Copolymerization of 1,4-dioxan-2-one and a cyclic ester monomer producing thermal stabilized 1, 4-dioxan-2-one (co) polymers
AssigneeBoard of Trustees of Michigan State University
InventorsRamani Narayan, Jean-Marie Raquez, Sunder Balakrishnan, Philippe Dubois, Philippe Degee
Life of this patent
Estimating the term…
Abstract
A polymerization process to derive a thermal-stabilized poly(1,4-dioxan-2-one) and cyclic ester monomer copolymer using a coordination-insertion catalyst/initiator. 1,4-dioxan-2-one and cyclic ester monomer, each containing less than 100-ppm water and having an acid value less than 0.5 mg KOH/g, and preferably less than 0.2 mg KOH/g, are copolymerized. Preferably the cyclic ester monomer is ε-caprolactone and the reaction is in an extruder.
Claims22
In a process for forming poly(1,4-dioxan-2-one) copolymer with a cyclic ester monomer, the improvement, which comprises:
- (i) providing a reactant mixture comprising 1,4-dioxan-2-one and a cyclic ester monomer each containing less than 100-ppm water and having an acid value less than 0.5 mg KOH/g, and an organometallic polymerization agent into a blending means, in the absence of a solvent;
- and (ii) blending the reactant mixture at a temperature between about 80° and 240° C. to form the poly(1,4-dioxan-2-one).
The process of any one of clams 1, 2 or 3 wherein the agent is a metal alkyl of the formula:
- M(Alk)y
- where Alk is an alkyl group, linear, branched or substituted with non-interfering groups containing 1 to 18 carbon atoms.
A process for forming poly(1,4-dioxan-2-one) and cyclic ester monomer copolymer, which comprises:
- (i) introducing a reactant mixture comprising 1,4-dioxan-2-one containing less than 100-ppm water and having an acid value less than 0.5 mg KOH/g, and a cyclic ester monomer containing less than 100-ppm water and having an acid value less than 0.5 mg KOH/g, and an organometallic polymerization agent into an extruder, in the absence of a solvent;
- and (ii) extruding the reactant mixture at a temperature between about 80° and 240° C. to form the poly(1,4-dioxan-2-one) and cyclic ester monomer copolymer.
The process of any one of clams 7, 8 or 9 wherein the agent is a metal alkyl of the formula:
- M(Alk)y
- where Alk is an alkyl group, linear, branched or substituted with non-interfering groups containing 1 to 18 carbon atoms.
A process for forming a poly(1,4-dioxan-2-one) and cyclic ester copolymer blended with additional ingredients, which comprises:
- (i) introducing a reactant mixture comprising 1,4-dioxan-2-one and a cyclic ester monomer each containing less than 100-ppm water and having an acid value less than 0.5 mg KOH/g, and an organometallic polymerization agent into an extruder, in the absence of a solvent;
- (ii) blending the reactant mixture at a temperature between about 80° and 240° C. to form the poly(1,4-dioxan-2-one) and cyclic ester copolymer;
- and (ii) admixing additional ingredients to the poly(1,4-dioxan-2-one) and cyclic ester copolymer selected from the group consisting of polymers, fillers and plasticizers.
The process of any one of clams 13, 14 or 15 wherein the agent is a metal alkyl of the formula:
- M(Alk)y
- where Alk is an alkyl group, linear, branched or substituted with non-interfering groups containing 1 to 18 carbon atoms.
An anhydrous poly(1,4-dioxan-2-one) copolymer which comprises a copolymerized anhydrous 1,4-dioxan-2-one, and an anhydrous cyclic ester monomer, and an organometallic polymerization agent wherein the copolymer contains less than 5% of 1,4-dioxan-2-one and cyclic ester monomer.
An anhydrous poly(1,4-dioxan-2-one) copolymer with a cyclic ester monomer comprised of a structure formula:
- wherein M is a metal selected from the group consisting of tin, titanium, zinc, aluminum, zirconium, and samarium and mixtures thereof;
- z is an integer between 1 and 4 representing a number of arms on M, attached to M;
- n is a number related to the degree of polymerization, which is between about zero and 2000 and which may be different for each arm, z;
- and R is selected from the group consisting of hydrogen, alkyls and substituted alkyls containing 1 to 18 carbon atoms, wherein the copolymer contains less than 5% of the polymerized cyclic ester monomer.
Dependencies are inferred from the claim text.