Anionic-cationic polyion complexes comprising zwitterionic monomer component

A polyion complex formed from a cationic polymer having an overall cationic charge and an anionic polymer having an overall anionic charge, in which the anionic polymer is water soluble and is obtainable by polymerising monomers including

• a) 5 to 100% anionic monomer having an anionic or anionisable group;
• and
• b) 0 to 85 mole % zwitterionic monomer having pendant zwitterionic group;
• c) 0 to 60 mole % non ionic monomer;
• and in which the cationic polymer is water soluble and is obtainable by polymerising ethylenically unsaturated monomers including
• d) 5 to 100 mole % cationic monomer having a cationic or cationisable group;
• e) 0 to 85 mole % zwitterionic monomer having a zwitterionic pendant group;
• f) 0 to 60 mole % nonionic monomer;
• and
• in which the total moles of units in the polyion complex derivable from zwitterionic monomers in the range 1 to 70 mole %, and in which the ratio of total moles anionic groups in excess of cationic groups in anionic polymer to total moles cationic groups in excess of anionic groups of cationic polymer is in the range 1.5:1 to 1:1.5.

A polyion complex according to any preceding claim in which the zwitterionic monomer preferably has the formula VI

• YBX VI
• wherein
• B is a straight or branched alkanediyl or alkanediyloxaalkanediyl or alkanediyloligo(oxaalkanediyl) chain optionally containing one or more fluorine atoms up to and including perfluorinated chains or, if X or Y contains a terminal carbon atom bonded to B, a valence bond;
• X is the zwitterionic group;
• and
• Y is an ethylenically unsaturated polymerisable group selected from
• 7
• CH2═C(R)—CH2—O—, CH2═C(R)—CH2OC(O)—, CH2═C(R)OC(O)—, CH2═C(R)—O—, CH2═C(R)CH2OC(O)N(R11)—, R12OCCR═CRC(O)—O—, RCH═CHC(O)O—, RCH═C(COOR12)CH2—C(O)—O—,
• 8
• wherein:
• R is hydrogen or a C1-4 alkyl group;
• R11 is hydrogen or a C1-4 alkyl group or R11 is —B—X where B and X are as defined above;
• and
• R12 is hydrogen or a C1-4 alkyl group or BX where B and X are as defined above;
• A is —O— or —NR11—;
• K is a group —(CH2)pOC(O)—, —(CH2)pC(O)O —, —(CH2)pOC(O)O—, —(CH2)pNR13—, —(CH)pNR13C(O)—, —(CH)pC(O)NR13—, —(CH2)pNR13C(O)O—, —(CH2)pOC(O)NR13—, —(CH)pNR13C(O)NR13— (in which the groups R13 are the sarne or different), —(CH)pO—, —(CH)pSO3—, or, optionally in combination with B, a valence bond and p is from 1 to 12 and R13 is hydrogen or a C1-4 alkyl group.

A polyion complex according to any preceding claim in which the anionic monomer and cationic monomer each have the formula VII

• Y1B1Q VII
• in which Y1 is an ethylenically unsaturated polymerisable group selected from
• 11
• CH2═C(R15)—CH2—O—, CH2═C(R15)—CH2 OC(O)—, CH2═C(R15)OC(O)—, CH2═C(R15—, CH2—(R15)CH2OC(O)N(R15)—, R17OOCCR15═CR15C(O—O—, R15CH═CHC(O)O—, R15CH═C(COOR17)CH2—C(O)—O—,
• 12
• wherein:
• R15 is hydrogen or a C1-4 alkyl group;
• is R16 is hydrogen or a C1-4 alkyl group or R16 is B1Q where B1 and Q are as defined below;
• R17 is hydrogen or a C1-4 alkyl group or B1Q where B1 and Q are as defined below;
• A1 is —O— or —NR16—;
• K1 is a group —(CH2)rOC(O)—, —(CH2)rC(O)O—, —(CH2)rOC(O)O—, —(CH2)rNR18—, —(CH2)rNR18C(O)—, —(CH2)rC(O)NR18—, —(CH2)rNR18C(O)O—, —(CH2)rNR18C(O)NR18—, —(CH2)rNR18C(O)NR18O— (in which the groups R18 are the same or different), —(CH2)rO—, —(CH2)rSO3—, or, optionally in combination with B1, a valence bond and r is from 1 to 12 and R18 is hydrogen or a C1-4 alkyl group;
• B1 is a straight or branched alkanediyl, oxaalkylene, alkanediyloxaalkanediyl, or alkanediyloligo(oxaalkanediyl) chain optionally containing one or more fluorine atoms up to and including perfluorinated chains or, if Q or Y1 contains a terminal carbon atom bonded to B1 a valence bond;
• and
• Q is the ionic or ionisable group.

A polyion complex according to any preceding claim in which the nonionic monomer has the general formula VIII

• Y2 R14 VIII
• in which Y2 is an ethylenically unsaturated polymerisable group selected from
• 13
• CH2═C(R19-CH2—O—, CH2═C(R19)—CH2OC(O)—, CH2═C(R19)OC(O)—, CH2═C(R19)—O—, CH2═C(R19)CH2OC(O)N(R20)—, R21OOCCR19═CR19C(O)—O—, R19CH═CHC(O)O—, R19CH═C(COOR21)CH2—C(O)—O—,
• 14
• wherein:
• R19 is hydrogen or a C1-4 alkyl group;
• R20 is hydrogen or a C1-4 alkyl group or R20 is R14;
• R21 is hydrogen or a C1-4 alkyl group or R21 is R14;
• A2 is —O— or NR20—;
• K2 is a group —(CH2)8OC(O)—, —(CH2)8C(O)O—, —(CH2)8OC(O)O—, —(CH2)8NR22—, —(CH2)8NR22C(O)—, —(CH),C(O)NR22—, —(CH2)8NR22C(O)O—, —(CH2)8OC(O)NR22—, —(CH2)8NR22C(O)NR22— (in which the groups R22 are the same or different), —(CH2)8O—, —(CH2)8SO3—, or a valence bond and s is from 1 to 12 and R22 is hydrogen or a C1-4 alkyl group;
• and
• R14 is an optically substituted C1-24-alkyl or -alkenyl group, optional substituents being hydroxyl groups;
• halogen atoms;
• alkoxy and oligo-alkoxy groups, in which the alkoxy groups have 1-6, preferably 2 or 3 carbon atoms;
• aryl groups, preferably optionally substituted phenyl groups (optional substituents in a phenyl group being hydroxyl groups, halogen atoms or alkyl groups);
• acyl groups, especially C1-6-alkanoyl groups;
• acyloxy groups, especially C1-6-alkanoyloxy groups;
• or acylamino groups, especially C1-6-alkanoyl amino;
• in any ofwhich alkanoyl groups there maybe substituents selected from halogen atoms and hydroxyl and alkoxyl groups.