US 4,772,678 A · Liquid crystalline polymer compositions, process, and products

Abstract

Novel liquid crystalline extended chain polymer compositions comprising a high concentration of one or more extended chain homopolymer(s), copolymer(s), or block polymer(s) and certain strong acids are prepared by admixing a high concentration of one or more selected homo- or hetero-bifunctional monomer(s) with or without oxidation protecting atoms or groups and one or more of a substantially non-oxidizing strong acid(s) having a high or low P.sub.2 O.sub.5 content. Such compositions are capable of exhibiting excellent cohesive strength, and are especially suited to the production of high molecular weight ordered polymer fibers by dry-jet wet spinning. These liquid crystalline compositions are capable of being drawn through long air gap distances and spun at exceptionally high spin draw ratios. Fibers, films and other articles formed from these liquid crystalline compositions exhibit exceptionally high physical and heat resistant properties.

Claims114

Dependent claims

In a process for the production of a liquid crystalline extended chain polymer composition of workable viscosity which is useful in the production of polymer articles, the improvement comprises the following steps:

(a) preparing a reaction medium suitable for polymerization by incorporating a high concentration of one or more of a selected monomer(s) in a substantially non-oxidizing strong acid, said reaction medium being prepared at a preselected surface-to-volume ratio greater than about 0.2 cm.sup.-1 and substantially within the shaded phosphorus pentoxide content profile area bounded by ABEFG of FIG. 16, said concentration of monomer(s) being present in said reaction medium in sufficient amounts to achieve a polymer concentration greater than about 10 percent by weight based on the total weight of said composition;
(b) conducting polymerization of said monomer(s) substantially within the shaded phosphorus pentoxide content profile area bounded by BCDE of FIG. 16.

(a) preparing a reaction medium suitable for polymerization by incorporating a high concentration of one or more of a selected monomer(s) in a substantially non-oxidizing strong acid having a phosphorus pentoxide content of at least about 80 percent by weight based on the total weight of said strong acid, said reaction medium being prepared at a preselected surface-to-volume ratio greater than about 0.2 cm.sup.-1 and substantially within the shaded phosphorus pentoxide content profile area bounded by ABEFG of FIG. 17, said concentration of monomer(s) in said reaction medium being present in sufficient amounts to achieve a polymer concentration greater than about 10 percent by weight based on the total weight of said composition;
(b) conducting polymerization of said monomer(s) substantially within the shaded phosphorus pentoxide content profile area bounded by BCDE of FIG. 17.

(a) preparing a reaction medium suitable for polymerization by incorporating a high concentration of one or more of a selected monomer(s) in a substantially non-oxidizing strong acid having a phosphorus pentoxide content of at least about 85 percent by weight based on the total weight of said strong acid, said reaction medium being prepared at a preselected surface-to-volume ratio greater than about 0.2 cm.sup.-1 and substantially within the shaded phosphorus pentoxide content profile area bounded by ABFG of FIG. 18, said monomer(s) in said reaction medium being present in sufficient polymerizable concentration so as to produce a liquid crystalline polymer phase in said composition;
(b) conducting polymerization of said monomer(s) substantially within the shaded phosphorus pentoxide content profile area bounded by BCDE of FIG. 18.

(a) mixing at least one of a selected first homo- or hetero-bifunctional monomer(s) with or without oxidation protecting atoms or groups with a preliminary solvent of a substantially non-oxidizing strong acid having a preselected phosphorus pentoxide content,
(b) heating and optionally placing the resulting mixture under reduced pressure to promote the removal of any volatilized protecting atoms or groups present and to provide a first mixture of the first monomer(s) in the preliminary solvent,
said mixing and heating steps (a) and (b) being performed sequentially or simultaneously at a selected same or different surface-to-volume ratio(s), said steps (a) and (b) being performed under a selected same or different set of conditions of time, temperature, pressure, rate and amount of said monomer(s) addition, and rate and amount of phosphorus pentoxide addition,
said temperature(s) of steps (a) and (b) being sufficient to maintain said mixture at a workable viscosity under said selected set of conditions,
said selected surface-to-volume ratio(s) of steps (a) and (b) being sufficient to control the removal of said volatilized protecting atoms or groups under said selected set of conditions, said selected surface-to-volume ratio being greater than 0.2 cm.sup.-1,
said rate and amount of said monomer(s) addition of steps (a) and (b) being controlled to facilitate the removal of said volatilized protecting atoms or groups under said selected set of conditions,
said rate and amount of phosphorus pentoxide addition being controlled to facilitate the removal of said volatilized protecting atoms or groups and prevent decomposition of said monomer(s) due to heating under said selected set of conditions,
(c) adding at least one of a selected second monomer(s) in the resulting mixture of step (b) when said selected first monomer(s) is a homo-bifunctional monomer so as to provide a first mixture of the first and second monomers in the preliminary solvent while maintaining said first mixture of the first and second monomers at a workable viscosity,
(d) then adjusting the phosphorus pentoxide content of the mixture resulting from step (b) or (c) as necessary to provide a first or a first and second monomer reaction medium of sufficient phosphorus pentoxide content suitable for polymerization and for achieving a degree of polymerization greater than about 40 while maintaining said reaction medium at a workable viscosity,
(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(s) 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 monomers in the preliminary solvent,
(2g) then adjusting 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 sufficient 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(s) or a first and second monomers in the preliminary solvent so as to form a monomer-oligomer mixture, and then adjusting the phosphorus pentoxide content of said monomer-oligomer mixture as necessary to provide a monomer-oligomer reaction medium of sufficient 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.

15 more elements

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 a substantially non-oxidizing strong acid having a preselected phosphorus pentoxide content,
(b) heating and optionally placing the resulting mixture under reduced pressure to promote the removal any volatilized protecting atoms or groups present and to provide a first mixture of the first monomer(s) in the preliminary solvent,
said mixing and heating steps (a) and (b) being performed sequentially or simultanously at a selected same or different surface-to-volume ratio(s), said steps (a) and (b) being performed under a selected same or different set of conditions of time, temperature, pressure, rate and amount of said monomer(s) addition, and rate and amount of phosphorus pentoxide addition,
said temperature(s) of steps (a) and (b) being sufficient to maintain said mixture at a workable viscosity under said selected set of conditions,
said selected surface-to-volume ratio(s) of steps (a) and (b) being sufficient to control the removal of said volatilized protecting atoms or groups under said selected set of conditions, said selected surface-to-volume ratio being greater than 0.2 cm.sup.-1
said rate and amount of said monomer(s) addition of steps (a) and (b) being controlled to facilitate the removal of said volatilized protecting atoms or groups under said selected set of conditions,
said rate and amount of phosphorus pentoxide addition being controlled to facilitate the removal of said volatilized protecting atoms or groups and prevent decomposition of said monomer(s) due to heating under said selected set of conditions,
(c) adding at least one of a selected second monomer(s) to the resulting mixture of step (b) when said selected first monomer(s) is a homo-bifunctional monomer so as to provide a first mixture of the first and second monomers in the preliminary solvent, while maintaining said mixture of the first and second monomers at a workable viscosity,
(d) then adjusting the phosphorus pentoxide content of the mixture resulting from step (b) or (c) as necessary to provide a first or a first and second monomer reaction medium of sufficient 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 rate 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 adjusting 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(s) 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(s) or a first and second monomers in the preliminary solvent so as to form a monomer-oligomer mixture, and then adjusting the phosphorus pentoxide content of said monomer-oligomer mixture as necessary to provide a monomer-oligomer reaction medium of sufficient 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(s) 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(s) 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.

14 more elements

Dependencies are inferred from the claim text.

Liquid crystalline polymer compositions, process, and products

Life of this patent

Liquid crystalline polymer compositions, process, and products

Life of this patent

Abstract

Claims114