CN114773163A - Preparation method of alkyl naphthol - Google Patents
Preparation method of alkyl naphthol Download PDFInfo
- Publication number
- CN114773163A CN114773163A CN202210035965.9A CN202210035965A CN114773163A CN 114773163 A CN114773163 A CN 114773163A CN 202210035965 A CN202210035965 A CN 202210035965A CN 114773163 A CN114773163 A CN 114773163A
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- CN
- China
- Prior art keywords
- naphthol
- catalyst
- olefin
- extractant
- heating
- 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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Links
- -1 alkyl naphthol Chemical compound 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims abstract description 30
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000001336 alkenes Chemical class 0.000 claims abstract description 21
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 20
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229940098779 methanesulfonic acid Drugs 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000001704 evaporation Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 230000008020 evaporation Effects 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- 239000004711 α-olefin Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 9
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 9
- 229940069096 dodecene Drugs 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- URVHSUKDZZAPTI-UHFFFAOYSA-N 2-dodecylnaphthalen-1-ol Chemical compound C1=CC=CC2=C(O)C(CCCCCCCCCCCC)=CC=C21 URVHSUKDZZAPTI-UHFFFAOYSA-N 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- KOMAOXYXIJGRQN-UHFFFAOYSA-N 2-pentylnaphthalen-1-ol Chemical compound C1=CC=CC2=C(O)C(CCCCC)=CC=C21 KOMAOXYXIJGRQN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- XWLUFINGMMDFPD-UHFFFAOYSA-N naphthalen-1-ol Chemical compound C1=CC=C2C(O)=CC=CC2=C1.C1=CC=C2C(O)=CC=CC2=C1 XWLUFINGMMDFPD-UHFFFAOYSA-N 0.000 description 1
- WHQDPSGUFIHZTE-UHFFFAOYSA-N naphthalen-2-ol Chemical compound C1=CC=CC2=CC(O)=CC=C21.C1=CC=CC2=CC(O)=CC=C21 WHQDPSGUFIHZTE-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
A preparation method of alkyl naphthol is characterized in that trifluoromethane sulfonic acid and/or methane sulfonic acid is used as a catalyst, naphthol and olefin are used as raw materials, the naphthol, the olefin and the catalyst are stirred and mixed, the temperature is controlled at 80-200 ℃, and the reaction lasts for 10-200 min; settling and layering the reaction product, and separating an upper oil phase and a lower catalyst phase; adding an extractant into the oil phase, stirring for 1-20 minutes, and then settling and layering to obtain an extractant phase and an oil phase; carrying out phase heating evaporation on the extracting agent to recover the extracting agent and obtain a recovered catalyst; heating the oil phase to separate the residual extractant, unreacted naphthol and olefin through evaporation to obtain alkyl naphthol.
Description
Technical Field
The invention belongs to the field of fine chemical engineering, and relates to a production method of alkyl naphthol. The international patent classification belongs to C10B.
Background
Alkyl naphthols are novel substances having a wide range of applications, and are expected to be used for petroleum additives, surfactants, and applications in other fields are also under constant search.
The synthetic method of alkyl naphthol is not reported at present. Naphthols including alpha-naphthol (1-naphthol) and beta-naphthol (2-naphthol) may be used as the raw material.
The patent provides a preparation method of alkyl naphthol, which can facilitate continuous production and can also produce intermittently. The method comprises the following steps:
1. the preparation method of alkyl naphthol is characterized by comprising the following steps:
(1) mixing naphthol and olefin to uniformly mix the naphthol and the olefin, then adding a catalyst, stirring and heating to 80-200 ℃, and keeping the reaction for 10-200 min;
(2) cooling to 40-70 deg.C, adding extractant, stirring for 1-20 min, settling for 5-300 min, and separating extractant layer;
(3) repeating the step (2) until the pH value of the extractant layer reaches more than 6;
(4) collecting the extractant phase, heating and evaporating to recover the extractant and the catalyst;
(5) heating the raffinate to 200-360 ℃, and separating the residual extracting agent, the unreacted naphthol and the olefin by evaporation to obtain the alkyl naphthol.
2. The process of claim 1 wherein the catalyst is trifluoromethanesulfonic acid.
3. The process of claim 1 wherein the catalyst is methanesulfonic acid.
4. The process according to 1, characterized in that the catalyst is a mixture of trifluoromethanesulfonic acid and methanesulfonic acid.
5. The process according to 1 and 2, characterized in that the amount of catalyst is 0.2% to 15% of the total amount (by weight) of naphthol and olefin.
6. The process according to 1 and 3, characterized in that the amount of catalyst is 1% to 10% of the total amount (by weight) of naphthol and olefin.
7. The process according to 1, characterized in that the olefin is a C5-C25 alpha-olefin.
8. The process according to 1, characterized in that the reaction temperature is 100-140 ℃.
9. The method according to 1, characterized in that the extractant is one or a mixture of several of water, methanol, ethanol and isopropanol.
In the method, the catalyst is trifluoromethane sulfonic acid or methane sulfonic acid, and can also be a mixture of trifluoromethane sulfonic acid and methane sulfonic acid. When trifluoromethanesulfonic acid is used, the amount of catalyst is 0.5% -3% of the total amount (by weight) of naphthol and olefin, and when methanesulfonic acid is used, the amount of catalyst is optimally 5% -10% of the total amount (by weight) of naphthol and olefin.
The olefin is C5-C25 alpha-olefin, and the mass ratio of the olefin to the naphthol is 1-3: 1. the reaction temperature in the process is 80-200 ℃, the optimum temperature is 100-140 ℃, of course, higher and lower temperatures are also possible, and the reaction temperature is generally not higher than 200 ℃ and not lower than 50 ℃. The extractant is one or more of water, methanol, ethanol and isopropanol.
When the extractant and unreacted naphthol and olefin are distilled off, atmospheric distillation, or distillation under reduced pressure and steam stripping can be used.
ADVANTAGEOUS EFFECTS OF INVENTION
The preparation of alkyl naphthol is carried out according to the method, the yield reaches over 80 percent, and the method can be used for batch production and can also realize continuous operation.
Detailed Description
The process of the present invention is further illustrated below with reference to examples.
Example 1:
100g of 1-naphthol, 130g of n-pentene and 0.5g of trifluoromethanesulfonic acid as a catalyst were added into a 500ml autoclave, the reaction temperature was 120 ℃ and the reaction time was 3 hours, after the reaction, the temperature was lowered to 70 ℃ and the catalyst was washed off with water, and the catalyst was settled for 5 to 300 minutes in each washing until the layer separation was significant (the same applies to the following examples), and the washing was carried out 4 times until the pH value of water reached 6, and unreacted naphthol and n-pentene were distilled off to obtain pentylnaphthol, with a yield of 90%.
Example 2:
adding 100g of naphthol and 300g of dodecene into a 500ml three-necked flask, heating to 100 ℃, uniformly stirring, reacting 1g of trifluoromethanesulfonic acid serving as a catalyst at the reaction temperature of 100 ℃ for 1 hour, cooling to 40 ℃ after the reaction, washing the catalyst with methanol, washing for 4 times until the pH value of the methanol reaches 6, and evaporating unreacted naphthol and dodecene to obtain the dodecyl naphthol, wherein the yield is 92%.
Example 3:
100g of naphthol, 200g of dodecene and 30g of methanesulfonic acid serving as a catalyst are added into a 500ml three-necked flask, the reaction temperature is 80 ℃, the reaction time is 6 hours, after the reaction, 200ml of ethanol is used for washing away the catalyst, the washing is carried out for 5 times until the pH value of methanol reaches 6, and unreacted naphthol and dodecene are evaporated out to obtain the dodecyl naphthol, wherein the yield is 81%.
Example 4:
100g of naphthol, 100g of dodecene and 30g of methanesulfonic acid serving as a catalyst are added into a 500ml three-necked flask, the reaction temperature is 130 ℃, the reaction time is 1 hour, the temperature is reduced to 50 ℃ after the reaction, and the mixture is stirred in a reactor by using 200ml of 1: 1 (volume) of the mixture is used for washing the catalyst in the product, the mixture is washed for 5 times until the pH value of the aqueous solution reaches 6, and unreacted naphthol and dodecene are evaporated to obtain the dodecyl naphthol, wherein the yield is 92%.
Example 5:
adding 100g of naphthol, 300g of C12-25 mixed alkene and 10g of trifluoromethanesulfonic acid serving as a catalyst into a 500ml three-necked flask, reacting at 150 ℃ for 5 minutes, cooling to 50 ℃ after reaction, and adding 200ml of ethanol and water according to the weight ratio of 1: 1, washing the catalyst for 3 times until the pH value of the aqueous solution reaches 6, and distilling out unreacted naphthol and dodecene to obtain the dodecyl naphthol with the yield of 93 percent.
Example 6:
100g of naphthol, 100g of dodecene, 10g of methanesulfonic acid serving as a catalyst and 2g of trifluoromethanesulfonic acid are added into a 500ml three-necked flask, the reaction temperature is 200 ℃, the reaction time is 10 minutes, the temperature is reduced to 50 ℃ after the reaction, the catalyst is washed away by 200ml of ethanol, the washing is carried out for 5 times until the pH value of the ethanol solution reaches 6, and unreacted naphthol and dodecene are evaporated to obtain the dodecyl naphthol, wherein the yield is 82%.
As can be seen from the above examples, acceptable alkylnaphthol products can be produced using this process. It should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
Claims (9)
1. The preparation method of alkyl naphthol is characterized by comprising the following steps:
(1) mixing naphthol and olefin to uniformly mix the naphthol and the olefin, adding a catalyst, stirring and heating to 80-200 ℃, and keeping the reaction for 10-200 min;
(2) cooling to 40-70 deg.C, adding extractant, stirring for 1-20 min, settling for 5-300 min, and separating extractant layer;
(3) repeating the step (2) until the pH value of the extractant layer reaches more than 6;
(4) collecting the extractant phase, heating and evaporating to recover the extractant and the catalyst;
(5) heating the raffinate to 200-360 ℃, and separating the residual extracting agent, the unreacted naphthol and the olefin by evaporation to obtain the alkyl naphthol.
2. The process according to claim 1, characterized in that the catalyst is trifluoromethanesulfonic acid.
3. The process of claim 1 wherein the catalyst is methane sulfonic acid.
4. The process according to claim 1, characterized in that the catalyst is a mixture of trifluoromethanesulfonic acid and methanesulfonic acid.
5. The process according to claims 1 and 2, characterized in that the amount of catalyst is 0.2% to 15% of the total amount (by weight) of naphthol and olefin.
6. A process according to claims 1 and 3, characterized in that the amount of catalyst is 1% to 10% of the total amount (by weight) of naphthol and olefin.
7. The process of claim 1, wherein the olefin is a C5-C25 α -olefin.
8. The method as claimed in claim 1, characterized in that the reaction temperature is 100-140 ℃.
9. The method of claim 1, wherein the extractant is one or more of water, methanol, ethanol, and isopropanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210035965.9A CN114773163A (en) | 2022-01-11 | 2022-01-11 | Preparation method of alkyl naphthol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210035965.9A CN114773163A (en) | 2022-01-11 | 2022-01-11 | Preparation method of alkyl naphthol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114773163A true CN114773163A (en) | 2022-07-22 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210035965.9A Pending CN114773163A (en) | 2022-01-11 | 2022-01-11 | Preparation method of alkyl naphthol |
Country Status (1)
| Country | Link |
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| CN (1) | CN114773163A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002275110A (en) * | 2001-03-14 | 2002-09-25 | Yoshitomi Fine Chemicals Ltd | Method for highly selectively producing 6-substituted-2- naphthol compound |
| CN103396294A (en) * | 2013-08-23 | 2013-11-20 | 杨锌荣 | Alkyl naphthol and preparation method thereof |
-
2022
- 2022-01-11 CN CN202210035965.9A patent/CN114773163A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002275110A (en) * | 2001-03-14 | 2002-09-25 | Yoshitomi Fine Chemicals Ltd | Method for highly selectively producing 6-substituted-2- naphthol compound |
| CN103396294A (en) * | 2013-08-23 | 2013-11-20 | 杨锌荣 | Alkyl naphthol and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 任凤霞: "壬基萘酚聚氧乙烯醚的制备及其溶液性质的研究", 中国优秀硕士学位论文全文数据库工程科技I辑, pages 016 - 91 * |
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Application publication date: 20220722 |
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