Novel telechelic polymers, block copolymers and processes for the preparation thereof
AssigneeThe University of Akron
InventorsJoseph P. Kennedy, Robert A. Smith, Louis R. Ross, Jr.
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Abstract
Novel telechelic halogenated polymers of cationically polymerizable olefin monomers are formed carrying from 2 to about 6 terminal halogens. The telechelic halogenated polymers are formed by reacting the monomer with an initiator transfer agent, carrying at least two tertiary halogens, and under cationic polymerization conditions. Additionally, novel thermoplastic elastomer block copolymers are formed from these telechelic halogenated polymers by reacting the latter with vinyl aromatic monomers in the presence of a coinitiator.
Claims25
A process for the synthesis of telechelic halogenated polymers comprising the steps of:
- charging a cationically polymerizable olefin monomer having from about 4 to about 12 carbon atoms per molecule and an inifer to a suitable reaction vessel, said inifer charged in a concentration from about 10.sup.-4 to about 10.sup.-1 moles per mole of said polymerizable olefin monomer;
- adding a solution of a fully chlorinated metal chloride Friedel-Crafts acid coinitiator in a solvent;
- and,
- polymerizing said olefin monomer to form said telechelic halogenated polymer;
- said inifer selected from the group consisting of AYn, BZ, and oligomers of .alpha.-chlorostyrene having from 2 to 6 units;
- where A is selected from the group consisting of condensed and noncondensed aromatic compounds having from 1 to 4 rings, and linear and branched aliphatic compounds having from 3 to 20 carbon atoms;
- where Y is represented by the formula:
- ##STR15## where R and R' are selected from the group consisting of hydrogen, methyl, and phenyl, and R and R' can be the same when A is an aromatic compound, or where R is phenyl when A is an aliphatic compound;
- where X is a halogen selected from the group consisting of fluorine, chlorine, and bromine, and where n is an integer from 2 to 6;
- and where B is selected from hydrocarbons having from 8 to 20 carbon atoms, and where Z is a tertiary halogen selected from the group consisting of tertiary fluorine, tertiary chlorine, or tertiary bromine.
A process for the synthesis of a thermoplastic block copolymer comprising the steps of:
- charging a cationically polymerizable olefin monomer having from about 4 to about 12 carbon atoms per molecule and an inifer to a suitable reaction vessel said inifer charged in a concentration from about 10.sup.-4 to about 10.sup.-1 moles per mole of said polymerizable olefin monomer;
- adding a solution of a Freidel-Crafts acid coninitiator in a solvent;
- polymerizing said olefin monomer to form a telechelic halogentated polymer;
- thereafter dissolving said telechelic polymer in said solvent;
- adding a vinyl aromatic monomer having from 8 to about 20 carbon atoms with mixing and addition of said solvent to form a homogeneous medium;
- adding a Friedel-Crafts acid coinitiator in said solvent to induce block polymerization of said vinyl aromatic monomer from said telechelic halogenated polymer to form said block copolymer;
- said inifer selected from the group consisting of AY.sub.n, BZ, and oligomers of .alpha.-chlorostyrene having from 2 to 6 units;
- where A is selected from the group consisting of condensed and noncondensed aromatic compounds having from 1 to 4 rings, linear and branched aliphatic compounds having from 3 to 20 carbon atoms;
- where Y is represented by the formula:
- ##STR16## where R and R' are selected from the group consisting of hydrogen, methyl, and phenyl, and R and R' can be the same when A is an aromatic compound, or where R is phenyl when A is an aliphatic compound;
- where X is a halogen selected from the group consisting of fluorine, chlorine, and bromine, and where n is an integer from 2 to 6;
- where B is selected from hydrocarbons having from 8 to 20 carbon atoms, and where Z is a tertiary halogen selected from the group consisting of tertiary fluorine, tertiary chlorine, or tertiary bromine.
A novel telechelic polymer formed from an inifer and a cationically polymerizable olefin monomer having from about 4 to about 12 carbon atoms, said polymer having a residue of said inifer in the backbone thereof and carrying at least two tertiary halogen termini;
- said inifer selected from the group consisting of AY.sub.n, and oligomers of .alpha.-chlorostyrene having from 2 to 6 units;
- where A is selected from the group consisting of condensed and noncondensed aromatic compounds having from 1 to 4 rings, linear and branched aliphatic compounds having from 3 to 20 carbon atoms;
- where Y is represented by the following formula:
- ##STR17## where R and R' are selected from the group consisting of hydrogen, methyl and phenyl, and R and R' can be the same when A is an aromatic compound, or where R or R' is phenyl when A is an aliphatic compound;
- where x is a halogen selected from the group consisting of fluorine, chlorine, and bromine, where n is an integer from 2 to 6.
A novel thermoplastic elastomer block copolymer comprising:
- a central elastomer moiety formed from a cationically polymerizable olefin monomer having from about 4 to about 12 carbon atoms, said elastomer moiety having at least two ends, each said end carrying;
- a glassy block polymer moiety formed from a vinyl aromatic monomer having from 8 to about 20 carbon atoms.
Dependencies are inferred from the claim text.