Rapid bulk polymerization of polybutadiene/nylon and related block copolymers

Claim 2

A process for the rapid bulk polymerization of polybutadiene/nylon-6 block copolymers comprising the steps of: preparing a mixture comprising from about 100 to about 50 parts by weight of a polybutadiene having a weight average molecular weight of about 3000 and terminated by a compound selected from the group consisting of isocyanates and isothiocyanates and end-capped with caprolactam to provide a stable imide type terminated polymer, with more than 0 to about 50 parts by weight of a branched high vinyl, 1,2-polybutadiene having a weight average molecular weight greater than 100,000 and neutralized with caprolactam; charging said polymer mixture, without hydrolyzing said end-capped polybutadiene, to a reaction vessel with caprolactam; and polymerizing said caprolactam at a temperature of at least about 120° C. said temperature being sufficient to flash off any solvents introduced during said step of preparing and for a time of up to about 30 minutes whereby polymerization proceeds in the absence of solvents to form a block copolymer with said end-capped polybutadiene.

Claim 3

A process, as set forth in claim 1, wherein said step of preparing a mixture comprises the steps of: anionically polymerizing 1,2-butadiene to form an active polybutadiene segment; terminating said polybutadiene segment with a compound selected from the group consisting of isocyanates and isothiocyanates; and end-capping said polybutadiene with caprolactam.

Claim 4

A process, as set forth in claim 1, including the further steps of: forming pellets of said block copolymer; and subjecting said pellets to a surface treatment whereby a coating of said pellets is provided to remove tack.

Claim 5

A process, as set forth in claim 3, wherein said step of subjecting said pellets includes immersing said pellets in an aqueous solution containing at least one member of the group consisting of Br 2 , Cl 2 , NaOCl, KOCl, Ca(OCl) 2 , KMnO 4 , K 2 Cr 2 O 7 , H 2 O 2 and OsO 4 .

Claim 6

A process, as set forth in claim 4, wherein said aqueous solution contains HCl and at least one member of the group consisting of NaOCl, KOCl, Ca(OCl) 2 , KMnO 4 and K 2 Cr 2 O 7 .

Claim 7

A process, as set forth in claim 3, wherein said step of subjecting said pellets comprises oxidation with an aqueous solution.

Claim 8

A process, as set forth in claim 3, wherein said step of subjecting said pellets comprises halogenation with an aqueous solution.

Claim 9

A process, as set forth in claim 3, wherein said step of subjecting said pellets comprises hydroxylation with an aqueous solution.

Claim 10

A process, as set forth in claim 3, wherein said step of subjecting said pellets includes coating said pellets with a finely powdered filler material.

Claim 11

A process for the rapid bulk polymerization of block copolymers comprising the steps of: preparing a mixture comprising from about 100 to 50 parts by weight of a stable, cold flowing rubber prepared by the anionic polymerization of monomers selected from the group consisting of olefin, conjugated diene, vinyl substituted aromatic, vinyl substituted pyridine, vinyl substituted quinoline, ##STR3## where A is O or S and R is H or an aliphatic, cycloaliphatic or aromatic group containing from 1 to 15 carbon atoms, inclusive, RCH═A where A is O or S and R is an aliphatic, cycloaliphatic or aromatic group containing from 1 to 15 carbon atoms, inclusive, ##STR4## where A is O or S and R is an aliphatic, cycloaliphatic or aromatic group containing from 1 to 15 carbon atoms, inclusive, and (R).sub.2 C═S where R is an aliphatic, cycloaliphatic or aromatic group containing from 1 to 15 carbon atoms, inclusive; and wherein said cold flowing rubber is end-capped by a compound selected from the group consisting of isocyanates and isothiocyanates and terminated with an amide containing compound providing a stable imide type terminated rubber, and more than 0 to 50 parts by weight of a dry non-cold flowing rubber selected from the group consisting of ethylene-propylene-hexadiene terpolymers, natural rubber, unvulcanized styrene-butadiene rubber, butyl rubber, branched high vinyl butadiene rubber having a weight average molecular weight greater than 100,000, polynorbornene, polypentamer and thermoplastic elastomers comprising block copolymers of styrene and conjugated dienes, and neutralized with an amide containing compound; charging said polymer mixture without hydrolyzing said end-capped cold flowing rubber to a reaction vessel with a monomer having an active hydrogen other than a monomer utilized to form a polymer present in said polymer mixture; and polymerizing said monomer at a temperature of at least about 120° C. said temperature being sufficient to flash off any solvents introduced during said step of preparing and for a time of up to about 30 minutes whereby polymerization proceeds in the absence of solvents to form a block copolymer with said end-capped polymer.

Claim 12

A process for the rapid bulk polymerization of block copolymers comprising the steps of: preparing a mixture comprising from about 100 to 50 parts by weight of a stable, cold flowing rubber prepared by the anionic polymerization of monomers selected from the group consisting of olefin, conjugated diene, vinyl substituted aromatic, vinyl substituted pyridine, vinyl substituted quinoline, ##STR3## where A is O or S and R is H or an aliphatic, cycloaliphatic or aromatic group containing from 1 to 15 carbon atoms, inclusive, RCH═A where A is O or S and R is an aliphatic, cycloaliphatic or aromatic group containing from 1 to 15 carbon atoms, inclusive, ##STR4## where A is O or S and R is an aliphatic, cycloaliphatic or aromatic group containing from 1 to 15 carbon atoms, inclusive, and (R).sub.2 C═S where R is an aliphatic, cycloaliphatic or aromatic group containing from 1 to 15 carbon atoms, inclusive; and wherein said cold flowing rubber is end-capped by a compound selected from the group consisting of isocyanates and isothiocyanates and terminated with an amide containing compound providing a stable imide type terminated rubber, and more than 0 to 50 parts by weight of a dry non-cold flowing rubber selected from the group consisting of ethylene-propylene-hexadiene terpolymers, natural rubber, unvulcanized styrene-butadiene rubber, butyl rubber, branched high vinyl butadiene rubber having a weight average molecular weight greater than 100,000, polynorbornene, polypentamer and thermoplastic elastomers comprising block copolymers of styrene and conjugated dienes, and neutralized with an amide containing compound; charging said polymer mixture without hydrolyzing said end-capped cold flowing rubber to a reaction vessel with a monomer having an active hydrogen other than a monomer utilized to form a polymer present in said polymer mixture; and polymerizing said monomer at a temperature of at least about 120° C. said temperature being sufficient to flash off any solvents introduced during said step of preparing and for a time of up to about 30 minutes whereby polymerization proceeds in the absence of solvents to form a block copolymer with said end-capped polymer.

Claim 13

A process, as set forth in claim 10, wherein said cold flowing rubber comprises low molecular weight polybutadiene having a weight average molecular weight of about 3000.

Claim 14

A process, as set forth in claim 10, wherein said non-cold flowing rubber is a branched high vinyl, high molecular weight, 1,2-polybutadiene.

Claim 15

A process, as set forth in claim 10, wherein said monomer having an active hydrogen is selected from the group consisting of lactams, ureas, urethanes and imides.

Claim 16

A process, as set forth in claim 13, wherein said monomer is caprolactam.

Claim 17

A process, as set forth in claim 10, including the further steps of: forming pellets of said block copolymer; and subjecting said pellets to a surface treatment whereby a coating of said pellets is provided to remove tack.

Claim 18

A process, as set forth in claim 15, wherein said step of subjecting said pellets includes immersing said pellets in an aqueous solution containing at least one member of the group consisting of Br 2 , Cl 2 , NaOCl, KOCl, Ca(OCl) 2 , KMnO 4 , K 2 Cr 2 O 7 , H 2 O 2 and OsO 4 .

Claim 19

A process, as set forth in claim 16, wherein said aqueous solution contains HCl and at least one member of the group consisting of NaOCl, KOCl, Ca(OCl) 2 , KMnO 4 and K 2 Cr 2 O 7 .

Claim 20

A process, as set forth in claim 15, wherein said step of subjecting said pellets comprises oxidation with an aqueous solution.

Claim 21

A process, as set forth in claim 15, wherein said step of subjecting said pellets comprises halogenation with an aqueous solution.

Claim 22

A process, as set forth in claim 15, wherein said step of subjecting said pellets comprises hydroxylation with an aqueous solution.

Claim 23

A process, as set forth in claim 15, wherein said step of subjecting said pellets includes coating said pellets with a finely powdered filler material.