A polypropylene carbonate) polyol composition characterized in that the composition has: i. at least 95% -OH end groups; ii. a glass transition temperature (Tg) from about -20°C to about 60 °C; iii. a polydispersity index (PDI) less than 2; iv. a Mn less than 15 kDa; and v. greater than 95% carbonate linkages between adjacent monomer units in the polycarbonate chains; wherein all parameters are determined as indicated in the specification; and the composition comprises polymer chains denoted P 1 having the formula T-Y-A-(Y-T) n wherein: each -T is a polycarbonate chain having a formula independently selected from the group consisting of: wherein: (i) E is a C 3 unit derived from propylene oxide; p ranges from about 5 to about 75; each Y group comprises one or multiple repeating groups of a C 1-4 ether moiety; -A- is a multivalent moiety; and n is from 2 to 10 inclusive; and the -Y-A-(Y-) n moiety is derived from a polyol having three, four, five or six hydroxyl groups; or (ii) E is a C 3 unit derived from propylene oxide; p ranges from about 5 to about 75; each Y group is independently the bound form of a functional group capable of initiating chain growth of epoxide CO 2 copolymers, optionally comprising one or multiple repeating units of a bivalent C 2-5 , straight or branched, saturated hydrocarbon chain, wherein one methylene unit of each hydrocarbon group is replaced with -O-; -A- is a polyester; and n is from 1 to 10 inclusive. i. at least 95% -OH end groups; ii. a glass transition temperature (Tg) from about -20°C to about 60 °C; iii. a polydispersity index (PDI) less than 2; iv. a Mn less than 15 kDa; and v. greater than 95% carbonate linkages between adjacent monomer units in the polycarbonate chains; wherein all parameters are determined as indicated in the specification; and (i) E is a C 3 unit derived from propylene oxide; p ranges from about 5 to about 75; each Y group comprises one or multiple repeating groups of a C 1-4 ether moiety; -A- is a multivalent moiety; and n is from 2 to 10 inclusive; and the -Y-A-(Y-) n moiety is derived from a polyol having three, four, five or six hydroxyl groups; or p ranges from about 5 to about 75; each Y group comprises one or multiple repeating groups of a C 1-4 ether moiety; -A- is a multivalent moiety; and n is from 2 to 10 inclusive; and the -Y-A-(Y-) n moiety is derived from a polyol having three, four, five or six hydroxyl groups; or (ii) E is a C 3 unit derived from propylene oxide; p ranges from about 5 to about 75; each Y group is independently the bound form of a functional group capable of initiating chain growth of epoxide CO 2 copolymers, optionally comprising one or multiple repeating units of a bivalent C 2-5 , straight or branched, saturated hydrocarbon chain, wherein one methylene unit of each hydrocarbon group is replaced with -O-; -A- is a polyester; and n is from 1 to 10 inclusive. p ranges from about 5 to about 75; each Y group is independently the bound form of a functional group capable of initiating chain growth of epoxide CO 2 copolymers, optionally comprising one or multiple repeating units of a bivalent C 2-5 , straight or branched, saturated hydrocarbon chain, wherein one methylene unit of each hydrocarbon group is replaced with -O-; -A- is a polyester; and n is from 1 to 10 inclusive. <EOS>