CN1220274A - Polystyrene-based thiosulfosalt resin, its preparing method and use - Google Patents
Polystyrene-based thiosulfosalt resin, its preparing method and use Download PDFInfo
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- CN1220274A CN1220274A CN 97122050 CN97122050A CN1220274A CN 1220274 A CN1220274 A CN 1220274A CN 97122050 CN97122050 CN 97122050 CN 97122050 A CN97122050 A CN 97122050A CN 1220274 A CN1220274 A CN 1220274A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
Abstract
The present invention relates to a polystyrene-based thiosulfosalt resin which can be selectively reacted with halogenated methylidyne compound. It is made up by using polystyrene-based sulfonyl chloride resin as raw material and making it react with sulfide or using polystyrene-based sulfinic acid or its salt as raw material and making it react with element sulfur, its reaction temp.: room temp.-100 deg.C, and reaction time: 1-8 hr. The reaction of said invented resin with halogenated methylidyne compound possesses strong specificity, and its reaction condition is very mild, so that said invented resin can be used for separation and structure analysis, also can be used for synthesizing unsym-dithioether, thioether and thioalcohoe, and removing toxic metal ion. The used resin also can be recovered and regenerated.
Description
The invention relates to a polystyrene-based thiosulfonate resin, a preparation method and application thereof.
Halogenated methine compounds in water are derived from the discharge of industrial wastewater (exhaust gas), the use of agricultural chemicals, and the like. In the process of using chlorine to disinfect drinking water, organic matters such as fulvic acid and the like in the water are also chlorinated to generate halogenated methine compound pollutants, and although the concentrations of the pollutants in the environment, particularly the drinking water are not high, the existence of the pollutants can cause alkylation of DNA bases in organisms to cause gene mutation, thereby affecting human health. But because of its low concentration, its analytical determination is severely disturbed by other organic substances in the environment with which it is mixed. The structures of only a small part of the compounds are clarified so far, and the structures of a considerable part of the compounds are still unknown, so that the evaluation work of the toxicity is influenced. This is mainly due to the lack of selective separation means. Thus, it is important to find a selective separation method for separating out the halogenated methine compounds.
The resins currently available for reaction with halomethine compounds are:
(1) polystyrene mercapto resin: [ S.H.L.Chiu and L.Anderson, carbohydrate research,50,227, (1976)]which can react with halogenated methine compounds to produce polystyrene based thioether resins are structurally quite stable and the structural moiety of the halogenated methine compounds is not easily dissociated for analysis.
(2) Polystyrylsulfinate resins [ J.M.J.Frechet and A.J.Hagen, Pure appl.chem.,54,2181, (1982)]which form polystyrylsulfone-like resins with halomethine compounds are also quite stable, unless there is a double bond at position α or an ethylene group which can form a double bond, the general halomethine compound moiety cannot be freed for direct analysis.
The invention aims to provide a resin which can selectively react with halogenated methine compounds, can replace the structural part of the halogenated methine compounds after the reaction and takes polystyrene resin as a basic framework, a preparation method and application thereof.
The invention uses the characteristic that halogenated methine compound has electrophilicity and can react with nucleophilic reagent to graft nucleophilic gene on polystyrene resin by chemical bonding mode. The present inventors have made extensive and intensive studies to select a suitable nucleophilic group and have studied a preparation method to successfully graft a specific nucleophilic group onto a polystyrene skeleton to prepare a resin which can selectively react with a halogenated methine compound, and the structural part of the halogenated methine compound can be dissociated and directly used for analysis, thereby completing the present invention.
The resin provided by the invention is a polystyrene-based thiosulfonate resin taking the following general formula as a structural unit:wherein, M is monovalent metal ion or quaternary ammonium ion, also can be divalent metal ion, the quaternary ammonium ion is:
wherein R is1～R4Each of which may be H, or the same or different C1-C18An alkyl group; the values of x and y are such that yPreferably,/(x + y) (which is referred to as the degree of crosslinking) is 1 to 8%; the particle size of the resin is 40-400 mesh.
The polystyrene-based thiosulfonate resin of the present invention can be prepared by the following two methods:
the method I comprises the following steps: polystyrene sulfonyl chloride resin is used as a raw material and reacts with sulfide in the presence of a solvent, the reaction temperature is room temperature to 100 ℃, and the reaction time is 1 to 80 hours. Wherein PS represents:is a polystyrene-based resin skeleton.
The granularity of the polystyrene sulfonyl chloride resin raw material can be in each fraction of 40-400 meshes. The molar ratio of the sulfide to the polystyrene sulfonyl chloride resin canbe 1.5: 1-15: 1, preferably 2: 1-10: 1. The solvent can be water or a polar organic solvent, and the dosage of the solvent is 4-20 ml per gram of resin. The sulfide is an inorganic sulfide soluble in water or an organic solvent, a sulfide or ammonium sulfide of a monovalent or divalent metal such as alkali metal, ammonium or alkaline earth metal, for example Na2S、K2S、NaHS、KHS、(NH4)2S and the like.
The polystyrene sulfonyl chloride resin starting material can be prepared from a commercially available spherical polystyrene resin (denoted by PS-H) by a conventional method (for example, documents [ David W. Emerson, et al., J. org, chem.,44 (25)) 4634-40(1979)]The method of (1):
and a method II: the resin of polystyrene sulfinic acid or salt thereof is used as a raw material to react with elemental sulfur in a solvent, wherein the reaction temperature is room temperature to 100 ℃, and the reaction time is 1 to 80 hours.
The molar ratio of the element sulfur to the polystyrene-based sulfinic acid or the salt resin thereof is 2: 1-15: 1, preferably 2: 1-5: 1. The solvent can be amine or pyridine or a mixture of the amine or pyridine and other conventional organic solvents, and the dosage of the solvent is 4-20 ml per gram of resin. The amine may be a primary, secondary, tertiary or quaternary alkyl amine compound. The granularity of the polystyrene sulfinic acid or the salt resin raw material thereof can be in each fraction of 40-400 meshes.
The polystyrene sulfinic acid or salt resin raw material thereof can be recovered from the resin of the invention after use. Process II is also a method for regenerating the resin of the present invention. The polystyrene sulfinic acid or salt resin raw materialcan also be prepared from a commercially available spherical polystyrene resin (denoted by PS-H) by a conventional method (e.g., documents [ J.M.J.Frechet and A.J.Hagen, Pure appl.chem.,54,2181, (1982)]Etc.). For example:
the resin of the present invention has high selectivity to halogenated methine compounds. The halogenated methine compound moiety can be liberated and used directly for structural analysis. Can be used for selectively separating halogenated methine compounds.
The resin can be used for structural analysis of halogenated methine compounds in an environment complex system:
XCH(R1)R2is a halogenated methine compound general formula, X is a halogen atom, R1、R2Is H, alkyl, aryl, substituted alkyl or aryl.
The polystyrene-based thiosulfonate resin obtained by the reaction is fully rinsed to remove interference of other organic matters, and then is reacted with mercaptan:
in the reaction product, the polystyrene sulfinic acid resin can be recovered, and the polystyrene sulfinic acid resin can be regenerated and processed according to the method II to obtain the polystyrene thiosulfonate resin, and the polystyrene thiosulfonate resin can be repeatedly used.
The solution part in the reaction product can be directly analyzed and identified by GC/MS, GC/FTIR and other instruments. Wherein the asymmetric disulfide corresponds to the primary halogenomethine compound one to one, and the structure of the primary halogenomethine compound can be deduced by measuring the structure of the asymmetric disulfide. The other product, the symmetric disulfide, is the oxidation product of the mercaptan added during the reaction, and its formation can be reduced if the reaction is carried out under the protection of nitrogen. It is known and does not affect the performance of the analysis.
The mercaptan used in the reaction may be either an aliphatic or aromatic mercaptan. Generally, aromatic thiols react faster than aliphatic thiols, so that the halogenated methine compounds can be labeled differently depending on the requirements of the instrument. For example, low boiling point mercaptan such as ethanethiol can be used for GC/MS measurement, and mercaptan with ultraviolet or fluorescent absorption gene can be used for ultraviolet or fluorescent detection to improve sensitivity.
The reaction of the above-mentioned polystyrene-based thiosulfonate resin with thiol may also be carried out in the presence of a base. The reaction is accelerated in the presence of a base, since the addition of a base promotes the dissociation of the thiol into the sulfide anion. However, the base must be removed from the system before it can be analyzed by the instrument.
In conclusion, the reaction of the resin and the halogenated methine compound has high specificity and repeatability, the reaction conditions are extremely mild, other substituents of the halogenated methine compound are not affected in the reaction, and the structural part of the halogenated methine compound can be dissociated after the reaction and directly used for structural analysis.
The polystyrene-based thiosulfonate resin of the present invention is an excellent sulfur donor, and can be used for the synthesis of sulfur-containing organic products or intermediates in organic synthesis, such as the following synthesis:
1. synthesis of asymmetric disulfides:
2. synthesis of asymmetric thioethers:
a. reacting the polystyrene-based thiosulfonate resin obtained in the step 1 with a metal organic compound containing carbanion to obtain asymmetric thioether:
b. For the synthesis of optically active α -hydroxysulfide:R1、R2、R3can be alkyl, aryl, or cycloalkyl. Wherein the thioether-based pyrone derivative has anti-HIV activity.3. Synthesizing mercaptan:
the resin of the present invention reacts with halocarbons or other electrophilic compounds to produce polystyrene-based thiosulfonate resins which can generate thiols under reducing conditions: can also be used for synthesizing thio carbohydrate.
In the organic synthesis described above, the resin in the reaction product is recovered and regenerated as described above in Process II.
The resin of the invention can also react with toxic heavy metal compounds such as Hg, Cd and the like, and can be used for removing toxic heavy metal ions in water, such as methyl mercury:
the reaction of the resin and the halogenated methine compound has high specificity and repeatability, the reaction condition is extremely mild, other substituent groups of the halogenated methine compound are not affected in the reaction, and the structural part of the halogenated methine compound can be dissociated after the reaction and directly used for structural analysis. The resin of the invention can also be used for synthesizing special asymmetric disulfide, asymmetric thioether and mercaptan, the reaction is simple and convenient, and the product is easy to purify. In addition, the resin can be used for removing toxic heavy metal ions in water.
The present invention will be further described by way of examples, which are not intended to limit the scope of the invention.
Examples 1 to 2
This example illustrates the preparation of a resin according to the invention according to method 1, starting from a polystyrene sulfonyl chloride resin (prepared according to the method of the literature [ David w. emerson, et al, j. org, chem.,44(25)4634-40(1979)]), in the presence of 10 ml of water per gram of resin, by reaction with a sulfide, the specific preparation conditions and the degree of functionalization of the resin obtained being shown in table 1:
TABLE 1
| Fruit of Chinese wolfberry Applying (a) to Example (b) | Raw material polystyrene base Sulfonyl chloride resins Degree of particle size crosslinking (mesh) (%) | Sulfide compound | Sulfides and polystyrene base Sulphonyl chlorides Molar ratio of | Reaction of Temperature of (℃) | Reaction of Time of day (h) | Functionalization Degree of (mmol/g) |
| 1 | 230-400 2 | Na2S·9H2O | 4∶1 | 90 | 72 | 0.32 |
| 2 | 80-120 7 | KSH | 2∶1 | 55 | 3 | 1.11 |
The degree of functionalization in the table indicates the number of mols of benzylethyl disulfide formed by reaction of 1g of the resin according to the invention prepared in the example with an excess of benzyl chloride and then with ethanethiol. The benzylethyl disulfide is quantitatively determined by external standard method using gas chromatography or high pressure liquid chromatography.
Example 3
This example illustrates the reaction of a resin of the present invention with a halogenated methine compound.
0.2g of the resin prepared in example 2 was reacted with a series of halogenated methine compound standards (0.3mmol) in ethanol (1ml) at 60 ℃ for 6 hours, filtered, rinsed thoroughly with ethanol and water, resuspended in 1ml of acetonitrile and 2 drops of ethanethiol were added. The mixture was stirred at room temperature overnight and the solution fractions were directly identified by GC/MS. The results are shown in Table 2. The product is asymmetric ethyl disulfide. The products correspond to the original halogenated methine compound standard samples one by one. In addition to the product, the solution had an excess of ethanethiol and the oxide diethyldisulfide of ethanethiol. They have a low boiling point and are very volatile and can be removed by concentration. Solvent delayed removal along with solvent on the GC/MS was also possible. Thus there is only a product peak on the GC/MS plot.
As seen from the results in Table 1, the reaction of the resin of the present invention with the halogenated methine compound is exclusive and the reaction conditions are also quite mild. The various substituents carried by the halomethine compound standard remain unchanged during the reaction. The structure of the orthohalomethine compound can therefore be deduced by determining the structure of the asymmetric disulfide. And by thoroughly rinsing the polystyrene-based thiosulfonate resin obtained after the resin of the present invention is reacted with a halogenated methine compound, other organic matters are washed away, thereby eliminating their interference.
Table 2: after the reaction of the polystyrene-based thiosulfonate resin and the halogenated methine compound
GC/MS results for asymmetric Ethyl disulfide treated with Ethyl mercaptan
GC analysis conditions were as follows: a.25m SE 54 column, initial temperature 50 ℃ (1min), final temperature 250 ℃ (10min), heating rate: 15 ℃/min.
| Halogeno-substituted methine group Compound standard sample | Product asymmetry Hexyl disulfide | Retention time (min) | Product Mass Spectrometry fragmentation (EI) m/z (% relative abundance) |
| CH3CHCHXBr | CH3CH2CH2SSC2H5 | 6.10a | 136(M+,47),94(64),79(8),66(46),43(100) |
| (CH3)2CHBr | (CH3)2CHSSC2H5 | 5.62a | 136(M+,32),94(100),66(66),43(84) |
| CH3(CH2)3Br | CH3(CH2)3SSC2H5 | 13.85b | 150(M+,74.7),94(100),79(7),66(25),57(32.5) |
| (CH3)2CHCH2Br | (CH3)2CHCH2SSC2H5 | 6.73a | 150(M+,75),94(71),79(10),66(26),57(100),41(90) |
| CH3(CH2)4Br | CH3(CH2)4SSC2H5 | 8.35a | 164(M+,17),94(44),66(10),43(100) |
| CH3(CH2)2CH(CH3)Br | C3H7CH(CH3)SSC2H5 | 7.77a | 164(M+,15),94(75),71(14),66(18),43(100) |
| C6H5CH2Cl | C6H5CH2SSC2H5 | 11.01a | 184(M+,10),91(100),65(17),45(14) |
| C6H5C(O)CH2Cl | C6H5C(O)CH2SSC2H5 | 13.60a | 212(M+,18.4),152(7),105(100),77(43),51(22) |
| CH3C(O)CH2Cl | CH3C(O)CH2SSC2H5 | 7.88a | 150(M+,15),107(6.5),79(20),43(100) |
| ClCH2CN | (CN)CH2SSC2H5 | 7.62a | 133(M+,40),105(14),93(20),64(20,45(30),41(100) |
| CH3CH(Cl)COOCH3 | CH3OC(O)CH(CH3)SSC2H5 | 7.85a | 180(M+,62),121(64),93(44),88(40),59(100) |
| ClCH2COOCH3 | CH3OC(O)CH2SSC2H5 | 7.48a | 166(M+,60),106(100),79(55),60(66),45(83) |
| ClCH2COOC2H5 | C2H5OC(O)CH2SSC2H5 | 18.12b | 180(M+,100),120(28.5),107(36),106(71),93(25),79(60),60(50) |
| BrCH2CH=CHCOOCH3 | CH3OC(O)CH=CH-CH2SSC2H5 | 10.06a | 192(M+,6.5),99(100),71(36),59(18) |
| ClCH2CH2OH | HOCH2CH2SSC2H5 | 14.31b | 138(M+,100),107(7),94(82),79(35),66(41),45(48) |
| ClCH2CH2Cl | C2H5SSCH2CH2SSC2H5 | 25.36b | 214(M+,2.5),154(12),121(58),93(100),61(17),59(22.5) |
30mx 25mm phenyl methyl polysiloxane column, initial temperature 30 deg.C (1min), final temperature 170 deg.C (15min), and heating rate 6 deg.C/min.
Examples 4 to 7
These examples illustrate the enrichment assay of halomethine compounds in water using the resin of the present invention.
0.3g of the resin prepared in example 2 above was placed in a glass column having an inner diameter of 6 mm. The column was then warmed to 60 ℃ and 3 liters of a tap water sample containing 10 to 20ppm of a halogenated methine compound standard was passed through the glass column at a rate of 3 ml/min. After the completion of the column cooling, the resin was taken out and placed in a small vial, and 1ml of methanol and excess sulfomethane were added to react at room temperature for 6 hours. After filtration, the resin was rinsed with water and ethanol, resuspended in 1ml acetonitrile, ethanethiol added and stirred at room temperature overnight. The supernatant was directly assayed at the GC/MS injection and the results are shown in table 3, where the mass spectral data are consistent with the corresponding samples in table 2.
TABLE 3
| Examples | Water sample composition (concentration) | GC/MS test article |
| 4 | ClCH2COOC2H5(10ppm) | Et S2 CH2COOC2H5 |
| 5 | ClCH2C6H5(10ppm) | Et S2 CH2C6H5 |
| 6 | ClCH2COOC2H5(20ppm) ClCH2CH2OH(20ppm) ClCH2CH2Cl(20ppm) | Et S2 CH2COOC2H5 Et S2 CH2CH2OH Et S2 CH2CH2S2Et |
| 7 | ClCH2CH2OH(20ppm) Br CH2CH2CH3(20ppm) Br CH2CH2CH2CH3(20ppm) | Et S2 CH2CH2OH Et S2 CH2CH2CH3 Et S2 CH2CH2CH2CH3 |
In examples 4 and 5, the detection was relatively successful as a single sample. The mixed samples of examples 6 and 7 were able to be detected. The resin of the present invention can detect the most active halogenated methine compound, and generally has high activity and great mutagenic toxicity.
Example 8
To 1ml of methanol, 0.2 mmol each of octane, dodecane, toluene, dibutyl phthalate, ferulic acid and chlorobenzene was added. Adding it to a solution containing ClCH2COOC2H5(10ppm) from 3 liters of a sample of tap water, the EtSSCH formed from ethyl chloroacetate was detected by passing through the column, reacting and detecting according to the method of example 42COOC2H5Without interference from other compounds.
Example 9
This example illustrates the synthesis of benzylethyl disulfide using the resin of the present invention.
0.5g of the resin prepared in example 1 was suspended in 2ml of ethanol, 100mg of benzyl chloride was added, the mixture was sealed with a cap and stirred at 60 ℃ for 6 hours, the mixture was filtered, the resin was thoroughly washed with water and ethanol, the filtrate was suspended in 2ml of a methanol solution containing 50mg of ethanethiol, the mixture was sealed with a cap by introducing nitrogen, and the mixture was stirred at room temperature overnight. Filtration, washing of the resin with methanol three times, combining the filtrates and concentrating to dryness gave 14.8mg of benzylethyl disulfide, pure as confirmed by gas chromatography:1H NMR:(CDCH3),δ7.34-7.25(m,5H,ArH),3.89(s,2H,SCH2Ph),2.42(q,2H,SCH2Me),1.20(t,3H,CH3)。
example 10
This example illustrates the recovery and regeneration of the resin of the present invention after use.
The resin prepared in example 2 is a polystyrene sulfinic acid resin after being used in examples 4 to 7. 2g of the polystyrene sulfinic acid resin recovered after use is suspended in 50ml of ethanol-water (1: 1) solution, 200mg of elemental sulfur and 50mg of cetyltrimethylammonium chloride are added, the mixture is stirred for 48 hours at the external bath temperature of 90 ℃, filtered, washed with water and ethanol and dried to obtain 2.64g of resin, and the degree of functionalization is 1.04 mmol/g.
In conclusion, the reaction of the resin and the halogenated methine compound has high specificity and repeatability, the reaction conditions are extremely mild, other substituents of the halogenated methine compound are not affected in the reaction, and the structural part of the halogenated methine compound can be dissociated after the reaction and directly used for structural analysis. The resin of the invention can also be used for synthesizing special asymmetric disulfide, asymmetric thioether and mercaptan, the reaction is simple andconvenient, and the product is easy to purify. In addition, the resin can be used for removing toxic heavy metal ions in water.
Other features, advantages and embodiments of the invention described herein will be readily apparent to those skilled in the art upon review of the foregoing disclosure. Thus, while particular embodiments of the present invention have been described in detail, any modifications and improvements to these embodiments are intended to be within the scope of the present invention.
Claims (10)
1. A polystyrene-based thiosulfonate resin having a structural unit of the following general formula:
wherein M is a monovalent metal ion or a quaternary ammonium ion, or a divalent metal ion. The values of x and y are preferably such that y/(x + y) (which is referred to as the degree of crosslinking) is 1 to 8%.
2. The resin of claim 1, wherein said quaternary ammonium ion is:
wherein R is1～R4May each be H or the same or different C1-C18An alkyl group.
3. A method for preparing the resin of claim 1, wherein polystyrene sulfonyl chloride resin is used as a raw material, and reacts with sulfide in the presence of a solvent, wherein the reaction temperature is room temperature to 100 ℃, and the reaction time is 1 to 80 hours.
4. The method according to claim 3, wherein the molar ratio of said sulfide to polystyrene sulfonyl chloride resin is 1.5: 1 to 15: 1; the solvent can be water or a polar organic solvent, and the dosage of the solvent is 4-20 ml per gram of resin.
5. A process according to claim 4, characterized in that the sulphide is an inorganic sulphide soluble in water or organic solvents, such as a sulphide of a monovalent or divalent metal, such as an alkali metal, quaternary ammonium or alkaline earth metal, or ammonium.
6. A process for preparing or regenerating the resin according to claim 1, characterized in that polystyrene sulfinic acid or its salt is used as raw material, and reacted with elemental sulfur in a solvent at room temperature to 100 ℃ for 1 to 80 hours.
7. The method of claim 6, wherein the molar ratio of said elemental sulfur to polystyrene based sulfinate resin is from 2: 1 to 15: 1; the solvent can be amine or pyridine or a mixture of the amine or pyridine and other conventional organic solvents, the dosage of the solvent is 4-20 ml per gram of resin, and the amine can be alkyl primary amine, secondary amine, tertiary amine or quaternary ammonium compound.
8. The resin according to claim 1, which is used for separating and detecting halogenated methine compounds.
9. The resin of claim 1, used for the synthesis of asymmetric disulfides, asymmetric sulfides, or thiols.
10. The resin of claim 1, for removing toxic heavy metal ions.
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| CN97122050A CN1075520C (en) | 1997-12-18 | 1997-12-18 | Polystyrene-based thiosulfosalt resin, its preparing method and use |
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| CN97122050A CN1075520C (en) | 1997-12-18 | 1997-12-18 | Polystyrene-based thiosulfosalt resin, its preparing method and use |
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| CN1649943B (en) * | 2002-02-28 | 2011-03-02 | 斯图加特大学 | Modified polymer or polymer blends or blend film or moulding body, and methods for producing the same and uses |
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| JPS56140967A (en) * | 1980-04-07 | 1981-11-04 | Takeda Chem Ind Ltd | Preparation of aromatic thiosulfonate |
| JPS56145268A (en) * | 1980-04-10 | 1981-11-11 | Takeda Chem Ind Ltd | Preparation of aromatic thiosulfonate |
| JPS5795960A (en) * | 1980-12-08 | 1982-06-15 | Takeda Chem Ind Ltd | Preparation of aromatic thiosulfonate salt |
| JP2689965B2 (en) * | 1995-08-21 | 1997-12-10 | 株式会社エンプラス | IC socket |
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