Silicone modified phospholipid compositions

Phospholipid compositions that may be represented by the following general formula: ##STR1## wherein: PA1 A is selected from H, M, and R--Y--; PA1 A.sub.1 is selected from H, OH, OM and R--Y--O--; PA1 x is 0 or an integer from 1 to 5; PA1 M is a cation; PA1 Y is alkylene or substitued alkylene; and PA1 R is a mixture of quaternized amidoamine and/or amine moieties selected from the group consisting of: PA0 a) a quaternized organosilicone amidoamine moiety of the formula: ##STR2## PA0 b) a quaternized organosilicone tertiary amine moiety of the formula: ##STR3## or a mixture of the quaternized organosilicone amidoamine moiety "a" and/or quaternized tertiary amine moiety "b" above and the moieties: PA0 c) a quaternized organic amidoamine moiety of the formula: ##STR4## PA0 d) an organic quaternized tertiary amine moiety of the formula: ##STR5## with the proviso that wherein R is a mixture of organosilicone amine and organic amine moieties, at least 5 equivalent weight percent to about 60 equivalent weight percent of the total equivalent weight of amine moieties of the phospholipid composition is a quaternized organosilicone amidoamine moiety, a quaternized organosilicone tertiary amine moiety or mixtures of the same.

FIELD OF THE INVENTION
 The present invention relates to novel organosilicone compounds and, more
 particularly, to silicone containing derivatives having at least one
 esterified phosphate group in the molecule.
 BACKGROUND OF THE INVENTION
 Phosphate esters, quaternary amine compounds, betaines and certain
 substituted betaines are known in the art and have been commercially used
 over the years for a variety of applications, including those requiring
 surfactant properties. More recently, various betaine derivatives having,
 in general, specific quaternary compounds linked to phosphate esters
 referred to as phosphobetaines, and more particularly "synthetic
 phospholipids," have been disclosed, for example, in U.S. Pat. Nos.
 4,215,064, 4,233,192, 4,380,637 and 4,382,036 to Lindemann et al.; U.S.
 Pat. Nos. 4,209,449, 4,336,385 and 4,503,002 to Mayhew et al.; U.S. Pat.
 Nos. 4,243,602, 4,283,542 and 4,336,386 to O'Lenick et al; and U.S. Pat.
 No. 4,617,404 to Lukenbach et al. These synthetic phospholipids are
 disclosed as exhibiting outstanding foaming, viscosity building, wetting,
 cleansing, detergency, anti-static, conditioning and emulsifying
 properties, making them useful in industrial applications calling for high
 performance surface active agents. The synthetic phospholipids are also
 described as being highly stable compositions which are well tolerated by
 human tissue (i.e. they exhibit exceptionally low oral toxicity and ocular
 irritation) and, hence, are well suited for use in a variety of personal
 care applications including cosmetic formulations as well as in industrial
 processes.
 A variety of organosiloxane compositions including compositions which
 exhibit excellent properties as surface active agents, lubricants and the
 like are well known and have been used commercially over the years,
 including for personal care and home care applications. In general,
 organosiloxane compositions are water-insoluble and the costs thereof are
 greater than many other commercial materials which has limited their use
 for many applications. Recently, particular types of betaine and
 phosphobetaine modified organosiloxanes have been disclosed, for example,
 in U.S. Pat. Nos. 4,609,750 and 4,654,161 to Kollmeier et al. and U.S.
 Pat. No. 5,091,493 to O'Lenick et al which have been suggested as
 exhibiting high foaming characteristics in water, substantivity to a
 variety of surfaces, reduced irritation to the eyes and skin and improved,
 although limited, water-solubility properties. While, as indicated,
 certain organosilicone compositions containing phosphobetaines and methods
 for preparing the same have been suggested, there has been no prior
 disclosure or suggestion of the novel silicone modified phospholipid
 compositions and preparation methods described in copending application
 Ser. No. 174,934, of which the present application is a continuation in
 part, or of the novel silicone modified phospholipid compositions and
 methods for preparing the same herein described which compositions exhibit
 a greater range of properties for different applications as well as
 providing means for closer control of the costs of the organosilicone
 products.
 SUMMARY OF THE INVENTION
 It is accordingly an object of the present invention to provide novel
 silicone-modified phospholipid compositions suitable for use in solvent
 and/or preferably aqueous based systems which exhibit excellent
 surface-active properties including high foaming, are well tolerated by
 human tissue, are substantive to the surface of natural and synthetic
 fiber, and the like.
 It is another object of the present invention to provide novel
 water-soluble silicone-modified phospholipid compositions containing
 terminal, lateral (pendant) or combinations of terminal and lateral
 (pendant) silicone moieties and wherein the compositions can be prepared
 with a variety of concentrations of silicone as desired or required.
 In accordance with the present invention, there has now been discovered
 novel phospholipid compositions that may be represented by the following
 general formula:
 ##STR6##
 wherein:
 A is selected from H, M, and R--Y--;
 A.sub.1 is selected from H, OH, OM, and R--Y--O--;
 x is o or an interger from 1 to 5;
 M is a cation, preferably an alkali metal;
 Y is alkylene or substitued alkylene; and
 R is selected from;
 a) a quaternized organosilicone amidoamine moiety of the formula:
 ##STR7##
 wherein:
 R.sub.1 is a silicone backbone chain as hereinafter described to which
 amidoamine and/or amine functional group(s) as herein described can be
 attached;
 R.sub.2 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 preferably from 2 to 5 carbon atoms within the
 oxyalkylene unit;
 R.sub.3 and R.sub.4, 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;
 X.sup.- is an anion, preferably a halogen;
 n is an integer from 2 to 12;
 n.sup.1 is zero or an integer from 1 to 12;
 n.sup.2 is 0 or 1;
 n.sup.3 is an integer from 1 to 5;
 B is sulfur (S) or oxygen (O); with the proviso that when n.sup.2 is 0,
 n.sup.1 or n.sup.3 is at least 1 and when n.sup.2 is 1, n.sup.1 and
 n.sup.3 each is at least 1; and d is one or greater, preferably 2-10;
 b) a quaternized organosilicone tertiary amine moiety of the formula:
 ##STR8##
 wherein:
 R.sub.1 is a silicone backbone claim as hereinafter described to which
 amidoamine and/or amine functional groups can be attached;
 R.sub.6 is alkylene, hydroxyalkylene, arylene, alkarylene, aralkylene,
 heteroalkylene wherein the heteroatom can be N, S or O and there can be
 more than one of such hetero atoms in the chain;
 X.sup.- is an anion, preferably a halogen;
 d.sup.1 is an integer of one or greater, preferably from 2 to 10; and
 R.sub.3 and R.sub.4 are as hereinabove defined;
 or a mixture of the quaternized organosilicone amidoamine moiety "a" and/or
 quaternized tertiary amine moiety "b" above and the moieties:
 c) a quaternized organic amidoamine moiety of the formula:
 ##STR9##
 wherein:
 R.sub.5 is alkyl, alkenyl, alkoxyalkyl or hydroxyalkyl of from 5 to 21
 carbon atoms each, alkaryl or aryl of up to 20 carbon atoms;
 R.sub.2 is hydrogen or alkyl, hydroxyalkyl or alkenyl of up to 6 carbon
 atoms each, cycloalkyl of up to 6 carbon atoms, or polyoxyalkylene of up
 to 10 carbon atoms, preferably of from 2 to 5 carbon atoms, within the
 oxyalkylene unit;
 R.sub.3 and R.sub.4 which may be the same or different, are selected from
 alkyl, hydroxyalkyl, carboxyalkyl of up to 6 carbon atoms in each alkyl
 moiety, and polyoxyalkylene of up to 10 carbon atoms; in addition R.sub.3
 and R.sub.4 taken together with the nitrogen to which they are attached
 may represent an N-heterocycle;
 X.sup.- is an anion, preferably a halogen;
 g is 0 or 1;
 n is integer from 2 to 12; and
 n.sup.4 is 1 or greater; and/or
 d) an organic quaternized tertiary amine moiety of the formula:
 ##STR10##
 wherein:
 R.sub.13, R.sub.14 and R.sub.15 are the same or different and are alkyl,
 substituted alkyl, alkyl aryl or alkenyl groups of up to 16 carbon atoms
 with the proviso that the total carbon atoms in R.sub.13 +R.sub.14
 +R.sub.15 is between 10 and 24;
 with the proviso that wherein R is a mixture of organosilicone amine and
 organic amine moieties, at least 5 equivalent weight percent to about 60
 equivalent weight percent of the total equivalent weight of amine moieties
 of the phospholipid composition is a quaternized organosilicone amidoamine
 moiety, a quaternized organosilicone tertiary amine moiety or mixtures of
 the same.
 The silicone backbone chain, R.sub.1, to which the amidoamine and/or amine
 functional groups as herein described are attached and which are shown
 herein as R.sub.11, corresponds to the general formula:
 ##STR11##
 wherein:
 R.sub.7 and R.sub.8, which may be the same or different are selected from
 alkyl, aryl, capped or uncapped polyoxyalkylene, alkaryl, aralkylene and
 alkenyl (vinyl);
 R.sub.10 can be the same or different and can be selected from alkyl, aryl
 and olefinic (vinyl);
 R.sub.11, which can be the same or different, can be selected from
 R.sub.10, --(CH.sub.2).sub.n1 --B.sub.n2 --(CH.sub.2).sub.n3
 --CO--NR.sub.2 --(CH.sub.2).sub.n --NR.sub.3 R.sub.4, --R.sub.6 --NR.sub.3
 R.sub.4 -- and mixtures thereof, wherein R.sub.2, R.sub.3, R.sub.4,
 R.sub.6, B, n, n.sup.1, n.sup.2 and n.sup.3 are as defined above; with the
 proviso that at least one of R.sub.11 is an amidoamine or tertiary amine;
 e can be an integer of O to 50,000;
 f can be an integer of 0 to 100.
 It is evident from the above general formula for phospholipid compositions
 of the invention that the functional phosphorus containing group(s) can be
 linked terminally, laterally or both terminally and laterally to the
 siloxane backbone chain.
 In another aspect of the present invention there is provided a method of
 preparing novel phospholipid compositions that may be represented by the
 general formula:
 ##STR12##
 wherein:
 A is selected from H, M, and R--Y--;
 A, is selected from H, OH, OM, and R--Y--O--;
 M is a cation, preferably an alkali metal;
 x is O or an integer from 1 to 5;
 Y is alkylene or substituted alkylene; and
 R is a mixture of quaternized amidoamine and/or tertiary amine moieties as
 hereinabove defined;
 which comprises reacting the combination of an organic amidoamine and/or
 organic tertiary amine reactant and a silicone modified amidoamine and/or
 silicone modified tertiary amine reactant with a polyphosphate, phosphite
 or phosphate ester reactant in the equivalent weight ratios of from about
 0.7 to 3.3, of total amidoamine and/or tertiary amine reactants to 1 of
 polyphosphate, phosphite or phosphate ester halide reactant until the
 amine reactant is completely reacted, with the proviso that at least 5
 equivalent weight percent to about 60 equivalent weight percent of the
 total equivalent weight of amine reactants will be silicone containing,
 said polyphosphate, phosphite or phosphate ester halide reactant being of
 the general formula:
 ##STR13##
 wherein:
 A.sub.2, is selected from H, M and X--Y--;
 A.sub.3 is selected from H, OH, OM, and R--Y--O--;
 x is O or an integer from 1 to 5;
 M is a cation, preferably alkali metal;
 Y is alkylene or substituted alkylene; and
 X is halogen.
 DESCRIPTION OF THE PREFERRED EMBODIMENTS
 The novel phospholipid compositions of the present invention comprise a
 class of compositions which may be represented by the general formula:
 ##STR14##
 wherein:
 A is selected from H, M, and R--Y--;
 A.sub.1 is selected from H, OH, OM and R--Y--O--;
 x is O or an integer from 1 to 5;
 M is a cation, preferably an alkali metal;
 Y may be alkylene, optionally interrupted by up to 3 oxygen atoms, of up to
 12 carbon atoms, which alkylene chain may optionally be substituted with
 lower alkyl, alkoxyxalkyl or hydroxyalkyl, e.g., of not more than 10
 carbon atoms each;
 R is selected from:
 a) a quaternized organosilicone amidoamine moiety of the formula:
 ##STR15##
 wherein:
 R.sub.1 is a silicone backbone chain hereinafter described to which amido
 amine functional group(s) as herein described can be attached;
 R.sub.2 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 10 to 10 carbon atoms, preferably from 2 to 5 carbon atoms, within the
 oxyalkylene unit;
 R.sub.3 and R.sub.4, 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;
 X.sup.- is an anion, preferably a halogen;
 n is an integer from 2 to 12;
 n.sup.1 is zero or an integer from 1 to 12;
 n.sup.2 is 0 or 1;
 n.sup.3 is an integer from 1 to 5;
 B is sulfur (S) or oxygen (O); with the proviso that when n.sup.2 is 0,
 n.sup.1 or n.sup.3 is at least 1 and when n.sup.2 is 1, n.sup.1 and
 n.sup.3 each is at least 1; and d is one or greater, preferably 2-10;
 b) a quaternized organosilicone tertiary amine moiety of the formula:
 ##STR16##
 wherein:
 R.sub.1 is a silicone backbone claim as hereinafter described to which
 amine functional groups can be attached;
 R.sub.6 is alkylene, hydroxyalkylene, arylene, alkarylene, aralkylene,
 heteroalkylene wherein the heteroatom can be N, S or O and there can be
 more than one of such hetero atoms in the chain;
 X.sup.- is an anion, preferably a halogen;
 d.sup.1 is an integer of one or greater, preferably from 2 to 10; and
 R.sub.3 and R.sub.4 are as hereinabove defined;
 or a mixture of the quaternized organosilicone amidoamine moiety "a" and/or
 quaternized organosilicone tertiary amine moiety "b" above and moieties
 selected from the group consisting of:
 c) a quaternized organic amidoamine moiety of the formula:
 ##STR17##
 wherein:
 R.sub.5 is alkyl, alkenyl, alkoxyalkyl or hydroxyalkyl of from 5 to 21
 carbon atoms each, alkaryl or aryl of up to 20 carbon atoms;
 R.sub.2 is hydrogen or alkyl, hydroxyalkyl or alkenyl of up to 6 carbon
 atoms each, cycoalkyl of up to 6 carbon atoms, or polyoxyalkylene of up to
 10 carbon atoms, preferably of from 2 to 5 carbon atoms within the
 oxyalkylene unit;
 R.sub.3 and R.sub.4 which may be the same or different, are selected from
 alkyl, hydroxyalkyl, carboxyalkyl of up to 6 carbon atoms in each alkyl
 moiety, and polyoxyalkylene of up to 10 carbon atoms; in addition R.sub.3
 and R.sub.4 taken together with the nitrogen to which they are attached
 may represent an N-heterocycle;
 X.sup.- is an anion, preferably a halogen;
 g is 0 or 1
 n is integer from 2 to 12; and
 n.sup.4 is an 1 or greater; and/or
 d) an organic quaternized tertiary amine moiety of the formula:
 ##STR18##
 wherein:
 R.sub.13, R.sub.14 and R.sub.15 are the same or different and are alkyl,
 substituted alkyl, alkaryl or alkenyl groups of up to 16 carbon atoms with
 the proviso that the total carbon atoms in R.sub.13 +R.sub.14 +R.sub.15 is
 between 10 and 24;
 x- is an anion, preferably a halogen.
 with the proviso that wherein R is a mixture of organosilicone amine and
 organic amine moieties, at least 5 equivalent weight percent to about 60
 equivalent weight percent of the total equivalent weight of amine moieties
 of the phospholipid composition is a quaternized organosilicone amidoamine
 moiety, a quaternized organosilicone tertiary amine moiety or mixtures of
 the same.
 A preferred phopholipid composition of the invention wherein Y is
 2-hydroxypropylene comprises a class of compositions which may be
 represented by the general formula:
 ##STR19##
 wherein
 A and R are as defined hereinabove.
 The silicone backbone chain R.sub.1 to which the amine functional groups as
 hereinabove shown are attached and which are shown herein as R.sub.11,
 corresponds to the general formula:
 ##STR20##
 wherein:
 R.sub.7 and R.sub.8, which may be the same or different are selected from
 alkyl, aryl, capped or uncapped polyoxyalkylene, alkaryl, aralkylene and
 alkenyl (vinyl);
 R.sub.10 can be the same or different and can be selected from alkyl, aryl
 and olefinic (vinyl);
 R.sub.11, which can be the same or different, may be selected from
 R.sub.10, --(CH.sub.2).sub.n1 --B.sub.n2 --(CH.sub.2).sub.n3 CO-- NR.sub.2
 --(CH.sub.2).sub.n --NR.sub.3 R.sub.4 --, --R.sub.6 --NR.sub.3 R.sub.4 --
 and mixtures thereof wherein R.sub.2, R.sub.3, R.sub.4, R.sub.6, B, n,
 n.sup.1, n.sup.2 and n.sup.3 are as defined above; with the proviso that
 at least one of R.sub.11 is an amidoamine or tertiary amine;
 e can be an integer of O to 50,000;
 f can be an integer of 0 to 100.
 It is evident from the general formula of the novel phospholipid
 compositions of the invention that the functional phosphorus containing
 group(s) can be linked terminally, laterally or both terminally and
 laterally to the siloxane chain.
 The phospholipid compositions of the invention can be prepared by reacting
 corresponding silicone-modified tertiary amine and/or amidoamine reactants
 or combinations of corresponding silicone modified tertiary amine and/or
 amidoamine reactants and organic tertiary amine and/or amidoamines
 reactants with polyphosphate, phosphite, or phosphate ester halide
 reactants in appropriate stoichiometric quantities as will be described in
 detail hereinafter to obtain the desired products of the formula:
 ##STR21##
 and preferably
 ##STR22##
 wherein:
 A is as defined hereinabove;
 A.sub.1 is as defined hereinabove;
 x is as defined hereinabove;
 M is as defined hereinabove;
 R is selected from a quaternized organosilicone amidoamine moiety, a
 quaternized organosilicone tertiary amine moiety, or a mixture of moieties
 selected from a quaternized organosilicone amidoamine moiety, a
 quaternized organosilicone tertiary amine moiety, an organic amidoamine or
 organic tertiary amine moiety or mixtures thereofas defined hereinabove;
 with the proviso that wherein R is a mixture of organosilicone amine and
 organoamine moieties at least 5 to about 60 equivalent weight percent of
 the total equivalent weight of amine moieties of the phospholipid
 composition is a quaternized organosilicone amidoamine, a quaternized
 organosilicone tertiary amine and mixtures of the same.
 The intermediate reactants required in the processes for preparing the
 phospholipid compositions of the invention can be prepared as follows:
 Phosphate, polyphosphate and/or phosphite ester halide intermediate
 reactants based on epichlorhydrin can be prepared by known procedures
 illustrated as follows:
 I
 ##STR23##
 wherein:
 A.sub.2 is selected from H, M and X--Y--;
 A.sub.3 is selected from H, OH, OM and X--Y--O--;
 A.sub.4 is H, OM or OH;
 A.sub.5 is H or M;
 a is from 0.5 to 3.5, preferably 1 to 3;
 b is from 1 to 3, preferably 1-2;
 X is 0 or an integer from 1-5;
 M is a cation, preferably alkali metal;
 x is halogen;
 Y is 2 hydroxyproplyene.
 The above coupling reaction is carried out in an aqueous media, preferably
 in the range of 30-50% concentration, having a pH range of 5.0-8.0.
 ##STR24##
 wherein:
 A.sub.7 is H, OH or X--Y--O--;
 A.sub.8 is H or --Y--X;
 a is from about 0.5 to 7, preferably, from about 1 to 3;
 x is 0 or an integer from 1-5;
 X is halogen;
 Y is 2 hydroxypropylene.
 The reaction is preferably carried out in absence of water with slight
 excess epichlorohydrin.
 Phosphate, phosphite and/or polyphosphate ester intermediate reactants for
 preparing phosphobetaine, pyrophosphobetaine and the like compositions of
 the invention can also be prepared by known procedures such as are
 disclosed, for example, in U.S. Pat. No. 4,617,414.
 Silicone-modified amidoamine intermediate reactants suitable for use in
 preparing the phospholipid composition of the invention can be prepared as
 follows:
 Also suitable as phosphate and phosphite intermediate reactants are such
 reactants prepared by known procedures illustrated as follows:
 ##STR25##
 wherein
 a is O or an integer from 1 to 2;
 X is halogen, preferably bromine;
 R.sub.16 is alkylene.
 ##STR26##
 wherein
 X is a halogen, preferably bromine;
 R.sub.16 is alkylene.
 Carrying out reactions III(a) and IV(b) in presence of a tertiary amine HCl
 acceptor is preferred to prevent formation of free acid.
 Silicone-modified amidoamine intermediate reactants suitable for use in
 preparing the phospholipid composition of the invention can be prepared as
 follows:
 ##STR27##
 wherein:
 R.sub.1 is a silicone backbone chain as herein defined;
 R.sub.2 is as hereinabove defined;
 R.sub.3 and R.sub.4 is as previously defined;
 R.sub.12 is hydrogen or alkyl;
 B is sulfur or oxygen; with the proviso that when n.sup.2 is 0, n.sup.1 or
 n.sup.3 is at least 1 and when n.sup.2 is 1, n.sup.1 and n.sup.3 each is
 at least 1;
 n is an integer from 2 to 12;
 n.sup.1 is zero or an integer of one or greater;
 n.sup.2 is 0 or 1;
 n.sup.3 is an integer of 1 to 5;
 d and D is an integer from 1 or greater, generally from 1-50 and preferably
 2-10. The reactant ratio of the amine reactant to the carboxyl reactant on
 the silicon is preferably 1:1 but can be varied in ratio of 0.8-1.2.
 The above coupling reaction (V) for preparing the silicone-modified
 amidoamine intermediate reactants can be carried out neat or can be
 carried out in an inert solvent such as xylene, toluene, benzene,
 chlorobenzene or the like.
 The polysiloxane-containing functional carboxylic acids or derivatives
 thereof (terminal, lateral or combination of terminal and lateral)
 applicable for use in preparing the silicone-modified amidoamine
 intermediate reactants as set forth in the reaction sequence illustrated
 above (III) can be prepared by a variety of known procedures such as
 illustrated by the following:
 ##STR28##
 wherein:
 h is an integer from 1-100;
 j is an integer from 0-1000.
 ##STR29##
 wherein:
 k is an integer from 1-1000.
 ##STR30##
 wherein:
 1 is an integer from 1-100;
 m is an integer from 0-1000.
 Suitable carboxyl functional silicone compositions having terminal, lateral
 or combinations of terminal and lateral functional groups are available
 commercially, for example, from Shin-Etsu. While the molecular weight of
 the silicone compositions which may be employed are not critical, and
 suitable compositions may have amine equivalent weights of 8000, or even
 higher, silicone compositions having amine equivalent weights from about
 1500 to about 6000 are in general preferred.
 Silicone-modified tertiary amine intermediate reactants which are suitable
 for use in preparing alternate embodiments of the silicone-modified
 phospholipid compositions of the invention can be silicone-modified
 tertiary amines (terminal, lateral or combinations thereof) which are
 prepared by a variety of known procedures such as disclosed, for example,
 in U.S. Pat. No. 3,389,160 which describes the preparation of a carbinol
 containing tertiary silicone amine encompassing the reaction of a
 secondary amine with an epoxy containing silicone fluid (example 1) and by
 Snow et al, J. Langmuir, 1990, 6(2), pp 336-39, wherein the preparation of
 tertiary amino functional siloxanes result from the hydrosilylation of
 olefinic tertiary amines with hydride siloxane fluids employing a platinum
 catalyst.
 In addition, the preparation of a suitable functional tertiary amino alkyl
 dimethylsilyl capped material is disclosed in U.S. Pat. No. 4,918,210, at
 example 1, part 2 which consists of the Pt catalyzed addition of a
 terminal hydride containing silicone fluid with N-allyl-diethylamine. In
 general, silicone containing tertiary amine intermediate reactants with
 molecular weights ranging, between about 1000 and 6000 are most
 advantageously employed.
 The organic amidoamine intermediate reactants suitable for use in preparing
 the phospholipid compositions of the invention can be prepared as follows:
 ##STR31##
 wherein:
 R.sub.5 is as hereinabove defined;
 R.sub.2 is as hereinabove defined;
 R.sub.3 and R.sub.4 is as hereinabove defined;
 R.sub.12 is hydrogen or alkyl;
 g is 0 or 1;
 n is an integer from 2 to 12; and
 n.sup.4 is 1 or greater.
 The organic amidoamine intermediate reactants suitable for use in preparing
 the phospholipid compositions shown in the above coupling reaction are
 known or are generally prepared in accordance with conventional
 techniques. A wide variety of commercially available tertiary amino alkyl
 amines are suitable for use in reaction with an acid or acid derivative to
 prepare suitable amidoamines, as are the amidoamines themselves. The
 suitable tertiary amino alkyl amines can be primary or secondary amines
 with the proviso that the total number of carbons in the acid portion of
 the molecule be greater than 6, i.e. to give a hydrophobic moiety
 necessary for surface activity properties. Suitable amidoamines include
 acyl derivatives of aminoacid products such as glycine and sarcosine
 (N-methylglycine) including for example, products available under the
 Tradename HAMPOSYL from the Hampshire Chemical Co.
 The organic tertiary amine reactants suitable for use in preparing the
 phospholipid compositions of the invention can be prepared using
 procedures well known in the art and many suitable compositions are
 available.
 Exemplary tertiary amines include:
 tributylamine
 bis(hydroxyethyl)hexylamine
 bis(2-hydroxyethyl)cocoamine
 N,N-dimethyl-dodecylamine
 N,N-dimethyl-tetradecylamine
 N,N-dimethyl-hexadecylamine
 N,N-dimethyl-cocoamine
 N,N-dimethyl-cetylamine
 dimethyl (C.sub.8 -C.sub.16) alkyl amine.
 N,N-dimethyl-octadecylamine
 As indicated, the phospholipid compositions of the invention can be
 prepared by reacting a tertiary amine or amidoamine functional silicones
 or combination of tertiary amine and/or amidoamine functional silicones
 and organic tertiary amine and/or amidoamine reactants with the phosphate
 ester halide reactants herein described in appropriate stoichiometric
 quantities as will be discussed in detail hereinafter.
 The reaction of silicone containing amidoamine or tertiary amine functional
 groups with phosphate, polyphosphate and/or phosphite ester halide
 reactants in molar equivalents from about 0.7 to 3.3 of the amine
 functional silicones to 1 of the phosphate, phosphite and/or polyphosphate
 ester halide reactants based on the reaction can be readily carried out in
 an aqueous or aqueous organic co-solvent reaction systems wherein the
 number of grams of silicone fluid containing an amine equivalent lie in
 the area up to about 1200. Reactions will go to completion as demonstrated
 by chlorine analysis, alkali number titration, and homogeneity of
 reaction. When the number of grams of fluid per amine equivalent weight of
 the silicone reactants is greater than about 1200 to 2000 the reactants
 are partially or completely insoluble in the reaction system and an
 incomplete reaction will result. With silicone composition reactants
 having amine equivalent weights above about 2000, the addition of a
 co-solvent to an aqueous reaction system will not increase the solubility
 of the reactants as evidenced by phase separation and/or other signs of
 incomplete reaction. Surprisingly and unexpectedly, it has been found that
 phospholipid compositions of the invention can be prepared in substantial
 complete reaction form and in completely soluble reaction systems using
 tertiary amine and/or amidoamine functional silicone reactants having
 amine equivalent weights of 6000, or even greater, by also incorporating
 in the reaction system, organic tertiary amine and/or amidoamine reactants
 as herein described in conjunction with the functional silicone reactants.
 The organic tertiary amine and/or amidoamine reactant is added to the
 reaction system as a partial replacement of a molar equivalent amount of
 the functional silicone reactant, which substantially maintains the above
 noted molar equivalent ratios of amine reactants to phosphate ester halide
 reactants in the reaction mixture.
 The reaction of a combination of organic tertiary amine and/or amidoamine
 reactants and silicone modified amine reactants with phosphate, phosphite
 and/or polyphosphate ester halide reactants will proceed to completion at
 an elevated temperature, preferably a temperature ranging from about
 75.degree. C. to 95.degree. C., with the formation of the
 silicone-modified phospholipid compositions. The order of addition of the
 reactants is not critical and while a heterogeneous mixture may result
 when all reactants are admixed, the system becomes homogenous as the
 reaction proceeds. The reaction may start slowly while the mixture is
 heterogeneous but the reaction mixture will become substantially clear as
 the reaction proceeds. In accordance with the process of the invention,
 silicone-modified phospholipid compositions which contain at least 5
 equivalent weight percent to about 60 equivalent weight percent silicone
 of the total amine containing moieties can be prepared, which
 silicone-containing phospholipid compositions will be completely soluble
 in aqueous/solvent or, preferably, aqueous systems while exhibiting
 surface active properties including low surface tension, high foaming and
 substantivity characteristics, low ocular and skin irritation and the
 like. Thus, it is possible by choice of particular amine functional
 silicone, organic amine and phosphate ester halide reactants to obtain
 soluble and preferably aqueous soluble silicone-modified phospholipid
 composition with a wide range of surface active agent properties for use
 in a variety of applications.

The preparation of specific compositions of the invention is illustrated by
 the following specific examples which are provided herein for purposes of
 illustration only and are not intended to limit the scope therein.
 EXAMPLE 1
 A carboxyl containing (pendant), trimethylsilyl capped silicone fluid
 obtained from Shin-Etsu under the designation X-22310 having a carboxyl
 content of 3.5% and an initial equivalent weight of 1289 is used in this
 example.
 1592.7 grams (1.235 moles) of the above polysiloxane fluid is combined with
 189 grams (50% excess) of dimethylaminopropyl amine (DMAPA) in a reaction
 vessel and heated slowly under nitrogen to about 185.degree. C. The
 reaction is carried out for 4 hours while volatiles come off and are
 collected. There is collected a total of 44 ml of volatiles as two layers,
 the bottom layer of 25 ml is water with some volatilized
 dimethylaminopropyl amine. The residue in the reaction vessel has an acid
 number less than 1.
 The materials are then heated to a temperature of 120.degree.`-140.degree.
 C. under a vacuum of 10 mm for 3 hours. At this point the
 polysiloxane/DMAPA reaction product is found to have an alkali number of
 42 and equivalent weight of 1335.
 264 grams (0.9428 moles) of cocoyl sarcosine obtained as HAMPOSYL C from
 Hampshire Chemical Corp. is reacted with 144 grams (an excess) of
 dimethylaminopropyl amine in 150 ml of refluxing xylene under a nitrogen
 atmosphere, with water being removed as it is formed. After 4 hours, water
 no longer evolves and the xylene and any volatiles are removed by heating
 the reaction mixture to 130.degree. C. at 10 mm vacuum for 3 hours. 348
 grams of a product having an alkali number of 185 is obtained.
 2.7 grams (0.002 mole) of the above silicone/DMAPA product are combined
 with 2.4 grams (0.008 moles) of the above sarcosine/DMAPA product; 3.12
 grams (0.0033 moles) of a 40% concentration of a phosphate ester halide
 reactant prepared by the reaction of 3 moles of epichlorohydrin with one
 mole of 85% phosphoric acid in the presence of one mole sodium hydroxide;
 and 13 grams water. The amidoamine reactants are used in an equivalent
 weight ratio of 4:1 of organic amidoamine to silicone amidoamine
 reactants.
 The reaction mixture is heated for 3 hours at 90.degree. C. at which time a
 hazy but homogeneous reaction product is obtained having a % NaCl content
 of 2.6 (2.8 theoretical).
 The resultant product when added to water forms a clear solution which
 foamed well, as compared to the silicone fluid starting material which
 forms a hazy, non-foaming mixture in water.
 EXAMPLE 2
 6.67 grams (0.005) of a silicone/DMAPA reaction product (equivalent weight
 1335) prepared as described in example 1 is mixed with 3.84 grams (0.010
 mole) of the reaction product of linoleic acid and dimethylaminopropyl
 amine prepared by well known, conventional techniques, 4.69 grams (0.005
 mole) of phosphate ester halide reactant prepared as described in example
 1, and 26 grams of water. The reaction mixture is heated at 90.degree. C.
 for 3 hours at which time a clear, viscous, yellow solution is obtained
 having a % NaCl content of 1.9% (2.1 theoretical).
 The resulting product added to water forms a clear solution which produces
 a stable foam.
 EXAMPLE 3
 A carboxyl containing (pendant) trimethylsilyl capped silicone fluid
 obtained from Shin Etsu under the designation X-223701E having a carboxyl
 content of 0.95% and initial equivalent weight of 4740 is used in this
 example.
 967 grams (0.204 mole) of the above silicone fluid is combined with 31.2
 grams (excess) of dimethylaminopropyl amine (DMAPA) and heated slowly
 under nitrogen to about 185.degree. C. while volatiles coming off are
 collected. After a period of 4 hours, 15.5 ml of volatiles are collected
 as two layers, the bottom one being water with some volatilized DMAPA.
 The reaction mixture having an acid number less than 1 is then heated to
 about 140.degree. C. at 5 mm vacuum for 4 hours to produce a product
 having an alkali number of 11.4 and an equivalent weight of 4921.
 9.8 grams (0.002 mole) of the above silicone/DMAPA reaction product are
 mixed with 2.4 grams (0.008 mole) of the cocyl sarcosine/DMAPA reaction
 product prepared as in example 1, 3.13 grams (0.0033 mole) of the
 phosphate ester halide reactant of example 2 and 29.5 grams water (30%
 solids concentration). The reaction mixture is heated for 3 hours at
 94.degree. to 95.degree. C. during which time a clear but somewhat hazy
 solution is obtained. The % NaCl content of the reaction product is 1.4.
 The resulting product forms a clear solution when added to water which
 produces a large amount of stable foam.
 EXAMPLE 4
 Using the silicone/DMAPA reaction product of example 3 (equivalent weight
 of 4921) and the phosphate ester halide reactant of example 1, a series of
 mixtures of the two reactants in equivalent weight ratios ranging from 0.1
 to 6:1 in water at solid content concentrations ranging from 10-70% are
 reacted. The various combination of reactants failed to form a homogeneous
 reaction mixture during reaction times ranging from 2 to 10 hours at
 temperatures up to 100.degree. C. Similar results are obtained with the
 addition of cosolvents such as isopropanol and propylene glycol to the
 reaction system.
 EXAMPLE 5
 A reaction mixture is prepared from 39.2 grams of the silicone/DMAPA
 reaction product of example 3, 12 grams of a linoleic acid/DMAPA reaction
 product, 15.92 grams of the cocoyl sarcosine/DMAPA reaction product of
 example 1, 28.2 grams of the phosphate ester halide reactant of example 1
 and 91.6 grams of water. The reaction mixture is heated to 90.degree. C.
 for four hours during which time a clear solution is formed having a %
 NaCl content of 2.7.
 EXAMPLE 6
 Trisiloxane 1,1,1,3,5,5,5-hepta methyl, 3-Dimethylamino propyl trisiloxane
 prepared by the platinum catalyzed addition of the corresponding
 heptamethyltrisiloxane to N,N Dimethyl allyl amine as described in U.S.
 Pat. No. 3,658,867 is used in this example. A reaction mixture containing
 2.4 grams of the above trisiloxane (0.008 mole), 3.2 grams (0.012 mole) of
 cetyldimethylamine, 6.24 grams of the phosphate ester halide reactant of
 example 1, and 15 ml water is prepared and heated to 90.degree. C. for 3
 hours. A homogeneous, clear solution is formed having an alkali number
 less than 2.
 A few drops of the product when added to 100 ml of water forms a clear
 solution which forms a stable foam when shaken. Although some preferred
 embodiments have been described, many modifications and variations may be
 made thereto in light of the above teachings. It is therefore to be
 understood that within the scope of the appended claims, the invention may
 be practiced otherwise than as specifically described and illustrated.
 EXAMPLE 7
 DiSodium 1,3 Bis 3 chloro-2 hydroxy propyl pyrophosphate is prepare by
 charging 446 Parts of Na.sub.4 P.sub.2 O.sub.7 10H.sub.2 O (1 mole) and
 178 parts H.sub.4 P.sub.2 O.sub.7 (1 mole) with 1000 parts deionized water
 to a reaction vessel and reacting the same with 320 parts epichlorohydrin
 at 60-80.degree. C. for 3-4 hours. 81.4 parts (0.2 equivalents) of the
 above reaction product is combined with a mixture of a pendant
 trimethylsilyl silicone amidoamine having an equivalent weight of 1335
 (0.05 equivalent) and 57.6 parts of N-Dimethylaminopropyl linoleamide
 (0.15 equivalents) and then diluted with 480 grams of water to a 30%
 concentration. After the solution is adjusted to a pH of 8, the reaction
 mixture is heated to 90-95.degree. C. for a period of 4-5 hours at which
 time a clear solution forms. The reaction is monitored via argentometric
 estimation for covalent chloride to ionic chloride and the reaction is
 completed in 5 hours.
 The reaction product foams well in water.
 EXAMPLE 8
 A 3-chloro-2 hydroxy propylester salt of phosphorous acid is prepared by
 charging 41 grams (0.5 mole) of phosphorus and, 409 grams of water and 50
 grams of a 50% NaOH solution (0.6 mole) to a reaction vessel and warmed to
 75.degree. C. 46.25 grams (0.5 mole) of epichlorohydrin is then added and
 the reaction mixture is heated at 75.degree. C. for 11/2 hours with
 stirring.
 196 parts of the combined epichlorohydrin-phosphite reaction mixture is
 admixed with a 50% sodium hydroxide solution to achieve a pH of 8 followed
 by adding the combination a pendant trimethylsilyl capped silicone
 amidoamine having an equivalent weight of 1335 (13.35 gram) and 27.3 parts
 of cocoyl sarcosine amidoamine (0.09 equivalents). The reaction mixture is
 diluted with water to achieve 25% solids.
 The reaction mixture is heated to 90.degree. C. for 2 hours whereupon a
 clear aqueous solution is formed.
 EXAMPLE 9
 3-Bromopropyl diacid phosphate (BrCH.sub.2 CH.sub.2 CH.sub.2 OPO(OH).sub.2)
 is prepared by reacting 3-Bromopropanol with POCI3 utilizing one
 equivalent of triethyamine in methylene chloride solvent. The Dichloride
 is isolated and hydroyzed to the diacid with water. The pH of the product
 in water is adjusted to 8 followed by the addition of an equivalent amount
 of the 50:50 combination of a trimethylsilyl capped silicone amidoamine
 having an equivalent weight of 1335 and N-Dimethyl aminopropyl derivative
 of linoleamide. The reaction mixture is adjusted with water to 30% total
 solids.
 The reaction mixture is heated for 4 hours at 90.degree. C. A clear
 solution is formed.