CN101538235B - Styrene monomer containing alkyl sodium (potassium) thiosulfate and preparation method thereof - Google Patents
Styrene monomer containing alkyl sodium (potassium) thiosulfate and preparation method thereof Download PDFInfo
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- CN101538235B CN101538235B CN200910030467XA CN200910030467A CN101538235B CN 101538235 B CN101538235 B CN 101538235B CN 200910030467X A CN200910030467X A CN 200910030467XA CN 200910030467 A CN200910030467 A CN 200910030467A CN 101538235 B CN101538235 B CN 101538235B
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Abstract
The invention relates to a styrene monomer containing alkyl sodium (potassium) thiosulfate and a preparation method thereof, belonging to the technical field of organic synthesis and high polymer. In the invention, styrene based compound containing halogenated methylene is used as raw materials, methanol or ethanol and water are used as mixed solvent, PEO400 is used as a phase transfer catalyst, the halogen on the halogenated methylene reacts with the Bunte Salts of excessive saturated sodium (potassium) thiosulfate and is stirred to react under the room temperature till the sodium (potassium) thiosulfate raw material is totally consumed, then the methanol or ethanol and part of water are removed from the mixture by pressure reduction, is cooled and crystallized and then carried out the pumping filtration and collection to obtain solid; and the solid is leached (eluted) sequentially by little cooling water and petroleum ether and dried under the temperature of 40 DEG C to obtain the monomer, the monomer releases active sulfhydryl-groups with the function of chain transfer under the action of strong polarity reagents or diluted acid such as DMSO, DMF, and the like to form an AB monomer containing polymerizable double bond as well as active sulfhydral-groups. The AB monomer has simple structure, is easily prepared and stored, and is expected to be applied to super branched polymer prepared by a sulfhydryl-group chain transfer super branched polymerization method.
Description
Technical field
The present invention relates to a kind of styrene monomer that contains alkyl thiosulfurie acid sodium (potassium) salt and preparation method thereof, belong to organic synthesis, technical field of macromolecules.
Background technology
The molecular designing of polymerisable monomer plays a part very important in organic synthesis, polymer manufacture, and can to give this monomer and polymkeric substance various special functional through in polymerisable monomer, introducing functional primitive.Sulfhydryl compound have the chain transfer function, with the excellent complexing function of metal, with the properties such as illumination polymerizable functional of two keys, therefore sulfydryl is effectively introduced in the polymerisable monomer, can make this monomer and polymkeric substance obtain the various functions of sulfydryl.Because sulfydryl and polymerizable double bond very easily react, make that sulfydryl and polymerisable monomer can not the while stable existences.
Summary of the invention
The purpose of this invention is to provide a kind of styrene monomer that contains alkyl thiosulfurie acid sodium (potassium) salt and preparation method thereof; This type monomer is the AB monomer that had not only contained polymerizable double bond but also contained sulfhydryl-group activity; The inventive method preparation technology is simple, and low production cost is workable.
Technical scheme of the present invention: a kind of preparation method who contains the styrene monomer of alkyl thiosulfurie acid sodium (potassium) salt; With the styrene compound that contains halogenated methylene is raw material; With first alcohol and water or second alcohol and water is mixed solvent, and oxyethane PEO400 is a phase-transfer catalyst, through the Bunte Salts reaction of halogen on the halogenated methylene and excessive saturated sodium thiosulfate (potassium) salts solution; Stirring reaction to Sulfothiorine (potassium) salt raw material consumption is complete under the room temperature; Methyl alcohol or ethanol and portion water are removed in decompression then, direct suction filtration, collection gained solid behind the crystallisation by cooling, and with a small amount of cold water and sherwood oil drip washing successively; 40 ℃ of oven dry down promptly get the styrene monomer that contains alkyl thiosulfurie acid sodium (potassium) salt;
Oxyethane PEO400 consumption is the weight fraction 1%-5% that contains the styrene compound of halogenated methylene;
Sulfothiorine (potassium): the mol ratio of the halogen in the styrene compound of halogenated methylene is 1: 1.3-1.3: 1, and the terminal point of reaction is judged through tlc.
With the styrene monomer that contains alkyl thiosulfurie acid sodium (potassium) salt of said method preparation, it has one or two or three to contain alkyl thiosulfurie acid sodium (potassium) salt substituting group on styryl;
Have three to contain the substituent styrene monomer structural formula of alkyl thiosulfurie acid sodium (potassium) salt and be:
Wherein, R
1, R
2And R
3Be alkyl, alkoxyl group, ester group or carboxamido-group; R
1, R
2And R
3Be primitive identical or inequality, and guarantee R at least
1, R
2And R
3In have one to be connected on the vinylbenzene; M is Na
+Or K
+Ion.
The described styrene monomer that contains alkyl thiosulfurie acid sodium (potassium) salt, structural formula is:
Wherein, R is the bridge joint group, selects ester bond, ehter bond or amido linkage for use; Perhaps alkyl sodium (potassium) thiosulfate directly and phenyl ring join; M is Na
+Or K
+Ion.
The described styrene monomer that contains alkyl thiosulfurie acid sodium (potassium) salt, structural formula is:
Described a kind of application that contains the styrene monomer of alkyl thiosulfurie acid sodium (potassium) salt; This monomer can be at strong polar reagent methyl-sulphoxide DMSO, N; N`-N DMF or diluted acid effect discharge the sulfhydryl-group activity of providing the chain transfer function down; Thereby form a kind of branched monomer that had not only contained polymerizable double bond but also contained sulfhydryl-group activity, be used for sulfydryl chain transfer legal system and be equipped with hyperbranched polymer.
With the styrene compound that contains halogenated methylene is raw material, and the Bunte Salts reaction through halogenated alkyl primitive and excessive saturated sodium thiosulfate (potassium) salts solution obtains a kind of styrenic polymerizable AB monomer that contains alkyl thiosulfurie acid sodium (potassium) salt.
Table 1. contains some instances and the reacted product of Bunte Salts of the styrene compound of halo methylene radical.
Beneficial effect of the present invention: the present invention is a raw material with the styrene compound that contains halogenated methylene, and the Bunte Salts reaction through halogenated alkyl primitive and excessive saturated sodium thiosulfate (potassium) salts solution obtains a kind of styrenic polymerisable monomer that contains alkyl thiosulfurie acid sodium (potassium) salt.This monomer can be at methyl-sulphoxide DMSO, N, and strong polar reagent such as N`-N DMF or diluted acid effect discharge down provides the sulfhydryl-group activity of chain transfer function, thereby forms a kind of AB monomer that had not only contained polymerizable double bond but also contained sulfhydryl-group activity.This AB monomer structure is simple, be easy to preparation preserves, and is expected to be applied to sulfhydryl chain transfer hyperbranched polymerization process (SCVP method) preparation hyperbranched polymer.This preparation method is with low cost, and is workable.
Description of drawings
Fig. 1 p-chloromethyl styrene and Sulfothiorine carry out the infared spectrum that Bunte Salts reacts back raw material and product.
Embodiment
Below in conjunction with embodiment the present invention is further described, but do not limit the present invention.
Embodiment 1:
In the 250mL round-bottomed flask that magnetic agitation is housed, add 3.00g PEO400,24.817g (0.1mol) Sulfothiorine and 30mL water, stir.In the beaker of 50mL, add 20.349g (0.12mol) p-chloromethyl styrene (massfraction 90%), 10mL ethanol is poured in the constant pressure funnel after stirring, and it is splashed in the round-bottomed flask of 250mL again.React stopped reaction after 6 hours under the room temperature.Revolve ethanol and portion water with Rotary Evaporators, obtain solid.Suction filtration collect solid and with a small amount of cold water and sherwood oil respectively drip washing remove unreacted p-chloromethyl styrene, Sulfothiorine, PEO400, obtain purified product---(4-vinyl)-dibenzylsulfide sodium thiosulfate, structural formula is following:
Embodiment 2:
In the three-necked bottle of the 250mL that magnetic agitation is housed, add 10.00g (0.18mol) Pottasium Hydroxide, 9.896g (0.1mol) 1,2-ethylene dichloride and 40mL absolute ethyl alcohol stir.In the beaker of 50mL, add 12.015g (0.1mol) 4-hydroxy styrenes, the 20mL absolute ethyl alcohol is poured in the constant pressure funnel after stirring; On the three-necked bottle of 250mL, load onto spherical condensation tube and constant pressure funnel; Be heated to reflux temperature, dropping liquid reacts stopped reaction after 14 hours; Remove by filter the salt of generation, obtain the etherificate product.It is for use to revolve half solvent with Rotary Evaporators normal temperature.
In the 250mL round-bottomed flask that magnetic agitation is housed, add 3.00g PEO 400,30.00g (0.12mol) Sulfothiorine and 30mL water, stir.The ethanolic soln of synthetic etherificate product is well poured in the constant pressure funnel, again it is splashed in the round-bottomed flask of 250mL.React stopped reaction after 6 hours under the room temperature.Revolve ethanol with Rotary Evaporators, obtain solid.Suction filtration collect solid and with a small amount of cold water and sherwood oil respectively drip washing remove various unreacting materials and by product, obtain purified product, structural formula is following:
Embodiment 3:
, the 250mL three-necked bottle of spherical condensation tube puts into magnetic agitation in being housed; Add 11.916g (0.1mol) 4-amino-benzene ethene, 9.896g (0.1mol) 1; 2-ethylene dichloride, 15.178g (0.15mol) triethylamine and 70mL absolute ethyl alcohol; Be heated to reflux temperature and react stopped reaction after 8 hours, remove by filter the salt of generation, obtain the nucleophilic substitution product.It is for use to revolve half solvent with Rotary Evaporators normal temperature.
In the 250mL round-bottomed flask that magnetic agitation is housed, add 3.00g PEO400,30.00g (0.12mol) Sulfothiorine and 30mL water, stir.The ethanolic soln of synthetic nucleophilic substitution product is well poured in the constant pressure funnel, again it is splashed in the round-bottomed flask of 250mL.React stopped reaction after 6 hours under the room temperature.Revolve ethanol with Rotary Evaporators, obtain solid.Suction filtration collect solid and with a small amount of cold water and sherwood oil respectively drip washing remove various unreacting materials and by product, obtain purified product, structural formula is following:
Embodiment 4:
, the 250mL three-necked bottle of spherical condensation tube puts into magnetic agitation in being housed; Add 10.514g (0.1mol) 4-vinylpridine, 9.896g (0.1mol) 1; 2-ethylene dichloride, 15.178g (0.15mol) triethylamine and 70mL absolute ethyl alcohol; React stopped reaction after 8 hours under the room temperature, remove by filter the salt of generation, obtain quaternized products.It is for use to revolve half solvent with Rotary Evaporators normal temperature.
In the 250mL round-bottomed flask that magnetic agitation is housed, add 3.00g PEO400,30.00g (0.12mol) Sulfothiorine and 30mL water, stir.The ethanolic soln of synthetic quaternized products is well poured in the constant pressure funnel, again it is splashed in the round-bottomed flask of 250mL.React stopped reaction after 6 hours under the room temperature.Revolve ethanol with Rotary Evaporators, obtain solid.Suction filtration collect solid and with a small amount of cold water and sherwood oil respectively drip washing remove various unreacting materials and by product, obtain purified product, structural formula is following:
Embodiment 5:
In the round-bottomed flask of the 500mL that magnetic agitation is housed, add 14.816g (0.1mol) 4-vinyl benzoic acid, 8.051g (0.1mol) ethylene chlorhydrin, 13.00g (0.11mol) N-succinimide (NHS) and 100mL N; Dinethylformamide (DMF) stirs.In the 200mL beaker, add 25.00g (0.13mol) 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and 150mL DMF dissolving back and add in the tap funnel, splash in the 500mL round-bottomed flask product of reaction after 12 hours repeatedly with chloroform extraction.Use Rotary Evaporators normal temperature to revolve the imitative solid that obtains of dechlorination and be esterification products.
In the 250mL round-bottomed flask that magnetic agitation is housed, add 3.00g PEO 400,30.00g (0.12mol) Sulfothiorine and 30mL water, stir.Synthetic good esterification products is poured in the constant pressure funnel with the 40mL dissolve with ethanol, again it is splashed in the round-bottomed flask of 250mL.React stopped reaction after 6 hours under the room temperature.Revolve ethanol with Rotary Evaporators, obtain solid.Suction filtration collect solid and with a small amount of cold water and sherwood oil respectively drip washing remove various unreacting materials and by product, obtain purified product, structural formula is following:
Embodiment 6:
, the 250mL three-necked bottle of spherical condensation tube puts into magnetic agitation in being housed; Add 10.450g (0.1mol) vinylbenzene, 12.697g (0.1mol) 3-chlorpromazine chloride, 15.178g (0.15mol) triethylamine and 70mL chloroform (dry) with Calcium Chloride Powder Anhydrous; React stopped reaction after 8 hours under the room temperature; Remove by filter the salt of generation, obtain the nucleophilic substitution product.Use Rotary Evaporators normal temperature to revolve the imitative liquid that obtains of dechlorination and be the nucleophilic substitution product.
In the 250mL round-bottomed flask that magnetic agitation is housed, add 3g PEO 400,30.00g (0.12mol) Sulfothiorine and 30mL water, stir.Synthetic good nucleophilic substitution product and 40mL ethanol mixed pour in the constant pressure funnel, again it is splashed in the round-bottomed flask of 250mL.React stopped reaction after 6 hours under the room temperature.Revolve ethanol with Rotary Evaporators, obtain solid.Suction filtration collect solid and with a small amount of cold water and sherwood oil respectively drip washing remove various unreacting materials and by product, obtain purified product, structural formula is following:
Claims (1)
1. preparation method who contains the styrene monomer of alkyl thiosulfurie acid sodium (potassium) salt; It is characterized in that: with the styrene compound that contains halogenated methylene is raw material; With first alcohol and water or second alcohol and water is mixed solvent, and oxyethane PEO400 is a phase-transfer catalyst, through the Bunte Salts reaction of halogen on the halogenated methylene and excessive saturated sodium thiosulfate (potassium) salts solution; Stirring reaction to Sulfothiorine (potassium) salt raw material consumption is complete under the room temperature; Methyl alcohol or ethanol and portion water are removed in decompression then, direct suction filtration, collection gained solid behind the crystallisation by cooling, and with a small amount of cold water and sherwood oil drip washing successively; 40 ℃ of oven dry down promptly get the styrene monomer that contains alkyl thiosulfurie acid sodium (potassium) salt;
Oxyethane PEO400 consumption is the weight fraction 1%-5% that contains the styrene compound of halogenated methylene;
Sulfothiorine (potassium): the mol ratio of the halogen in the styrene compound of halogenated methylene is 1: 1.3-1.3: 1, and the terminal point of reaction is judged through tlc;
The described styrene monomer that contains alkyl thiosulfurie acid sodium (potassium) salt, its structural formula is:
Wherein, R is the bridge joint group, selects ester bond, ehter bond or amido linkage for use; Perhaps alkyl sodium (potassium) thiosulfate directly and phenyl ring join; M is Na
+Or K
+Ion.
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| CN101538235B true CN101538235B (en) | 2012-08-15 |
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| CN101891858B (en) * | 2010-03-04 | 2014-02-05 | 江苏工业学院 | Method for preparing branched polymer by conventional free radical polymerization |
| CN102304076A (en) * | 2011-07-05 | 2012-01-04 | 江苏兄弟维生素有限公司 | Preparation method of sodium n-propyl thiosulfate |
| CN104119259A (en) * | 2014-07-11 | 2014-10-29 | 江苏兄弟维生素有限公司 | A synthetic process of sodium n-propyl thiosulfate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1143330B (en) * | 1961-09-09 | 1963-02-07 | Hoechst Ag | Process for the preparation of polymers containing several Bunte salt groups in the molecule |
| CN101143916A (en) * | 2007-08-30 | 2008-03-19 | 复旦大学 | Method for preparing three hetero arms asteroid polymer |
| CN101166769A (en) * | 2005-04-27 | 2008-04-23 | 大金工业株式会社 | Fluoropolymer having S-Sulfate group and water/oil repellent composition containing the polymer |
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2009
- 2009-04-14 CN CN200910030467XA patent/CN101538235B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1143330B (en) * | 1961-09-09 | 1963-02-07 | Hoechst Ag | Process for the preparation of polymers containing several Bunte salt groups in the molecule |
| CN101166769A (en) * | 2005-04-27 | 2008-04-23 | 大金工业株式会社 | Fluoropolymer having S-Sulfate group and water/oil repellent composition containing the polymer |
| CN101143916A (en) * | 2007-08-30 | 2008-03-19 | 复旦大学 | Method for preparing three hetero arms asteroid polymer |
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