Soil release agents having allylderived sulfonated end caps

Claim 2

A sulfonated oligomeric ester composition, characterized in that it comprises the sulfonated product of a preformed, substantially linear ester oligomer containing, per mole, (a) from 1 mole to 2 moles, preferably 2 moles, of terminal units characterized in that they are olefinically unsaturated; said terminal units preferably being allyl or methallyl, most preferably allyl; (b) from 1 mole to 4 moles, preferably 2 moles, of nonionic hydrophile units, further characterized in that they are poly(oxyalkylene)oxy units and in that 50% by weight or more, preferably 100% of any such unit is derived from ethylene oxide; said nonionic hydrophile units preferably being -(OCH₂CH₂)₄₋₃₀O-, more preferably -(OCH₂CH₂)₈₋₂₀O-; (c) from 1.1 moles to 20 moles, preferably 2 to 7 moles, of repeat units characterized in that they are aryldicar­bonyl repeat units, and in that 50% by weight or more, preferably 80% to 100%, most preferably 100% thereof are terephthaloyl; and (d) from 0.1 moles to 19 moles, preferably 2 to 14 moles, of repeat units characterized in that they are oxyalkylene­oxy repeat units derived from a diol component selected from C₂₋, C₃₋ and C₄ glycols, preferably 1,2-propylene glycol or a mixture of ethylene glycol and 1,2-propyl­ene glycol further characterized by an ethylene glycol : 1,2-propylene glycol mole ratio in the range from 0:1 to 0.9:0.1, more preferably 0:1 to 0.4:0.6; said sulfonated product further being characterized in that it is sulfonated to the extent of chemically modifying the terminal units, (a), by: (e) from 1 mole to 4 moles, preferably 2 to 4 moles, most preferably 4 moles, of terminal unit substituent groups of formula -SO x M wherein x is 2 or 3 and M is a conventional water-soluble cation, preferably sodium or potassium.

Claim 3

A sulfonated oligomeric ester composition according to Claim 1 which is further characterized in that it consists of the sulfonated product of said preformed, substantially linear ester oligomer wherein the preformed, substantially linear ester oligomer is the product of transesterifying and oligomerizing a mixture of (I) ethoxylated allyl alcohol, preferably 2 moles allyl alcohol ethoxylate 8-20; (II) 2 to 7 moles dimethyl terephthalate and (III) 1,2-propylene glycol or mixture thereof with ethylene glycol in a molar amount exceeding the molar amount of dimethylterephthalate; and wherein the sulfonated product is produced by sulfonating the preformed, substantially linear ester oligomer, preferably with sodium bisulfite, whereby the sulfonated terminal substituent groups (e) are introduced.

Claim 4

A sulfonated oligomeric ester composition according to either Claim 1 or Claim 2 which is further characterized in that it comprises the sulfonated product of said preformed, substantially linear ester oligomer wherein the preformed, substantially linear ester oligomer is made by a step of transesterification, characterized in that it comprises reacting a mixture of (I) ethoxylated allyl alcohol, preferably 2 moles allyl alcohol ethoxylate 8-20; (II) 2 to 7 moles dimethyl terephthalate and (III) 2 to 14 moles 1,2-propylene glycol or mixture thereof with ethylene glycol, provided that the number of moles of glycol exceeds the number of moles of dimethyl terephthalate; (I)-(III) being reacted in the presence of a conventional transesterification catalyst at a transesterification temperature of 120 o C to 250 o C, preferably 160 o C to 230 o C; at a transesterification pressure of 0.75 atm. to 3 atm., preferably 1 atm. to 2 atm., for a transesterification time of from 2 hrs. to 60 hrs., preferably 5 hrs. to 25 hrs.; followed by a step of oligomerization, characterized in that it comprises further reacting the mixture resulting from said transesterifi­cation at an oligomerization temperature of from 170 o C to 250 o C, preferably 180 o C to 220 o C;, at an oligomerization pressure in the range from 1 x 10⁻⁶ atm. to 0.5 atm., preferably 1 x 10⁻⁴ atm. to 0.05 atm., for an oligomerization time of from about 2 hrs. to 60 hrs., preferably 5 hrs. to 25 hrs., whereby methanol and the excess of glycol are removed, and whereby said preformed, substantially linear ester oligomer is achieved in a sulfonation-ready form.

Claim 5

A sulfonated oligomeric ester composition according to any of the preceding Claims, further characterized in that the sulfur-containing units (e) are produced by a radical-initiated olefin sulfonation reaction having at least one step of sulfonating said preformed, substantially linear ester oligomer, preferably in the allyl form, in the presence of water, with a low temperature, free-radical sulfonation initiator, preferably an azo initiator, and a conventional bisulfite sulfonating reagent, preferably sodium bisulfite; and wherein the sulfonation reaction is preferably further characterized in that the reactants are effectively cocontacted in an aqueous reaction mixture, the level of said conventional bisulfite sulfonating agent is from 1 mole to 4 moles per mole of said preformed, substantially linear ester oligomer and the following sulfonation conditions are respected: sulfonation temperature: 0 o C to 100 o C, preferably 40 o C to 65 o C; sulfonation pressure: 0.5 atm. to 3 atm., preferably 1 atm. to 3 atm.; and sulfonation time period: 0.1 hrs. to 90 hrs., preferably 10 hrs. to 30 hrs.

Claim 6

A sulfonated oligomeric ester composition according to any of the preceding Claims, further characterized in that it results from a process having transesterification, oligomerization and sulfonation steps together with an additional step of oxidizing said terminal unit substituent groups of formula -SO x M wherein x is 2 and concurrently increasing the proportion of said terminal unit substituent groups of formula -SO x M wherein x is 3, preferably by means of hydrogen peroxide.

Claim 7

The sodium salt form of a sulfonated oligomeric ester, according to any of Claims 1-5, characterized in that it consists essentially of (i) a substantially linear oligomeric ester backbone, which is comprised of from 85% to 100% by weight of terephthalolyl and oxy-1,2-propyleneoxy repeat units; and (ii) terminal moieties covalently attached to said backone; wherein said terminal moieties are comprised of from 70% to 100% of moieties selected from the group consisting of: -(E n )-(CH₂-CH{SO₃Na}-CH₂{SO₃Na}), -(E n )-(CH₂-CH{SO₂Na}-CH₂{SO₃Na}), and -(E n )-(CH₂-CH₂-CH₂{SO₃Na}), wherein (E n ) is poly(oxyethylene)oxy and n is from 8 to 20 and the end-cap moieties -(CH₂-CH{SO₃Na}-CH₂{SO₃Na}), -(CH₂-CH{SO₂Na}-­CH₂{SO₃Na}) and -(CH₂-CH₂CH₂{SO₃Na}) are from 5% to 40%, more preferably 5% to 30%, most preferably 10%-30% by weight of the total composition; and wherein the mole ratio of the doubly sulfonated end-cap moieties: -(CH₂-CH{SO₃Na}-CH₂{SO₃Na}) and -(CH₂-CH{SO₂Na}-CH₂{SO₃Na}) in relation to the singly sulfonated end-cap moieties: -(CH₂-CH₂CH₂{SO₃Na}), is preferably in the range from 1:5 to 1:0, more preferably 5:1 to 1:0.

Claim 8

In a process for preparing sulfonated ester compositions useful as functional materials, especially soil release agents, in detergent compositions, wherein the process has at least one ester-bond forming procedure and at least one sulfonation procedure, the improvement whereby a particular terminally sulfonated, substantially linear co-oligomeric ester composition is secured as product without reliance upon a chlorinated compound and without reliance upon a procedure having a sulfonation step followed by an ethoxylation step; said improvement being characterized by the ordered sequence of: a) in an ester-bond forming procedure, a transesterification step, comprising reacting a mixture of I) 2 moles of allyl alcohol ethoxylate 8 - 20; II) 2 to 7 moles of dimethyl terephthalate; and III) 2 to 14 moles of a C₂-C₄ glycol; the reactants (I)-(III) being transesterified in the presence of a conventional transesterification catalyst at a transesterification temperature of 120 o C to 250 o C , at a transesterification pressure of 0.75 atm. to 3 atm., for a transesterification time of 2 hrs. to 60 hrs.; followed by an oligomerization step comprising further reacting the transesterified mixture at an oligomerization temperature of 170 o C to 250 o C, at an oligomerization pressure of 1 x 10 ⁻⁶ atm. to 0.5 atm., for an oligomerization time of 2 hrs. to 60 hrs.; thereby producing an allyl end-capped co-oligomeric ester precursor; and b) in a radical-initiated olefin sulfonation procedure, at least one step of sulfonating said allyl end-capped co-oligomeric ester precursor, in the presence of water, with a low temperature, free-radical sulfonation initiator and a conventional bisulfite sulfonating reagent; wherein the reactants are effectively cocontacted in an aqueous reaction mixture and wherein the level of said conventional bisulfite sulfonating agent is 1 mole to 4 moles per mole of said allyl end-capped co-oligomeric ester precursor and wherein the following sulfonation conditions are respected: sulfonation temperature: 0 o C to 100 o C; sulfonation pressure: 0.5 atm. to 3 atm.,; and sulfonation time period: 0.1 hrs. to 90 hrs.

Claim 9

In a process for preparing sulfonated ester compositions useful as functional materials, especially soil release agents, in detergent compositions, wherein the process has at least one ester-bond forming procedure and at least one sulfonation procedure, the improvement whereby a particular terminally sulfonated, substantially linear co-oligomeric ester composition is secured as product without reliance upon a chlorinated compound and without reliance upon a procedure having a sulfonation step followed by an ethoxylation step; said improvement being characterized by the ordered sequence of: a) in an ester-bond forming procedure, a transesterification step, comprising reacting a mixture of I) 2 moles of allyl alcohol ethoxylate 8 - 20; II) 2 to 7 moles of dimethyl terephthalate; and III) 2 to 14 moles of a C₂-C₄ glycol; the reactants (I)-(III) being transesterified in the presence of a conventional transesterification catalyst at a transesterification temperature of 120 o C to 250 o C , at a transesterification pressure of 0.75 atm. to 3 atm., for a transesterification time of 2 hrs. to 60 hrs.; followed by an oligomerization step comprising further reacting the transesterified mixture at an oligomerization temperature of 170 o C to 250 o C, at an oligomerization pressure of 1 x 10 ⁻⁶ atm. to 0.5 atm., for an oligomerization time of 2 hrs. to 60 hrs.; thereby producing an allyl end-capped co-oligomeric ester precursor; and b) in a radical-initiated olefin sulfonation procedure, at least one step of sulfonating said allyl end-capped co-oligomeric ester precursor, in the presence of water, with a low temperature, free-radical sulfonation initiator and a conventional bisulfite sulfonating reagent; wherein the reactants are effectively cocontacted in an aqueous reaction mixture and wherein the level of said conventional bisulfite sulfonating agent is 1 mole to 4 moles per mole of said allyl end-capped co-oligomeric ester precursor and wherein the following sulfonation conditions are respected: sulfonation temperature: 0 o C to 100 o C; sulfonation pressure: 0.5 atm. to 3 atm.,; and sulfonation time period: 0.1 hrs. to 90 hrs.

Claim 10

A detergent composition, preferably in the form of a built laundry detergent, comprising at least about 0.05% by weight of a sulfonated oligomeric ester composition according to any of the preceding Claims.

Claim 11

A built laundry detergent composition in accordance with Claim 8, which is further characterized in that it contains from about 5% to about 50% by weight of a detersive surfactant and from about 5% to about 60% by weight of detergency builder, the builder preferably being a polycarboxylate builder, zeolite builder, phosphate builder or a mixture thereof.

Claim 12

A built liquid laundry detergent composition in accordance with either of Claims 8 and 9, wherein the builder is a polycarboxylate further characterized in that it is comprised of one or more of: oxodisuccinate salts, tartrate monosuccinate salts, tartrate disuccinate salts, and mixtures thereof; and wherein the detersive surfactant is further characterized in that it is a conventional anionic surfactant, nonionic surfactant or mixture thereof.