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Publication numberUS3799956 A
Publication typeGrant
Publication dateMar 26, 1974
Filing dateOct 12, 1970
Priority dateOct 14, 1969
Publication numberUS 3799956 A, US 3799956A, US-A-3799956, US3799956 A, US3799956A
InventorsS Aman, K Kojima, Y Nakamura, R Ito
Original AssigneeToho Chem Ind Co Ltd
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Surface active agent and method of preparing the same
US 3799956 A
Abstract  available in
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Description  (OCR text may contain errors)

United States Patent US. Cl. 260-403 Claims ABSTRACT OF THE DISCLOSURE A novel surface active agent comprisin a phosphorous triester-type compound having the following formula:

wherein R is a conventional nonionic surface active agent residue to which ethylene oxide or both ethylene oxide and propylene oxide is added, and R and R are a con ventional nonionic surface active agent residue to which ethylene oxide or both ethylene oxide and propylene oxide is added or an alkyl group having 8 to 22 carbon atoms and its preparation are described. The surface active agent is superior in surface activity, heat-resisting stability and a reduced foaming property.

This invention relates to a novel surface active agent and a method of preparing the same.

An object of the present invention is to provide a novel surface active agent which has superior surface activities, a heat-resisting stability and a reduced foaming property.

Other objects and advantages of the present invention will become apparent from the following description.

The surface active agent of the present invention comprises a compound having the following general formula:

wherein R is a conventional nonionic surface active agent residue to which one or more moles of ethylene oxide or one or more moles of both ethylene oxide and propylene oxide is added, and R and R are a member selected from the group consisting of a conventional nonionic surface active agent residue to which one or more moles of ethylene oxide or one or more moles of both ethylene oxide and propylene oxide is added and an alkyl group having 8 to 22 carbon atoms.

The above conventional nonionic surface active agent includes, for example, (1) a nonionic surface active agent of such a type as an addition product of l to 100 moles of ethylene oxide or 1 to 100 moles of both ethylene oxide and propylene oxide to one mole of higher alcohol having 8 to 22 carbon atoms such as octyl alcohol, lauryl alcohol, coconut alcohol, cetyl alcohol, stearyl alcohol, oleyl alcop CC hol, tridecyl alchol, etc.; (2) that of such a type as an addition product of 1 to moles of ethylene oxide or 1 to 100 moles of both ethylene oxide and propylene oxide to one mole of alkyl phenol containing an alkyl group having 4 to 22 carbon atoms such as butyl phenol, octyl phenol, nonyl phenol, dodecyl phenol, dinonyl phenol, etc.; (3) that of such a type as an addition product of 1 to 100 moles of ethylene oxide or 1 to 100 moles of both ethylene oxide and propylene oxide to one mole of higher fatty acid having 8 to 22 carbon atoms such as coconut fatty acid, lauric acid, oleic acid, stearic acid, palmitic acid, etc.; (4) that of such a type as an addition product of 1 to 100 moles of ethylene oxide or 1 to 100 moles of both ethylene oxide and propylene oxide to one mole of alkyl amine having 8 to 22 carbon atoms such as coconut amine, lauryl amine, stearyl amine, hexadecyl amine, etc.; (5) that of such a type as an addition product of 1 to 100 moles of ethylene oxide or 1 to 100 moles of both ethylene oxide and propylene oxide to one mole of higher fatty acid amide having 8 to 22 carbon atoms such as lauric acid amide, stearic acid amide, palmitic acid amide, oleic acid amide, etc., and (6) that of such a type as an addition product of 1 to 100 moles of ethylene oxide or 1 to 100 moles of both ethylene oxide and propylene oxide to one mole of aryl phenol having 2 to 5 benzene rings such as p-phenyl phenol, benzyl naphthol and tri-ethylbenzene phenol, etc.

The surface active agent of the present invention is prepared by the following method:

The compound wherein all of R R and R in the above formula are conventional surface active agent residues, is prepared by reacting one mole of triaryl phosphite or trichloroaryl phosphite with at least about 3 moles of a conventional surface active agent using a strong basic catalyst, which results in ester interchange of the former with the latter.

The compound wherein one or two of R and R in the formula are alkyl groups having 8 to 22 carbon atoms, is prepared by reacting one mole of triaryl phosphite or trichloroaryl phosphite with at least about three moles of both conventional surface active agent and higher alcohol, wherein the mole ratio of the surface active agent to the higher alcohol is approximately /2 to 2, using a strong basic catalyst.

A strong basic catalyst, which is used in the present invention, includes, for example, metal alcoholates such as sodium methylate, potassium phenolate, etc.; quaternary ammonium hydroxides; inorgamc strong bases such as sodium hydroxide, potassium hydroxide, etc; and alkali metals such as sodium, potassium, etc. As to the proportion of the basic catalyst, from 0.001 to 0.20 mole based on the moles of triaryl phosphite or trichloroaryl phosphite is preferable.

Triaryl phosphite or trichloroaryl phosphite, which is used in the present invention, includes, for example, triphenyl phosphite, tri-p-cresyl phosphite, tri-o-cresyl phosphite, tri-m-cresyl phosphite, tri-butylphenyl phosphite, tri-o-chlorophenyl phosphite, tri-p-chlorophenyl phosphite, tri-m-chlorophenyl phosphite, etc.

Conventional surface active agents, which are used in the present invention, are listed hereinbefore.

The higher alcohol, which is used in the present invention, is a saturated or unsaturated alcohol containing an 3 alkyl group having 8 to 22 carbon atoms which includes, for example, octanol, decanol, lauryl alcohol, myristyl alcohol, palmityl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, coconut alcohol, tridecyl alcohol, etc.

The ester interchange reaction of the present invention is effected at a temperature of 100 to 250 C. under atmospheric or reduced pressure, preferably a reduced pressure of l to mm. Hg.

The surface active agent of the present invention has several predominant characteristics; first, it exhibits heatresisting stability. Particularly, in the case where a nonionic surface active agent, which is used as raw material, has saturated alkyl group and does not contain amino or amide group and contains 1 to mols of either ethylene oxide or both ethylene oxide and propylene oxide, and Where the higher alcohol, which is used as the raw material, has a saturated alkyl group, the resultant surface active agent exhibits less weight-reduction due to volatilization and also less change in hue even if it is left in the atmosphere at a high temperature exceeding 200 C. for a long time. Such a high heat resistance couldnot be expected in conventional surface active agents. Secondly, all of the surface active agent of the present invention has remarkably reduced foaming property in comparison with conventional surface active agents.

The surface active agent of the present invention is widely used as an emulsifier, solubilizer, detergent, dispersant, lubricant, antistatic agent, defoaming agent, etc. in the similar manner to that of conventional sunface active agents. Among the surface active agents of the presuses as, for example, an antistatic agent and lubricant for synthetic fibers which are treated at a high temperature, additive for metal-lubricating oil which has antioxidative property, internal antistatic agent for synthetic molded article or synthetic fiber, and purifying and dispersing agent for engine oil, etc.

In order that the invention may be more fully under- Y stood, examples are given below.

EXAMPLE 1 490 g. of poly[8]oxyethylene lauryl ether, which were prepared by adding an average of 8 moles of ethylene oxide to 1 mole of commercial lauryl alcohol, 103 g. of triphenyl phosphite and 0.5 g. of potassium hydroxide were charged into a four neck flask equipped with an agitator, thermometer and vacuum apparatus. The resultant mixture was heated to 130 C. and stirred for one hour and then, treated under a reduced pressure of 10 mm. Hg at a temperature of 130 to 180 C. for three hours to effect dephenolization. 93 g. of phenol was distilled off. After filtration, colorless and transparent oily product having a speeific gravity of 1.014 (ZS/4 C.) was obtained. The resultant product proved that it did not have an infrared absorption spectrum corresponding to an OH product was tested as will be described later.

A numerical value within the brackets indicates an average number of moles of ethylene oxide added to the conventional surface active agent.

EXAMPLE 2 group. The

980 g. of poly[l5]oxyethylene-poly[2]oxypropylene g 4 hol, 103 g. of triphenyl phosphite and 0.5 g. of potassium hydroxide were treated in the same manner as'described in- Example 1 to effect dephenolization. 93 g. of phenol was distilled off. After filtration, a white waxy product was obtained. The product proved that it did not have an infrared absorption spectrum corresponding to an OH group. The product was tested as will be described later.

EXAMPLE 3 162 g. poly[9]oxyethylene lauryl ether, 138 g. of tri- (o-chlorophenyl) phosphite and 0.2 g. of sodium hydroxide were charged into a four neck flask equipped with an agitator, thermometer and vacuum apparatus. The mixture was heated to C. and then treated at a temperature from 130 to 180 C. .under a reduced pressure of 5 mm. Hg for two hours to effect dephenolization and to distill off 42 g. of o-chlorophenol. Further, 126' g. of commercial lauryl alcohol were added to the above product. Then, the mixture was treated at a temperature from 180 to 250 C. under a reduced pressure of 5 mm. Hg for 4 hours to effect dephenolization. 84 g. of o-chlorophenol were distilled off. After filtration, colorless and transparent oily product having a specific gravity of 0.952 (25/ 4 C.) was obtained. The resultant product proved that it did not exhibit an infrared absorption spectrum corresponding to an OH group. The product was also tested as will be described Methods similar to those described in Examples 1 to 3 were repeated except that starting materials and reacting conditions were as listed in Table l and Table 2, respectively.

OH group. They were tested as will. be described later.

TABLE 1 Ex. Nonionic surfactant Ph No. Higher alcohol G. este r i G. 4. Poly[8]oxyethy1ene 00!; l 560 Tri hl h phenol ether. y phii ph ii i enyl 138 5- Polylaloxypropylenepoly[10] 834 .....do 138 orgethylene nonyl phenol e er. I

6. Poly[10]oxyethylene oleyl 708 Trl-p-cresyl phos- 119 ether. phlte. 7. Polt3lr1[15]oxyethylenecetyl Y 902 .....do 119 Y a e er. 8. .-..Polyl2loxyethy1ene non l 308 Ti-o-cre 1 l1" I v phenol ether. y q phite. 9. Poly[18]oxyethylene trl-ethyl 1,199 .....do .119

benzene phenol ether. v 10--.- Poly[10]oxyethylene lauric I 654 'I'rl-butylphenyl am ester. 1 a phosphite. v, 11- Polyl3loxypropylene-polylQ] 710 ..-Ld0......'.'.-..-.-.'.

otxlyethylene butylphenol e er. 12- Poly[l0]oxyethylene hexa- 681 'Iri-phenyl phos- 103 decylamjne. phite. 13-... Poly[10]oxyethylene stearie 1722 -..-.do 103 acid amide. 14- Po1y[60]oxyethylene nonyl- 2,860 103 1 plhenol ether. 15 gggi 0157] 'lrl-o-chlorophenyl 138 Lam-y] alcohol; p "I i i 16 Poalggllilgoxyethylenelauryl 208 w t lphenyl 135 f li% 1------,;----=...-.- 87 PMSPM- o y oxyet lene oct 1- 395 I phenol ether. y 135 Decanol I 53 18 Poly[10]oxyethylene-poly[5 338 oxypropylene stearyl ether.

gtearlgll alcoh olim 187 oy oxye yeneol 4 261 i 19- i opylenelaurib e e id Tn'phenyl phosl 103 T amide. phite. p auryl alcohol 262 "'{P0lt[6]oxyethylene lauryl 296 103 e er. Lauryl alcohol 60 Poly[6]oxyethylene oleyl ether. 354 m3 glelsylzzallcoholifiul 90 0y oxye ene di-non l- 818 phenol ether. y 103 Myrlstyl alcohol 57 All of the resultant products proved that they did not"- have an infrared absorption spectrum corresponding to an TABLE 2 Amount of phenolic Reaction oompd. distilled Temp. Time ofi(g.) 0.) (hr.) Catalyst G. Appearance oiproduct Example No.

0. 2 Pale yellow and transparent oily. 0. 4 Colorless and transparent oily. 0. 3 Pale yellow and transparent oily. 8 NaOlight of the prodof 30 parts by 0.3 Pale yellow waxy.

(2) Emulsification At 220 C. for hr.

Decrement by volatilization (percent by weight) Each of the mixtures of parts by we net in Example 1 and parts by weight of refined mineral oil having a viscosity of sec., weight of the product in Example 15 and 70 parts by given in weight of refined mineral oil having a viscosity of 100 30 sec., and of 30 parts by weight of the product in Example 20 and 70 parts by weight of refined mineral oil having Heat-resisting stability At 220 C, for 1 hr.

Decrement by volatili- (p Hue weight) change stability Properties of the products obtained in the above Ex- TABLE 3 Testing items Foaming prop- (dyne/cm.) erty (mm.)

Immedi- 3 min; ately after after Hue 1% 0.5% dripping dripping change Properties of the surface active agent of the present tion is hereinafter described.

(1) Surface tension, foaming property and heat-resisting Surface tension v i i 0 n t I w m w v 0 v m m v n t n p t n 0 m 0 m m o t t t n M n m M n m p. m t .p. m 8 S a 0 m 8 D m n. n as P w a m aye". m B u m n mam u 0 m a n a my Y i m. mum hwhw n ls s SHUWS... 1. .SV 90 OOOM OBX m tmDDD e D t a m d mm m M C PWC YPYP 0% 55338559551559% 0 0 0 0 00 0 0 &0 00 0 & n rm u n n u u u n n Tm u u n n n n r .r u u .v. .m u n n n u "m n e :mm m u n m "awa t: "we .tt e m .tH .68 H mArHHmHHm Hmm Oaa MOOaOO aOaa KNN TKKNKKKNKNN 54333344332708 3 1 0000000000 000 mmwwmmwwwmmwmmm 11111 111111 11 778888443337444 220000229992222 11111111 1111 n u 4 amples 1 to 22 were determined. Results are Table 3 in comparison with conventional surface active agents.

inven Surfactants 3894678385255599621949 alzLnmomLLlfiz mkfiiamzamiLamnm nnnnncnnnnnocsccnnnnfln 3082377355 18161744487 LLL10 0 0 0 0 2 L0 &2 2 LL2LLQ 1.-.-..-..---.---.- S 165 c r 1 Control surface active agents are as follows: 1 poly[8]oxyethylene lauryl ether, 2 poly [8]oxyethy1ene octyl phenol ether, 3=poly[l0]oxyethylene oleyl phenol ether, 4=poly[20]oxyethylene sorbitan tristearate, 5=poly[10]oxyethylene stearic acid amide. 9 Surface tension was determined by a Du N oily-type tension meter at 25 C. a Foaming properties were tested by Ross Meiles method at 40 C. using 0.25% by weight solution of surfactant. Height of foams were determined immediately after and 3 min. after dripping.

4 Heat-resisting stability was tested by the following method; 30 g. of each sample surfactant were charged into a test tube (36 mm. x 200 mm.). Aiter the sam e was left in a thermostat at 220 C. r 6 hours without corking the test tube, decrement of the sample by volatlllzation and hue change of the sample were measured. Marks "n," gfilfiz" and r" designate no change," "slightly changed," changed" and remarkably changed," respec ve y.

a viscosity of 100 Saybolt sec. could be uniformly dispersed in water at room temperature.

In the case where a mixture of 30 parts by weight of the product in Example 6 and 70 parts by weight of butyl stearate was heated to 50 C. and then, 150 parts by weight of warm water at 60 C. were poured into the heated mixture while being gradually stirred, a uniform emulsion was obtained.

Further, in the case where a mixture of parts by weight of the product in Example 8 and 50 parts by weight of spindle oil having a viscosity of 150 sec. was heated to 80 C. and then, 35 parts by weight of warm water at 80 C. were gradually poured into the heated mixture while being stirred, a uniform and stable emulsion of w/o type was obtained.

Still further, in the case where 2 g. of the product in Example 14 was dissolved in 30 g. of water and then, 70 g. of commercial gasoline was dripped for min. while being violently stirred, a highly viscous emulsion having a viscosity of 20,000 cps. at 20 C. was obtained. The resultant emulsion was found to be useful for printing.

(3) Detergency As to the products in Examples 1, 4, 5, 10 and 17, detergency was tested by a detergency testing procedure determined by the Japan Oil Chemists Society using a Launder- O-Meter under the following conditions; temperature, 40i1 C.; time, 30 min.; 20 steel balls each having a diameter of M4 inch were used; number of revolutions, 40 r.p.m.; concentration of surfactant, 0.3% by weight. Spectral reflectance was determined by a spectrophotometer made by Hitachi Seisakusho, Japan, wherein a meas ured value of magnesium carbonate specimen was 100 in relation to the standard value. Detergency efficiency was calculated from the following equation:

Detergency efficiency (percent) 55 X 100 where;

D=Detergency efliciency of deterged fabric,

S=Detergency efficiency of stained fabric,

O=Detergency efficiency of original fabric. Results are given in Table 4.

TABLE 4 Detergency Surfactant efliciency Product in Example:

(4) Antistatic property to pick-up OWF, the taffeta was air-dried. -Anti'static property of the resultant taffeta was measured-by a Tex- I I and TABLE 5 Surface electric resistance (ohm) Nylon Surfactant Product in Example:

Tetoron Further as to the products in Examples 1-3, 13, 18, 19 and 20, antistatic property was tested by the following method:

0.2 g. of each product was added to g. of polyethylene ("Sumikasen L-702 made by Sumitomo Chemical, Japan) and the mixture was roll-milled at C. for 10 min. and then, subjected to press molding at C. for 10 min. to form a sheet having a thickness of 2 mm.

When the resultant sheet was superposed above the ash of cigarette at a distance of 1 cm. after it was rubbed with nylon cloth ten times, the ash was not attracted to the sheet, resulting in proof that the sheet contained a favorable antistatic property. On the other hand, in the case of the sheet which did not contain the product, the ash was attracted to it.

Color of both sheets did not change through the above press moulding.

What we claim is:

1. A surface active compound having the formula R1O\ RzO-P wherein R R and R are each the same residue of a nonionic surface active compound, said residue having a formula selected from a member of the group consisting of wherein in each of said formulas, n is an integer of 1 to 20.

2. A surface active compound according to claim 1 wherein each of R R and 3 is represented by the formula C EH11 wherein n is an integer of 1 to 20.

3. A surface active compound according to claim 1 wherein each of R R and R is represented by the wherein each of R R and R is represented by the forformula mula CnHro 5 @mmmon-cm.

-O(C3H40) r-CzHrwherein n is an integer of 1 to 20.

wherein n is an integer of 1 to 20.

4. A surface active compound according to claim 1 wherein each of R R and R is represented by the for- 10 References Cited UNITED STATES PATENTS mula 2,361,022 10/ 1944 Gilbert 260-403 c H 2,987,385 6/1961 De Gray 44-66 3,004,057 10/ 1961 Nunn, Jr 260-461 O (CIHO)H CZH V V 15 3,682,988 8 /1972 Lewls 260-403 C H ELBERT L. ROBERTS, Primary Examiner US. Cl. X.R.

wherein n is an integer of 1 to 20.

5. A surface active compound according to claim 1 25232.5, 351; 260-950, 951, 944

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4568480 *Nov 17, 1983Feb 4, 1986Basf Wyandotte CorporationMicroemulsions
US5202056 *Dec 30, 1991Apr 13, 1993Texaco Inc.Composition of matter for oligomeric aliphatic ethers as asphaltene dispersants
US5922897 *May 29, 1998Jul 13, 1999Xerox CorporationSurfactant processes
US5944650 *Oct 29, 1997Aug 31, 1999Xerox CorporationSurfactants
Classifications
U.S. Classification558/186, 987/217, 558/118, 554/78, 516/DIG.100, 516/24, 516/56, 508/431, 516/57, 558/117
International ClassificationC07F9/141, C09K3/16, B01F17/00, C11D1/78
Cooperative ClassificationY10S516/01, C11D1/78, C07F9/1411, C09K3/16, B01F17/0064
European ClassificationC07F9/141A1, C11D1/78, C09K3/16, B01F17/00R