Washing and cleaning agent containing a sulfonated polybutadiene builder salt
von Praun et a1.  
 WASHING AND CLEANING AGENT CONTAINING A SULFONATED POLYBUTADIENE BUILDER SALT Inventors: Ferdinand von Praun,  
 Lippramsdorf-Freheit; Kurt Kosswig, Marl, both of Germany Assignee: Chemische Werke I&#39;IueIs, A.G.,  
 Marl, Germany Filed: Dec. 6, 1972 Appl. No.: 312,751  
 Foreign Application Priority Data [11] 3,875,070 Apr. 1, 1975 [56] References Cited UNITED STATES PATENTS 2,913,429 11/1959 Floria et a1. 117/6 X 1 3,079,284 2/1963 Boucher et al.. 252/121 UX 3,431,206 3/1969 Hilton 252/99 3,503,892 3/1970 Weyna et al..... 252/531 X 3,579,455 5/1971 Sabatelli et a1. 252/99 X 3,598,744 8/1971 Smeets 252/99 3,741,912 6/1973 Kanedo 252/99 X Primary Examiner-Benjamin R. Padgett Assistant Examiner-P. A. Nelson Attorney, Agent, or Firm-Millen, Raptes &amp; White [57] ABSTRACT 20 Claims, No Drawings WASHING AND CLEANING AGENT CONTAINING A SULFONATED POLYBUTADIENE BUILDER SALT BACKGROUND OF THE INVENTION The present invention relates to washing and cleaning agents containing customary detergents and additives, in combination with a phosphorus-free builder.  
  It is known that the cleaning power of tensides in washing and cleaning agents is increased by the addition of certain supporting compounds which have no cleansing power in themselves. Such substances are variously known as improvers, surfactants, or builders.  
  The theoretical basis for the effects of such builders has not been fully clarified in detail; therefore, it is impossible to predict which types of compounds will be suitable as a builder. However. it is generally assumed that a plurality of individual effects determines the special properties of the builders, primarily:  
  Increase in the cleaning power of tensides; dispersion of dirt in order to avoid redeposition; solubilization and/or emulsification of poorly soluble components; preventing deposition of low-solubility salts, especially of calcium and magnesium salts; buffering acidic substances; regulation of the washing liquor sudsing action; compatibility with other conventional detergent components, specifically with bleaching agents; and a minor corrosive effect. Furthermore, biodegradability has in recent years become recognized as an important property.  
  Various inorganic, alkaline-acting substances are known as builders, e.g. the alkali bicarbonates, carbonates, borates, phosphates. polyphosphates and silicates.  
  In the most common washing and cleaning agents, the polyphosphates, especially pentasodium triphosphate (sodium tripolyphosphate), are utilized almost exclusively as detergent building agents. The polyphosphate content in the washing and cleaning agents ranges up to 70% by weight, based on the total mixture, in correspondence with the laundering habits of various countries. However, in spite of their excellent builder properties, the use of phosphates is accompanied by increasingly recognized grave ecological disadvantages. Limnologists have for some years observed with increasing anxiety the eutrophication, i.e. overfertilization, of waters and lakes by an excess concentration of nutrients, resulting in a severe disturbance of the biological balance due to strong algae growth. The consequence is a rapid reduction in oxygen content, primarily at the bottom of the lakes, together with a concomitant increase in decay processes which finally effect the destruction of plant and animal life. In part, detergent phosphates are held responsible for this damage; c.f. Tensides 8 (2); 82 (1971).  
  Polyphosphates also exhibit practical disadvantages in storage and use, as they are readily hydrolyzed into meta-and ortho-phosphates, which are low-quality builders.  
  The corrosive properties of the polyphosphates on metals and alloys are another problem, mentioned by K. Lindner, in Tensides Textile Adjuvants Laundry Raw Materials, Wissenschaftliche Verlagsgesellschaft mbH, Stuttgart, 1964, Vol. II. pp. 1189 and 1195.  
  In order to circumvent these and other disadvantages of the polyphosphates, the prior art has proposed several phosphate-free builders for use in washing and cleaning agents. In the United States, for example, nitrilotriacetate or nitrilotriacetic acid (NTA) was utilized for a time in detergent recipes. However, it has since been found disadvantageous because NTA cannot be readily biodegraded under all commonly encountered conditions. Additionally, the nitrogen interferes as a eutrophication-enhancing factor. Another property of NTA now evoking misgivings is the excel-.  
 lent complexing capacity for heavy metals and transition metals which is particularly undesirable with respect to mercury and arsenic, and which can result in an undesired concentration of these substances. Finally, it was found that NTA and perborate neutralize each other; NTA, with the perborate bleaching agent being consumed, is degraded to form amine oxides and other oxidation products Tensides 8 (l): 2 (1971).  
 OBJECTS OF THE INVENTION Accordingly, it is an object of this invention to provide improved detergent building agents.  
  Another object of this invention is to provide improved phosphate-free detergent compositions.  
  An additional object of this invention is to provide an improved process for preparing detergent composition.  
  A further object of this invention is to provide an im&#39;- proved laundering process.  
  Upon further study of the specification and appended claims, further objects and advantages of this invention will become apparent to those skilled in the art.  
 SUMMARY OF THE INVENTION Briefly, the above and other objects are attained in one aspect of this invention by providing in a washing and cleaning composition comprising an anionic or nonionic tenside, the improvement which comprises 10-70% by weight, based on the total weight of the composition, of a water-soluble salt of a 17-100 molar percent sulfonated polybutadiene polymer having a molecule weight prior to sulfonation of SOD-10,000.  
 DETAILED DISCUSSION presence of alkyl aluminum halides and organo-nickel compounds, e.g. nickel acetylacetonate. In this connec- 1 tion, it can be advantageous to add minor amounts of electron donors, e.g. ethers or amines. See B. Schleimer and H. Weber, Applied Macromolecular Chemistry, 16/17: 253-269 (1971), incorporated by reference herein. The polybutadienes prepared in this manner contain 30-90%, preferably 50-85% 1,4-cisdouble bonds, 65-10%, preferably 50-15%, 1,4-transdouble bonds, and 5-0%, preferably less than 1% vinyl double bonds.  
 The polybutadiene sulfonates of this invention are produced by sulfonation with S0 advantageously utilized in the form of a complex, e.g. an etherate, such as SO dioxane. The liquid polymer, suitably dissolved in an organic solvent (which can be, if desired, the polymerization solvent), is reacted with 1.0-1.5 mol, preferably 1.25 mol per monomer unit of the polybutadiene, of S; or an SO -complex, at a temperature 25-30 C. Thereafter, the reaction mixture is neutralized with alkali. After the working-up process, the product is obtained primarily as the alkali salt of the sulfonated polybutadiene, optionally in a mixture with residual alkali sulfate which generally need not be separated for use as the building substances of this invention. Preferred are the sodium and potassium salts.  
 Although any water-soluble sulfonate of the polybutadienes having the molecular weights of 500-l0,000 can be employed as a builder, the alkali salts are preferred, especially the alkali metal salts, i.e. Li, Na, K, Cs, N11,, etc. and particularly Na and K.  
  The builders of this invention are to be used in an amount of -70% by weight, preferably -60%, especially 35-60% by weight, based on the total mixture of the washing and cleaning agent. The weight ratio of builder to tenside is generally 1:3 to 10:1. They can also be utilized in combination with other builders or can replace a portion of the phosphates in washing agents, but in general are preferably employed as substantially the only builder, i.e. with less than 50%, preferably less than 10% of other builders.  
  The laundry-active substances and additives are added in the customary quantitative proportions, for example:  
 &#39; The washing and cleaning agents according to the invention can contain one or more of conventional anionic and nonionic detergents and additives; cationic detergents are generally not satisfactory, for laundry purposes, because they are absorbed by the negatively charged textile fibers and so tend to act as soil fixatives. Some catio&#39;nic detergents may be used, however, in small concentrations as fabric softeners, if the active ingredient is a nonionic detergent.  
  Suitable anionic tensides include but are not limited to the alkyl sulfonates, alkyl benzenesulfonates, olefin sulfonates, alkyl sulfate, alkyl ether sulfates, alcohol oxyethylate sulfates, alkyl phosphates, alkyl ether phosphates, etc.  
 Suitable nonionic tensides include but are not limited to the alkyl polyglycol ethers, alkyl phenol polyglycol EXAMPLE 1 60 g. of polybutadiene having a molecular weight of drogen peroxide and heated to the boiling point for 10 minutes under a reflux condenser. After removing the water in a forced circulation evaporator, 161 g. of polybutadiene sulfonate containing 13.8% sodium sulfate is obtained. The degree of substitution of the thussulfonated polybutadiene amounts to 0.42.  
  The following pertinent recipes of several standard household detergents and gentle detergents will further explain the invention:  
 EXAMPLE 2 n-Dodecylbenzenesulfonate Palmityl alcohol oxyethylate 15 mol of ethylene oxide) Talgolit soap Sodium-salt of a C,,,-C,,, carboxylic acid, (iodine no. 1 to 3) Sodium salt of the sulfonated polybutadiene m.w. 1500, produced according to Example 1 Sodium sulfate Sodium toluenesulfonate Carboxymethylcellulose (CMC Sodium perborate &#39;4 H O Sodium silicate Optical brightener EXAMPLE 3 a-Olefin sulfonate (C C Sperm oil alcohol oxyethylate (25 mol of ethylene oxide) Sodium salts of sulfonated pol butadiene m.w. 1500, produced according to Example 1 Sodium silicate Sodium cumenesulfonate Carboxymethylcellulose (CMC) Sodium perborate &#39;4 H O Optical brightener EXAMPLE 4 n-Dodecylbenzenesulfonate C m C Fatty alcohol oxyethylate (1 1 mol of ethylene oxide) &#34;Talgolit&#34; soa Sodium salt of sulfonated polybutadiene m.w. 3500, produced according to Example 1 Sodium carbonate Sodium chloride Sodium toluenesulfonate Carboxymethylcellulose (CMC) Sodium perborate 4 H O Optical brightener QAML n-Dodecylbenzenesulfonate Palmityl alcohol oxyethylate (15 mol of ethylene oxide) &#34;Talgolit soap Sodium salt of sulfonated polybutadiene m.w. 1500. produced according to Example 1 Sodium sulfate Carboxymethylcellulose (CMC) Sodium toluenesulfonate Optical brightener EXAMPLE 6 The washing power of the above-mentioned anionic and nonionic detergents is noticeably enhanced by adding the builders of the present invention. Furthermore, these builders retard deposition of the laundry-active substance as salts of low solubility, e.g. calcium salts, so that encrustation of the fabric is prevented. The substances of this invention are further distinguished by a very high suspension power (tested on iron oxide), which represents a measure of dirt-carrying capacity; a very good compatibility with perborate bleaching agents; and a comparatively low corrosive effect with respect to metals.  
  The builders to be employed according to the invention can thus not only replace the phosphates hitherto mainly used as builders in the washing and cleaning agents, especially pentasodium triphosphate, but also exhibit with respect to these phosphates an improved total property spectrum.  
  For determining the cleaning power of detergents wherein a proportion of phosphate is replaced by the builders of this invention. test-soiled WFK (Wascherei- Forschunganstalt Krefeld) cotton fabric is washed in a Launder-Ometer&#34;. a standardized laboratory washing machine (Atlas Electric Co., Chicago, Illinois) in an aqueous bath at 90 C. for 30 minutes. For the washing tests, a drinking water of l2d German hardness (1 d 0.357 alkaline earth ions mval/l. or 17.8 ppm. of CaCO- DlN539l) is employed. By comparison with both the test-soiled unwashed fabric and the unsoiled fabric, the percent washing value is calculated according to the following equation:  
  Washing Value a b/c b wherein a reflectance of the washed fabric b reflectance of the test-soiled fabric 0 reflectance of the unsoiled fabric The reflectance is a measure of brightening caused by the washing process and is measured at 570m .t on the dried and pressed fabric using a Zeiss Elrepho&#34; photometer with a R 57 filter which is calibrated against the standard No. 20707. The percent washing value is reported as the average of 24 single measurements on the test fabrics.  
  In order to further explain this invention and the advances in the art attainable thereby, the following examples and results of experiments will be set forth:  
 EXAMPLES 7-9 In the following compilation, the percent washing values are indicated obtained with 1 g./l. of sodium dodecylbenzenesulfonate as the laundry-active substance (LAS) and l or 2 g./l. of builder in the washing liquor. The values were determined after each of three consecutive washing cycles.  
 TABLE! Washing I Cycles 1. 2. 3.  
 Ex. Washing Values 7 l EJI.  
 l g./l.  
 EXAMPLES 10-12 For determining hardness stability, variously concentrated solutions of sodium dodecylbenzenesulfonate and builder are examined for turbidity in water samples having varying hardness values. From a series of measurements, a total value is then derived, which can range between 15 for poor hardness stability and for very good hardness stability. According to a certain key, stability values can be determined therefrom, on a scale of from 1 to 5. Details of this test can be found in DIN 53 905. In the ideal case of maximum insensitivity with respect to hardening agents in the water, this value is I 5. As can be seen from the following compilation, the builders of the present invention in conjunction with 5 sodium dodecylbenzenesulfonate clearly show a better hardness stability than pentasodium triphosphate.  
  In all further examples, builders of this invention were used which were produced in accordance with j Example 1.  
 EXAMPLES 13-5 The compatibility of the builders of this invention with the remaining components of the detergent was examined with sodium perborate, frequently employed as a bleaching agent. Perborate stability was evaluated by first determining iodometrically the active oxygen content of a 0.004 mol/l. solution of perborate in distilled water without the addition of foreign substances, and assigning this active oxygen content a value of Thereafter, a solution containing 0.004 mol/1.  
 TABLE 111 1 Active Oxygen After Ex. Builder 30 60 150 min.  
 min. min.  
 13 Pentasodium triphosphate EXAMPLES 16-18 One measure of the dirt-carrying capacity of a builder is its suspending power, e.g. with respect to pulverized iron oxide. For this purpose, a testing method 25 was devised wherein pulverulent red Fe O with a specific surface of l5,7 m&#39; /g (commercial available as Oxidrot AKF from Sigle, Stuttgart (W.-Germany) is shaken intensively for one minute in a vibrating cylinder with an aqueous solution of the builder and sodium dodecylbenzenesulfonate. 24 Hours later the magnitude of the remaining turbidity is determined by photometry. The relative values obtained by measuring the extinction coefficients indicate the suspending power of the builders, wherein values from 100 upwards are 35 denoted as good.  
 TABLE IV Extinction Coefficient m 1 cm. layer thickness EX. Builder l6 Pentasodium triphosphate (comparison) 160 17 Na salt of sulfonated polyhutadienc, m.w. 1500 211 18 Na salt of sulfonated polyhutadicne. m.w. 3500 129 EXAMPLES 19-21 The procedure used to determine the corrosive properties of the builders of this invention with respect to steel was as follows: Degreased steel sheets made of St &#39;37 (DIN 17,100) were arranged in a glass flask with a Thereafter, the test sheets were sequentially washed with water, acetone and benzene, and then dried. The total weight loss incurred by the sheets during the treatment, corresponding to the amount of iron corroded, was determined. As can be seen from the following 8 compilation, pentasodium triphosphate exhibits a far stronger corrosive effect than the builders of this invention.  
  TABLE V EX. Builder Corrosion in gJm l9 Pentasodium triphosphate (comparison) 61.4 20 Na salt of sulfonated poly- 1 butadiene m.w. 1500 22.1  
 21 Na salt of sulfonated polybutadiene m.w. 3500 23.8  
  The above examples demonstrate the high-quality washing and cleaning agents are obtained using the builders according to the present invention.  
  The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.  
  From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.  
 What is claimed is:  
  1. In a washing and cleaning composition comprising an anionic or nonionic tenside, the improvement which comprises 10-70% by weight, based on the total weight of the composition, of a builder comprising a watersoluble salt of a 17-100 molar percent sulfonated polybutadiene polymer having a molecular weight prior to sulfonation of SOD-10,000.  
  2. A composition according to claim 1, wherein said polybutadiene contains 30-90% cis-l,4 double bonds, 65-10% trans-1,4 double bonds and less than 5% vinyl- 1,2 double bonds.  
  3. A composition according to claim 2, wherein said molecular weight is l,500-3,500.  
  4. A composition according to claim 2, wherein said polybutadiene is 22-70 molar percent sulfonated.  
  5. A composition according to claim 4, wherein said polybutadiene contains 50-85% cis-l,4 double bonds, 50-l5% trans-1,4 double bonds, and less than 1% vinyl-1,2 double bonds.  
  6. A composition according to claim 5, wherein said polybutadiene is 33-50 molar percent sulfonated.  
  7. A composition according to claim 6, wherein said polybutadiene builder is present in an amount of -60 weight 70.  
  8. A composition according to claim 7, wherein the ratio of builder to tenside is about 1:3 to 10:1.  
  9. A composition according to claim 1, wherein said water-soluble salt is an alkali metal salt.  
  10. A composition according to claim 9, wherein said composition is substantially free of builders other than said polybutadiene.  
  11. A composition according to claim 1, consisting essentially of 5-30 weight of said tenside, said builder, 0-20 weight sodium perborate, 0-40 weight 70 sodium sulfate, 0-20 weight sodium carbonate and 0-15 weight 7c silicates.  
  12. A composition according to claim 11, wherein said tenside is an anionic tenside selected from the group consisting of alkyl sulfonates, alkyl benzenesulfonates, olefin sulfonates, alkyl sulfates, alkyl ether suln-Dodecylbenzenesulfonate Palmityl alcohol oxyethylate 15 mol of ethylene oxide) Sodium salt of a (T -C carboxylic acid having an iodine number of l-3 Sodium salt of sulfonatcd polybutadiene having a molecular weight pnor to sulfonation Of 1500 Sodium sulfate Sodium toluenesulfonate C arboxymethylcellulose C MC Sodium perboratc 4 H O Sodium silicate Optical hrightener.  
  15. A composition according to claim 11, consisting essentially of:  
 a-Olcfin sulfonate (C -C Sperm oil alcohol oxyethylate (25 mol of ethylene oxide) Sodium salt of sulfonated polybutadiene having a molecular weight prior to sulfonation of I500 Sodium silicate Sodium cumenesulfonate Carboxymethylccllulose (CMC&#39;) Sodium perhorate 4 H O Optical hrightener.  
  16. A composition according to claim 11, consisting essentially of:  
 0.2% Optical brightener.  
  17. A composition according to claim 11, consisting essentially of: 4  
 n-Dodecylbenzenesulfonate Palmityl alcohol oxyethylate l5 mol of ethylene oxide) i Talgolit soa Sodium salt of sulfonated polybutadiene having a molecular weight prior to sulfonation of 1500 Sodium sulfate C arboxymethylcellulose (C MC Sodium toluenesulfonate Optical brightener.  
  18. A composition according to claim 11, consisting essentially of:  
 a-Olefin sulfonate (C H C Palmityl alcohol oxyethylate 15 mol of ethylene oxide) 1 Talgolit soap Sodium salt of sulfonated polybutadiene having a molecular weight prior to sulfonation of 1500 Sodium sulfate Sodium toluenesulfonate Sodium carbonate Carboxymethylcellulose (CMC) Optical brightcner.  
  19. A process for preparing washing and cleaning agents containing a phosphorus-free builder which comprises:  
 a. sulfonating a polybutadiene having a molecular weight of SOD-10.000 and containing 30-90% cisl,4 double bonds, 65-10% trans-1.4 double bonds and less than 5% vinyl-1,2 double bonds with a sulfonating agent selected from the group consisting of sulfur trioxide and sulfur trioxide complexes to form a 17-100 molar 7c sulfonated polybutadiene; b. neutralizing the resultant reaction mixture with an alkali solution whereby an alkali sulfate is formed; and  
 c. adding the resultant sulfonated polybutadiene and alkali sulfate without separation thereof as a phosi phorus-free builder to a washing and cleaning i agent comprising an anionic or nonionic tenside.  
  20. In a process for laundering textiles, the improvement which comprises using as the washing and cleaning agent the composition according to claim 1.  
  5475;! 7 UNITED STATES PA&#39;IENI OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3875070 DATED April 1, 1975 IN E O I Ferdinand von Praun et a1 It is certified that error appears in the above-Identified patent and that smd Letters Patent are hereby corrected as shown below:  
 Claim 1 line 1:  
 Claims 16, 17 and 18, line 6: change &#39;Talgolit soap&#34; to --sodium salt of a C C carboxylic. acid having an iodine number of 1-3- Signed and Scaled this .4 next:  
 RUTH C. MASON .1 111&#39;s! ing ()fll ire&#39;r C. MARSHALL DANN (&#39;unrnrrlrxrmrcr u I&#39;urcnrs uml &#39;lrutlcmurlu before &#34;washing&#34; insert texti1e--.  
 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 1 3875070 DATED April 1, 1975 INVENTOR(5) i Ferdinand von Praun et a1 It is certified that error appears in the above-rdenrified patent and that sard Letters Patent are hereby corrected as shown below:  
 Claim 1 line 1: before &#34;washing&#34; insert --texti1e-.  
 Claims 16, 17 and 18, line 6: change &#39;Talgolit soap&#34; to --sodium salt of a C C carboxylicacid having an iodine number of 13- Signed and Scaled this twelfth Day of August1975 [SEAL] Arrest:  
 RUTH C. MASON (.MARSHALL DANN r-Ilu&#39;su&#39;ng Officer (&#39;nnrmissm/u&#39;r n] lulr&#39;HlA um! TfrJr/(IHUF/fl