Preparation method of aromatic derivative
By introducing hydrophilic groups into the aromatic derivatives, the problem of insufficient hydrophilicity of existing aromatic derivatives is solved by introducing hydrophilic groups into the aromatic derivatives, and the application range and product quality are improved.
Patent Information
- Application Number
- CN202510378935.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-28
- Publication Date
- 2025-07-01
AI Technical Summary
The existing aromatic derivatives have weak hydrophilicity, which limits their use in essential oils, oily aromatic components or water-in-oil emulsions.
Hydrophilic groups are introduced to improve the performance of aromatic derivatives by inorganic acid modification, epoxide modification or organic acid modification methods. Specific methods include esterification reaction, alkoxylation modification and esterification capping treatment.
By introducing hydrophilic groups, the hydrophilicity of aromatic derivatives is improved, the cost is reduced, and the product quality and scope of use are improved.
Smart Images
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of fine chemical engineering, and in particular to a preparation method of an aromatic derivative. Background Art
[0002] Aromatics are the main fragrance control components of essential oils, perfumes, and aromatic soap products. For example, the main components concentrated from lavender extracts include lavandulol, linalyl acetate, lavandyl acetate, linalool, geraniol, coumarin, etc. Among them, the content of lavandulol is less than 0.5%, and currently, most of them are synthesized by the ethyl acetoacetate method. Similarly, dihydrolavandulol and tetrahydrolavandulol obtained through chemical synthesis and hydrogenation treatment also retain their aromatic properties. Substances with structures similar to these aromatic substances, although they do not have an aromatic odor themselves, can obtain excellent derivative products with good application effects through modification. These aromatic substances and substances with similar structures to them have weak hydrophilicity and are mostly used in the formulation of essential oils, oily aromatic components, or water-in-oil emulsions. As fragrance improvers for soaps, emulsions, etc., a certain amount of additional emulsifying components need to be added, which limits the application of such substances. Summary of the Invention
[0003] In order to solve the above technical deficiencies, the present invention provides a preparation method of an aromatic derivative, which can introduce hydrophilic groups, thereby improving the performance of the aromatic derivative and expanding its application scope.
[0004] The present invention discloses a preparation method of an aromatic derivative, which is obtained by modifying a starting modifier with an inorganic acid, an epoxide, or an organic acid; specifically as follows:
[0005] Method 1, Inorganic Acid Modification Method:
[0006] (1) Inorganic acid modification, as shown in Formula 1:
[0007]
[0008] In Formula 1, R1 is H or H2 or CH3(CH3)CH or CH2(CH3)CH, R2 is CH3(CH3)CH or CH3(CH3)C= or CH2(CH3)C or CH3(CH3)CH(CH2)2 or CH3(CH3)C=CHCH2, and R3 is one of a pyrophosphate group, a sulfonic acid group, and a nitro group; the catalyst is one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and p-toluenesulfonic acid;
[0009] (2) Alkoxylation modification, as shown in Formula 2:
[0010]
[0011] In Formula 2, m is the degree of polymerization of propylene oxide, where m = 0 to 5; n is the degree of polymerization of ethylene oxide, where n = 1 to 120; the alkoxylation catalyst is one or more of potassium hydroxide, sodium hydroxide, sodium methoxide, barium hydroxide, and lithium hydroxide;
[0012] (3) Esterification end-capping, as shown in Formula 3:
[0013]
[0014] In Formula 3, R4 is CH2=CH or CH2=(CH3)C; the catalyst is one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and p-toluenesulfonic acid;
[0015] Method 2: First, perform inorganic acid modification as shown in Formula 1, and then perform epoxide modification method, as shown in Formula 4:
[0016]
[0017] In Formula 4: R1 is H or H2 or CH3(CH3)CH or CH2(CH3)CH, R2 is CH3(CH3)CH or CH3(CH3)C= or CH2(CH3)C or CH3(CH3)CH(CH2)2 or CH3(CH3)C=CHCH2, R3 is H or pyrophosphate group; y is the degree of polymerization of propylene oxide, where y = 0 to 10; x is the degree of polymerization of ethylene oxide, where x = 1 to 100; the alkoxylation catalyst is one or more of potassium hydroxide, sodium hydroxide, sodium methoxide, barium hydroxide, and lithium hydroxide;
[0018] Method 3: Organic acid modification method, as shown in Formula 5:
[0019]
[0020] In Formula 5: R1 is H or H2 or CH3(CH3)CH or CH2(CH3)CH, R2 is CH3(CH3)CH or CH3(CH3)C= or CH2(CH3)C or CH3(CH3)CH(CH2)2 or CH3(CH3)C=CHCH2, R5 is a carboxylic acid group of C8-C 20 ; the catalyst is one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and p-toluenesulfonic acid.
[0021] The starting agent for modification is:
[0022] Formula 6: Formula 7: Formula 8: Formula 9:
[0023]
[0024] Formula 10: Formula 11:
[0025] Among them: Formula 6 is applicable to the inorganic acid modification method, the epoxide modification method, and the organic acid modification method; Formulas 7 and 8 are isomers of each other and are applicable to the inorganic acid modification method, the epoxide modification method, and the organic acid modification method; Formulas 9, 10, and 11 are lavender alcohol-based aromatic substances and are applicable to the epoxide modification method and the organic acid modification method.
[0026] When the starting agent for modification contains an unsaturated double bond, a polymerization inhibitor is added during the reaction process, and the polymerization inhibitor is one or more of hydroquinone, hydroquinone monomethyl ether, and sodium hypophosphite.
[0027] A preparation method of an aromatic derivative obtained by the present invention improves the performance of the aromatic derivative from the molecular structure level by introducing a hydrophilic group, so as to reduce costs and improve the product quality and scope of use. Detailed implementation manners
[0028] To further elaborate on the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the following, in combination with preferred embodiments, details the specific implementation manners, structures, features, and effects according to the present invention as follows.
[0029] Example 1:
[0030] The present invention discloses a preparation method of an aromatic derivative, using Formula 6 as the starting agent: Carry out inorganic acid modification:
[0031] Such as Formula 12:
[0032]
[0033] Using the compound of Formula 6 as the starting agent, carry out an esterification reaction with pyrophosphoric acid. The molar ratio of the starting agent to pyrophosphoric acid is 1.05 - 1.20:1; the catalyst is preferably phosphoric acid, and the dosage of the catalyst is 2 - 8‰ of the total mass of the reactants.
[0034] Specifically: Put the compound of Formula 6 into a heterogeneous polymerization kettle, and add the catalyst phosphoric acid. Replace with nitrogen 3 - 5 times, and keep the pressure in the heterogeneous polymerization kettle at 0.01 - 0.03 MPa. Stir, heat up to 125°C, and introduce pyrophosphoric acid into the heterogeneous polymerization kettle. After the mixture of water vapor and the compound of Formula 6 generated during the reaction is separated by a low-boiling substance separation tower, a low-boiling substance condenser, and a two-phase separator, the compound of Formula 6 returns to the heterogeneous polymerization kettle to participate in the reaction again. The reaction temperature is 125 - 185°C, and the reaction time is 3 - 8 h. The obtained product is denoted as Formula 6-1-PP, and the water is transported to the liquid phase collection tank through the water phase separation pump for use in other emulsion compounding.
[0035] Alkoxylation modification:
[0036] As shown in Formula 13:
[0037]
[0038] Using Formula 6-1-PP as the initiator, through addition polymerization with ethylene oxide and propylene oxide, modified products with different degrees of addition are obtained.
[0039] First step: Preparation of sesqui-modified products,
[0040] The initiator of Formula 6-1-PP is added with ethylene oxide, and the molar ratio is 1:0.5 - 1.8. The addition product is separated by rectification, and modified products with ethylene oxide addition degrees of 0.5, 1.0, and 1.5 can be obtained, which are respectively denoted as Formula 6-1-PP-0.5, Formula 6-1-PP-1.0, and Formula 6-1-PP-1.5. The separated heavy components are denoted as Formula 6-1-PP-X. The catalyst is selected as potassium hydroxide, and the catalyst dosage is 3 - 10‰ of the total amount of reactants. The neutralizing agent can be acetic acid, and the molar ratio of the catalyst to the neutralizing agent is 1:1 - 1.5.
[0041] Specifically: Put the initiator of Formula 6-1-PP into the polymerization reactor, add the catalyst potassium hydroxide, and displace with nitrogen for 2 - 5 times. Start the circulation pump, heat up to 95°C, and start dehydration. The dehydration temperature is 95 - 105°C, and dehydration is carried out for 15 - 30 minutes. Continue to heat up to 130°C and add ethylene oxide. The reaction temperature is 130 - 165°C, the reaction pressure is 0.05 - 0.4 MPa, and aging is carried out for 0.5 - 1.0 h. Cool down to 110°C and discharge it into the blending kettle, add the neutralizing agent acetic acid, and carry out neutralization and dehydration for 15 - 30 minutes. Feed the material to the evaporator through the feed pump of the blending kettle, and the temperature in the evaporator is 150 - 180°C. The evaporated material is treated by the light component removal tower, the light components are recycled, and the heavy components enter the sesqui-separation tower for treatment. The overhead products of the sesqui-separation tower can obtain Formula 6-1-PP-0.5, Formula 6-1-PP-1.0, and Formula 6-1-PP-1.5, and the three can be used as daily chemical emulsifiers or used as chemical intermediates. The heavy component Formula 6-1-PP-X is enriched for standby.
[0042] The overhead operating temperature of the light component removal tower is 110 - 150°C, and the operating pressure is -0.1 - -0.05 MPa; the overhead operating temperature of the sesqui-separation tower is 150 - 180°C, and the operating pressure is -0.05 - -0.03 MPa.
[0043] Second step: Epoxide addition,
[0044] After enrichment, Formula 6-1-PP-X is subjected to block addition with ethylene oxide and propylene oxide, and the molar ratio of the three is 1:5 to 20:0.5 to 1. The catalyst is potassium hydroxide, and the catalyst dosage is 3 to 10‰ of the total amount of reactants. The neutralizing agent is acetic acid, and the molar ratio of the catalyst to the neutralizing agent is 1:1 to 1.5. The obtained product is denoted as Formula 6-1-PP-EP.
[0045] Specifically: Put Formula 6-1-PP-X into a polymerization reactor, add the catalyst potassium hydroxide, and displace with nitrogen 2 to 5 times. Start the circulation pump, heat up to 95°C, and start dehydration. The dehydration temperature is 95 to 110°C, and dehydration is carried out for 15 to 30 minutes. Continue to heat up to 135°C, and add ethylene oxide. The reaction temperature is 135 to 170°C, the reaction pressure is 0.05 to 0.4 MPa, and aging is carried out for 0.5 to 1.0 h. Cool down to 110°C and discharge it into a blending kettle, add the neutralizing agent acetic acid, and carry out neutralization dehydration for 15 to 30 minutes. The obtained product Formula 6-1-PP-EP can be used as a hydrophilic emulsifier, a washing and water treatment aid.
[0046] Esterification end-capping:
[0047] Such as Formula 14:
[0048]
[0049] Formula 6-1-PP-EP and methacrylic acid are subjected to esterification polymerization, and the molar ratio of the two is 1:1 to 1.1. The catalyst is p-toluenesulfonic acid, and the catalyst dosage is 0.5 to 3% of the total amount of reactants. A polymerization inhibitor needs to be added, preferably methylhydroquinone, and the dosage is 0.2 to 1‰ of the total amount of reactants. The reaction temperature is 110 to 180°C, and the reaction time is 1 to 4 h.
[0050] Specifically: Put Formula 6-1-PP-EP into a heterogeneous polymerization kettle, add the catalyst p-toluenesulfonic acid, heat up and stir. When the temperature rises to 100°C, carry out dehydration for 15 to 30 minutes. Continue to heat up to 110°C, introduce methacrylic acid into the kettle. After adding, carry out aging for 1 to 2 h. The obtained product is denoted as Formula 6-1-PP-EP-MAA. This product can be used in paper-making and leather auxiliaries, and can also be used for synthesizing polycarboxylate-based high-performance water reducers or grinding aids. When used as a synthesis monomer for polycarboxylate-based high-performance water reducers, the recommended dosage is 5 to 10% of the total mass of the polyether macromonomer.
[0051] Example 2:
[0052] The present invention discloses a preparation method of an aromatic derivative, starting with Formula 6: For organic acid modification with:
[0053] Formula 6 and C8-C 20React with an organic carboxylic acid to obtain an organic acid-modified product. In this example, lauric acid is preferably used. The catalyst is p-toluenesulfonic acid, and the catalyst dosage is 3 to 25‰ of the total amount of reactants.
[0054] Specifically: Put lauric acid into a heterogeneous polymerization kettle, and add the catalyst p-toluenesulfonic acid. Replace with nitrogen 3 to 5 times, keep the pressure in the heterogeneous polymerization kettle at 0.01 to 0.03 MPa, heat up and stir. Pass the compound of formula 6 into the heterogeneous polymerization kettle. After the mixture of water vapor and the compound of formula 6 generated during the reaction is separated by a low-boiling substance separation tower, a low-boiling substance condenser, and a two-phase separator, the compound of formula 6 returns to the heterogeneous polymerization kettle to participate in the reaction. The reaction temperature is 125 to 185 °C, and the reaction time is 4 to 10 h. The obtained product is denoted as formula 6-1-LA. This product can be used as an oil-soluble emulsifier or a phase dispersant, and can also be used as an organic synthesis intermediate. The water is transported to the liquid-phase collection tank through a water-phase separation pump for use in compounding other emulsions.
[0055] Example 3:
[0056] The present invention discloses a preparation method of an aromatic derivative, starting from formula 7: Perform epoxide modification with it, and first perform inorganic acid modification, such as formula 15:
[0057]
[0058] Using the compound of formula 7 as the starting agent, carry out an esterification reaction with pyrophosphoric acid. The molar ratio of the starting agent to pyrophosphoric acid is 1.05 to 1.20:1; the catalyst is selected as phosphoric acid, and the catalyst dosage is 2 to 8‰ of the total mass of the reactants. A polymerization inhibitor needs to be added, preferably hydroquinone, and the polymerization inhibitor dosage is 0.5 to 1.5‰ of the total amount of the reactants.
[0059] Specifically: Put the compound of formula 7 into a heterogeneous polymerization kettle, and add the catalyst phosphoric acid. Replace with nitrogen 3 to 5 times, keep the pressure in the heterogeneous polymerization kettle at 0.01 to 0.03 MPa. Stir and heat up to 110 °C, and pass pyrophosphoric acid into the heterogeneous polymerization kettle. After the mixture of water vapor and the compound of formula 7 generated during the reaction is separated by a low-boiling substance separation tower, a low-boiling substance condenser, and a two-phase separator, the compound of formula 7 returns to the heterogeneous polymerization kettle to participate in the reaction. The water is transported to the liquid-phase collection tank through a water-phase separation pump for use in compounding other emulsions. The reaction temperature is 110 to 165 °C, and the reaction time is 3 to 8 h. The obtained product is denoted as formula 7-1-PP.
[0060] Alkoxylation modification, such as formula 16:
[0061]
[0062] Using formula 7-1-PP as the initiator, by addition polymerization with ethylene oxide and propylene oxide, modified products with different degrees of addition are obtained.
[0063] Step 1: Preparation of sesqui-modified product,
[0064] The formula 7-1-PP initiator is added with ethylene oxide, and the molar ratio is 1:0.5 - 2. The addition product is separated by distillation, and modified products with ethylene oxide addition degrees of 0.5, 1.0, and 1.5 can be obtained, which are denoted as formula 7-1-PP-0.5, formula 7-1-PP-1.0, and formula 7-1-PP-1.5 respectively. The separated heavy components are denoted as formula 7-1-PP-X. The catalyst selected is sodium hydride, and the catalyst dosage is 2 - 15‰ of the total amount of reactants. The neutralizing agent is acetic acid, and the molar ratio of the catalyst to the neutralizing agent is 1:1 - 1.5.
[0065] Specifically: Put the formula 7-1-PP initiator into the polymerization reactor, add the catalyst sodium hydride, and displace with nitrogen for 2 - 5 times. Start the circulation pump, heat up to 85°C, start dehydration, the dehydration temperature is 85 - 105°C, dehydrate for 15 - 20 minutes, continue to heat up to 110°C, add ethylene oxide, the reaction temperature is 110 - 145°C, the reaction pressure is -0.05 - 0.4 MPa, age for 0.5 - 1.0 h, cool down to 110°C and discharge into the blending kettle, add the neutralizing agent acetic acid, and neutralize and dehydrate for 15 - 30 minutes. Feed the material to the evaporator through the feed pump of the blending kettle. The temperature in the evaporator is 150 - 180°C. The evaporated material is treated by the light component removal tower, the light components are recycled, and the heavy components enter the sesqui-separation tower for treatment. The overhead product of the sesqui-separation tower can obtain formula 7-1-PP-0.5, formula 7-1-PP-1.0, and formula 7-1-PP-1.5, and the three can be used as daily chemical emulsifiers or as chemical intermediates. The heavy component formula 7-1-PP-X is enriched for standby.
[0066] The overhead operating temperature of the light component removal tower is 110 - 150°C, and the operating pressure is -0.1 - -0.05 MPa; the overhead operating temperature of the sesqui-separation tower is 150 - 180°C, and the operating pressure is -0.05 - -0.03 MPa.
[0067] Step 2: Epoxide addition,
[0068] After formula 7-1-PP-X is enriched, it is then subjected to block addition with ethylene oxide and propylene oxide, and the molar ratio of the three is 1:5 - 20:0.5 - 2. The catalyst selected is potassium hydroxide, and the catalyst dosage is 3 - 10‰ of the total amount of reactants. The neutralizing agent is acetic acid, and the molar ratio of the catalyst to the neutralizing agent is 1:1 - 1.5. The obtained product is denoted as formula 7-1-PP-EP.
[0069] Specifically: Charge the compound of formula 7-1-PP-X into a polymerization reactor, add potassium hydroxide as a catalyst, and displace with nitrogen for 2-5 times. Start the circulation pump, heat up to 85°C, and start dehydration. The dehydration temperature is 85-105°C, and the dehydration time is 15-30 minutes. Then continue to heat up to 135°C, add ethylene oxide and propylene oxide, and the reaction temperature is 135-170°C, the reaction pressure is 0.05-0.4 MPa, and the aging time is 0.5-1.0 hour. Then cool down to 110°C and discharge it into a blending kettle, add acetic acid as a neutralizing agent, and carry out neutralization and dehydration for 15-30 minutes. The obtained product of formula 7-1-PP-EP can be used as a hydrophilic dispersant or as a component of a cement grinding aid. When used as a cement grinding aid, it has a better application effect when combined with triethanolamine.
[0070] Example 4:
[0071] The present invention discloses a preparation method of an aromatic derivative, starting from formula 7: For organic acid modification using this as a starting agent:
[0072] Formula 7 reacts with an organic carboxylic acid having 8 to C 20 to obtain an organic acid modified product. In this example, lauric acid is preferably used. p-Toluenesulfonic acid is preferably used as the catalyst, and the catalyst dosage is 3-30‰ of the total amount of the reactants.
[0073] Specifically: Charge lauric acid into a heterogeneous polymerization kettle, add p-toluenesulfonic acid as a catalyst. Displace with nitrogen for 3-5 times, keep the pressure in the heterogeneous polymerization kettle at 0.01-0.03 MPa, heat up and stir. Pass the mixture of water vapor and the compound of formula 7 generated during the reaction through a low-boiling point separation tower, a low-boiling point condenser, and a two-phase separator for separation. Then the compound of formula 7 returns to the heterogeneous polymerization kettle to participate in the reaction again. The reaction temperature is 125-185°C, and the reaction time is 4-10 hours. The obtained product is denoted as formula 7-1-LA. This product can be used as an oil-soluble emulsifier or a phase dispersant, and can also be used as an organic synthesis intermediate for pharmaceutical synthesis and pesticide emulsifier synthesis. Water is transported to the liquid phase collection tank through a water phase separation pump for use in other emulsion compounding.
[0074] Example 5:
[0075] The present invention discloses a preparation method of an aromatic derivative, starting from formula 8: For epoxide modification using this as a starting agent:
[0076] Inorganic acid modification, such as formula 17:
[0077]
[0078] Using the compound of formula 8 as the initiator, an esterification reaction is carried out with pyrophosphoric acid, and the molar ratio of the initiator to pyrophosphoric acid is 1.05 - 1.20:1; the catalyst is preferably phosphoric acid, and the dosage of the catalyst is 2 - 10‰ of the total mass of the reactants. A polymerization inhibitor needs to be added, preferably hydroquinone, and the dosage of the polymerization inhibitor is 0.5 - 1.5‰ of the total amount of the reactants.
[0079] Specifically: Put the compound of formula 8 into a heterogeneous polymerization kettle, and add the catalyst phosphoric acid. Replace with nitrogen for 3 - 5 times, keep the pressure in the heterogeneous polymerization kettle at 0.01 - 0.03 MPa, stir, heat up to 110°C, and introduce pyrophosphoric acid into the heterogeneous polymerization kettle. After the mixture of water vapor and the compound of formula 8 generated during the reaction is separated by a low-boiling point separation tower, a low-boiling point condenser, and a two-phase separator, the compound of formula 8 returns to the heterogeneous polymerization kettle to participate in the reaction again. The reaction temperature is 110 - 165°C, and the reaction time is 3 - 8 h. The obtained product is denoted as formula 8-1-PP, and the water is transported to the liquid-phase collection tank through a water-phase separation pump for use in the compounding of other emulsions.
[0080] Alkoxylation modification, such as formula 18:
[0081]
[0082] Using the compound of formula 8-1-PP as the initiator, through addition polymerization with ethylene oxide and propylene oxide, modified products with different degrees of addition are obtained.
[0083] The first step: Preparation of sesqui-modified products,
[0084] The compound of formula 8-1-PP initiator is added with ethylene oxide, and the molar ratio is 1:0.5 - 2. The addition product is separated by rectification, and modified products with ethylene oxide addition degrees of 0.5, 1.0, and 1.5 can be obtained, which are denoted as formula 8-1-PP-0.5, formula 8-1-PP-1.0, and formula 8-1-PP-1.5 respectively. The separated heavy components are denoted as formula 8-1-PP-X. The catalyst is selected as sodium hydride, and the dosage of the catalyst is 2 - 15‰ of the total amount of the reactants. The neutralizing agent is acetic acid, and the molar ratio of the catalyst to the neutralizing agent is 1:1 - 1.5.
[0085] Specifically, the initiator of formula 7-1-PP is put into the polymerization reactor, and sodium hydride as the catalyst is added. The reactor is purged with nitrogen for 2 - 5 times. The circulation pump is started, and the temperature is raised to 85°C to start dehydration. The dehydration temperature is 85 - 105°C, and dehydration is carried out for 15 - 20 minutes. Then the temperature is further raised to 110°C, and ethylene oxide is added. The reaction temperature is 110 - 145°C, the reaction pressure is -0.05 - 0.4 MPa, and aging is carried out for 0.5 - 1.0 h. Then the temperature is lowered to 110°C and the product is discharged into the blending kettle, and acetic acid as the neutralizing agent is added. Neutralization and dehydration are carried out for 15 - 30 minutes. The material is fed to the evaporator through the feed pump of the blending kettle. The temperature in the evaporator is 150 - 180°C. The evaporated material is treated in the light component removal tower, and the light components are recycled. The heavy components enter the sesquioxide separation tower for treatment. The overhead product of the sesquioxide separation tower can obtain formula 8-1-PP-0.5, formula 8-1-PP-1.0, and formula 8-1-PP-1.5, and the three can be used as daily chemical emulsifiers or chemical intermediates. The heavy component of formula 8-1-PP-X is enriched for standby.
[0086] The operating temperature at the top of the light component removal tower is 110 - 150°C, and the operating pressure is -0.1 - -0.05 MPa; the operating temperature at the top of the sesquioxide separation tower is 150 - 180°C, and the operating pressure is -0.05 - -0.03 MPa.
[0087] The second step: Epoxide addition,
[0088] After formula 8-1-PP-X is enriched, it is subjected to block addition with ethylene oxide and propylene oxide. The molar ratio of the three is 1:3 - 20:0.2 - 25. Potassium hydroxide is selected as the catalyst, and the dosage of the catalyst is 3 - 10‰ of the total amount of the reactants. The neutralizing agent is acetic acid, and the molar ratio of the catalyst to the neutralizing agent is 1:1 - 1.5. The obtained product is denoted as formula 8-1-PP-EP.
[0089] Specifically, formula 8-1-PP-X is put into the polymerization reactor, and potassium hydroxide as the catalyst is added. The reactor is purged with nitrogen for 2 - 5 times. The circulation pump is started, and the temperature is raised to 85°C to start dehydration. The dehydration temperature is 85 - 105°C, and dehydration is carried out for 15 - 30 minutes. Then the temperature is further raised to 135°C, and a mixture of ethylene oxide and propylene oxide is added. The reaction temperature is 135 - 170°C, the reaction pressure is 0.05 - 0.4 MPa, and aging is carried out for 0.5 - 1.0 h. Then the temperature is lowered to 110°C and the product is discharged into the blending kettle, and acetic acid as the neutralizing agent is added. Neutralization and dehydration are carried out for 15 - 30 minutes. The obtained product of formula 7-1-PP-EP can be used as a hydrophilic dispersant, a reactive emulsifier, or a component of a cement grinding aid. When used as a cement grinding aid, it has a better application effect when compounded with triethanolamine. It can also be used in the synthesis of polycarboxylate-based superplasticizers, and the amount of replacing the traditional polyether macromonomer by equal mass is 3 - 6%.
[0090] Example 6:
[0091] The present invention discloses a preparation method of an aromatic derivative, with formula 8: Use an organic acid to modify with [starting agent]:
[0092] React compound of formula 8 with an organic carboxylic acid having 8 to 20 carbon atoms to obtain an organic acid-modified product. Oleic acid is preferably used in this example. p-Toluenesulfonic acid is preferably used as the catalyst, and the amount of the catalyst is 3 to 30‰ of the total amount of the reactants. A polymerization inhibitor needs to be added. p-Methoxyphenol is preferably used, and the amount of the polymerization inhibitor is 0.5 to 1.5‰ of the total amount of the reactants.
[0093] Specifically: Put oleic acid into a heterogeneous polymerization kettle, and add the catalyst p-toluenesulfonic acid and the polymerization inhibitor p-methoxyphenol. Replace with nitrogen for 3 to 5 times, keep the pressure in the heterogeneous polymerization kettle at 0.01 to 0.03 MPa, raise the temperature, stir, and introduce the compound of formula 8 into the heterogeneous polymerization kettle. After the mixture of water vapor and the compound of formula 8 generated during the reaction is separated by a low-boiling substance separation tower, a low-boiling substance condenser, and a two-phase separator, the compound of formula 8 returns to the heterogeneous polymerization kettle to participate in the reaction again. The reaction temperature is 125 to 185 °C, and the reaction time is 4 to 10 h. The obtained product is denoted as formula 8-1-OE. This product can be used as a lipophilic emulsifier or a phase dispersant, and can also be used as an organic synthesis intermediate for pharmaceutical synthesis and pesticide emulsifier synthesis. Water is transported to the liquid-phase collection tank through a water-phase separation pump for use in the compounding of other emulsions.
[0094] Example 7:
[0095] Due to formula 9: Formula 10:
[0096] Formula 11: All three have the fragrance of lavender extract. Their modification is mainly adjusted by adding ethylene oxide. The operations of the three are basically similar. Only formula 9 is used as an illustration in this example, and formulas 10 and 11 can be operated in sequence.
[0097] The present invention discloses a preparation method of an aromatic derivative, using formula 9: As a starting agent for modification to carry out epoxide modification:
[0098] Its preparation principle is as formula 4:
[0099]
[0100] In formula 4: R1 is CH3(CH3)CH or CH2(CH3)CH, R2 is CH3(CH3)CH(CH2)2 or CH3(CH3)C=CHCH2, and R3 is H.
[0101] Using formula 9 as the starting agent, through addition polymerization with ethylene oxide and propylene oxide, modified products with different degrees of addition are obtained.
[0102] Step 1: Preparation of sesqui-modified product,
[0103] The compound of formula 9 is added with ethylene oxide, and the molar ratio is 1:0.3 - 2. The addition product is separated by rectification to obtain modified products with ethylene oxide addition degrees of 0.5, 1.0, and 1.5 respectively, denoted as formula 9-1-EO-0.5, formula 9-1-EO-1.0, and formula 9-1-EO-1.5 respectively. The separated heavy components are denoted as formula 9-1-EO-X. Potassium hydroxide is selected as the catalyst, and the catalyst dosage is 2 - 15‰ of the total amount of reactants. The neutralizing agent is acetic acid, and the molar ratio of the catalyst to the neutralizing agent is 1:1 - 1.5.
[0104] Specifically: Put the compound of formula 9 into the polymerization reactor, add the catalyst potassium hydroxide, and displace with nitrogen for 2 - 5 times. Start the circulation pump, heat up to 85°C, and start dehydration. The dehydration temperature is 85 - 105°C, dehydrate for 15 - 20 minutes, continue to heat up to 110°C, add ethylene oxide, the reaction temperature is 110 - 145°C, the reaction pressure is -0.05 - 0.4 MPa, age for 0.5 - 1.0 h, cool down to 110°C and discharge into the blending kettle, add the neutralizing agent acetic acid, and neutralize and dehydrate for 15 - 30 minutes. Feed the material to the evaporator through the feed pump of the blending kettle, and the temperature in the evaporator is 150 - 180°C. The evaporated material is treated by the light component removal tower, the light components are recycled, and the heavy components enter the sesqui-separation tower for treatment. The overhead product of the sesqui-separation tower can obtain formula 9-1-EO-0.5, formula 9-1-EO-1.0, and formula 9-1-EO-1.5. The heavy component formula 9-1-EO-X is enriched for standby.
[0105] The three substances, formula 9-1-EO-0.5, formula 9-1-EO-1.0, and formula 9-1-EO-1.5, can be used as aromatic emulsifiers and can be used as fragrance modifiers for essences, hydrophilic essential oils, aromatic soaps, washing lotions, hair lotions, etc. These can be used alone or in combination with formula 9, formula 10, and formula 11.
[0106] In the same way, the six substances, formula 10-1-EO-0.5, formula 10-1-EO-1.0, formula 10-1-EO-1.5, formula 11-1-EO-0.5, formula 11-1-EO-1.0, and formula 11-1-EO-1.5, can be used as aromatic emulsifiers and can be used as fragrance modifiers for essences, hydrophilic essential oils, aromatic soaps, washing lotions, hair lotions, etc. These can be used alone or in combination with formula 9, formula 10, and formula 11.
[0107] The overhead operating temperature of the light component removal tower is 110 - 150°C, and the operating pressure is -0.1 - -0.05 MPa; the overhead operating temperature of the sesqui-separation tower is 150 - 180°C, and the operating pressure is -0.05 - -0.03 MPa.
[0108] Step 2: Epoxide addition,
[0109] After enrichment, Formula 9-1-EO-X is subjected to block addition with ethylene oxide and propylene oxide, and the molar ratio of the three is 1:3 to 10:0 to 0.5. Potassium hydroxide is selected as the catalyst, and the catalyst dosage is 3 to 10‰ of the total amount of reactants. The neutralizing agent is acetic acid, and the molar ratio of the catalyst to the neutralizing agent is 1:1 to 1.5. The obtained product is denoted as Formula 9-1-EP.
[0110] Specifically: Charge Formula 9-1-EO-X into the polymerization reactor, add the catalyst potassium hydroxide, and displace with nitrogen 2 to 5 times. Start the circulation pump, heat up to 85°C, start dehydration, the dehydration temperature is 85 to 105°C, dehydrate for 15 to 30 minutes, continue to heat up to 135°C, add ethylene oxide and propylene oxide respectively, the reaction temperature is 130 to 170°C, the reaction pressure is 0.05 to 0.4 MPa, cure for 0.5 to 1.0 h, cool down to 110°C and discharge into the blending kettle, add the neutralizing agent acetic acid, and carry out neutralization dehydration for 15 to 30 minutes. The obtained product Formula 9-1-EP can be used as a hydrophilic dispersant, an emulsifier, or a fragrance modifier for daily chemical or cosmetic products. Formula 10-1-EP and Formula 11-1-EP can be obtained in the same way and can be used as hydrophilic dispersants, emulsifiers, or fragrance modifiers for daily chemical or cosmetic products.
[0111] Example 8:
[0112] Due to Formula 9: Formula 10:
[0113] Formula 11: All three have the fragrance of lavender extract, and their modification is mainly adjusted by adding ethylene oxide. The operations of the three are basically similar. Only Formula 9 is taken as an example in this embodiment, and Formula 10 and Formula 11 can be operated accordingly.
[0114] The present invention discloses a preparation method of an aromatic derivative, using Formula 9: as the starting modifier for organic acid modification:
[0115] Formula 9 reacts with C8-C20 organic carboxylic acids to obtain an organic acid modified product. In this embodiment, lauric acid, oleic acid, and stearic acid are preferably reacted with Formula 9 respectively. p-Toluenesulfonic acid is preferably used as the catalyst, and the catalyst dosage is 3 to 35‰ of the total amount of reactants.
[0116] Specifically: Put lauric acid into a heterogeneous polymerization kettle, and add the catalyst p-toluenesulfonic acid. Replace with nitrogen for 3 to 5 times, and keep the pressure in the heterogeneous polymerization kettle at 0.01 to 0.03 MPa. Heat up and stir. Introduce the compound of Formula 9 into the heterogeneous polymerization kettle, with the reaction temperature at 135 to 230 °C and the reaction time at 4 to 12 h. The obtained product is denoted as Formula 9-1-LA. The product obtained by reacting Formula 9 with oleic acid is denoted as Formula 9-1-OE. The product obtained by reacting Formula 9 with stearic acid is denoted as Formula 9-1-SG. After the mixture of water vapor and the compound of Formula 9 generated during the reaction is separated by a low-boiling point separation tower, a low-boiling point condenser, and a two-phase separator, the compound of Formula 9 returns to the heterogeneous polymerization kettle to participate in the reaction, and the water is transported to the liquid phase collection tank by a water phase separation pump for use in the compounding of other emulsions.
[0117] Formula 9-1-LA or Formula 9-1-OE or Formula 9-1-SG can be used as a lipophilic emulsifier or a phase dispersant, and can also be used as a textile auxiliary. React with Formula 10 or Formula 11 in the same way, and the obtained products Formula 10-1-LA, Formula 10-1-OE, Formula 10-1-SG, Formula 11-1-LA, Formula 11-1-OE, Formula 11-1-SG can be used as a lipophilic emulsifier or a phase dispersant, and can also be used as a textile auxiliary.
[0118] As described above, it is only a preferred embodiment of the present invention, and it does not impose any form of limitation on the present invention. Although the present invention has been disclosed as above with preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some changes or modifications to equivalent embodiments by using the disclosed technical content without departing from the technical solution scope of the present invention. However, as long as it does not depart from the content of the technical solution of the present invention, any simplification, equivalent change, and modification made to the above embodiments based on the technical essence of the present invention still fall within the scope of the technical solution of the present invention.
Claims
1. A method for preparing a fragrance derivative, characterized in that: The modified initiator is obtained by inorganic acid modification, epoxide modification or organic acid modification; specifically as follows: Method 1, inorganic acid modification method: (1) Inorganic acid modification, such as formula 1: In formula 1, R1 is H or H2 or CH3(CH3)CH or CH2(CH3)CH, R2 is CH3(CH3)CH or CH3(CH3)C= or CH2(CH3)C or CH3(CH3)CH(CH2)2 or CH3(CH3)C=CHCH2, R3 is one of pyrophosphate, sulfonic acid and nitro; the catalyst is one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and p-toluenesulfonic acid; (2) Alkoxylation modification, such as formula 2: In formula 2, m is the degree of polymerization of propylene oxide, m=0-5; n is the degree of polymerization of ethylene oxide, n=1-120; the alkoxylation catalyst is one or more of potassium hydroxide, sodium hydroxide, sodium methoxide, barium hydroxide, and lithium hydroxide; (3) Esterification end-capping, such as formula 3: In formula 3, R4 is CH2=CH or CH2=(CH3)C; the catalyst is one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and p-toluenesulfonic acid; Method 2, first perform inorganic acid modification as shown in Formula 1, and then perform epoxide modification method, as shown in Formula 4: In formula 4: R1 is H or H2 or CH3(CH3)CH or CH2(CH3)CH, R2 is CH3(CH3)CH or CH3(CH3)C= or CH2(CH3)C or CH3(CH3)CH(CH2)2 or CH3(CH3)C=CHCH2, R3 is H or a pyrophosphate group; y is the degree of polymerization of propylene oxide, y=0-10; x is the degree of polymerization of ethylene oxide, x=1-100; the alkoxylation catalyst is one or more of potassium hydroxide, sodium hydroxide, sodium methoxide, barium hydroxide and lithium hydroxide; Method three, organic acid modification method, such as formula 5: In formula 5: R1 is H or H2 or CH3(CH3)CH or CH2(CH3)CH, R2 is CH3(CH3)CH or CH3(CH3)C= or CH2(CH3)C or CH3(CH3)CH(CH2)2 or CH3(CH3)C=CHCH2, R5 is C8~C 20 The catalyst is one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and p-toluenesulfonic acid.
2. The method for preparing a fragrance derivative according to claim 1, characterized in that: The modified initiator is: Formula 6: Formula 7: Formula 8: Formula 9: Formula 10: Formula 11: Among them: Formula 6 is applicable to the inorganic acid modification method, the epoxide modification method, and the organic acid modification method; Formula 7 and Formula 8 are isomers of each other and are applicable to the inorganic acid modification method, the epoxide modification method, and the organic acid modification method; Formula 9, Formula 10, and Formula 11 are lavender alcohol-based aromatic substances and are applicable to the epoxide modification method and the organic acid modification method.
3. The method for preparing a fragrance derivative according to claim 1, characterized in that: When the modified initiator contains unsaturated double bonds, a polymerization inhibitor is added during the reaction process, and the polymerization inhibitor is one or more of hydroquinone, hydroquinone monomethyl ether, and sodium hypophosphite.