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
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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.
Claims20
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 consisting essentially of 1,4-dioxan-2-one and a cyclic ester monomer in an amount of 20 mole percent or less based upon the 1,4-dioxan-2-one each containing less than 100-ppm water and having an acid value less than 0.5 mg KOH/g, and an organometallic polymerization agent selected from the group consisting of a metal alkoxide and a metal alkyl 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) branched from the metal, wherein less than 5 wt. percent of unreacted 1,4-dioxan-2-one is present in the copolymer.
A process for forming poly(1,4-dioxan-2-one) and cyclic ester monomer copolymer, which comprises:
- (i) introducing a reactant mixture consisting essentially of 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 in an amount of 20 mole percent or less based upon the 1,4-dioxan-2-one containing less than 100-ppm water and having an acid value less than 0.5 mg KOH/g, and an organometallic polymerization agent selected from the group consisting of a metal alkoxide and a metal alkyl 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 branched from the metal, wherein less than 5 wt. percent of unreacted 1,4-dioxan-2-one is present in the copolymer.
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 in an amount of 20 mole percent or less based upon the 1,4-dioxan-2-one each containing less than 100-ppm water and having an acid value less than 0.5 mg KOH/g, and an organometallic polymerization agent selected from the group consisting of a metal alkoxide and a metal alkyl 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 branched from the metal, wherein less than 5 wt. percent of unreacted 1,4-dioxan-2-one is present in the 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, plasticizers and mixtures thereof.
An anhydrous poly(1,4-dioxan-2-one) copolymer which comprises a reaction product, a copolymerized anhydrous 1,4-dioxan-2-one, and an anhydrous cyclic ester monomer in an amount of 20 mole percent or less based upon the 1,4-dioxan-2-one, and an organometallic polymerization agent selected from the group consisting of a metal alkoxide and a metal alkyl wherein the copolymer contains less than 5% of 1,4-dioxan-2-one and cyclic ester monomer, and wherein the copolymer is branched from the metal.
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.