US 4,155,892 AGranted

Polyurethane thickeners for aqueous compositions

AssigneeRohm and Haas Company

InventorsWilliam D. Emmons, Travis E. Stevens

Life of this patent

Estimating the term…

Abstract

Latex and other aqueous systems are thickened by incorporation of a low molecular weight polyurethane characterized by at least three hydrophobic groups interconnected by hydrophilic polyether groups. The thickeners are nonionic, hydrolytically stable and are resistant to biodegradation.

Claims19

Dependent claims

A composition consisting essentially of water and an amount of a thickener polymer selected from polymers of Groups A, B and C defined below effective to thicken the water:

Group A:
a--b.sub.p --E.sub.q --B--E).sub.n B.sub.r --E.sub.t --A
where each of p, q, r and t independently is zero or 1, at least one of q and r is 1,
t is zero when r is zero, and n is at least 1;
provided that,
when q is 1, then
(a) each of p, r and t is zero;
or
(b) p is zero and each of r and t is 1;
or
(c) t is zero and each of r and p is 1;
and when q is zero, then r is 1 and each of p and t is zero;
Group B:
[h--e--och.sub.2 ].sub.s L[Q.sub.v --D.sub.u --E--A).sub.w R.sub.z ].sub.m
where L is X, Y or --O--, Q is --CH.sub.2 C, D is --CH.sub.2 O--, m is 2-4, s is zero to 2, the sum of m and s is 2-4, w is 1-3, and each of u, v and z independently is zero or 1;
and where X is a tri- or tetravalent hydrophobic hydrocarbon radical containing at least 3 carbon atoms;
and Y is a trivalent hydrophobic radical selected from
--OCONH(CH.sub.2).sub.6 N[CONH(CH.sub.2).sub.6 NHCO--O--.sub.2,
ch.sub.3 c[ch.sub.2 o--ocnhc.sub.7 h.sub.6 nhco].sub.3 and
CH.sub.3 CH.sub.2 C[CH.sub.2 O--OCNHC.sub.7 H.sub.6 NHCO].sub.3 ;
provided that,
(a) when L is X, then u and w are each 1, v and z are each zero, m is at least 2, and the sum of m and s if 4;
(b) when L is Y, then u, v and s are each zero, m is 3, w is 2-3, and z is zero or 1;
and
(c) when L is --O--, then v and u are each 1, w is 1-3, m is 2 and each of s and z is zero;
and where, in each of the polymers of Groups A and B:
A and R are hydrophobic organic radicals;
B is a divalent hydrophobic group of the structure ##STR10## where G is the residue of an organic di- or triisocyanate, said residue having no remaining unreacted isocyanate groups;
and
E is a divalent, hydrophilic, nonionic polyether group;
Group C:
A composition prepared by reacting (a) a polyfunctional reactant selected from an organic polyol having at least three hydroxyl groups, an organic polyisocyanate having at least three isocyanate groups, and mixtures thereof;
(b) a difunctional reactant selected from an organic diol, and organic diisocyanate, and mixtures thereof, said diol being present in the reaction mixture when said polyisocyanate is present and said diisocyanate being present when said polyol is present;
(c) a monofunctional hydroxyl or amino compound in an amount sufficient to cap any unreacted isocyanate remaining from the reaction of reactants (a) and (b) and to prevent gelation of the reaction mixture;
and optionally (d) an organic monoisocyanate to cap hydroxyl groups remaining from the reaction of reactants (a) and (b);
wherein at least one of said polyol and diol contains at least one water soluble polyether segment of at least 1500 molecular weight, and wherein the sum of the carbon atoms in said isocyanate-containing reactants, said hydroxyl compound and said amino compound is at least 20 and the average molecular weight of the components of the composition is about 10,000-200,000.

33 more elements

A composition consisting essentially of (a) water, (b) at least one substance selected from a water insoluble polymeric material, a cosmetically active material, a topical pharmaceutical, and a pesticidal or herbicidal toxicant, and (c) an effective amount of a thickener selected from polymers of Groups A, B and C as follows:

Group A:
a--b.sub.p --E.sub.q --B--E).sub.n 3.sub.r --E.sub.t --A
where each of p, q, r and t independently is zero or 1;
at least one of q and r is 1, t is zero when r is zero, and n is at least 1;
provided that, when q is 1, then
(a) each of p, r and t is zero;
or
(b) p is zero and each of r and t is 1;
or
(c) t is zero and each of r and p is 1;
and when q is zero, then r is 1 and each of p and t is zero;
Group B:
[h--e--och.sub.2 ].sub.s L[Q.sub.v --D.sub.u --E--A).sub.w R.sub.z ].sub.m
where L is X, Y or --O--, Q is --CH.sub.2 C.tbd., D is --CH.sub.2 O--, m is 2-4, s is zero to 2, the sum of m and s is 2-4, w is 1-3, and each of u, v and z independently is zero or 1;
and where X is a hydrocarbon radical containing at least 1 carbon atom;
and Y is a trivalent radical selected from
--OCONH(CH.sub.2).sub.6 N[CONH(CH.sub.2).sub.6 NHCO--O].sub.2
ch.sub.3 c[ch.sub.2 o--ocnhc.sub.7 h.sub.6 nhco].sub.3 and
CH.sub.3 C[CH.sub.2 O--OCNHC.sub.7 H.sub.6 NHCO].sub.3
provided that,
(a) when L is X, then u and w are each 1, v and z are each zero, m is at least 2, and the sum of m and s is 4;
(b) when L is Y, then u, v and s are each zero, m is 3, w is 2-3, and z is zero or 1;
and
(c) when L is --O--, then v and u are each 1, w is 1-3, m is 2 and each of s and z is zero;
and where, in each of the polymers of Groups A and B:
A and R are hydrophobic organic radicals;
B is a divalent hydrophobic group of the structure ##STR11## where G is the residue of an organic di- or triisocyanate, said residue having no remaining unreacted isocyanate groups;
and
E is a divalent, hydrophilic, nonionic polyether group;
Group C:
A composition prepared by reacting (a) a polyfunctional reactant selected from an organic polyol having at least three hydroxyl groups, an organic polyisocyanate having at least three isocyanate groups, and mixtures thereof;
(b) a difunctional reactant selected from an organic diol, an organic diisocyanate, and mixtures thereof, said diol being present in the reaction mixture when said polyisocyanate is present and said diisocyanate being present when said polyol is present;
(c) a monofunctional hydroxyl or amino compound in an amount sufficient to cap any unreacted isocyanate remaining from the reaction of reactants (a) and (b) and to prevent gelation of the reaction mixture;
and optionally (d) an organic monoisocyanate to cap hydroxyl groups remaining from the reaction of reactants (a) and (b);
wherein at least one of said polyol and diol contains at least one water soluble polyether segment of at least 1500 molecular weight, and wherein the sum of the carbon atoms in said isocyanate-containing reactants, said hydroxyl compound and said amino compound is at least 20 and the average molecular weight of the components of the composition is about 10,000-200,000.

32 more elements

A method of thickening a latex composition which comprises incorporating in said composition a polymer selected from polymers of Groups A, B and C as follows:

Group A:
a--b.sub.p --E.sub.q --B--E).sub.n B.sub.r --E.sub.t --A
where each of p, q, r, and t independently is zero or 1;
at least one of q and r is 1, t is zero when r is zero, and n is at least 1;
provided that,
when q is 1, then
(a) each of p, r and t is zero;
or
(b) p is zero and each of r and t is 1;
or
(c) t is zero and each of r and p is 1;
and when q is zero, then r is 1 and each of p and t is zero;
Group B:
[h--e--och.sub.2 ].sub.s L[Q.sub.v--D.sub.u --E--A).sub.w R.sub.z ].sub.m
where L is X, Y or --O--, Q is --CH.sub.2 C.tbd., D is --CH.sub.2 O--, m is 2-4, s is zero to 2, the sum of m and s is 2-4, w is 1-3, and each of u, v and z independently is zero or 1;
and where X is a tri- or tetravalent hydrocarbon radical containing at least 1 carbon atom;
and Y is a trivalent radical selected from
--OCONH(CH.sub.2).sub.6 N[CONH(CH.sub.2).sub.6 NHCO--O].sub.2,
ch.sub.3 c[ch.sub.2 o--ocnhc.sub.7 h.sub.6 nhco].sub.3 and
CH.sub.3 CH.sub.2 C[CH.sub.2 O--OCNHC.sub.7 H.sub.6 NHCO].sub.3
provided that,
(a) when L is X, then u and w are each 1, v and z are each zero, m is at least 2, and the sum of m and s is 4;
(b) when L is Y, then u, v and s are each zero, m is 3, w is 2-3, and z is zero or 1;
and
(c) when L is --O--, then v and u are each 1, w is 1-3, m is 2 and each of s and z is zero;
and where, in each of the polymers of Groups A and B:
A and R are hydrophobic organic radicals;
B is a divalent hydrophobic group of the structure ##STR12## where G is the residue of an organic di- or triisocyanate, said residue having no remaining unreacted isocyanate groups;
and
E is a divalent, hydrophilic, nonionic polyether group;
Group G:
A composition prepared by reacting (a) a polyfunctional reactant selected from an organic polyol having at least three hydroxyl groups, an organic polyisocyanate having at least three isocyanate groups, and mixtures thereof;
(b) a difunctional reactant selected from an organic diol, an organic diisocyanate, and mixtures thereof, said diol being present in the reaction mixture when said polyisocyanate is present and said diisocyanate being present when said polyol is present;
(c) a monofunctional hydroxyl or amino compound in an amount sufficient to cap any unreacted isocyanate remaining from the reaction of reactants (a) and (b) and to prevent gelation of the reaction mixture;
and optionally (d) an organic monoisocyanate to cap hydroxyl groups remaining from the reaction of reactants (a) and (b);
wherein at least one of said polyol and diol contains at least one water soluble polyether segment of at least 1500 molecular weight, and wherein the sum of the carbon atoms in said isocyanate-containing reactants, said hydroxyl compound and said amino compound is at least 20 and the average molecular weight of the components of the composition is about 10,000-200,000.

33 more elements

A method of thickening an aqueous composition consisting essentially of (a) water and (b) at least one substance selected from a water insoluble polymeric material, a cosmetically active material, a topical pharmaceutical, and a pesticidal or herbicidal toxicant, which method comprises incorporating in said dispersion a polymer selected from polymers of Groups A, B and C as follows:

Group A:
a--b.sub.p --E.sub.q --B--E).sub.n B.sub.r --E.sub.t --A
where each of p, q, r and t independently is zero or 1;
at least one of q and r is 1, t is zero when r is zero, and n is at least 1;
provided that,
when q is 1, then
(a) each of p, r and t is zero;
or
(b) p is zero and each of r and t is 1;
or
(c) t is zero and each of r and p is 1;
and when q is zero, then r is 1 and each of p and t is zero;
Group B:
[h--e--och.sub.2 ].sub.s L[Q.sub.v --D.sub.u --E--A).sub.w R.sub.z ].sub.m
where L is X, Y or --O--, Q is --CH.sub.2 C.tbd., D is --CH.sub.2 O--, m is 2-4, s is zero to 2, the sum of m and s is 2-4, w is 1-3, and each of u, v and z independently is zero or 1;
and where X is a hydrocarbon radical containing at least 1 carbon atom;
and Y is a trivalent hydrophobic radical selected from
--OCONH(CH.sub.2).sub.6 N[CONH(CH.sub.2).sub.6 NHCO--O].sub.2,
ch.sub.3 c[ch.sub.2 o--ocnhc.sub.7 h.sub.6 nhco].sub.3 and
CH.sub.3 CH.sub.2 C[CH.sub.2 O--OCNHC.sub.7 H.sub.6 NHCO].sub.3 ;
provided that,
(a) when L is X, then u and w are each 1, v and z are each zero, m is at least 2, and the sum of m and s is 4;
(b) when L is Y, then u, v and s are each zero, m is 3, w is 2-3, and z is zero or 1;
and
(c) when L is --O--, then v and u are each 1, w is 1-3, m is 2 and each of s and z is zero;
and where, in each of the polymers of Groups A and B:
A and R are hydrophobic organic radicals;
B is a divalent hydrophobic group of the structure ##STR13## where G is the residue of an organic di- or triisocyanate, said residue having no remaining unreacted isocyanate groups;
and
E is a divalent, hydrophilic, nonionic polyether group;
Group C:
A composition prepared by reacting (a) a polyfunctional reactant selected from an organic polyol having at least three hydroxyl groups, an organic polyisocyanate having at least three isocyanate groups, and mixtures thereof;
(b) a difunctional reactant selected from an organic diol, an organic diisocyanate, and mixtures thereof, said diol being present in the reaction mixture when said polyisocyanate is present and said diisocyanate being present when said polyol is present;
(c) a monofunctional hydroxyl or amino compound in an amount sufficient to cap any unreacted isocyanate remaining from the reaction of reactants (a) and (b) and to prevent gelation of the reaction mixture;
and optionally (d) an organic monoisocyanate to cap hydroxyl groups remaining from the reaction of reactants (a) and (b);
wherein at least one of said polyol and diol contains at least one water soluble polyether segment of at least 1500 molecular weight, and wherein the sum of the carbon atoms in said isocyanate-containing reactants, said hydroxyl compound and said amino compound is at least 20 and the average molecular weight of the components of the composition is about 10,000-200,000.

33 more elements

Dependencies are inferred from the claim text.

Facts

Application: 05/838,690Filed 3 Oct 1977 · division
Priority: 3 Oct 1975
Granted: 22 May 1979
Term ends: Not estimatedThe source records don’t support an estimate.

Classification25 codes

D21H 19/62
Characterised by the other ingredients, e.g. the binder or dispersing agent: macromolecular organic compounds or oligomers thereof obtained…
A01N 25/10
Containing solids as carriers or diluents: macromolecular compounds
A61K 8/87
Obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds: polyurethanes
A61K 47/34
Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates: macromolecular compounds obtained otherwise than by reactions only…

Family

Serial619,549Parent of this continuation-in-part · filed 3 Oct 1975
Serial686,751Parent of this division · filed 17 May 1976
US 4,079,028 AParent of this division
US 4,155,892 AThis patent

From the US filing history. Foreign family members aren’t listed.

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Abstract

A composition consisting essentially of water and an amount of a thickener polymer selected from polymers of Groups A, B and C defined below effective to thicken the water:

Group A:
a--b.sub.p --E.sub.q --B--E).sub.n B.sub.r --E.sub.t --A
where each of p, q, r and t independently is zero or 1, at least one of q and r is 1,
t is zero when r is zero, and n is at least 1;
provided that,
when q is 1, then
(a) each of p, r and t is zero;
or
(b) p is zero and each of r and t is 1;
or
(c) t is zero and each of r and p is 1;
and when q is zero, then r is 1 and each of p and t is zero;
Group B:
[h--e--och.sub.2 ].sub.s L[Q.sub.v --D.sub.u --E--A).sub.w R.sub.z ].sub.m
where L is X, Y or --O--, Q is --CH.sub.2 C, D is --CH.sub.2 O--, m is 2-4, s is zero to 2, the sum of m and s is 2-4, w is 1-3, and each of u, v and z independently is zero or 1;
and where X is a tri- or tetravalent hydrophobic hydrocarbon radical containing at least 3 carbon atoms;
and Y is a trivalent hydrophobic radical selected from
--OCONH(CH.sub.2).sub.6 N[CONH(CH.sub.2).sub.6 NHCO--O--.sub.2,
ch.sub.3 c[ch.sub.2 o--ocnhc.sub.7 h.sub.6 nhco].sub.3 and
CH.sub.3 CH.sub.2 C[CH.sub.2 O--OCNHC.sub.7 H.sub.6 NHCO].sub.3 ;
provided that,
(a) when L is X, then u and w are each 1, v and z are each zero, m is at least 2, and the sum of m and s if 4;
(b) when L is Y, then u, v and s are each zero, m is 3, w is 2-3, and z is zero or 1;
and
(c) when L is --O--, then v and u are each 1, w is 1-3, m is 2 and each of s and z is zero;
and where, in each of the polymers of Groups A and B:
A and R are hydrophobic organic radicals;
B is a divalent hydrophobic group of the structure ##STR10## where G is the residue of an organic di- or triisocyanate, said residue having no remaining unreacted isocyanate groups;
and
E is a divalent, hydrophilic, nonionic polyether group;
Group C:
A composition prepared by reacting (a) a polyfunctional reactant selected from an organic polyol having at least three hydroxyl groups, an organic polyisocyanate having at least three isocyanate groups, and mixtures thereof;
(b) a difunctional reactant selected from an organic diol, and organic diisocyanate, and mixtures thereof, said diol being present in the reaction mixture when said polyisocyanate is present and said diisocyanate being present when said polyol is present;
(c) a monofunctional hydroxyl or amino compound in an amount sufficient to cap any unreacted isocyanate remaining from the reaction of reactants (a) and (b) and to prevent gelation of the reaction mixture;
and optionally (d) an organic monoisocyanate to cap hydroxyl groups remaining from the reaction of reactants (a) and (b);
wherein at least one of said polyol and diol contains at least one water soluble polyether segment of at least 1500 molecular weight, and wherein the sum of the carbon atoms in said isocyanate-containing reactants, said hydroxyl compound and said amino compound is at least 20 and the average molecular weight of the components of the composition is about 10,000-200,000.

33 more elements

Facts

Application

05/838,690Filed 3 Oct 1977 · division

Priority

3 Oct 1975

Granted

22 May 1979

Term ends

Not estimatedThe source records don’t support an estimate.

Classification25 codes

D21H 19/62
Characterised by the other ingredients, e.g. the binder or dispersing agent: macromolecular organic compounds or oligomers thereof obtained…
A01N 25/10
Containing solids as carriers or diluents: macromolecular compounds
A61K 8/87
Obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds: polyurethanes
A61K 47/34
Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates: macromolecular compounds obtained otherwise than by reactions only…