Monsanto Company

Victor D Papanu

Marvin M Crutchfield

David R Dyroff

Craig B Warren

Charles J Upton

Gary J Lynch

The disclosure relates to pharmaceutically acceptable amide-imide derivatives of low molecular weight homopolymers of itaconic anhydride having antitumor activity.

Polymeric antitumor agent

A polyacetal carboxylate is provided having the following empirical formula: ##STR1## where M is selected from the group consisting of akali metal, ammonium, tetra-alkyl ammonium groups and alkanol ammonium groups, and n averages at least 4. Such polyacetal carboxylates can be used as complexing agents and detergency builders.

Polyacetal carboxylates

The alkali metal, ammonium and alkanol amine salts of acetal carboxylate polymers are known to be stable detergent builders and chelating agents which depolymerize in acid media making the polymer fragments more readily biodegradable in waste streams. Now, according to the present invention, the hydrolytic stability of an acetal carboxylate polymer can be controlled by bringing together under polymerization conditions an ester of glyoxylic acid and a polymerization initiator and adding to the termini of the resulting polymer end groups having substituents which are selected to be more electron withdrawing as the desired hydrolytic stability increases.

Selectively controlling the hydrolytic stability of acetal carboxylate

The alkali metal, ammonium and alkanol amine salts of polymeric acetal carboxylates are stable detergent builders and chelating agents. Now, in the improved process of the present invention for preparing an acetal carboxylate polymer wherein a glyoxylate ester and a polymerization initiator are brought together under polymerization conditions and a chemically stable end group is added to the termini of the resulting polymer to stabilize the polymer against rapid depolymerization in alkaline solution, the improvement comprises contacting the resulting polymer in the presence of an acid catalyst with a sufficient amount of an acetal having 3 to 20 carbon atoms to stabilize the resulting polymer against rapid depolymerization in alkaline solution, and an agent to remove liberated alcohol.

Stabilization of polymeric acetal carboxylates using an acetal

The alkali metal, ammonium and alkanol ammonium salts of polymeric acetal carboxylates are stable detergent builders under laundry use conditions but depolymerize in acid media, making the polymer fragments more readily biodegradable in waste streams. Such polymeric acetal carboxylates can now be made by the process of the present invention which comprises:

Process for the preparation of polymeric acetal carboxylates

The alkali metal, ammonium and alkanol ammonium salts of polymeric acetal carboxylates are stable detergent builders under laundry use conditions but depolymerize at lower pH, making the polymer fragments more readily biodegradable in waste streams. Such polymeric acetal carboxylates can now be made by an improved process which includes the steps of bringing together in a reaction zone under polymerization conditions an ester of glyoxylic acid and a polymerization initiator, and adding an alkyl vinyl ether to the resulting polymer in the presence of a solvent having a dielectric constant of at least 15, such as an alkyl nitrile and a haloacetic acid catalyst, such as trifluoroacetic acid, to stabilize the polymer against rapid depolymerization in alkaline solution. The preferred solvent is acetonitrile.

The alkali metal, ammonium and alkanol ammonium salts of polymeric acetal carboxylates are stable detergent builders under laundry use conditions but depolymerize in mildly acidic media, making the polymer fragments more readily biodegradable in waste streams. Such polymeric acetal carboxylates can now be made by a process which comprises bringing together in a reaction zone under polymerization conditions an ester of glyoxylic acid and a polymerization initiator, and adding to the resulting polymer an alkyl vinyl ether and an organoaluminum compound to stabilize the resulting polymer against rapid depolymerization in alkaline solution. The preferred alkyl vinyl ether is ethyl vinyl ether, and the preferred organoaluminum compounds are alkyl aluminum halides and trialkyl aluminum.

Preparation of polymeric acetal carboxylates using organoaluminum

The alkali metal, ammonium and alkanol ammonium salts of polymeric acetal carboxylates are stable detergent builders under laundry use conditions but depolymerize in acid media, making the polymer fragments more readily biodegradable in waste streams. Such polymeric acetal carboxylates can now be made by a process which comprises bringing together in a reaction zone under polymerization conditions an ester of glyoxylic acid and a molecular sieve, and adding an alkyl vinyl ether to the resulting polymer in the presence of the molecular sieve to stabilize the polymer against rapid depolymerization in alkaline solution. The preferred alkyl vinyl ether is ethyl vinyl ether.

Preparation of polymeric acetal carboxylates using molecular sieves

A detergent composition is provided which comprises at least 5 percent by weight of a surfactant selected from the group consisting of anionic, nonionic, zwitterionic, ampholytic and amphoteric surfactants; and at least 1 weight percent of a copolymer having the following general formula ##STR1## where Y is one or more comonomers selected from the group consisting of olefins and aldehydes having from 1 to about 3 carbon atoms; n averages at least 2; p is at least 1; and M is selected from the group consisting of alkali metal, ammonium and alkanol ammonium groups having 1 to about 4 carbon atoms in the alkyl chain; R.sub.1 and R.sub.2 are individually any chemically stable group which stabilize the polymer against rapid depolymerization in alkaline solution. The copolymers are stable under laundry use conditions, but depolymerize in acid media, making the fragments more readily biodegradable in waste streams.

Copolymers of keto dicarboxylates

Copolymers of acetal carboxylates are provided which have the following empirical formula ##STR1## where Y is one or more comonomers randomly distributed in the copolymer; the product of n and q averages at least 4; p is at least 1; and M is selected from the group consisting of alkali metal, ammonium, alkyl groups having 1 to about 4 carbon atoms, and alkanol ammonium groups having 1 to about 4 carbon atoms in the alkyl chain. Such copolymers are useful as detergent builders to replace sodium tripolyphosphate (STP) in detergent formulations. The copolymers are stable under laundry use conditions, but depolymerize in acid media, making the fragments more readily biodegradable in waste streams.

Copolymers of acetal carboxylates

Ether carboxylates represented by the formula: ##STR1## wherein R.sub.1 and R.sub.2 are individually selected from the group consisting of alkyl containing up to 20 carbon atoms and M.sub.1 and M.sub.2 are individually selected from the group consisting of alkyl containing up to about 4 carbon atoms, are useful as intermediates to prepare the corresponding acid or alkali metal, ammonium and alkanol amine salts, which are useful as chelants, sequestrants and detergent builders.

Ether dicarboxylates

Copolymers of keto dicarboxylates are provided which have the following general formula ##STR1## WHERE Y is one or more comonomers; n averages at least 2; p is at least 1; and M is selected from the group consisting of alkali metal, ammonium, alkyl groups having 1 to about 4 carbon atoms, and alkanol amine groups having 1 to about 4 carbon atoms in the alkyl chain. Such copolymers are useful as detergent builders to replace sodium tripolyphosphate (STP) in detergent formulations. The copolymers are stable under laundry use conditions, but depolymerize in acid media, making the fragments more readily biodegradable in waste streams.

Ether and acetal carboxylates useful as detergent builders to replace sodium tripolyphosphate (STP) in detergent formulations are known to the art. Certain polymeric polycarboxylates are also known to the art but all of these products suffer from either having poor builder properties or they are not readily biodegradable. According to the present invention, new and novel polyacetal carboxylates are provided which are stable under laundry use conditions, but depolymerize in acid media, making the fragments more readily biodegradable in waste streams.

Detergent compositions comprising polyacetal carboxylates

Ether and acetal carboxylates useful as detergent builders to replace sodium tripolyphosphate (STP) in detergent formulations are known to the art. According to the present invention, new and novel polymeric acetal carboxylates are provided which are stable under laundry use conditions, but depolymerize in acid media, making the polymer fragments more readily biodegradable in waste streams.

Growing community of inventors

Maryland Heights, MO, United States of America

Victor D Papanu