In one aspect, the present disclosure encompasses polymerization systems for the copolymerization of CO.sub.2 and epoxides comprising 1) a catalyst including a metal coordination compound having a permanent ligand set and at least one ligand that is a polymerization initiator, and 2) a chain transfer agent having two or more sites that can initiate polymerization. In a second aspect, the present disclosure encompasses methods for the synthesis of polycarbonate polyols using the inventive polymerization systems. In a third aspect, the present disclosure encompasses polycarbonate polyol compositions characterized in that the polymer chains have a high percentage of —OH end groups and a high percentage of carbonate linkages. The compositions are further characterized in that they contain polymer chains having an embedded polyfunctional moiety linked to a plurality of individual polycarbonate chains.

Polymers and methods of making the same are described whereby the polymers generically include one or more units each of which necessarily has a 1,2,4-substituted cyclohexane group or a 1,1,2,4-substituted cyclohexane group. According to specific disclosures herein, polymers and methods of making the same are described whereby the polymers have one or more S1 units represented by the formula: ##STR00001##
wherein n is an integer equal to or higher than 1, m is 0 or 1, A is H or CH.sub.3, and wherein each of X and Y is a specifically defined group.

Methods of recovering and/or reusing activators and/or initiators following polycarbonate synthesis may include: contacting an amine compound with a carboxylic acid compound to form a first ammonium salt including a first ammonium cation associated with a carboxylate group; mixing the first ammonium salt with a reaction solution to obtain a first solution comprising a protonated polycarbonate, an activator adduct, and a second ammonium salt in which the second ammonium cation is associated with the carboxylate group from the first ammonium salt; contacting the first solution to precipitate the polycarbonate out of solution; separating the activator adduct from the precipitated polycarbonate and the second ammonium salt to obtain a second solution; separating the precipitated polycarbonate from the second ammonium salt to recover the second ammonium salt; and separating the activator adduct from the second solution to recover an activator capable of being reused for synthesizing additional polycarbonates.

Methods of recovering and/or reusing activators and/or initiators following polycarbonate synthesis may include: contacting an amine compound with a carboxylic acid compound to form a first ammonium salt including a first ammonium cation associated with a carboxylate group; mixing the first ammonium salt with a reaction solution to obtain a first solution comprising a protonated polycarbonate, an activator adduct, and a second ammonium salt in which the second ammonium cation is associated with the carboxylate group from the first ammonium salt; contacting the first solution to precipitate the polycarbonate out of solution; separating the activator adduct from the precipitated polycarbonate and the second ammonium salt to obtain a second solution; separating the precipitated polycarbonate from the second ammonium salt to recover the second ammonium salt; and separating the activator adduct from the second solution to recover an activator capable of being reused for synthesizing additional polycarbonates.

Embodiments of the present disclosure describe a method of synthesizing a glycidyl azide homopolymer comprising contacting a glycidyl azide monomer, an initiator, and a Lewis acid sufficient to form the glycidyl azide homopolymer; wherein the glycidyl azide homopolymer is directly polymerized from the glycidyl azide monomer. Embodiments of the present disclosure further describe a method of making a glycidyl azide polymer comprising contacting one or more of a glycidyl azide monomer, an epoxide monomer, carbon dioxide, an initiator, and a Lewis acid in a reaction medium to form a glycidyl azide polymer.

Embodiments of the present disclosure describe a method of synthesizing a glycidyl azide homopolymer comprising contacting a glycidyl azide monomer, an initiator, and a Lewis acid sufficient to form the glycidyl azide homopolymer; wherein the glycidyl azide homopolymer is directly polymerized from the glycidyl azide monomer. Embodiments of the present disclosure further describe a method of making a glycidyl azide polymer comprising contacting one or more of a glycidyl azide monomer, an epoxide monomer, carbon dioxide, an initiator, and a Lewis acid in a reaction medium to form a glycidyl azide polymer.

The present invention relates to a method for preparing a high molecular weight polyether carbonate, by reacting an epoxide and carbon dioxide in the presence of a catalyst of formula (1), and a double metal cyanide (DMC) catalyst. The catalyst of formula (I) has the following structure:

##STR00001##

The present invention relates to a method for preparing a high molecular weight polyether carbonate, by reacting an epoxide and carbon dioxide in the presence of a catalyst of formula (1), and a double metal cyanide (DMC) catalyst. The catalyst of formula (I) has the following structure:

##STR00001##

A (poly)ol block copolymer of general structure B-A-(B)n, wherein block A is a polycarbonate block or polyester block, n=t−1 and t=the number of reactive end residues on block A, wherein block B is a polyethercarbonate block and wherein >70% of the copolymer chain ends are terminated by primary hydroxyl groups, and a process of producing such copolymers and products incorporating such copolymers.

A method for quenching a polymerisation process is described. The reaction of carbon dioxide with an epoxide in the presence of a bimetallic metal complex catalyst to produce a polymer comprises the quenching step of deactivation of the catalyst by contacting the catalyst with an acid effective to deactivate the catalyst. The deactivated catalyst may be removed from the polymer product by contacting the catalyst and polymer product with a solid phase and/or by precipitation; and the catalyst may also be optionally reactivated by contacting the deactivated catalyst with an anion. The acid may contain an anion effective to initiate the polymerisation process and effective to deactivate the catalyst and the molar ratio of acid to catalyst in the deactivation step may be less than or equal to 20:1 of the acid to catalyst mole ratio for the reaction.