US3691108A

US3691108A - Olefin sulfonate detergent composition

Info

Publication number: US3691108A
Application number: US68042A
Authority: US
Inventors: Eiichi Ichiki; Kazuo Iida; Yasuhiko Inoue; Keizo Uyeo
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 1969-08-29
Filing date: 1970-08-28
Publication date: 1972-09-12
Anticipated expiration: 1989-09-12
Also published as: NL162132C; GB1304565A; DE2042871A1; FR2059411A5; NL7012790A; NL162132B; JPS505722B1; BE755471A

Abstract

An olefin sulfonate detergent composition containing, as active ingredients, a mixture consisting essentially of (a) 25 to 75 parts by weight of a sulfonate of a straight chain a-olefin represented by the general formula

Description

United States Patent Ichikiet al.

[ OLEFIN SULFONATE DETERGENT COMPOSITION [73] Assignee: Sumitomo Chemical Co., Ltd.,

l-ligashi-ku, Osaka, Japan 22 Filed: Aug. 28, 1970 [21] Appl.No.: 68,042

30 Foreign Application Priority new Aug. 29, 1969 Japan ..44/68853 [52] US. Cl. .Q. ..252/555, 252/531, 252/536, 252/539, 252/550, 252/558 [51] Int. Cl. ..Clld 3/065,Cl1d 1/12 [58] Field of Search ..252/l38, 161; 260/513 [56] References Cited UNITED STATES PATENTS 3,544,475 12/1970 Tomiyama et al ..252/161 3,492,239 1/1970 Baumann et a1 ..252/l6l FOREIGN PATENTS OR APPLICATIONS 1,042,854 9/ 1966 Great Britain 1,139,158 1/1969 Great Britain 1 Sept. 12, 1972 Primary Examiner-Leon D. Rosdol Assistant Examiner-P. E. Willis Attorney-Wenderoth, Lind & Ponack [57] ABSTRACT An olefin sulfonate detergent composition containing, as active ingredients, a mixture consisting essentially of (a) 25 to 75 parts by weight of a sulfonate of a straight chain a-olefin represented by the general formula R' CH CH,

wherein R' is an alkyl radical of 12 to 20 carbon atoms, and the average number of bonded S0, radicals of said sulfonate is 1.05 to 1.7, and (b) 75 to 25 parts by weight of a sulfonate of a vinylidene olefin represented by the general formula wherein R" and R'" each is an alkyl radical of one to 19 carbon atoms and the sum of the carbon atoms of R" and R'" is 12 to 22, and the average number of bonded S0 radicals of said sulfonate is 1.05 to 1.7.

5 Claims, No Drawings OLEFIN SULFONATE DETERGENT COMPOSITION This invention relates to a detergent composition and more particularly to an olefin sulfonate detergent composition which is excellent particularly in detergent and wetting characteristics and comprises, as active ingredients, a mixture of a sulfonate of a straight chain type a-olefin and a sulfonate of a vinylidene type olefin.

it is known, for example, from British Patent No. 1,042,854 to use a sulfonate of a straight chain type aolefin as an active ingredient of a detergent. Such a sulfonate is comparatively high in detergent and wetting properties among the active ingredients for detergents now commercially available.

We have now found that, when sulfonates of two different kinds of olefins in the carbon chain structure, Le. a straight chain type a-olefin and a vinylidene type olefin are mixed together in particular proportions, there is obtained outstanding detergent characteristics which cannot be expected from each sulfonate alone.

An object of the present invention is to provide an olefin sulfonate detergent composition comprising, as its active ingredient, a mixture comprising (a) 20 to 80 parts by weight of a sulfonate of a straight chain type aolefin represented by the general formula wherein R is an alkyl radical of 12 to 20 carbon atoms,

mula wherein R" and R'" each is an alkyl radical of one to 19 carbon atoms and the sum' of the carbon atoms of R" andR' is 12 to 22.

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

become ln this specification, the term a sulfonate of a straight chain type a-olefin is used in an ordinary meaning including an alkenesulfonate and hydroxyalkanesulfonate synthesized from a straight chain type aolefin. The term a sulfonate of a vinylidene type olefin is used also in the same meaning as is mentioned above.

Generally the sulfonate of the straight chain type aolefin and the sulfonate of the vinylidene type olefin are mixed in such a proportion that the sulfonate of the straight chain type a-olefin to the sulfonate of the vinylidene type olefin is 20 to 80:80 to 20 by weight, preferably 30 to 70:70 to 30 by weight. When the amount of the sulfonate of the straight chain type aolefin is lessthan 20 parts by weight or more than 80 parts by weight, the desired synergistic effect becomes slight so that the increase in the detergency intended by the present invention can not be obtained.

The sulfonate of the straight chain type a-olefin to be used in the present invention may be produced by any known process. Thus, for example, the straight chain type a-olefin to be used for the production of the sulfonate of the straightchain type a-olefin has 14 to 22 carbon atoms, preferably 15 to 18 carbon atoms and may be used alone or as a mixture of two or more olefin. Such a straight chain type a-olefin may be produced, for example, by the low molecular weight polymerization of ethylene or by the decomposition of wax. The straight chain type a-olefin to be obtained by such process need not be exactly inthe above mentioned range of carbon atoms but may well contain up to about l0 parts by weight of olefin(s) having carbon atoms outside the above mentioned range. As typical straight chain type a-olefins, there may be enumerated tetradecene-l, pentadecene-l, hexadecene-l, heptadene-l, octadecene-l, nonadecene-l, eicosene-l, heneicosene-l and docosene- 1. Then the straight chain type a-olefin is sulfonated with a sulfonating agent such as sulfur trioxide diluted with an inert gas, chlorosulfonic acid, fuming sulfuric acid or a dioxane complex of sulfur trioxide. The sulfonating condition is not critical and may be any known one. However, generally the sulfonation is carried out at a temperature'in the range of 0 to C., preferably from 10 to 40C. Further, it is preferable that the sulfonation is conducted until the average number of bonded S0 radicals perolefin is 1.05 to 1.72. The sulfonated reaction product is then hydrolyzed with an alkali or acid and is then neutralized, for example, with an aqueous solution of a hydroxide of an alkali metal or an alkaline earth metal, ammonia or an organic amine compound. Further, in some cases, the sulfonated product or the neutralized product may be bleached with a proper bleaching agent such as sodium hypochlorite. The sodium salt of the sulfonate of the straight chain type a-olefin is used as an active ingredient.

The sulfonate of the vinylidene type olefin which is another essential ingredient of the detergent according to the present invention may also be produced by any known process such as follows. The vinylidene type olefin to be used for the production of the sulfonate of the vinylidene type olefin has 14 to 24 carbon atoms, preferably 17 to 22 carbon atoms in average. Such vinylidene type olefin may be used alone or preferably as a mixture of two or more. The vinylidene type olefin in the above-mentioned range of carbon atoms may be produced, for example, by a process wherein a low molecular weight straight chain type a-olefin obtained by the low molecular weight polymerization or decomposition of wax is dimerized or codimerized. The thus obtained vinylidene type olefin need not be exactly in the above-mentioned range of the number of carbon atoms but may well contain up to about 10 percent of olefin(s) having carbon atoms outside the above-mentioned range.

As typical vinylidene type olefins, there may be enumerated 2-methyltetradecene-l, 2-methyloctadecenel Z-methyleicoserie-l 2-hexyloctene-l tyldodecene-l, 2-hepty1decene-l, 2-octyldecene-l, 2- hexyldodecene-l 2-heptylundecene-l Z-hexyltridenel, 2-heptyldodecene-l, 2-octylundecene-l, 2-nonyldecene-l 2-octyldodecene-l, Z-hexyItetradecene-l 2- heptyltridecene-l, 2-nonylundecene-l, 2-decyldecenel, 2-heptyltetradecene-l, 2-octyltridecene-l, 2-nonyldodecenel 2-decylundecenel, 2-octyltetradecenel, 2-nonyltridecenel 2-decyltridecenel 2-nonyltetradecene-l and Z-decyltetradecenel 2-butyldecene-l, 2-butylundecene-l, 2-hexyldecene-l, 2-bu- Thevinylidene type olefin is sulfonated with a known sulfonating agent such as sulfur trioxide diluted with an inert gas, chlorosulfonic acid, fuming sulfuric acid or a dioxane complex of sulfur trioxide. The sulfonating condition is not critical and may be any known one. However, generally the sulfonation is carried out at a temperature in the range of to 100C. Further, it is preferable that the resulting sulfonate has 1.0 1.9, preferably 1.05 1.7 in the average number of bonded S0 radicals per olefin. Then the product may be treated in the same manner as explained before in respect of the production of the sulfonate of the straight chain type a-olefin.

The sodium salt of the sulfonate of the vinylidene type olefin is used as an active ingredient.

In the production of the active ingredients to be used in the present invention, the above-mentioned two kinds of olefins differing in the carbon chain structure may be respectively separately sulfonated, hydrolyzed and neutralized and then mixed together or may be first mixed together and then sulfonated, hydrolyzed and neutralized.

The detergent composition of the present invention may also contain other additives.

Thus, for example, the detergent composition may contain a builder which may be organic or inorganic salt. Examples of such builders are trisodium phosphate, tetrasodium pyrophosphate, acid sodium pyrophosphate, sodium tripolyphosphate, sodium metasilicate, sodium silicate, sodium carbonate, sodium sulfate, borax, ethylenediamine sodium tetracetate or sodium nitrilotriacetate A mixture of two or more of them may also be used. Among them, particularly the polyphosphate salt of an alkali metal ispreferable because it enhances the detergent effect of an anionic surface active agent.

Further, the detergent composition may also contain other additives which are usually used in this field. Examples of such additives are hydrotropic stabilizers such as sodium xylenesulfonate or sodium toluenesulfonate, antidepositing agents such as sodium carboxymethyl cellulose or polyvinyl alcohol, an optical or fluorescent brightening agent, a sterilizer or a perfume.

The active ingredients of the present invention may also be used in combined with other known active ingredients such as, for example, a sodium alkylbenzenesulfonate or sodium alkylsulfate. In this way, there can be obtained remarkably higher detergent and wetting characteristics than in the case where the known active ingredient is used alone. In such cases, it is desirable to use the active ingredient mixture of the present invention in an amount more than 20 parts by weight based on the total active ingredients, although it may be used even below 20 parts by weight.

Though the amount of the active ingredients is dependent on the particular use, the active ingredients are used generally in an amount more than parts by weight, preferably to 50 parts by weight based on the total detergent composition.

The invention will be further explained by referring to the following examples wherein all percentages are by weight unless otherwise specified and various tests were conducted as follows:

Detergency test l. The detergent composition used in the detergency test was consisted of 25 percent by weight of active ingredient(s) 40 percent by weight sodium tripolyphosphate, 10 percent by weight sodium silicate, 1 percent by weight carboxymethyl cellulose and 24 percent by weight sodium sulfate.

2. The stained cloth to be cleaned in the test was prepared by dipping a white cotton cloth (100 mm. long and 50 mm. wide) in a liquid consisting of 0.5 g. of beef tallow, 0.5 g. of active carbon, 1.4 g. of fluid paraffin and 400 g. of carbon tetrachloride, for 1 minute.

3. Washing condition was as follows. Thus 100 ml. of an aqueous solution containing 0.1 percent (or 0.2 percent) by weight of the active ingredient(s) were prepared and three sheets of the above mentioned stained cloth were perfectly immersed in the solution and were washed with a Launder-O-Meter (with rubber balls having 15 mm. diameter) at 42 rpm. The washing was conducted at 30C. for 30 minutes. Then the stained cloth was rinsed with clean water for 5 minutes and was then air-dried and ironed.

4. The detergency value was calculated by the following formula:

Detergency value (R R /R R X 100 wherein R is a reflection factor of a white cotton cloth, R is a reflection factor of a stained cloth and R is a reflection factor of a washed cloth. The reflection factor was shown with the reflection degree (100) of a white plate of MgO as standard. Wetting force test The wetting force was determined according to the method by G. Schwen (Melliand Textilber 32 910 (1951)). Thus, a felt cloth 1 mm. thick was preparatorily washed, a test piece 15 mm. in diameter was made thereof. The test piece was floated on an aqueous solution of an active ingredient and the time until it began to sink was measured at a temperature of 30C.

PREPARATION In a four-necked flask (200 ml.) fitted with an agitator, thermometer, gas inlet and gas outlet provided with a reflux condenser, 95.5 g. of hexadecene-l were charged. Then, while keeping the temperature at 20 to 25C., 50;, gas diluted to be 3 percent by volume with nitrogen gas was introduced at a rate of 1 liter/minute to start the reaction. After 48 g. of SO were blown in, the reaction was stopped.

Then an aqueous solution of NaOH of 1.5N was added to the system to adjust the pH to 7. The system was then heated to C. to conduct the hydrolysis. During the reaction, the aqueous solution of NaOH was added to the system so as to keep the pH at 7.

Then 20 ml. of 5 percent aqueous solution of NaOCl were added to the reaction product and the product was bleached at 95C. for 2 hours. The reaction product was extracted with hexane to remove unreacted olefin and then water was evaporated away to recover a solid product. The solid product was then dissolved in methanol and the alcohol-insoluble part was separated. The methanol was evaporated to obtain 1 16 g. of refined sodium sulfonate of hexadecene- 1.

The sulfonate of the straight chain type a-olefin and the sulfonate of the vinylidene type olefin used in the following examples were prepared in the same manner as explained above.

5 EXAMPLEI Detergent compositions shown in Table l and containing sodium sulfonate of hexadecene-l (straight chain type) having an average number of bonded S radicals of 1.05 and mixed sodium sulfonate of an equivalent mixture of 2-hexyldodecene-l and 2-octyldecene-l (vinylidene type) having an average number of bonded S0 radicalsof 1.05 were prepared and their detergency values and wetting forces were measured. The results are shown in Table l.

It is clear fromTable 1 that 20 to 80 percent of a sulfonate of a straight chain type a-olefin must be contained in the detergent composition in order to obtain an excellent effect.

,EXAMPLEZ Sodium sulfonate synthesized from 2-hexyldecene-l (vinylidene type) and having an average number of bonded S0 radicals of 1105 and sodium sulfonate synthesized from hexadecene-l (straight chain type) and having an average number of bonded S0 radials of 1.05 were mixed together as shown in Table 2. The detergency values and wetting forces of the thus obtained detergent compositions were measured. The results are shown in Table 2.

TABLE2 ExperimentiNo. vr vn Vlll Active Straight chain type I00 50 0 ingredient vinylidene type 0 50 100 Deter- Active ingredient congency centration: value 0.1 k by weight 52 55 48 i v I 0.2 by weight 54 56 54 Wett- Active ingredient coning centration: force (sec.) l0 moi/liter 30 5 1 EXAMPLE 3 A mixed sodium sulfonate of a straight chain type 0:- olefin mixture consisting of 14 percent tetradecene-l, 20 percent pentadecenel, 21 percent hexadecene-l, 23 percent heptadecener-l percent octadecene-l, 5 percent nonadecene-l and 2 percent of other olefins and having an average number of bonded S0 radicals of .l .05 and a mixed sodium sulfonate of a vinylidene type olefin mixture consisting of 13 percent 2-hexyloctene-l, 14 percent 2-butyldecene-l, 22 percent 2-hexyldecene-l, 12 percent 2-butyldodecene, 16 percent 2- octyldecene-l, 15 percent 2-hexyldodecene-l and 6 percent of other olefins were mixed together as shown in Table 3. The detergency values and wetting forces of the obtained detergent compositions were measured. The results are shown in Table 3. i

TABLE 3 Experiment No. XI

Active I00 50 ingre dient Detergency value Straight chain type Vinylidene type 0 50 mo Active ingredient concentration:

0.1 by weight 0.2 by weight Active ingredient concentration:

5 l 5 7 Wetting force (sec.)

10' mol/liter 29 5 3 EXAMPLE 4 TABLE 4 Experiment No. X]! Xlll XlV Active ingredient Detergency value Straight chain type I00 50 vinylidene type 0 Active ingredient concentration:

0.l by weight 0.2 by weight Active ingredient concentration:

56 60 Wetting force (sec.)

l0 mol/liter 29 5 2 EXAMPLE 5 A mixed sodium sulfonate of a straight chain type aolefin mixture consisting of 30 percent octadecene, 32 percent eicocene-l, 25 percent dodecene-l and 3 percent of others and having an average number of bonded S0 radicals of 1.3 and a mixed sulfonate of a vinylidene type olefin mixture consisting of 9 percent 2- heptylundecene, 9 percent Z-heptyldodecene, 10 percent 2-octylundecene, 22 percent 2-octyldodecene, 8 percent 2 nonylundecene -l, 11 percent 2-octyltridecenel, 10 percent 2-nonyldodecene l 12 percent 2-nonyltridecene-l, and 9 percent of other olefins and having an average number of bonded S0 radicals of 1.5 were mixed together as shown in Table 5 and the detergency values and wetting forces were measured. The results are shown in Table 5.

TABLE Experiment No. XV XVI XVII Active Straight chain type 100 50 0 ingredialnt Vinylidene type 0 50 100 Dcter- Active ingredient congcncy centration: value ('k) 0.1% by weight 53 57 48 0.2 70 by weight 55 62 S3 Wetting Active ingredient conforce centration: (sec.)

" moi/liter 27 5 4 It will understood from Tables 1 to 5 that the detergent composition containing the combined active ingredients according to the present invention is far better in detergent characteristics than each of the sulfonates of the straight chain type a-olefin and vinylidene type olefin as used alone and is higher in wetting force thanv the sulfonate of the straight chain type aolefin.

EXAMPLE 6 A sodium alkylbenzenesulfonate (A) of an average number of carbon atoms of the alkyl radical of 12, sodium laurylsulfonate (B), sodium sulfonate of hexadecene-l (straight chain type) of an average number of bonded S0 radicals of 1.05 and an equivalent olefin mixture of 2-hexyldodecene-1 and 2-octyldodecene-1 (vinylidene type) and of an average number of bonded S0 radials of 1.05 were mixed together as shown in Table 6, the detergency values and wetting forces were measured and the results are shown in Table 6;

It will be understood from Table 6 that, when the combined active ingredients of the present invention are used together with a known sodium alkylbenzenesulfonate or sodium laurylsulfate, there can be obtained a product higher in both detergent and wetting characteristics than in the case of using each alone.

What is claim is:

1. An olefin sulfonate detergent composition consisting essentially of a mixture of (a) to 25 parts by weight of a sulfonate of a straight chain a-olefin represented by the general formula v R'CI-l=C1-l wherein R' is an alkyl radical of 12 to 20 carbon atoms, and the average number of bonded S0 radicals of said sulfonate is 1.05 to 1.7, and (b) 75 to 25 parts by weight of a sulfonate of a vinylidene olefin represented by the general formula wherein R" and R'" each is an alkyl radical of one to 19 carbon atoms and the sum of the carbon atoms of R" and R'" is 12 to 22, and the average number of bonded S0 radicals of said sulfonate is 1.05 to 1.7.

2. The detergent composition of claim 1 wherein each of the sulfonate of thestraight chain a-olefin and the sulfonate of the vinylidene olefin is the sodium salt thereof.

3. An olefin sulfonate detergent composition according to claim 1, wherein the number of the carbon atoms of the sulfonate of the straight chain a-olefin is 15 to 18 and the number of the carbon atoms of the sulfonate of the vinylidene olefin is 17 to 22 in average.

4. An olefin sulfonate detergent composition according to claim 1, wherein the straight chain a-olefin is a member selected from the group consisting of tetradecene-l, pentadecene-l, hexadecene-l, heptadecene-l, octadecene-l, nonadecene-l, eicosene-l, heneicosenel docosene-l and a mixture thereof.

5. An olefin sulfonate detergent composition according to claim 1, wherein the vinylidene olefin is a member selected from the group consisting of 2- methyletradecene- 1, 2-methy1octadecene- 1 2- methyleicosene- 1, 2-hexyloctene-1, Z-butyIdecene-l 2-butylundecene- 1, 2-hexyldecene-l, 2-butyldodecene-l, Z-heptyldecene-l, 2-octyldecene-l, 2- hexyldodecene- 1, 2-heptylundecene- 1 2-hexyltridecene- 1, 2-heptyldodecene- 1, 2-octy1undecene-1, 2-nonyldecene-l, 2-octyldodecene- 1, 2-hexyltetradecene-l 2-hepty1tridecene-1, 2-nony1undecene- 1, 2-decyldecene-1, 2-heptyltetradecene-1, 2-octy1- tridecene- 1 2-nonyldodecenel 2-decy1undecene- 1, 2-octyltetradecenel, 2-nonyltridene-l 2-decyltridecene-l 2-nonyltetradecene- 1, 2-decyltetradecene-l and a mixture thereof.

Claims

2. The detergent composition of claim 1 wherein each of the sulfonate of the straight chain Alpha -olefin and the sulfonate of the vinylidene olefin is the sodium salt thereof.
3. An olefin sulfonate detergent composition according to claim 1, wherein the number of the carbon atoms of the sulfonate of the straight chain Alpha -olefin is 15 to 18 and the number of the carbon atoms of the sulfonate of the vinylidene olefin is 17 to 22 in average.
4. An olefin sulfonate detergent composition according to claim 1, wherein the straight chain Alpha -olefin is a member selected from the group consisting of tetradecene-1, pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1, nonadecene-1, eicosene-1, heneicosene-1, docosene-1 and a mixture thereof.
5. An olefin sulfonate detergent composition according to claim 1, wherein the vinylidene olefin is a member selected from the group consisting of 2-methyletradecene-1, 2-methyloctadecene-1, 2-methyleicosene-1, 2-hexyloctene-1, 2-butyldecene-1, 2-butylundecene-1, 2-hexyldecene-1, 2-butyldodecene-1, 2-heptyldecene-1, 2-octyldecene-1, 2-hexyldodecene-1, 2-heptylundecene-1, 2-hexyltridecene-1, 2-heptyldodecene-1, 2-octylundecene-1, 2-nonyldecene-1, 2-octyldodecene-1, 2-hexyltetradecene-1, 2-heptyltridecene-1, 2-nonylundecene-1, 2-decyldecene-1, 2-heptyltetradecene-1, 2-octyltridecene-1, 2-nonyldodecene-1, 2-decylundecene-1, 2-octyltetradecene-1, 2-nonyltridene-1, 2-decyltridecene-1, 2-nonyltetradecene-1, 2-decyltetradecene-1 and a mixture thereof.