Scale-up process of bifunctionalized triblock copolymers with secondary and tertiary amines, with application in dewatering and desalting of heavy crude oils

Patent metadata

Field	Value
Publication number	US-10125226-B2
Application number	US-201414296097-A
Country	US
Kind code	B2
Filing date	Jun 4, 2014
Priority date	Jun 5, 2013
Publication date	Nov 13, 2018
Grant date	Nov 13, 2018

Abstract

A chemical synthesis process is provided for the functionalization of monodispersed triblock copolymer (POE w -POP y -POE w ) with secondary or tertiary amines at a semi-industrial level in glass reactors having a capacity between 1 L and 100 L. The process includes two stages where the first stage uses an alkylsulfonyl or arylsulfonyl chloride to obtain better leaving groups, and the second stage is the nucleophilic substitution with secondary or tertiary amines, to obtain the bifunctionalized triblock copolymers. The main advantage for this process is to reduce the quantity of unitary process done in each stage, the optimization of reaction times, and the stoichiometric relationships.

First claim

What is claimed is:

1. A process to carry out a semi-industrial and industrial scale bifunctionalization with secondary or tertiary amines of a block copolymer poly(oxyethylene) w -poly(oxypropylene) y -poly(oxyethylene) w (POE w -POP y -POE w ) in glass-reactor with capacity between 1 and 100 , where w and y are a number in the range of 10-60, said process comprising two stages, wherein:
Stage 1 is the formation of the am-dialkylsulfonyl ester or α,ω-diarylsulfonyl ester of poly(oxyethylene) w -poly(oxypropylene) y -poly(oxyethylene) w (POE w -POP y -POE w ), from a reaction of alkylsulfonyl or arylsulfonyl chloride with a triblock copolymer poly(oxyethylene) w ,poly(oxypropylene) y -poly(oxyethyIene) w , (POEw-POP y -POE w ), the reaction is carried out at a molar ratio of triblock copolymer POE w -POP y -POE w /alkylsulfonyl or arylsulfonyl chloride of 1.0/2.0 to 1.0/6.0; in the presence of a base selected from the group consisting of bicarbonates (sodium, potassium, calcium or magnesium), carbonates (sodium, potassium, calcium or magnesium), triethylamine, tripropylamine, N,N-dimethylaniline and pyridine, with a triblock copolymer POE w -POP y -POE w /base ratio between 1.0/2.0 to 1.0/8.0 in a solvent selected from the group consisting of acetonitrile, benzonitrile, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dioxane, dimethylformamide, dimethylsulfoxide, dimethylether ethyleneglycol, 2-methoxyethylether or tetrahydrofurane, in a weight (grams)/volume (ml) triblock copolymer triblock POE w -POP y POE w /solvent of 1.0/1.0 to 1.0/10.0, at a reaction temperature of from 5 to 50 ° C., with a reaction time of 1 to 8 hours, the reaction product is filtered at vacuum; the solvent is not eliminated from the product;
Stage 2 is carried out the nucleophilic substitution reaction of secondary or tertiary amines with, α,ω-dialkylsulfonyl ester or α,ω-diarylsulfonyl ester of poly(oxyethylene) w -poly(oxypropylene) y -poly(oxyethylene) w (POE w -POP y -POE w ), wherein the synthesis of Y-POE w ,-POP y -POE w -Y where Y is a secondary amine is carried out with a molar ratio of a,α,ω)-dialkylsulfonyl ester or α,ω-diarylsulfonyl ester of triblock copolymer poly(oxyethylene) w -poly(oxypropylene) y -poly(oxyethylene) w (POE w -POP y -POE w )/secondary amine between 1.0/2.0 to 1.0/10.0; in a base selected from the group consisting of bicarbonates (sodium, potassium, calcium or magnesium), carbonates (sodium, potassium, calcium or magnesium), triethylamine, tripropylamine, N,N-dimethylaniline and pyridine in molar relationship regarding copolymer between 2 to 10 moles per mole of POE w ,-POP y -POE w , temperature range of 30 to 100° C., a reaction time in a range of 2 to 10 hours, a solvent selected from the group consisting of acetonitrile, benzonitrile, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dioxane, dimethylformamide, dimethylsulfoxide, dimethyl-ether ethyleneglycol, 2-methoxyethyl-ether and tetrahydrofurane in a weight (g)/volume (ml) ratio (w/v) of αω-dialkylsulfonyl ester or αω-diarylsulfonyl ester of triblock copolymer (POE w -POP y -POE w )/solvent between 1.0/1.0 to 1.0/10.0, the resulting bifunctionalized with amines the triblock copolymer poly(oxyethylene) w -poly(oxypropylene) y -poly(oxyethylene) w , the chemically modified product is filtered at reduced pressure and solvent is evaporated at reduced pressure, or the synthesis of Z-POE w -POP y -POE w -Z where Z is a tertiary amine, the reaction is carried out with a molar ratio αω-dialkylsulfonyl ester or αω-diarylsulfonyl ester of triblock copolymer poly(oxyethylene) w -poly(oxypropylene) y -poly(oxyethylene) w (POE w -POP y -POE w )/tertiary amine of 1.0/2.1 to 1.0/5.0, at a temperature between 50 to 130° C., a reaction time 7 to 17 hours, in a solvent selected from the group consisting of acetonitrile, benzonitrile, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dioxane, dimethylformamide, dimethylsulfoxide, dimethylether ethyleneglycol, 2methoxyethylether and tetrahydrofurane at weight/volume relationship (w/v) of αω-dialkylsulfonyl ester or αω-diarylsulfonyl ester of triblock copolymer (POE w -POP y -POE w )/solvent between 1.0/1.0 to 1.0/15.0, the resulting bifunctionalized products with amines the triblock copolymer poly(oxyethylene) w -poly(oxypropylene) y -poly(oxyethylene) w , the chemically modified product is filtered at reduced pressure and solvent is evaporated at reduced pressure.

2. The process for the bifunctionalization with secondary or tertiary amines of triblock copolymer poly(oxyethylene) w -poly(oxypropylene) y -poly(oxyethylene) w (POE w -POP y -POE w ), according to claim 1 , where the triblock copolymer poly(oxyethylene) w -poly(oxypropylene) y -poly(oxyethylene) w (POE w -POP y -POE w ) has a molecular weight in number M n between 600 and 10,000 g/mol.

3. The process for the bifunctionalization with secondary or tertiary amines of triblock copolymer poly(oxyethylene) w -poly(oxypropylene) y -poly(oxyethylene)(POE w -POP y -POE w ), according to claim 2 , where the alkylsulfonyl or arylsulfonyl chloride is selected from the group consisting of methanesulfonyl chloride, trichloromethanesulfonyl chloride, ethanesulfonyl chloride, 2-methoxyethane-1-sulfonyl chloride, 1-propanosulfonyl chloride, isopropylsulfonyl chloride, 3,3,3-trifluoropropane-1-sulfonyl chloride, 1-butanesulfonyl chloride, benzenesulfonyl chloride, 2-chlorobenzenesulfonyl chloride, 3 -methylbutane-1-sulfonyl chloride, 3-benzenesulfonyl chloride, cyclopentanesulfonyl chloride, 4-benzenesulfonyl chloride, para-toluenesulfonyl chloride, trifluoromethylbenzenesulfonyl chloride, nitrobenzenesulfonyl chloride, 1,4-benzodioxane-6-sulfonyl chloride, biphenyl-4-sulfonyl chloride, 4′-chlorobiphenyl-4-sulfonyl chloride, 4′-metoxybiphenyl-4-sulfonyl chloride, 4′-fluorobiphenyl-4-sulfonyl chloride, 4′-methylbiphenyl-4-sulfonyl chloride, and 4-bromobenzenesulfonyl chloride.

4. The process for bifunctionalization with secondary or tertiary amines of triblock copolymer poly(oxyethylene) w -poly(oxypropylene) y -poly(oxyethylene) w (POE w -POP y -POE w ), according to claim 3 , where in the stage 1 the molar ratio of the triblock copolymer POE w -POP y -POE w to the alkylsulfonyl or arylsulfonyl chloride is between 1.0/2.2 to 1.0/4.5.

5. The process for bifunctionalization with secondary or tertiary amines of triblock copolymer poly(oxyethylene) w -poly(oxypropylene) y -poly(oxyethylene) w (POE w -POP y -POE w ), according to claim 4 , where in the stage 1 the alkylsulfonyl or arylsulfonyl chloride is added in reagent-starved conditions at mass flow between 1 to 50 g/min.

6. The process for bifunctionalization with secondary or tertiary amines of triblock copolymer poly(oxyethylene) w -poly(oxypropylene) y -poly(oxyethylene) w (POE w -POP y -POE w ), according to claim 5 , where in the stage 1 the molar ratio of the base is selected from the group consisting of bicarbonates (sodium, potassium,calcium or magnesium), carbonates (sodium, potassium, calcium or magnesium),triethylamine, tripropylamine, N,N-dimethylaniline or pyridine, with triblock copolymer poly(oxyethylene) w -poly(oxypropylene) y -poly(oxyethylene) w is between 2.5 to 6.0 moles per mole of POE w -POP y -POE w .

7. The process for bifunctionalization with secondary or tertiary amines of triblock copolymer poly(oxyethylene) w -poly(oxypropylene) y -poly(oxyethylene) w (POE w -POP y -POE w ), according to claim 6 , where in the stage 1 the base is added in reagent-starved conditions at mass flow between 1 to 70 g/min.

8. The process for bifunctionalization with secondary or tertiary amines of triblock copolymer poly(oxyethylene) w -poly(oxypropylene) y -poly(oxyethylene) w (POE w -POP y -POE w ), according to cl

Assignees

• Mexicano Inst Petrol

Inventors

• Flores Sandoval Cesar Andres
• Flores Oropeza Eugenio Alejandro
• Lopez Ortega Alfonso
• Hernandez Cortez Jose Gonzalo
• Estrada Buendia Aristeo
• Castro Sotelo Laura Veronica
• Reyes Martinez Reyna
• Alvarez Ramirez Fernando
• Estrada Martinez Arquimedes
• Vazquez Moreno Flavio Salvador

Classifications

• C08G65/3344

  containing oxygen in addition to sulfur · CPC title

• C08G65/333 Primary

  containing nitrogen · CPC title

• C08G65/08

  Saturated oxiranes · CPC title

• C08G2650/58

  Ethylene oxide or propylene oxide copolymers, e.g. pluronics · CPC title

• C08G2650/50

  containing nitrogen, e.g. polyetheramines or Jeffamines(r) · CPC title