Gasoline detergent and preparation method thereof
By synthesizing Mannichamine adducts containing propylene oxide polyether segments and long-chain fat or aromatic amine groups, the problem of insufficient thermal stability of existing gasoline detergents under high temperature conditions is solved, and a kind of A new gasoline detergent with excellent purification and dispersion properties is significantly better than similar products.
Patent Information
- Application Number
- CN202411453353.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-17
- Publication Date
- 2024-12-31
AI Technical Summary
The existing gasoline detergent has low thermal stability under high temperature conditions, making it difficult to effectively control the generation of high-temperature parts of the engine. The cleaning effect is limited when used alone, and it cannot have both multifunctional cleaning and dispersive performance.
A new gasoline detergent is prepared by synthesizing a Mannichamine adduct containing propylene oxide polyether segments and long-chain fat or aromatic amine groups and mixing it with carrier oil and solvent oil. The Mannich reaction process of the Nehemian adduct combines the excellent properties of alkyl or aryl amines to form a product with excellent purification and dispersion properties.
This new gasoline detergent significantly inhibits the formation of deposits under high temperature conditions, and its effect is better than that of Afton H6581C and polyisobutenamine and polyetheramine products. It has better purification effect and dispersion performance, and is suitable for multifunctional gasoline Detergent.
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Figure CN119219907A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of gasoline detergent preparation, and relates to a gasoline detergent with excellent cleaning and dispersing properties, a synthesis method and application thereof. Background Art
[0002] At present, the main agents of gasoline detergents on the market can be divided into four types: polyisobutylene succinimide (PIBSI), polyisobutylene amine (PIBA), polyether amine (PEA), and Mannich amine. Among them, PIBA and PEA are the main agents of the third and fourth generation gasoline detergents, respectively, and are the most widely used.
[0003] Mannich amine detergents have high thermal stability. When added to gasoline, they can control the low-temperature components of the engine and effectively control the formation of deposits in the high-temperature components of the gasoline engine. If Mannich amine detergents are compounded with detergents such as polyetheramines, polyether polyols, amides, and alcoholamines, they can also effectively control the formation of deposits in the engine fuel intake system, fuel injectors, and combustion chambers. When used alone, Mannich amine detergents also have a good cleaning effect. Therefore, Mannich base detergents are multifunctional and efficient detergents, and are widely used as the main agent of the fifth-generation gasoline detergent. Summary of the invention
[0004] The purpose of the present invention is to provide a Mannich amine adduct and a synthesis method and application thereof, a novel gasoline detergent based on the Mannich amine adduct and a preparation method thereof.
[0005] The purpose of the present invention is achieved through the following technical solutions:
[0006] The structure of the Mannich amine adduct containing a propylene oxide polyether segment and a long-chain fatty amine or aromatic amine group is shown in Formula I:
[0007]
[0008] Wherein, A is a polypropylene oxide chain segment, and RN is a long-chain aliphatic amine or aromatic amine group with ≥6 C atoms.
[0009] A method for synthesizing the Mannich amine adduct comprises:
[0010] Step (1), using alkane solvent oil as a reaction solvent, under the catalytic action of a catalyst, allyl alcohol polypropylene oxide ether and phenol undergo an alkylation substitution reaction to obtain polypropylene oxide substituted phenol;
[0011] Step (2), the polypropylene oxide substituted phenol undergoes a Mannich reaction with formaldehyde and an amine to obtain a Mannich amine adduct.
[0012] In step (1), the para-substitution of phenol is a kinetic reaction, so the phenol is always in excess during the reaction. The molar ratio of the allyl alcohol polyoxypropylene ether to phenol is 1:1.05 to 1:1.2.
[0013] Specifically, the molar ratio of the allyl alcohol polypropylene oxide ether to phenol can be 1:1.05, 1:1.095, 1:1.1, or 1:1.2.
[0014] The number average molecular weight (Mn) of the allyl alcohol polypropylene oxide ether is 500-1000; specifically, the allyl alcohol polypropylene oxide ether can be selected from P-90, P-80, P-50 and the like.
[0015] The mass ratio of the catalyst to the allyl alcohol polypropylene oxide ether is about 5:1000 to 10:1000.
[0016] The catalyst is selected from at least one of boron trifluoride etherate, trifluoromethanesulfonic acid and the like.
[0017] The reaction solvent is alkane solvent oil, and specifically D40 solvent oil can be selected.
[0018] The temperature of the alkylation substitution reaction is 25-35° C., and the time of the alkylation substitution reaction is 12-24 hours.
[0019] Specifically, allyl alcohol polypropylene oxide ether is dissolved in a reaction solvent to obtain an allyl alcohol polypropylene oxide ether solution; phenol and a catalyst are dissolved in a reaction solvent to obtain a phenol solution; the allyl alcohol polypropylene oxide ether solution is added dropwise to the phenol solution at a temperature of 25 to 35° C., and after the addition is completed, the temperature is maintained at 25 to 35° C. to continue the reaction.
[0020] After the reaction is completed, deionized water at a temperature of 60 to 80° C. is added to the reaction system to quench the reaction, and the mixture is allowed to stand for stratification after stirring, and the lower aqueous phase is separated to wash away the catalyst and excess phenol, and the operation is repeated 1 to 5 times; the organic phase is subjected to a temperature of 150 to 160° C. and a negative pressure of -0.1 to -0.08 MPa to remove the solvent oil and residual phenol to obtain a refined polypropylene oxide substituted phenol.
[0021] In step (2), the polypropylene oxide substituted phenol is calculated as allyl alcohol polypropylene oxide ether, and the molar ratio of the polypropylene oxide substituted phenol to formaldehyde and amine is 1:1.1:1.
[0022] The amine is an arylamine or an alkylamine.
[0023] The arylamine is a diphenylamine, including but not limited to phenylenediamine, etc. Specifically, the arylamine can be selected from p-phenylenediamine, m-phenylenediamine, and o-phenylenediamine.
[0024] The alkylamine is a dibasic fatty amine, and the number of carbon atoms in the fatty chain is ≥ 6. Preferably, the prime alkylamine includes but is not limited to 1,6-hexanediamine, 1,9-nonanediamine, and the like.
[0025] The temperature of the Mannich reaction is 70-90° C., and the time of the Mannich reaction is 4-5 hours.
[0026] Specifically, polypropylene oxide substituted phenol and amine are mixed, the temperature is raised to the reaction temperature, 40% formaldehyde is added dropwise, and the mixture is kept warm and refluxed for reaction.
[0027] After the reaction is completed, the residual water and unreacted formaldehyde raw material are removed at a temperature of 100 to 150° C. and a negative pressure of -0.1 to -0.08 MPa to obtain a Mannich amine adduct.
[0028] Another object of the present invention is to provide the use of the Mannich amine adduct in the preparation of gasoline detergent.
[0029] Another object of the present invention is to provide a gasoline detergent, wherein the gasoline detergent contains the Mannich amine adduct.
[0030] As a preferred embodiment of the gasoline detergent described in the present invention, the gasoline detergent is prepared by dissolving the Mannich amine adduct in carrier oil and solvent oil; the content of the Mannich amine adduct is 20% to 40%, the content of the carrier oil is 10% to 20%, and the balance is solvent oil.
[0031] The carrier oil is base oil 500SN; the solvent oil is 1500# aromatic solvent oil.
[0032] Preferably, in the gasoline detergent, the content of the Mannich amine adduct is 30%, the content of the carrier oil is 10%, and the balance is solvent oil.
[0033] Another object of the present invention is to provide a method for preparing the gasoline detergent, comprising: dissolving the Mannich amine adduct in carrier oil and solvent oil, and stirring evenly to obtain the gasoline detergent.
[0034] Beneficial effects of the present invention:
[0035] Compared with the prior art, the present invention creatively combines propylene oxide polyether chain segments and long-chain fatty amines or aromatic amine groups together in an organic manner through a Mannich amine adduct, thereby combining the excellent properties of polyether amines and alkyl / aryl amines. The Mannich adduct has excellent cleaning and dispersing properties, can effectively inhibit the formation of deposits in various parts, and can be used as a main agent for gasoline detergents.
[0036] In a gasoline intake valve simulation evaluation test, the gasoline detergent prepared from the Mannich adduct product of the present invention has a slightly better effect than the similar imported product Afton H6581C, and is far better than polyisobutylene amine products and polyether amine products. DETAILED DESCRIPTION
[0037] The technical solution of the present invention is further described in detail below through specific implementation methods.
[0038] The compounds used in the examples are all commercially available, and the technical means not specified in the examples are all based on existing technologies. The central control index detection adopts liquid chromatography analysis, wherein an Agilent 1200 liquid chromatograph is used, the mobile phase is 90% n-heptane + 10% ethyl acetate, the flow rate is 1 mL / min, and the ultraviolet absorption wavelength is 270 nm.
[0039] Example 1
[0040] Weigh 100g of allyl alcohol polypropylene oxide ether (Jiangsu Zhongshan New Material Co., Ltd., brand P-90, number average molecular weight Mn1000), add 80g of D40 solvent oil to dissolve, and obtain allyl alcohol polypropylene oxide ether solution. Weigh 10.3g of phenol and 0.5g of boron trifluoride etherate (catalyst), add 20g of D40 solvent oil to dissolve, and obtain phenol solution. At a temperature of 30°C, the allyl alcohol polypropylene oxide ether solution is added dropwise to the phenol solution, and the dropping time is controlled for 3h. After the dropwise addition is completed, the reaction system is kept at 30°C to continue the reaction. The reaction degree is analyzed by liquid chromatography, and the phenol peak area ratio is controlled to be less than 10%. The total reaction time (including the dropping time and the time after the dropwise addition is completed) is 24 hours. At this time, the liquid chromatography analysis of the phenol peak area ratio is 8.6%.
[0041] After the reaction, deionized water at 80°C was added to the reaction solution to quench the reaction. After stirring, the mixture was allowed to stand for stratification to transfer boron trifluoride etherate and excess phenol into the water. The lower aqueous phase was separated. This operation was repeated 5 times. The organic phase was desolventized and residual phenol was removed at a temperature of 150°C and a negative pressure (-0.1 MPa) to obtain about 109 g of polyoxypropylene phenol.
[0042] The prepared polypropylene oxide-based phenol (about 109 g) and 10.8 g of p-phenylenediamine were mixed, the temperature was raised to 80° C., 8.3 g of 40% formaldehyde was added dropwise for 1 hour. After the addition was completed, the mixture was kept warm and refluxed for 4 hours. After the reaction was completed, water and a small amount of unreacted formaldehyde were removed at a temperature of 100° C. and a negative pressure (-0.1 MPa) to obtain about 121 g of a Mannich amine adduct containing a propylene oxide polyether segment and an aromatic amine group (referred to as Mannich amine adduct 1).
[0043] Example 2
[0044] Weigh 50g of allyl alcohol polypropylene oxide ether (Jiangsu Zhongshan New Materials Co., Ltd., brand P-50, number average molecular weight Mn500), add 30g of D40 solvent oil to dissolve, and obtain allyl alcohol polypropylene oxide ether solution. Weigh 11.3g of phenol and 0.5g of boron trifluoride etherate, add 20g of D40 solvent oil to dissolve, and obtain phenol solution. At a temperature of 35°C, the allyl alcohol polypropylene oxide ether solution is added dropwise to the phenol solution for 3h. After the dropwise addition is completed, the reaction system is kept at 35°C to continue the reaction. The reaction degree is analyzed by liquid chromatography to control the phenol peak area ratio <20%, and the total reaction time is 12 hours. At this time, the phenol peak area ratio of liquid chromatography analysis is 15.4%.
[0045] After the reaction, deionized water at 80°C was added to the reaction solution to quench the reaction. After stirring, the mixture was allowed to stand for stratification to transfer boron trifluoride etherate and excess phenol into the water. The lower aqueous phase was separated. This operation was repeated 5 times. The organic phase was desolventized and residual phenol was removed at a temperature of 150°C and a negative pressure (-0.1 MPa) to obtain about 59 g of polyoxypropylene phenol.
[0046] The prepared polypropylene oxide-based phenol (about 59 g) and p-phenylenediamine 10.8 g were mixed, the temperature was raised to 80° C., 8.3 g of 40% formaldehyde was added dropwise for 1 hour, and the mixture was kept at reflux for 4 hours. After the reaction, water and a small amount of unreacted formaldehyde were removed at a temperature of 100° C. and a negative pressure (-0.1 MPa) to obtain about 71 g of Mannich amine adduct 2 containing propylene oxide polyether segments and aromatic amine groups (referred to as Mannich amine adduct 2).
[0047] Example 3
[0048] Weigh 80g of allyl alcohol polypropylene oxide ether (Jiangsu Zhongshan New Materials Co., Ltd., brand P-80, number average molecular weight Mn800), add 60g of D40 solvent oil to dissolve, and obtain allyl alcohol polypropylene oxide ether solution. Weigh 10.3g of phenol and 0.7g of boron trifluoride etherate, add 20g of D40 solvent oil to dissolve, and obtain phenol solution. At a temperature of 25°C, the allyl alcohol polypropylene oxide ether solution is added dropwise to the phenol solution, and the dropping time is 3h. After the dropwise addition is completed, the reaction system is kept at 25°C. The reaction degree is analyzed by liquid chromatography to control the phenol peak area ratio <10%, and the total reaction time is 24 hours. At this time, the liquid chromatography analysis of the phenol peak area ratio is 9.2%.
[0049] After the reaction, deionized water at 80° C. was added to the reaction solution to quench the reaction. After stirring, the mixture was allowed to stand for stratification to transfer boron trifluoride etherate and excess phenol into the water. The lower aqueous phase was separated. This operation was repeated 5 times. The organic phase was desolventized and residual phenol was removed at a temperature of 150° C. and a negative pressure (-0.1 MPa) to obtain about 89 g of polyoxypropylene phenol.
[0050] The prepared polypropylene oxide-based phenol (about 89 g) and 10.8 g of p-phenylenediamine were mixed, the temperature was raised to 80° C., 8.3 g of 40% formaldehyde was added dropwise for 1 hour, and the mixture was kept at reflux for 4 hours. After the reaction, water and a small amount of unreacted formaldehyde were removed at a temperature of 150° C. and a negative pressure (-0.1 MPa) to obtain about 101 g of Mannich amine adduct 3 containing propylene oxide polyether segments and aromatic amine groups (referred to as Mannich amine adduct 3).
[0051] Example 4
[0052] Weigh 80g of allyl alcohol polypropylene oxide ether (Jiangsu Zhongshan New Materials Co., Ltd., brand P-80, number average molecular weight Mn800), add 50g of D40 solvent oil to dissolve, and obtain allyl alcohol polypropylene oxide ether solution. Weigh 10.3g of phenol and 0.7g of boron trifluoride etherate, add 20g of D40 solvent oil to dissolve, and obtain phenol solution. At a temperature of 30°C, the allyl alcohol polypropylene oxide ether solution is added dropwise into the phenol solution for 3h. After the dropwise addition is completed, the reaction system is kept at 30°C to continue the reaction. The reaction degree is analyzed by liquid chromatography to control the phenol peak area ratio <10%, and the total reaction time is 24 hours. At this time, the phenol peak area ratio of liquid chromatography analysis is 8.2%.
[0053] After the reaction, deionized water at 80° C. was added to the reaction solution to quench the reaction. After stirring, the mixture was allowed to stand for stratification to transfer boron trifluoride etherate and excess phenol into the water. The lower aqueous phase was separated. This operation was repeated 5 times. The organic phase was desolventized and residual phenol was removed at a temperature of 150° C. and a negative pressure (-0.1 MPa) to obtain about 89 g of polyoxypropylene phenol.
[0054] The prepared polypropylene oxide based phenol (about 89 g) and 11.6 g of 1,6-hexanediamine were mixed, the temperature was raised to 80°C, 8.3 g of 40% formaldehyde was added dropwise for 1 hour, and the mixture was kept at reflux for 4 hours. After the reaction, water and a small amount of unreacted formaldehyde were removed at a temperature of 150°C and a negative pressure (-0.1 MPa) to obtain about 102 g of Mannich amine adduct 4 containing propylene oxide polyether segments and alkylamine groups (referred to as Mannich amine adduct 4).
[0055] Example 5
[0056] Weigh 80g of allyl alcohol polypropylene oxide ether (Jiangsu Zhongshan New Materials Co., Ltd., brand P-80, number average molecular weight Mn800), add 50g of D40 solvent oil to dissolve, and obtain allyl alcohol polypropylene oxide ether solution. Weigh 10.3g of phenol, add 0.7g of boron trifluoride etherate, add 20g of D40 solvent oil to dissolve, and obtain phenol solution. At a temperature of 30°C, the allyl alcohol polypropylene oxide ether solution is added dropwise into the phenol solution for 3h. After the dropwise addition is completed, the reaction system is kept at 30°C to continue the reaction. The reaction degree is analyzed by liquid chromatography to control the phenol peak area ratio <10%, and the total reaction time is 24 hours. At this time, the phenol peak area ratio of liquid chromatography analysis is 8.8%.
[0057] After the reaction, deionized water at 80° C. was added to the reaction solution to quench the reaction. After stirring, the mixture was allowed to stand for stratification to transfer boron trifluoride etherate and excess phenol into the water. The lower aqueous phase was separated. This operation was repeated 5 times. The organic phase was desolventized and residual phenol was removed at a temperature of 150° C. and a negative pressure (-0.1 MPa) to obtain about 89 g of polyoxypropylene phenol.
[0058] The prepared polypropylene oxide phenol (about 89 g) and 15.8 g of 1,9-nonanediamine were mixed, the temperature was raised to 80°C, 8.3 g of 40% formaldehyde was added dropwise for 1 hour, and the mixture was kept at reflux for 4 hours. After the reaction, water and a small amount of unreacted formaldehyde were removed at a temperature of 150°C and a negative pressure (-0.1 MPa) to obtain about 106 g of Mannich amine adduct 5 containing propylene oxide polyether segments and alkylamine groups (referred to as Mannich amine adduct 5).
[0059] Example 6
[0060] 30 parts by mass of Mannich adduct 1 to Mannich adduct 5 were added to 10 parts by mass of base oil 500SN and 60 parts by mass of 1500# aromatic solvent oil, and stirred evenly to obtain gasoline detergent 1 to gasoline detergent 5 respectively.
[0061] Comparative Example 1
[0062] Referring to Example 6, the Mannich adduct was replaced with an equal mass of BASF 3866CN (polyisobutylene amine product), and gasoline detergent 6 was prepared according to the method of Example 6. The effective content of organic amine in gasoline detergent 6 was 30%.
[0063] Comparative Example 2
[0064] Referring to Example 6, the Mannich adduct was replaced with an equal mass of Huntsman Fl1000 (polyetheramine product), and gasoline detergent 7 was prepared according to the method of Example 6. The effective content of organic amine in gasoline detergent 7 was ensured to be 30%.
[0065] Comparative Example 3
[0066] Referring to Example 6, the Mannich adduct was replaced with an equal mass of Afton HC65830 (Mannich amine), and gasoline detergent 8 was prepared according to the method of Example 6. The effective content of organic amine in gasoline detergent 8 was 30%.
[0067] Performance Testing
[0068] A gasoline intake valve simulation evaluation test was performed on gasoline detergents 1 to 8.
[0069] Instrument: L-2 gasoline cleanliness tester (Lanzhou Weike Petrochemical Instrument Co., Ltd.).
[0070] Method: Refer to Appendix B of standard GB19592-2004.
[0071] Table 1. Evaluation results
[0072] Coke yield mg After washing mg Gasoline detergent 1 18.4 0.32 Gasoline detergent 2 19.6 0.44 Gasoline detergent 3 16.9 0.48 Gasoline detergent 4 16.5 0.56 Gasoline detergent 5 18.2 0.28 Gasoline detergent 6 17.4 1.63 Gasoline detergent 7 17.3 1.23 Gasoline detergent 8 15.6 0.95
[0073] From the evaluation results in Table 1, it can be seen that the Mannich adduct products of the present invention are prepared into gasoline detergents (gasoline detergents 1 to gasoline detergents 5), and the effect is slightly better than the similar imported product Afton H6581C in the gasoline intake valve simulation evaluation test, and is far better than polyisobutylene amine products and polyether amine products.
[0074] It should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, ordinary technicians in the field should understand that the specific implementation methods of the present invention can still be modified or some technical features can be replaced by equivalents without departing from the spirit of the technical solution of the present invention, which should be included in the scope of the technical solution for protection of the present invention.
Claims
1. A Mannich amine adduct containing a propylene oxide polyether segment and a long-chain fatty amine or aromatic amine group, as shown in Formula I: in, A is a polypropylene oxide chain segment, and RN is a long-chain aliphatic amine or aromatic amine group with ≥6 C atoms.
2. A method for synthesizing the Mannich amine adduct according to claim 1, characterized in that: include: Step (1), using alkane solvent oil as a reaction solvent, under the catalytic action of a catalyst, allyl alcohol polypropylene oxide ether and phenol undergo an alkylation substitution reaction to obtain polypropylene oxide substituted phenol; Step (2), the polypropylene oxide substituted phenol undergoes a Mannich reaction with formaldehyde and an amine to obtain a Mannich amine adduct.
3. The method for synthesizing the Mannich amine adduct according to claim 2, characterized in that: In step (1), the molar ratio of the allyl alcohol polypropylene oxide ether to phenol is 1:1.05 to 1:1.2; and the mass ratio of the catalyst to the allyl alcohol polypropylene oxide ether is 5:1000 to 10:1000.
4. The method for synthesizing the Mannich amine adduct according to claim 2 or 3, characterized in that: In step (1), the number average molecular weight of the allyl alcohol polypropylene oxide ether is 500-1000; and the catalyst is selected from at least one of boron trifluoride etherate and trifluoromethanesulfonic acid.
5. The method for synthesizing the Mannich amine adduct according to claim 2, characterized in that: In step (2), the polypropylene oxide substituted phenol is calculated as allyl alcohol polypropylene oxide ether, and the molar ratio of the polypropylene oxide substituted phenol to formaldehyde and amine is 1:1.1:1; the amine is an aromatic amine or an alkyl amine; the aromatic amine is dianiline; and the alkyl amine is a dibasic fatty amine.
6. The method for synthesizing the Mannich amine adduct according to claim 2, characterized in that: In step (1), the temperature of the alkylation substitution reaction is 25-35° C., and the time of the alkylation substitution reaction is 12-24 hours; in step (2), the temperature of the Mannich reaction is 70-90° C., and the time of the Mannich reaction is 4-5 hours.
7. The method for synthesizing the Mannich amine adduct according to claim 2, characterized in that: In step (1), after the reaction is completed, deionized water at a temperature of 60 to 80° C. is added to the reaction system, and the mixture is allowed to stand for stratification after stirring, and the lower aqueous phase is separated to wash away the catalyst and excess phenol, and the operation is repeated 1 to 5 times; the organic phase is subjected to a temperature of 150 to 160° C. and a negative pressure of -0.1 to -0.08 MPa to remove the solvent oil and residual phenol to obtain a refined polypropylene oxide substituted phenol. In step (2), after the reaction is completed, water and unreacted formaldehyde raw material are removed at a temperature of 100 to 150° C. and a negative pressure of -0.1 to -0.08 MPa to obtain a Mannich amine adduct.
8. A gasoline detergent, characterized in that: The gasoline detergent contains the Mannich amine adduct according to claim 1.
9. A gasoline detergent, characterized in that: The gasoline detergent is prepared by dissolving the Mannich amine adduct according to claim 1 in carrier oil and solvent oil; the content of the Mannich amine adduct is 20% to 40%, the content of the carrier oil is 10% to 20%, and the balance is solvent oil.
10. A method for preparing the gasoline detergent according to claim 9, characterized in that: include: The Mannich amine adduct is dissolved in carrier oil and solvent oil, and stirred evenly to obtain the product.