Organosilicone having a carboxyl functional group thereon

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FIELD OF THE INVENTION

The present invention relates to novel organosilicone compositions and, more particularly, to silicone compositions having a carboxyl functional group thereon.

BACKGROUND OF THE INVENTION

While carboxyl functional organosilicones are known, they are generally difficult and expensive to prepare and the commercial use thereof has therefore been limited. Heretofore, no convenient method for directly preparing polysiloxanes containing functional carboxylic acid groups is known and indirect routes for their preparation have generally been used, including hydrosilylation of an unsaturated ester followed by hydrolysis, or alternatively, by hydrolysis of nitrile-containing silicone fluids. However, polysiloxanes containing one or more functional groups such as amino groups are well known and readily available and have been used in a variety of commercial applications. Accordingly, the development of a method for readily and more directly preparing polysiloxanes containing one or more functional carboxyl groups would be desirable and it would be particularly advantageous if such method employed readily available materials such as amino functional polysiloxanes for not only preparing carboxyl functional polysiloxanes but a variety of organosilicone derivatives thereof as well, including silicone containing compositions which are readily soluble in a variety of solvents, preferably soluble in water such as silicone-containing phospholipid compositions and the like.

While, as indicated, polysiloxanes containing functional carboxylic acid groups and methods for preparing the same have heretofore been suggested, there is no disclosure or suggestion of the novel carboxyl functional silicone compositions described in copending application Ser. No. 174,660 filed Dec. 28, 1993 and application Ser. No. 298,565 filed Aug. 31, 1994 (now both abandoned) of which the present application is continuation in part or of the novel carboxyl functional silicone compositions of the present invention.

SUMMARY OF THE INVENTION

It is accordingly an object of the present invention to provide novel organosilicone compositions having at least one carboxyl functional group thereon.

It is another object of the present invention to provide a method for directly and readily preparing organosilicone compositions having at least one carboxyl functional group thereon.

In accordance with the present invention, there has now been discovered novel polysiloxanes containing one or more carboxylic acid groups and/or the ester derivatives thereof that may be represented by the following general formula: ##STR3## wherein: R.sub.1, which can be the same or different, can be selected from R.sub.2, H, a primary amine containing group, and a pyrrolidone containing carboxyl functional group of the formula: ##STR4## wherein at least one of R.sub.1 is a pyrrolidone containing carboxyl or ester functional group or salt derivative thereof as shown; F, which can be the same or different, is linear or branched alkylene of 1-12 carbon atoms; R.sub.2 is as defined below; R.sub.5 can be hydrogen, lower alkyl (C.sub.1-6) or alkali metal; n is zero or 2; n.sup.1 is zero or 1; n.sup.2 is zero or 1; and B is --NR.sub.9, sulfur (S) or oxygen (O), wherein R.sub.9 is hydrogen or lower alkyl (C.sub.1-6), with the proviso that when n is 0 and n.sup.2 is 1, n.sup.1 is 1, when n is 2 and , n.sup.2 is 1, n.sup.1 is 0 or 1 and when n is 2 and n.sup.2 is 0, n.sup.1 is 0;

R.sub.2 can be the same or different and can be selected from alkyl, aryl and olefinic (vinyl);

R.sub.3 and R.sub.4, which may be the same or different, are selected from alkyl, aryl, capped or uncapped polyoxyalkylene, alkaryl, aralkylene and alkenyl (vinyl);

a can be an integer from 0 to 50,000; and

b can be an integer from 0 to 100.

In another aspect of the present invention there is provided a method for preparing polysiloxanes containing one or more carboxylic acid pyrrolidone groups and/or the ester derivatives thereof, which comprises reacting an organosilicone fluid or composition having at least one primary amine functional group with itaconic acid or an ester thereof at an elevated temperature (preferably from about 90.degree. C. to about 150.degree. C.) for a time sufficient to react, preferably substantially completely react (generally ranging from about 1-5 hours), the itaconic and or ester thereof with the functional primary amine group(s) on the silicone fluid or composition to form an organosilicone composition having at least one pyrrolidone-containing carboxyl functional group.

In yet another aspect of the present invention there is provided an alternate method for preparing polysiloxanes containing one or more ester derivatives of carboxylic acid pyrrolidone groups which comprises reacting an organosilicone fluid or composition having one or more hydride groups (terminal or lateral) on the polysiloxane chain with an N-alkenyl carboalkoxy containing a pyrrolidone nucleus portion in the presence of a noble metal catalyst, preferably soluble platinum catalyst, at an elevated temperature (preferably between about 65.degree. C. and 130.degree. C.) for the time sufficient to react, preferably substantially completely react, the hydride groups on the silicone fluid or composition with the pyrrolidone group.

In a still further aspect of the present invention there is provided a novel silicone-modified amidoamine composition having the formula: ##STR5## wherein: R.sub.10 is the silicone backbone chain as herein described to which at least one pyrrolidone containing amidoamine derivative of a carboxyl functional group can be attached as shown;

R.sub.6 is hydrogen or alkyl, hydroxyalkyl or alkenyl of up to 6 carbon atoms each, or cycloalkyl of up to 6 carbon atoms, or polyoxyalkylene of up to 10 carbon atoms within the oxyalkylene unit;

R.sub.7 and R.sub.8, which may be the same or different, are selected from alkyl, hydroxyalkyl, carboxyalkyl of up to 6 carbon atoms in each alkyl; and polyoxyalkylene of up to 10 carbon atoms; in addition R.sub.7 and R.sub.8 taken together with the nitrogen to which they are attached may represent an N-hetercycle.

n is 0 or 2;

n.sup.1 is zero or 1;

n.sup.2 is zero or 1;

n.sup.3 is an integer from 2 to 12;

B is --NR.sub.9, sulfur or oxygen, wherein R.sub.9 is hydrogen or lower alkyl (C.sub.1-6); with the proviso that when n is 0 and n.sup.2 is 1, n.sup.1 is 1, when n is 2 and n.sup.2 is 1, n.sup.1 is 0 or 1, and when n is 2 and n.sup.2 is 0, n.sup.1 is 0;

F, which may be the same or different is branched or linear alkylene of 1-12 carbon atoms; and

d is at least one.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In accordance with the present invention there are provided novel polysiloxanes comprising a class of carboxyl functional polysiloxanes which may be represented by the general formula: ##STR6## wherein: R.sub.1, which can be the same or different, can be selected from R.sub.2, H, a primary amine containing group and a pyrrolidone containing carboxyl functional group of the general formula: ##STR7## wherein at least one R.sub.1 is a pyrrolidone-containing carboxyl or ester functional group or salt derivative thereof as shown; F, which can be the same or different, is linear or branched alkylene of 1-12 carbon atoms; R.sub.2 is as defined below; R.sub.5 is hydrogen, alkyl, preferably lower alkyl (C.sub.1-6), or an alkali metal; n is 0 or 2; n.sup.1 is 0 or 1; n.sup.2 is 0 or 1; and B is --NR.sub.9, sulfur (S) or oxygen (O), wherein R, is hydrogen or lower alkyl (C.sub.1-6); with the proviso when n is 0 and n.sup.2 is 1, n.sup.1 is 1, when n is 2 and n.sup.2 is 1, n.sup.1 is 0 or 1 and when n is 2 and n.sup.2 is 0, n.sup.1 is 0;

R.sub.2 can be the same or different and can be selected from alkyl, aryl and olefinic (vinyl);

R.sub.3 and R.sub.4, which may be the same or are selected from alkyl, aryl, capped or uncapped polyoxyalkylene, alkaryl, aralkylene and alkenyl (vinyl);

a can be an integer from 0 to 50,000;

b can be an integer from 0 to 100;

It is evident from the general formula above that the polysiloxane compositions of the present invention have one or more pyrrolidone containing functional carboxyl or ester group(s) or salt derivative thereof linked terminally, laterally or both terminally and laterally to the silicone (polysiloxane) chain through a hydrocarbon linkage which may contain a hetero atom.

The polysiloxane compositions according to the present invention are useful, for example, for reducing the friction of petroleum flow through pipelines as well as being precursors for a wide range of personal care products, fiber treating agents and the like which impart such advantages as improved feel, substantivity, reduced surface tension, and anti-stick characteristics.

The novel carboxyl functional polysiloxanes of the present invention surprisingly and unexpectedly can be readily and directly prepared by the reaction of corresponding silicone compositions or fluids having one or more functional primary amine groups with up to about one equivalent, preferably about stoichiometric quantities, of itaconic acid or its ester per functional primary amine group(s) at an elevated temperature for the time sufficient for substantially all of the itaconic acid or its ester to react with the functional primary amine group(s). In general from about 0.5, preferably, from about 0.9 to about 1.1 equivalents of itaconic acid or its ester per functional primary amine group is reacted with the silicone fluid wherein substantially all the itaconic acid and preferably all the functional primary amine group(s) are reacted and polysiloxane compositions with at least one pyrrolidone containing functional carboxyl group(s) and/or its ester are formed.

The reaction can be carried out neat or in an inert solvent such as alcohol, hydrocarbon solvent, chlorinated hydrocarbon and the like, as desired, in general, at elevated temperature, preferably from about 90.degree. C. to about 130.degree. C. The reaction proceeds readily and generally complete reaction of the itaconic acid or its ester with the available functional primary amine groups will occur in from about 1 to 5 hours, with routine analytical techniques for amine and acid values as well as monitoring water and/or alcohol evolution being used to determine completion of the reaction.

Primary amine functional silicone fluids suitable for use in accordance with the practice of the invention, having one or more primary amine functional group(s) linked terminally, laterally or both terminally and laterally, as desired, are well known and are available commercially, for example, from Dow Corning, Th. Goldschmidt AG and Shin-Etsu. While the equivalent weight of the silicone fluids or compositions which may be employed in the preparation of the polysiloxanes of the present invention is not critical, and suitable compositions may have equivalent weights of 5,000 to 10,000 or even higher, silicone fluids having equivalent weights from about 500 to about 5,000 are in general preferred.

As indicated, the polysiloxane compositions of the present invention are readily prepared by reaction of primary amine functional silicone fluids with itaconic acid or its ester. Itaconic acid (methylene succinic acid) is a compound of the formula:

CH.sub.2 =C(COOR.sub.9)CH.sub.2 COOR.sub.9

wherein

R.sub.9, which can be the same or different, is hydrogen or lower alkyl (1-6 carbon atoms).

The compound itaconic acid is available commercially from Pfizer Chemicals Division whereas ester derivatives thereof are available from Morflex Inc., Greensboro, N.C. The compounds are produced by known fermentation techniques although chemical synthesis methods are also known.

The novel carboxyl functional polysiloxanes, or ester derivatives thereof, of the present invention can also be readily prepared by a hydrosilylation reaction wherein a silicone fluid or composition having one or more hydride substituents on the silicone chain (terminal, lateral or combination or terminal and lateral) is added to a N-alkenyl carboalkoxy containing pyrrolidone nucleus in the presence of a noble metal (Group VIII metal) catalyst, preferably soluble platinum, at an elevated temperature (65.degree. C. to 130.degree. C.) for a time sufficient for substantially all of the N-alkenyl carboalkoxy containing pyrrolidone to react with the hydride group(s). The N-alkenyl carboalkoxy containing pyrrolidone reactant can have a N-allyl or higher olefinic group of 3 or more carbon atoms which can also include at least one hetero atom. The reaction can be carried out neat or in inert solvents such as toluene, benzene, chlorobenzene, heptane and the like. In general, from about 0.5 up to about one equivalent, preferably from about 0.9 to about 1.1 equivalents of the N-alkenyl pyrrolidone groups per functional hydride groups is reacted with the silicone fluid wherein substantially all the N-alkenyl carboalkxy containing pyrrolidone and, preferably all of the functional hydride groups are reacted. Suitable platinum catalysts include solubilized platinum or platinum metal on inert supports such as alumina, charcoal and the like. In general from about 10-.sup.3 to 10-.sup.6 moles of platinum per mole of hydride group can be used. In another aspect of the present invention, there are provided novel silicone-containing amidoamines suitable for use as a surfactants and a variety of other applications as well as intermediate reactants which are preferably derivatives of the novel polysiloxane compositions of the invention as hereinabove described. The novel amidoamine compositions of the invention may be represented by the general formula: ##STR8## wherein: R.sub.10 is a silicone backbone chain as herein described to which at least one pyrrolidone containing carboxyl functional group or amidoamine derivative thereof is attached as hereinabove shown;

R.sub.6 is hydrogen or alkyl, hydroxyalkyl or alkenyl up to 6 carbon atoms each, cycloalkyl of up to 6 carbon atoms or polyoxyalkylene of up to 10 carbon atoms, preferably from 2 to 5 carbon atoms, within the oxyalkylene unit and at least one R.sub.6 is hydrogen;

R.sub.7 and R.sub.8, which may be the same or different, are selected from alkyl, hydroxyalkyl, carboxyalkyl of up to 6 carbon atoms in each alkyl, and polyoxyalkylene of up to 10 carbon atoms; in addition R.sub.7 and R.sub.8 taken together with the nitrogen to which they are attached may represent N-heterocycle.

F, which can be time same or different is linear or branched alkylene of 1-12 carbon atoms;

B is --NR.sub.9, sulfur or oxygen, wherein R.sub.9 is hydrogen or lower alkyl (C.sub.1-6); with the proviso that when n is 0 and n.sup.2 is 1, n.sup.1 is 1, when n is 2 and n.sup.2 is 1, n.sup.1 is 0 or 1, and when n is 2 and n.sup.2 is 0, n.sup.1 is 0;

n is 0 or 2;

n.sup.1 is zero or 1;

n.sup.2 is zero or 1;

n.sup.3 is an integer from 2 to 12;

d is an integer from 1 or greater,