Polycarbonate polyol compositions and methods

Patent metadata

Field	Value
Publication number	US-9850345-B2
Application number	US-201615191901-A
Country	US
Kind code	B2
Filing date	Jun 24, 2016
Priority date	May 24, 2012
Publication date	Dec 26, 2017
Grant date	Dec 26, 2017

Abstract

In one aspect, the present disclosure encompasses polymerization systems for the copolymerization of CO 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 one or more sites capable of initiating copolymerization of epoxides and CO 2 , wherein the chain transfer agent contains one or more masked hydroxyl groups. 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, a high percentage of carbonate linkages, and substantially all polycarbonate chains having hydroxyl end groups have no embedded chain transfer agent.

First claim

What is claimed is:

1. A polymerization system for the copolymerization of CO 2 and epoxides, the system comprising:
a metal complex including a permanent ligand set and at least one ligand that is a polymerization initiator, and
a chain transfer agent having one or more sites capable of initiating copolymerization of epoxides and CO 2 , wherein the chain transfer agent contains one or more masked hydroxyl groups,
wherein the chain transfer agent is selected from the group consisting of methanol, t-butanol, allyl alcohol, and benzyl alcohol.

2. A polymerization system for the copolymerization of CO 2 and epoxides, the system comprising:
a metal complex including a permanent ligand set and at least one ligand that is a polymerization initiator, and

a chain transfer agent having one or more sites capable of initiating copolymerization of epoxides CO 2 , wherein the chain transfer agent contains a masked hydroxyl group, wherein the chain transfer agent is a hydroxy acid, wherein any hydroxyl group of the hydroxy acid capable of initiating copolymerization of epoxides and CO 2 is protected.

3. The polymerization system of claim 2 ,
wherein the hydroxy acid is selected from the group consisting of:

where each R PG is independently a hydroxyl protecting group.

4. The polymerization system of claim 1 or 2 , wherein the metal complex has the formula L p -M-(L I ) n , where L p is a permanent ligand set, M is a metal atom, L I is a ligand that is a polymerization initiator, and n is an integer between 0 and 2, inclusive, representing the number of initiating ligands present; and
wherein M is selected from the group consisting of Cr, Mn, V, Fe, Co, Mo, W, Ru, Al, and Ni.

5. The polymerization system of claim 4 , wherein the L p -M moiety of the metal complex has a formula selected from the group consisting of:

wherein,
Q, at each occurrence is independently O or S;
R 1 and R 1′ are independently selected from the group consisting of: —H, optionally substituted C 1 to C 12 aliphatic; optionally substituted 3- to 14-membered carbocycle; optionally substituted 3- to 14-membered heterocycle; and R 21 ;
R 2 and R 2′ are independently selected from the group consisting of: —H; optionally substituted C 1 to C 12 aliphatic; optionally substituted 3- to 14-membered carbocycle; optionally substituted 3- to 14-membered heterocycle; R 14 ; R 20 ; and R 21 ;
R 3 and R 3′ are independently selected from the group consisting of: —H; optionally substituted C 1 to C 12 aliphatic; optionally substituted 3- to 14-membered carbocycle; optionally substituted 3- to 14-membered heterocycle, and R 21 ;
R c at each occurrence is independently selected from the group consisting of: —H; optionally substituted C 1 to C 12 aliphatic; an optionally substituted 3- to 14-membered carbocycle; an optionally substituted 3- to 14 membered heterocycle; R 20 ; and R 21 , where two or more R c groups may be taken together with intervening atoms to form one or more optionally substituted rings and, when two R c groups are attached to the same carbon atom, they may be taken together along with the carbon atom to which they are attached to form a moiety selected from the group consisting of: an optionally substituted 3- to 8-membered spirocyclic ring, a carbonyl, an oxime, a hydrazone, and an imine;
R d at each occurrence is independently selected from the group consisting of: optionally substituted C 1 to C 12 aliphatic; optionally substituted 3- to 14-membered carbocycle; optionally substituted 3- to 14-membered heterocycle; R 20 ; and R 21 , where two or more R d groups may be taken together with intervening atoms to form one or more optionally substituted rings; and
represents an optionally substituted moiety covalently linking two nitrogen atoms,
where any of [R 2′ and R 3′ ], [R 2 and R 3 ], [R 1 and R 2 ], and [R 1′ and R 2′ ] may optionally be taken together with intervening atoms to form one or more rings which may in turn be substituted with one or more groups selected from R 14 ; R 20 ; and R 21 ; and where
R 14 at each occurrence is independently selected from the group consisting of: a (Z) p group; halogen; optionally substituted C 1 to C 12 aliphatic; optionally substituted 3- to 14-membered carbocycle; optionally substituted 3- to 14-membered heterocycle; —OR 10 ; —OC(O)R 13 ; —OC(O)OR 13 ; —OC(O)NR 11 R 12 ; —CN; —CNO; —C(R 13 ) z H (3-z) ; —C(O)R 13 ; —C(O)OR 13 ; —C(O)NR 11 R 12 ; —NR 11 R 12 ; —NR 11 C(O) R 13 ; —NR 11 C(O) 13 ; —NR 11 SO 2 R 13 ; —N + R 11 R 12 R 13 X − ; —P + (R 11 ) 3 X − ; —P(R 11 ) 3 ═N + ═P(R 11 ) 3 X − ; —As + R 11 R 12 R 13 X − ; —NCO; —N 3 ; —NO 2 ; —S(O) x R 13 ; and —SO 2 NR 11 R 12 ;
R 20 at each occurrence is independently selected from the group consisting of: a (Z) p group; halogen; —OR 10 ; —OC(O)R 13 ; —OC(O)OR 13 ; —N + (R 11 ) 3 X − ; —P + (R 11 ) 3 X − ; —P(R 11 ) 3 ═N + ═P(R 11 ) 3 X − ; —As + R 11 R 12 R 13 X − ; —OC(O)NR 11 R 12 ; —CN; —CNO; —C(O)R 13 ; —C(O)OR 13 ; —C(O)NR 11 R 12 ; —C(R 13 ) z H (3-z) ; —NR 11 R 12 ; —NR 11 C(O)R 13 ; —NR 11 C(O)OR 13 ; —NCO; —NR 11 SO 2 R 13 ; —S(O) x R 13 ; —S(O) 2 NR 11 R 12 ; —NO 2 ; —N 3 ; and —Si(R 13 ) (3-z) [(CH 2 ) k R 14 ] z ;
R 21 at each occurrence is independently selected from the group consisting of: a (Z) p group; —(CH 2 ) k R 20 ; —(CH 2 ) k —Z—(CH 2 ) k R 20 ; —C(R 17 ) z H (3-z) ; —(CH 2 ) k C(R 17 ) z H (3-z) ; —(CH 2 ) m —Z—(CH 2 ) m C(R 17 ) z H (3-z) ; —(CH 2 ) k —Z—R 16 ;
X − is any anion;
Z is a divalent linker selected from the group consisting of —(CH═CH) a —; —(CH≡CH) a —; —C(O)—; —C(═NOR 11 )—; —C(═NNR 11 R 12 )—; —O—; —OC(O)—; —C(O)O—; —OC(O)O—; —N(R 11 )—; —N(C(O)R 13 )—; —C(O)NR 13 —; —N(C(O)R 13 )O—; —NR 13 C(O)R 13 N—; —S(O) x —; a polyether; and a polyamine;
R 10 at each occurrence is independently selected from the group consisting of: —H; optionally substituted C 1-12 aliphatic; an optionally substituted 3- to 14-membered carbocycle; an optionally substituted 3- to 14-membered heterocycle —S(O) 2 R 13 ; —Si(R 15 ) 3 ; —C(O)R 13 ; and a hydroxyl protecting group;
R 11 and R 12 at each occurrence are independently selected from the group consisting of: —H; optionally substituted C 1 to C 12 aliphatic; an optionally substituted 3- to 14-membered carbocycle; an optionally substituted 3- to 14-membered heterocycle; where two or more R 11 or R 12 groups can optionally be taken together with intervening atoms to form an optionally substituted 3- to 10-membered ring;
R 13 at each occurrence is independently selected from the group consisting of: —H; optionally substituted C 1 to C 12 aliphatic; an optionally substituted 3- to 14-membered carbocycle; and optionally substituted 3- to 14-membered heterocycle, where two or more R 13 groups on the same molecule may optionally be taken together to form ring;
R 15 at each occurrence is independently selected from the group consisting of: optionally substituted C 1-12 aliphatic, an optionally substituted 3- to 14-membered carbocycle; and an optionally substituted 3- to 14-membered heterocycle;
R 16 at each occurrence is independently selected from the group consisting of: optionally substituted C 1 -C 12 aliphatic, an optionally substituted 3- to 14-membered carbocycle; an optionally substituted 3- to 14-membered heterocycle; and —C(R 17 ) z H (3-z) ;
R 17 at each occurrence is independently selected from the group con

Assignees

• Saudi Aramco Tech Co

Inventors

• Farmer Jay J

Classifications

• C08G18/44

  Polycarbonates · CPC title

• C08G64/34 Primary

  and cyclic ethers · CPC title

• B01J31/2243

  At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand · CPC title

• C08G64/0208

  saturated · CPC title

• B01J2531/025

  Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles · CPC title