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

Abstract

A chemical synthesis process is provided for the functionalization of monodispersed triblock copolymer (POE.sub.w-POP.sub.y-POE.sub.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.

Claims

1. A process to carry out a semi-industrial and industrial scale bifunctionalization with secondary or tertiary amines of a block copolymer poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.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 ,-diarylsulfonyl ester of poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w), from a reaction of alkylsulfonyl or arylsulfonyl chloride with a triblock copolymer poly(oxyethylene).sub.w,poly(oxypropylene).sub.y-poly(oxyethyIene).sub.w, (POEw-POP.sub.y-POE.sub.w), the reaction is carried out at a molar ratio of triblock copolymer POE.sub.w-POP.sub.y-POE.sub.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.sub.w-POP.sub.y-POE.sub.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.sub.w-POP.sub.yPOE.sub.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, ,-dialkylsulfonyl ester or ,-diarylsulfonyl ester of poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w(POE.sub.w-POP.sub.y-POE.sub.w), wherein the synthesis of Y-POE.sub.w,-POP.sub.y-POE.sub.w-Y where Y is a secondary amine is carried out with a molar ratio of a,,)-dialkylsulfonyl ester or ,-diarylsulfonyl ester of triblock copolymer poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.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.sub.w,-POP.sub.y-POE.sub.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 -dialkylsulfonyl ester or -diarylsulfonyl ester of triblock copolymer (POE.sub.w-POP.sub.y-POE.sub.w)/solvent between 1.0/1.0 to 1.0/10.0, the resulting bifunctionalized with amines the triblock copolymer poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w, the chemically modified product is filtered at reduced pressure and solvent is evaporated at reduced pressure, or the synthesis of Z-POE.sub.w-POP.sub.y-POE.sub.w-Z where Z is a tertiary amine, the reaction is carried out with a molar ratio -dialkylsulfonyl ester or -diarylsulfonyl ester of triblock copolymer poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.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 -dialkylsulfonyl ester or -diarylsulfonyl ester of triblock copolymer (POE.sub.w-POP.sub.y-POE.sub.w)/solvent between 1.0/1.0 to 1.0/15.0, the resulting bifunctionalized products with amines the triblock copolymer poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.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).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w), according to claim 1, where the triblock copolymer poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w(POE.sub.w-POP.sub.y-POE.sub.w) has a molecular weight in number M.sub.nbetween 600 and 10,000 g/mol.

3. The process for the bifunctionalization with secondary or tertiary amines of triblock copolymer poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene)(POE.sub.w-POP.sub.y-POE.sub.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).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w), according to claim 3, where in the stage 1 the molar ratio of the triblock copolymer POE.sub.w-POP.sub.y-POE.sub.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).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.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).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.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).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w is between 2.5 to 6.0 moles per mole of POE.sub.w-POP.sub.y-POE.sub.w.

7. The process for bifunctionalization with secondary or tertiary amines of triblock copolymer poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.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).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w), according to claim 1, where in the stage 1 the solvent is in weight (g)/volume (ml) relationship of triblock copolymer POE.sub.w-POP.sub.y-POE.sub.w/solvent between 1.0/2.0 to 1.0/7.0.

9. The process for bifunctionalization with secondary or tertiary amines of triblock copolymer poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w), according to claim 8, where in the stage 1 the reaction temperature is from 15 C. to 35 C.

10. The process for bifunctionalization with secondary or tertiary amines of triblock copolymer poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w), according to claim 9, where in the stage 1 the reaction time is between 3 to 6 hours.

11. The process for bifunctionalization with secondary amines of triblock copolymer poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w), according to claim 1, where in the stage 2 the secondary amine is selected from the group consisting of (2,2-dimethylpropyl)(methyl)amine, N-methyl-N-(1-pentylethyl)amine, (4 chloro-benzyl)-methylamine bis-(2-ethyhylhexyl)amine, N-benzyl-N -(2-methoxyethyl)amine, diisopropylamine, 2-(methylamine)-ethanol, 2-(butylamine) -ethanol, 2-(benzylamine)-ethanol, 2-(cyclohexylamine)-ethanol, 2-(ter-butylamine) -ethanol, 2-(phenylamine)-ethanol, 2-(n-propylamine)-ethanol, 2-(iso-propylamine) -ethanol, 2-(hydroxymethylamine)-ethanol, 2,2-imidodiethanol,1,1-iminodi -2-propanol, 4-(butylamine)-1-butanol, 1-benzylpiperazine, 1-phenylpiperazine, 2-(hexylamino)-ethanol, 1-acetylpiperazine, 1-(ortho-clorophenyl)-piperazine, 1-ethylpiperazine, 1-(methyl-tolyl) -piperazine, 1(4-nitrophenyl)-piperazine, 4-benzyipiperidine, 4-methylpiperidine, 2-methylpiperidine, 2-ethylpiperidine, 3,5-dimethylpiperidine, piperidine-3-ol, piperidine-4-ol, trans-3,5-dimethylpiperidine, cis-3,5-dimethylpiperidine, 3-methylpiperidine, piperidine-3-ylmethanol, 3,3-dimethylpiperidine, 4-phenylpiperidine-3-ol, 4-phenyl -piperidine, 4-(piperidine-4-il)morpholine, 4,4-bipiperidine, pyrrolidine-3-amine, 2,6-dimethylmorpholine, morpholine, pyrrolidine-2-ylmethanol, trans-2,5-dimethylpyrrolidine, cis-2,5-dimethylpyrrolidine, diphenylamine, 2-nitro-diphenylamine, 4-nitro-diphenylamine, pyrrolidine, 4,4-bis(dimethylamine)-diphenylamine, 2,4-dinitro -diphenylamine, 4,4-dimethoxy-diphenylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dioctylamine, didecylamine, didodecylamine, dinonylamine, N-methyl-hexylamine, di-iso-propylamine, N-iso-propyl-tert-butylamine, N-ethyl-ter-butylamine, N-ethyl-butylamine, di-isobutylamine, iso-butyl-sec-butylamine, di-iso-pentylamine, ethyl-n-dodecylamine, di-ter-amyl-amine, N-methyl-pentylamine, N -methyl-butylamine, N-methyl-ter-butylamine, N-ethyl-iso-propylamine, N-ethyl -propylamine, N-methyl-octylamine, and piperidine.

12. The process for bifunctionalization with secondary amines of triblock copolymer poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w), according to claim 11, where in the stage 2 the molar ration of said ,-dialkylsulfonyl ester or ,-diarylsulfonyl ester of triblock copolymer POE.sub.w-POP.sub.y-POE.sub.w/secondary amine is between 1.0/2.5 and 1.0/8.5.

13. The process for bifunctionalization with secondary amines of triblock copolymer poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w), according to claim 1, where in the stage 2 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, in a molar ratio of ,-dialkylsulfonyl ester or -diarylsulfonyl ester of triblock copolymer POE.sub.w-POP.sub.y-POE.sub.wbetween 3.0 and 6.5 moles.

14. The process for bifunctionalization with secondary amines of triblock copolymer poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w), according to claim 13, where in the stage 2 a base is included in an excess of the amine for the nucleophilic substitution reaction and the secondary amine is in a molar excess of ,-dialkylsulfanyl ester or ,-diarylsulfonyl ester of triblock copolymer POE.sub.w-POP.sub.y-POE.sub.w between 3 and 10 moles.

15. The process for bifunctionalization with secondary amines of triblock copolymer poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w), according to claim 14, where in the stage 2 the base or excess of amine is added in reagent-starved conditions at mass flow between 1 and 70 g/min.

16. The process for bifunctionalization with secondary amines of triblock copolymer poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w(POE.sub.w -POP.sub.y-POE.sub.w) according to claim 1,where in the stage 2 the weight (g)/volume (ml) ratio of ,-dialkylsulfonyl ester or ,-diarylsulfonyl ester of triblock copolymer POE.sub.w-POP.sub.y-POE.sub.w/solvent is between 1.0/1.0 and 1.0/10.0.

17. The process for bifunctionalization with secondary amines of triblock copolymer poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w), according to claim 16, where in the stage 2 the reaction is carried out at temperature of 35 to 85 C.

18. The process for bifunctionalization with secondary amines of triblock copolymer poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w), according to claim 17, where in the stage 2 the reaction times are in range of 3 to 8 hours.

19. The process for bifunctionalization with tertiary amines of triblock copolymer poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w), according to claim 1, where in the stage 2 the tertiary amines are selected from the group consisting of dibutylhexadecylamine, triisooctylamine, trioctylamine, 2-ethyl-N,N-bis(2-ethylhexyl)-hexylamine, dimethyl-docosyl-amine, N,N-dimethylhexadecylamine, trihexylamine, 1-benzyl-1H-imidazole, 1-methyl-1H-imidazole, 1-phenyl-1H-imidazole, 1-butyl-1H-imidazole, 1-vinyl-1H-imidazole, 1-ethyl-1H-imidazole, 1-lauryl-1H -imidazole, 1-cyano-1H-imidazole, 1-hexyl-1H-imidazole, 1-propyl-1H-imidazole, 1-benzyloxy-1H-imidazole, 1-ethoxy-1H-imidazole, 1-methoxy-1H-imidazole, 1-methoxymethyl-1H-imidazole, 1-benzydryl-1H-imidazole, 1-(diethoxymethyl)-1H -imidazole, 1-(triphenylmethyl)-1H-imidazole, 1-(2-methyl-phenyl)-isoquinoline, 1-(4-methyl-phenyl)-isoquinoline,1-(4-phenyl-phenyl)-isoquinoline, 3-(4-methoxy-phenyl) -isoquinoline, 3-(4-piperazinyl)-isoquinoline, 3-nitro-isoquinoline, 4-bromo-isoquinoline, 4-phenyl-sulfanyl-isoquinoline, 4-methyl-sulfanyl-isoquinoline, 5-nitro-isoquinoline, 5-bromo-isoquinoline, 6-bromo-isoquinoline, 7-octyloxy-isoquinoline, 5,8-dibromo -isoquinoline, quinoline, 8-(2-phenoxy-ethoxy)-quinoline, 2,8-dimethyl-quinoline, 3-nitroquinoline, 3-(3-methyl-phenyl)-quinoline, 3-(2-methyl-phenyl)-quinoline, -3-(4-methoxy-phenyl)-quinoline, 3-(3-methoxy-phenyl)-quinoline, 3-(2-methoxy-phenyl) -quinoline, 2-(benzyloxy)-quinoline, 2-(4-methyl-phenyl)-quinoline, 2-(2-methoxy -phenyl)-quinoline, 8-(4-nitro-phenoxy)-quinoline, 8-(4-phenoxy-butoxy)-quinoline,2,8-dimethyl-quinoline, 3,4-dimethyl-pyridine, 4-(4-nitro-phenyl)-pyridine, 3-(4-bromo-phenyl)-pyridine,3-(4-nitro-phenyl)-pyridine, and 4-(cyclohexyl-methyl)-pyridine.

20. The process for bifunctionalization with tertiary amines of triblock copolymer poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w), according to claim 1, where in the stage 2 the molar relationship of ,-dialkylsulfonyl ester or ,-diarylsulfonyl ester of triblock copolymer POE.sub.w-POP.sub.y-POE.sub.w/tertiary amine is between 1.0/2.2 and 1.0/4.5.

21. The process for bifunctionalization with secondary or tertiary amines of triblock copolymer poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w), according to claim 1, where in the stage 2 the amine is added at reagent-starved conditions at mass flow between 1 and 60 g/min.

22. The process for bifunctionalization with tertiary amines of triblock copolymer poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w), according to claim 1, where in the stage 2 the weight (g)/volume relationship (ml) ratio of ,-dialkylsulfonyl ester or ,-diarylsulfonyl ester of triblock copolymer POE.sub.w-POP.sub.y-POE.sub.w/solvent is between 1.0/2.0 and 1.0/7.0.

23. The process for bifunctionalization with tertiary amines of triblock copolymer poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w), according to claim 22, where in the stage 2 the reaction is carried out at temperature of 60 to 110 C.

24. The process for bifunctionalization with tertiary amines of triblock copolymer poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w), according to claim 23, where in the stage 2 the reaction times are in the range between 9and 15hours.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows the process diagram for the present invention. In stage 1, once the reaction time is complete, the reaction product is filtered. The organic phase is again charged to the reactor, and a secondary or tertiary amine is added and the reaction of stage 2 is carried out at the solvent boiling point. At the end of reaction time, the reaction product is filtered and solvent is eliminated by vacuum pressure distillation.

DETAILED DESCRIPTION OF THE INVENTION

(2) The synthesis process of the invention for the functionalization of triblock copolymers is described as follows. Stage 1 comprises the replacement of the ending hydroxyl group (OH) for the leaving group (TsCl). In stage 2, the substitution of tosylate ester for secondary or tertiary amines is carried out to obtain the triblock copolymer bifunctionalized with amines. This laboratory process is described in the Mx/a/2008/015756 and Mx/a/2013/002359. One example of the process according to the present invention is shown in the following reaction scheme:

(3) ##STR00003##

(4) Therefore, the present invention is the development of a synthesis process at semi-industrial and industrial scales to functionalize the monodispersed block copolymers with secondary or tertiary amines from the laboratory methods described in the patents mentioned earlier. The total synthesis of functionalized block copolymers takes into account two stages: 1) Stage 1 comprises or consists of the alkylsulfonation or arylsulfonation of triblock copolymer poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w), with average molecular weight M.sub.n in a range between 600 and 10,000 g/mol, to obtain the ,-dialkylsulfonyl ester or ,-diarylsulfonyl ester of poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w), where the number w and y are in the range of 10 to 60, more preferably between 15 and 50. 2) Stage 2 takes into account the nucleophilic substitution reaction of secondary or tertiary amines over the ,-dialkylsulfonyl ester or ,-diarylsulfonyl ester of poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w in order to obtain diamines of poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w copolymers.

(5) Outstanding characteristics of this development are: a) solvent is the same for stage 1 and 2; b) reduction of one unitary process in stage 1; c) reduction of two unitary process in the stage 2, when secondary amines are used; and d) modifications in the reaction conditions (temperature, reagents and molar relations) for both stages, having impact in a lower reaction time in each stage. FIG. 1 shows the process diagram for both stages of the present invention. The reactor should be of glass with a capacity of 1 to 100 L, with propeller stirrer of Teflon to avoid corrosion problems caused by alkylsulfonyl or arylsulfonyl chloride.

(6) Stage 1. Reaction temperature, which is carried out in stage 1, is set in a range between 5 to 50 C., preferably between 10 to 45 C., and more preferably between 15 to 35 C. Reaction times are set in a range between 1 to 8 hours, preferably of 3 to 6 hours. Molar relationship of triblock copolymer POE.sub.w-POP.sub.y-POE.sub.w/alkylsulfonyl or arylsulfonyl chloride is between 1.0/2.0 to 1.0/6.0, preferably between 1.0/2.2 to 1.0/4.5, and more preferably between 1.0/2.5 to 1.0/3.5. Alkylsulfonyl or arylsulfonyl chloride is added in reactant-starved condition at mass flow between 1 to 50 g/min, preferably between 5 to 40 g/min, and more preferably between 15 to 30 g/min. It is important that the usage of a base such as: bicarbonates (sodium, potassium, calcium or magnesium), carbonates (sodium, potassium, calcium or magnesium), triethylamine, tripropylamine, N,N-dimethylaniline or pyridine, in triblock copolymer POE.sub.w-POP.sub.y-POE.sub.w/base in a molar ratio between 1.0/2.0 to 1.0/8.0, preferably between 1.0/2.5 to 1.0/6.0 The base reacts in reagent-starved conditions at mass flow between 1 to 70 g/min, preferably between 5 to 60/g/min, and more preferably between 15 to 45 g/min. The reaction is carried out in solvents such as: acetonitrile, benzonitrile, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dioxane, dimethylformamide, dimethylsulfoxide, dimethylether ethyleneglycol, 2-methoxyethylether or tetrahydrofurane, at weight/volume ratio (w/v) of triblock POE.sub.w-POP.sub.y-POE.sub.w/solvent between 1.0/1.0 to 1.0/10.0, preferably between 1.0/2.0 to 1.0/7.0, and more preferably between 1.0/2.5 to 1.0/5.0. Finally, the product is filtered at reduced pressure or by a filter press. In one embodiment, the solvent is not removed from the resulting product.

(7) Stage 2 Synthesis of Y-POE.sub.w-POP.sub.y-POE.sub.w-Y (with Secondary Amines). Reaction temperature is set in a range between 30 to 100 C., preferably between 35 to 85 C. Reaction times are set in a range of 2 to 10 hours, preferably between 3 to 8 hours. Molar reaction of the secondary amine with respect to the ,-dialkylsulfonylester or ,-diarylsulfonyl ester of triblock copolymer POE.sub.w-POP.sub.y-POE.sub.w obtained in stage 1 is between 2.0 to 10.0 moles, preferably between 2.5 to 8.5 moles, and more preferably between 3.0 to 6.5 moles per mole of the POE.sub.w-POP.sub.y-POE.sub.w. In one embodiment, the ratio of POE.sub.w-POP.sub.y-POE.sub.w/tertiary amine is 1.0/2.1 to 1.0/5.0. The amine is added in reactant-starved conditions at mass flow between 1 to 60 g/min, preferably between 10 to 55 g/min, and more preferably between 15 to 45 g/min. The base in this stage are mainly: bicarbonates (sodium, potassium, calcium or magnesium), carbonates (sodium, potassium, calcium or magnesium), triethylamine, tripropylamine, N,N-dimethylaniline or pyridine, in a molar ratio of ,-dialkylsulfonyl ester or ,-diarylsulfonyl ester of triblock copolymer POE.sub.w-POP.sub.y-POE.sub.w between 2.0 to 8.0 moles, preferably between 3.0 to 6.5 moles. In one embodiment, the ratio of the POE.sub.w-POP.sub.y-POE.sub.w to the base can be 1:2 to 1:10. Also, a secondary amine can be used in an excess in molar relationship regarding the ,-dialkylsulfonyl ester or ,-diarylsulfonyl ester of triblock copolymer POE.sub.w-POP.sub.y-POE.sub.w between 3.0 to 10.0 moles, preferably between 4.0 to 8.0 moles. The base or amine excess is added in reagent-starved conditions at mass flow between 1 to 70 g/min, preferably between 10 to 60 g/min, and more preferably between 15 to 45 g/min. The reaction is carried out in solvents such as: acetonitrile, benzonitrile, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dioxane, dimethylformamide, dimethylsulfoxide, dimethylether ethyleneglycol, 2-methoxyethylether or tetrahydrofurane, at weight/volume relationship (w/v) of triblock POE.sub.w-POP.sub.y-POE.sub.w/solvent between. 1.0/1.0 to 1.0/10.0, preferably between 1.0/2.0 to 1.0/7.0, and more preferably between 1.0/2.5 to 1.0/5.0. In one embodiment, the POE.sub.w-POP.sub.y-POE.sub.w/solvent ratio is 1.0/1.0 to 1.0/15.0. Finally, the product is filtered at reduced pressure or by a filter press.

(8) Stage 2 Synthesis of Z-POE.sub.w-POP.sub.y-POE.sub.w-Z (with Tertiary Amines).

(9) Reaction temperature is set in range between 50 to 130 C., preferably between 60 to 110 C. Reaction times are set in a range from 7 to 17 hours, preferably between 9 to 15 hours. Molar relationship of the tertiary amine regarding ,-dialkylsulfonyl ester or ,-diarylsulfonyl ester of triblock copolymer POE.sub.w-POP.sub.y-POE.sub.w is between 2.1 to 5.0 moles, preferably between 2.2 to 4.5 moles, and more preferably between 2.5 to 4.0 moles per mole of POE.sub.w-POP.sub.y-POE.sub.w. The amine is added in reagent-starved conditions at mass flow between 1 to 60 g/min, preferably between 10 to 55 g/min, and more preferably between 15 to 45 g/min. The reaction is carried out in a solvent such as: acetonitrile, benzonitrile, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dioxane, dimethylformamide, dimethylsulfoxide, dimethylether ethyleneglycol, 2-methoxyethylether or tetrahydrofurane, a weight:volume ratio (w/v) of triblock POE.sub.w-POP.sub.y-POE.sub.w/solvent between 1.0/1.0 to 1.0/15.0, or 1.0/1.0 to 1.0/10.0, preferably between 1.0/2.0 to 1.0/7.0, and more preferably between 1.0/2.5 to 1.0/5.0. Finally, the product is filtered at reduced pressure or by a filter press, and solvent is eliminated by distillation at reduced pressure.

(10) In stage 1 of the process, the alkylsulfonyl or arylsulfonyl chloride can be 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, biphenyle-4-sulfonyl chloride, 4-chlorobiphenyle-4-sulfonyl chloride, 4-metoxybiphenyl-4-sulfonyl chloride, 4-fluorobiphenyl-4-sulfonyl chloride, 4-methylbiphenyle-4-sulfonyl chloride, and 4-bromobenzenesulfonyl chloride.

(11) In stage 2 of the process, the secondary amine can be selected from the group consisting of ammonia, amylamine, iso-amylamine, tert-amylamine, 1-ethylpropylamine, hexylamine, 2-amine-5-methylhexane, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, undecylamine, 3-(cyclohexyl)propane-1-amine, (2-methylbutyl)amine, tris-(2-ethylhexyl)amine, 1-ethoxypropane-2-amine, (3-methylpentyl)amine, 2-phenylbutane-1-amine, tetrahydro-2H-pirane-3-amine, methoxy-polyethyleneglycolamine, (3-butoxyphenyl)amine, (2-cyclooctylethyl)amine, (2-cycloheptyl)amine, (3-cyclopentylpropyl)amine, 3-(4-isopropylphenyl)propane-1-amine, 2-ethyl-1-phenylbutane-1-amine, cyclopentylamine, cycloheptylamine, cycloheptylmethylamine, cyclohexylamine, cyclooctylamine, benzylamine, (2,2-dimethylpropyl)(methyl)amine, N-methyl-N-(1-pentylethyl)amine, (4-chloro-benzyl)-methylamine, bis-(2-ethylhexyl)amine, N-benzyl-N-(2-methoxyethyl)amine, diisopropylamine, 2-(methylamine)-ethanol, 2-(butylamine)-ethanol, 2-(benzylamine)-ethanol, 2-(cyclohexylamine)-ethanol, 2-(ter-butylamine)-ethanol, 2-(phenylamine)-ethanol, 2-(n-propylamine)-ethanol, 2-(iso-propylamine)-ethanol, 2-(hydroxymethylamine)-ethanol, 2,2-imidoethanol, 1,1-iminodi-2-propanol, 4-(butylamine)-1-butanol, 1-benzylpiperazine, 1-phenylpiperazine, 2-(hexylamino)-ethanol, 1-acetylpiperazine, 1-(ortho-chlorophenyl)-piperazine, 1-ethylpiperazine, 1-(methyl-tolyl)-piperazine, 1-(4-nitrophenyl)-piperazine, 4-benzylpiperidine, 4-methylpiperidine, 2-methylpiperidine, 2-ethylpiperidine, 3,5-dimethylpiperidine, piperidine-3-ol, piperidine-4-ol, trans-3,5-dimethylpiperidine, cis-3,5-dimethylpiperidine, 3-methylpiperidine, piperidine-3-ylmethanol, 3,3-dimethylpiperidine, 4-phenylpiperidine-3-ol, 4-phenyl-piperidine, 4-(piperidine-4-il)morpholine, 4,4-bipiperidine, pyrrolidine-3-amine, 2,6-dimethylmorpholine, morpholine, pyrrolidine-2-ylmethanol, trans-2,5-dimethylpyrrolidine, cis-2,5-dimethylpyrrolidine, diphenylamine, 2-nitro-diphenylamine, 4-nitro-diphenylamine, pyrrolidine, 4,4-bis(dimethylamine)-diphenylamine, 2,4-dinitro-diphenylamine, 4,4-dimethoxy-diphenylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dioctylamine, didecylamine, didodecylamine, dinonylamine, N-methyl-hexylamine, di-iso-propylamine, N-iso-propyl-tert-butylamine, N-ethyl-ter-butylamine, N-ethyl-butylamine, di-isobutylamine, iso-butyl-sec-butylamine, di-iso-pentylamine, ethyl-n-dodecylamine, di-ter-amyl-amine, N-methyl-pentylamine, N-methyl-butylamine, N-methyl-ter-butylamine, N-ethyl-iso-propylamine, N-ethyl-propylamine, N-methyl-octylamine, and piperidine.

(12) In stage 2of the process, the secondary amine can be selected from the group consisting of ammonia, amylamine, iso-amylamine, tert-amylamine, 1-ethylpropylamine, hexylamine, 2-amine-5-methylhexane, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, undecylamine, 3-(cyclohexyl)propane-l-amine, (2-methylbutyl)amine, tris-(2-ethylhexyl)amine, 1-ethoxypropane-2-amine, (3-methylpentyl)amine, 2-phenylbutane-l-amine, tetrahydro-2H-pirane-3-amine, methoxy-polyethyleneglycolamine, (3-butoxyphenyl)amine, (2-cyclooctylethyl)amine, (2-cycloheptyl)amine, (3-cyclopentylpropyl)amine, 3-(4-isopropylphenyl)propane-1-amine, 2-ethyl-l-phenylbutane-1-amine, cyclopentylamine, cycloheptylamine, cycloheptylmethylamine, cyclohexylamine, cyclooctylamine, benzylamine, (2,2-dimethylpropyl)(methyl)amine, N-methyl-N-(1-pentylethyl)amine, (4-chloro-benzyl)-methylamine, bis-(2-ethylhexyl)amine, N-benzyl-N-(2-methoxyethyl)amine, diisopropylamine, 2-(methylamine)-ethanol, 2-(butylamine)-ethanol, 2-(benzylamine)-ethanol, 2-(cyclohexylamine)-ethanol, 2-(ter-butylamine)-ethanol, 2-(phenylamine)-ethanol, 2-(n-propylamine)-ethanol, 2-(iso-propylamine)-ethanol, 2-(hydroxymethylamine)-ethanol, 2,2-imidodiethanol, 1,1-iminodi-2-propanol, 4-(butylamine)-1-butanol, 1-benzylpiperazine, 1-phenylpiperazine, 2-(hexylamino)-ethanol, 1-acetylpiperazine, 1-(ortho-chlorophenyl)-piperazine, 1-ethylpiperazine, 1-(methyl-tolyl)-piperazine, 1-(4-nitrophenyl)-piperazine, 4-benzylpiperidine, 4-methylpiperidine, 2-methylpiperidine, 2-ethylpiperidine, 3,5-dimethylpiperidine, piperidine-3-ol, piperidine-4-ol, trans-3,5-dimethylpiperidine, cis-3,5-dimethylpiperidine, 3-methylpiperidine, piperidine-3-ylmethanol, 3,3-dimethylpiperidine, 4-phenylpiperidine-3-ol, 4-phenyl-piperidine, 4-(piperidine-4-il)morpholine, 4,4-bipiperidine, pyrrolidine-3-amine, 2,6-dimethylmorpholine, morpholine, pyrrolidine-2-ylmethanol, trans-2,5-dimethylpyrrolidine, cis-2,5-dimethylpyrrolidine, diphenylamine, 2-nitro-diphenylamine, 4-nitro-diphenylamine, pyrrolidine, 4,4-bis(dimethylamine)-diphenylamine, 2,4-dinitro-diphenylamine, 4,4-dimethoxy-diphenylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dioctylamine, didecylamine, didodecylamine, dinonylamine, N-methyl-hexylamine, di-iso-propylamine, N-iso-propyl-tert-butylamine, N-ethyl-ter-butylamine, N-ethyl-butylamine, di-isobutylamine, iso-butyl-sec-butylamine, di-iso-pentyl amine, ethyl-n-dodecylamine, di-ter-amyl-amine, N-methyl-pentylamine, N-methyl-butylamine, N-methyl-ter-butylamine, N-ethyl-iso-propylamine, N-ethyl-propylamine, N-methyl-octylamine, and piperidine.

(13) Stage 1. Alkylsulfonation or Arylsulfonation of Triblock Copolymer Poly(Oxyethylene).sub.w-Poly(Oxypropylene).sub.y-Poly(Oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w)

EXAMPLE 1

(14) In a 1 L reactor having a Teflon mechanical stirrer and temperature regulator bath, is added 250 g (0.1051 mol) of poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w) copolymer dissolved in 250 mL of a solvent. At a temperature of 15 C. is added with a dispenser pump 0.2261 moles of alkylsulfonyl or arylsulfonyl chloride dissolved in 75 mL of solvent at reagent-starved conditions. Afterwards, 0.3153 mol of base in 75 mL of solvent is added at reagent-starved conditions. The reactor mixture is agitated for 3 hours, followed by filtration at reduced pressure. 270 g of ,-dialkylsulfonyl ester or ,-diarylsulfonyl ester of poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w) in 400 mL of solvent was obtained as a yellow viscous liquid. Spectroscopic characterization of ,-dialkylsulfonyl ester or ,-diarylsulfonyl ester of poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w) is the following: .sup.13C NMR (CDCl.sub.3) 9.47, 17.32, 17.44, 18.27, 46.09, 68.57, 68.65, 68.70, 69.54, 70.61, 70.79, 70.89, 72.93, 73.41, 75.11, 75.31, 75.34, 75.50, 127.92, 129.71, 133.77, 135.26.

EXAMPLE 2

(15) In a 1 L reactor having a Teflon mechanical stirrer and temperature regulator bath, 250 g (0.1051 mol) of poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w) copolymer dissolved in 250 mL of solvent was added. At a temperature of 25 C., 0.2261 mol of alkylsulfonyl or arylsulfonyl chloride at reagent-starved conditions was added with a dispenser pump. Afterwards, from 0.2628 mol to 0.3153 mol of base at reagent-starved conditions was added by a dispenser pump. The reaction mixture is agitated for 6 hours, followed by filtration at reduced pressure. 270 g of ,-dialkylsulfonyl ester or ,-diarylsulfonyl ester of poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w) in 250 mL of solvent was obtained.

(16) Stage 2. Nucleophilic Substitution Over ,-Dialkylsulfonyl Ester or ,-Diarylsulfonyl Ester of Triblock Copolymer Poly(Oxyethylene)w-Poly(Oxypropylene)y-Poly(Oxyethylene)w (POE.sub.w-POP.sub.y-POE.sub.w)

(17) Stage 2 Synthesis of Y-POE.sub.w-POP.sub.y-POE.sub.w-Y (With Secondary Amines).

EXAMPLE 3

(18) In a 1 L reactor provided with a Teflon mechanical stirrer and temperature regulator bath, 270 g (0.1016 mol) of product of example 2, ,-dialkylsulfonyl ester or ,-diarylsulfonyl ester of poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w) dissolved in 250 mL of solvent, and from 0.2032 mol to 0.3048 mol of base in reagent-starved conditions are added; subsequently 0.2184 mol of secondary amine in reagent-starved conditions is added, and the mixture is heated at a temperatures between 42 to 62 C. for 6 hours. Such mixture is filtered at reduced pressure and solvent was distilled at reduced pressure.

EXAMPLE 4

(19) In a 1 L reactor provided with a Teflon mechanical stirrer and temperature regulator bath, is added 270 g (0.1016 mol) of product of example 2, ,-dialkylsulfonyl ester or ,-diarylsulfonyl ester of poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w) dissolved in 250 mL of solvent, from 0.2032 mol to 0.3048 mol of basis at reagent-starved conditions is added; subsequently from 0.2184 mol to 0.4064 mol of secondary amine at reagent-starved conditions is added, the mixture is heated at a temperature between 60 to 85 C. for 3 hours. Once phases are separated, the inferior phase is filtered at reduced pressure and the solvent is distilled at reduced pressure.

EXAMPLE 5

(20) In an 8 L reactor provided with a mechanical stirrer, reflux system and temperature regulator bath, 2700 g (1.0160 mol) of product of example 2, ,-dialkylsulfonyl ester or ,-diarylsulfonyl ester of poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w) dissolved in 2500 mL of solvent is added, and between 4.0640 mol to 8.1280 mol of secondary amine at reagent-starved conditions is added, the mixture is heated at a temperature between 50 to 75 C. for 10 hours. At the end of the reaction time, the phases are separated, the inferior phase is filtered at reduced pressure and solvent is distilled at reduced pressure.

EXAMPLE 6

(21) In an 8 L reactor provided with a mechanical stirrer, reflux system and temperature regulator bath, 2700 g (1.0160 mol) of product of example 2, ,-dialkylsulfonyl ester or ,-diarylsulfonyl ester of poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w) dissolved in 2500 mL of solvent is added, and from 2.0320 mol to 3.0480 mol of secondary amines is added, the mixture is heated at temperature between 80 to 100 C. for 5 hours. At the end of the reaction time, the phases are separated, the inferior phase is filtered at reduced pressure and solvent is distilled at reduced pressure.

(22) Stage 2 Synthesis of Z-POE.sub.w-POP.sub.y-POE.sub.w-Z (With Tertiary Amines).

EXAMPLE 7

(23) In a 1 L reactor provided with a Teflon mechanical stirrer and temperature regulator bath, 270 g (0.1016 mol) of product of example 1, ,-dialkylsulfonyl ester or ,-diarylsulfonyl ester of poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w) dissolved in 250 mL of solvent is added, 0.2184 mol of tertiary amine under reagent-starved conditions is added, the mixture is heated at solvent boiling point at temperature between 55 to 75 C. for 17 hours. Such mixture is filtered at reduced pressure and solvent is distilled at reduced pressure.

EXAMPLE 8

(24) In a 1 L reactor provided with a Teflon mechanical stirrer and temperature regulator bath, 270 g (0.1016 mol) of product of example 1, ,-dialkylsulfonyl ester or ,-diarylsulfonyl ester of poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w) dissolved in 250 mL of solvent is added, 0.3084 mol of tertiary amine at regent-starved conditions is added, the mixture is heated at solvent boiling point at temperature between 75 to 95 C., for 12 hours. Once the phases are separated, the inferior phase is filtered at reduced pressure and solvent is distilled at reduced pressure.

EXAMPLE 9

(25) In an 8 L reactor provided by mechanical stirrer, reflux system and temperature regulator bath, 2160 g (0.8128 mol) of product of example 2, ,-dialkylsulfonyl ester or ,-diarylsulfonyl ester of poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w (POE.sub.w-POP.sub.y-POE.sub.w) dissolved in 2000 mL of solvent is added, 3.2512 mol of tertiary amine at reagent-starved conditions is added, the mixture is heated at solvent boiling point at temperature between 100 to 130 C., for 7 hours. Once the phases are separated, the inferior phase is filtered at reduced pressure and solvent is distilled at reduced pressure.