RU2725885C1 - Method of producing alkenylphthalamido- and amidophthalideno succinimides based on ethylenediamine and triethylene tetramine - Google Patents

Abstract

FIELD: chemistry.SUBSTANCE: invention relates to a method of producing alkenylphthalamido- and alkenylamidophthalideno-succinimides. Method comprises reacting maleic anhydride with polyalphaolefin of molecular weight 700–900, or with polyisobutylene with molecular weight of 750–950, or with ethylene oligomer with molecular weight of 800–950, or with copolymer of ethylene and propylene, containing 60–65 % of propylene units, with molecular weight of 850–1,000. Process is carried out in the presence of an initiator first at temperature of 80–100 °C for 1.5–2.5 hours, then at 170–190 °C for 4–5.5 hours at a molar ratio of polyalphaolefin, polyisobutylene, ethylene oligomer, copolymer of ethylene and propylene : maleic anhydride = 1:1–1.02 with subsequent condensation of obtained alkenyl succinic anhydride in industrial oil with N-ethyleneamino-N'-triethylene triaminophthaldiamide or N-ethyleneamino-N'-triethylene triaminoamidophthalidene at a molar ratio of alkenylsuccinic anhydride : N-ethyleneamino-N'-triethylene triaminopthalaldiamide or N-ethyleneamino-N'-triethylene triaminoamidophthalidene = 1–2:1 first at 80–95 °C for 1.5–2 hours, then at 155–170 °C for 4–4.5 hours, then water and impurities contained in initial raw material are distilled and formed due to insignificant decomposition of synthesis products at temperature 140–148 °C/10–16 mm Hg.EFFECT: disclosed is a method of producing alkenylphthalamido- and alkenylamidophthalideno-succinimides.5 cl, 3 tbl, 10 ex

Description

The invention relates to the field of petrochemical synthesis, in particular to a method for producing alkenyl succinimides which can be used as anti-corrosion, detergent and dispersant additives in lubricating oils to reduce the formation of carbon deposits on parts of internal combustion engines.

A known method of producing alkenyl succinimides by the interaction of alkenyl substituted succinic acid or its anhydride with a mixture of amines in a molar ratio of 1: 0.8-1.5 at a temperature of 125-135 ° C in the presence of an aromatic solvent for 3.5 hours, followed by filtration of the resulting product. The first stage of the attachment of alkenyls to maleic anhydride takes place at a temperature of 150-250 ° C for 15 hours. To prevent turbidity, add up to 10% (per alkenylsuccinimide) polyglycolalkylphenol formaldehyde resin. As amines in the second stage, a mixture is used containing 5-70% aminoethylethanolamine, 5-30% aminoethyl piperazine 0-25% triethylenetetramine (TETA), 0-20% hydroxyethyl piperazine, 0-10% diethylenetriamine (DETA), 10-15% oligomers these amines [US 4863487 A, 09/05/1989].

The disadvantage of this method is the high temperature in the first stage of the synthesis and the duration of the process. The closest way to obtain alkenylsuccinimides in technical essence and the achieved result is a method for producing polyisobutenyl and ethylene propylene succinimide additives, consisting of 70-99% lubricating oil and 0.1-30% of jointly acting additives with antioxidant-dispersant action [US 6117825 Yraword Norris Roland , Ymamata Ray. Isamu. N071879401 (2000)].

The disadvantage of the method for producing succinimides is the use of alkenyl succinic anhydride (AA) with a molecular weight of 96-9600, as well as the use of complex mixtures and high temperature. The molecular mass of an AA without an alkene radical (R) is 99 (C ₄ H ₃ O ₃ = 99).

The problem to which the invention is directed, is to develop a resource-saving method for the production of alkenylphthalamido- and amidophthalidene succinimides based on ethylene diamine and triethylenetetramine for motor oils, the use of secondary raw materials, production waste and expanding the range of products.

The technical result, when using the invention, is expressed in obtaining new alkenylphthalamido- and amidophthalidene succinimides of ethylenediamine and triethylenetetramine, which have strongly pronounced anticorrosion properties, and expanding the range of manufactured additives.

The above technical result is achieved by the method of producing alkenylphthalamido and amidophthalidene succinimides by reacting maleic anhydride (MA) with polyalphaolefin (PAO) with a molecular weight of 700-900 or polyisobutylene (PIB) with a molecular weight of 750-950, or an ethylene oligomer (OE) with a molecular -950, or a copolymer of ethylene and propylene (SOP) containing 60-65% of propylene units with a molecular weight of 850-1000, the process is carried out in the presence of an initiator at a temperature of 80-100 ° C for 1.5-2.5 hours, then at 170-190 ° C for 4-5.5 hours at a molar ratio of PAO (PIB, OE, SOP): MA = 1: 1-1.02, followed by condensation of the obtained alkenyl succinic anhydride (AAA) in an oil with phthalamide or amidophthalidene , or toluylamide, with a molar ratio of AAA: phthaloamide or amide, oftal idea equal to 1-2: 1 and AAA: toluylamide equal to 1: 1, first at a temperature of 80-95 ° C for 1.5-2 hours, then at 155- 170 ° C for 4-4.5 hours, with a molar ratio of AA: compounds (1-2) = 2: 1 and AGA: compound (3), equal to 1: 1, first at a temperature of 80-95 ° C for 1.5-2 hours, then at 155-170 ° C for 4-4.5 hours, then water is distilled off and impurities contained in the feedstock and formed due to slight decomposition of the products during synthesis, at a temperature of 140-148 ° C / 10-16 mm Hg

In this case, N-ethyleneamino, N'-triethylenetriaminophthaldiamide (compound 1) obtained by the interaction of 75% aqueous solutions of ethylenediamine and triethylenetetramine with terephthalic acid in a molar ratio of 1: 1 at a temperature of 95 ° C for 4 hours is used as phthalamide. at 115-120 ° C for 3-4 hours

As amidophthalidene, N-ethyleneamino, N'-triethylenetriaminoamidophthalidene (compound 2) is used, obtained by reacting 70% aqueous solutions of ethylenediamine and triethylenetetramine in a 1: 1 molar ratio with carboxybenzaldehyde, first at a temperature of 80-95 ° C for 3-4 hours , then at 110-115 ° C for 5.5 hours

As toluylamide, N-ethyleneaminotoluylamide (compound 3) is used, obtained by the interaction of a 70% aqueous solution of ethylenediamine with toluic acid at a molar ratio of 1: 1 at a temperature of 100-105 ° C for 2.5 hours, then at 140-145 ° C for 4.5 hours

DTB peroxide or methyl ethyl ketone peroxide (MEK) is used as an initiator in an amount of 0.1-1.3% by weight of PAO + MA or PIB + MA, or OE + MA, or SOP + MA taken into the reaction, without taking into account a slight excess MA As oil, industrial oils of the I-20A or I-40A brand are used, or their mixture in a ratio of 1: 1 (GOST No. 20799-88 with a change of 1-5). The yield of target products is 94.2-98.2%. The output when deviating from the synthesis conditions of compounds (1-8) is (example 9-10) 68.3-71.2%, respectively.

Amide production (1-3) based on EDA and THETA and phthalic acids - waste of the Polyef enterprise (Blagoveshchensk, Republic of Bashkortostan):

Obtaining amides (1-3) based on phthalic acids and TETA:

2. Amide and Schiff base based on carboxybenzaldehyde (CBA), EDA and THETA:

3. EDA-based toluic acid amide (TC):

Compounds (1-3) form with AAA the corresponding alkenylphthalamidosuccinimides APSI (4-8):

As the initiator, ditretbutyl peroxide (DTB) or methyl ethyl ketone peroxide (MEK) is used in amounts of 0.1-1.3% of the weight of the starting products - PAO + MA or PIB + MA, or OE + MA, or SOP + MA.

As industrial oil, I-20A or I-40A brand oil is used (GOST No. 20799-88 with amendment: 1-5).

Compounds 4 and 6 with AAA form compounds 5 and 7, respectively.

The invention is illustrated by the following examples.

Example 1. In a reactor with a stirring device, a thermometer, a refrigerator and a dropping funnel, 70.0 g (0.1 mol) of PAO, with a molecular weight of 700, 9.89 g (0.101 mol) of MA (molar ratio of PAO: MA = 1: 1,101) and 0.08 g of ditretbutyl peroxide (DTB) (0.1% by weight of PAO and MA). The reaction mixture is stirred at a temperature of 85-90 ° C for 1.5 hours, then at 180 ° C for 4.5 hours. The resulting AAA is cooled to 65 ° C, diluted with I-20A oil (weight ratio AAA: oil = 1 : 1), filtered through a cloth filter (you can use other filter materials) and transferred to an intermediate container. The reactor was charged with 33.6 g (0.1 mol) of N-ethyleneamino, N'-triethylenetriaminophthaldiamide (1) obtained by dosing a 75% aqueous EDA solution to TFA in oil heated to 95 ° C for 4 hours and adding at this temperature TETA (molar ratio of EDA: TETA is 1: 1). The reaction mixture is stirred at a temperature of 115-120 ° C for 3-4 hours. After that, AA ratios are dosed (molar ratios AAA: compounds = 1: 1) and maintained at 160 ° C for 4 hours, then water and impurities are distilled off (insignificant decomposition of the target product) at 140-145 ° C / 10-15 mm RT. Art. 109.2 g (94.2%) of compound 4 are obtained. Found,%: N, 7.11. C ₇₀ H ₁₂₇ N ₆ O ₄ . Calculated,%: N 7.53.

Example 2. Under the conditions of example 1, 180.0 g (0.2 mol) of PAO, with a molecular weight of 900, 19.78 g (0.202 mol) of MA (molar ratio of PAO: MA = 1: 1.01) 1 are loaded into the reactor 99 g of MEK peroxide (1% by weight of reacting substances). The reaction mixture was stirred at 85 ° C for 2.5 hours, then at 180 ° C for 5.5 hours. The resulting AAA was cooled to 70 ° C, diluted with I-40A oil (weight ratio AAA: oil = 1: 1) , filtered and transferred to a container. 33.6 g (0.1 mol) of compound 1, 33.6 g of I-40A oil are loaded into the reactor (weight ratios of compound 1: oil = 1: 1). The mixture is heated at 95 ° C for 2 hours and at this temperature, AA is dosed in oil (molar ratios of AA: compound 1 = 2: 1, weight ratios of AA: oil = 1: 1). The mixture was kept at 165 ° C for 4.5 hours, then water and low boiling impurities were distilled off at 140-145 ° C / 10-15 mm Hg. Art. 219.95 g (95.8%) of compound 5 are obtained. Found,%: N 4.04. C ₁₅₂ H ₂₈₂ N ₆ O ₆ . Calculated,%: N 3.67.

Example 3. Under the conditions of example 1, 75.0 g (0.1 mol) of polyisobutylene (PIB), with a molecular weight of 750, 9.8 g (0.1 mol) of MA (molar ratio of PIB: MA = 1: 1), 1.10 g of DTB peroxide (1.3% by weight of PIB and MA). The reaction mixture was stirred at 85 ° C for 2 hours, then at 175 ° C for 5 hours. The resulting AAA was cooled to 65 ° C, diluted with I-20A + I-40A oil in a 1: 1 ratio (weight ratios of AAA: oil = 1: 1), filtered and transferred to a container. 32.0 g (0.1 mol) of compound 2, (obtained by dosing 70% aqueous solutions of EDA and TETA at a molar ratio of EDA: THETA = 1: 1 to carboxybenzaldehyde heated to 80-95 ° С) are charged to the reactor for 3-4 hours, then the mixture is stirred at 110-115 ° C for 5.5 hours), 32.0 g of oil (mixture of I-20A + I-40A = 1: 1) (weight ratio of compound 2: oil = 1: 1). The mixture is kept at 165 ° C for 4.5 hours, then water and low boiling impurities are distilled off at 142-158 ° C / 11-16 mm Hg. Art. 111.20 g (96.7%) of product 6 are obtained. Found,%: N 6.86. C ₇₄ H ₁₃₅ N6O ₃ . Calculated,%: N 7.27.

Example 4. Under the conditions of example 1, 190.0 g (0.2 mol) of PIB, with a molecular weight of 950, 19.99 g (0.204 mol) of MA, 0.419 g (0.2% of the weight of PIB + MA) are loaded into the reactor peroxide DTB. The mixture was stirred at 100 ° C for 2.5 hours, then at 185 ° C for 5 hours. The resulting AA was cooled to 70 ° C, diluted with I-20A oil (weight ratio AAA: oil = 1: 1), filtered and transferred to a container. 32.0 g (0.1 mol) of compound 2, 32.0 g of oil (weight ratio of compound 2: oil = 1: 1) are charged to the reactor. The mixture is heated at 95 ° C for 2 hours, the AAA is dosed in oil (molar ratio of AAA: compound 2 = 2: 1, weight ratio of AAA: oil = 1: 1). The mixture is kept at 165 ° C for 4.5 hours, then water and low boiling impurities are distilled off at 140-148 ° C / 10-16 mm Hg. Art. 233.47 g (98.1%) of product 7 are obtained. Found,%: N 3.12. C ₁₆₀ H ₂₉₈ N ₆ O ₅ . Calculated,%: N 3.52.

Example 5. Under the conditions of example 1, 80.0 g (0.1 mol) of ethylene oligomer (OE), with a molecular weight of 800, 9.8 g (0.1 mol) of MA, 0.718 g of MEK peroxide (0, 8% by weight of OE + MA). The mixture is stirred at 80 ° C for 1.5 hours, then at 185 ° C for 5.5 hours. The resulting AAA is cooled to 60 ° C, diluted with I-40A oil (weight ratio AAA: oil = 1: 1), filtered and transferred to an intermediate container. 33.6 g (0.1 mol) of compound 1, 33.6 g of oil are charged into the reactor. The mixture is heated at 90 ° C for 2 hours and at this temperature, AA is dosed in oil (molar ratios of AA: compound 1 = 1: 1, weight ratios of AA: oil = 1: 1). The mixture was kept at 165 ° C for 4.5 hours, then water and low boiling impurities were distilled off at 140-146 ° C / 10-15 mm Hg. Art. 119.41 g (98.2%) of product 4 are obtained. Found,%: N 6.52. C ₇₇ H ₁₄₁ N ₆ O ₄ . Calculated,%: N 6.92.

Example 6. Under the conditions of example 1, 190.0 g (0.2 mol) of ethylene oligomer (OE), with a molecular weight of 950, 19.99 g, (0.204 mol) of MA, 1.04 g of DTB peroxide (0 , 5% by weight of MA and MA). The mixture is stirred at a temperature of 90 ° C for 2 hours, then at 190 ° C for 5 hours. The resulting AAA is cooled to 70 ° C, diluted with I-20A oil (weight ratio AAA: oil = 1: 1), filtered and transferred into the intermediate tank. 32.0 g (0.1 mol) of compound 2, 32.0 g of I-20A oil (weight ratio of compound 2: oil = 1: 1) are loaded into the reactor. The mixture is heated to 95 ° C for 2 hours and at this temperature, AA is dosed in oil (molar ratio of compound 2: oil = 1: 1). The reaction mixture was kept at 170 ° C for 4 hours, then water and low boiling impurities were distilled off at 140-145 ° C / 10-15 mm Hg. Art. 232.05 g (97.5%) of product 7 are obtained. Found,%: N 3.89. C ₁₆₁ H ₂₉₈ N ₆ O ₅ . Calculated,%: N 3.52.

Example 7. Under the conditions of example 1, 85.0 g (0.1 mol) of a copolymer of ethylene and propylene SOP, with a molecular weight of 850, 9.8 g (0.1 mol) of MA, 0.948 g of DTB peroxide (1%) are loaded into the reactor by weight of SOP and MA). The mixture is stirred at 90 ° C for 1.5 hours, then at 185 ° C for 4.5 hours. The resulting AAA is cooled to 65 ° C, diluted with I-40A oil (weight ratio AAA: oil = 1: 1), filtered and transferred to a container. 32.0 g (0.1 mol) of compound 2, 32.0 g of I-40A oil (weight ratio of compound 2: oil = 1: 1) are loaded into the reactor. The mixture is heated to 95 ° C for 2 hours and at this temperature, AA is dosed in oil (molar ratios of AA and compound 2 = 1: 1, weight ratios of AA and oil: 1: 1). The mixture was kept at 170 ° C for 4 hours, then water and low boiling impurities were distilled off at 140-145 ° C / 10-15 mm Hg. Art. 120.0 g (96.0%) of product 6 are obtained. Found,%: N, 6.26. C ₈₁ H ₁₄₉ N ₆ O ₃ . Calculated,%: N 6.70.

Example 8. Under the conditions of example 1, 70.0 g (0.1 mol) of PAO, with a molecular weight of 700, 9.8 g, (0.1 mol) of MA, 0.47 g (0.6% of weight PAO and MA) peroxide IEC. The mixture was stirred at 95 ° C for 2 hours, then at 170 ° for 4 hours. The resulting AA was cooled to 60 ° C, diluted with I-20A + I-40A oil, 1: 1 (weight ratios of AAA: oil = 1 : 1), filtered and transferred to a container. 17.8 g (0.1 mol) of compound 3, (obtained by heating a 70% aqueous solution of ethylenediamine (EDA) with toluic acid at a molar ratio of EDA: TK = 1: 1 for 2.5 hours at a temperature 100-105 ° C, then at 145-150 ° C for 4.5 hours), 17.8 g of oil (I-20A + I-40A, 1: 1). The mixture is heated at 80-85 ° C for 1.5 hours and at this temperature, AA is dosed in oil (molar ratios of AA and compounds 3 = 1: 1, weight ratios of AA and oils: 1: 1). The mixture is kept at 155 ° C for 4 hours, then water and low boiling impurities are distilled off at 140-145 ° C / 10-15 mm Hg. Art. 93.4 g (97.5%) of product 8 are obtained. Found,%: N 3.35. C ₆₄ H ₁₁₃ N ₂ O ₃ . Calculated,%: N 2.92.

Example 9. Under the conditions of example 1, 200.0 g (0.2 mol) of SOP, with a molecular weight of 100, 19.6 g, (0.2 mol) of MA, 0.219 g (0.1% of the weight of SOP) are loaded into the reactor and MA) IEC peroxide. The mixture is stirred at a temperature of 60-70 ° C for 4 hours, then at 150-160 ° C for 3 hours. The resulting AAA is cooled to 60 ° C, diluted with I-20A oil (weight ratio AAA: oil = 1: 1) , filtered and transferred to a container. 33.6 g (0.1 mol) of compound 1 are loaded into the reactor, 33.6 g of oil (weight ratio of compound 1 to oil = 1: 1). The mixture is heated at 60 ° C for 3 hours and at this temperature, AA is dosed in oil (molar ratios of AA and compounds 1 = 1: 1, weight ratios of AA and oils: 1: 1). The reaction mixture was kept at 145 ° C for 4 hours, then water and low boiling impurities were distilled off at 140-145 ° C / 10-15 mm Hg. Art. 169.79 g (68.3%) of product 5 are obtained. Found,%: N 2.88. C ₁₆₈ H ₃₁₄ N ₆ O ₆ . Calculated,%: N 3.34.

Example 10. Under the conditions of example 1, 75.0 g (0.1 mol) of PIB, with a molecular weight of 750, 9.8 g (0.1 mol) of MA, 0.93 g of DTB peroxide (1.1%) are loaded into the reactor by weight of PIB and MA). The mixture is stirred at a temperature of 110 ° C for 1 h, then at a temperature of 210 ° C for 5 h. The resulting AAA is cooled to 55 ° C, diluted with I-40A oil (weight ratio AAA: oil = 1: 1), filtered and transferred to a container. 17.8 g (0.1 mol) of compound 3, 17.8 g of I-40A oil (weight ratio of compound 3: oil = 1: 1) are loaded into the reactor. The mixture is heated to 60 ° C for 4 hours and at this temperature, AA is dosed in oil (molar ratios of AA and compound 3 = 1: 1). The reaction mixture was kept at 180-190 ° C for 4 hours, then water and low boiling impurities were distilled off at 140-145 ° C / 10-15 mm Hg. Art. 71.78 g (71.2%) of product 8 are obtained. Found,%: N 3.14. C ₆₈ H ₁₂₁ N ₂ O ₃ . Calculated,%: N 2.76.

Examples 1-8, provided that the claimed parameters of the process for the production of alkenylphthaldiamido- and alkenylamidophthalidene succinimides based on EDA and TETA are maintained, a high yield of 94.2-98.2% and the conformity of test results TU-38101146-77 for succinimide additives are confirmed.

Examples 9-10, subject to deviations from the claimed process parameters for the production of alkenylphthaldiamido-alkenylphthalidene succinimides, demonstrate a decrease in the yield and protective effect of the product. Products 9-10 do not correspond in terms of “mass fraction of mechanical impurities”, “mass fraction of free polyamines”, “mass fraction of active substance”, “flash point in open crucible, ° С, not less than 160 ° С”.

The IR spectra of the obtained compounds (1-10) have absorption bands at 1720 cm ^-1 , 1780 cm ^-1 , characteristic of CO in five-membered cycles.

Claims (5)

1. The method of producing alkenylphthalamido- and alkenylamidophthalidene-succinimides based on ethylenediamine and triethylenetetramine by reacting maleic anhydride with olefins at an elevated temperature followed by the reaction of alkenyl succinic anhydride with amines in the presence of a solvent, characterized in that the maleic anhydride polymer has an amount of 700 and or polyisobutylene with a molecular weight of 750-950, or with an ethylene oligomer with a molecular weight of 800-950, or a copolymer of ethylene and propylene containing 60-65% of propylene units, with a molecular weight of 850-1000, the process is carried out in the presence of an initiator first at a temperature 80-100 ° C for 1.5-2.5 hours, then at 170-190 ° C for 4-5.5 hours with a molar ratio of polyalphaolefin, polyisobutylene, ethylene oligomer, ethylene-propylene copolymer: maleic anhydride = 1 : 1-1.02 followed by condensation of the obtained alkenyl succinic anhydride in an industrial oil with N-ethyleneamino-N'-three ethylene triaminophthaldiamide or N-ethyleneamino-N'-triethylenetriaminoamidophthalide with a molar ratio of alkenyl succinic anhydride: N-ethyleneamino-N'-triethylenetriaminophthaldiamide or N-ethyleneamino-N'-triethylenetriaminoamide-1: 80 ° C 5-2 hours, then at 155-170 ° С for 4-4.5 hours, then water and impurities contained in the feedstock and formed due to insignificant decomposition of the synthesis products are distilled off at a temperature of 140-148 ° С / 10 -16 mmHg 2. The method according to p. 1, characterized in that the product obtained by the interaction of 75% aqueous solutions of ethylenediamine and triethylenetetramine in a molar ratio = 1: 1 with terephthalic acid at a temperature of 95 ° C for 4 hours is used as phthalamides at 115-120 ° C for 3-4 hours 3. The method according to p. 1, characterized in that the product obtained by reacting 70% aqueous solutions of ethylenediamine and triethylenetetramine in a molar ratio of 1: 1 with carboxybenzaldehyde is first used at a temperature of 80-95 ° C for 3 -4 hours, then at 110-115 ° C for 5.5 hours 4. The method according to p. 1, characterized in that as the initiator use tertiary butyl peroxide or methyl ethyl ketone peroxide in an amount of 0.1-1.3% by weight of the starting products - polyalphaolefin or polyisobutylene, or ethylene oligomer, or ethylene-propylene copolymer and maleic anhydride. 5. The method according to p. 1, characterized in that industrial oils use industrial oils of the brand I-20A or I-40A.