Perfluoropolyether polymers comprising pendant functional groups

A block copolymer, copolymer (PF), comprising

• a first and a second perfluoropolyether chain [PFPE chain] each having two chain ends, wherein the first chain end of each one of said first and second PFPE chain is a chain end of copolymer (PF) and each one comprises a group selected from:
• a perfluorinated linear or branched alkyl chain having from 1 to 6 carbon atoms;
• —COOH and salts thereof with an organic cation or an inorganic cation;
• —COOR wherein R is a linear or branched alkyl chain comprising from 1 to 6 carbon atoms;
• —COF;
• —CONH2;
• —CON(R100)(R101) wherein each of R100 and R100 have the same meanings defined for R;
• —(R)cOH with c being 0 or 1;
• and R being as defined —C(O)—O—C(O)R;
• with the proviso that (i) at least one chain end of said first and second PFPE chain comprises a group different from a perfluorinated linear or branched alkyl chain having from 1 to 6 carbon atoms and (ii) when one chain end comprises group —COF, the other chain end does not comprise a perfluorinated linear or branched alkyl chain having from 1 to 6 carbon atoms or —COF;
• and the second chain ends of said first and second PFPE chain are bonded to each other via a block of formula (I):
• -[A-B]z— (I)
• wherein
• z is an integer from 1 to 100,
• (A) is a PFPE chain, and
• (B) is at least one group of formula (II):
• wherein
• n is an integer from 1 to 5;
• R1 to R4, each independently, is selected from the group consisting of —F, perfluorinated linear or branched alkyl chain having from 1 to 6 carbon atoms, and group of formula (III):
• —R10—(X)b (III)
• wherein
• R10 is a linear or branched perfluoroalkyl chain comprising from 1 to 12 carbon atoms, optionally containing one or more oxygen atoms,
• X is a functional group, selected from:
• —COOH and salts thereof with an organic cation or an inorganic cation;
• —COOR with R being a linear or branched alkyl chain comprising from 1 to 6 carbon atoms;
• —COF;
• —CON(R100)(R101) wherein each of R100 and R100 are a hydrogen atom or have the same meanings defined for R;
• —(R)cOH with c being 0 or 1 and R being a linear or branched alkyl chain comprising from 1 to 6 carbon atoms;
• —C(O)—O—C(O)R with R being a linear or branched alkyl chain comprising from 1 to 6 carbon atoms;
• —Br;
• —CN;
• and
• b is an integer equal to 1 or 2;
• wherein
• in said formula (I), said (A) and (B) are statistically (randomly) disposed;
• in formula (II), at least one of R1 to R4 is group of formula (III);
• and
• the total number of said groups B in said copolymer (PF) is from 1 to 100.

A block copolymer, copolymer (PO—O), comprising

• a first and a second perfluoropolyether chain, PFPE chain, complying with formula A or (RfO—O), wherein A is a PFPE chain and (RfO—O) is a repeating units complying with any one of formulae (i) to (v):
• (i) —CFXO—, wherein X is —F or —CF3;
• (ii) —CFXCFXO—, wherein X, equal or different at each occurrence, is —F or —CF3, with the proviso that at least one of X is —F:
• (iii) —CF2CF2CF2O—;
• (iv) —CF2CF2CF2CF2O—;
• (v) —(CF2)j—CFZ—O— wherein j is an integer from 0 to 3 and Z is a group of general formula —O—R(f-a)-T, wherein R(f-a) is a fluoropolyoxyalkene chain comprising a number of repeating units from 0 to 10, said recurring units being chosen among the following:
• —CFXO—, —CF2CFXO—, —CF2CF2CF2O—, —CF2CF2CF2CF2O—, with each of X being independently —F or —CF3 and T being a C1-C3 perfluoroalkyl alkyl chain;
• and having a peroxidic content (PO), defined as grams of active oxygen (Mw=16) in 100 g of PFPE peroxy between 0.1 and 4, each of said first and second PFPE chain having two chain ends, wherein the first chain end of each one of said first and second PFPE chain is a chain end of copolymer (P) and each one comprises a group selected from:
• a perfluorinated linear or branched alkyl chain having from 1 to 6 carbon atoms;
• —COOH and salts thereof with an organic cation or an inorganic cation;
• —COOR wherein R is a linear or branched alkyl chain comprising from 1 to 6 carbon atoms;
• —COF;
• —CONH2;
• —CON(R100)(R101) wherein each of R100 and R100 have the same meanings defined for R;
• —(R)cOH with c being 0 or 1;
• —C(O)—O—C(O)R;
• and the second chain ends of said first and second PFPE chain are bonded to each other via a block of formula (IO—O):
• -[A-B—(RfO—O)]z— (IO—O)
• wherein
• z is an integer from 1 to 100,
• (A) is a PFPE chain, and
• (B) is at least one group of formula (II):
• wherein
• n is an integer from 1 to 5;
• R1 to R4, each independently, is selected from the group consisting of, —F, perfluorinated linear or branched alkyl chain having from 1 to 6 carbon atoms, and group of formula (III):
• —R10—(X)b (III)
• wherein
• R10 is a linear or branched perfluoroalkyl chain comprising from 1 to 12 carbon atoms,
• X is a functional group;
• and
• b is an integer equal to 1 or 2;
• and
• wherein
• in formula (IO—O), A, B and (RfO—O) are statistically (randomly) disposed and
• the total number of said groups B in said copolymer (PO—O) is from 1 to 100.