The resin of the present invention is prepared under the condition of the existence of carbon disulfide and alkali by using polystyrene sulfonyl hydrazino as raw material. The resin of the present invention can be used for removing halogenated hydrocarbon in water; used resin is regenerated for reuse. The resin of the present invention can be used for solid phase organic synthesis and can be also used as a metal chelating agent.
Description
The present invention relates to polystyrene sulfonyl hydrazino dithio formate resin, its preparation method, and use.
The contaminated with halogenated hydrocarbons thing is from the discharging of plant effluent (waste gas) and the use of agricultural chemicals etc. in the water, in the process with the disinfection by chlorine tap water, also can make in the water organism chlorinations such as xanthohumic acid, and produce the contaminated with halogenated hydrocarbons thing.Although the concentration of this compounds is not high, can cause the direct alkylation of DNA base in the organism, and cause transgenation, be typical mutagenic compounds.At present, the method for removal mainly is that subtraction and biological degradation method fall in active carbon adsorption, qi exhaustion method, membrane filter method, catalyzed oxidation or reduction.First three is planted to the physical removal method, though removed pollutent has migrated out former system, but still is present among the environment.The two kinds of methods in back can make the contaminated with halogenated hydrocarbons thing resolve into non-toxic substance, but the water after handling still needs further processing, comprise removing catalyzer, active sludge etc.These five kinds of methods generally speaking, equal non-selectivities, just organism in the water no matter the toxicity size is unified to be disposed, increased energy consumption and workload like this, so be necessary to seek new removal method, particularly selectively remove method.
Polystyrene-based sulfonate resin has suitability for industrialized production, and polystyrene-based-sulfinate resin has bibliographical information (yellow Wen Qiang etc., ion-exchange and absorption, 4 (2), 121-123,1988), but do not have the report of relevant polystyrene sulfonyl hydrazino dithio formate resin so far.
The purpose of this invention is to provide a kind of can selective removal the resin of halohydrocarbon in the water, and this resin is recyclable after saturated.The present invention also provides the preparation method and the using method of this resin.
The contaminated with halogenated hydrocarbons thing has Electron Affinities, can react with nucleophilic compound.The present invention is the resin that has nucleophilic group by synthesizing, and contaminated with halogenated hydrocarbons thing chemistry is bonded on the resin, and reaches the purpose of selective removal halohydrocarbon.
Resin provided by the invention be a kind of be the spherical polystyrol sulfonyl hydrazino dithio formate resin of structure unit with following general formula:
Wherein: M is monovalent metallic ion or level Four ammonium ion, also divalent-metal ion; Y/ (x+y) is 1～8%, claims degree of crosslinking.
Polystyrene sulfonyl hydrazino dithio formate resin of the present invention can polystyrene-based sulfonyl hydrazide resin be a raw material, preparation in the presence of dithiocarbonic anhydride and alkali:
Wherein: PS represents
Be polystyrene-based skeleton.
The granularity of said polystyrene-based sulfonyl hydrazide resin raw material can be each fraction between 80～400 orders, and the mole ratio of said dithiocarbonic anhydride and polystyrene-based sulfonyl hydrazide resin can be 1.5: 1～5: 1, and said alkali can be K
2CO
3, NaOH, KOH, NaOCH
3, KOt-Bu, NaH and organic bases, organic bases can be a triethylamine, pyridine etc.; Temperature of reaction can be-15 ℃～30 ℃, best 0 ℃～15 ℃; Reaction times can be 2 hours to 24 hours, best 2.5～5 hours.
In above-mentioned reaction, excessive dithiocarbonic anhydride helps reaction, and the dithiocarbonic anhydride amount is the reaction times weak point at most.Alkali is the prerequisite of reaction, but catalyzed reaction is carried out; Along with the increase of alkaline intensity, the reaction times can shorten, and temperature of reaction also can decrease.
Polystyrene-based sulfonyl hydrazide resin can be a raw material from the commercial polysterol Archon, makes [for example people's such as Ai Mosen method (David W.Emerson, et al. according to a conventional method, J.Org.Chem., 44 (25), 4634-40,1979), this method is listed this paper in as a reference].
Polystyrene sulfonyl hydrazino dithio formate resin of the present invention can be used for removing the halohydrocarbon in the water, particularly the halo methylidyne compound.Under neutrallty condition, resin of the present invention can generate following polystyrene sulfonyl hydrazino dithio manthanoate resin with halides:
PS-SO
2NHNHCS
2M+R-X→PS-SO
2NHNHCS
2R
(1) (2) under alkaline condition, resin (2) can be further obtain following polystyrene sulphonyl hydrazone resin (3) with second halides reaction:
Wherein R and R ' are that X is a halogen with or without substituent alkyl or aryls such as ester group, carboxyl, carbonyl, cyano group.Therefore resin of the present invention can be at go down contaminated with halogenated hydrocarbons thing in dewatering of neutrality to the condition of alkalescence, and with the increase of pH value, resin removal ability increasing of the present invention.
In using polystyrene sulfonyl hydrazino dithio formate resin removal water of the present invention, behind the contaminated with halogenated hydrocarbons thing, pass through the renewable processing of polystyrene-based-sulfinic acid resin that reduction obtains.Regenerative process is that the polystyrene-based SULPHURYL CHLORIDE resin that earlier oxidation of polystyrene-based-sulfinic acid resin, chlorination is obtained obtains polystyrene-based sulfonyl hydrazide resin with the hydrazine hydrate reaction again, generates polystyrene sulfonyl hydrazino dithio formate resin of the present invention with the dithiocarbonic anhydride reaction more at last.
Polystyrene sulfonyl hydrazino dithio formate resin of the present invention can be used for the solid phase organic synthesis, and polystyrene sulfonyl hydrazino dithio formate resin can generate resin 3 with two halohydrocarbon molecular reactions, and resin 3 can become carbene (Cabbeen) under alkaline condition:
It is as lively as a cricket organic intermediate, can participate in many organic reactions.For example under reductive condition, carbene resin 4 can decompose the asymmetric dithio formal of generation:
The synthetic past of the asymmetric dithio formal of product does not have universal method, and cumbersome, and this can be used as a kind of easier universal synthesis method.And for example, if among R in the resin 4 or the R ' allyl group is arranged, [2,3] σ can take place this allylic pair of key resets, and obtains terminal optically active dithiocarboxylic esters that has for two keys:
More than the nitrogen in the reaction gained mixture has volatilized in reaction, and remaining polystyrene-based-sulfinic acid resin can the filter type reclaiming, and product is easy to purifying in solution.
After polystyrene sulfonyl hydrazino dithio formate resin of the present invention used in aforesaid method, the polystyrene-based-sulfinic acid resin that obtains can be by above-mentioned renovation process regeneration.
Polystyrene sulfonyl hydrazino dithio formate resin of the present invention can be used as the preparation metal chelator, lone-pair electron are all arranged on the nitrogen-atoms of polystyrene sulfonyl hydrazino dithio formate resin and the sulphur atom, energy and transition metal complex are the good metal sequestrants.
In a word, the alternative halohydrocarbon of removing in the water of resin of the present invention, and, therefore compared advantages such as easy and simple to handle, with low cost with traditional method at the renewable recovery resin in saturated back.The preparation method of this resin is also very simple.Resin of the present invention also provides favourable approach for the solid phase organic synthesis, and byproduct of reaction is a resin, purification reaction product very easily, make asymmetric dithio formal, terminally the synthetic more economic, easy and practical of optically active dithiocarboxylic esters etc. arranged for two keys.Resin of the present invention also can be used as the good metal sequestrant.
Accompanying drawing 1 is a kind of infrared spectrum of resin of the present invention.
Accompanying drawing 2 is a kind of resins of the present invention and the static reaction curve of different original concentration bromoacetophenones.
To be described further the present invention by embodiment below, but these embodiment can not limit this
Scope of invention.
Embodiment 1
This example is the preparation method of explanation resin of the present invention.
Get polystyrene-based sulfonyl hydrazide resin beads (the granularity 230-400 order of 1 gram, degree of crosslinking 2%) is suspended in 20 milliliters of ethanol, add 1.5 milliliters of dithiocarbonic anhydride, under agitation slowly drip 0.5 gram NaOH saturated aqueous solution, reacted 5 hours down, filter at 0 ℃, be washed with water to neutrality, use washing with alcohol then, drying gets 1.22 grams polystyrene sulfonyl hydrazino dithio formate resin of the present invention.Its functionalization degree sees Table 1.
Embodiment 2-6
These examples are preparation methods of explanation resin of the present invention.
Prepare resin of the present invention according to example 1 method, the functionalization degree of concrete preparation condition and gained resin sees Table 1:
Table 1
Functionalization degree in the table heats under acidic conditions by its functional group and discharges equimolar dithiocarbonic anhydride and measure:
The dithiocarbonic anhydride that is discharged is absorbed by diethylamine-neutralized verdigris ethanolic soln, generate the waste propylhomoserin copper of yellow diethyl ethanolic soln, under the 430nm wavelength, with colorimeter photometry transmitance, obtain dithiocarbonic anhydride quality (mg), calculate the function degree of resin, promptly every gram resin contains the millimole number of diazanyl dithio formate functional group:
Wherein x is the dithiocarbonic anhydride quality (milligram) that m milligram resin is discharged.The efficient of resin is directly proportional with the functionalization degree.By the table in as seen, resin of the present invention has functionalization degree preferably.The infrared spectrum of embodiment 1 gained resin is seen Fig. 1, wherein 1321 and 1159cm
-1Be the flexible absorption peak of the alkylsulfonyl that links to each other with nitrogen, 1237cm
-1Be carbon sulphur double bond absorption peak, 998cm
-1It is the carbon-sulfur bond absorption peak.The infrared spectrum of other embodiment gained resin similarly.
| Embodiment | Polystyrene Archon granularity degree of crosslinking (order) (%) | CS 2With the polystyrene mole ratio | Alkali | Temperature of reaction (℃) | Reaction times (hour) | Functionalization degree (mmole/gram) | |
| 2 | 80～120 | 7 | 1.5 | KOH | 15 | 5 | 0.11 |
| 3 | 80～120 | 7 | 3 | KOH | 15 | 5 | 0.47 |
| 4 | 80～120 | 7 | 5 | NaOH | 25 | 5 | 0.74 |
| 5 | 80～120 | 7 | 5 | NaOH | 0 | 2 | 1.29 |
| 6 | 80～120 | 7 | 5 | NaOH | 0 | 20 | 1.22 |
| 1 | 230～400 | 2 | 5 | NaOH | 0 | 5 | 1.62 |
Embodiment 7
This example is the static halohydrocarbon experiment of removing.
100 milligrams of embodiment gained resins are added respectively in the 1 ml water solution that contains 0.05 and 0.1 mmole bromoacetophenone, with high pressure liquid chromatography (C-18 post; Moving phase: methyl alcohol: water, 70: 30; UV-detector: 254nm) in the residual concentration of different time measuring space bromoacetophenone, the results are shown in Figure 1, after for some time handled, the effect of removing bromoacetophenone was fine as can be seen from Figure.
Embodiment 8
This embodiment is the synthetic of Ethylbenzyl dithio formal.
0.5 the resin of the embodiment of gram at room temperature reacts 3 hours with the excess chlorination benzyl in ethanol-water solution after, filter, water and ethanol flush away excess chlorination benzyl, resin is suspended in 0.01N sodium ethylate-ethanolic soln at room temperature reacted 5 hours with iodoethane, water and ethanol rinsing resin are removed resin with sodium borohydride reduction resin after-filtration, filtrate concentrates the too short silicagel column in back, use ethyl acetate drip washing, concentrate leacheate, get 48 milligrams of Ethylbenzyl dithio formal products.Product mass spectrum (EI) Z/e:198 (M
+), 136 ([M-C
2H
5SH]
+), 107 ([M-CH
2Ph]
+), 91 (PhCH
2 +); 1H-NMR: δ 7.25 (m, 5H, Ar-H), 3.80 (s, 2H, SCH
2Ph), 3.49 (s, 2H, SCH
2S), 2.63 (q, 2H, SCH
2Me), 1.23 (t, 3H, CH
3).
The routine techniques personnel are readily appreciated that other features of the present invention, advantage and embodiment in this description after having read the front disclosure content.So far, though described the specific embodiment of the present invention in detail, any modification that these embodiments are made and improving still within the scope of the present invention.
Claims (10)
1. polystyrene sulfonyl hydrazino dithio formate resin, it is a structure unit with following general formula:
Wherein: M is monovalent metallic ion or level Four ammonium ion, or divalent-metal ion; Y/ (x+y) is 1～8%.
2. a method for preparing the described resin of claim 1 is characterized in that with polystyrene-based sulfonyl hydrazide be raw material, prepares in the presence of dithiocarbonic anhydride and alkali, and its temperature of reaction is-15 ℃～30 ℃.
3. method according to claim 2, the granularity that it is characterized in that said polystyrene-based sulfonyl hydrazide raw material is each fraction between 80～400 orders, the mole ratio of said dithiocarbonic anhydride and polystyrene-based sulfonyl hydrazide is 1.5: 1～5: 1, and said alkali is K
2CO
3, NaOH, KOH, NaOCH
3, KOt-Bu, NaH and organic bases; Temperature of reaction is-15 ℃～30 ℃; Reaction times is 2 hours to 24 hours.
4. according to the described method of claim 3, it is characterized in that said organic bases is triethylamine or pyridine.
5. a method of removing the halohydrocarbon in the water is characterized in that using resin according to claim 1 as remover in neutrality to alkaline condition.
6. method according to claim 5, after it is characterized in that using profit to require 1 described resin to remove halohydrocarbon in the water, produce polystyrene-based-sulfinic acid resin through reduction, regeneration is reclaimed, said regenerative process is earlier with the oxidation of polystyrene-based-sulfinic acid resin, chlorination, the polystyrene-based SULPHURYL CHLORIDE resin of gained obtains polystyrene-based sulfonyl hydrazide resin with the hydrazine hydrate reaction again, gets final product with the dithiocarbonic anhydride reaction more at last.
7. a solid phase methodology of organic synthesis is characterized in that having used in this method the described polystyrene sulfonyl hydrazino dithio formate resin of claim 1.
8, according to the described method of claim 7, it is characterized in that having used in this method by after polystyrene sulfonyl hydrazino dithio formate resin and two the halohydrocarbon molecular reactions, under reductive condition, decompose and generate asymmetric dithio formal.
9, according to the described method of claim 7, it is characterized in that having used in this method by after polystyrene sulfonyl hydrazino dithio formate resin and two the halohydrocarbon molecular reactions, one of them halohydrocarbon has allyl group, the following carbene that generates under alkaline condition
[2,3] σ can take place the allylic pair of key of alkyl of wherein linking to each other with sulphur atom resets, and generates its terminal optically active dithiocarboxylic esters that has for two keys.
10, polystyrene sulfonyl hydrazino dithio formate resin according to claim 1 is as metal chelator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97122185A CN1075521C (en) | 1997-11-28 | 1997-11-28 | Polystyrene sulfonyl hydrazino dithio formate resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97122185A CN1075521C (en) | 1997-11-28 | 1997-11-28 | Polystyrene sulfonyl hydrazino dithio formate resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1218815A CN1218815A (en) | 1999-06-09 |
| CN1075521C true CN1075521C (en) | 2001-11-28 |
Family
ID=5176729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97122185A Expired - Fee Related CN1075521C (en) | 1997-11-28 | 1997-11-28 | Polystyrene sulfonyl hydrazino dithio formate resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1075521C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329432C (en) * | 2004-12-03 | 2007-08-01 | 宁波大学 | Water soluble chelated resin and its synthetic method and use |
| CN101831036B (en) * | 2009-03-13 | 2011-12-21 | 黄汉平 | Manufacturing method of modified unsaturated polyester resin |
| CN107376874A (en) * | 2017-08-18 | 2017-11-24 | 江苏海普功能材料有限公司 | Heavy metal absorbent and preparation method thereof |
| CN108452777A (en) * | 2018-01-09 | 2018-08-28 | 同济大学 | A kind of macroreticular resin method of modifying for adsorbing low-concentration sulfur dioxide in air |
| CN109081417B (en) * | 2018-08-18 | 2022-03-04 | 烟台中科荣达新材料有限公司 | Production method of heavy metal trapping agent piperazine-N, N-bis-dithiocarbamate potassium |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50146697A (en) * | 1974-05-17 | 1975-11-25 |
-
1997
- 1997-11-28 CN CN97122185A patent/CN1075521C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50146697A (en) * | 1974-05-17 | 1975-11-25 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1218815A (en) | 1999-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Flyunt et al. | Determination of• OH, O2•-, and hydroperoxide yields in ozone reactions in aqueous solution | |
| US4009251A (en) | Process for the removal of hydrogen sulfide from gaseous streams by catalytic oxidation of hydrogen sulfide to sulfur while inhibiting the formation of sulfur oxides | |
| Pagano et al. | Peroxymonosulfate–Co (II) oxidation system for the removal of the non-ionic surfactant Brij 35 from aqueous solution | |
| RS49519B (en) | Recovery of acetic acid from dilute aqueous streams formed during a carbonylation process | |
| GEP20012514B (en) | Method for Removal of Carbon Dioxide From a Process Gas | |
| US20040062705A1 (en) | Process for lowering the content of organic matter and nitrogenous products contained in bromide-containing effluents | |
| CN1075521C (en) | Polystyrene sulfonyl hydrazino dithio formate resin | |
| JP2007181833A (en) | Method for treating tetraalkylammonium ion-containing solution | |
| George et al. | Poly (N-bromoacrylamide): a new polymeric recyclable oxidizing and brominating reagent | |
| EP0156414B1 (en) | Process for the dissolution of deoxyribonucleic acids in non-aqueous solvents and mixed non-aqueous/aqueous solvent systems, solutions thereby obtained and their use | |
| JPH0649721B2 (en) | Method for purifying liquid reaction and / or washing medium obtained when producing cellulose ether from at least one of cellulose, alkali metal hydroxide and etherifying agent | |
| Kumar et al. | Aerobic organocatalytic photoinitiated arene oxidations: application to electron transfer initiated cyclization reactions | |
| US4731165A (en) | Method of decoloration of triethylenetetramine using sulfonic acid ion exchange resins | |
| Zarchi | Polymer‐Supported Thiocyanate as New, Versatile and Efficient Polymeric Reagent for Conversion of Alkyl Halides to Corresponding Alkyl Thiocyanates under Mild Conditions | |
| US6075166A (en) | Photolytically cleavable encoding and linking agents for use in combinatorial chemistry | |
| Sukhdev et al. | Decolorization of reactive orange 16 azo dye in wastewater using CAT/IrCl3/HClO4 redox system: delineation of kinetic modeling and mechanistic approaches | |
| JP3968678B2 (en) | Method for treating tetraalkylammonium ion-containing liquid | |
| EP0730560A1 (en) | Process for the treatment of waste water containing organic and inorganic compounds | |
| US4130580A (en) | Sodium ion removal from acetone cyanohydrin | |
| Kraus et al. | A simple synthesis of hexakis (6-O-carboxymethyl-2, 3-di-O-methyl) cyclomaltohexaose and heptakis (6-O-carboxymethyl-2, 3-di-O-methyl) cyclomaltoheptaose | |
| CA1141364A (en) | Oxidation of organic substances using a ruthenate catalyst | |
| US5264132A (en) | Method of removing alkaline materials from waste water | |
| DE69610563D1 (en) | METHOD FOR HYDRATING IMINES | |
| US20040060874A1 (en) | Process for stripping amine borane complex from an electroless plating solution | |
| JP3838274B2 (en) | How to deodorize hydrazine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |