CN106432022A - Preparation method for alkyl xanthate allyl ester compound - Google Patents
Preparation method for alkyl xanthate allyl ester compound Download PDFInfo
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- CN106432022A CN106432022A CN201510475571.5A CN201510475571A CN106432022A CN 106432022 A CN106432022 A CN 106432022A CN 201510475571 A CN201510475571 A CN 201510475571A CN 106432022 A CN106432022 A CN 106432022A
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- CN
- China
- Prior art keywords
- alkyl
- allyl ester
- acid
- preparation
- xanthate
- 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.)
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- -1 alkyl xanthate allyl ester compound Chemical class 0.000 title claims abstract description 45
- 239000012991 xanthate Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000000746 allylic group Chemical group 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 235000011149 sulphuric acid Nutrition 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims 1
- 229920001285 xanthan gum Polymers 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 150000004808 allyl alcohols Chemical class 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 9
- 238000005303 weighing Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- RZFBEFUNINJXRQ-UHFFFAOYSA-M sodium ethyl xanthate Chemical compound [Na+].CCOC([S-])=S RZFBEFUNINJXRQ-UHFFFAOYSA-M 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- GNVMUORYQLCPJZ-UHFFFAOYSA-M Thiocarbamate Chemical compound NC([S-])=O GNVMUORYQLCPJZ-UHFFFAOYSA-M 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- SARKRSWCLHYVGQ-UHFFFAOYSA-N ethoxymethanedithioic acid;sodium Chemical compound [Na].CCOC(S)=S SARKRSWCLHYVGQ-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- AAJRIJBGDLLRAE-UHFFFAOYSA-M sodium;butoxymethanedithioate Chemical class [Na+].CCCCOC([S-])=S AAJRIJBGDLLRAE-UHFFFAOYSA-M 0.000 description 1
- IRZFQKXEKAODTJ-UHFFFAOYSA-M sodium;propan-2-yloxymethanedithioate Chemical class [Na+].CC(C)OC([S-])=S IRZFQKXEKAODTJ-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method for an alkyl xanthate allyl ester compound. The preparation method for the alkyl xanthate allyl ester compound is used for preparing alkyl xanthate allyl ester beneficiation reagents, and is characterized in that instead of allyl chlorine compounds which are inflammable and extremely volatile, allyl alcohol compounds which are safe and free of corrosivity are used as raw materials, and react with alkyl xanthate to prepare the alkyl xanthate allyl ester compound, the alkyl xanthate allyl ester compound is subjected to skimming, washing and drying, and then alkyl xanthate allyl ester is obtained. Therefore, the production process is made more environmentally friendly and safer.
Description
Technical field
The present invention relates to a kind of preparation method for mine ore dressing pharmaceutical techniques field alkyl xanthogenic acid allyl ester type compound, belong to Mine chemistry product preparing technical field.
Background technology
Alkyl xanthogenic acid esters collecting agent, as the derivant of xanthate, is the important mine ore dressing medicament of a class, and its industrial process is that alkyl xanthogenic acid salt compound generates alkyl xanthogenic acid esters compound with active halogen ester, halohydrocarbons reaction.Wherein United States Patent (USP) US2808931 with caustic soda (potassium), Carbon bisulfide as raw material, synthesis of alkyl xanthates, then react with active allyl chloride, through a point liquid, wash, be dried to obtain alkyl xanthogenic acid allyl ester.
Said method does raw material using allyl chloride, and allyl chloride boiling point is 45 DEG C, and highly volatile is simultaneously again inflammable, stronger corrosivity and higher toxicity, therefore there is potential safety hazard in storage, transport with during using.
Chinese patent CN1153774A produces in beneficiation reagent thiocarbamate and is used allyl chloride to be reacted as raw material, Chinese patent CN101367755A replaces allyl chloride to do raw material using 1-propenol-3 on the basis of Chinese patent CN1153774A, prepare thiocarbamate and produce preferable result, successfully solve the volatile of allyl chloride, the inflammable and explosive shortcoming waiting deficiency.
Content of the invention
The purpose of the present invention is, using 1-propenol-3 (97 DEG C of boiling point, non-corrosiveness) replace allyl chloride, prepare alkyl xanthogenic acid allyl ester with alkyl xanthogenic acid reactant salt, overcome with allyl chloride (45 DEG C of boiling point, volatile, inflammable and explosive) prepare the problem of alkyl xanthogenic acid allyl ester for raw material, thus providing a kind of safer alkyl xanthogenic acid allyl ester preparation method.
Its reaction equation is as follows：
R1OCSSNa+HOCH2CH=CHR2→R1OCSSCH2CH=CHR2+NaOH
2NaOH+H2SO4→Na2SO4+2H2O
Specific embodiment
The technical solution adopted in the present invention is：
A kind of preparation method of alkyl xanthogenic acid allyl ester type compound, generates alkyl xanthogenic acid allyl ester including using the alcohol containing allylic structure and alkyl xanthate, and promotes the process of reaction with mineral acid.It is characterized in that：The alkyl R of the alkyl xanthate reacting with 1-propenol-31Alkyl for C2 to C8；The alcohol containing allylic structure with alkyl xanthogenic acid reactant salt is R ' OH, i.e. HOCH2CH=CHR2, wherein R ' is the alkyl containing allylic structure.
Its technological process is：
1st, alkyl xanthate is soluble in water.
2nd, the certain 1-propenol-3 of Deca.Mol ratio with alkyl xanthate is 1: 1.05-2, and reaction temperature is 90 DEG C -100 DEG C.
3rd, the certain inorganic acid solution of Deca promotes reaction.Response time is 2-10 hour.
4th, divide liquid, washing and desalting, dry alkyl xanthogenic acid allyl ester.
Used in the present invention, alcohol is the three carbon alcohol containing allylic structure, four carbon alcohols, five carbon alcohol, and that is, the structure of R ' OH is R2CH=CHCH2OH, R2=H- or CH3- or C2H5-.
In the inventive method, play and promote the acid of reaction to be sulphuric acid or hydrochloric acid, alkyl xanthate is sodium salt and potassium salt, the alkyl of the alkyl xanthate alkyl for C2 to C8.
Compared with prior art, the invention has the beneficial effects as follows process is simple, replace allyl chloride to reduce the risk that hazardous materials bring with 1-propenol-3, make production technology more Environmental Safety.
Embodiment
Example 1：Add 2mol ethoxy-dithioformic acid sodium salt in the reactor, 500 milliliters of water, stirring makes it dissolve, then accurately weigh a certain amount of 1-propenol-3 (2mol), 30 minutes completion of dropping, 100 grams of concentrated sulphuric acids (98%) of Deca are added in reactor (30 minutes completion of dropping) again, continue stirring 3 hours, make reaction complete.In whole process, temperature keeps 90 DEG C.After reaction terminates, by the material in reactor under room temperature, transfer in separatory funnel, standing a period of time, profit is layered, then gained yellow oil reservoir is washed 3 times (each 500ml water) with water, with remove water-solubility impurity and remain in oil reservoir product reaction generated in sodium sulfate.It is subsequently adding a certain amount of anhydrous MgSO4To in oily product, it is dried overnight, the MgSO after filtering water suction4, gained oily product 313g of then weighing.
Example 2：Add 2mol 1-propenol-3 in the reactor, it is subsequently adding 100 grams of concentrated sulphuric acids (98%) in reactor, then be slowly added dropwise the ethoxy-dithioformic acid sodium solution (2mol sodium ethylxanthate, 500ml water) preparing in advance, continue stirring 3 and a half hours, make reaction complete.In whole process, temperature keeps 90 DEG C.Other conditions same 1, gained oily product 310g of weighing.
Example 3：Add 2mol ethoxy-dithioformic acid sodium salt in the reactor, 500 milliliters of water, stirring makes it dissolve, then accurately weigh a certain amount of 2-butylene -1- alcohol (2mol), 30 minutes completion of dropping, add 100 grams of concentrated sulphuric acids (98%) to be added in reactor (30 minutes completion of dropping), continue 3 hours of stirring, make reaction complete.In whole process, temperature keeps 90 DEG C.Other conditions same 1, gained oily product 340g of weighing.
Example 4：Add 2mol ethoxy-dithioformic acid sodium salt in the reactor, 500 milliliters of water, stirring makes it dissolve, then accurately weigh a certain amount of 2- amylene-1-ol (2mol), 30 minutes completion of dropping, add 100 grams of concentrated sulphuric acids (98%) to be added in reactor (30 minutes completion of dropping), continue stirring 3 and a half hours, make reaction complete.In whole process, temperature keeps 90 DEG C.Other conditions same 1, gained oily product 371g of weighing.
Example 5：Add 2mol sodium isopropyl xanthate salt in the reactor, 500 milliliters of water, stirring makes it dissolve, then accurately weigh a certain amount of 1-propenol-3 (2mol), 30 minutes completion of dropping, add 100 grams of concentrated sulphuric acids (98%) to be added in reactor (30 minutes completion of dropping), continue stirring 3 and a half hours, make reaction complete.In whole process, temperature keeps 90 DEG C.Other conditions same 1, gained oily product 339g of weighing.
Example 6：Add 2mol sodium n-butyl xanthate salt in the reactor, 500 milliliters of water, stirring makes it dissolve, then accurately weigh a certain amount of 1-propenol-3 (2mol), 30 minutes completion of dropping, add 100 grams of concentrated sulphuric acids (98%) to be added in reactor (30 minutes completion of dropping), continue stirring 3 and a half hours, make reaction complete.In whole process, temperature keeps 90 DEG C.Other conditions same 1, gained oily product 368g of weighing.
Example 7：Add 2mol sodium isobutyl xanthan salt in the reactor, 500 milliliters of water, stirring makes it dissolve, then accurately weigh a certain amount of 1-propenol-3 (2mol), 30 minutes completion of dropping, add 100 grams of concentrated sulphuric acids (98%) to be added in reactor (30 minutes completion of dropping), continue stirring 3 and a half hours, make reaction complete.In whole process, temperature keeps 90 DEG C.Other conditions same 1, gained oily product 365g of weighing.
Claims (6)
1. a kind of preparation method of alkyl xanthogenic acid pi-allyl ester type compound, generates alkyl xanthogenic acid allyl ester including using the alcohol containing allylic structure and alkyl xanthate, and promotes the process of reaction with mineral acid.It is characterized in that：The alkyl for C2 to C8 for the alkyl of the alkyl xanthate reacting with 1-propenol-3；The alcohol containing allylic structure with alkyl xanthogenic acid reactant salt is R ' OH, and wherein R is the alkyl containing allylic structure.
2. a kind of preparation method of alkyl xanthogenic acid pi-allyl ester type compound according to claim 1 is it is characterised in that alkyl xanthate used is ethyl xanthate, isopropyl xanthan hydrochlorate, normal-butyl xanthates and isobutyl group xanthates.
3. a kind of preparation method of alkyl xanthogenic acid pi-allyl ester type compound according to claim 1 is it is characterised in that the alcohol R ' OH containing allylic structure used is 1-propenol-3,2-butylene -4- alcohol, 3- amylene -5- alcohol.
4. a kind of preparation method of alkyl xanthogenic acid pi-allyl ester type compound according to claim 1 is it is characterised in that alkyl xanthate used is alkyl xanthogenic acid potassium salt and sodium salt.
5. a kind of preparation method of alkyl xanthogenic acid pi-allyl ester type compound according to claim 1 is it is characterised in that promote reaction mineral acid used to be sulphuric acid, phosphoric acid, hydrochloric acid.
6. the preparation method of a kind of alkyl xanthogenic acid pi-allyl ester type compound according to claim 1, it is characterized in that alkyl xanthate is reacted with the alcohol containing allylic structure, its mol ratio is 1: 1.05-2, and reaction temperature is 90 DEG C -100 DEG C, and the response time is 2-10 hour.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510475571.5A CN106432022B (en) | 2015-08-06 | 2015-08-06 | The preparation method of alkyl xanthogenic acid pi-allyl ester type compound |
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| CN201510475571.5A CN106432022B (en) | 2015-08-06 | 2015-08-06 | The preparation method of alkyl xanthogenic acid pi-allyl ester type compound |
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| CN106432022B CN106432022B (en) | 2017-09-01 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256316A (en) * | 2019-06-09 | 2019-09-20 | 沈阳有研矿物化工有限公司 | A kind of isobutyl group xanthic acid propynyl ester and preparation method thereof |
| CN110280393A (en) * | 2019-06-09 | 2019-09-27 | 沈阳有研矿物化工有限公司 | A kind of isopropyl xanthan acid propynyl ester and preparation method thereof |
| CN110280394A (en) * | 2019-06-09 | 2019-09-27 | 沈阳有研矿物化工有限公司 | A kind of isopentyl xanthic acid propynyl ester and preparation method thereof |
| CN110862337A (en) * | 2019-12-04 | 2020-03-06 | 沈阳有色金属研究院有限公司 | Preparation method of alkyl xanthate acrylate collecting agent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2808931A (en) * | 1951-05-01 | 1957-10-08 | American Cyanamid Co | Allyl esters of alkyl xanthates |
| CN1153774A (en) * | 1995-11-02 | 1997-07-09 | 北京矿冶研究总院 | Preparation method of thiocarbamate compound |
-
2015
- 2015-08-06 CN CN201510475571.5A patent/CN106432022B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2808931A (en) * | 1951-05-01 | 1957-10-08 | American Cyanamid Co | Allyl esters of alkyl xanthates |
| CN1153774A (en) * | 1995-11-02 | 1997-07-09 | 北京矿冶研究总院 | Preparation method of thiocarbamate compound |
Non-Patent Citations (1)
| Title |
|---|
| NEIL F.HALEY等: "Facile syntheses of 1,3-dithiol-2-ones and 1,3-dithiole-2-thiones", 《J.ORG.CHEM》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256316A (en) * | 2019-06-09 | 2019-09-20 | 沈阳有研矿物化工有限公司 | A kind of isobutyl group xanthic acid propynyl ester and preparation method thereof |
| CN110280393A (en) * | 2019-06-09 | 2019-09-27 | 沈阳有研矿物化工有限公司 | A kind of isopropyl xanthan acid propynyl ester and preparation method thereof |
| CN110280394A (en) * | 2019-06-09 | 2019-09-27 | 沈阳有研矿物化工有限公司 | A kind of isopentyl xanthic acid propynyl ester and preparation method thereof |
| CN110862337A (en) * | 2019-12-04 | 2020-03-06 | 沈阳有色金属研究院有限公司 | Preparation method of alkyl xanthate acrylate collecting agent |
| CN110862337B (en) * | 2019-12-04 | 2021-06-01 | 沈阳有色金属研究院有限公司 | Preparation method of alkyl xanthate acrylate collecting agent |
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