CA1037966A - Maleic acid telomers as detergent builders - Google Patents
Maleic acid telomers as detergent buildersInfo
- Publication number
- CA1037966A CA1037966A CA173,030A CA173030A CA1037966A CA 1037966 A CA1037966 A CA 1037966A CA 173030 A CA173030 A CA 173030A CA 1037966 A CA1037966 A CA 1037966A
- Authority
- CA
- Canada
- Prior art keywords
- sodium
- solution
- telomer
- detergent
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/22—Tricarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/24—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms containing more than three carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/30—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings
- C07C57/34—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings containing more than one carboxyl group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/235—Saturated compounds containing more than one carboxyl group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/235—Saturated compounds containing more than one carboxyl group
- C07C59/245—Saturated compounds containing more than one carboxyl group containing hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/235—Saturated compounds containing more than one carboxyl group
- C07C59/305—Saturated compounds containing more than one carboxyl group containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/235—Saturated compounds containing more than one carboxyl group
- C07C59/325—Saturated compounds containing more than one carboxyl group containing —CHO groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/235—Saturated compounds containing more than one carboxyl group
- C07C59/347—Saturated compounds containing more than one carboxyl group containing keto groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/76—Unsaturated compounds containing keto groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
- C07D319/12—1,4-Dioxanes; Hydrogenated 1,4-dioxanes not condensed with other rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Detergent Compositions (AREA)
- Furan Compounds (AREA)
- Pyrane Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A washing composition containing an organic water-soluble detergent surfactant and a builder compound of the formula wherein n is an integer of 1 to 8; X is R-?H-OH, -C(O)-R, -CH2C(CH3)=CHOOCH3, -C(OR)3, an .alpha.-dialkyl ether group of 2 to 20 carbon atoms, R-?H-O(CH2CH2O)p-R, -CH(COOH)R, -S(CH2)1-2COOH, -C(R1)2, 2-tetrahydrofuranyl, 2-(1,3-dioxolanyl), p-dioxanyl and 2-tetrahydropyranyl wherein R is hydrogen or alkyl of 1 to 10 carbon atoms;
R1 is alkyl of 1 to 2 carbon atoms; Y is hydrogen or -CH(R1)2 and p is an integer of 1 to 5.
A washing composition containing an organic water-soluble detergent surfactant and a builder compound of the formula wherein n is an integer of 1 to 8; X is R-?H-OH, -C(O)-R, -CH2C(CH3)=CHOOCH3, -C(OR)3, an .alpha.-dialkyl ether group of 2 to 20 carbon atoms, R-?H-O(CH2CH2O)p-R, -CH(COOH)R, -S(CH2)1-2COOH, -C(R1)2, 2-tetrahydrofuranyl, 2-(1,3-dioxolanyl), p-dioxanyl and 2-tetrahydropyranyl wherein R is hydrogen or alkyl of 1 to 10 carbon atoms;
R1 is alkyl of 1 to 2 carbon atoms; Y is hydrogen or -CH(R1)2 and p is an integer of 1 to 5.
Description
7~6 .: `. ~:-This invention relates to cleansing and laundering ~ ;
compositions. It is particularly concerned with such compositions containing a soluble polycarboxylic acid salt as a builder. --In the cleansing art it is known that the detergency level of soaps and synthetic surfactants can be increased ~ .
by the presence of certain materials commonly referred to as builders. Such cleansing fortifiers make possible the attain~ent of superior cleaning performance and at .
: 10 lower cost than can be realized with the so-called non-built detergent compositions.
The mechanism by which builders enhance the cleans-ing action of detergents is not fully understood. .
Although several explanations have been advanced, the detergent builder art is still pretty much in the empirical stage. This is not too surprising considering ;
the complex nature of detergency and the countless ~ . .
factors which contribute to overall performance. It isgenerally agreed that builder compounds exhibit at least some effect in such areas as stabilization of solid soil suspension, emulsification of soil particles, the surface activity of aqueous detergent solutions, solubllization of water-insoluble materials, foaming or suds-producing characteristics of the washing solution, peptization of soil agglomerates, neutralization of acid soil, and the inactivation of mineral constituents present in the washing solution. Thus, any theoretical discussion of the boosting capacity of a builder compound should give due consideration to all the significant individual actions involved in the detergent process and must apply
compositions. It is particularly concerned with such compositions containing a soluble polycarboxylic acid salt as a builder. --In the cleansing art it is known that the detergency level of soaps and synthetic surfactants can be increased ~ .
by the presence of certain materials commonly referred to as builders. Such cleansing fortifiers make possible the attain~ent of superior cleaning performance and at .
: 10 lower cost than can be realized with the so-called non-built detergent compositions.
The mechanism by which builders enhance the cleans-ing action of detergents is not fully understood. .
Although several explanations have been advanced, the detergent builder art is still pretty much in the empirical stage. This is not too surprising considering ;
the complex nature of detergency and the countless ~ . .
factors which contribute to overall performance. It isgenerally agreed that builder compounds exhibit at least some effect in such areas as stabilization of solid soil suspension, emulsification of soil particles, the surface activity of aqueous detergent solutions, solubllization of water-insoluble materials, foaming or suds-producing characteristics of the washing solution, peptization of soil agglomerates, neutralization of acid soil, and the inactivation of mineral constituents present in the washing solution. Thus, any theoretical discussion of the boosting capacity of a builder compound should give due consideration to all the significant individual actions involved in the detergent process and must apply
-2- 1 , ~3~
equally to all the usual conditions of soiling and washing.
Builder materials should exhibit certain ancillary properties in order to be acceptable in current washing processes and consumer marketing techniques. Thus, a builder should preferably be white, inexpensive, non-toxic, stable to oxidizers, non-corrosive, non-hygro-scopic, stable to hot alkaline detergent solutions and ~ -stable during spray drying operations. More recently, the environmental safety of detergent builders has become a prime ancillary property.
Examples of known inorganic builder materials are the water-soluble, inorganic alkaline builder salts which can be used alone or in combination, including alkali metal carbonates, borates, phosphates, poly-phosphates, bicarbonates and silicates.
Examples of known organic builder materials are alkali metal, ammonium or substituted ammonium amino-polycarboxylates, e.g. sodium and potassium ethylene- -diaminetetraacetate, sodium and potassium N(2-hydroxy-ethyl)~ethylenediaminetriacetate, sodium and potassium and triethanolammonium -N - (2-hydroxyethyl) nitrilo-diacetate. Alkali metal salts of phytic acid, e.g., sodium phytate/ are also suitable as organic builders.
Of all of the known builders the condensed inorganic --phosphates find the widest commercial acceptance. ~
Sodium tripolyphosphate (STPP) has been especially favored -being used in both home and industrial cleansing. However, .
~, ~3~g~
considerable work is being done in an effort to find organic substitutes for some or all of the inorganic builders.
Among the materials whlch have been investigated ~;
as a source of new builders are various polyelectrolytes `
such as the water-soluble sal~s of polycarboxylic acid polymers disclosed in U. S. Patent 3,308,067 to Diehl.
According to the patent specification, one of the . . ., ", highly preferred members is the alkali metal salt of polymaleic acid. This is obtained by polymerizing maleic anhydride using 5% benzoyl peroxide as initiator following the procedure of Lang, Pavelick and Clarey, ~`
J. Polymer Sci., issue 162, page 532 (1961). The resulting product is treated with an alkali metal hydroxide such as sodium hydroxide to form sodium polymaleate. Generally speaking, the sodium polymaleate ls a satis~actory builder although it falls short with `
respect to solubility, and mineral precipitation.
However, the principal fault of sodium polymaleate is its resistance to bacterial attack, being virtually non-biodegradable. In fact, such biological behavior is a -~
common characteristic of high molecular weight poly~
,.. ..
electrolytes, thereby mitigating against their utility as builders.
Low molecular weight derivatives of maleic acid have also been investigated as detergent additives.
For instance, U. S. Patent 2,264,103 discloses cleansillg compositions containing the sodium salt of butanetetra- ~
"..''' i"''.'`' ,.
~ .
carboxylic acid. Although these polycarboxylic acids are biodegradable, their builder performance is generally unsatisfactory. Another low molecular weight class of polymaleic acids are the maleic acid telomers such as are described in U.S. Patent 3,474,114. So far as is ~ ;
known, maleic acid telomers have not been investigated as detergent builders.
It has now been discovered that excellent builder properties together with a high degree of biodegradability are possessed to a remarkable extent by a class of maleic acid telomers having the following formula:
:. 1 ".
-~ H - _ CH CH ¦ X
COOH COOH J
wherein n is an integer of 1 to 8; X is R-CH-OH, -C(O)-R, -CH2C(CH3)=CHCOCH3, -C(OR)3, an ~-dialkyl , ether group of 2 to 20 carbon atoms, R-CH-O(CH2CH2O) -R, -CH(COOH)R, -S(CH2) COOH, -C(Rl)2 ~ ,2-tetrahydro-furanyl, 2-(1,3-dioxolanyl), p-dioxanyl and 2-tetra-hydropyranyl wherein R is hydrogen or alkyl of 1 to 10 carbon atoms; Rl is alkyl of 1 to 2 carbon atoms; Y
is hydrogen or -CH(Rl)2 and p is an integer of 1 to 5.
,., ~. -.
The provision of such maleic acid telomers and detergent . ::
compositions containing them constitutes the principal object and purpose of the invention. Other objects and purposes will become manifest subsequently.
As can be seen from an inspection of the formula ~ ' .
.' :,' :
'` .
:, -. ~ .
::.:. ` ~,.
.,, ,; .:
~ 7~ti$
aforesaid, the builders of the inventions are telomers oE
maleic acid. According to the Encyclopedia of Polymer Science and Technology 3 605 (1965), John Wiley & Sons, Inc., a telomer is a low molecular weight polymer formed by reacting a chain transfer agent or telogen with an olefinic monomer or taxogen. Such polymerization process ~?
is known as telomerization and the end products are referred to as telomers. The telomerization of maleic anhydride with a chain transfer agent can be depicted by the following scheme ;
~C~ ,~ chain transfer ~ 0]
n lCo \ / C0 J agent or telogen C \ O /C n ;~
telomer taxogen `; H ~ CH CH `~X
COOH COOH n acid form wherein n and X have the significance aforesaid. The ~
anhydride form of the telomer is saponified with a base `~ ;
such as sodium hydroxide to give the telomer salt.`~
In conducting the telomerization reaction herein, .~
the maleic anhydride and telogen are heated together in - -the presence of a free radical source such as an organic peroxide. The ratio of maleic anhydride to telogen in the product is determined by the mole ratio of maleic anhydride to telogen in the polymerization mixture, the activity of the telogen as a chain transfer agent and the temperature. `~
The reaction is desirably carried out in the presence .. .~ , .
.
':'.' '~ ' -; :
7~
of an inert solvent at mildly elevated temperatures preferably in the neighborhood of 100C. In general, the reaction is patterned after the known telomerization procedures.
The following is a list of exemplary telogens which are suitable in forming the telomer builders of the invention.
Saturated Aliphatic Alcohols Methanol, ethanol, 2-propanol, 1-butanol,2-methyl-l-propanol, 3-pentanol, l-hexanol, 3-methyl~
hexanol, 2-ethyl-1-hexanol, l-heptanol, l-octanol, 2,3,4-trimethyl-2-hexanol, l-decanol.
Saturated Aliphatic Aldehydes - Formaldehyde, acetaldehyde, l-propanal, l-butanal, 2-methyl-1-propanal, l-pentanal, 2-methyl-1-pentanal, l-hexanal, l-heptanal, l-octanal, l-decanal.
Saturated Aliphatic Orthoformates Trimethyl orthoformate, triethyl orthoformate, `
- tri)2-propyl) ortho~ormate, tri (l-butyl) ortho-formate, tri (3-pentyl) orthoformate, tri (l-hexyl) orthoformate, tri (2,2-dimethyl-1-butyl) ortho-formate, tri (l-decyl) orthoformate, trimethyl and `"~
triethyl orthoacetates and orthopropionates. `
Saturated Aliphatic Ethers Dimethyl ether, diethyl ether, dipropyl e~her, di (2-propyl) ether, dibutyl ether, dipentyl ether, ~ -dihexyl ether, dioctyl ether, didecyl ether and such cyclic ethers as tetrahydrofuran, dioxane and 1,3-clioxolane.
Saturated Aliphatic Carboxylic Acids ~-', ' ' ' ~ ' ' ' -7- ~`
, ' 375~i~
Acetic acid, propionic acid, l-butanoic acid, 2-methyl-l-butanoic acid, 1-pentanoic acid, 1- ~-hexanoic acid, 2-ethyl-1-hexanoic acid, l-heptanoic acid, l-octanoic acid, 2-ethyl-1-oetanoie acid, l-decanoie aeid.
Other Telogen Components Ethyleneglycol dimethyl ether, ethyleneglycol diethyl ether, diethyleneglycol dimethyl ether, .
tetraethyleneglycol dimethyl ether, HSCH2COOH, HSCH2CH2COOH, diisopropylbenzene and isopropyl ~'~
benzene. ~ ~`
.
In preparing the detergent compositions of this -invention, the essential ingredients are ~a) an organic water-soluble detergent surface aetive material as defined `;~
and illustrated below and (b) a novel polyeleetrolyte ; ;~
builder compound meeting the structural requirements `~
specified and exemplified above. The detergent composi- ~`
tions of this invention, therefore, contain the essential ingredients in a ratio of polyelectrolyte builder to `
detergent surfactant in the range of about 1:3 to about i~
10:1 by weight, with such compositions providing in aqueous solution a p~ of about 8-to about 12. The preferred ratio of polyelectrolyte builder to detergent surfaetant is about 1:2 to about 5:1 and the optimum pH range is 9.5 to about 11.5.
The organie detergent compounds, i.e. surface active agents, whieh can be utilized in the compos-tions of this ` `
invention are anionic, nonionic, ampholytic and ;
2witterionic synthetic detergents and mixtures thereof . . ~ . .
30 and- are exemplified as follows: -,~
~'' '. ~;
,. . .
equally to all the usual conditions of soiling and washing.
Builder materials should exhibit certain ancillary properties in order to be acceptable in current washing processes and consumer marketing techniques. Thus, a builder should preferably be white, inexpensive, non-toxic, stable to oxidizers, non-corrosive, non-hygro-scopic, stable to hot alkaline detergent solutions and ~ -stable during spray drying operations. More recently, the environmental safety of detergent builders has become a prime ancillary property.
Examples of known inorganic builder materials are the water-soluble, inorganic alkaline builder salts which can be used alone or in combination, including alkali metal carbonates, borates, phosphates, poly-phosphates, bicarbonates and silicates.
Examples of known organic builder materials are alkali metal, ammonium or substituted ammonium amino-polycarboxylates, e.g. sodium and potassium ethylene- -diaminetetraacetate, sodium and potassium N(2-hydroxy-ethyl)~ethylenediaminetriacetate, sodium and potassium and triethanolammonium -N - (2-hydroxyethyl) nitrilo-diacetate. Alkali metal salts of phytic acid, e.g., sodium phytate/ are also suitable as organic builders.
Of all of the known builders the condensed inorganic --phosphates find the widest commercial acceptance. ~
Sodium tripolyphosphate (STPP) has been especially favored -being used in both home and industrial cleansing. However, .
~, ~3~g~
considerable work is being done in an effort to find organic substitutes for some or all of the inorganic builders.
Among the materials whlch have been investigated ~;
as a source of new builders are various polyelectrolytes `
such as the water-soluble sal~s of polycarboxylic acid polymers disclosed in U. S. Patent 3,308,067 to Diehl.
According to the patent specification, one of the . . ., ", highly preferred members is the alkali metal salt of polymaleic acid. This is obtained by polymerizing maleic anhydride using 5% benzoyl peroxide as initiator following the procedure of Lang, Pavelick and Clarey, ~`
J. Polymer Sci., issue 162, page 532 (1961). The resulting product is treated with an alkali metal hydroxide such as sodium hydroxide to form sodium polymaleate. Generally speaking, the sodium polymaleate ls a satis~actory builder although it falls short with `
respect to solubility, and mineral precipitation.
However, the principal fault of sodium polymaleate is its resistance to bacterial attack, being virtually non-biodegradable. In fact, such biological behavior is a -~
common characteristic of high molecular weight poly~
,.. ..
electrolytes, thereby mitigating against their utility as builders.
Low molecular weight derivatives of maleic acid have also been investigated as detergent additives.
For instance, U. S. Patent 2,264,103 discloses cleansillg compositions containing the sodium salt of butanetetra- ~
"..''' i"''.'`' ,.
~ .
carboxylic acid. Although these polycarboxylic acids are biodegradable, their builder performance is generally unsatisfactory. Another low molecular weight class of polymaleic acids are the maleic acid telomers such as are described in U.S. Patent 3,474,114. So far as is ~ ;
known, maleic acid telomers have not been investigated as detergent builders.
It has now been discovered that excellent builder properties together with a high degree of biodegradability are possessed to a remarkable extent by a class of maleic acid telomers having the following formula:
:. 1 ".
-~ H - _ CH CH ¦ X
COOH COOH J
wherein n is an integer of 1 to 8; X is R-CH-OH, -C(O)-R, -CH2C(CH3)=CHCOCH3, -C(OR)3, an ~-dialkyl , ether group of 2 to 20 carbon atoms, R-CH-O(CH2CH2O) -R, -CH(COOH)R, -S(CH2) COOH, -C(Rl)2 ~ ,2-tetrahydro-furanyl, 2-(1,3-dioxolanyl), p-dioxanyl and 2-tetra-hydropyranyl wherein R is hydrogen or alkyl of 1 to 10 carbon atoms; Rl is alkyl of 1 to 2 carbon atoms; Y
is hydrogen or -CH(Rl)2 and p is an integer of 1 to 5.
,., ~. -.
The provision of such maleic acid telomers and detergent . ::
compositions containing them constitutes the principal object and purpose of the invention. Other objects and purposes will become manifest subsequently.
As can be seen from an inspection of the formula ~ ' .
.' :,' :
'` .
:, -. ~ .
::.:. ` ~,.
.,, ,; .:
~ 7~ti$
aforesaid, the builders of the inventions are telomers oE
maleic acid. According to the Encyclopedia of Polymer Science and Technology 3 605 (1965), John Wiley & Sons, Inc., a telomer is a low molecular weight polymer formed by reacting a chain transfer agent or telogen with an olefinic monomer or taxogen. Such polymerization process ~?
is known as telomerization and the end products are referred to as telomers. The telomerization of maleic anhydride with a chain transfer agent can be depicted by the following scheme ;
~C~ ,~ chain transfer ~ 0]
n lCo \ / C0 J agent or telogen C \ O /C n ;~
telomer taxogen `; H ~ CH CH `~X
COOH COOH n acid form wherein n and X have the significance aforesaid. The ~
anhydride form of the telomer is saponified with a base `~ ;
such as sodium hydroxide to give the telomer salt.`~
In conducting the telomerization reaction herein, .~
the maleic anhydride and telogen are heated together in - -the presence of a free radical source such as an organic peroxide. The ratio of maleic anhydride to telogen in the product is determined by the mole ratio of maleic anhydride to telogen in the polymerization mixture, the activity of the telogen as a chain transfer agent and the temperature. `~
The reaction is desirably carried out in the presence .. .~ , .
.
':'.' '~ ' -; :
7~
of an inert solvent at mildly elevated temperatures preferably in the neighborhood of 100C. In general, the reaction is patterned after the known telomerization procedures.
The following is a list of exemplary telogens which are suitable in forming the telomer builders of the invention.
Saturated Aliphatic Alcohols Methanol, ethanol, 2-propanol, 1-butanol,2-methyl-l-propanol, 3-pentanol, l-hexanol, 3-methyl~
hexanol, 2-ethyl-1-hexanol, l-heptanol, l-octanol, 2,3,4-trimethyl-2-hexanol, l-decanol.
Saturated Aliphatic Aldehydes - Formaldehyde, acetaldehyde, l-propanal, l-butanal, 2-methyl-1-propanal, l-pentanal, 2-methyl-1-pentanal, l-hexanal, l-heptanal, l-octanal, l-decanal.
Saturated Aliphatic Orthoformates Trimethyl orthoformate, triethyl orthoformate, `
- tri)2-propyl) ortho~ormate, tri (l-butyl) ortho-formate, tri (3-pentyl) orthoformate, tri (l-hexyl) orthoformate, tri (2,2-dimethyl-1-butyl) ortho-formate, tri (l-decyl) orthoformate, trimethyl and `"~
triethyl orthoacetates and orthopropionates. `
Saturated Aliphatic Ethers Dimethyl ether, diethyl ether, dipropyl e~her, di (2-propyl) ether, dibutyl ether, dipentyl ether, ~ -dihexyl ether, dioctyl ether, didecyl ether and such cyclic ethers as tetrahydrofuran, dioxane and 1,3-clioxolane.
Saturated Aliphatic Carboxylic Acids ~-', ' ' ' ~ ' ' ' -7- ~`
, ' 375~i~
Acetic acid, propionic acid, l-butanoic acid, 2-methyl-l-butanoic acid, 1-pentanoic acid, 1- ~-hexanoic acid, 2-ethyl-1-hexanoic acid, l-heptanoic acid, l-octanoic acid, 2-ethyl-1-oetanoie acid, l-decanoie aeid.
Other Telogen Components Ethyleneglycol dimethyl ether, ethyleneglycol diethyl ether, diethyleneglycol dimethyl ether, .
tetraethyleneglycol dimethyl ether, HSCH2COOH, HSCH2CH2COOH, diisopropylbenzene and isopropyl ~'~
benzene. ~ ~`
.
In preparing the detergent compositions of this -invention, the essential ingredients are ~a) an organic water-soluble detergent surface aetive material as defined `;~
and illustrated below and (b) a novel polyeleetrolyte ; ;~
builder compound meeting the structural requirements `~
specified and exemplified above. The detergent composi- ~`
tions of this invention, therefore, contain the essential ingredients in a ratio of polyelectrolyte builder to `
detergent surfactant in the range of about 1:3 to about i~
10:1 by weight, with such compositions providing in aqueous solution a p~ of about 8-to about 12. The preferred ratio of polyelectrolyte builder to detergent surfaetant is about 1:2 to about 5:1 and the optimum pH range is 9.5 to about 11.5.
The organie detergent compounds, i.e. surface active agents, whieh can be utilized in the compos-tions of this ` `
invention are anionic, nonionic, ampholytic and ;
2witterionic synthetic detergents and mixtures thereof . . ~ . .
30 and- are exemplified as follows: -,~
~'' '. ~;
,. . .
3~
(a) Anionic synthetic non-soap detergents can be ; broadly described as the water-soluble salts, particularlythe alkali metal salts, of organic sulfuric reaction products having in their molecular structure an alkyl radical containing ~rom about 8 to about 22 carbon atoms ~`
and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. Important examples of the synthetic detergents are the sodium or potassium alkyl sulfates, sodium or potassium alkylben-zenesulfonates, in which the alkyl group contains from `
- about 9 to about 15 carbon atoms (the alkyl radical can be a straigt or branched aliphatic chain); alkyl (glycerylsulfate) ether; sodium coconut oil fat-ty acid ~ `
monoglyceride sulfates and sulfonates; sodium or ;
potassium salts or sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols) and about 1 to 6 moles of ethylene oxide, sodium or potassium salts of alkyl ~ `
phenol ethylene oxide ether sulfate with about 1 to --about 10 units of ethylene oxide per molecule and in -which the alkyl radicals contain from 8 to about 12 ;
carbon atoms: the reaction product of fatty acids ~;
esterified with isothionic acid and neutralized with ;
sodium hydroxide, sodium or potassium salts of fatty acid amide of a methyl tauride, and sulfonated olefins.
(b) Nonionic synthetic detergents: One class can be broadly defined as compounds produced by the -condensation of alkylene oxide groups (hydrophilic in ' nature) with an organic hydrophobic compound, which may be allphatic or alkyl aromatic in nature. The length oi _ g_ . ~
~7~
the hydrophilic or polyoxyallcylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound `~
having the desired degree of balance between hydrophilic and hydrophobic elements. Another class has semi-polar characteristics. Preferred classes of nonionic synthetic detergents are as follows~
(1) A class of nonionic synthetic detergents under the trade name of "Pluronic"*. These compounds are formed ~;
by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene ~;
glycol;
- (2) The polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols ; : :
having an alkyl group containing from about 6 to 12 - carbon atoms in either a straight chain or branched chain configuration with ethylene oxide;
(3) Those nonionic synthetic detergents derived from the condensation of ethylene oxide with the ; 20 product resulting from the reaction of propylene oxide `~
and ethylene diamine;
; (4) The condensation product of aliphatic ;~
alcohols having from 8 to 22 carbon atoms, in either straight chain or branched chain configuration, with - `~
ethylene oxide; .`
(5) The ammonia, monoethanol and diethanol amides of fatty acids having an acyl moiety of from about 8 to about 18 carbon atoms; ~ ;~
(6) Long chain tertiary amine oxides such as dimethyldodecylamine oxide; cetyldimethylamine oxide;
* Trade Mark .' ' .
-10- ~
' . . ~ ~ . .:
7~5 bis-(2-hydroxyethyl)-dodecylamine oxide; bis-(2-hydroxy-ethyl)-3-dodecoxy-l-hydroxypropylamine oxidei (7) Long chain tertiary phosphine oxides such as dimethyldodecylphosphine oxide; diethyldodecylphosphine ;
oxide; dimethyl-(2-hydroxydodecyl) phosphine oxide;
(8) Long chain sulfoxides such as dodecyl methyl sulfoxide; 3-hydroxytridecyl methyl sulfoxide; 3- ` "
methoxytridecyl methyl sulfoxide; 3-hydroxy-4-dodecoxy-butyl methyl sulfoxide. ;
., ;'. ' (c) Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic secondary and tertiary amines, in which the aliphatic radical may be -- straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 `~
carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfo, sulfato, ;~
phosphate, or phosphono. Examples of compounds falling within this definition are sodium-3-dodecyl- -~
aminopropionate and sodium-3-dodecylaminopropanesulfon- ~;
ate. ~
(d) Zwitterionic synthetic detergents can be ~;
broadly described as derivatives of aliphatic quaternary `~
ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radical may be straigt chain or branched, and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group; e.g. carboxy, sulfo, ;
sulfato, phosphato, or phosphono. Examples of compounds falling within this definition are 3-(N,N-dimethyl-N-hexadecylammonio)propane-l-sulfonate and 3-(N,N-dimethyl-`,' ~
.: ~ .
. .
. . . - ,. - .~. ~ ~
~3~
N-hexadecylammonio)-2-hydroxy propane-l-sulfonate.
In the novcl cletergent formulations o~ this invention, -the weight ratio of surface active agent to builder ranges from about 3:1 to 1:10. These two ingredients generally represent at least about 45% of the total detergent formulation.
It should be noted that the novel builders herein are used either in the form of their alkali metal salts or in acid-form together with a sufficient quantity of an alkali metal base, such as the carbonate or hydroxide, ., ~
in order to neutralize the carboxyl group and adjust the pH level of the final detergent solution to within the ~ ~
desired 9.5-11.5 range. ~ ;
The formulations may also contain minor amounts of ~ ~
optional additives in order to modify certain properties `~ ;
thereof. Among such optional additives are included~
foam builders and stabilizers, antiredeposition agents such as sodium carboxymethylcellulose, corrosion inhibitors such as benzotriazole, optical brighteners, bactericides, perfumes, bleaches, enzymes, dyes, blueing `~
agents, inorganic salts, solvents and the like. These ~;
total optional ingredients commonly range from about 30% to about 55%, by weight of the formulation. Such formulations can be used for a variety of cleaning ;~
purposes including machine and hand washing of textiles, dishes, various utensils, hard and soft surfaces and the like. When compounded for machine washing as with ::~:: ~
- automatic dishwashers, the formulations may incorporate a relatively high percentage of bleach and alkali compared to hand washing compositions. Generally ' ~ :
~:
~ speaking, those skilled in the art know how to blend .. .! . .
detergent mixtures to suit a given cleansing operation.
Methods for preparing detergent formulations are also `~;
well known to those skilled in the art, a typical method `
involving drying the ingredients, forming them into an aqueous slurry and then spray drying. The final detergent formulations may be a mixture of dry ingredients, ``~
a concentrated aqueous solution or a solid mix resulting ;~
from the drying thereof, or a combination of dry solids `.'.; ' ~ ' ~
.
,. `'. ` ~ '~' .
'',, ~. ",,' ,",~ '`';
, ,., ~ ~;, :~
; - , ~ ~:
~, ~:
,`
`'.', : ~ ..: .
~ '7~i$
and dry ingredients as is common in the art.
The following examples will further illustrate the embodiments of this invention. In these examples and the tables, unless noted otherwise, all parts given are by weight and temperatures are in degrees centigrade. `~
Example 1 - Sodium Salt of Maleic Acid - Triet~yl Ortho~
formate Telomer Maleic anhydride (98.0 g, 1.0 mole) and 20.8 ml (0.125 mole) of triethyl orthoformate were dissolved in ;`~
100 ml of chlorobenzene in a l-liter, steam-~acketed reactor equipped with stirrer, addition - funnel, thermo- `
meter and reflux condenser. The clear, light amberg solution was heated to 100 with stirring and 20 ml of a 25% solution of diacetyl peroxide in dimethyl phthalate added in 5-ml portions over a 1-hr. period. The maximum temperature reached was 112. Following the diacetyl peroxide addition the reaction mixture was maintained at 100 for 1 hr. The resulting dark red sirupy precipitate i~
was vacuum stripped at 20 m~ and 95 to give a clear ;
dark red sirup. Further vacuum stripping at 160-170 ;
and 2-3 mm to remove monomeric maleic anhydride gave 48.1 g of dark red glass. Maleic anhydride monomer content was : 1.7% by a polarographic method. NMR analysis in d6 acetone gave an n value of 8. Yield: 41.3% of theory for n=8.
A 20.0 g sample of the anhydride telomer (.0215 mole) .. ` ~
` was dissolved in 100 ml of water and the pH adjusted to ~-8-9 by the addition of ~7 ml of 5N sodium hydroxide (~34 mole). The solution was bleached by heating at reflux for 1 hr. with 20 ml of 30% hydrogen peroxide. The ~`
resulting solution was vacuum stripped at 20 mm and 95 ~
t~
and oven dried at 60~ and 2-3 mm to c~ive 22.9 g of a yellow glass.
Elemental Analysis - Calculated for n = 8 C39H32O35Nal6: C, 32.77;H, 2.24; Na, 25.77; Na~C=0-41 Found: C, 32.88; ~I, 3.16; Na, 23.84; Na/C=0.38.
Sample purity based on maleic anhydride monomer content of 1.7% was estimated to be 98.2%.
Performance of this material is shown in Tables IA and IIA. ;
10Example 2 - Sodium Salt of Maleic Acid - Ethylene~lycol ~;
Dimethyl Ether Telomer -~;
~ . .
Maleic anhydride (98.0 g, 1.0 mole) and 26.2 ml (0.25 mole) of ethyleneglycol dimethyl ether were dissolved in 100 ml of chlorobenzene in a reactor like that described in Example 1. The clear light yellow solution was heated to 100 and 20 ml of a 25% solution of diacetyl peroxide in dimethyl phthalate added in 5-ml `
portions over a 1.5-hr. period. The maximum temperature reached was 116. Following the diacetyl peroxide 20addition the reaction mixture was maintained at 100 ~^`
for 1 hr. A viscous polymeric mass formed. The entire reaction mixture was vacuum stripped at 160-170 and ~ `
2-3 mm to give 81.4 g of dark amber glass. Maleic anhydride monomer content was 0.9%. Yield: 67.5% of `~
theory for n = 4.
A 20.0 g sample of the anhydride telomer (.0415 mole) was dissolved in 100 ml of water and the pH
adjusted to 8-9 by addition of 62 ml of 5N sodium hydroxide (0.31 mole). The solution was bleached by heating at reflux for 1 hr. with 30 ml of 30% hydrogen . ' ' , . , ~ . .
'1 ~
-15- ~ ~
peroxide. The resulting solution was vacuum stripped `
at 20 mm and 95 and oven dried at 60 and 2-3 mm to ~ -give 28.9 g of yellow glass.
Elemental Analysis - Calculated for n = 4 C20H18O18Na8: C, 32.89; H, 2.49; Na, 25.18; Na/C=0.40 Found: C, 33.10; H, 3.32; Na, 23.84; Na/C=0.38.
Sample purity based on ma]eic anhydride monomer `~
- content of 0.9% was estimated to be 99.2%.
. ..
Performance of this material is shown in Tables IA and IIA.
,; ~ . .
Example 3 - Sodium Salt of Maleic Acid - n-Butyralde-hyde Telomer ~ ;
Maleic anhydride (98.0 g, 1.0 mole) and 8.8 ml ~ . ..
(0.10 mole) of n-butyraldehyde were dissolved in 100 ml of chlorobenzene. The clear, colorless solution was -heated to 100 and 20 ml of a 25% solution of diacetyl peroxide in dimethyl phthalate added in 5-ml portions ~`
over a l-hr. period. The maximum temperature reached `~
was 108. Following the diacetyl peroxide addition the reaction mixture was maintained at 100 for 1 hr. A
medium amber taffy-like polymer formed. The entire -~
reaction mixture was vacuum stripped at 160-170 and 2-3 mm to give 48.0 g of dark amber glass. Maleic anhydride monomer content was 0.3%. Yield: 131% of theory for n = 3.
Elemental Analysis - Calculated for n = 3 C16H14Olo: C, 52.47; H, 3.85; C/H=1.14 Found: C, 54~20; H, 3.94; C/H=1.14.
A 20.0 g sample of the anhydride telomer ~.0546 . .
mole) was dissolved in 100 ml of water and the pH
~:
~;
:, 7~
adjusted to 8-9 by addition of 63 ml oE 5N sodium hydroxide (0.32 mole). The solution was bleached by heating at reflux for 1 hr. with 10 ml of 30% hydrogen peroxide. The resulting solution was vacuum stripped at 20 mm and 95 and oven dried at 60 and 2-3 mm to give 27.3 g of a yellow glass.
Elemental Analysis - Calculated for n = 3 .. , C16H14O13Na6: C, 34.81; H, 2.56; Na, 24.97; Na/C=.38 Found: C, 35.23; H, 3.20; Na, 24.23; Na/C=.36. `~
Sample purity based on maleic anhydride monomer content of 0.3% was estimated to be 99~5%. -Performance of this material is shown in Tables IA and IIA.
Example 4 - Sodium Salt of Maleic Acid - Tetraethylene-glycol Dimethyl Ether Telomer Maleic anhydride (98.0 g, 1.0 mole) and 55.6 g (0.25 mole) of tetraethyleneglycol dimethyl ether were `
dissolved in 100 ml of chlorobenzene. The clear, -~
colorless solution was heated to 100 and 20 ml of a 25% solution of diacetyl peroxide in dimethyl phthalate added in 5-ml portions over a 1.5-hr. period. The maximum temperature reached ~as141. Following the diacetyl peroxide addition the reaction mixture was `~
maintained at l00 for 1 hr. A dark red taffy-like mass formed. On cooling it became brittle. It was ground to a powder under chlorobenzene, separated by -filtration and washed exhaus-tively with chlorobenzene at room temperature. The cake was vacuum dried at 60 ;~
and 2-3 mm to give 126.9 g of a light amber powder.
Maleic anhydride monomer content was 0.05%. Yield:
'': - ~
: -:- ... - . . ~ , . - , 3~
101~ of theory for n = 8.
A 20.0 g sample of the anhydride telomer (0.0199 `
mole) was dissolved in 100 ml of water and the pH
adjusted to 8-9 by addition of 60 ml of 5N sodium hydroxide ~0.30 mole). The solution was bleached by heating at reflux for 1 hr. with 10 ml of 30% hydrogen peroxide. The resulting solutic)n was vacuum stripped at 20 mm and 95 and finally dried at 60 and 2-3 mm ~`
to give 28.3 g of light tan glassy solid. ;
Elemental Analysis - Calculated for n = 8 - `
C42H38O37Nal6: C, 33,57; H, 2.55; Na/ 24.47; Na/C=0-38 Found: C, 33.77; H, 3.60; Na, 25.20; Na/C=0.39.
Sample purity based on maleic anhydride monomer content of 0.05% was estimated to be 100%.
Performance of this material is shown in Tables IA and IIA. `
Example 5 - Sodium Salt of Maleic Acid - Mesityl Oxide ~;
.. --- :
Telomer Maleic anhydride (98.0 g, 1.0 mole) and 28.6 ml (0.25 mole) of mesityl oxide were dissolved in 100 ml of chlorobenzene, the solution heated to 100 and 20 ml of a 25% solution of diacetyl peroxide in dimethyl ~-phthalate added in 5-ml portions over a 0.5-hr. period.
The maximum temperature reached was 113. Following the diacetyl peroxide addition the reaction mixture was maintained at 100 for 1 hr. The resulting clear dark red amber solution was vacuum stripped at 160-170 and 2-3 mm to give 27.7 g of dark red amber glass.
Maleic anhydride monomer content was 1.5%. Yield:
37.7% of theory for n = 2.
~.
~ 3P;'~ ;6 A 20.0 g sample of the anhydride telomer (.0680 mole) was dissolved in 100 ml of water and the pH
adjusted to 8-9 by addition o~ 50 ml of 5N sodium ~ `
hydroxide (0.25 mole). The solution was bleached by `~
heating at reflux for 1 hr. with 30 ml of 30% hydrogen ;
peroxide. The resulting solution was vacuum stripped at 20 mm and 95 and finally dried at 60 and 2-3 mm to give 27.8 g of yellow glass.
Elemental Analysis - Calculated for n = 2 C14H14OgNa4: C, 40.22; H, 3.37; Na, 21.99; Na/C=0.29 Found: C, 40.01; ~, 4.12; Na, 20.13; Na/C, 0.26.
Sample purity based on maleic anhydride monomer content of 1.5% was estimated to be 98.4%.
Performance of this material is shown in Tables IA and IIA.
Example 6 - Sodium Salt of Maleic Acid - iso-Prop~
Alcohol Telomer - Maleic anhydride (98.0 g, 1.0 mole) and 38.3 ml (0.50 mole) of isopropyl alcohol were dissolved in 100 ml of chlorobenzene, the solution heated to 100 and 20 - ml of a 25% solution of diacetyl peroxide in dimethyl phthalate added in 5-ml portions over an 0.8-hr. period.
The maximum temperature reached was 107. Following the diacetyl peroxide addition the reaction mixture was maintained at 100 for 1 hr. The resuliing clear light ~ -orange solution was vacuum stripped at 160-170 and 2-3 mm to give 30.5 g of medium amber glass. Maleic anhydride monomer content was 0.7%. Yield: 38.6% of theory for n=l.
Elemental Analysis - Calculated for n = 1 ~ `
... . . .. . .
.:: . . - . . .
- ~3~tj~ ~
C7H1004: C, 53.15; H, 6.37 Found: C, 54,47; H, 5.24.
A 20. 0 g sample of the anhydride telomer ~.1265 mole) was dissolved in lO0 ml of water and the pH adjusted to 8~9 by addition of 44 ml of 5N sodium hydroxide (0.22 mole). -The solution was bleached by heating at reflux for 1 hr.
with 20 ml of 30% hydrogen peroxide. The resulting `
solution was vacuum stripped at 20 mm and 95 and finally dried at 60 and 2-3 mm to give 24.7 g of light tan glass.
Elemental Analysis - Calculated for n ~ 1 C7H10O5Na2: C, 38.20; H, 4.58; Na, 20.89; Na/C=0.29 Found: C, 36.92, H, 4.18; Na, 18.41; Na/C=0.26.
Sample purity based on maleic anhydride monomer -` ;
content of 0.7% was estimated to be 99.0%. ~`~
Performance of this material is shown in Tables IA and IIA.
Example 7 - Sodium Salt of Maleic Acid - Methyl Alcohol i~
Telomer Maleic anhydride (588 g, 6.0 moles), 121 ml (3.0 moles) of methyl alcohol were mixed in a l-liter steam-jacketed reactor equipped with a mechanical stirrer, -~
thermometer, reflux condenser, additional funnel, nitrogen `~
purge tube and gas exit tube. The temperature was raised to 60 to form a clear, colorless solution. An exotherm ;-occurred causing the temperature to rise briefly to 95.
While sweepingwithnitrogen and with the temperature at 30-35, 21.1 ml of 90% hydrogen peroxide was added drop-wise over a 5 minute period. After allowing to stir at 30-35 for 15 minutes, 163.2 ml of acetic anhydride was :
added dropwise over a 20 minute period. The clear, colorless -reaction mixture waq ~tirred for an additional 40 min. during ~--, , ~ 7~
which time an exotherm occurred requiring jacket water cooling to keep the temperature from rising above 60. -The resulting clear, colorless nonviscous solution after stirring for 1 hr. at 30-60 was added dropwise over a 1.2-hour period to 600 ml of chlorobenzene in a 3-liter steam-jacketed reactor equipped as described `
above while maintainlng the temperature at 100-110.
Stirring was continued at 100-110 for an additional 2.6 hours. ,~
- 10 The clear light amber reaction mixture was vacuum stripped at 20 mm and 95 (with continuous addition of ~
- chlorobenzene to serve as a carrier for removing `~;
.?'. ::
maleic anhydride) to a constant weight of 421 g.
- The clear light amber glassy telomer anhydride was dissolved in 800 ml of water and neutralized with 557 ml of 50% sodium hydroxide to give a turbid dark orange solution with a p~ of 9.6. To this solution at about 70, `~ `
was added slowly, 70 ml of 30% hydrogen peroxide after which most of the color had been removed. The so-treated ``!' solution was poured into 5 liters of methyl alcohol with ~ mechanical stirring at room temperature. The white -~ precipitate was separated by filtration, slurried with 300 ml of toluene, vacuum stripped at 20 mm and 95 and finally dried at 60 and 1-2 mm to give 523 g of slightly off-white powder.
Sample composition based on maleate monomer content and water analysis was 76.4% sodium telomerate, 7.5%
wat~r and 16.1% disodium maleate; n equals 3-4.
Performance of this material is shown in Tables `
IA and IIA.
. " I .
,.,.-.-, . . , . . ~ ,, ,. - . - , .. . - , . :
Although the telomer compounds herein are depicted as being linear, it is to be understood that non-linear configurations may also be formed during the telomeriza- ;~
tion reaction due to chain branching. However, in the interest of convenience and simplicity only the linear :.
formula is shown.
Deter~ent Fo~mul:ation `
- The builder compounds of the invention were tested and evaluated using the following cleansing formulation -~
Parts ; ~ -:
Sodium linear alkylarylsulfonate 20.0 -Builder 50.0 tor 25) Sodium metasilicate 5-hydrate 12.0 Sodium carboxymethylcellulose 0.5 Sodium sulfate 17.5 (or 42.5) In each instance the formulation was prepared by blending the various ingredients. A variety of the novel builders ;~
were respectively substituted into the detergent formula~
tion. In order to determine the performance characteristics , 1~37~
of the resulting detergent formulations, they were sub-jected to the following test procedures in which water hardness in ppm is expressed as calcium and magnesium carbonate with a Ca/Mg gram ion ratio of 1.5.
Test Procedures Detergency Test~
A full description of thi~; detergency test may be ~;
found in the article by Spangler et al., Journal of the American Oil Chemists Society, 42, 723 (1965).
The test was conducted in a Terg-O-Tometer utilizing swatches of four different fabrics - cotton, cotton-dacron (50:50), cotton-dacron (35:65), and nylon - which had been soiled with a combination of airborne particulate matter and synthetic sebum. Unsoiled swatches of the `~
fabrics were included to measure soil redeposition, one unsoiled swatch of each fabric type for each wash load along with three soiled swatches o~ each fabric type. ` ~-Three soil-wash cycles were conducted on each fabric utilizing the following test conditions: water hardness of 150 ppm and 300 ppm respectively; detergent formulation - concentration of 0.15%; temperature of 120F; and a pH
level of 9.5; washing time 10 minutes; rinsing time 2 `~
minutes. ~ ;
Reflectance readings on the washed swatches were then taken with a Hunter Reflectometer, Model D-10 The results were expressed in terms of "percent reflect- -ance" with the arbitrary standard of "100% reflectance" ,;; -~
~ being established for the reflectance value obtained on - a cotton swatch which had been washed with the standard ~ ~`
detergent formulation containing 50~ sodium tripoly-~ . .
:~:
7~
phosphate builder in water of 150 ppm hardness. Soil redeposition results are given as the decrease in reflectance units (~rd) of the unsoiled swatches after washing, rinsing and drying. Test results for various builders of the invention are shown in Table IIA. In the case of the blended and non-cotton fabrics, the soil removal values are expressed relative to the reflectance of a standard cotton swatch washed in the standard detergent formulation.
Sequestering_Capacity Since the ability to sequester calcium ions is a critical feature of an effective detergent builder, the various new builders were subjected to the following ~
test procedures in order to determine their sequestering -capacity. Thus, an aqueous solution of the sample was titrated potentiometrically with a standard calcium nitrate solution at a pH of 10.0 and a temperature of 25C. using a divalent cation activity electrode (Orion Research, Inc.) as the indicator electrode.
The sequestering capacity was espressed as grams Ca per 100 g of sample = 4.008 . M . V
W
where M = molarity of the calcium nitrate solution V =volume in ml of the above solution required to reach the inflection point, and W =weight of the sample in g.
Dispersing Efficiency: ~;
A procedure patterned after that described by ; VanWazer and Besmertnuk, J. Phys. Colloid Chem., 54, 89 (1950), was used for measuring the deflocculating ability of the telomers.
... . . . .. . . . . . . . . ..
~317~$
A kaolin slurry is prepared by mixing 80 g of washed and ignited powdered kaolin and 150 ml o~ water in a 200-ml tall-form bea~er. After p~I adjustment to 10.0 with 5N NaOH the slurry is thermostatted at 25C.
Viscosity readings are taken with a Brookfield viscometer Model LVT. Incremental weights of the builder whose dispersent activity is being determined are added as a standard solution adjusted to pH 10.0 and after ~ -thorough mixing the viscosity is determined. A plot of viscosity versus percent builder added based on ~
kaolin is prepared and the percent builder required - ~ -to lower viscosity to 200 centipoise determined.
Results are expressed in terms of the performance of sodium tripolyphosphate (STPP) which is arbitrarily set at 100%. ~
Mineral Precipitation: ~-A detergent formulation containing the builder under evaluation is dissolved in 300 ppm hard water to give a 0.15% formulation solution. A 50 ml `~
aliquot of the solution is diluted to 1000 ml with 300 ~-ppm hard water and the resulting solution filtered successively through 8, 4.5 and 0.1 micron cellulose millipore filters. The filter mats are then dried and `~
weighed to obtain the recorded insolubles. All samples `
were run on a sodium salt basis. Results are shown in `
Table IA.
`~ Biodegradability: ~;
Biodegradability of the builder was measured as -; the extent to which it is metabolically oxidized to carbon dioxide in a sewage-inoculated culture medium.
~' ' ,. :.
~U3~
The compound to be tested was added a-t a concentra-tion of 20 ppm to 6 liters of biological oxygen demand (BOD) dilution water containing yeast extract which had been inoculated with settled primary sewage effluents (10~ of total volume). The solution was stirred and aerated in a dark bottle for two or three weeks to adapt the culture to the test compound. After the -adaption period, a subculture was prepared by adding one volume of the original culture solution to 9 volumes of fresh soD dilution water containing yeast extract, and 20 ppm of the test compound was added to the subculture solution. While the subculture was stirred and aerated with CO2-free air in a dark bottle for two ;~
weeks, the effluent gases containing CO2 were scrubbed i~
in caustic soda traps and the collected CO2 was determined by titration. Net CO2 evolved from the test compound was estimated by ccmparison with a suitable ~
blank culture. Extent of biodegradation was taken as ` ;`
the percentage of theoretically available carbon in the test compound evolved as net CO2. A second subculture was prepared from one volume of first subculture solution ;
and 9 volumes of fresh BOD dilution water containing ~;
yeast extract, and 20 ppm of test compound was again added. Aeration, gas collection, and analysis for CO
were conducted as above. Typical results are summarized in Table IIIA.
- Example 8 - Built Dishwashing Composition A method of evaluating formulations for utility - in commercial dishwashing is as follows:
A Kitchen Aid automatic dishwasher, Model KD517, `~
: '`'" ~
~ -26-, .~ ~
is used. In the upper rack of the dishwasher are placed six large plates, twelve small plates, and six saucers, arranged in the order: saucer, large plate, small plate, small plate, saucer, large plate, etc., to fill all the rack spaces. The machine is operated on the light soil setting. For each cycle 40 grams of a mixture of ~our parts oleomargarine to one part powdered dried milk are ;~ ;
weighed out and smeared over the six large plates, and ~ ~
20 grams of the detergent formulation being tested are -placed in each of the two dispenser cups of the machine.
The water supply having a hardness of about 160 ppm, `
enters the machine at about 140F. At the end of each cycle, the glass tumblers are removed and set up for ;
evaluation in a specially constructed apparatus consisting of a rectangular wooden box with open front, painted dull black, containing two diffused fluorescent lights at the top. When the tumblers are placed in this box and the room darkened, the light coming from above makes e~ery `~
spot and streak show distinctly. ;
After each cycle the glasses are rated as follows: ~-1. Light spotting 2. Medium spotting 3. Heavy spotting Failure is defined as the point at which half of the glasses are rated as medium spotting or worse.
A formulation was prepared using the following materials where the usual builders in dishwashing detergents are replaced by a telomer of maleic acid and methanol from Example 7. i 7~
Parts Sodium silicate 15.0 Sodium Dichloroiso~
cyanurate 1.5 Sodium carbonate 20.0 Plurafac* (Trade Mark) 3.5 Sodium Sulfate 15.0 Telomer (Example 7) 45.0 * A modified oxyethylated surface active, non-ionic, ::
low-foaming straight chain alcohol sold by Wyandotte Chemical Corporation.
The composition of Example 8 gave excellent ~
results up to about 6 cycles. ~ -:
The detergency properties and related characteristic of the builders of the invention are set forth in the Tables below. ~:~
.
,,.'~
~'"''' " '~
~.' ..
-28- ~
.,l ~:
~ 66 `: ~:
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, ~~ ui '~
. ~ o ~r ~r ~D ~ ~ ~ In ~ ~ co ~r o o ~ ~ ~ co O - '~
~ u~~ O ~ ~ ~ ~ ~ o u~ r ~ ~ oo ~ ~ ~ O -';' `"' ., rl d~ ~ N ~ ~ ~I t~ ~1 ~ ~ H N ~1 t~l t`~l r-l ~1 ~ ~1 ~1 ` ~
c) ~ a~
. rl o :,. ::
. 4 a~
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a)~ ~ ;;~. ;: ` ' rl d ~ o u~ a) o ., .. , I¢ S~t~ ~ \~ /'~) O 00 (~) H ~1 ~ O ~ . . . . . . . . . . . . . . . . ~' ~qu~ U ~d ~ ~ o ~ co ~ ~ ~ o ~ ~ ~ o o ~' ' `. ~ .' ' -~ a ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
_~ . U-- :. . . -E~ ~0 ~ U~
U O
. ~ ~.
S " S E~
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U ~ 3 ~ o ~ o o ~ a ~ N , ~ N N O P~
.. O O O ~1 ~ ,~ J ~ ~ ~1 X r-l 0 ~1 r~ ' ' `
a~ o ~1 o a~ 0 ~c~ o o 0 o o Q"¢
E~ ~) ~ h ~ ~ ~1 0 0 ~ O ~1 ~ 0 ~ ~ o~ ~ ~ 0~ ~
S~ o ~ m m~rl o ~ ~n o ~ ~ ~ ~ ~ ~
~ ~ ~ I ~ I I ~ I I ~-~ ~ ~ U~ ~ O O ... ~ ., ~ a ~ ~ a ~
~ 37~
TABLE I IA
.
N c~ ~ ~ ~) N (~ U~ ~ N If ~3 N ~rl 3 Nr~ ~1 ~I N ~1 ~1 ~. -1 ~I N ~1 ~
~)a~ l 3 N S 3 r~l ~1 ~ O ~ C~\ O ~)~ ~ O
N~J ~1 ~ ~1 ~ ~ ~1 ~ ~ ~ ~ ~ .~ ~ ~ ~ -~ O ~ ~
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As can be seen ~rom an inspection of the data in the tables, the sodium maleate telomers of the invention exhibit those overall characteristics associated with -~
effective builder performance. Thus, calcium sequestering capacities range from 0.0 to 15 g Ca/100 g as compared to `
21 g Ca/100 g for a typical sodium polymaleate (Table IA).
Dispersing efficiencies are approximately 2 to 3 times that of sodium polymaleate and appear to be largely independent of sequestering capacity.
Some correlation appears to exist between telogen content and calcium sequestering capacity and mineral precipitation as shown in Table IV. Both calcium sequestering capacity and mineral precipitation decrease with increasing telogen content.
Water solubility of the telomer salts herein all ... ~.
exceeded 50% at 25 with the exception of n-octyl ether so that with this exception the telomers are more than 1000 times more soluble than a typical sodium polymaleate; -Table V. Water solubility does not appear to be a function of telogen content but rather of telogen structure.
Builder performance of the telomers (Table IIA) on -, cotton was as good as STPP or sodium polymaleate with the ~xceptions of diisopropylbenzene, n-octyl ether, n~
- decanoic acid, n-butyl ether, lower molecular weight - n-butyraldehyde and isopropyl alcohol telomers. Perfor-mance of the telomers on finished 65/35 polyester-cotton was good or better than STPP and sodium polymaleate with the exceptions of the lower molecular weight diisopropyl- ~ ~ -benzene and dioxane telomers. Performance on unfinished ~-30 50/50 polyester-cotton was as good or better than STPP ~
:. , ', -34- ~
~ .
with the exceptions of the ethyleneglycol dimethyl ether and lower molecular weight diisopropylbenzene telomers. Performance of the telomers on nylon was as good or better than STPP with the exceptions of the diisopropylbenzene, n-butyl ether, dioxane and ethylene-glycol dimethyl ether telomers. Only the ethyleneglycol dimethyl ether telomer was the equivalent of sodium polymaleate on nylon.
Redeposition results on cotton, finished 65/35 polyester-cotton and unfinished 50/50 polyester-cotton were all the equivalent of STPP and sodium polymaleate.
Redeposition results on nylon were equivalent or better than STPP with the exceptions of the ethyleneglycol dimethyl ether, dioxane and lower molecular weight diisopropylbenzene telomers. ~ -The maleic acid telomers of the invention thus provide the art with a new class of builder materials -which combine generally superior detergent properties -~
with environmental compatibility.
. ,,'' ~ ~ :.
,`~ ' :'.~
~' ~` ' ~ - . .
(a) Anionic synthetic non-soap detergents can be ; broadly described as the water-soluble salts, particularlythe alkali metal salts, of organic sulfuric reaction products having in their molecular structure an alkyl radical containing ~rom about 8 to about 22 carbon atoms ~`
and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. Important examples of the synthetic detergents are the sodium or potassium alkyl sulfates, sodium or potassium alkylben-zenesulfonates, in which the alkyl group contains from `
- about 9 to about 15 carbon atoms (the alkyl radical can be a straigt or branched aliphatic chain); alkyl (glycerylsulfate) ether; sodium coconut oil fat-ty acid ~ `
monoglyceride sulfates and sulfonates; sodium or ;
potassium salts or sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols) and about 1 to 6 moles of ethylene oxide, sodium or potassium salts of alkyl ~ `
phenol ethylene oxide ether sulfate with about 1 to --about 10 units of ethylene oxide per molecule and in -which the alkyl radicals contain from 8 to about 12 ;
carbon atoms: the reaction product of fatty acids ~;
esterified with isothionic acid and neutralized with ;
sodium hydroxide, sodium or potassium salts of fatty acid amide of a methyl tauride, and sulfonated olefins.
(b) Nonionic synthetic detergents: One class can be broadly defined as compounds produced by the -condensation of alkylene oxide groups (hydrophilic in ' nature) with an organic hydrophobic compound, which may be allphatic or alkyl aromatic in nature. The length oi _ g_ . ~
~7~
the hydrophilic or polyoxyallcylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound `~
having the desired degree of balance between hydrophilic and hydrophobic elements. Another class has semi-polar characteristics. Preferred classes of nonionic synthetic detergents are as follows~
(1) A class of nonionic synthetic detergents under the trade name of "Pluronic"*. These compounds are formed ~;
by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene ~;
glycol;
- (2) The polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols ; : :
having an alkyl group containing from about 6 to 12 - carbon atoms in either a straight chain or branched chain configuration with ethylene oxide;
(3) Those nonionic synthetic detergents derived from the condensation of ethylene oxide with the ; 20 product resulting from the reaction of propylene oxide `~
and ethylene diamine;
; (4) The condensation product of aliphatic ;~
alcohols having from 8 to 22 carbon atoms, in either straight chain or branched chain configuration, with - `~
ethylene oxide; .`
(5) The ammonia, monoethanol and diethanol amides of fatty acids having an acyl moiety of from about 8 to about 18 carbon atoms; ~ ;~
(6) Long chain tertiary amine oxides such as dimethyldodecylamine oxide; cetyldimethylamine oxide;
* Trade Mark .' ' .
-10- ~
' . . ~ ~ . .:
7~5 bis-(2-hydroxyethyl)-dodecylamine oxide; bis-(2-hydroxy-ethyl)-3-dodecoxy-l-hydroxypropylamine oxidei (7) Long chain tertiary phosphine oxides such as dimethyldodecylphosphine oxide; diethyldodecylphosphine ;
oxide; dimethyl-(2-hydroxydodecyl) phosphine oxide;
(8) Long chain sulfoxides such as dodecyl methyl sulfoxide; 3-hydroxytridecyl methyl sulfoxide; 3- ` "
methoxytridecyl methyl sulfoxide; 3-hydroxy-4-dodecoxy-butyl methyl sulfoxide. ;
., ;'. ' (c) Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic secondary and tertiary amines, in which the aliphatic radical may be -- straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 `~
carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfo, sulfato, ;~
phosphate, or phosphono. Examples of compounds falling within this definition are sodium-3-dodecyl- -~
aminopropionate and sodium-3-dodecylaminopropanesulfon- ~;
ate. ~
(d) Zwitterionic synthetic detergents can be ~;
broadly described as derivatives of aliphatic quaternary `~
ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radical may be straigt chain or branched, and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group; e.g. carboxy, sulfo, ;
sulfato, phosphato, or phosphono. Examples of compounds falling within this definition are 3-(N,N-dimethyl-N-hexadecylammonio)propane-l-sulfonate and 3-(N,N-dimethyl-`,' ~
.: ~ .
. .
. . . - ,. - .~. ~ ~
~3~
N-hexadecylammonio)-2-hydroxy propane-l-sulfonate.
In the novcl cletergent formulations o~ this invention, -the weight ratio of surface active agent to builder ranges from about 3:1 to 1:10. These two ingredients generally represent at least about 45% of the total detergent formulation.
It should be noted that the novel builders herein are used either in the form of their alkali metal salts or in acid-form together with a sufficient quantity of an alkali metal base, such as the carbonate or hydroxide, ., ~
in order to neutralize the carboxyl group and adjust the pH level of the final detergent solution to within the ~ ~
desired 9.5-11.5 range. ~ ;
The formulations may also contain minor amounts of ~ ~
optional additives in order to modify certain properties `~ ;
thereof. Among such optional additives are included~
foam builders and stabilizers, antiredeposition agents such as sodium carboxymethylcellulose, corrosion inhibitors such as benzotriazole, optical brighteners, bactericides, perfumes, bleaches, enzymes, dyes, blueing `~
agents, inorganic salts, solvents and the like. These ~;
total optional ingredients commonly range from about 30% to about 55%, by weight of the formulation. Such formulations can be used for a variety of cleaning ;~
purposes including machine and hand washing of textiles, dishes, various utensils, hard and soft surfaces and the like. When compounded for machine washing as with ::~:: ~
- automatic dishwashers, the formulations may incorporate a relatively high percentage of bleach and alkali compared to hand washing compositions. Generally ' ~ :
~:
~ speaking, those skilled in the art know how to blend .. .! . .
detergent mixtures to suit a given cleansing operation.
Methods for preparing detergent formulations are also `~;
well known to those skilled in the art, a typical method `
involving drying the ingredients, forming them into an aqueous slurry and then spray drying. The final detergent formulations may be a mixture of dry ingredients, ``~
a concentrated aqueous solution or a solid mix resulting ;~
from the drying thereof, or a combination of dry solids `.'.; ' ~ ' ~
.
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and dry ingredients as is common in the art.
The following examples will further illustrate the embodiments of this invention. In these examples and the tables, unless noted otherwise, all parts given are by weight and temperatures are in degrees centigrade. `~
Example 1 - Sodium Salt of Maleic Acid - Triet~yl Ortho~
formate Telomer Maleic anhydride (98.0 g, 1.0 mole) and 20.8 ml (0.125 mole) of triethyl orthoformate were dissolved in ;`~
100 ml of chlorobenzene in a l-liter, steam-~acketed reactor equipped with stirrer, addition - funnel, thermo- `
meter and reflux condenser. The clear, light amberg solution was heated to 100 with stirring and 20 ml of a 25% solution of diacetyl peroxide in dimethyl phthalate added in 5-ml portions over a 1-hr. period. The maximum temperature reached was 112. Following the diacetyl peroxide addition the reaction mixture was maintained at 100 for 1 hr. The resulting dark red sirupy precipitate i~
was vacuum stripped at 20 m~ and 95 to give a clear ;
dark red sirup. Further vacuum stripping at 160-170 ;
and 2-3 mm to remove monomeric maleic anhydride gave 48.1 g of dark red glass. Maleic anhydride monomer content was : 1.7% by a polarographic method. NMR analysis in d6 acetone gave an n value of 8. Yield: 41.3% of theory for n=8.
A 20.0 g sample of the anhydride telomer (.0215 mole) .. ` ~
` was dissolved in 100 ml of water and the pH adjusted to ~-8-9 by the addition of ~7 ml of 5N sodium hydroxide (~34 mole). The solution was bleached by heating at reflux for 1 hr. with 20 ml of 30% hydrogen peroxide. The ~`
resulting solution was vacuum stripped at 20 mm and 95 ~
t~
and oven dried at 60~ and 2-3 mm to c~ive 22.9 g of a yellow glass.
Elemental Analysis - Calculated for n = 8 C39H32O35Nal6: C, 32.77;H, 2.24; Na, 25.77; Na~C=0-41 Found: C, 32.88; ~I, 3.16; Na, 23.84; Na/C=0.38.
Sample purity based on maleic anhydride monomer content of 1.7% was estimated to be 98.2%.
Performance of this material is shown in Tables IA and IIA. ;
10Example 2 - Sodium Salt of Maleic Acid - Ethylene~lycol ~;
Dimethyl Ether Telomer -~;
~ . .
Maleic anhydride (98.0 g, 1.0 mole) and 26.2 ml (0.25 mole) of ethyleneglycol dimethyl ether were dissolved in 100 ml of chlorobenzene in a reactor like that described in Example 1. The clear light yellow solution was heated to 100 and 20 ml of a 25% solution of diacetyl peroxide in dimethyl phthalate added in 5-ml `
portions over a 1.5-hr. period. The maximum temperature reached was 116. Following the diacetyl peroxide 20addition the reaction mixture was maintained at 100 ~^`
for 1 hr. A viscous polymeric mass formed. The entire reaction mixture was vacuum stripped at 160-170 and ~ `
2-3 mm to give 81.4 g of dark amber glass. Maleic anhydride monomer content was 0.9%. Yield: 67.5% of `~
theory for n = 4.
A 20.0 g sample of the anhydride telomer (.0415 mole) was dissolved in 100 ml of water and the pH
adjusted to 8-9 by addition of 62 ml of 5N sodium hydroxide (0.31 mole). The solution was bleached by heating at reflux for 1 hr. with 30 ml of 30% hydrogen . ' ' , . , ~ . .
'1 ~
-15- ~ ~
peroxide. The resulting solution was vacuum stripped `
at 20 mm and 95 and oven dried at 60 and 2-3 mm to ~ -give 28.9 g of yellow glass.
Elemental Analysis - Calculated for n = 4 C20H18O18Na8: C, 32.89; H, 2.49; Na, 25.18; Na/C=0.40 Found: C, 33.10; H, 3.32; Na, 23.84; Na/C=0.38.
Sample purity based on ma]eic anhydride monomer `~
- content of 0.9% was estimated to be 99.2%.
. ..
Performance of this material is shown in Tables IA and IIA.
,; ~ . .
Example 3 - Sodium Salt of Maleic Acid - n-Butyralde-hyde Telomer ~ ;
Maleic anhydride (98.0 g, 1.0 mole) and 8.8 ml ~ . ..
(0.10 mole) of n-butyraldehyde were dissolved in 100 ml of chlorobenzene. The clear, colorless solution was -heated to 100 and 20 ml of a 25% solution of diacetyl peroxide in dimethyl phthalate added in 5-ml portions ~`
over a l-hr. period. The maximum temperature reached `~
was 108. Following the diacetyl peroxide addition the reaction mixture was maintained at 100 for 1 hr. A
medium amber taffy-like polymer formed. The entire -~
reaction mixture was vacuum stripped at 160-170 and 2-3 mm to give 48.0 g of dark amber glass. Maleic anhydride monomer content was 0.3%. Yield: 131% of theory for n = 3.
Elemental Analysis - Calculated for n = 3 C16H14Olo: C, 52.47; H, 3.85; C/H=1.14 Found: C, 54~20; H, 3.94; C/H=1.14.
A 20.0 g sample of the anhydride telomer ~.0546 . .
mole) was dissolved in 100 ml of water and the pH
~:
~;
:, 7~
adjusted to 8-9 by addition of 63 ml oE 5N sodium hydroxide (0.32 mole). The solution was bleached by heating at reflux for 1 hr. with 10 ml of 30% hydrogen peroxide. The resulting solution was vacuum stripped at 20 mm and 95 and oven dried at 60 and 2-3 mm to give 27.3 g of a yellow glass.
Elemental Analysis - Calculated for n = 3 .. , C16H14O13Na6: C, 34.81; H, 2.56; Na, 24.97; Na/C=.38 Found: C, 35.23; H, 3.20; Na, 24.23; Na/C=.36. `~
Sample purity based on maleic anhydride monomer content of 0.3% was estimated to be 99~5%. -Performance of this material is shown in Tables IA and IIA.
Example 4 - Sodium Salt of Maleic Acid - Tetraethylene-glycol Dimethyl Ether Telomer Maleic anhydride (98.0 g, 1.0 mole) and 55.6 g (0.25 mole) of tetraethyleneglycol dimethyl ether were `
dissolved in 100 ml of chlorobenzene. The clear, -~
colorless solution was heated to 100 and 20 ml of a 25% solution of diacetyl peroxide in dimethyl phthalate added in 5-ml portions over a 1.5-hr. period. The maximum temperature reached ~as141. Following the diacetyl peroxide addition the reaction mixture was `~
maintained at l00 for 1 hr. A dark red taffy-like mass formed. On cooling it became brittle. It was ground to a powder under chlorobenzene, separated by -filtration and washed exhaus-tively with chlorobenzene at room temperature. The cake was vacuum dried at 60 ;~
and 2-3 mm to give 126.9 g of a light amber powder.
Maleic anhydride monomer content was 0.05%. Yield:
'': - ~
: -:- ... - . . ~ , . - , 3~
101~ of theory for n = 8.
A 20.0 g sample of the anhydride telomer (0.0199 `
mole) was dissolved in 100 ml of water and the pH
adjusted to 8-9 by addition of 60 ml of 5N sodium hydroxide ~0.30 mole). The solution was bleached by heating at reflux for 1 hr. with 10 ml of 30% hydrogen peroxide. The resulting solutic)n was vacuum stripped at 20 mm and 95 and finally dried at 60 and 2-3 mm ~`
to give 28.3 g of light tan glassy solid. ;
Elemental Analysis - Calculated for n = 8 - `
C42H38O37Nal6: C, 33,57; H, 2.55; Na/ 24.47; Na/C=0-38 Found: C, 33.77; H, 3.60; Na, 25.20; Na/C=0.39.
Sample purity based on maleic anhydride monomer content of 0.05% was estimated to be 100%.
Performance of this material is shown in Tables IA and IIA. `
Example 5 - Sodium Salt of Maleic Acid - Mesityl Oxide ~;
.. --- :
Telomer Maleic anhydride (98.0 g, 1.0 mole) and 28.6 ml (0.25 mole) of mesityl oxide were dissolved in 100 ml of chlorobenzene, the solution heated to 100 and 20 ml of a 25% solution of diacetyl peroxide in dimethyl ~-phthalate added in 5-ml portions over a 0.5-hr. period.
The maximum temperature reached was 113. Following the diacetyl peroxide addition the reaction mixture was maintained at 100 for 1 hr. The resulting clear dark red amber solution was vacuum stripped at 160-170 and 2-3 mm to give 27.7 g of dark red amber glass.
Maleic anhydride monomer content was 1.5%. Yield:
37.7% of theory for n = 2.
~.
~ 3P;'~ ;6 A 20.0 g sample of the anhydride telomer (.0680 mole) was dissolved in 100 ml of water and the pH
adjusted to 8-9 by addition o~ 50 ml of 5N sodium ~ `
hydroxide (0.25 mole). The solution was bleached by `~
heating at reflux for 1 hr. with 30 ml of 30% hydrogen ;
peroxide. The resulting solution was vacuum stripped at 20 mm and 95 and finally dried at 60 and 2-3 mm to give 27.8 g of yellow glass.
Elemental Analysis - Calculated for n = 2 C14H14OgNa4: C, 40.22; H, 3.37; Na, 21.99; Na/C=0.29 Found: C, 40.01; ~, 4.12; Na, 20.13; Na/C, 0.26.
Sample purity based on maleic anhydride monomer content of 1.5% was estimated to be 98.4%.
Performance of this material is shown in Tables IA and IIA.
Example 6 - Sodium Salt of Maleic Acid - iso-Prop~
Alcohol Telomer - Maleic anhydride (98.0 g, 1.0 mole) and 38.3 ml (0.50 mole) of isopropyl alcohol were dissolved in 100 ml of chlorobenzene, the solution heated to 100 and 20 - ml of a 25% solution of diacetyl peroxide in dimethyl phthalate added in 5-ml portions over an 0.8-hr. period.
The maximum temperature reached was 107. Following the diacetyl peroxide addition the reaction mixture was maintained at 100 for 1 hr. The resuliing clear light ~ -orange solution was vacuum stripped at 160-170 and 2-3 mm to give 30.5 g of medium amber glass. Maleic anhydride monomer content was 0.7%. Yield: 38.6% of theory for n=l.
Elemental Analysis - Calculated for n = 1 ~ `
... . . .. . .
.:: . . - . . .
- ~3~tj~ ~
C7H1004: C, 53.15; H, 6.37 Found: C, 54,47; H, 5.24.
A 20. 0 g sample of the anhydride telomer ~.1265 mole) was dissolved in lO0 ml of water and the pH adjusted to 8~9 by addition of 44 ml of 5N sodium hydroxide (0.22 mole). -The solution was bleached by heating at reflux for 1 hr.
with 20 ml of 30% hydrogen peroxide. The resulting `
solution was vacuum stripped at 20 mm and 95 and finally dried at 60 and 2-3 mm to give 24.7 g of light tan glass.
Elemental Analysis - Calculated for n ~ 1 C7H10O5Na2: C, 38.20; H, 4.58; Na, 20.89; Na/C=0.29 Found: C, 36.92, H, 4.18; Na, 18.41; Na/C=0.26.
Sample purity based on maleic anhydride monomer -` ;
content of 0.7% was estimated to be 99.0%. ~`~
Performance of this material is shown in Tables IA and IIA.
Example 7 - Sodium Salt of Maleic Acid - Methyl Alcohol i~
Telomer Maleic anhydride (588 g, 6.0 moles), 121 ml (3.0 moles) of methyl alcohol were mixed in a l-liter steam-jacketed reactor equipped with a mechanical stirrer, -~
thermometer, reflux condenser, additional funnel, nitrogen `~
purge tube and gas exit tube. The temperature was raised to 60 to form a clear, colorless solution. An exotherm ;-occurred causing the temperature to rise briefly to 95.
While sweepingwithnitrogen and with the temperature at 30-35, 21.1 ml of 90% hydrogen peroxide was added drop-wise over a 5 minute period. After allowing to stir at 30-35 for 15 minutes, 163.2 ml of acetic anhydride was :
added dropwise over a 20 minute period. The clear, colorless -reaction mixture waq ~tirred for an additional 40 min. during ~--, , ~ 7~
which time an exotherm occurred requiring jacket water cooling to keep the temperature from rising above 60. -The resulting clear, colorless nonviscous solution after stirring for 1 hr. at 30-60 was added dropwise over a 1.2-hour period to 600 ml of chlorobenzene in a 3-liter steam-jacketed reactor equipped as described `
above while maintainlng the temperature at 100-110.
Stirring was continued at 100-110 for an additional 2.6 hours. ,~
- 10 The clear light amber reaction mixture was vacuum stripped at 20 mm and 95 (with continuous addition of ~
- chlorobenzene to serve as a carrier for removing `~;
.?'. ::
maleic anhydride) to a constant weight of 421 g.
- The clear light amber glassy telomer anhydride was dissolved in 800 ml of water and neutralized with 557 ml of 50% sodium hydroxide to give a turbid dark orange solution with a p~ of 9.6. To this solution at about 70, `~ `
was added slowly, 70 ml of 30% hydrogen peroxide after which most of the color had been removed. The so-treated ``!' solution was poured into 5 liters of methyl alcohol with ~ mechanical stirring at room temperature. The white -~ precipitate was separated by filtration, slurried with 300 ml of toluene, vacuum stripped at 20 mm and 95 and finally dried at 60 and 1-2 mm to give 523 g of slightly off-white powder.
Sample composition based on maleate monomer content and water analysis was 76.4% sodium telomerate, 7.5%
wat~r and 16.1% disodium maleate; n equals 3-4.
Performance of this material is shown in Tables `
IA and IIA.
. " I .
,.,.-.-, . . , . . ~ ,, ,. - . - , .. . - , . :
Although the telomer compounds herein are depicted as being linear, it is to be understood that non-linear configurations may also be formed during the telomeriza- ;~
tion reaction due to chain branching. However, in the interest of convenience and simplicity only the linear :.
formula is shown.
Deter~ent Fo~mul:ation `
- The builder compounds of the invention were tested and evaluated using the following cleansing formulation -~
Parts ; ~ -:
Sodium linear alkylarylsulfonate 20.0 -Builder 50.0 tor 25) Sodium metasilicate 5-hydrate 12.0 Sodium carboxymethylcellulose 0.5 Sodium sulfate 17.5 (or 42.5) In each instance the formulation was prepared by blending the various ingredients. A variety of the novel builders ;~
were respectively substituted into the detergent formula~
tion. In order to determine the performance characteristics , 1~37~
of the resulting detergent formulations, they were sub-jected to the following test procedures in which water hardness in ppm is expressed as calcium and magnesium carbonate with a Ca/Mg gram ion ratio of 1.5.
Test Procedures Detergency Test~
A full description of thi~; detergency test may be ~;
found in the article by Spangler et al., Journal of the American Oil Chemists Society, 42, 723 (1965).
The test was conducted in a Terg-O-Tometer utilizing swatches of four different fabrics - cotton, cotton-dacron (50:50), cotton-dacron (35:65), and nylon - which had been soiled with a combination of airborne particulate matter and synthetic sebum. Unsoiled swatches of the `~
fabrics were included to measure soil redeposition, one unsoiled swatch of each fabric type for each wash load along with three soiled swatches o~ each fabric type. ` ~-Three soil-wash cycles were conducted on each fabric utilizing the following test conditions: water hardness of 150 ppm and 300 ppm respectively; detergent formulation - concentration of 0.15%; temperature of 120F; and a pH
level of 9.5; washing time 10 minutes; rinsing time 2 `~
minutes. ~ ;
Reflectance readings on the washed swatches were then taken with a Hunter Reflectometer, Model D-10 The results were expressed in terms of "percent reflect- -ance" with the arbitrary standard of "100% reflectance" ,;; -~
~ being established for the reflectance value obtained on - a cotton swatch which had been washed with the standard ~ ~`
detergent formulation containing 50~ sodium tripoly-~ . .
:~:
7~
phosphate builder in water of 150 ppm hardness. Soil redeposition results are given as the decrease in reflectance units (~rd) of the unsoiled swatches after washing, rinsing and drying. Test results for various builders of the invention are shown in Table IIA. In the case of the blended and non-cotton fabrics, the soil removal values are expressed relative to the reflectance of a standard cotton swatch washed in the standard detergent formulation.
Sequestering_Capacity Since the ability to sequester calcium ions is a critical feature of an effective detergent builder, the various new builders were subjected to the following ~
test procedures in order to determine their sequestering -capacity. Thus, an aqueous solution of the sample was titrated potentiometrically with a standard calcium nitrate solution at a pH of 10.0 and a temperature of 25C. using a divalent cation activity electrode (Orion Research, Inc.) as the indicator electrode.
The sequestering capacity was espressed as grams Ca per 100 g of sample = 4.008 . M . V
W
where M = molarity of the calcium nitrate solution V =volume in ml of the above solution required to reach the inflection point, and W =weight of the sample in g.
Dispersing Efficiency: ~;
A procedure patterned after that described by ; VanWazer and Besmertnuk, J. Phys. Colloid Chem., 54, 89 (1950), was used for measuring the deflocculating ability of the telomers.
... . . . .. . . . . . . . . ..
~317~$
A kaolin slurry is prepared by mixing 80 g of washed and ignited powdered kaolin and 150 ml o~ water in a 200-ml tall-form bea~er. After p~I adjustment to 10.0 with 5N NaOH the slurry is thermostatted at 25C.
Viscosity readings are taken with a Brookfield viscometer Model LVT. Incremental weights of the builder whose dispersent activity is being determined are added as a standard solution adjusted to pH 10.0 and after ~ -thorough mixing the viscosity is determined. A plot of viscosity versus percent builder added based on ~
kaolin is prepared and the percent builder required - ~ -to lower viscosity to 200 centipoise determined.
Results are expressed in terms of the performance of sodium tripolyphosphate (STPP) which is arbitrarily set at 100%. ~
Mineral Precipitation: ~-A detergent formulation containing the builder under evaluation is dissolved in 300 ppm hard water to give a 0.15% formulation solution. A 50 ml `~
aliquot of the solution is diluted to 1000 ml with 300 ~-ppm hard water and the resulting solution filtered successively through 8, 4.5 and 0.1 micron cellulose millipore filters. The filter mats are then dried and `~
weighed to obtain the recorded insolubles. All samples `
were run on a sodium salt basis. Results are shown in `
Table IA.
`~ Biodegradability: ~;
Biodegradability of the builder was measured as -; the extent to which it is metabolically oxidized to carbon dioxide in a sewage-inoculated culture medium.
~' ' ,. :.
~U3~
The compound to be tested was added a-t a concentra-tion of 20 ppm to 6 liters of biological oxygen demand (BOD) dilution water containing yeast extract which had been inoculated with settled primary sewage effluents (10~ of total volume). The solution was stirred and aerated in a dark bottle for two or three weeks to adapt the culture to the test compound. After the -adaption period, a subculture was prepared by adding one volume of the original culture solution to 9 volumes of fresh soD dilution water containing yeast extract, and 20 ppm of the test compound was added to the subculture solution. While the subculture was stirred and aerated with CO2-free air in a dark bottle for two ;~
weeks, the effluent gases containing CO2 were scrubbed i~
in caustic soda traps and the collected CO2 was determined by titration. Net CO2 evolved from the test compound was estimated by ccmparison with a suitable ~
blank culture. Extent of biodegradation was taken as ` ;`
the percentage of theoretically available carbon in the test compound evolved as net CO2. A second subculture was prepared from one volume of first subculture solution ;
and 9 volumes of fresh BOD dilution water containing ~;
yeast extract, and 20 ppm of test compound was again added. Aeration, gas collection, and analysis for CO
were conducted as above. Typical results are summarized in Table IIIA.
- Example 8 - Built Dishwashing Composition A method of evaluating formulations for utility - in commercial dishwashing is as follows:
A Kitchen Aid automatic dishwasher, Model KD517, `~
: '`'" ~
~ -26-, .~ ~
is used. In the upper rack of the dishwasher are placed six large plates, twelve small plates, and six saucers, arranged in the order: saucer, large plate, small plate, small plate, saucer, large plate, etc., to fill all the rack spaces. The machine is operated on the light soil setting. For each cycle 40 grams of a mixture of ~our parts oleomargarine to one part powdered dried milk are ;~ ;
weighed out and smeared over the six large plates, and ~ ~
20 grams of the detergent formulation being tested are -placed in each of the two dispenser cups of the machine.
The water supply having a hardness of about 160 ppm, `
enters the machine at about 140F. At the end of each cycle, the glass tumblers are removed and set up for ;
evaluation in a specially constructed apparatus consisting of a rectangular wooden box with open front, painted dull black, containing two diffused fluorescent lights at the top. When the tumblers are placed in this box and the room darkened, the light coming from above makes e~ery `~
spot and streak show distinctly. ;
After each cycle the glasses are rated as follows: ~-1. Light spotting 2. Medium spotting 3. Heavy spotting Failure is defined as the point at which half of the glasses are rated as medium spotting or worse.
A formulation was prepared using the following materials where the usual builders in dishwashing detergents are replaced by a telomer of maleic acid and methanol from Example 7. i 7~
Parts Sodium silicate 15.0 Sodium Dichloroiso~
cyanurate 1.5 Sodium carbonate 20.0 Plurafac* (Trade Mark) 3.5 Sodium Sulfate 15.0 Telomer (Example 7) 45.0 * A modified oxyethylated surface active, non-ionic, ::
low-foaming straight chain alcohol sold by Wyandotte Chemical Corporation.
The composition of Example 8 gave excellent ~
results up to about 6 cycles. ~ -:
The detergency properties and related characteristic of the builders of the invention are set forth in the Tables below. ~:~
.
,,.'~
~'"''' " '~
~.' ..
-28- ~
.,l ~:
~ 66 `: ~:
~ ~~ a~ ~ ~ ~ ) ~ ~ I~ o ~ ~ o 1~ ~r o ~ u~ ~ "
- ~ ................. .-a) ~ I~ ~r o , ~D U. ~ a~ o o ~ ~ o ,, O t~
~:
... ~ .
... ~ _ .`~
.. ~ ~ .... ..
, ~~ ui '~
. ~ o ~r ~r ~D ~ ~ ~ In ~ ~ co ~r o o ~ ~ ~ co O - '~
~ u~~ O ~ ~ ~ ~ ~ o u~ r ~ ~ oo ~ ~ ~ O -';' `"' ., rl d~ ~ N ~ ~ ~I t~ ~1 ~ ~ H N ~1 t~l t`~l r-l ~1 ~ ~1 ~1 ` ~
c) ~ a~
. rl o :,. ::
. 4 a~
.~ :, ~
a)~ ~ ;;~. ;: ` ' rl d ~ o u~ a) o ., .. , I¢ S~t~ ~ \~ /'~) O 00 (~) H ~1 ~ O ~ . . . . . . . . . . . . . . . . ~' ~qu~ U ~d ~ ~ o ~ co ~ ~ ~ o ~ ~ ~ o o ~' ' `. ~ .' ' -~ a ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
_~ . U-- :. . . -E~ ~0 ~ U~
U O
. ~ ~.
S " S E~
. ~ ~
U ~ 3 ~ o ~ o o ~ a ~ N , ~ N N O P~
.. O O O ~1 ~ ,~ J ~ ~ ~1 X r-l 0 ~1 r~ ' ' `
a~ o ~1 o a~ 0 ~c~ o o 0 o o Q"¢
E~ ~) ~ h ~ ~ ~1 0 0 ~ O ~1 ~ 0 ~ ~ o~ ~ ~ 0~ ~
S~ o ~ m m~rl o ~ ~n o ~ ~ ~ ~ ~ ~
~ ~ ~ I ~ I I ~ I I ~-~ ~ ~ U~ ~ O O ... ~ ., ~ a ~ ~ a ~
~ 37~
TABLE I IA
.
N c~ ~ ~ ~) N (~ U~ ~ N If ~3 N ~rl 3 Nr~ ~1 ~I N ~1 ~1 ~. -1 ~I N ~1 ~
~)a~ l 3 N S 3 r~l ~1 ~ O ~ C~\ O ~)~ ~ O
N~J ~1 ~ ~1 ~ ~ ~1 ~ ~ ~ ~ ~ .~ ~ ~ ~ -~ O ~ ~
~'1 P~ =S N ~ U ~) J ~ N 3 ~ N 3 ~ ~1~3 ~ ~ 3 t~ `J ~ ~ N ~ ~13 315~ 3 N 3 ~) U:l ~
O ~ ~: :
C~ ~ ~~ ~r) o b~ 1:~ ~ ~ O ~ .D ~ ~ 1~ N ~
O 1~ ~ Z; O
l~lr~ 0~3 ~a 1~
a~ P N O
^ ~ ^ ^ N C.) "a C) ~1 ~J 3 ~ NN ~ N 0 3 N O ~I N ~ N ~r) ~ I
~ 1 ~ N N ~r) ~ ~13 N ~I N N n ~ N N ~ P~
.` I ~ ~ ~
: ~ p ~ :
.~ ) ~1 ~ ~ N ~ 3 N N ~3 N N3 ~ ~1 ~ N
C~ ) (X) ~ oO CO CO C~ o co ~ o ~o CO 0:) ~ ~O ) :1 .
1~ ~ O
P~ Z `~ `~ ~ O
O IS~ O ~I N 3 ~1~ O~ o 3 ~ D I I O
~ , N
h C~ ~I N ~ N 3 ~D N 3 r~ oo ~1 ~1 00 N N r~
~a ~1 ~ ~ Irl ~ ~ .
~: ~ ~ o w ~d ~ a~ N a~ 3 N ~ N N a~ ~I CJ~3 0~ 00 ~1 0 Lr~
<1 ~ - ' I h 0 C:~ ~ ~ ~ ~ ~ ~ ~ ~ h O~ ~1 O O N N O N a~ o ~ ) ~o. o O O 0~ ~rl ~ ,~
~ ~ O r~l 0~) N N I--I N I--I ~I N ~ a~ l 0 ~ tr~
r-l 1~ c~oo ~ 000 oc~ OOOD ~--Ot) ~D ~ 0~7~ ~C~3 0 <; ~ 0 ~1 '`
:' ~ ~ 0~ ;
O h ~rl Q.,~ ..
a~ ocoo oo oooooooo ooooo ~1s~ qo.
~ O~O OO OOOOOOOO OOOOO ~r~O~O0 rl ~ ~ O C-- 0 ~ ~1 ~1 ~ ~ OO O
$ ~ O ~'o~
O -'' C) ~ S~
: S~ ~a h ~ :
~ *
I ~ O o ~ :, ~ h ~ h s::~ ~ O J~
cC o a) 1~ ) ~ s 0 ~ ~ c~ o ~ N ~ Il) ~ S '1:1 N a~ N h O 0 ~ :1~ I tq ,~ ; .
rl S ~ O S ~ I h C~ ~ h ~ a) O S ~ ~/ 0 0 ~J ~ P~
~: ~ ~ ~ c) ~ S ~ ¢ .cl ~) .C ~ c) J~ ~ CC S Ei rl rl ~ ~ ~ :
a) a) h ~1 ~ S --I ,S o r-l :~1 rl o ~ .~ P
~ c~ o ~, ~ a ~1 ~ a :~, ~I x ~I c> r~l rl rl V~ 0 O t;) p~ bo~l ~1 ~ S ~ rl Q, ~ ~I Q, ~0~1 0 ~--I O 0 C) ~
~1 O r-l O a~ :" 0 ~ ~ O O 0 O ~ ~ ¢
a~ ~ ~ h ~: S h ~ a~ ~ ~, h --I h h a~ 1 o ra ra O ~
E~ ~4 S ~ ~ ~ Q. ~ ~ R. ~ ~ ~ ~ h ~ ~ O o ~ O O
~ ~ o ,1 a~ ~ ~ ~ ~ c.> o ~ ~ o 0 ~1 a~ 5 h h ~--h-rl-rlS m~ o~mm~ os ~ o~ o a~ h rl ~ I ~ I I rl I I r1 rl ~ ~ Ul ~ O ~Y; D~:; ~- - C) :~ , .
.
. :
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. ~ ~ ~
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:~
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~n ~ .~ , . h P~ a~ ~ ~ o s o ~3 ~L~ o ~ o ~ ~ ~ O ',' O ~c~ D O O ~D O ~l 1~ 0 ' ' W ~ ~ ~
a) : -, ~' a) ~
r~ ,:;:
Pq ::
al . .
H~ ~ ~f7 o 1 ~ O~ a~ o L~ co o U~ ~ J N
o ~ . 0 . ` ~ , ~
O ~; r~
~a ~d r-i a) *
rl 13 0 (1) ~ ~ r-l a) ~
;' O h O ~ ~ ri O ~ ~ ~ ;
:~ C~ O >a ~ ~) ~ S C~
-~ r-l N ~ a) N O ~ ~ri ~ c~ O ~ rl O r-l r1 a~
bl) rl S <U C~ o ~ (1~ 0 a) rl O ~d : O ~ ~ ~ .n cC S ~ 0 ~5 ~ S
~l a) h ~) r-l O rl ~rl O :~
a) o o r-l ~ ~ ~ r~ X r~ c~ r~
E~ ~ rl rl Q~ bO O ~ r-l O rl O rl S O O ~d O a~
:~ ~ h ~ h ~ r~ O O
R~ S (~ r~
t~ ~ ~i O O ~ O t~t H ~ ~ rl ~i c~ X ~ rl i S rl O -~
h rl ~ rl ~ Iq rl O S ~
(1~ h a~ rl I I rl rl ~ O u~ ~) O
~ a r~ *
. ,:
~:
.: .: . ~ . . .' ' : ! " ' : ~: " ' ' ~ ; ' " ' ' ~` ~
:` :
~ ~'7~
" C~ bC
o ,. "
o ".
~ o~ o ~ cr~c~3 ~ ~ ~ ~ c~ o o C> ~ .
~1 ~1 `_ 0 ~ V
~ . ~
h E~ ~rl ~ ~ ~:
0~ ~ Lr~7 mJ `C' ~ ~3 ~ u~o .
be ~
~ ~ o .
~ bo~ ~ 0 ~ ~0 0 ~ 3 0 H O ~i l ~ 1~1~ 3 L~ O 00 ~O ~ ~ 0 0 ~ N O ~1 0 .
~ O
P~ ~ ~ . O :
.. V . o ~r)~ ol~ ~O ~ ~) oO ~ U~3 ~; C O 1~1 OI~Or-l~ 31~ CO
:~ ,.' a~ o I) .
E~ . ~ a) S a hr ~ o ~ A ~ a s C~ ,0 ,I c~
~1 O ~l S ~ O ~ a): O h C) O h :~ ~ O ~1> r-l` `
a) rC ~ ~ .a C~ S ~: S O ¢ ~ a~ s ~ c) ~:; ¢
O 0~ h ~ ~ ~ ~ ~ ~I S
~: o ,l o4 bD ~d S ,~ ~ ~o o~ ~ o4 ~
h ~ ~ h ~ ~ ~J ~ h ~4 ~S P. ~ ~ S ~ '~ 4 ~ 4 s~
~ h~ s ~ m ~ ~ o a~ m .~, ,o, s z~ a~ a ~ ~ ac~
.
-32- .
:~
" :
1~37~
,' ~
.- . ~ ~ . ~
h ~rl ~ :~
~ ~1 ~;--~l~t--O ~--I~C--~L~ ``
O Q O ~ ~ ~ A
r I ~ o ~rl o o E~ ~0 ~ u~
U~ , i`' ~ , ~ ' ~¦ h ~ o ~1 ~,, ~, 11 : '`''; ~ ~' rl ~ L~
:~ C~ h ~ ~1 o ¢ o O ~ N ~ rl ~ ~ ~
U~ C) 0 5~ r~l ~ bO rl ~ C~ ,~ ,1 : ;:~ : ':
rl ~ ~ O ~ O a) r-l O ~ '"~`'''; -'`' h ~ ~ R C~ O ¢ o ~) ~ o ~ s ,S ~ O ~ '~
C) O ~ ~1 ~ ~ ~ C~ ~ ~ X ~ O ~1 "''~
td b~ t~ 0 0 ~ r-l O
O o ~1 o ~ ~ ~ o q~ ,C~cC P~ "'''~ ''''' ' ' ,1 ~ ~ ~ S: h ~ ~J ~ r I o ~
c~ h C~ X ~rl I .C~rl h~,l~sr~o~m os co o~
;
.. , . . ; ~ . ~. . , , . ~
7~
As can be seen ~rom an inspection of the data in the tables, the sodium maleate telomers of the invention exhibit those overall characteristics associated with -~
effective builder performance. Thus, calcium sequestering capacities range from 0.0 to 15 g Ca/100 g as compared to `
21 g Ca/100 g for a typical sodium polymaleate (Table IA).
Dispersing efficiencies are approximately 2 to 3 times that of sodium polymaleate and appear to be largely independent of sequestering capacity.
Some correlation appears to exist between telogen content and calcium sequestering capacity and mineral precipitation as shown in Table IV. Both calcium sequestering capacity and mineral precipitation decrease with increasing telogen content.
Water solubility of the telomer salts herein all ... ~.
exceeded 50% at 25 with the exception of n-octyl ether so that with this exception the telomers are more than 1000 times more soluble than a typical sodium polymaleate; -Table V. Water solubility does not appear to be a function of telogen content but rather of telogen structure.
Builder performance of the telomers (Table IIA) on -, cotton was as good as STPP or sodium polymaleate with the ~xceptions of diisopropylbenzene, n-octyl ether, n~
- decanoic acid, n-butyl ether, lower molecular weight - n-butyraldehyde and isopropyl alcohol telomers. Perfor-mance of the telomers on finished 65/35 polyester-cotton was good or better than STPP and sodium polymaleate with the exceptions of the lower molecular weight diisopropyl- ~ ~ -benzene and dioxane telomers. Performance on unfinished ~-30 50/50 polyester-cotton was as good or better than STPP ~
:. , ', -34- ~
~ .
with the exceptions of the ethyleneglycol dimethyl ether and lower molecular weight diisopropylbenzene telomers. Performance of the telomers on nylon was as good or better than STPP with the exceptions of the diisopropylbenzene, n-butyl ether, dioxane and ethylene-glycol dimethyl ether telomers. Only the ethyleneglycol dimethyl ether telomer was the equivalent of sodium polymaleate on nylon.
Redeposition results on cotton, finished 65/35 polyester-cotton and unfinished 50/50 polyester-cotton were all the equivalent of STPP and sodium polymaleate.
Redeposition results on nylon were equivalent or better than STPP with the exceptions of the ethyleneglycol dimethyl ether, dioxane and lower molecular weight diisopropylbenzene telomers. ~ -The maleic acid telomers of the invention thus provide the art with a new class of builder materials -which combine generally superior detergent properties -~
with environmental compatibility.
. ,,'' ~ ~ :.
,`~ ' :'.~
~' ~` ' ~ - . .
Claims
1. A telomer detergent building product formed by the telomerization of maleic anhydride with methanol followed by saponification of the resulting anhydride telomer to give a polycarboxylic telomer having a poly-meric structure of the formula:
wherein n is 4 to 5.
wherein n is 4 to 5.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US26209972A | 1972-06-12 | 1972-06-12 | |
| US28375372A | 1972-08-25 | 1972-08-25 | |
| US30183072A | 1972-10-30 | 1972-10-30 | |
| US36076473A | 1973-05-16 | 1973-05-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1037966A true CA1037966A (en) | 1978-09-05 |
Family
ID=27500731
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA173,030A Expired CA1037966A (en) | 1972-06-12 | 1973-06-01 | Maleic acid telomers as detergent builders |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS504103A (en) |
| BE (1) | BE800727A (en) |
| CA (1) | CA1037966A (en) |
| DE (1) | DE2329814A1 (en) |
| FR (1) | FR2202073B3 (en) |
| GB (1) | GB1410567A (en) |
| IT (1) | IT985368B (en) |
| NL (1) | NL7307946A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6458752B1 (en) * | 1999-03-23 | 2002-10-01 | National Starch And Chemical Investment Holding Corporation | Powder laundry detergent having enhanced soils suspending properties |
-
1973
- 1973-06-01 CA CA173,030A patent/CA1037966A/en not_active Expired
- 1973-06-06 GB GB2704673A patent/GB1410567A/en not_active Expired
- 1973-06-07 NL NL7307946A patent/NL7307946A/xx unknown
- 1973-06-08 FR FR7321089A patent/FR2202073B3/fr not_active Expired
- 1973-06-08 IT IT5058073A patent/IT985368B/en active
- 1973-06-08 BE BE132112A patent/BE800727A/en unknown
- 1973-06-12 DE DE19732329814 patent/DE2329814A1/en active Pending
- 1973-06-12 JP JP6545573A patent/JPS504103A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| NL7307946A (en) | 1973-12-14 |
| IT985368B (en) | 1974-11-30 |
| GB1410567A (en) | 1975-10-15 |
| FR2202073A1 (en) | 1974-05-03 |
| DE2329814A1 (en) | 1974-01-03 |
| BE800727A (en) | 1973-12-10 |
| JPS504103A (en) | 1975-01-17 |
| FR2202073B3 (en) | 1976-05-28 |
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