Surfactant and surfactant composition

Abstract

The present invention provides: a surfactant that has outstanding emulsifiability in oil, wetting properties with respect to matter, osmotic properties with respect to fiber products, and washability; and a surfactant composition that contains the surfactant. This surfactant contains at least one compound represented by a Chemical Formula (1). ##STR00001##
(In the formula: R.sup.1 is a hydrogen atom or an aliphatic hydrocarbon group with a carbon number of 1-33; R.sup.2 is an aliphatic hydrocarbon group with a carbon number of 1-33; the total carbon number of R.sup.1 and R.sup.2 is 1-34; X is a single bond or an aliphatic hydrocarbon group with a carbon number of 1-5; either A.sup.1 or A.sup.2 is —OH; and the other is —O—CH.sub.2—CH(OH)—CH.sub.2OH or —O—CH(—CH.sub.2—OH).sub.2.)

Claims

1. A surfactant comprising at least one kind of a compound represented by a Chemical Formula (1): ##STR00006## wherein R.sup.1 is a hydrogen atom or an aliphatic hydrocarbon group having 1 or more and 33 or less carbon atoms, R.sup.2 is an aliphatic hydrocarbon group having 1 or more and 33 or less carbon atoms, a total number of carbon atoms of R.sup.1 and R.sup.2 is 1 or more and 34 or less, X is a single bond or an aliphatic hydrocarbon group having 1 or more and 5 or less carbon atoms, and one of A.sup.1 and A.sup.2 is —OH and the other is —O—CH.sub.2—CH(OH)—CH.sub.2OH or —O—CH(—CH.sub.2—OH).sub.2.

2. The surfactant according to claim 1, wherein in the compound represented by the Chemical Formula (1), X is a single bond.

3. The surfactant according to claim 1, wherein in the compound represented by the Chemical Formula (1), R.sup.1 is an aliphatic hydrocarbon group having 1 or more and 33 or less carbon atoms.

4. The surfactant according to claim 1, comprising a compound 1 in which in the Chemical Formula (1), one of A.sup.1 and A.sup.2 is —OH and the other is —O—CH.sub.2—CH(OH)—CH.sub.2OH, and a compound 2 in which in the Chemical Formula (1), one of A.sup.1 and A.sup.2 is —OH and the other is —O—CH(—CH.sub.2—OH).sub.2.

5. The surfactant according to claim 1, comprising in the compound represented by the Chemical Formula (1), two or more kinds of the compound between which total numbers of carbon atoms of R.sup.1 and R.sup.2 are the same, but numbers of carbon atoms of R.sup.1 and numbers of carbon atoms of R.sup.2 are each different.

6. A surfactant composition comprising the surfactant according to claim 1.

7. The surfactant according to claim 1, being an agent for oil recovery.

8. The surfactant composition according to claim 6, being a composition for oil recovery.

9. The surfactant according to claim 2, wherein in the compound represented by the Chemical Formula (1), R.sup.1 is an aliphatic hydrocarbon group having 1 or more and 33 or less carbon atoms.

10. The surfactant according to claim 2, comprising a compound 1 in which in the Chemical Formula (1), one of A.sup.1 and A.sup.2 is —OH and the other is —O—CH.sub.2—CH(OH)—CH.sub.2OH, and a compound 2 in which in the Chemical Formula (1), one of A.sup.1 and A.sup.2 is —OH and the other is —O—CH(—CH.sub.2—OH).sub.2.

11. The surfactant according to claim 3, comprising a compound 1 in which in the Chemical Formula (1), one of A.sup.1 and A.sup.2 is —OH and the other is —O—CH.sub.2—CH(OH)—CH.sub.2OH, and a compound 2 in which in the Chemical Formula (1), one of A.sup.1 and A.sup.2 is —OH and the other is —O—CH(—CH.sub.2—OH).sub.2.

12. The surfactant according to claim 2, comprising in the compound represented by the Chemical Formula (1), two or more kinds of the compound between which total numbers of carbon atoms of R.sup.1 and R.sup.2 are the same, but numbers of carbon atoms of R.sup.1 and numbers of carbon atoms of R.sup.2 are each different.

13. The surfactant according to claim 3, comprising in the compound represented by the Chemical Formula (1), two or more kinds of the compound between which total numbers of carbon atoms of R.sup.1 and R.sup.2 are the same, but numbers of carbon atoms of R.sup.1 and numbers of carbon atoms of R.sup.2 are each different.

14. The surfactant according to claim 4, comprising in the compound represented by the Chemical Formula (1), two or more kinds of the compound between which total numbers of carbon atoms of R.sup.1 and R.sup.2 are the same, but numbers of carbon atoms of R.sup.1 and numbers of carbon atoms of R.sup.2 are each different.

15. A surfactant composition comprising the surfactant according to claim 2.

16. A surfactant composition comprising the surfactant according to claim 3.

17. A surfactant composition comprising the surfactant according to claim 4.

18. A surfactant composition comprising the surfactant according to claim 5.

19. The surfactant according to claim 2, being an agent for oil recovery.

20. The surfactant according to claim 3, being an agent for oil recovery.

Description

EXAMPLES

(1) Hereinafter, a specific description is made of the present invention with reference to Examples. The content of each component is expressed in mass % unless otherwise indicated in Tables. Various measuring methods are as follows.

(2) Method for Measuring Double Bond Distribution in Olefin

(3) The double bond distribution in olefin was measured by gas chromatography (hereinafter, abbreviated as GC). Specifically, dimethyl disulfide was reacted with olefin to form a dithioated derivative, and then respective components were separated by GC. The double bond distribution in olefin was determined from respective peak areas. The apparatus used for measurement and analyzing conditions are as follows.

(4) GC apparatus: Trade name HP6890 (manufactured by Hewlett-Packard Company)

(5) Column: Trade name Ultra-Alloy-1 HT capillary column 30 m×250 μm×0.15 μm (manufactured by Frontier Laboratories, Ltd.)

(6) Detector: Hydrogen flame ion detector (FID)

(7) Injection temperature: 300° C.

(8) Detector temperature: 350° C.

(9) Oven: 60° C. (0 min.).fwdarw.2° C./min..fwdarw.225° C..fwdarw.20° C./min. 350° C..fwdarw.350° C. (5.2 min.)

(10) <Method for Measuring Content Ratio of Structural Isomer>

(11) Measurement was performed by .sup.1H-NMR for a mixture of 0.05 g of alkyl glyceryl ether, 0.2 g of trifluoroacetic anhydride, and 1 g of deuterated chloroform. Measuring conditions are as follows.

(12) Nuclear magnetic resonance apparatus: Agilent 400-MR DD2, manufactured by Agilent Technologies, Inc.

(13) Observation range: 6410.3 Hz

(14) Data point: 65536

(15) Measurement mode: Presat

(16) Pulse width: 45°

(17) Pulse delay time: 10 sec

(18) Cumulative number: 128 times

(19) <Production of Internal Olefin>

Production Example A1

(20) (Production of internal olefin having 16 carbon atoms (internal olefin 1))

(21) A flask equipped with a stirrer was charged with 7000 g (28.9 mol) of 1-hexadecanol (Product name: KALCOL 6098, manufactured by Kao Corporation) and 700 g (10 wt % with respect to the raw material alcohol) of γ-alumina (STREM Chemicals, Inc.) as a solid acid catalyst, followed by reaction at 280° C. for 32 hours under stirring with circulation of nitrogen (7000 mL/min) in the system. The alcohol conversion after completion of the reaction was 100%, and the purity of C16 olefin was 99.6%. The obtained crude C16 internal olefin was transferred to a distiller, followed by distillation at 136 to 160° C./4.0 mmHg to yield an internal olefin 1 having an olefin purity of 100%. The double bond distribution in the obtained internal olefin 1 was 0.2% at the C1 position, 15.8% at the C2 position, 14.5% at the C3 position, 15.7% at the C4 position, 17.3% at the C5 position, 16.5% at the C6 position, and 20.0% at the C7 position and the C8 position in total.

Production Example A2

(22) (Production of Internal Olefin having 18 Carbon Atoms (Internal Olefin 2))

(23) A reactor equipped with a stirrer was charged with 800 kg (3.0 kmol) of 1-octadecanol (Product name: KALCOL 8098, manufactured by Kao Corporation) and 80 kg (10 wt % with respect to the raw material alcohol) of activated alumina GP-20 (Mizusawa Industrial Chemicals, Ltd.) as a solid acid catalyst, followed by reaction at 280° C. for 16 hours under stirring with circulation of nitrogen (15 L/min) in the system. The alcohol conversion after completion of the reaction was 100%, and the purity of C18 olefin was 98.7%. The obtained crude C18 internal olefin was transferred to a distiller, followed by distillation at 163 to 190° C./4.6 mmHg to yield an internal olefin 2 having an olefin purity of 100%. The double bond distribution in the obtained internal olefin 2 was 0.3% at the C1 position, 13.3% at the C2 position, 12.6% at the C3 position, 13.9% at the C4 position, 14.8% at the C5 position, 13.7% at the C6 position, 12.6% at the C7 position, and 18.8% at the C8 position and the C9 position in total.

Production Example A3

(24) (Production of Internal Olefin having 14 Carbon Atoms (Internal Olefin 3))

(25) An internal olefin 3 was obtained in the same manner as in Production Example A1 except that 28.9 mol of 1-tetradecanol (Product name: KALCOL 4098, manufactured by Kao Corporation) was used in place of 28.9 mol of 1-hexadecanol (Product name: KALCOL 6098, manufactured by Kao Corporation) for Production Example A1. The double bond distribution in the obtained internal olefin 3 was 1.3% at the C1 position, 31.8% at the C2 position, 23.8% at the C3 position, 21.0% at the C4 position, 8.5% at the C5 position, and 13.6% at the C6 position and C7 position in total.

(26) <Production of Internal Epoxide>

Production Example B1

(27) (Production of Internal Epoxide having 16 Carbon Atoms (Internal Epoxide 1))

(28) A flask equipped with a stirrer was charged with the internal olefin 1 (800 g, 3.56 mol) obtained in Production Example A1, 107 g (1.78 mol) of acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.), 15.6 g (0.15 mol) of sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.), 415.7 g (4.28 mol) of 35% hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.), and 25.3 g (0.18 mol) of sodium sulfate (manufactured by Wako Pure Chemical Industries, Ltd.), followed by reaction at 50° C. for 4 hours. Thereafter, the temperature was raised to 70° C. to allow the mixture to react further for 2 hours. After the reaction, the layers were separated to remove an aqueous layer, and an oil layer was washed with ion-exchanged water, a saturated aqueous sodium carbonate solution (manufactured by Wako Pure Chemical Industries, Ltd.), a saturated aqueous sodium sulfite solution (manufactured by Wako Pure Chemical Industries, Ltd.), and 1% saline (manufactured by Wako Pure Chemical Industries, Ltd.), followed by concentration in an evaporator to yield 820 g of an internal epoxide 1.

Production Example B2

(29) (Production of Internal Epoxide having 18 Carbon Atoms (Internal Epoxide 2))

(30) A flask equipped with a stirrer was charged with the internal olefin 2 (595 g, 2.38 mol) obtained in Production Example A2, 71.7 g (1.20 mol) of acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.), 9.8 g (0.10 mol) of sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.), and 324 g (4.00 mol) of 35% hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.), followed by reaction at 50° C. for 4 hours. Thereafter, the temperature was raised to 80° C. to allow the mixture to react further for 5 hours. After the reaction, the layers were separated to remove an aqueous layer, and an oil layer was washed with ion-exchanged water, a saturated aqueous sodium carbonate solution (manufactured by Wako Pure Chemical Industries, Ltd.), a saturated aqueous sodium sulfite solution (manufactured by Wako Pure Chemical Industries, Ltd.), and ion-exchanged water, followed by concentration in an evaporator to yield 629 g of an internal epoxide 2.

Production Example B3

(31) (Production of Internal Epoxide having 14 Carbon Atoms (Internal Epoxide 3))

(32) An internal epoxide 3 was obtained in the same manner as in Production Example B1 except that the internal olefin 3 (3.56 mol) obtained in Production Example A3 was used in place of the internal olefin 1 (3.56 mol) obtained in Production Example A1.

(33) <Production of Reactant of Epoxide and Glycerin (Alkyl Glyceryl ether, AGE)>

(34) Hereinafter, the alkyl glyceryl ether is referred to as AGE. In addition, AGE1, AGE2, AGE3, and the like represent alkyl glyceryl ether 1, alkyl glyceryl ether 2, alkyl glyceryl ether 3, and the like, respectively.

Production Example C1

(35) (Production of Reactant of Internal Epoxide 1 and Glycerin (AGE1))

(36) A flask equipped with a stirrer was charged with 2298 g (25.0 mol) of glycerin (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.122 g (1.25 mmol) of 98% sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.), and the temperature was raised to 130° C. Thereafter, the internal epoxide 1 (300 g, 1.25 mol) obtained in Production Example B1 was added dropwise over 1 hour, followed by reaction at 130° C./8 hours. Hexane was added to the liquid obtained by this reaction, followed by washing with ion-exchanged water. Subsequently, concentration was performed under reduced pressure in an evaporator to yield 400 g of AGE1. The obtained AGE1 wherein in the Chemical Formula (1), R.sup.1 and R.sup.2 each contain an alkyl group having 1 to 13 carbon atoms, the total number of carbon atoms of R.sup.1 and R.sup.2 is 14, X is a single bond, one of A.sup.1 and A.sup.2 is —OH and the other is —O—CH.sub.2—CH(OH)—CH.sub.2OH or —O—CH(—CH.sub.2—OH).sub.2, contained 73% ether alcohol 1 (AGE obtained by reacting the hydroxyl group at the 1-position of glycerin with the epoxy group) in which A.sup.1 or A.sup.2 was —O—CH.sub.2—CH(OH)—CH.sub.2OH, and 27% ether alcohol 2 (AGE obtained by reacting the hydroxyl group at the 2-position of glycerin with the epoxy group) in which A.sup.1 or A.sup.2 was —O—CH(—CH.sub.2—OH).sub.2.

Production Example C2

(37) (Production of Reactant of Internal Epoxide 2 and Glycerin (AGE2))

(38) An AGE2 was obtained in the same manner as in Production Example C1 except that the internal epoxide 2 (1.25 mol) obtained in Production Example B2 was used in place of the internal epoxide 1 (1.25 mol) obtained in Production Example B1. The obtained AGE2 wherein in the Chemical Formula (1), R.sup.1 and R.sup.2 each contain an alkyl group having 1 to 15 carbon atoms, the total number of carbon atoms of R.sup.1 and R.sup.2 is 16, X is a single bond, one of A.sup.1 and A.sup.2 is —OH and the other is —O—CH.sub.2—CH(OH)—CH.sub.2OH or —O—CH(—CH.sub.2—OH).sub.2, contained 72% AGE obtained by reacting the hydroxyl group at the 1-position of glycerin with the epoxy group, and 28% AGE obtained by reacting the hydroxyl group at the 2-position of glycerin with the epoxy group.

Production Example C3

(39) (Production of Reactant of Internal Epoxide 3 and Glycerin (AGE3))

(40) An AGE3 was obtained in the same manner as in Production Example C1 except that the internal epoxide 3 (1.25 mol) obtained in Production Example B3 was used in place of the internal epoxide 1 (1.25 mol) obtained in Production Example B1. The obtained AGE3 wherein in the Chemical Formula (1), R.sup.1 and R.sup.2 each contain an alkyl group having 1 to 11 carbon atoms, the total number of carbon atoms of R.sup.1 and R.sup.2 is 12, X is a single bond, one of A.sup.1 and A.sup.2 is —OH and the other is —O—CH.sub.2—CH(OH)—CH.sub.2OH or —O—CH(—CH.sub.2—OH).sub.2, contained 74% AGE obtained by reacting the hydroxyl group at the 1-position of glycerin with the epoxy group, and 26% AGE obtained by reacting the hydroxyl group at the 2-position of glycerin with the epoxy group.

Production Example C4

(41) (Production of Reactant of C16 Terminal Epoxide and Glycerin (AGE4))

(42) An AGE4 was obtained in the same manner as in Production Example C1 except that 1.25 mol of a C16 terminal epoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) was used in place of the internal epoxide 1 (1.25 mol) obtained in Production Example B1. The obtained AGE4 wherein in the Chemical Formula (1), R.sup.1 is a hydrogen atom, R.sup.2 is an alkyl group having 14 carbon atoms, the total number of carbon atoms of R.sup.1 and R.sup.2 is 14, X is a single bond, one of A.sup.1 and A.sup.2 is —OH and the other is —O—CH.sub.2—CH(OH)—CH.sub.2OH or —O—CH(—CH.sub.2—OH).sub.2, contained 50% AGE obtained by reacting the hydroxyl group at the 1-position of glycerin with the epoxy group, and 50% AGE obtained by reacting the hydroxyl group at the 2-position of glycerin with the epoxy group.

(43) The following measurement and evaluation were performed using the produced AGEs 1 to 4. Unless otherwise specified, the measurement and evaluation were performed at room temperature (20° C.). In Tables 1 to 5, AGE represents alkyl glyceryl ether.

(44) <Evaluation of Emulsifiability>

Example 1 (Examples 1-1 to 1-9, Comparative Examples 1-1 to 1-4)

(45) In a 50 mL glass sample bottle, 0.5 g of a surfactant described in Table 1, 10 mL of ion-exchanged water, and 10 mL of each of various oils were put, and shaken for 30 seconds. Then, one droplet was placed on a slide glass, covered with a cover glass, and observed at a magnification of 500 times using a digital microscope VHX-6000 (manufactured by KEYENCE CORPORATION). The particle diameters of the droplets were measured and evaluated according to the following criteria. The results are shown in Table 1.

(46) 1: Average particle diameter is less than 100 μm

(47) 2: Average particle diameter is more than 100 μm

(48) 3: Separation occurs and no droplet is observed.

(49) <Evaluation of Wettability>

Example 2 (Examples 2-1 to 2-4, Comparative Examples 2-1 to 2-2)

(50) A polypropylene substrate (80 mm×30 mm×1 mm) was horizontally placed on the stage of a contact angle meter (DM-701 manufactured by Kyowa Interface Science Co., Ltd.), 2 μL of a composition described in Table 2 (a surfactant composition or the like) was dropped onto the placed slide glass with a syringe, and the contact angle was measured after 10 seconds. The results are shown in Table 2.

(51) <Evaluation of Permeability>

Example 3 (Examples 3-1 to 3-3, Comparative Example 3-1)

(52) In a 100 mL beaker, 50 mL of a composition described in Table 3 (a surfactant composition or the like) adjusted to 20° C. was put. On the composition, a cotton canvas cloth (gray fabric, knitting, 2.0×2.0 cm) was gently floated. Then, the time until the cotton canvas cloth started to sink below the water surface was measured. The measurement was performed five times to derive the average value. The results are shown in Table 3.

(53) <Evaluation of Detergency>

Example 4 (Examples 4-1 to 4-2, Comparative Examples 4-1 to 4-2)

(54) Onto a hard polyvinyl chloride resin plate (50 mm×20 mm×2 mm), 80 μL of beef tallow heated to 80° C. and completely dissolved was dropped. Then, the hard polyvinyl chloride resin plate was allowed to stand at room temperature overnight for solidification. This resin plate was immersed in 50 g of a composition (a surfactant composition or the like) described in Table 4 adjusted to 30° C., and the time during which the beef tallow peeled off from the resin plate was measured as a washing time. The results are shown in Table 4.

(55) <Evaluation of Microemulsion forming Ability>

Example 5 (Examples 5-1 to 5-3, Comparative Examples 5-1 to 5-6)

(56) To ion-exchanged water, NaCl (20 mass %) and CaCl.sub.2 (6 mass %) were added to prepare a salt aqueous solution.

(57) In a 100 mL screw tube, 80 mL of each of oils described in Table 5 and the salt aqueous solution was put at a volume ratio of 1:1, and further 0.8 mL of each of surfactants described in Table 5 was added. Then, the tube was sealed, and shaken for 30 seconds. After standing at 80° C. for 3 days, the volume and appearance of the aqueous phase were observed.

(58) The microemulsion forming ability was evaluated as follows: in a case where the volume of the aqueous phase in the lower part was 55% or more, and the aqueous phase was not cloudy, the case was determined that “there is microemulsion formation”, and the other cases were determined that “there is no microemulsion formation”. The results are shown in Table 5. Comparative products 1 to 3 shown in Table 5 are as follows.

(59) Comparative Product 1: 2-ethylhexylglyceryl ether (2-ethylhexyl glyceryl ether can be produced, for example, by the method described in paragraphs [0002] and [0003] of JP-A-2008-156289.)

(60) Comparative Product 2: polyoxyethylene (3) lauryl ether (EMULGEN 103, manufactured by Kao Corporation)

(61) Comparative Product 3: alkyl glucoside (MYDOL 12, manufactured by Kao Corporation)

(62) TABLE-US-00001 TABLE 1 Evaluation of Surfactant Oil Emulsifiability Example 1-1 AGE 1 Decane 1 Example 1-2 Toluene 1 Example 1-3 Triolein 2 Example 1-4 AGE 2 Decane 1 Example 1-5 Toluene 1 Example 1-6 Oleic Acid 1 Example 1-7 Triolein 1 Example 1-8 AGE 3 Decane 1 Example 1-9 Oleic Acid 1 Comparative — Decane 3 Example 1-1 Comparative — Toluene 3 Example 1-2 Comparative — Oleic Acid 3 Example 1-3 Comparative — Triolein 3 Example 1-4

(63) TABLE-US-00002 TABLE 2 Surfactant Position of Blending Amount (Mass%) of Each Component in Composition Contact Glyceryl Ether Diethylene Glycol Ion Exchanged Angle Kind Group Surfactant Monobutyl Ether Water Total (°) Example 2-1 AGE1 Internal 1 20 Balance 100 24 Example 2-2 AGE2 Internal 1 20 Balance 100 24 Example 2-3 AGE3 Internal 1 20 Balance 100 20 Example 2-4 AGE4 Terminal 1 20 Balance 100 22 Comparative — 0  0 Balance 100 97 Example 2-1 Comparative — 0 20 Balance 100 41 Example 2-2

(64) TABLE-US-00003 TABLE 3 Time to Start Blending Amount (Mass %) of Each Component in Composition to Sink Surfactant Surfactant Ion Exchanged Water Total (s) Example 3-1 AGE 1 0.1 Balance 100  25 Example 3-2 AGE 2 0.1 Balance 100  44 Example 3-3 AGE 3 0.1 Balance 100  10 Comparative — 0   Balance 100 >600  Example 3-1

(65) TABLE-US-00004 TABLE 4 Blending Amount (Mass %) of Each Component in Composition Washing Diethylene Glycol Ion Exchanged Time Surfactant Surfactant Monobutyl Ether Water Total (h) Example 4-1 AGE1 3 16 Balance 100 1 Example 4-2 AGE2 3 16 Balance 100 1 Comparative — 0 0 Balance 100 >72 Example 4-1 Comparative — 0 16 Balance 100 >72 Example 4-1

(66) TABLE-US-00005 Example Example Example Comparative Comparative Comparative Comparative Comparative Comparative 5-1 5-2 5-3 Example 5-1 Example 5-2 Example 5-3 Example 5-4 Example 5-5 Example 5-6 Surfactant AGE2 AGE1 AGE3 — Comparative Comparative Comparative — — Product 1 Product 2 Product 3 Oil Octane Octane Octane Octane Octane Octane Octane Toluene Hexadecane Volume of 65 64 64 50 49 49 51 50 50 Aqueous Phase after Standing at 80° C. for 3 Days [%] Appearance of Slight Slight Slight Transparent Transparent Transparent Transparent Transparent Transparent Aqueous Phase Cloudiness Cloudiness Cloudiness after Standing at 80° C. for 3 Days Formation of Yes Yes Yes No No No No No No Microemulsion

INDUSTRIAL APPLICABILITY

(67) The surfactant and the surfactant composition of the present invention are useful as, for example, a detergent such as a liquid detergent for clothing, a detergent for dishware, a detergent for hair, a detergent for body, a detergent for precision parts, and a detergent for hard surfaces.