Cleaning compositions for solid surfaces – auxiliary compositions – Cleaning compositions or processes of preparing – For cleaning a specific substrate or removing a specific...
Reexamination Certificate
2000-01-07
2003-05-20
Ogden, Necholus (Department: 1751)
Cleaning compositions for solid surfaces, auxiliary compositions
Cleaning compositions or processes of preparing
For cleaning a specific substrate or removing a specific...
C510S424000, C510S426000, C510S428000
Reexamination Certificate
active
06566319
ABSTRACT:
FIELD OF THE INVENTION
This invention is in the field of cleaning compositions, especially laundry detergents and the like, comprising modified alkylarylsulfonate surfactants, e.g., modified alkylbenzenesulfonates having specific light branching, which are the product of particular processes. The compositions further comprise specified cleaning adjuncts, such as enzymes or bleaches. The invention is also in the field of processes for making cleaning products, including processes comprising vinylidene olefin (VO) production, alkylation of arenes, sulfonation and domestic cleaning product formulation. VO production is used to introduce particular limited branching into an olefinic feedstock, preferably alpha-olefinic feedstock having carbon number consistent with making VO of from about 10 to about 16, preferably from about 10 to about 13 carbon atoms, effectively providing a “delinearized” long-chain olefin. Preferred processes maximize the amount of VO useful for detergent manufacture, and minimize deep internal olefin production. Further, an alkylation step, preferably having an internal isomer selectivity of from 0 to no more than about 40 is used, in which the VO monoalkylates arenes such as benzene, in presence of an alkylation catalyst, preferably comprising an at least partially crystalline, porous zeolite-containing solid, the zeolite being at least partially acidic and having intermediate pore size. Preferred alkylation catalysts include at least partially dealuminized acidic mordenites.
BACKGROUND OF THE INVENTION
Historically, highly branched alkylbenzenesulfonate surfactants, such as those based on tetrapropylene (known as “ABS” or “TPBS”) were used in detergents. However, these were found to be very poorly biodegradable. A long period followed of improving manufacturing processes for alkylbenzenesulfonates, making them as linear as practically possible (“LAS”). The overwhelming part of a large art of linear alkylbenzenesulfonate surfactant manufacture is directed to this objective. All relevant large-scale commercial alkylbenzenesulfonate processes in use today are directed to linear alkylbenzenesulfonates. However, linear alkylbenzenesulfonates are not without limitations; for example, they would be more desirable if improved for hard water and/or cold water cleaning properties.
In the petroleum industry, various processes have more recently been developed, for example for producing low viscosity lube oil, which the inventors have now discovered provide new insight on how to delinearize hydrocarbons for detergent manufacture to a limited and controlled extent. Such delinearization, however, is not a feature of any current commercial processes in the different field of alkylbenzenesulfonate surfactant manufacture for consumer products. This is not surprising, in view of the overwhelming volume of LAS surfactant art teaching toward linear compounds and away from delinearization.
The majority of commercial processes for making alkylbenzenes rely on HF or aluminum chloride catalyzed alkylation of benzene. Quite recently, it has been discovered that certain zeolite catalysts can be used for alkylation of benzene with olefins. Such a process step has been described in the context of otherwise conventional processes for manufacture of linear alkylbenzenesulfonates. For example, the DETAL® process of UOP uses a zeolite alkylation catalyst. The DETAL® process and all other current commercial processes for alkylbenzenesulfonate manufacture as currently practiced are well characterized based on the product they produce and all fail to meet the internal isomer selectivity requirements of the preferred inventive process and alkylation catalyst defined hereinafter. Other recent literature describes the use of mordenite as an alkylation catalyst, but no such disclosure makes the combination of specific process steps required by the instant invention. Moreover, in view of the linearity desired in alkylbenzenesulfonate products of conventionally known processes, they also generally include steps directed to the provision or making of a substantially linear hydrocarbon, not a delinearized one, prior to the alkylation. A possible exception is in U.S. Pat. No. 5,026,933 which includes, for example, oligomerization of lower olefin such as propylene under narrowly defined conditions using collidine-deactivated ZSM-23 to form a composition comprising a tetramer assertedly having 1.3 methyl branches per chain, followed by fractionation and an alkylation using mordenite catalyst. See Example XVII. See also U.S. Pat. No. 4,990,718 in the field of lubricant manufacture, in which an alkylbenzene is made for petrochemical industry additive purposes via a process that produces a vinylidene olefin by dimerization in presence of chromium catalyst but in which the vinylidene yield is adversely affected by oligomerization and deep internal olefin production and in which, in fact, the vinylidene dimer is not the major product, requiring removal of major amounts of non-vinylidene olefin prior to alkylation. The processes of '933 and '718 have numerous shortcomings from the standpoint of the detergent industry in terms of cost, catalyst limitations in the propylene oligomerization or olefin dimerization stage, presence of large volumes of distillation fractions that would need to be discarded or find nondetergent customers, and limited range of product compositions, including mixtures of chainlengths attainable. Such developments by the petroleum industry are, in short, not optimal from the standpoint of the expert formulator of detergent products.
Also of interest herein are U.S. Pat. Nos. 5,625,105 and 4,973,788 which relate to recent innovations in the manufacture of vinylidene olefins. These processes do not identify the desirability of arriving at modified alkylbenezenesulfonate surfactants or cleaning products as described herein, nor do they describe how best to accomplish such objectives. The inventors have now found that VO production according to '105 or '788 can be particularly useful as sub-processes in the context of the present invention.
BACKGROUND ART
U.S. Pat. Nos. 5,625,105; 4,973,788; 5,026,933; 4,990,718; 4,301,316; 4,301,317; 4,855,527; 4,870,038; 2,477,382; EP 466,558, Jan. 15, 1992; EP 469,940, Feb. 5, 1992; FR 2,697,246, Apr. 29, 1994; SU 793,972, Jan. 7, 1981; U.S. Pat. Nos. 2,564,072; 3,196,174; 3,238,249; 3,355,484; 3,442,964; 3,492,364; 4,959,491; WO 88/07030, Sep. 25, 1990; U.S. Pat. Nos. 4,962,256, 5,196,624; 5,196,625; EP 364,012 B, Feb. 15, 1990; U.S. Pat. No. 3,312,745; 3,341,614; 3,442,965; 3,674,885; 4,447,664; 4,533,651; 4,587,374; 4,996,386; 5,210,060; 5,510,306; WO 95/17961, Jul. 6, 1995; WO 95/18084; and U.S. Pat. No. 5,087,788 are useful by way of background to the invention. The manufacture of alkylbenzenesulfonate surfactants has recently been reviewed. See Vol. 56 in “Surfactant Science” series, Marcel Dekker, New York, 1996, including in particular Chapter 2 entitled “Alkylarylsulfonates: History, Manufacture, Analysis and Environmental Properties”, pages 39-108 which includes 297 literature references. Documents referenced herein are incorporated in their entirety.
SUMMARY OF THE INVENTION
The present invention is predicated on an unexpected discovery of superior consumer cleaning products such as laundry detergents, dishwashing agents and the like incorporating modified alkylarenesulfonate surfactants, especially modified alkylbenzenesulfonate surfactants which are made by a process which combines a specifically defined delinearization step, involving the manufacture of a vinylidene olefin, with a particularly defined selective alkylation step. The invention also relates to processes for the manufacture of such surfactants and cleaning products.
Accordingly, in one aspect, the present invention relates to a cleaning product comprising: (i) from about 0.1% to about 99% of a modified alkylarylsulfonate surfactant, wherein said modified alkylarylsulfonate surfactant (preferably a modified alkylbenzenesulfonate surfactant) is the product
Burckett-St. Laurent James Charles Theophile Roger
Connor Daniel Stedman
Cripe Thomas Anthony
Kott Kevin Lee
Scheibel Jeffrey John
Cook C. Brant
Ogden Necholus
Robinson Ian S.
Zerby Kim W.
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