CN104557681A - Method for synthesizing 4-vinyl pyridine propanesulfonic acid ylide - Google Patents
Method for synthesizing 4-vinyl pyridine propanesulfonic acid ylide Download PDFInfo
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- CN104557681A CN104557681A CN201310503637.8A CN201310503637A CN104557681A CN 104557681 A CN104557681 A CN 104557681A CN 201310503637 A CN201310503637 A CN 201310503637A CN 104557681 A CN104557681 A CN 104557681A
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- vinylpridine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/20—Quaternary compounds thereof
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Abstract
The invention provides a method for synthesizing 4-vinyl pyridine propanesulfonic acid ylide. The method comprises the following steps: respectively weighing 4-vinylpyridine, 1,3-propane sultone, an organic solvent and additives; averagely dividing the organic solvent into three parts, and respectively mixing the three parts of organic solvent with 4-vinylpyridine, 1,3-propane sultone and the additives; sequentially adding the mixed solutions into a reactor, reacting for 1-10 hours at 20-90 DEG C, and filtering, washing and drying to prepare the 4-vinyl pyridine propanesulfonic acid ylide. According to the method provided by the invention, the additives are added to ensure a high product yield, which can be higher than 90%, moreover, a high-purity product can be directly obtained without carrying out a recrystallization step, and the purity of the product is not smaller than 95%. The method provided by the invention is short in reaction time and is simple to operate, and no glue is left on the reactor after the reaction, so that the reactor is easy to clean and maintain; and the method is conducive to industrial production and is suitable for industrial application.
Description
Technical field
The present invention relates to a kind of synthetic method of 4-vinylpridine propanesulfonic acid inner salt.
Background technology
4-vinylpridine propanesulfonic acid inner salt (4-VPPS) is a kind of pyridine derivatives monomer, and its molecular formula is: C
10h
13nO
3s, molecular weight is: 227.28.
4-VPPS is a kind of white or pale yellow powder shape solid, soluble in water, is slightly soluble in majority of organic solvent.4-VPPS as a kind of new type water-solubility ampholytic monomer, because its chemistry and Heat stability is good, hydratability are strong and affect containing not being subject to solution ph, receiving much attention to the quaternary ammonium cation of the numbers such as salt is insensitive and sulfonate anionic.Compared with the water soluble anionic only containing a kind of electric charge or cation type polymer, the performance of 4-VPPS is comparatively unique.In intermolecular and molecule intrachain force properties, the polyelectrolyte only containing a kind of electric charge, electrostatic force is only electrostatic repulsion; And for amphiphilic polymers, electrostatic interaction both can be repulsion, also can be gravitation, depend on the relative number of positive and negative charge in molecular chain.In SOLUTION PROPERTIES, macromole net charge be zero or molecular chain on the equal amphiphilic polymers of positive and negative charge group numbers, the viscosity of its salt brine solution does not only reduce, increase on the contrary, present fairly obvious " anti-polyelectrolyte effect " (antipolyelectrolyte effect).The character of this uniqueness gives the function of amphiphilic polymers uniqueness.Stablize high hexa-atomic conjugate ring containing sexual in the structure of 4-VPPS, the polymkeric substance heat resistance that obtains of homopolymerization or copolymerization is splendid thus.
At present, in view of the feature that formation temperature in oil drilling is high and salinity is high, make to reach wellbore stability in drilling process, the effect of safety drilling, polymkeric substance must have good tackifying ability and very strong heatproof, anti-salt and anti-shear ability.Obviously, 4-VPPS amphiphilic polymers can meet such requirement.
About the synthesis of 4-VPPS, have 70 ~ eighties of last century a small amount of foreign language literature to report, but the 4-VPPS yield obtained according to literature procedure is low, purity is not high, also needs to obtain high purity product through recrystallization method, and product loss is large.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of synthetic method of 4-vinylpridine propanesulfonic acid inner salt.The method has that the reaction times is short, product yield is high, product purity is high, be suitable for the advantages such as industrial application.
The invention provides a kind of synthetic method of 4-vinylpridine propanesulfonic acid inner salt, step is as follows:
(1) be 1:1.1 ~ 1:1.3 according to mol ratio, preferred 1:1.1 ~ 1:1.2 takes 4-vinylpridine (4-VP) and PS (PS) respectively;
(2) take organic solvent, the total mass ratio of organic solvent and 4-vinylpridine and PS is 2:1 ~ 8:1, is preferably 3:1 ~ 5:1;
(3) take auxiliary agent, the mass ratio of the organic solvent in the 4-vinylpridine in auxiliary agent and step (1) and PS and step (2) is 0.001 ~ 0.01, is preferably 0.005 ~ 0.01;
(4) organic solvent in step (2) is divided into three parts, dissolves with 4-vinylpridine, PS, auxiliary agent respectively and mix;
(5) three kinds of mixing solutionss that step (4) obtains are added reactor successively, at 20 DEG C ~ 90 DEG C, preferably reaction 1 ~ 10h, preferred reaction 2 ~ 5h under the condition of 60 ~ 80 DEG C, then after filtration, washing, dry obtained 4-vinylpridine propanesulfonic acid inner salt.
In the inventive method, described organic solvent is any one in benzene, toluene, ethyl acetate, acetone, pimelinketone, propylene carbonate.
In the inventive method, described auxiliary agent can be hydroxylamine compound and nitrobenzene compounds, and wherein hydroxylamine compound is specifically as follows any one in dimethyl hydroxylamine, diethyl hydroxylamine, dipropyl azanol, isopropylhydroxyla, dibutylhydroxylamine, methyl ethylhydroxylamine; Nitrobenzene compounds is specifically as follows any one in 1,2-dinitrobenzene, 1,3-dinitrobenzene, Isosorbide-5-Nitrae-dinitrobenzene, 1，3，5-trinitrobenzene.
In the inventive method, filter operation described in step (5) is be transferred to by the product be obtained by reacting in funnel to cross to filter solvent and unreacted raw material.Be preferably and use Büchner funnel to carry out decompress filter.
In the inventive method, washing operation described in step (5) is for using organic solvent washing described in step (2) 2 ~ 5 times.
In the inventive method, drying described in step (5) is dry 10 ~ 20h at 40 ~ 60 DEG C.。
Compared with prior art, the synthetic method tool that the invention provides a kind of 4-vinylpridine propanesulfonic acid inner salt has the following advantages: the inventive method is by adding auxiliary agent, not only make to synthesize the 4-vinylpridine propanesulfonic acid inner salt product yield obtained high, can more than 90% be reached, and do not need directly to obtain high purity product through re-crystallization step, product is Powdered, product purity >=95%.It is short, simple to operate that the inventive method has the reaction times, and reaction post-reactor not kiss-coating, is easy to clean and maintenance, is conducive to suitability for industrialized production, be suitable for industrial application.
Accompanying drawing explanation
Fig. 1 is the product infrared spectrum of the embodiment of the present invention 1.
Fig. 2 is the product hydrogen spectrum nmr spectrum of the embodiment of the present invention 1.
Embodiment
Illustrate the effect of the inventive method below in conjunction with embodiment, but following examples do not form the restriction to the present invention program.
Embodiment 1
(1) 4-vinylpridine (4-VP) of 10.5g, the PS (PS) of 12.5g, the organic solvent-benzene of 50g, the diethyl hydroxylamine of 0.075g is taken respectively;
(2) organic solvent-benzene is divided into three parts, dissolves with 4-vinylpridine, PS, auxiliary agent diethyl hydroxylamine respectively and mix;
(3) obtain three kinds of mixing solutionss are added reactor successively, 2h is reacted at 70 DEG C, then through decompress filter, then benzene washing 2 ~ 3 times are used, dry 15h at 50 DEG C, obtained 4-vinylpridine propanesulfonic acid inner salt, finally obtains faint yellow solid powdery product 21.36g as calculated, yield is 94.1wt%, and purity is 95.8%.
Embodiment 2
(1) 4-vinylpridine (4-VP) of 10.5g, the PS (PS) of 13g, the organic solvent ethyl acetate of 130g, 1, the 3-dinitrobenzene of 0.75g is taken respectively;
(2) organic solvent ethyl acetate is divided into three parts, dissolves with 4-vinylpridine, PS, auxiliary agent diethyl hydroxylamine respectively and mix;
(3) obtain three kinds of mixing solutionss are added reactor successively, 4h is reacted at 80 DEG C, then through decompress filter, then ethyl acetate washing 2 ~ 3 times are used, dry 10h at 40 DEG C, obtained 4-vinylpridine propanesulfonic acid inner salt, finally obtains faint yellow solid powdery product 21.04g as calculated, yield is 92.7%, and purity is 96.3%.
Embodiment 3
(1) 4-vinylpridine (4-VP) of 10.5g, the PS (PS) of 11.5g, the organic solvent pimelinketone of 200g, the isopropylhydroxyla of 2.1g is taken respectively;
(2) organic solvent pimelinketone is divided into three parts, dissolves with 4-vinylpridine, PS, auxiliary agent diethyl hydroxylamine respectively and mix;
(3) obtain three kinds of mixing solutionss are added reactor successively, 7h is reacted at 65 DEG C, then through decompress filter, then pimelinketone washing 2 ~ 3 times are used, dry 20h at 60 DEG C, obtained 4-vinylpridine propanesulfonic acid inner salt, finally obtains faint yellow solid powdery product 20.63g as calculated, yield is 90.9%, and purity is 95.4%.
Comparative example 1
(1) 4-vinylpridine (4-VP) of 10.5g, the PS (PS) of 12.5g, the organic solvent-benzene of 50g is taken respectively;
(2) organic solvent-benzene is divided into two parts, mixes with 4-vinylpridine, PS respectively;
(3) obtain two kinds of mixing solutionss are added reactor successively, 2h is reacted at 70 DEG C, then through decompress filter, then benzene washing 2 ~ 3 times are used, dry 15h at 50 DEG C, obtained 4-vinylpridine propanesulfonic acid inner salt, finally obtains faint yellow solid powdery product 16.45g as calculated, yield is 72.5wt%, and purity is 81.4%.
Claims (11)
1. a synthetic method for 4-vinylpridine propanesulfonic acid inner salt, step is as follows:
(1) be that 1:1.1 ~ 1:1.3 takes 4-vinylpridine and PS respectively according to mol ratio;
(2) take organic solvent, the total mass ratio of organic solvent and 4-vinylpridine and PS is 2:1 ~ 8:1;
(3) take auxiliary agent, the mass ratio of the organic solvent in the 4-vinylpridine in auxiliary agent and step (1) and PS and step (2) is 0.001 ~ 0.01;
(4) organic solvent in step (2) is divided into three parts, dissolves with 4-vinylpridine, PS, auxiliary agent respectively and mix;
(5) three kinds of mixing solutionss that step (4) obtains are added reactor successively, under the condition of 20 DEG C ~ 90 DEG C, react 1 ~ 10h, then after filtration, washing, dry obtained 4-vinylpridine propanesulfonic acid inner salt.
2. in accordance with the method for claim 1, it is characterized in that: in step (1), the mol ratio of 4-vinylpridine and PS is 1:1.1 ~ 1:1.2.
3. in accordance with the method for claim 1, it is characterized in that: in step (2), the total mass ratio of organic solvent and 4-vinylpridine and PS is 3:1 ~ 5:1.
4. in accordance with the method for claim 1, it is characterized in that: the mass ratio of the organic solvent in the 4-vinylpridine in auxiliary agent and step (1) and PS and step (2) is 0.005 ~ 0.01.
5. in accordance with the method for claim 1, it is characterized in that: three kinds of mixing solutionss that step (4) obtains add reactor successively, under the condition of 60 ~ 80 DEG C, react 2 ~ 5h.
6. in accordance with the method for claim 1, it is characterized in that: described organic solvent is any one in benzene, toluene, ethyl acetate, acetone, pimelinketone, propylene carbonate.
7. in accordance with the method for claim 1, it is characterized in that: described auxiliary agent is hydroxylamine compound and nitrobenzene compounds.
8. in accordance with the method for claim 1, it is characterized in that: hydroxylamine compound is specifically as follows any one in dimethyl hydroxylamine, diethyl hydroxylamine, dipropyl azanol, isopropylhydroxyla, dibutylhydroxylamine, methyl ethylhydroxylamine.
9. in accordance with the method for claim 1, it is characterized in that: nitrobenzene compounds is specially any one in 1,2-dinitrobenzene, 1,3-dinitrobenzene, Isosorbide-5-Nitrae-dinitrobenzene, 1，3，5-trinitrobenzene.
10. in accordance with the method for claim 1, it is characterized in that: washing operation described in step (5) is for using organic solvent washing described in step (2) 2 ~ 4 times.
11. in accordance with the method for claim 1, it is characterized in that: dry described in step (5) is 10 ~ 20h dry at 40 ~ 60 DEG C.
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| CN201310503637.8A CN104557681B (en) | 2013-10-24 | 2013-10-24 | A kind of synthetic method of 4 vinylpyridine propane sulfonic acid inner salt |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110016325A (en) * | 2018-01-10 | 2019-07-16 | 中国石油化工股份有限公司 | A kind of water-base drilling fluid extracting and cutting agent and preparation method thereof |
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2013
- 2013-10-24 CN CN201310503637.8A patent/CN104557681B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| V.M.MONROY SOTO 等: "Poly(sulphopropylbetaines): 1. Synthesis and characterization", 《POLYMER》 * |
| 桂张良 等: "含磺酸甜菜碱两性离子共聚物P（AM-co-VPPS）的合成及盐溶液性质", 《高分子学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110016325A (en) * | 2018-01-10 | 2019-07-16 | 中国石油化工股份有限公司 | A kind of water-base drilling fluid extracting and cutting agent and preparation method thereof |
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