Surfactant composition comprising ether compound and catalytic process for manufacturing thereof

Abstract

Disclosed is a process for preparing at least one ether compound, comprising reacting at least one alcohol (I) with at least one polyol (II) in the presence of a functional polymer [polymer (F)] as a catalyst (X), wherein: the alcohol (I) is represented by the general formula (1): R1-OH (1) wherein R1 is a hydrocarbon group having 1 to 36 carbon atoms, the polyol (II) is represented by the general formula (2): R2-(OH) m (2) wherein R2 represents the skeleton moiety of the polyol and m is an integer of from 2 to 20, and polymer (F) is a polymer comprising recurring units derived from at least one ethylenically unsaturated monomer [monomer (M)] and bearing at least one cation exchange group. Further disclosed is a surfactant composition obtained by said process, and featuring an excellent detergency performance.

Claims

1. A process for preparing at least one ether compound, the process comprising reacting at least one alcohol (I) with at least one polyol (II) in the presence of a functional polymer [polymer (F)] as a catalyst (X), wherein: the alcohol (I) is a compound represented by the general formula (1):
R.sub.1OH(1) wherein R.sub.1 is a hydrocarbon group having 1 to 36 carbon atoms, the polyol (II) is represented by the general formula (2):
R.sub.2(OH).sub.m(2) wherein R.sub.2 represents the skeleton moiety of the polyol and m is an integer of from 2 to 20, and the polymer (F) is a polymer comprising recurring units derived from at least one ethylenically unsaturated monomer [monomer (M)] and bearing at least one cation exchange group; wherein the reaction of the at least one alcohol (I) with the at least one polyol (II) in the presence of the functional polymer [polymer (F)] as the catalyst is performed in the absence of a solvent, and a medium for the reaction of the at least one alcohol (I) with the at least one polyol (II) in the presence of the functional polymer [polymer (F)] as the catalyst is substantially free of any surfactant at the start of the reaction.

2. The process of claim 1, wherein the at least one cation exchange group in the polymer (F) is selected from the group consisting of: SO.sub.2X, wherein X is halogen or O.sup.M.sup.+, wherein M.sup.+ is a cation selected from the group consisting of H.sup.+, NH.sub.4.sup.+, K.sup.+, Li.sup.+, Na.sup.+, and mixtures thereof; COY, wherein Y is halogen; O.sup.M.sup.+, wherein M.sup.+ is a cation selected from the group consisting of H.sup.+, NH.sub.4.sup.+, K.sup.+, Li.sup.+, and Na.sup.+; OR.sub.Hy wherein R.sub.Hy is a C.sub.1-C.sub.6 hydrocarbon group; OR.sub.Hf wherein R.sub.Hf is a C.sub.1-C.sub.6 fluorocarbon or per(halo)fluorocarbon group; N(R.sub.Hy*).sub.2, wherein R.sub.Hy*, equal or different at each occurrence, is hydrogen or a C.sub.1-C.sub.6 hydrocarbon group, or mixtures thereof; and PO.sub.2Z, wherein Z is halogen; O.sup.M.sup.+, wherein M.sup.+ is a cation selected from the group consisting of H.sup.+, NH.sub.4.sup.+, K.sup.+, Li.sup.+, and Na.sup.+; OR.sub.Hy wherein R.sub.Hy is a C.sub.1-C.sub.6 hydrocarbon group, OR.sub.Hf wherein R.sub.Hf is a C.sub.1-C.sub.6 fluorocarbon or per(halo)fluorocarbon group, or mixture thereof.

3. The process of claim 2, wherein each of X, Y and Z is independently O.sup.H.sup.+.

4. The process of claim 2, wherein the cation exchange group complies with formula SO.sub.2X.

5. The process of claim 2, wherein the polymer (F) comprises recurring units derived from styrene.

6. The process of claim 4, wherein the polymer (F) is selected from a group consisting of sulfonated styrene-divinylbenzene copolymers, sulfonated crosslinked styrene polymers, phenol-formaldehyde-sulfonic acid copolymers, and benzene-formaldehyde-sulfonic acid copolymers.

7. The process of claim 1, wherein the polymer (F) consists essentially of: recurring units derived from one or more than one ethylenically unsaturated monomer comprising at least one fluorine atom and free from hydrogen atoms; and recurring units derived from one or more than one ethylenically unsaturated monomer comprising at least one fluorine atom and at least one cation exchange group, and free from hydrogen atoms (except those optionally in the cation exchange group).

8. The process of claim 7, wherein the polymer (F) consists essentially of: from 5 to 25% by moles of recurring units derived from (perfluoro-2-(2-fluorosulfonylethoxy)propylvinyl ether) (PSEPVE) and/or perfluoro-5-sulphonylfluoride-3-oxa-1-pentene (SFVE), in their SO.sub.2F or SO.sub.2X form, wherein X is halogen or O.sup.M.sup.+, wherein M.sup.+ is a cation selected from the group consisting of H.sup.+, NH.sub.4.sup.+, K.sup.+, Li.sup.+, Na.sup.+, or mixtures thereof; and from 95 to 75% by moles of recurring units derived from tetrafluoroethylene (TFE).

9. The process of claim 1, wherein the polymer (F) is used as a supported catalyst (X).

10. The process of claim 1, wherein the polymer (F) is grafted to or supported on solid particles having a medium diameter between 2 and 200 nm.

11. The process of claim 9, wherein the polymer (F) comprises recurring units derived from styrene.

12. A surfactant composition [composition (S)] consisting of: (i) more than one ether compound of formula (3) [ether (E1)], ##STR00022## wherein: p is an integer from 1 to 36, and radicals R.sup.1, R.sup.2, and R.sup.3, being same or different, are independently a hydrogen atom or a hydrocarbon group having 1 to 36 carbon atoms and optionally containing oxygen atom, provided that R.sup.2 and R.sup.3 are not hydrogen at the same time, and wherein R.sup.2 optionally join together with R.sup.1 or R.sup.3 to form at least one oxygen-containing cyclic group having 3 to 7 carbon atoms; (ii) at least one polyol (II) compound represented by the general formula (2):
R.sub.2(OH).sub.m(2) wherein R.sub.2 represents the skeleton moiety of the polyol and m is an integer of from 2 to 20; and, (ii) optionally, at least one mono alkyl glyceryl ether (MAGE) compound of formula (4): ##STR00023## wherein a is an integer of from 1 to 20, and radical R.sub.1 is a hydrocarbon group having 1 to 36 carbon atoms, wherein the ether (M1) components contain at least one ether compound of formula (5) [ether (E1-A)]: ##STR00024## wherein: n is an integer from 0 to 36, and radicals R.sup.4, R.sup.5 and R.sup.6, being same or different, are independently a hydrogen atom or a hydrocarbon group having 1 to 36 carbon atoms and optionally containing oxygen atom, wherein R.sup.5 optionally join together with R.sup.4 or R.sup.6 to form at least one oxygen-containing cyclic group having 3 to 7 carbon atoms.

13. The process of claim 1, wherein the process comprises the following steps: a) mixing the at least one alcohol (I), the at least one polyol (II), and the catalyst (X); b) proceeding to the reaction of the ether compound by setting a temperature (T); and c) isolating the ether compound, wherein the ether compound includes at least one MAGE compound of formula (4) ##STR00025## wherein a is an integer of from 1 to 20, and radical R.sub.1 is a hydrocarbon group having 1 to 36 carbon atoms, and wherein the isolation step c) may be carried out according to the following steps: c1) adding ethanol, water or mixture thereof into the reaction mixture obtained from step b); c2) neutralizing the resultant solution of step c1) and filtering to obtain a filtrate; c3) washing the filtrate obtained from step c2) with a polar solvent; c4) concentrating the washed filtrate obtained from step c3) to obtain a concentrated liquid; and, c5) drying the concentrated liquid from step c4) and obtaining a crude MAGE compound.

14. The process of claim 2, wherein the halogen is Cl, F, Br, or I.

15. The process of claim 8, wherein M.sup.+ is H.sup.+.

16. The process of claim 10, wherein the solid particles having a medium diameter between 10 and 50 nm.

17. An application for home care or personal care comprising the composition (S) of claim 12.

Description

DESCRIPTION OF EMBODIMENTS

(1) The present invention will be further illustrated with reference to the following examples.

EXAMPLES

Raw Materials

(2) NAFION NR50 polymer: a TFE/PSEPVE copolymer commercially available from Aldrich. Aquivion D66-20BSX polymer: a TFE/SFVE copolymer in pellet form, available from Solvay Specialty Polymers Italy S.p.A. 732 Cation exchange resin: a sulfonated styrene-divinylbenzene copolymer from Sinopharm Chemical Reagent Co., Ltd AEO7: Fatty alcohol polyoxyethylene (7) ether from Rhodia, Rhodasurf L-7/90. MAGE4: Dodecyl polyglyceryl ether from Daicel Chemical Industries Ltd.
Preparation and Characterization of Ether Compositions

Example 1

Etherification of Glycerol and Dodecanol with a TFE/PSEPVE Copolymer as Catalyst

(3) In a 20 mL Schlenk tube fitted with inside water trap, dodecanol (1.60 g), glycerol (3.16 g) and Nafion NR50 (0.58 g, 6% eq. to dodecanol) were added. The reaction mixture was vigorously stirred at 150 C. for 24 hrs under static vacuum. After the mixture cooled, pyridine was added to neutralize the catalyst, then precipitated in large excess of THF/diethyl ether (1:1). The obtained solution was concentrated by a rotavap. After most of dodecanol were removed through distillation under high vacuum, the residue was dissolved in methanol/H.sub.2O (10:1 V:V) solution, further washed with heptane. The remaining solution was concentrated by rotavap and further dried in vacuum oven at 50 C. overnight. 1.92 g of viscous product was obtained.

(4) GC analysis wt %: C12OH=0.75; MAGE1=0.31; DE=0.15; MAGE2=2.28.

(5) .sup.1H NMR (CDCl.sub.3): 0.9 ppm (t, 3H, CH.sub.3 of dodecane groups), 1.3 ppm (s, 17.99H, CH.sub.3CH.sub.2CH.sub.2 of dodecane groups), 1.65 ppm (sextuplet, 2.77H, CH.sub.3CH.sub.2CH.sub.2 of dodecane groups), 3.25-4.20 ppm (m, 14.77H, CH.sub.2O and >CHO glyceryl units and dodecyl group).

Example 2

Etherification of Glycerol and Dodecanol with a TFE/SFVE Copolymer as Catalyst

(6) In a 250 mL two-neck round-bottomed flask fitted with magnetic stir bar and a water trap on one neck, dodecanol (24.1 g), glycerol (47.8 g) and Aquivion D66-20BSX (4.44 g, 6% eq. to dodecanol) were added. The reaction mixture was vigorously stirred at 150 C. for 24 hrs under static vacuum. After the mixture cooled, pyridine was added to neutralize the catalyst, then precipitated in large excess of THF/diethyl ether (1:1). The obtained solution was concentrated by rotavap. After most of dodecanol was removed through distillation under high vacuum, the residue was dissolved in methanol/H.sub.2O (10:1 V:V), further washed with heptane. The remaining solution was concentrated by rotavap and further dried in vacuum oven at 50 C. overnight. 23.0 g of viscous product was obtained. The obtained product was characterized by .sup.1H NMR, GC and HPLC to get the average compositions which was listed in Table 1.

Example 3

Etherification of Glycerol and Dodecanol with a TFE/SFVE Copolymer as Catalyst

(7) In a 250 mL jacket reactor fitted with mechanic stir and a water trap on one neck, dodecanol (16.0 g), glycerol (32.6 g) and Aquivion D66-20BSX (2.94 g, 6% eq. to dodecanol) were added. The reaction mixture was vigorously stirred at 150 C. for 18 hrs under moderate vacuum (200 mbar). After the mixture cooled, pyridine was added to neutralize the catalyst, then precipitated in large excess of THF/diethyl ether (1:1). The obtained solution was concentrated by rotavap. After most of dodecanol was removed through distillation under high vacuum, the residue was dissolved in methanol/H.sub.2O (10:1 V:V), further washed with heptane. The remaining solution was concentrated by rotavap and further dried in vacuum oven at 50 C. overnight. 20.0 g of viscous product was obtained. The obtained product was characterized by .sup.1H NMR, GC and HPLC to get the analysis results listed in Table 1.

Example 4

Etherification of Triglycerol and Dodecanol with a TFE/SFVE Copolymer as Catalyst

(8) In a 250 mL two-neck round-bottomed flask fitted with magnetic stir bar and a water trap on one neck, dodecanol (20.0 g), triglycerol (39.5 g) and Aquivion D66-20BSX (2.11 g, 3% eq. to dodecanol) were added. The reaction mixture was vigorously stirred at 156 C. for 23 hrs under static vacuum. After the mixture cooled, diluted with THF and neutralized by pyridine, then centrifuged to remove insoluble polyglycerol and catalysts. The concentrated mixture from solution was diluted in 90 mL of MeOH and 30 mL of water, the product is extracted twice with 30 mL of heptane, then concentrated and dried overnight in the oven, 38.92 g of product was obtained as a highly viscous oil. The thus obtained product was characterized by .sup.1H NMR, GC and HPLC to get the analysis results listed in Table 1.

Example 5

Etherification of Triglycerol and Dodecanol with a TFE/SFVE Copolymer as Catalyst

(9) In a 250 mL two-neck round-bottomed flask fitted with magnetic stir bar and a water trap on one neck, dodecanol (15.0 g), triglycerol (44.5 g) and Aquivion D66-20BSX (1.59 g, 3% eq. to dodecanol) were added. The reaction mixture was vigorously stirred at 156 C. for 34.5 hrs under static vacuum. After the mixture cooled, diluted with THF and neutralized by pyridine, then centrifuged to remove insoluble polyglycerol and catalysts. The concentrated mixture from solution was diluted in 90 mL of MeOH and 30 mL of water, the product is extracted twice with 30 mL of heptane, then concentrated and dried overnight in the oven, 36.82 g of product are obtained as a very viscous oil. The obtained product was characterized by .sup.1H NMR, GC and HPLC to get the analysis results listed in Table 1.

Example 6

Etherification of Triglycerol and Dodecanol with a TFE/SFVE Copolymer as Catalyst

(10) In a 250 mL two-neck round-bottomed flask fitted with magnetic stir bar and a water trap on one neck, dodecanol (11.0 g), triglycerol (43.5 g) and Aquivion D66-20BSX (1.30 g, 3% eq. to dodecanol) were added. The reaction mixture was vigorously stirred at 156 C. for 20 hours under static vacuum. After the mixture cooled, diluted with THF and neutralized by pyridine, then centrifuged to remove insoluble polyglycerol and catalysts. The concentrated mixture from solution was diluted in 90 mL of MeOH and 30 mL of water, the product is extracted twice with 30 mL of heptane, then concentrated and dried overnight in the oven, 36.1 g of product are obtained as a very viscous oil. The obtained product was characterized by .sup.1H NMR, GC and HPLC to get the analysis results listed in Table 1.

Example 7

Etherification of Glycerol and Dodecanol with a TFE/SFVE Copolymer as Catalyst

(11) In a 250 mL two-neck round-bottomed flask fitted with magnetic stir bar and a water trap on one neck, glycerol (44.6 g) and Aquivion D66-20BSX (1.34 g) were added. The mixture was dehydrated at 156 C. with stirring for 18.5 hours, about 7.14 g of water was collected. 15.01 g of dodecanol are added to the mixture and the system again was sealed under vacuum as before, continued being reacted for another 35 hours. After the mixture cooled, diluted with THF and neutralized by pyridine, then centrifuged to remove insoluble polyglycerol and catalysts. The concentrated mixture from solution was diluted in 90 mL of MeOH and 30 mL of water, the product is extracted twice with 30 mL of heptane, then concentrated and dried overnight in the oven, 33.1 g of product are obtained as a very viscous oil. The obtained product was characterized by .sup.1H NMR, GC and HPLC to get the analysis results listed in Table 1.

Example 8

Etherification of Glycerol and Dodecanol with a TFE/SFVE Copolymer as Catalyst

(12) In a 250 mL two-neck round-bottomed flask fitted with magnetic stir bar and a water trap on one neck, glycerol (47.5 g) and Aquivion (1.42 g) were added. The mixture was dehydrated at 156 C. with stirring for 18 h30, about 6.24 g of water was collected. 12.01 g of dodecanol are added to the mixture and the system again was sealed under vacuum as before, continued being reacted for another 16 hours. After the mixture cooled, diluted with THF and neutralized by pyridine, then centrifuged to remove insoluble polyglycerol and catalysts. The concentrated mixture from solution was diluted in 90 mL of MeOH and 30 mL of water, the product is extracted twice with 30 mL of heptane, then concentrated and dried overnight in the oven, 35.5 g of product are obtained as a very viscous oil. The obtained product was characterized by .sup.1H NMR, GC and HPLC to get the analysis results listed in Table 1.

Example 11

Etherification of Glycerol and Dodecanol with a Strong Acidic Polystyenic Exchange Resin as Catalyst

(13) In a 20 mL Schlenk tube fitted with inside water trap, dodecanol (1.60 g), glycerol (3.16 g) and 732 Cation exchange resin (0.19 g, 10% eq. to dodecanol) were added. The reaction mixture was vigorously stirred at 150 C. under static vacuum for 48 hrs. After the mixture was cooled and diluted with THF, the catalyst was collected by centrifuge. The obtained solution was concentrated by rotavap. After most of dodecanol were removed through distillation under high vacuum, the residue was dissolved in methanol/H.sub.2O (10:1 V:V), further washed with heptane. The remaining solution was concentrated by rotavap and further dried in vacuum oven at 50 C. overnight. 1.82 g of viscous product was obtained.

(14) GC analysis wt %: C12OH=0.75; MAGE1=0.31; DE=0.15; MAGE2=2.28.

(15) .sup.1H NMR (CDCl.sub.3): 0.9 ppm (t, 3H, CH.sub.3 of dodecane groups), 1.3 ppm (s, 17.99H, CH.sub.3CH.sub.2CH.sub.2 of dodecane groups), 1.65 ppm (sextuplet, 2.77H, CH.sub.3CH.sub.2CH.sub.2 of dodecane groups), 3.25-4.20 ppm (m, 14.77H, CH.sub.2O and >CHO glyceryl units and dodecyl group).

Example 12

Etherification of Glycerol and Dodecanol with a Strong Acidic Polystyrenic Exchange Resin as Catalyst

(16) In a 20 mL Schlenk tube fitted with inside water trap, glycerol (6.32 g) and 732 Cation exchange resin (0.19 g, 0.9 eq. H.sup.+) were added. The reaction mixture was vigorously stirred at 150 C. under static vacuum for 12 hrs. Then, dodecanol (1.60 g) was added to the produced mixture, and the system again was sealed under vacuum as before, continued being reacted for another 16 hours. After the mixture cooled, diluted with mixture of water and methanol (20 mL, 10:1, v/v), the catalysts were recovered through centrifugation. The solution was extracted twice with 10 mL of heptane, then concentrated and dried overnight in the oven. 4.5 g of product was obtained as a very viscous oil.

(17) GC analysis wt %: C.sub.12OH=1.75; MAGE1=0.51; DE=0.35; MAGE2=3.28.

(18) .sup.1H NMR (CDCl.sub.3): 0.9 ppm (t, 3H, CH.sub.3 of dodecane groups), 1.3 ppm (s, 17.99H, CH.sub.3CH.sub.2CH.sub.2 of dodecane groups), 1.65 ppm (sextuplet, 2.77H, CH.sub.3CH.sub.2CH.sub.2 of dodecane groups), 3.25-4.20 ppm (m, 18.6, CH.sub.2O and >CHO glyceryl units and dodecyl group).

(19) TABLE-US-00001 TABLE 1 Composition characterized by .sup.1H NMR, GC and HPLC (wt %) Ether Effective C12OH C12-ether (P)glycerol product G/D molar Sample (%).sup.a (%).sup.a (%).sup.b (%).sup.c ratio.sup.d Ex. 2 0.71 n.d.* 12.9 86.4 1.43 Ex. 3 1.69 0.48 11.2 86.6 3.24 Ex. 4 4.01 1.74 13.6 80.0 3.43 Ex. 5 2.06 0.67 34.2 62.3 3.79 Ex. 6 0.55 0.24 41.4 57.9 3.90 Ex. 7 1.55 0.60 14.2 83.1 3.75 Ex. 8 1.52 0.16 22.0 76.3 4.64 *not detectable .sup.aThe weight concentrations of dodecanol (C12OH) and dodecyl ether (C12-ether) were analysed by GC .sup.b(P)glycerol concentration was analysed by HPLC .sup.cThe weight concentration of the ether products formed by (poly)glycerol and dodecanol reactants in each Example was deducted from the measured weight concentrations of dodecanol (C12OH), dodecyl ether (C12-ether), and (P)glycerol. .sup.dThe ratio of glyceryl to dodecyl (G/D) in the product was obtained from .sup.1H NMR characterization data after subtracting the contribution of impurities, i.e. C12OH, C12-ether and (P)glycerol.

(20) Properties of the obtained ether compositions are detailed in Table 2 below, in which several commercially available surfactants (AEO7 and MAGE4) were used for comparison of surfactant properties with the ether compositions obtained by Examples 2-8.

(21) TABLE-US-00002 TABLE 2 CMC ST at CMC Foam at 2.5 Sample (%).sup.e (mN/m).sup.e g/l (mm).sup.f Ex. 2 NA 28 67 Ex. 3 NA 25 23 Ex. 4 0.068 28 85 Ex. 5 0.053 27 105 Ex. 6 0.093 28 117 Ex. 7 0.050 29 57 Ex. 8 0.142 27 85 AEO7 0.023 32 143 MAGE4 0.024 31 150 .sup.eCritical Micelle Concentration (CMC) and Surface Tension (ST) at CMC was measured on a Sigma 700 tensiometer from BiolinScientific AB equipped with a Wilhelmy plate and a Du Noy ring .sup.fFoam height was tested by the standard Ross-Miles method, using a 2.5 g/L test solution.

(22) As seen from Table 2, the ether compositions obtained from Examples 2-8 according to the present invention achieved equally good surfactant properties as the two commercially available surfactants, especially in terms of surface tension and Ross mile foam height. Noticeably, Examples 4-7 each obtained a same level of critical micelle concentration (CMC) compared with benchmarks of AEO7 and MAGE4. Ross mile foam height of examples 5-6 is also similar to benchmarks. Significantly, the surface tension at CMC of example 2-8 is even lower than the benchmarks.

(23) Additionally, wash tests on primary detergency of the ether composition products were carried out by measuring the amount of stain removed from regulated prestained soil cloths, in comparison with the abovementioned benchmarks of AEO7 and MAGE4. The different stains were recorded by the following codes: JB01carbon black with oil on cotton cloth JB02egg protein on cotton cloth JB03sebum on cotton cloth CS61Beef lard on cotton cloth EMPAlipstick on cotton cloth 20Cpigment, lanolin on polyester/cotton 65/35 cloth 20Dpigment, sebum on polyester/cotton 65/35 cloth 20PFpigment, vegetable fat on polyester/cotton 65/35 cloth 30Cpigment, lanolin on polyester cloth 30Dpigment, sebum on polyester cloth 30PFpigment, vegetable fat on polyester cloth

(24) The wash tests were performed with a Launderometer with the test conditions summarized below: 0.5 L of 250 ppm hard water Washing temperature: 30 C. Duration: 1 hour Detergent concentration: 1 g/L Performance measurement: L value ( lightness) Prestained cloth samples: 55 cm, 4 pieces per type

(25) Table 3 showed the accumulative detergency performance on cotton, cotton & polyester and polyester cloth samples, for Examples 2-8 and the commercial samples of AEO7 and MAGE4. Specifically, the data in Table 3 indicated the average stain removal rate for different prestained samples by each tested detergent composition.

(26) TABLE-US-00003 TABLE 3 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 AEO7 MAGE4 JB01 13.3 14.1 16.4 17.6 16.2 15.6 16.0 18.5 18.4 JB02 5.42 6.73 6.94 7.17 7.06 7.04 6.08 5.66 6.52 JB03 6.90 9.20 11.6 12.5 11.7 12.3 12.9 15.1 15.8 CS61 32.3 22.9 23.0 23.4 23.1 22.6 24.6 27.2 25.7 EMPA 8.93 10.3 10.2 11.7 10.9 10.3 10.6 11.1 10.3 Sum on 66.8 63.2 68.1 72.4 69.0 67.7 70.2 77.5 76.6 cotton.sup.1 20C 0.34 0.25 1.48 2.29 1.53 1.32 2.35 5.10 3.39 20D 4.92 3.94 8.20 8.28 7.77 7.77 9.30 13.7 9.83 20PF 1.95 2.07 5.08 5.98 5.21 4.86 6.36 10.7 8.42 Sum on 7.20 6.26 14.8 16.6 14.5 14.0 18.0 29.5 21.6 PE&Cotton.sup.1 30C 2.44 6.64 16.5 16.7 16.1 15.0 17.1 19.8 18.6 30D 1.10 1.34 10.1 12.3 9.44 8.87 9.48 17.9 13.9 30PF 0.76 1.86 5.71 5.02 5.55 4.41 5.27 10.4 7.15 Sum on 4.29 9.85 32.3 34.0 31.1 28.3 31.9 48.0 39.7 PE.sup.1 AVERAGE.sup.2 7.12 7.21 10.5 11.1 10.4 10.0 10.9 14.1 12.5 .sup.1The sum of stain removal rates for different cloth material .sup.2The average stain removal rate for different stains and cloth material

(27) As shown from Table 3, overall detergency performance of Example 2-8 is at the same level of benchmark AEO7 and MAGE4. Noticeably, Examples 2-8 showed better detergent performance on cotton samples than polyesters, which is particularly suited for the current trend of cotton cloth preference.

Example 13

Etherification of Glycerol and Dodecanol with Sulfonated Polystyrene as Catalyst

(28) Two types of sulfonated polystyrene copolymers (PSt-co-PSSA and PSt-b-PSSNa/PSSA) were prepared as shown in Scheme 1. In the case of random copolymer, polystyrene (PSt) samples were synthesized in the lab following a standard ATRP procedure with 4-(bromomethyl) benzoic acid as initiator, copper chloride or bromide for the dormant/active species equilibrium and 2,2-bipyridine to complex the copper. Two series of samples were made, with an average number molecular weight of 12500 g/mol and 26600 g/mol and a polydispersity index of 1.2. Random sulfonation of the samples was done by mixing PSt with the calculated amounts of acetic anhydride and sulfuric acid in 1,2-dicholoroethane to obtain polystyrene-co-polystyrene sulfonic acid (PSt-co-PSSA).

(29) Blocked type ones (PSt-b-PSSNa/PSSA) were prepared through sequential polymerization through nitroxide mediated polymerization. Specifically, sodium polystyrene sulfonate (PSSNa) was prepared by nitroxide mediated polymerization with TEMPO and K.sub.2S.sub.2O.sub.8+Na.sub.2S.sub.2O.sub.5 in ethylene glycol:water of 3:1 weight. A polymer with 6500 g/mol average number molecular weight and a polydispersity index of 1.3 was obtained. The second block of polystyrene (PSt) was added in the same conditions. At the end, PSSNa-b-PSt was stirred with a cation exchange resin (previously conditioned with H.sub.2SO.sub.4, 4.2 eq/g) in water and tetrahydrofuran (THF) to yield a partially or fully protonated block polymer PSt-b-PSSNa/PSSA.

(30) ##STR00020##

(31) In a 250 mL two-neck round-bottomed flask fitted with magnetic stir bar and a water trap on one neck, dodecanol (24.1 g), glycerol (47.8 g) and a certain amount of sulfonated polystyrene (see Table 4) were added. The reaction mixture was vigorously stirred at 150 C. for 24 hrs. After the mixture cooled, pyridine was added to neutralize the catalyst. Optionally, the reaction was carried out with water removal (WR) under static vacuum. The obtained product composition was analysed by .sup.1H NMR, GC-MS and HPLC, see Table 4.

(32) TABLE-US-00004 TABLE 4 Composition characterized by .sup.1H NMR, GC and HPLC (wt %) Dodecanol Catalyst Catalyst C12OH C12-ether Ether Conversion Sample.sup.1 Quality.sup.2 (%) (%) product (%) (%) RC.sub.211S.sub.21 0.1 21 35.9 43 79 RC.sub.211S.sub.56-WR 0.1 40 6.2 53 60 BC.sub.46S.sub.50-WR 0.05 32 10.8 57 68 .sup.1R represents random sulfonated polystyrene PSt-co-PSSA samples, B represents blocked copolymer of PSt-b-PSSNa/PSSA samples, C.sub.x means that the number of styrene on the polystyrene chain is x, and S.sub.y means that the sulfonation degree of polystyrene is y %. WR indicates that the reactions were done with water removal under static vacuum. .sup.2Expressed as acidity eg. dodecanol

Example 14

Etherification of Glycerol and Dodecanol with Sulfonated Polystyrene-Grafted Silica Particles as Catalyst

(33) Synthesis of silica nanoparticles grafted with PSt-co-PSSA was adapted from the general Scheme 2, except that CuCl.sub.2 was also added together with CuCl to better control the polymerization of styrene in bulk. Silica (SiO.sub.2) nanoparticles (10 g) were first stirred in 10% HCl for 1 hour, in a 3-neck round bottomed flask and at room temperature. After drying, 200 mL of dried toluene and initiator ((chloromethyl)phenylethyl) trimethoxysilane (CPMS, 16.7 ml, 67.9 mmol) were added to the 3-neck round bottom flask, under a nitrogen flow, and the mixture was refluxed for 4 hours, to have the CPMS initiator grafted on the particle surface. Styrene was grafted on the silica particle surface by ATRP (Atom Transfer Radical Polymerization) and using CuCl, CuCl.sub.2 and 2,2-bipyridine in a 50 mL Schlenk, and the polymerization was performed at 90 C. for 29 hours. The obtained PSt grafted silica nanoparticles were subsequently submitted to sulfonation under the same sulfonation condition for making random PSt-co-PSSA samples.

(34) Three samples (Samples 1-3 in Table 5) with different sulfonation degree were thus prepared and related data are listed at Table 5. TGA measurements showed that the grafting degree on the nanoparticles is 5.9 wt %, and the consequent calculation showed that roughly 23% of silanol groups were connected to PSt chain, whose particle size and specific surface area remaining similar to parent silica particles. The sulfonation degrees of PSt were measured to vary from 42 to 90 mol % (calculated by TGA and titration methods), with acidity varying between 1.2 to 2.7 mmol/g (measured by titration).

(35) ##STR00021##

(36) Next, in a 250 mL two-neck round-bottomed flask fitted with magnetic stir bar and a water trap on one neck, dodecanol (24.1 g) and glycerol (47.8 g) were added together with a grafted silica nanoparticle sample (Sample 1, 2 or 3, 0.05 H.sup.+ eq. dodecanol). The reaction mixture was vigorously stirred at 150 C. for 24 hrs under static vacuum. After the mixture cooled, pyridine was added to neutralize the catalyst. Viscous product was obtained. The obtained product was characterized by .sup.1H NMR and GC to get the average compositions which was listed in Table 5.

(37) TABLE-US-00005 TABLE 5 Composition characterized by .sup.1H Grafted NMR, GC and HPLC (wt %) silica Sulfonation Ether particle Degree Acidity C12OH C12-ether product sample (molar %/PSt) (mmol/g) (%) (%) (%) Sample 1 42 1.2 29 24.5 46 Sample 2 59 1.8 39 13.4 48 Sample 3 90 2.7 37 10.7 52

(38) Recycling of Polymer Catalyst after the Etherification Reaction

Example 15

Recycling of Catalyst Nafion NR50 for the Etherification of Triglycerol and Dodecanol

(39) In a 20 mL Schlenk tube fitted with an inside water trap, dodecanol (1.60 g), glycerol (3.16 g) and Nafion NR50 (0.29 g, 3% eq. to dedecanol) were added. The reaction mixture was vigorously stirred at 150 C. under static vacuum until conversion of dodecanol was reached to be above 80% (verified by GC). Then, until the mixture was cooled and diluted with THF, the catalyst was collected by centrifuge. After washing with methanol and subsequent drying, the recovered catalyst was put in next cycle for the same etherification reaction as before. The conversion rate of dodecanol in the subsequent cycles was listed below in Table 6.

(40) TABLE-US-00006 TABLE 6 Sampling time after Conversion of Selectivity of Cycle the initial catalyst Dodecanol ether product No. addition (hr) (%) (%) 1 43 91 22 2 47 95 8 3 48 93 18 4 54 88 23

(41) As seen from Table 6, the recycled polymer catalyst of Nafion NR50 exhibited nearly unmodified catalytic behaviour when re-used in the same type of etherification reaction.

Example 16

Recycling of Aquivion Catalyst for the Etherification of Triglycerol and Dodecanol

(42) In a 20 mL Schlenk tube fitted with an inside water trap, dodecanol (1.60 g), glycerol (3.16 g) and Aquivion D66-20BSX (0.60 g, 6% eq. to dedecanol) were added. The reaction mixture was vigorously stirred at 150 C. under static vacuum until conversion of dodecanol reached 80% (measured by GC). Then, until the mixture was cooled and diluted with THF, the catalyst was collected by centrifuge. After washing with methanol and subsequent drying, the recovered catalyst was put in next cycle for the same etherification reaction as before. The conversion rate of dodecanol in the subsequent cycles was listed below in Table 7.

(43) TABLE-US-00007 TABLE 7 Sampling time after Conversion of Selectivity of Cycle the initial catalyst Dodecanol ether product No. addition (hr) (%) (%) 1 26.5 85 22 2 27.0 93 18 3 32.5 87 37

(44) As seen from Table 7, the recycled polymer catalyst of Aquivion D66-20BSX also exhibited nearly unmodified catalytic behaviour when re-used in the same type of etherification reaction.