Claims
- 1. A shaped polyphosphazene article comprising a polyphosphazene polymer having at least one type of repeating units of the formula ##STR29## wherein R.sup.1 and R.sup.2 in the first and second side chains --OR.sup.1 and OR.sup.2 respectively represent, independently from each other, a member selected from aliphatic, cycloaliphatic and aromatic radicals; whereon on at least a portion of the surface of the article, the first and second side chains --OR.sup.1 and --OR.sup.2 in the polyphosphazene polymer located in the above-mentioned portion are converted, to an extent of at least 5 molar% thereof, to at least one type of third side chains of the formula --OR.sup.3 in which R.sup.3 represents a member selected from aliphatic, cycloaliphatic and aromatic radicals and which are different from the first and second side chains --OR.sup.1 and --OR.sup.2 ; and wherein only the surface portion of the shaped article is modified.
- 2. The shaped article as claimed in claim 1, wherein the third side chains --OR.sup.3 are formed in a degree of conversion (T) of 20 molar% or less based on the entire molar amount of the side chains --OR.sup.1, --OR.sup.2 and --OR.sup.2 in the entire article, and are in a degree of conversion (S) of 5 molar% or more based on the total molar amount of the side chains --OR.sup.1, --OR.sup.2 and --OR.sup.3 in the surface portion of the article, and the S/T ratio is 2.0 or more.
- 3. The shaped article as claimed in claim 1, which is in the form of a film.
- 4. The shaped article as claimed in claim 1, which is in the form of a wire or filament.
- 5. The shaped article as claimed in claim 1, wherein in the formula (I), R.sup.1 and R.sup.2 respectively represent independently from each other, a member selected from the group consisting of:
- (i) aliphatic and cycloaliphatic hydrocarbon radicals having 1 to 12 carbon atoms, which may be substituted by at least one fluorine atom; and
- (ii) unsubstituted or substituted aromatic hydrocarbon radicals of the formulae: ##STR30## wherein R.sup.4 represents a member selected from the group consisting of a hydrogen atom, halogen atoms, --CN radical, primary alkyl radicals having 1 to 12 carbon atoms, secondary alkyl radicals having 3 to 14 carbon atoms, .alpha.,.alpha.-dimethyl alkyl radicals having 4 to 14 carbon atoms, and unsaturated aliphatic hydrocarbon radicals having 2 to 6 carbon atoms, which radicals may contain at least one hetero atom selected from oxygen and sulfur atoms; Ar' represents a member selected from aromatic radicals of the formulae: ##STR31## A represents a member selected from oxygen and sulfur atoms; d represents zero or an integer of one; c represents an integar of 1 to 3; e represetns an integer of 1 to 4, and in the group represented by --(A).sub.d --R.sup.4 in the above-indicated formulae, R.sup.4 may be --CN or a halogen atom only when d is zero.
- 6. The shaped article as claimed in claim 1, wherein the third side chains represented by --OR.sup.3 are selected from those of the formulae: ##STR32## in which formulae R.sup.5 represents a member selected from aliphatic and cycloaliphatic radicals having 1 to 15 carbon atoms, which may have at least one member selected from ether bond structures and double bond structures; R.sup.5' represents an aromatic hydrocarbon radicals having 6 to 22 carbon atoms, which may have at least one ether bond structure; Y represents a member selected from --CH.sub.3 and --CH.sub.2 H.sub.5 ; Z represents a member selected from --OH, --COOH and ##STR33## in which R.sup.6 and R.sup.7 respectively represents, independently from each other, a member selected from the group consisting of a hydrogen atom, alkyl radicals having 1 to 4 carbon atoms which may contain at least one hetero atom selected from oxygen and sulfur atoms and interposed between carbon atoms; Z' represents at least one member selected from the group consisting of --OH, --COOH, ##STR34## in which R.sup.6 and R.sup.7 are as defined above, --CN, and halogen atoms; and p and q respectively represent, independently from each other, zero or an integer of 1 or 2.
- 7. The shaped article as claimed in claim 1, wherein the third side chains represented by --OR.sup.3 are selected from those of the formulae: ##STR35## in which formulae R.sup.5, R.sup.5', R.sup.6, and R.sup.7 are respectively as defined above, X represents a chlorine atom and R.sup.8 represents a member selected from saturated and unsaturated aliphatic hydrocarbon radicals having 2 to 34 carbon atoms, radicals of the formulae:
- --CH.sub.2).sub.i --(B)--(D), --C.sub.3 H.sub.6 B).sub.k --(D)
- and
- --CH.sub.2 CH.sub.2 B).sub.j --(D)
- wherein B represents a divalent bonding member selected from oxygen and sulfur atoms, i represents an integer of 1 to 24, j represents an integer of 1 to 12, k represents an integer of 1 to 8 and D represents a member selected from alkyl radicals having 1 to 4 carbon atoms, benzyl radical, phenyl radical, phenylalkyl radical in which the alkyl radical has 1 to 4 carbon atoms; and radicals of the formula: ##STR36## wherein R.sup.9 represents a member selected from a hydrogen atom, primary alkyl radicals having 1 to 12 carbon atoms, secondary alkyl radicals having 3 to 13 carbon atoms, .alpha.,.alpha.-dimethyl alkyl radicals having 4 to 14 carbon atoms, and unsaturated organic radicals having 2 to 12 carbon atoms, which radicals represented by R.sup.9 may contain at least one hetero atom selected from oxygen and sulfur atoms and interposed between carbon atoms.
- 8. The shaped article as claimed in claim 7 wherein the third side chains represented by ##STR37## are selected from those of the formulae: ##STR38##
- 9. The shaped article as claimed in claim 7, wherein the third side chains represented by --OR.sup.5 COOH, --OR.sup.5 OH, --OR.sup.5' CN and ----OR.sup.5' X are selected from those of the formulae: ##STR39##
- 10. The shaped article as claimed in claim 7, wherein the third side chains represented by --OR.sup.8 are selected from those of the formulae: ##STR40##
- 11. The shaped article as claimed in claim 1, wherein the repeating units of the formula (I) in the polyphosphazene polymer are in a molar amount of 50% or more.
- 12. The shaped article as claimed in claim 1, wherein the surface portion has a thickness of at least 10 angstroms.
Parent Case Info
This application is a continuation, of application Ser. No. 040,485, filed 4/20/87, now abandoned.
US Referenced Citations (2)
Foreign Referenced Citations (2)
Number |
Date |
Country |
60-87829 |
May 1985 |
JPX |
60-156505 |
Aug 1985 |
JPX |
Non-Patent Literature Citations (1)
Entry |
"Macromolecules", vol. 5, No. 2, pp. 231-232 (1972). |
Continuations (1)
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Number |
Date |
Country |
Parent |
40485 |
Apr 1987 |
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