Polymers and their synthesis
AssigneeUnilever Home & Personal Care USA, Division of Conopco, Inc.
InventorsSusanne Henning Rogers, Brodyck James Royles, Michael Stephen White
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Abstract
The invention relates to polysaccharide graft polymers useful for incorporation as benefit agents in laundry detergent and fabric treatment compositions, and their preparation. The invention also relates to substituted polysaccharides useful as macroinitiator intermediates for the preparation of the polysaccharide graft polymers, and the preparation of the macroinitiators. The polysaccharide graft polymers may be used, for example, to impart soil release and/or fabric care benefits to laundry detergent or fabric treatment compositions.
Claims27
A substituted polysaccharide useful as a macroinitiator for preparing graft polysaccharide polymers by controlled graft polymerisation, in which at least one sugar unit of the polysaccharide is substituted by a group of the general formula
- —W—(X)p-(L)q-(Y)r-Z
- in which
- W represents a group —O— or —NR1—, where R1 represents a hydrogen atom or an optionally substituted alkyl group, preferably a hydrogen atom;
- p, q and r are each Independently 0 or 1;
- L represents an optionally substituted alkylene, cycloalkylene, arylene or heteroarylene group;
- X and Y each independently represent a group —CH2—, —CO—, —O—CO—, —CO—O—, —NH—CO—, —CO—NH—, —CH(OH)—CH2—, —CH2—CH(OH)—, —CH2—O—CO—, —CO—O—CH2—, —CH2—CO—O—, —O—CO—CH2—, —O—CO—NH—, —NH—CO—O—, —(CR2R3)s—CO—, —CO—(CR2R3)s—, —(CR2R3)t—O—, —O—(CR2R3)t—, —(CR2R3)u—SO—, —SO—(CR2R3)u—, —(CR2R3)v—SO2—, SO2—(CR2R3)v— or —NH—CO—NH, where s, t, u and v are each Independently 0, 1, 2 or 3 and R2 and R3 each independently represent a hydrogen atom or an optionally substituted alkyl group, preferably a hydrogen atom;
- and
- Z is a group of the general formula
- 12
- wherein Hal1 represents a halogen atom, preferably a chlorine or bromine atom, more preferably a bromine atom;
- w is 0, 1, 2, 3 or 4;
- R8 represents a halogen atom or an optionally substituted alkly group;
- and
- R7 represents a hydrogen atom or an optionally substituted alkyl group;
- the substituted polysaccharide having the general formula
- 13
- wherein each SU represents a sugar unit in a polysaccharide backbone;
- a represents the number of unsubstituted sugar units as a percentage of the total number of sugar units and is in the range from 0 to 999%, preferably 65 to 99%, more preferably 80 to 99%;
- b represents the number of substituted sugar units as a percentage of the total number of sugar units and is in the range from 0.1 to 100%, preferably 1 to 35%, more preferably 1 to 20%;
- m represents the degree of substitution per sugar unit and is from 1 to 3.
A substituted polysaccharide according to any one of the preceding claims in which the polysaccharide has a β-linked backbone, preferably a β-1,4-linked backbone.
A substituted polysaccharide useful as a macroinitiator for preparing graft polysaccharide polymers by controlled graft polymerisation, in which at least one sugar unit of the polysaccharide is substituted by a group of the general formula
- —W—(X)p-(L)q-(Y)r-Z
- in which
- W represents a group —O— or NR1—, where R1 represents a hydrogen atom or an optionally substituted alkyl group, preferably a hydrogen atom;
- p, q and r are each independently 0 or 1;
- L represents an optionally substituted alkylene, cycloalkylene, arylene, or heteroarylene group;
- X and Y each Independently represent a group CH2—, —CO—, —O—CO—, —CO—O—, —NH—CO—, —CO—NH—, —CH(OH)—CH2—, —CH2CH(OH)—, —CH2—O—CO—, —CO—O—CH2—, —CH2—CO—O—, —O—CO—CD2—, —O—CO—NH—, —NH—CO—O—, —(CR2R3)s—CO—, —CO—(C2R3)s—, —(CR2R3)r—O—, —NH—CO—NH, where s, t, u and v are each Independently 0, 1, 2 or 3 and R2 and R3 each independently represent a hydrogen atom or an optionally substituted alkyl group, preferably a hydrogen atom;
- and
- Z is a group of the general formula
- 14
- wherein Hal represents a halogen-atom, preferably a chlorine or bromine atom, more preferably a bromine atom;
- and
- R4 and R5 each independently represent an optionally substituted alkyl, cycloalkyl or aralkyl group;
- the substituted polysaccharide having the general formula
- 15
- wherein each SU represents a sugar unit in a polysaccharide backbone, the polysaccharide having a β-linked backbone, preferably a β-1,4-linked backbone;
- a represents the number of unsubstituted sugar units as a percentage of the total number of sugar units and is in the range from 0 to 99.9%, preferably 65 to 99%, more preferably 80 to 99%;
- b represents the number of substituted sugar units as a percentage of the total number of sugar units and is in the range from 0.1 to 100%, preferably 1 to 35%, more preferably 1 to 20%;
- m represents the degree of substitution per sugar unit and is from 1 to 3.
A substituted polysaccharide according to any one of the preceding claims in which W represents a group —O— or —NH—.
A substituted polysaccharide according to any one of the preceding claims in which q is 1 and L is a —CH2— group.
A substituted polysaccharide according to any one of the preceding claims in which p and/or r is 1 and X and/or Y represents a group —CH2—, —CO—, —CO—NH— or —NH—CO—.
A substituted polysaccharide according to any one of the preceding claims in which the polysaccharide is selected from the group consisting of cellulose, cellulose derivatives (preferably cellulose sulphate, cellulose acetate, sulphoethyl cellulose, cyanoethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethylcellulose, hydroxyethylcellulose or hydroxypropylcellulose), xyloglucans (preferably those derived from Tamarind seed gum), glucomannans (preferably Konjac glucomannan), galactomannans (preferably Locust Bean glum, Guar gum and Xanthan gum), chitosan and chitosan salt.
A substituted polysaccharide according to any one of the preceding claims, having the general formula
- 16
- wherein at least one or more —OR groups of the polymer are independently replaced by a group —W—(X)p-(L)q-(Y)r-Z, in which p, q, r, W, X, L, Y and Z are as defined in any one of the preceding claims, and at least one or more R groups am independently selected from hydrogen atoms and groups of formulae:—
- 17
- wherein each R8 is independently selected from C1-20 (preferably C1-6) alkyl, C2-20 (preferably C2-6) alkenyl (e.g. vinyl) and C5-7 aryl (e.g. phenyl) any of which is optionally substituted by one or more substituents independently selected from C1-4 allyl, C1-12 (preferably C1-4) alkoxy, hydroxyl, vinyl and phenyl groups;
- each R9 is independently selected from hydrogen and groups R8 as hereinbefore defined;
- R10 is a bond or is selected from C1-4 alkylene, C2-4 alkenylene and C5-7 arylene (e.g. phenylene) groups, the carbon atoms in any of these being optionally substituted by one or more substituents independently selected from C1-12 (preferably C1-4) alkoxy, vinyl, hydroxyl, halo and amine groups;
- each R11 is independently selected from hydrogen, counter cations such as alkali metal (preferably Na) or ½Ca or ½Mg, and groups R8 as hereinbefore defined;
- R12 is selected from C1-20 (preferably C1-6) alkyl, C2-20 (preferably C2-5) alkenyl (e.g. vinyl) and C5-7 aryl (e.g. phenyl), any of which is optionally substituted by one or more substituents independently selected from C1-4 alkyl, C1-12 (preferably C1-4) alkoxy, hydroxyl, carboxyl, cyano, sulfonato, vinyl and phenyl groups;
- x is from 1 to 3;
- and
- groups R which together with the oxygen atom forming the linkage to the respective saccharide ring forms an ester or hemi-ester group of a tricarboxylic- or higher polycarboxylic- or other complex acid such as citric acid, an amino acid, a synthetic amino acid analogue or a protein;
- any remaining R groups being selected from hydrogen and ether substituents.
A process for preparing a substituted polysaccharide as defined in any one of the preceding claims which comprises reacting a polysaccharide with a compound of the general formula
- Q-(X)p-(L)q-(Y)r-Z (III)
- wherein p, q, r, X, L, Y and Z are as defined in any one of the preceding claims and Q represents a leaving group.
A graft polysaccharide polymer useful for incorporation in laundry detergent and fabric treatment compositions, having the general formula
- 18
- Wherein which SU, a, b and m, p, q, r, W, X, L and Y are as defined in any one of the preceding claims, Z1 represents a control agent site from which a polymer may propagate during a free radical polymerisation process from which a halogen atom has been removed, P represents a polymer chain, Hal2 represents a halogen, preferably chlorine or bromine and more preferably a bromine, atom and k is from 10 to 200, preferably 10 to 100.
A graft polysaccharide polymer according to any one of claims 14 to 20, in which P represents a polymer chain which is a copolymer derived from a monomer as defined in claim 22 or claim 23 and a monomer selected from the group consisting of alkly methacrylates (e.g. stearyl methacrylate), perfluoroalkyl methacrylates (e.g. 1H,1H,2H,2H-heptadecafluorodecyl methacrylate), and siloxane methacrylates (e.g. monomethacryloxypropyl terminated polydimethysiloxane).
A process for preparing a graft polysaccharide polymer as defined in any one of claims 14 to 23 which comprises polymerising at least one free radically polymerisable monomer as defined in any one of claims 21 to 24 from the control agent site of a substituted polysaccharide according to any one of claims 1 to 13 in the presence of a transition metal compound and a ligand, and isolating the (co)polymer so formed.
A process according to any one of claims 25 to 27 in which the molecular weight of the polymer chain P is controlled to a desired point based on living-type kinetics.
Dependencies are inferred from the claim text.