US3647899A

US3647899A - Linear alkylbenzene compositions

Info

Publication number: US3647899A
Application number: US832293A
Authority: US
Inventors: Alan E Straus
Original assignee: Chevron Research and Technology Co
Current assignee: Chevron USA Inc
Priority date: 1969-06-11
Filing date: 1969-06-11
Publication date: 1972-03-07
Anticipated expiration: 1989-03-07
Also published as: US3769243A

Abstract

SULFONATED DERIVATIVES OF NOVEL DETERGENT ALKYLATE COMPOSITIONS EXHIBITING SUPERIOR SYNERGISTIC DETERGENT CHARACTERISTICS COMPRISE MIXTURES OF SECONDARY C11 AND C15 SULFONATED PHENYL-N-ALKANES IN A WEIGH RATIO OF FROM 1:10 TO ABOUT 4:1, RESPECTIVELY.

Description

March 7, 1972 PLATES WASHED A. E. STRAUS LINEAR ALKYLBENZENE C.R.D COMPOSITIONS Filed June 11, 1969 SYNERGISM IN MIXTURES OF SECONDARY C11 AND INTERNAL C15 SULFONATED PHENYL-N-ALKANES OBSERVED 7 l l l l 100 80 6O 4O 20 O l l I I I I O 20 4O 6O 80 100 WEIGHT PERCENT INVENTOR ALAN E. STRAUS BYMML aATTQRNEYE United States Patent Olfice 3,647,899 Patented Mar. 7, 1972 U.S. Cl. 260-668 3 Claims ABSTRACT OF THE DISCLOSURE sulfonated derivatives of novel detergent alkylate compositions exhibiting superior synergistic detergent characteristics comprise mixtures of secondary C and C sulfonated phenyl-n-alkanes in a weight ratio of from 1:10 to about 4: 1, respectively.

BACKGROUND OF THE INVENTION Field of the invention This invention relates to the field of synthetic detergent compositions and, more particularly, to biodegradable, synergistic mixtures of sulfonated phenyl-n-alkane detergent compositions.

Prior art In recent years, a significant emphasis has been placed upon finding suitable detergent compositions which do not deleteriously affect the ecological balance of water bodies used for receiving treated or untreated municipal and industrial waste. As a result, biodegradable sulfonated phenyl-n-alkanes have been substituted on a large commercial basis for the less biodegradable branched-chain alkylbenzene sulfonates. Much effort and research have been devoted to developing sulfonated phenyl-n-alkane mixtures approaching or equalling the high detergent efficiency of the alkylbenzene sul fonates. For example, U.S. 3,340,141, and Ser. No. 676,707, filed Oct. 20, 1967, disclose detergent alkylate and sulfonated detergent alkylate compounds which exhibit high detersive characteristics comprising mixtures of secondary phenyl-n-alkanes containing 11 to 14 carbon atoms in the alkane portion of the molecule. In particular, these mixtures are low in 2- and 3-phenyl-n-alkane isomers which impair detersive effectiveness. As indicated in the aforementioned patent, it is known that the C sulfonated phenyl-n-alkanes show very poor detergency. In addition, heretofore the C sulfonated phenyl-n-alkanes have not shown acceptable detersive characteristics. In fact, most references in the art prefer and are limited to mixtures of C sulfonated phenyl-n-alkanes.

SUMMARY OF THE INVENTION Surprisingly, We have now found that mixtures of secondary C and C sulfonated phenyl-n-alkanes exhibit excellent synergistic detergency which is not expected or predictable from their individual detersive characteristics. In particular, the novel compositions of the present invention comprise mixtures of sulfonated phenyl-nalkanes containing secondary C and C sulfonated phenyl-n-alkanes in a weight ratio of from about 1:10 to 4:1 and, preferably, 1:4 to 1.5 :1. More preferably, the C sulfonated phenyl-n-alkane portion is low in the 2- and 3-phenyl isomers.

In addition, the C and C components may be combined within the described ratio with other satisfactory sulfonated phenyl-n-alkanes detergents, with no adverse effect on the overall detergency. That is, for example, an excellent detergent composition may contain 30 percent of secondary C and C sulfonated phenyl-n-alkanes in the proper proportions, and percent of a mixture of C C sulfonated phenyl-n-alkanes low in the 2- and 3-phenyl isomers.

DESCRIPTION OF DRAWING The figure graphically depicts the observed synergistic effect of mixtures of C and C sulfonated phenyl-nalkanes as compared to the predicted effect.

DETAILED DESCRIPTION OF INVENTION The secondary phenyl-n-alkanes utilized in the present invention may be prepared by conventional methods as known in the art. These methods include the alkylation of benzene or its derivatives, such as toluene and xylene, with n-alkenes or n-haloalkanes containing from 11 to 15 or more carbon atoms. The n-alkenes or n-haloalkanes may be derived from distillate cracking or wax cracking, catalytic dehydrogenation of n-alkanes, chlorination-dehydrochlorination of n-alkanes, ethylene polymerization and chlorination of n-alkanes. In addition, the raw materials from which the straight-chain stock is to be derived may be subjected to iso-normal separation processes, such as molecular sieves, and urea clathration to produce a more linear product than can otherwise be obtained.

After alkylation of the benzene ring or its derivative, the aromatic portion is sulfonated by known methods with such agents as chlorosulfonic acid, sulfur trioxide, and oleum, etc.

The mixtures of secondary C and C sulfonated phenyl-n-alkanes may be directly used as the active ingredient to form excellent detergent compositions, or may be beneficially combined with mixtures of other sulfonated phenyln-alkanes. In the latter use where the other sulfonated phenyl-n-alkanes are superior in dishwashing ability to the secondary C and C mixture, the C and C component may range from as much as 30 to 40 percent and, preferably, from 5 to 20 percent by weight of the active ingredient of the detergent composition. However, where the other sulfonated phenyl-n-alkanes are equivalent or less in dishwashing ability, there is no limitation on the amount of the C and C utilized. Preferably, the C and C mixtures are combined with C C mixtures low in the 2- and 3-phenyl isomers. In effect, the incorporation of C and C mixtures into other sulfonated phenyl-n-alkanes often increases the average molecular weight, broadens the acceptable range of usable phenyl-n-alkanes and, accordingly, provides significant economic advantages and incentives.

The secondary C sulfonated phenyl-n-alkane component may comprise isomers containing internal phenyl attachment (4-, 5-, and 6-isomers), end phenyl attachment (2-, and 3-isomers) or a distribution over the whole isomer range. All distributions of the C isomers exhibited the excellent synergistic effect upon combination with the C compound.

The C sulfonated phenyl-n-alkanes also showed excellent synergism for the end phenyl attachment (2-, and 3-isomers) and for distribution over the whole range of isomers. Surprisingly, however, the internal phenyl attachment (5-, 6-, 7-, and 8-isomers) exhibited substantially increased synergism over the end and whole isomer distributions. In general, mixtures of C sulfonated phenyl-n-alkanes containing at least 70% by weight of internal isomers and preferably from to showed this increased synergism.

In general, the ratio of C to C sulfonated phenyl-nalkanes may vary from about 1:10 to about 4:1, respectively. Preferably, however, the ratio ranges from 1:4 to about 1521.

Additional compatible ingredients may be incorporated into the detergent compositions prepared in accordance with the present invention to enhance their detergent properties. Such ingredients may include, but are not limited to, anticorrosion, anti-redeposition, bleaching and sequestering agents, optical whiteners and certain organic and inorganic alkali and alkaline earth salts, such as inorganic phosphates, sulfates, carbonates or borates, and the organic salts, such as sulfosuccinates, Xylene sulfonates, and the alkali metal salts of polycarboxylic acids; e.g., trisodium salt of nitrilo triacetic acid, tetrasodium salt of ethylenediaminetetraacetic acid, etc.; and the sodium salt of the copolymer of maleic anhydride and ethylene. The appropriate quantities and compositions of these additives, agents and builders are well described in the art.

An effective means for evaluating the detersive characteristics of detergent compositions is known as the Hand Dishwashing Test which is based on a procedure presented at the ASTM D-12 Subcommittee on Detergents, Mar. 10, 1949, New York, NY. The test measures, under simulated home washing conditions, the number of plates or dishes Washed before the foam collapses. This test was utilized to evaluate the improved performance of the disclosed detergent compositions.

Detergent formulations were prepared from the sulfonated phenyl-n-alkane mixtures of the present invention, water and other ingredients. The formulations were adjusted until the percentage of sulfonated phenyl-n-alkanes equalled about 25 percent by weight of the total detergent formulation.

In the following examples, the concentrations employed in the Hand Dishwashing Test were 0.15 percent by weight of the total detergent formulation.

Example 1 illustrates a suitable detergent formulation prepared from the sulfonated phenyl-n-alkane mixtures of the present invention.

EXAMPLE 1 A detergent formulation was prepared containing the following percentages of each ingredient, based on the total weight of the formulation:

The formulation was tested and found effective in accordance with the Hand Dishwashing Test for a rating of 18 plates.

Example 2 is an analysis of the mass distribution of the side chains in the C1144 sulfonated phenyl-n-alkanes used in subsequent evaluation.

[Mass distribution of side chains] W ght, Mole, percent ei Mass distribution of side chains percent Average molecular weight Table I, discloses the phenyl isomer distribution of the C and C alkylates of the present invention.

Straight-chain isomer distribution, Weight percent fi-phenyl through Ex. Phcnyl-nalkanes S-phenyl 4-phenyl B-phenyl Z-phenyl 10 13 27 50 84 11 4 1 10 1 (end 15 16 29 C15 (whole) 61 13 12 14 7 011-14 3 16 16 23 8 80% Oil-ll 3 plus 20% 52 15 14 19 'nternal 15. 9 80% 011-14 3 plus 20% 48 16 15 21 whole C15.

15 1 Contains 6% C14.

2 Two parts internal/one part end; contains 4% Cu. 3 Sulfonatcd phenyl-n-aikane of Example 2.

Table II, illustrates the synergistic effect of the C C sulfonated phenyl-n-alkane blends of the present 20 invention. It is noted that the synergistic effect for the C internal isomers in Example 15 is almost double that of the C whole isomers of Example 17.

TABLE II [Dishwashing performance of 0.15% concentrations of formulations 1 containing C11 and C15 suifonated phcnyl-n-alkanes (50 ppm. hardness)] 13-... C1 (whole) Gil-Q1? internal) mixtures by 1 2:1 17...- C15 (Whole) l/l:Cu-Ci5-..-

u- 19. Cir-14 plus 20% 015 (internal). 20---- 80% Gil-14 Plus 20% C15 (whole).--

1 24/40/7/1/20/8 formulation. 2 Suliouated plienyl-n-alkane of Example 2. N orE.See Table I for compositions.

While the character of this invention has been described in detail with numerous examples, this has been done by way of illustration only and without limitation of the invention. It will be apparent to those skilled in the art that modifications and variations of the illustrative examples may be made in the practice of the invention within the scope of the following claims.

What is claimed is:

1. A detergent alkylate composition comprising from about 10 to percent by weight of secondary C phenyln-alkanes and from about 15 to percent by weight of secondary C phenyl-n-alkanes.

2. A detergent alkylate composition as in claim 1, wherein from 50 to Weight percent of the C phenyl-nalkanes are the 5-, 6-, 7-, and 8-positional isomers.

3. A detergent alkylate composition as in claim 2, wherein the secondary C phenyl-n-alkanes are present in an amount of from about 20 to 70 percent and the secondary C phenyl-n-alkanes are present in an amount of from about 30 to 80 percent.

References Cited UNITED STATES PATENTS U.S. Cl. X.'R.