Liquid crystalline polymer compositions, process, and products

An extended chain crystalline polymer having the general formulas:

• ##STR910## wherein Ar.sup.1 is ##STR911## X.sub.1 and X.sub.2 are the same or different and are sulfur, oxygen, or NR (R being hydrogen or an organic group), the nitrogen atoms and X.sub.1 and X.sub.2 being bonded to aromatic carbon atoms of Ar.sup.1, N and X.sub.1 or X.sub.2 of each hetero ring are disposed ortho to one another and Y.sup.2 is nil or is ##STR912## n being a positive integer;
• ##STR913## wherein Ar.sup.3 is ##STR914## X.sub.3 is sulfur, oxygen, or NR (R being hydrogen or an organic group), the nitrogen atoms and X.sub.3 being bonded to aromatic carbon atoms of Ar.sup.3, N and X.sub.3 of each hetero ring are disposed ortho to one another, n being a positive integer;
• ##STR915## wherein Ar.sup.1 is ##STR916## and Ar.sup.4 is ##STR917## the nitrogen atoms being bonded to aromatic carbon atoms of Ar.sup.1 and the carbon atoms being bonded to aromatic carbon atoms of Ar.sup.4, n being a positive integer;
• ##STR918## wherein Ar.sup.5 is ##STR919## the nitrogen atoms being bonded to Ar.sup.5, n being a positive integer;
• ##STR920## wherein Ar.sup.6 is ##STR921## Ar.sup.1 is ##STR922## X.sub.1 and X.sub.2 are the same or different and are sulfur, oxygen, or NR (R being hydrogen or an organic group), the NH groups and X.sub.1 and X.sub.2 being bonded to aromatic carbon atoms of Ar.sup.6 and Ar.sup.1, NH and X.sub.1 or X.sub.2 of each hetero ring are disposed ortho to one another, n being a positive integer;
• ##STR923## wherein Ar.sup.9 is ##STR924## X.sub.4 is sulfur, oxygen or NR (R being hydrogen or an organic group), the NH group and X.sub.4 being bonded to aromatic carbon atoms of Ar.sup.9, n being a positive integer;
• ##STR925## wherein Ar.sup.1 is ##STR926## Y.sup.7 is ##STR927## the nitrogen atoms being bonded to aromatic carbon atoms of Ar.sup.1 and bonded to adjacent carbon atoms of Y.sup.7, n being a positive integer;
• or ##STR928## wherein Ar.sup.1 is ##STR929## Y.sup.8 is ##STR930## X.sub.1 and X.sub.2 are the same or different and are sulfur, oxygen, or NR (R being hydrogen or an organic group), the nitrogen atoms and X.sub.1 and X.sub.2 being bonded to aromatic carbon atoms of Ar.sup.1 and adjacent carbon atoms of Y.sup.8, N and X.sub.1 or X.sub.2 of each hetero ring are disposed ortho to one another, n being a positive integer, wherein said polymers I, II, III, IV, V, VI, VII, and VIII are characterized as having a molecular weight with an n value corresponding to an intrinsic viscosity greater than about 7 dL/g as determined in methanesulfonic acid at 30.degree. C., with the proviso that when said polymer is poly([benzo-(1,2-d:4,5-d') bisthiazole-2,6-diyl]-1,4-phenylene) that the molecular weight of said poly([benzo-(1,2-d:4,5-d')bisthiazole-2,6-diyl]-1,4-phenylene) correspond to an intrinsic viscosity greater than 30.3 dL/g as determined in methanesulfonic acid at 30.degree. C.

A process for preparing a liquid crystalline extended chain polymer composition of workable viscosity which is useful in the production of fibers and films comprising the following steps:

• (a) mixing at least one of a selected first homo- or hetero- bifunctional monomer with or without oxidation protecting atoms or groups with a preliminary solvent of phosphoric acid having a relatively low phosphorus pentoxide content,
• (b) heating and optionally placing the resulting mixture under reduced pressure to remove any volatilized protecting atoms or groups present and provide a first mixture of the first monomer(s) in the preliminary solvent,
• (c) adding at least one of a selected second monomer in the resulting mixture of step (b) when said selected first monomer is a homo-bifunctional monomer so as to provide a first mixture of the first and second monomers in the preliminary solvent,
• (d) then increasing the phosphorus pentoxide content of the mixture resulting from step (b) or (c) to provide a first or a first and second monomer reaction medium of greater phosphorus pentoxide content suitable for polymerization and for achieving a degree of polymerization greater than about 40,
• (e) causing polymerization of the first or the first and second monomer(s) at a temperature sufficient to effect reaction at a rate to form a first homo-oligomeric product or a first co-oligomeric product having a preselected intrinsic viscosity, or
• (f) causing polymerization of the first or the first and second monomer(s) at a temperature sufficient to effect reaction at a rate to form a first homo-polymeric product or a first copolymeric product,
• (g) mixing a selected amount of the first homo-oligomeric product with a selected amount of at least one of a selected second homo-oligomeric product so as to form a first poly-oligomeric product, said second homo-oligomeric product being formed by like steps (a) and (b) followed by:
• (1g) adding at least one of a selected second monomer in the resulting mixture of step (b) when said selected first monomer is a homo-bifunctional monomer so as to provide a mixture of a first and second monomer in the preliminary solvent,
• (2g) then increasing the phosphorus pentoxide content of the mixture resulting from step (b) or (1g) to provide a first or a first and second monomer reaction medium of greater phosphorus pentoxide content suitable for polymerization,
• (3g) causing polymerization of the first or first and second monomer(s) at a temperature sufficient to effect reaction at a rate to form said second homo-oligomeric product having a preselected intrinsic viscosity,
• with the overall proviso that at least one of the selected monomer(s) of step (a) or (1g) which forms the second homo-oligomeric product be different from at least one of the selected monomer(s) of step (a) or (c) which forms the first homo-oligomeric product, or
• (h) mixing a selected amount of the first homo-oligomeric product with a selected amount of a second mixture of at least one of a selected first monomer or a first and second monomer in the preliminary solvent so as to form a monomer-oligomer mixture, and then increasing the phosphorus pentoxide content of said monomer-oligomer mixture to provide a monomer-oligomer reaction medium of greater phosphorus pentoxide content suitable for polymerization, said first monomer of said second mixture being formed by like steps (a) and (b) and said first and second monomer of said second mixture being formed by like steps (a), (b) and (c), with the overall proviso that at least one of the selected monomer of step (a) or (c) which forms the first or first and second monomer(s) of said second mixture, be different from at least one of the selected monomer(s) of step (a) or (c) which forms the first homo-oligomeric product,
• (i) causing polymerization of the poly-oligomeric product resulting from step (g) or the monomer-oligomer resulting from step (h) at a temperature sufficient to effect reaction at a rate to form a first block-oligomeric product having a preselected intrinsic viscosity or a first blockpolymeric product.

A process for preparing a liquid crystalline extended chain polymer composition of workable viscosity which is useful in the production of fibers and films comprising the following steps:

• (a) preparing a reaction medium suitable for polymerization, said reaction medium comprising at least one of a selected monomer and polyphosphoric acid;
• and
• (b) causing polymerization of said monomer;
• said step (a) being conducted substantially within the shaded phosphorus pentoxide content profile area bounded by ABCGHI of FIG. 14;
• and said step (b) being conducted substantially within the shaded phosphorus pentoxide content profile area bounded by DCGFE of FIG. 14.

A process for preparing a liquid crystalline extended chain homopolymer composition of workable viscosity which is useful in the production of fibers and films comprising the following steps:

• (a) mixing a selected first homo- or hetero- bifunctional monomer with or without oxidation protecting atoms or groups with a preliminary solvent of phosphoric acid having a relatively low phosphorus pentoxide content,
• (b) heating and optionally placing the resulting mixture under reduced pressure to remove any volatilized protecting atoms or groups present and provide a first mixture of the first monomer in the preliminary solvent,
• (c) adding a selected second monomer to the resulting mixture of step (b) when said selected first monomer is a homo-bifunctional monomer so as to provide a first mixture of the first and second monomer in the preliminary solvent,
• (d) then increasing the phosphorus pentoxide content of the mixture resulting from step (b) or (c) to provide a first or a first and second monomer reaction medium of greater phosphorus pentoxide content suitable for polymerization and for achieving a degree of polymerization greater than about 40,
• (e) causing polymerization of the first or the first and second monomer(s) at a temperature sufficient to effect reaction at a rate to form a first homo-oligomeric product having a preselected intrinsic viscosity, or
• (f) causing polymerization of the first or the first and second monomer(s) at a temperature sufficient to effect reaction at a rate to form a first homopolymeric product.

A process for preparing a liquid crystalline extended chain block polymer composition of workable viscosity which is useful in the production of fibers and films comprising the following steps:

• (a) mixing at least one of a selected first homo- or hetero-bifunctional monomer with or without oxidation protecting atoms or groups with a preliminary solvent of phosphoric acid having a relatively low phosphorus pentoxide content,
• (b) heating and optionally placing the resulting mixture under reduced pressure to remove any volatilized protecting atoms or groups present and provide a first mixture of the first monomer in the preliminary solvent,
• (c) adding at least one of a selected second monomer to the resulting mixture of step (b) when said selected first monomer is a homo-bifunctional monomer so as to provide a first mixture of the first and second monomers in the preliminary solvent,
• (d) then increasing the phosphorus pentoxide content of the mixture resulting from step (b) or (c) to provide a first or a first and second monomer reaction medium of greater phosphorus pentoxide content suitable for polymerization and for achieving a degree of polymerization greater than about 40,
• (e) causing polymerization of the first or the first and second monomer at a temperature sufficient to effect reaction at a ratio to form a first homo-oligomeric product or a first co-oligomeric product having a preselected intrinsic viscosity, or
• (f) mixing a selected amount of the first homo-oligomeric product with a selected amount of at least one of a selected second homo-oligomeric product so as to form a first poly-oligomeric product, said second homo-oligomeric product being formed by like steps (a) and (b) followed by:
• (1f) adding at least one of a selected second monomer in the resulting mixture of step (b) when said selected first monomer is a homo-bifunctional monomer so as to provide a mixture of a first and second monomer in the preliminary solvent,
• (2f) then increasing the phosphorus pentoxide content of the mixture resulting from step (b) or (1f) to provide a first or a first and second monomer reaction medium of greater phosphorus pentoxide content suitable for polymerization,
• (3f) causing polymerization of the first or first and second monomer(s) at a temperature sufficient to effect reaction at a rate to form said second homo-oligomeric product having a preselected intrinsic viscosity, with the overall proviso that at least one of the selected monomer of step (a) or (1f) which forms the second homo-oligomeric product be different from at least one of the selected monomer of step (a) or (c) which forms the first homo-oligomeric product, or
• (g) mixing a selected amount of the first homo-oligomeric product with a selected amount of a second mixture of at least one of a selected first monomer or a first and second monomer in the preliminary solvent so as to form a monomer-oligomer mixture, and then increasing the phosphorus pentoxide content of said monomer-oligomer mixture to provide a monomer-oligomer reaction medium of greater phosphorus pentoxide content suitable for polymerization, said first monomer of said second mixture being formed by like steps (a) and (b) and said first and second monomer of said second mixture being formed by like steps (a), (b) and (c), with the overall proviso that at least one of the selected monomer of step (a) or (c) which forms the first or first and second monomer of said second mixture, be different from at least one of the selected monomer of step (a) or (c) which forms the first homo-oligomeric product,
• (h) causing polymerization of the poly-oligomeric product resulting from step (f) or the monomer-oligomer resulting from step (g) at a temperature sufficient to effect reaction at a rate to form a first block-oligomeric product having a preselected intrinsic viscosity or a first block-polymeric product.

A process for preparing a liquid crystalline extended chain homopolymer composition of workable viscosity which is useful in the production of fibers and films comprising the following steps:

• (a) mixing a selected first homo-bifunctional monomer with or without oxidation protecting atoms or groups with a preliminary solvent of phosphoric acid having a relatively low phosphorus pentoxide content,
• (b) heating and optionally placing the resulting mixture under reduced pressure to remove any volatilized protecting atoms or groups present and provide a mixture of the first monomer in the preliminary solvent,
• (c) adding a selected second monomer in the resulting mixture of step (b) to provide a mixture of the first and second monomer in the preliminary solvent,
• (d) then increasing the phosphorus pentoxide content of the mixture resulting from step (c) to provide a first and second monomer reaction medium of greater phosphorus pentoxide content suitable for polymerization and for achieving a degree of polymerization greater than about 40,
• (e) causing polymerization of the first and second monomers at a temperature sufficient to effect reaction at a rate to form a first homo-oligomeric product having a preselected intrinsic viscosity or a first homopolymeric product.

A process for preparing a liquid crystalline extended chain block polymer composition of workable viscosity which is useful in the production of fibers and films comprising the following steps:

• (a) mixing at least one of a selected first homo-bifunctional monomer with or without oxidation protecting atoms or groups with a preliminary solvent of phosphoric acid having a relatively low phosphorus pentoxide content,
• (b) heating and optionally placing the resulting mixture under reduced pressure to remove any volatilized protecting atoms or groups present and provide a mixture of the first monomers in the preliminary solvent,
• (c) adding at least one of a selected second monomer in the resulting mixture of step (b) to provide a mixture of the first and second monomers in the preliminary solvent,
• (d) then increasing the phosphorus pentoxide content of the mixture resulting from step (c) to provide a first and second monomer reaction medium of greater phosphorus pentoxide content suitable for polymerization and for achieving a degree of polymerization greater than about 40,
• (e) causing polymerization of the first and second monomers at a temperature sufficient to effect reaction at a rate to form a first homo- or co-oligomeric product having a preselected intrinsic viscosity,
• (f) mixing a selected amount of the first homo- or co-oligomeric product with a selected amount of at least one of a selected second homo- or co-oligomeric product so as to form a first poly-oligomeric product, said second homo- or co-oligomeric product being formed by like steps (a), (b), (c), (d), and (e) with the overall proviso that at least one of the selected monomer of step (a) or (c) which forms the second homo-oligomeric product be different from at least one of the selected monomer of step (a) or (c) which forms the first homo-oligomeric product,
• (g) causing polymerization of the poly-oligomeric product at a temperature sufficient to effect reaction at a rate to form a first block-oligomeric product having a preselected intrinsic viscosity or a first blockpolymeric product.

A process for preparing a liquid crystalline extended chain block polymer composition of workable viscosity which is useful in the production of fibers and films comprising the following steps:

• (a) mixing at least one of a selected first homo-bifunctional monomer with or without oxidation protecting atoms or groups with a preliminary solvent of phosphoric acid having a relatively low phosphorus pentoxide content,
• (b) heating and optionally placing the resulting mixture under reduced pressure to remove any volatilized protecting atoms or groups present and provide a mixture of the first monomer(s) in the preliminary solvent,
• (c) adding at least one of a selected second monomer to the resulting mixture of step (b) to provide a first mixture of the first and second monomers in the preliminary solvent,
• (d) then increasing the phosphorus pentoxide content of the mixture resulting from step (c) to provide a first and second monomer reaction medium of greater phosphorus pentoxide content suitable for polymerization and for achieving a degree of polymerization greater than about 40,
• (e) causing polymerization of the first and second monomers at a temperature sufficient to effect reaction at a rate to form a first homo-oligomeric product having a preselected intrinsic viscosity,
• (f) mixing a selected amount of the first homo-oligomeric product with a selected amount of a second mixture of a different first and second monomer in the preliminary solvent, said second mixture being formed by like steps (a), (b) and (c) with the overall proviso that at least one of the selected monomers of step (a) or (c) which forms the second mixture be different from at least one of the selected monomers of step (a) or (c) which forms the first homo-oligomeric product,
• (g) then increasing the phosphorus pentoxide content of the mixture resulting from step (f) to provide a first oligomer-monomer reaction medium of greater phosphorus pentoxide content suitable for polymerization,
• (h) causing polymerization of the mixture resulting from step (g) at a temperature sufficient to effect reaction at a rate to form a first block-oligomeric product having a preselected intrinsic viscosity or a first blockpolymeric product.

A process for preparing a liquid crystalline extended chain block polymer composition of workable viscosity which is useful in the production of fibers and films comprising the following steps:

• (a) mixing at least one of a selected first hetero-bifunctional monomer with or without oxidation protecting atoms or groups with a preliminary solvent of phosphoric acid having a relatively low phosphorus pentoxide content,
• (b) heating and optionally placing the resulting mixture under reduced pressure to remove any volatilized protecting atoms or groups present and provide a mixture of the first monomer(s) in the preliminary solvent,
• (c) then increasing the phosphorus pentoxide content of the mixture resulting from step (b) to provide a first monomer reaction medium of greater phosphorus pentoxide content suitable for polymerization and for achieving a degree of polymerization greater than about 40,
• (d) causing polymerization of the first monomer at a temperature sufficient to effect reaction at a rate to form a first homo- or co-oligomeric product having a preselected intrinsic viscosity,
• (e) mixing a selected amount of the first homo- or co-oligomeric product with a selected amount of at least one of a selected second homo- or co-oligomeric product so as to form a first poly-oligomeric product, said second homo- or co-oligomeric product being formed by like steps (a) (with the proviso that the selected first monomer is a homo-bifunctional monomer) and (b) followed by:
• (1e) adding at least one of a selected second monomer in the resulting mixture of step (b) to provide a mixture of a first and second monomers in the preliminary solvent,
• (2e) then increasing the phosphorus pentoxide content of the mixture resulting from step (1e) to provide a first and second monomer reaction medium of greater phosphorus pentoxide content suitable for polymerization and for achieving a degree of polymerization greater than about 40,
• (3e) causing polymerization of the first and second monomers at a temperature sufficient to effect reaction at a rate to form said second homo- or co-oligomeric product having a preselected intrinsic viscosity, with the overall proviso that at least one of the selected monomers of step (a) or (1e) which forms the second homo- or co-oligomeric product be different from at least one of the selected monomers of step (a) which forms the first homo- or co-oligomeric product,
• (f) causing polymerization of the poly-oligomeric product at a temperature sufficient to effect reaction at a rate to form a first block-oligomeric product having a preselected intrinsic viscosity or a first blockpolymeric product.

A process for preparing a liquid crystalline extended chain block polymer composition of workable viscosity which is useful in the production of fibers and films comprising the following steps:

• (a) mixing at least one of a selected first hetero-bifunctional monomer with or without oxidation protecting atoms or groups with a preliminary solvent of phosphoric acid having a relatively low phosphorus pentoxide content,
• (b) heating and optionally placing the resulting mixture under reduced pressure to remove any volatilized protecting atoms or groups present and provide a mixture of the first monomer(s) in the preliminary solvent,
• (c) mixing a selected amount of the mixture of step (b) with a selected amount of at least one of a selected first homo-oligomeric product so as to form a first oligomeric-first monomer reaction medium, said first homo-oligomeric product being formed by like steps (a) with the proviso that the selected first monomer is a homo-bifunctional monomer) and (b) followed by:
• (1c) adding at least one of a selected second monomer to the resulting mixture of step (b) to provide a mixture of a first and second monomer in the preliminary solvent,
• (2c) then increasing the phosphorus pentoxide content of the mixture resulting from step (1c) to provide a first and second monomer reaction medium of greater phosphorus pentoxide content suitable for polymerization and for achieving a degree of polymerization greater than about 40,
• (3c) causing polymerization of the first and second monomers at a temperature sufficient to effect reaction at a rate to form said first homo-oligomeric product having a preselected intrinsic viscosity,
• (d) then increasing the phosphorus pentoxide content of the mixture resulting from step (c) to provide a reaction medium of greater phosphorus pentoxide content suitable for polymerization and for achieving a degree of polymerization greater than about 40,
• (e) causing polymerization of the first oligomer-monomer at a temperature sufficient to effect reaction at a rate to form a first block-oligomeric product having a preselected intrinsic viscosity or a first blockpolymeric product.