US2626900A - Polypropylene benzene sulfonate - Google Patents

Polypropylene benzene sulfonate Download PDF

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US2626900A
US2626900A US2626900DA US2626900A US 2626900 A US2626900 A US 2626900A US 2626900D A US2626900D A US 2626900DA US 2626900 A US2626900 A US 2626900A
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polypropylene
benzene
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sulfonate
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143Sulfonic acid esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146Sulfuric acid esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29Sulfates of polyoxyalkylene ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/37Mixtures of compounds all of which are anionic
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/046Salts
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/06Phosphates, including polyphosphates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/34Organic compounds containing sulfur
    • C11D3/3418Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates

Definitions

  • alkyl benzene sulfonate detergents normally involves alkylation of benzene, sulfonation of the alkylatedbenzene, and neutralization of the sulfonic acid product. Neutralized products obtained in this manner may be used without further treatment or with only removal of water, and in this condition are effective and eiiicient detergent compositions. Such compositions normally contain between 30% and,45% of alkyl benzene sodium sulfonate, and between 55% and 70% of sodiumsulfate. In some cases the mixtures are treated for removal of the sodium sulfate to roduce alkyl benzene sodium sulfonates substantially free of inorganic salts.
  • benzene has been alkylated by several methods and by several types of" alkylating compounds.
  • benzene has been condensed with chlorinated kerosene fractions in the presence of an aluminum chloride condensing agent.
  • Benzene has been condensed also with.
  • oleflns from various sourcesfer'nploying aluminum chloride, sulfuric acid, or other suitable condensing agent.
  • Olefln's employed for this alkyli tion have been obtained by dehydration of alcohols, by cracking of'petroleum products, and by polymerization processes.
  • oleiins obtained by polymerizationof propylene, butylenefisobutylene and amylene have been proposed:
  • the most suitable alkylating compounds are those providing alkyl groups containing between 9 and 18 carbon atoms.
  • compositions of my invention comprise such "polypropylene" benzenesodium sulfonates in which the "polypropylene radicals contain an average of 13 to 15 carbon atoms, and in addition to the sulfonate. between 1 and -3 parts of sodium sulfate and between 1 and [4 parts of tetrasodium pyrophosphate for 'each part by weight of the sulfonate, these proportionsbeing determined on the dry basis.
  • the products'of the invention when employed inwater atfaconcentration of 54% provide a pH between 19 and 10.4.
  • Polypropylene fractions of ab0ut2 00 to -2'70" C. boiling range boiling for the most part between-210 and 260 C. have the required average molecular carbon content and contain penta- .propylenes as the major component.
  • 'Such polypropylene fractions. suitable forpreparingihe products of the invention are available commercially. They are' normally produced by the superatmospheric poLvmerization of propylene 1'12 parts of 95% msoi is mixed with 42 parts of benzeneat 10 to 20 C. 65 parts of polypropylene, distilling at normal atmospheric presthe mixture is stirred for 1% hours at a temperature not above 30' C. The product is then woven cotton fabric soiled with a suspension of graphite in lubricating oil and cottonseed oil. The proportion of soil removed was determined photometrically.
  • The" pH of the slurry is adjusted finally to ap'-' proximately '7 by the addition of sulfuric acid and the/slurry is then dried. Drying may be eflected by means of a drum drier or a spray drier at 110 C.
  • the dry product contains about 38% of alkyl benzene-sodium sulfonate and 62% of sodium sulfate.
  • the content'of alkyl benzene sodium sulfonatel and sodium sulfate may vary 5%; above'or below these values.
  • a detergent composition consisting essentlally; of "polypropylene benzene sodium -.sulfonate, in .which the polypropylene radicals conv tain anaverage of between 13 and 15 carbon atoms and comprise a substantial proportion of pentapropylene" radicals, and for about. each' one part by, weight ofpolypropylenebenzene so-- dium sulfonate. (dry basis), between 1 and 3 parts. of sodium sulfate and between 5 -and,. 4-.parts.of t'etrasodiurn pyrophosphate.
  • a detergent composition consisting. essential: ly of "polypropylene? benzene sodiumsulfonate, in which the polypropyleno radicals correspond substantially entirelyto. olefins boiling between 200 anda270 0., comprise as the major com ponent-pentapropylene radicals and contain an averageof between-13 and 15 carbon atoms; and for about each one part by weight of polypropylene benzene sodium sulfonate-(dry basis), .-be-, tweenf1.3, and 2'parts oi. sodium sulfate and between 1 and 8 partsf'of tetrasodium pyrophos pirate;
  • composition consisting'essential ly of polypropylene" --benzene sodium sulfonat'e'; in which the polypropylene" radicals correspond substantially entirely to oleilns boiling between sdnwemdveain a standard inyolving a 200' and 270 d. and predominantly between 210 "pentapropylene radicals and contain an average of between 13 and 15 carbon atoms, and for about each one part by weight of polypropylene benzene sodium sulfonate (dry basis) about 1 /10. parts of sodium sulfate, and for each part of total sulfonate and sulfate about to 1 part of tetrasodium pyrophosphate.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Description

latented 27, 1953 orrlcs POLYPROPYLENE BENZENE SULFONATE DETERGENT COMPOSITIONS CON- TAINING TETRASODIUM PYROPHQS- PHATE Samuel A. Russell, III, Chicago, 111., assignor to Allied Chemical-d: Dye Corporation, New York, N. Y., a corporation of New York No Drawing. Application January 29, 1949,
. Serial No. 73559 3 Claims. (cuss-13s) This invention relates to the manufacture of detergent compositions. It is particularly'concemed with improvements in detergent compositions of the alkyl benzene 'sulfonate type.
The manufacture of alkyl benzene sulfonate detergents normally involves alkylation of benzene, sulfonation of the alkylatedbenzene, and neutralization of the sulfonic acid product. Neutralized products obtained in this manner may be used without further treatment or with only removal of water, and in this condition are effective and eiiicient detergent compositions. Such compositions normally contain between 30% and,45% of alkyl benzene sodium sulfonate, and between 55% and 70% of sodiumsulfate. In some cases the mixtures are treated for removal of the sodium sulfate to roduce alkyl benzene sodium sulfonates substantially free of inorganic salts.
For the manufacture of detergents of the above types benzene has been alkylated by several methods and by several types of" alkylating compounds. For example, benzene has been condensed with chlorinated kerosene fractions in the presence of an aluminum chloride condensing agent. Benzene has been condensed also with. oleflns from various sourcesfer'nploying aluminum chloride, sulfuric acid, or other suitable condensing agent. Olefln's employed for this alkyli tion have been obtained by dehydration of alcohols, by cracking of'petroleum products, and by polymerization processes. Thus oleiins obtained by polymerizationof propylene, butylenefisobutylene and amylene have been proposed:
Regardless of the source. the most suitable alkylating compounds are those providing alkyl groups containing between 9 and 18 carbon atoms.
'Alkyl benzene sulfonate detergents have been marketed alone andalso in admixture with other detergent materials, among which may be mentioned the phosphates, such as trisodium phosphate and sodium triphosphate. -Experimental tests have demonstrated that while'such phosphates may improve some commercial alkyl-aromatic sulfonate detergents slightly, the immovement is not great. Moreover, tetrasodium pyrophosphate does not always promote the detergent action of such alkyl benzenesulionates.
as illustrated by its effect, in a normal hard I water, upon a commercially available detergent comprising alkyl benzene sulfonates derived from chlorinated kerosene and upon such; a detergent derived from polypropylene fractions having an average molecular carbon "content-"of 12 carbon atoms, as shown in Table 11 below.
- a decidedly "beneficial effect upon polypro' pylene benzene sulfonate detergents having an average of 13 to 15 carbon atoms in the polypropylene radicals and containing a substantial proportion of pentamers among 'the "polypropylene radicals. This discovery has ,led to the production of superior detergent compositions and furthermore has permitted utilizing for the production of such compositions .substantially less expensive starting-materials.
The compositions of my invention comprise such "polypropylene" benzenesodium sulfonates in which the "polypropylene radicals contain an average of 13 to 15 carbon atoms, and in addition to the sulfonate. between 1 and -3 parts of sodium sulfate and between 1 and [4 parts of tetrasodium pyrophosphate for 'each part by weight of the sulfonate, these proportionsbeing determined on the dry basis. The products'of the invention when employed inwater atfaconcentration of 54% provide a pH between 19 and 10.4.
Polypropylene fractions of ab0ut2 00 to -2'70" C. boiling range boiling for the most part between-210 and 260 C. have the required average molecular carbon content and contain penta- .propylenes as the major component. 'Such polypropylene fractions. suitable forpreparingihe products of the invention, are available commercially. They are' normally produced by the superatmospheric poLvmerization of propylene 1'12 parts of 95% msoi is mixed with 42 parts of benzeneat 10 to 20 C. 65 parts of polypropylene, distilling at normal atmospheric presthe mixture is stirred for 1% hours at a temperature not above 30' C. The product is then woven cotton fabric soiled with a suspension of graphite in lubricating oil and cottonseed oil. The proportion of soil removed was determined photometrically.
- when the above detergents were mixed with tetrasodium pyrophosphate and tested at a total detergent concentration of 0.25%, employing an identical test, substantially diflerent results were allowed to stratify and the heavy H2504 layer is obtained. The following table shows the variawithdrawn. The alkylate which remains is hell-' tion of "these results with varying proportions of tralized with aqueous sodium carbonate solution; pyrophosphate.
,racliz -;1?etes'gentTBPP Ratio Dem- 1'' 00-10 ao-ao vo-ao 00-40 50-50 40-00 Pol pylons (Cu) Benzene Bodiunr 1 I 8 cute Detergent (62% No.80 i7 22 2Q 30 48 51 44 Pol pylene (Cu) Benuno Sodium 1 ..B ionataDet rs t(62%Nu80|).. .40 N 33 34 'Keryl Benzene Sodium flulionate 1 DOm (a% N28 4)----' as so as as as as an stripped with steam to. remove bnreacted benzene... After removal ofthe benzene the ,alkylate is again permittedto stratify muse water andsodium' sulfate and sodiumcarbonate are drawn The remaining, alkylate isthenj dried anhydrouscalciunrchloride and separated fromthis drying agent. i
' Toeflect sulionatiori ,oithe alkylate 50 parts of si lete is cooled to between l0'fi-and c.
an 190 parts off 20% oleum is added w llie the mixture is s i r vis mus v w t ca in to maintain the temperature below 20' C. when-all ofi'th'e oleum has been added. ag'ii'ntior is conunseat until the end of 4 hoursif'rorn the tin e of starting the addition of oleum, the temperature being maintained during this period below CI 1' The sulfonation mixture is then'int'roduced gradually into 285 parts of -aque'ous 25%- NaOH'liolution at a temperature of about -C.
The" pH of the slurry is adjusted finally to ap'-' proximately '7 by the addition of sulfuric acid and the/slurry is then dried. Drying may be eflected by means of a drum drier or a spray drier at 110 C. The dry product contains about 38% of alkyl benzene-sodium sulfonate and 62% of sodium sulfate. Upon application of the'pr'ocess oha' large scale. the content'of alkyl benzene sodium sulfonatel and sodium sulfate may vary 5%; above'or below these values.
, Arne. following tables show the results of,
launderometer' tests 'of this detergentIpmduct-incomparison with" a commercial product made from chlorinated 'kerosene and a: polypropylene benzene s'ulfonate having'an'average of-only 12 efirbonatoms 'in the polypropylene? radicals. Thesertests were made employingha'vlng a hardness corresponding -to 300 parts per million of calcium carbonate.
Table! Pol ro ylene Be an; 8111- t IBen. innate Detergent Goneentration, Percent a acne B ul flie values in thistable represent' the percentage removal than the'b'ir polypropylene benzene sulfon'ate deterde'ntjbut uponladd'itionjof tetra- W"! -PYIPPK SR 'FE. gave p0prer, and... poorer results, and'in nepase gave better results than -the 'ab ence of the i'etrssodi m ymphosphate. ereas It ac poly op ene ul m t upon addition of e r -s di m p rop bhete s better, and better results; until .at a 59-60 ratio this detergentl'was substantially. superior to any of the mixtures of keryl benzene sulf onate. as'well as to this product without the tetrasodium pyro phosphate. The product from 12 carbon atom (average) polypropylene .resembled the keryl product in its behavior and all its mixtures with 'I'SPPtested were inferior tothe 100% detergent product. l
I claim: 1
.1. A detergent composition consisting essentlally; of "polypropylene benzene sodium -.sulfonate, in .which the polypropylene radicals conv tain anaverage of between 13 and 15 carbon atoms and comprise a substantial proportion of pentapropylene" radicals, and for about. each' one part by, weight ofpolypropylenebenzene so-- dium sulfonate. (dry basis), between 1 and 3 parts. of sodium sulfate and between 5 -and,. 4-.parts.of t'etrasodiurn pyrophosphate. I
2. A detergent composition consisting. essential: ly of "polypropylene? benzene sodiumsulfonate, in which the polypropyleno radicals correspond substantially entirelyto. olefins boiling between 200 anda270 0., comprise as the major com ponent-pentapropylene radicals and contain an averageof between-13 and 15 carbon atoms; and for about each one part by weight of polypropylene benzene sodium sulfonate-(dry basis), .-be-, tweenf1.3, and 2'parts oi. sodium sulfate and between 1 and 8 partsf'of tetrasodium pyrophos pirate;
. 3. ll-detergent composition consisting'essential ly of polypropylene" --benzene sodium sulfonat'e'; in which the polypropylene" radicals correspond substantially entirely to oleilns boiling between sdnwemdveain a standard inyolving a 200' and 270 d. and predominantly between 210 "pentapropylene radicals and contain an average of between 13 and 15 carbon atoms, and for about each one part by weight of polypropylene benzene sodium sulfonate (dry basis) about 1 /10. parts of sodium sulfate, and for each part of total sulfonate and sulfate about to 1 part of tetrasodium pyrophosphate.
SAMUEL A. RUSSELL, III.
REFERENCES CITED The following references are of record in the file of this patent:
6 UNITED STATES PATENTS Number Name Date Riegler Oct. 5, 1943 Trefiier June 13, 1944 McGhie Feb. 5, 1946 Lind Mar. 12, 1946 Lewis July 26, 1949 Lewis July 26, 1949 Strain Nov. 1, 1949 OTHER REFERENCES Oil and Soap, vol. 23, 1946, page 105.

Claims (1)

1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF "POLYPROPYLENE" BENZENE SODIUM SULFONATE, IN WHICH THE "POLYPROPYLENE" RADICALS CONTAIN AN AVERAGE OF BETWEEN 13 AND 15 CARBON ATOMS AND COMPRISE A SUBSTANTIAL PROPORTION OF "PENTAPROPYLENE" RADICALS, AND FOR ABOUT EACH ONE PART BY WEIGTH OF POLYPROPYLENE BENZENE SODIUM SULFONATE (DRY BASIS), BETWEEN 1 AND 3 PARTS OF SODIUM SULFATE AND BETWEEN 1/3 AND 4 PARTS OF TETRASODIUM PYROPHOSPHATE.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2330922A (en) * 1941-12-22 1943-10-05 Allied Chem & Dye Corp Manufacture of sulphonated detergents
US2351559A (en) * 1944-06-13 Process for the preparation of
US2394320A (en) * 1942-05-19 1946-02-05 Colgate Palmolive Peet Co Organic detergent compositions
US2396278A (en) * 1933-11-15 1946-03-12 Procter & Gamble Detergent composition
US2477382A (en) * 1946-05-04 1949-07-26 California Research Corp Aryl substituted alkanes and process of making the same
US2477383A (en) * 1946-12-26 1949-07-26 California Research Corp Sulfonated detergent and its method of preparation
US2486922A (en) * 1945-11-09 1949-11-01 Procter & Gamble Stabilized detergent composition

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2351559A (en) * 1944-06-13 Process for the preparation of
US2396278A (en) * 1933-11-15 1946-03-12 Procter & Gamble Detergent composition
US2330922A (en) * 1941-12-22 1943-10-05 Allied Chem & Dye Corp Manufacture of sulphonated detergents
US2394320A (en) * 1942-05-19 1946-02-05 Colgate Palmolive Peet Co Organic detergent compositions
US2486922A (en) * 1945-11-09 1949-11-01 Procter & Gamble Stabilized detergent composition
US2477382A (en) * 1946-05-04 1949-07-26 California Research Corp Aryl substituted alkanes and process of making the same
US2477383A (en) * 1946-12-26 1949-07-26 California Research Corp Sulfonated detergent and its method of preparation

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