CN113511969A - Preparation process of alkyl hydroxybenzoic acid - Google Patents
Preparation process of alkyl hydroxybenzoic acid Download PDFInfo
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- CN113511969A CN113511969A CN202110804052.4A CN202110804052A CN113511969A CN 113511969 A CN113511969 A CN 113511969A CN 202110804052 A CN202110804052 A CN 202110804052A CN 113511969 A CN113511969 A CN 113511969A
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- hydroxybenzoic acid
- olefin
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- acid
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- -1 alkyl hydroxybenzoic acid Chemical compound 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002904 solvent Substances 0.000 claims abstract description 54
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 150000001336 alkenes Chemical class 0.000 claims abstract description 35
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000004711 α-olefin Substances 0.000 claims abstract description 30
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 22
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 22
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000010992 reflux Methods 0.000 claims abstract description 12
- 238000004821 distillation Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 24
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 16
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 15
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 12
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 8
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 8
- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical group CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 231100000572 poisoning Toxicity 0.000 abstract description 4
- 230000000607 poisoning effect Effects 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 238000011282 treatment Methods 0.000 abstract description 3
- 238000009835 boiling Methods 0.000 abstract description 2
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 2
- 230000002779 inactivation Effects 0.000 abstract description 2
- 239000002253 acid Substances 0.000 description 10
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 3
- 238000007065 Kolbe-Schmitt synthesis reaction Methods 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 3
- 229960004889 salicylic acid Drugs 0.000 description 3
- OBDUMNZXAIUUTH-HWKANZROSA-N (e)-tetradec-2-ene Chemical compound CCCCCCCCCCC\C=C\C OBDUMNZXAIUUTH-HWKANZROSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- LLWKIYGBECGCKZ-UHFFFAOYSA-N docosa-1,3-diene Chemical compound CCCCCCCCCCCCCCCCCCC=CC=C LLWKIYGBECGCKZ-UHFFFAOYSA-N 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- VAMFXQBUQXONLZ-UHFFFAOYSA-N icos-1-ene Chemical compound CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- ZDLBWMYNYNATIW-UHFFFAOYSA-N tetracos-1-ene Chemical compound CCCCCCCCCCCCCCCCCCCCCCC=C ZDLBWMYNYNATIW-UHFFFAOYSA-N 0.000 description 1
- WMZHDICSCDKPFS-UHFFFAOYSA-N triacont-1-ene Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCC=C WMZHDICSCDKPFS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation process of alkyl hydroxybenzoic acid, which comprises the following steps: s1, adding hydroxybenzoic acid, long-chain alpha-olefin, catalyst and hydrocarbon solvent into a bottle with a water separator, heating to 110-160 ℃, and preserving heat under the reflux state of the solvent; s2, adding short chain olefin to continue reacting and then cooling; s3, adding a hydrocarbon solvent, stirring uniformly, standing, and separating out a lower-layer catalyst; and S4, removing the solvent and unreacted olefin from the upper layer material by reduced pressure distillation to obtain the alkyl hydroxybenzoic acid. The invention uses short chain alpha-olefin to consume unreacted hydroxybenzoic acid, thus improving the conversion rate of raw materials; the short chain alpha-olefin has low boiling point and can be recycled after being removed under reduced pressure; the catalyst used in the invention is easy to separate from the product and can be reused without treatment; the reaction solvent has the function of carrying water, so that the poisoning and inactivation of the catalyst are avoided; the catalyst has good recycling effect and high recycling rate.
Description
Technical Field
The invention relates to the technical field of metal detergents, in particular to a preparation process of alkyl hydroxybenzoic acid.
Background
The alkyl hydroxybenzoic acid is an important raw material for preparing the metal detergent, namely the alkyl hydroxybenzoate, and at present, two synthetic processes of Kolbe-Schmitt and Friedel-Crafts are mainly used. US6348438B1, US08030258B2 both report the detailed procedure of the Kolbe-Schmitt process for preparing alkylhydroxybenzoic acids, wherein an alkylphenol is neutralized with an alkali metal base such as potassium hydroxide to obtain potassium alkylphenolate, which is contacted with carbon dioxide and carboxylated under high temperature and pressure conditions to produce potassium alkylhydroxybenzoate, which is finally acidified to obtain alkylhydroxybenzoic acids. Among them, the Kolbe-Schmitt process requires high temperature and pressure, requires high requirements on reaction equipment, and is usually a mixture of alkylphenol and alkylhydroxybenzoic acid as the ortho-alkylphenol is not easy to undergo the carboxylation reaction.
The Friedel-Crafts process is to obtain alkyl hydroxybenzoic acid by taking hydroxybenzoic acid and long-chain alpha-olefin as raw materials and carrying out alkylation reaction under the action of an acid catalyst. The Friedel-Crafts reaction conditions are mild, the operation steps are few, but the existence of carboxyl reduces the reactivity of hydroxybenzoic acid, so that the reaction conversion rate is low.
CN1323062C mixes C6-C50 olefin with ortho-hydroxybenzoic acid, i.e. salicylic acid, at 50-150 deg.C, and prepares alkyl salicylic acid under the action of supported heteropoly acid catalyst, CN103508882 discloses a preparation method of alkyl salicylic acid, which takes mixed acid of methanesulfonic acid and 98% concentrated sulfuric acid as catalyst, and carries out alkylation reaction at 80-150 deg.C, and the conversion rate is about 60% -80%. These processes have low conversion rates and also suffer from the problem that the catalyst is not easily recovered or has low catalytic activity after recovery.
Disclosure of Invention
The invention aims to provide a preparation process of alkyl hydroxybenzoic acid, which solves the problems of low process conversion rate and high catalyst use cost in the prior art.
The technical scheme adopted by the invention for solving the technical problem is as follows: a preparation process of alkyl hydroxybenzoic acid comprises the following steps:
s1, adding hydroxybenzoic acid, long-chain alpha-olefin, catalyst and hydrocarbon solvent into a bottle with a water separator, heating to 110-160 ℃, and preserving heat under the reflux state of the solvent;
s2, adding short chain olefin to continue reacting and then cooling;
s3, adding a hydrocarbon solvent, stirring uniformly, standing, and separating out a lower-layer catalyst;
and S4, removing the solvent and unreacted olefin from the upper layer material by reduced pressure distillation to obtain the alkyl hydroxybenzoic acid.
In the production process of the present invention, the catalyst separated in step S3 is directly recycled and used in steps S1-S4.
In the preparation process of the present invention, the hydroxybenzoic acid comprises at least one of ortho-hydroxybenzoic acid and para-hydroxybenzoic acid; the long-chain alpha-olefin comprises a combination of two or more of alpha-olefins with carbon numbers of 14-30, wherein the long-chain alpha-olefin comprises linear and/or branched alpha-olefin; the catalyst comprises at least one of p-toluenesulfonic acid and methanesulfonic acid; the hydrocarbon solvent comprises at least one of D20, D30, D40; the short-chain olefin comprises at least one of styrene, n-dodecene and tetrapropylene.
In the preparation process, the hydroxybenzoic acid is o-hydroxybenzoic acid or p-hydroxybenzoic acid.
In the preparation process, the mass ratio of the long-chain alpha-olefin to the hydroxybenzoic acid is 1.0-2.0.
In the preparation process of the present invention, the long chain alpha-olefin comprises two or three alpha-olefins having carbon numbers of 14 to 30.
In the preparation process, the catalyst is p-toluenesulfonic acid or methanesulfonic acid, and the mass ratio of the catalyst to the hydroxybenzoic acid is 0.1-0.4.
In the preparation process of the present invention, the hydrocarbon solvent is D20, D30 or D40; in step S1, the mass ratio of the hydrocarbon solvent to the hydroxybenzoic acid is 0.5 to 1.0; in step S3, the mass ratio of the hydrocarbon solvent to the hydroxybenzoic acid is 1.5 to 2.0.
In the preparation process, the short-chain olefin is styrene, n-dodecene or tetrapropylene, and the mass ratio of the short-chain olefin to the hydroxybenzoic acid is 0.2-0.6.
In the preparation process, in step S1, the temperature is kept for 15-25h under the reflux state of the solvent;
in step S2, the short-chain olefin is added for continuous reaction for 3-10 h.
The preparation process of the alkyl hydroxybenzoic acid has the following beneficial effects: the invention uses short chain alpha-olefin to consume unreacted hydroxybenzoic acid, thus improving the conversion rate of raw materials; the short chain alpha-olefin has low boiling point and can be recycled after being removed under reduced pressure; the catalyst used in the invention is easy to separate from the product and can be reused without treatment; the reaction solvent has the function of carrying water, so that the poisoning and inactivation of the catalyst are avoided; the catalyst has good recycling effect and high recycling rate.
Detailed Description
The process for preparing alkylhydroxybenzoic acids according to the present invention is further illustrated by the following examples:
the invention provides a preparation process of alkyl hydroxybenzoic acid, which comprises the following steps:
s1, adding hydroxybenzoic acid, long-chain alpha-olefin, a catalyst and a hydrocarbon solvent into a four-mouth bottle with a water separator, heating to 110-160 ℃, and preserving heat for 15-25h under the reflux state of the solvent; wherein the hydroxybenzoic acid comprises at least one of o-hydroxybenzoic acid and p-hydroxybenzoic acid; the long-chain alpha-olefin comprises a combination of two or more than two of alpha-olefins with carbon numbers of 14-30, wherein the long-chain alpha-olefin comprises linear and/or branched alpha-olefin, preferably, the long-chain alpha-olefin comprises two or three of alpha-olefins with carbon numbers of 14-30; the catalyst comprises at least one of p-toluenesulfonic acid and methanesulfonic acid; the hydrocarbon solvent comprises at least one of D20, D30, D40; preferably, the hydroxybenzoic acid is one of o-hydroxybenzoic acid and p-hydroxybenzoic acid; the catalyst adopts one of p-toluenesulfonic acid or methanesulfonic acid; the hydrocarbon solvent is one of D20, D30 or D40;
s2, adding short-chain olefin to continue reacting for 3-10h, cooling and standing; the short-chain olefin comprises at least one of styrene, n-dodecene and tetrapropylene; preferably, the short-chain olefin adopts one of styrene, n-dodecene or tetrapropylene;
it should be noted that the chain length of the olefin has a great influence on the oil solubility of the alkyl hydroxybenzoic acid, and the more the long-chain olefin is, the better the oil solubility is, and the better the oil solubility of the alkyl hydroxybenzoate detergent prepared by the method is. Thus long chain olefins are predominantly used in the reaction; the reaction activity of the short-chain olefin is high, and the purpose of the later reaction is mainly to consume the unreacted hydroxybenzoic acid;
s3, adding a hydrocarbon solvent, and separating out the lower catalyst; the hydrocarbon solvent comprises at least one of D20, D30, D40; preferably, the same hydrocarbon solvent as that used in step S1 is used;
the adopted catalysts of p-toluenesulfonic acid and methanesulfonic acid are strong polar substances, the polarity of the reaction product alkyl hydroxybenzoic acid is small, the p-toluenesulfonic acid and the alkyl hydroxybenzoic acid are incompatible, after the reaction is finished and D20, D30 or D40 solvent is added to dilute the product, the catalyst and the product are quickly separated, the upper layer is the product and the solvent, the lower layer is the catalyst, the catalyst does not need to be processed, and the catalyst can be directly recycled, so that the method is convenient and quick;
and S4, removing the solvent and the reacted olefin from the upper layer material by reduced pressure distillation to obtain the alkyl hydroxybenzoic acid.
Wherein the catalyst separated in step S3 can be directly recycled and used in steps S1-S4. Because the catalyst poisoning phenomenon does not exist in the process, the catalyst can be directly recycled without other operations and treatments. The water in the process mainly comes from raw materials such as hydroxybenzoic acid and alkane solvent oil D20-40 to play a role in carrying water, and the principle of carrying water is that the solvent continuously reflows at the reaction temperature, and evaporated water is carried out together. If the catalyst is miscible with water, the water can severely reduce the activity of the catalyst, resulting in catalyst poisoning.
Wherein the mass ratio of the long-chain alpha-olefin to the hydroxybenzoic acid is 1.0-2.0. The mass ratio of the catalyst to the hydroxybenzoic acid is 0.1-0.4. In step S1, the mass ratio of the hydrocarbon solvent to the hydroxybenzoic acid is 0.5 to 1.0; in step S3, the mass ratio of the hydrocarbon solvent to the hydroxybenzoic acid is 1.5 to 2.0. The mass ratio of the short chain to the hydroxybenzoic acid is 0.2-0.6. The proportion of the reaction raw materials can ensure that the conversion rate achieves the best effect and is extremely high.
The following is a detailed description of specific examples.
Example 1: adding 120g of o-hydroxybenzoic acid, 100g of n-tetradecene, 45g of n-hexadecene, 15g of methanesulfonic acid and 60g D20 solvent oil into a four-necked bottle with a water separator, heating to 120 ℃, and preserving heat for 20 hours under the reflux state of the solvent; and then adding 24g of styrene to continue reacting for 5 hours, cooling to room temperature, adding 200g D20, separating out the catalyst at the lower layer, and removing the solvent and unreacted olefin from the material at the upper layer through reduced pressure distillation to obtain the alkylhydroxybenzoic acid. Wherein, the content of hydroxybenzoic acid is 0.52%, the content of olefin is 1.30%, and the content of alkyl hydroxybenzoic acid is 98.18%.
Example 2: adding 120g of o-hydroxybenzoic acid, 98g of n-octadecene, 90.5g of n-hexadecene, 25g of methanesulfonic acid and 100g D20 solvent oil into a four-necked bottle with a water separator, heating to 120 ℃, and preserving heat for 20 hours under the reflux state of the solvent; and then adding 63g of styrene to continue reacting for 5 hours, cooling to room temperature, adding 200g D20, separating out the catalyst at the lower layer, and removing the solvent and unreacted olefin from the material at the upper layer through reduced pressure distillation to obtain the alkylhydroxybenzoic acid. Wherein, the content of hydroxybenzoic acid is 1.26%, the content of olefin is 2.17%, and the content of alkyl hydroxybenzoic acid is 96.57%.
Example 3: adding 120g of o-hydroxybenzoic acid, 88g of n-octadecene, 100.5g of n-hexadecene, 12g of p-toluenesulfonic acid and 100g D30 solvent oil into a four-mouth bottle with a water separator, heating to 140 ℃, and preserving heat for 15 hours under the solvent reflux state; and then adding 55g of n-dodecene to continue reacting for 5 hours, cooling to room temperature, adding 180g D30, filtering and collecting a filter cake, and removing the solvent and unreacted olefin from the filtrate through reduced pressure distillation to obtain the alkylhydroxybenzoic acid. Wherein, the content of hydroxybenzoic acid is 1.81%, the content of olefin is 2.55%, and the content of alkyl hydroxybenzoic acid is 95.64%.
Example 4: adding 120g of p-hydroxybenzoic acid, 38.6g of n-eicosene, 83.5g of n-docosadiene, 64.5g of n-tetracosene, 40g of methanesulfonic acid and 100g D30 solvent oil into a four-mouth bottle with a water separator, heating to 140 ℃, and preserving heat for 25 hours under the reflux state of the solvent; and then adding 60g of styrene to continue reacting for 5 hours, cooling to room temperature, adding 200g D30, separating out the lower-layer catalyst, and removing the solvent and unreacted olefin from the upper-layer material through reduced pressure distillation to obtain the alkylhydroxybenzoic acid. Wherein, the content of hydroxybenzoic acid is 1.06%, the content of olefin is 3.39%, and the content of alkyl hydroxybenzoic acid is 95.55%.
Example 5: adding 120g of p-hydroxybenzoic acid, 240g of n-triacontene, 48g of methanesulfonic acid and 80g D30 and 40g D40 solvent oil into a four-mouth bottle with a water separator, heating to 140 ℃, and preserving heat for 25 hours under the reflux state of the solvent; and then adding 72g of tetrapropylene to continue reacting for 5 hours, cooling to room temperature, adding 240g D30, separating out the catalyst at the lower layer, and removing the solvent and unreacted olefin from the material at the upper layer through reduced pressure distillation to obtain the alkylhydroxybenzoic acid. Wherein, the content of hydroxybenzoic acid is 1.72%, the content of olefin is 4.26%, and the content of alkyl hydroxybenzoic acid is 94.02%.
Catalyst recovery
Example 6: adding 120g of o-hydroxybenzoic acid, 40g of n-tetradecene, 72g of n-hexadecene, 80g of n-octadecene, 32g of the recovered catalyst in examples 4 and 5 and 80g D20 solvent oil into a four-neck bottle with a water separator, heating to 130 ℃, and preserving heat for 15 hours under the reflux state of the solvent; then 20g of dodecene is added to continue reacting for 5h, the temperature is reduced to room temperature, 200g D20 is added, and the solvent and unreacted olefin are removed from the upper layer material through reduced pressure distillation to obtain the alkyl hydroxybenzoic acid. Wherein, the content of hydroxybenzoic acid is 1.35%, the content of olefin is 3.29%, and the content of alkyl hydroxybenzoic acid is 95.36%.
It will be appreciated that modifications and variations are possible to those skilled in the art in light of the above teachings and are within the purview of the appended claims.
Claims (10)
1. The preparation process of alkyl hydroxybenzoic acid is characterized by comprising the following steps:
s1, adding hydroxybenzoic acid, long-chain alpha-olefin, catalyst and hydrocarbon solvent into a bottle with a water separator, heating to 110-160 ℃, and preserving heat under the reflux state of the solvent;
s2, adding short chain olefin to continue reacting and then cooling;
s3, adding a hydrocarbon solvent, stirring uniformly, standing, and separating out a lower-layer catalyst;
and S4, removing the solvent and unreacted olefin from the upper layer material by reduced pressure distillation to obtain the alkyl hydroxybenzoic acid.
2. The process of claim 1, wherein the catalyst separated in step S3 is directly recycled and used in steps S1-S4.
3. The process according to claim 1, wherein the hydroxybenzoic acid comprises at least one of ortho-hydroxybenzoic acid and para-hydroxybenzoic acid; the long-chain alpha-olefin comprises a combination of two or more of alpha-olefins with carbon numbers of 14-30, wherein the long-chain alpha-olefin comprises linear and/or branched alpha-olefin; the catalyst comprises at least one of p-toluenesulfonic acid and methanesulfonic acid; the hydrocarbon solvent comprises at least one of D20, D30, D40; the short-chain olefin comprises at least one of styrene, n-dodecene and tetrapropylene.
4. The process according to claim 3, wherein the hydroxybenzoic acid is o-hydroxybenzoic acid or p-hydroxybenzoic acid.
5. The process according to claim 4, wherein the mass ratio of the long-chain α -olefin to the hydroxybenzoic acid is 1.0 to 2.0.
6. The process of claim 5, wherein the long chain alpha olefins comprise two or three alpha olefins of carbon number 14-30.
7. The process according to claim 4, wherein the catalyst is p-toluenesulfonic acid or methanesulfonic acid, and the mass ratio of the catalyst to the hydroxybenzoic acid is 0.1 to 0.4.
8. The process of claim 4, wherein the hydrocarbon solvent is D20, D30, or D40; in step S1, the mass ratio of the hydrocarbon solvent to the hydroxybenzoic acid is 0.5 to 1.0; in step S3, the mass ratio of the hydrocarbon solvent to the hydroxybenzoic acid is 1.5 to 2.0.
9. The process according to claim 4, wherein the short-chain olefin is styrene, n-dodecene or tetrapropylene, and the mass ratio of the short-chain olefin to the hydroxybenzoic acid is 0.2 to 0.6.
10. The process according to claim 1, wherein in step S1, the temperature is maintained for 15 to 25 hours in a solvent reflux state;
in step S2, the short-chain olefin is added for continuous reaction for 3-10 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237392A (en) * | 2015-11-24 | 2016-01-13 | 辽宁渤大化工有限公司 | Preparing method for aralkyl salicylic acid and derivative thereof |
| CN105777537A (en) * | 2014-12-23 | 2016-07-20 | 中国石油天然气股份有限公司 | Alkylation method for salicylic acid |
| WO2019014255A1 (en) * | 2017-07-11 | 2019-01-17 | Si Group, Inc. | Process for preparing alkyl salicylic acid and products thereof |
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| CN105777537A (en) * | 2014-12-23 | 2016-07-20 | 中国石油天然气股份有限公司 | Alkylation method for salicylic acid |
| CN105237392A (en) * | 2015-11-24 | 2016-01-13 | 辽宁渤大化工有限公司 | Preparing method for aralkyl salicylic acid and derivative thereof |
| WO2019014255A1 (en) * | 2017-07-11 | 2019-01-17 | Si Group, Inc. | Process for preparing alkyl salicylic acid and products thereof |
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