Aliphatic polycarbonate macropolyol and aliphatic polycarbonate-co-aromatic polyester macropolyol

Abstract

Provided is an aliphatic polycarbonate macropolyol including —OAO— and Z(O—) a as repeating units. In the aliphatic polycarbonate macropolyol, the repeating units —OAO— and Z(O—) a are linked to each other via carbonyl (—C(O)—) linkers or are bonded to hydrogen to form terminal —OH groups. The number of moles of the terminal —OH groups is from aZ to aZ+0.2Z (where Z represents the number of moles of the repeating unit Z(O—) a ). Further provided is an aliphatic polycarbonate-co-aromatic polyester macropolyol including —OAO— and Z(O—) a as repeating units. In the aliphatic polycarbonate-co-aromatic polyester macropolyol, the repeating units —OAO— and Z(O—) a are linked via carbonyl (—C(O)—) and —C(O)YC(O)— as linkers or are bonded to hydrogen to form terminal —OH groups.

1 . An aliphatic polycarbonate macropolyol comprising —OAO— and Z(O—) a  as repeating units in which the repeating units —OAO— and Z(O—) a  are linked to each other via carbonyl (—C(O)—) linkers or are bonded to hydrogen to form terminal —OH groups and the number of moles of the terminal —OH groups is from aZ to aZ+0.2Z (where Z represents the number of moles of the repeating unit Z(O—) a ), wherein A is a substituted or unsubstituted C 3 -C 60  alkylene or a combination of two or more substituted or unsubstituted C 3 -C 60  alkylenes, and a is an integer from 2 to 4, provided that when a is 2, Z is a substituted or unsubstituted C 3 -C 60  alkylene, when a is 3, Z is a substituted or unsubstituted C 3 -C 60  trialkylene, and when a is 4, Z is a substituted or unsubstituted C 4 -C 60  tetraalkylene. 
     
     
         2 . The aliphatic polycarbonate macropolyol according to  claim 1 , wherein HOAOH as a raw material for the repeating unit —OAO— is selected from the group consisting of Formulae 1a to 1c: 
       
         
           
           
               
               
           
         
         a in the repeating unit Z(O—) a  is 2, and 
         Z(OH) 2  as a raw material for the Z(O—) 2  is selected from the group consisting of Formulae 1d to 1h: 
       
       
         
           
           
               
               
           
         
       
     
     
         3 . The aliphatic polycarbonate macropolyol according to  claim 2 , wherein the HOAOH as a raw material for the repeating unit —OAO— is a mixture of 80 to 95 mol % of the diol compound represented by Formula 1a and 5 to 20 mol % of the diol compound represented by Formula 1b or 1c and the Z(O—) 2  repeating units are present in an amount of 5 to 20 mol % with respect to the —OAO— repeating units. 
     
     
         4 . The aliphatic polycarbonate macropolyol according to  claim 1 , wherein HOAOH as a raw material for the repeating unit —OAO— is selected from the group consisting of Formulae 1a to 1h: 
       
         
           
           
               
               
           
         
       
       and
 Z(OH) a  as a raw material for the repeating unit Z(O—) a  is selected from the group consisting of Formulae 2a to 2d: 
 
       
         
           
           
               
               
           
         
       
     
     
         5 . The aliphatic polycarbonate macropolyol according to  claim 4 , wherein the HOAOH as a raw material for the repeating unit —OAO— is a mixture of 80 to 95 mol % of the diol compound represented by Formula 1a and 5 to 20 mol % of the diol compound selected from Formulae 1b to 1h and the Z(O—) 2  repeating units are present in an amount of 5 to 20 mol % with respect to the —OAO— repeating units. 
     
     
         6 . The aliphatic polycarbonate macropolyol according to  claim 5 , wherein Z(OH) a  as a raw material for the repeating unit Z(O—) a  is the compound represented by Formula 2a. 
     
     
         7 . An aliphatic polycarbonate-co-aromatic polyester macropolyol comprising —OAO— and Z(O—) a  as repeating units in which the repeating units —OAO— and Z(O—) a  are linked via carbonyl (—C(O)—) and —C(O)YC(O)— as linkers or are bonded to hydrogen to form terminal —OH groups, wherein A is a substituted or unsubstituted C 3 -C 60  alkylene or a combination of two or more substituted or unsubstituted C 3 -C 60  alkylenes, a is an integer from 2 to 4, provided that when a is 2, Z is a substituted or unsubstituted C 3 -C 60  alkylene, when a is 3, Z is a substituted or unsubstituted C 3 -C 60  trialkylene, and when a is 4, Z is a substituted or unsubstituted C 4 -C 60  tetraalkylene, and Y is a substituted or unsubstituted C 5 -C 20  arylene, a combination of two or more substituted or unsubstituted C 5 -C 20  arylenes, a substituted or unsubstituted C 5 -C 20  heteroarylene or a combination of two or more substituted or unsubstituted C 5 -C 20  heteroarylenes. 
     
     
         8 . The aliphatic polycarbonate-co-aromatic polyester macropolyol according to  claim 7 , wherein HOAOH as a raw material for the repeating unit —OAO— is the compound of Formula 1a: 
       
         
           
           
               
               
           
         
         the Z(O—) a  is Z(O—) 2 , 
         Z(OH) 2  as a raw material for the repeating unit Z(O—) 2  is selected from the group consisting of Formulae 1a to 1h: 
       
       
         
           
           
               
               
           
         
       
       and
 HOC(O)YC(O)OH as a raw material for the linker —C(O)YC(O)— is selected from phthalic acid, isophthalic acid, and terephthalic acid. 
 
     
     
         9 . The aliphatic polycarbonate-co-aromatic polyester macropolyol according to  claim 8 , wherein the —C(O)YC(O)— linkers are present in an amount of 5 to 50 mol %, based on the —OAO— repeating units, and Z(O—) 2  repeating units are present in an amount of 5 to 20 mol % with respect to the —OAO— repeating units. 
     
     
         10 . The aliphatic polycarbonate-co-aromatic polyester macropolyol according to  claim 9 , wherein the HOC(O)YC(O)OH as a raw material for the linker —C(O)YC(O)— is isophthalic acid or phthalic acid. 
     
     
         11 . The aliphatic polycarbonate-co-aromatic polyester macropolyol according to  claim 7 , wherein HOAOH as a raw material for the repeating unit —OAO— is the compound of Formula 1a: 
       
         
           
           
               
               
           
         
         Z(OH) a  as a raw material for the repeating unit Z(O—) a  is selected from the group consisting of Formulae 2a to 2d: 
       
       
         
           
           
               
               
           
         
         HOC(O)YC(O)OH as a raw material for the linker —C(O)YC(O)— is selected from phthalic acid, isophthalic acid, and terephthalic acid. 
       
     
     
         12 . The aliphatic polycarbonate-co-aromatic polyester macropolyol according to  claim 11 , wherein the —C(O)YC(O)— linkers are present in an amount of 5 to 50 mol %, based on the —OAO— repeating units, and Z(O—) a  repeating units are present in an amount of 5 to 20 mol % with respect to the —OAO— repeating units. 
     
     
         13 . The aliphatic polycarbonate-co-aromatic polyester macropolyol according to  claim 12 , wherein the HOC(O)YC(O)OH as a raw material for the linker —C(O)YC(O)— is isophthalic acid or phthalic acid and the Z(OH) a  as a raw material for the repeating unit Z(O—) a  is represented by Formula 2a. 
     
     
         14 . A method for producing an aliphatic polycarbonate macropolyol, comprising condensing HOAOH with dimethyl carbonate in the presence of a base catalyst while removing methanol to prepare an aliphatic polycarbonate with a number average molecular weight of 10000 or higher (first step) and transesterifying the condensation product with Z(OH) a  (second step), wherein A is a substituted or unsubstituted C 3 -C 60  alkylene or a combination of two or more substituted or unsubstituted C 3 -C 60  alkylenes, a is an integer from 2 to 4, provided that when a is 2, Z is a substituted or unsubstituted C 3 -C 60  alkylene, when a is 3, Z is a substituted or unsubstituted C 3 -C 60  trialkylene, and when a is 4, Z is a substituted or unsubstituted C 4 -C 60  tetraalkylene. 
     
     
         15 . The method according to  claim 14 , wherein the base catalyst is composed of a lithium, sodium or potassium cation and an alkoxy anion formed by deprotonation of the HO-A-OH and is used in an amount of 0.01 mol % to 0.1 mol %, based on the HO-A-OH. 
     
     
         16 . A method for producing an aliphatic polycarbonate-co-aromatic polyester macropolyol, comprising condensing HOAOH, dimethyl carbonate, and MeOC(O)YC(O)OMe in the presence of a base catalyst while removing methanol to prepare an aliphatic polycarbonate-co-aromatic polyester with a number average molecular weight of 10000 or higher (first step) and transesterifying the condensation product with Z(OH) a  (second step), wherein A is a substituted or unsubstituted C 3 -C 60  alkylene or a combination of two or more substituted or unsubstituted C 3 -C 60  alkylenes, a is an integer from 2 to 4, provided that when a is 2, Z is a substituted or unsubstituted C 3 -C 60  alkylene, when a is 3, Z is a substituted or unsubstituted C 3 -C 60  trialkylene, and when a is 4, Z is a substituted or unsubstituted C 4 -C 60  tetraalkylene, and Y is a substituted or unsubstituted C 5 -C 20  arylene, a combination of two or more substituted or unsubstituted C 5 -C 20  arylenes, a substituted or unsubstituted C 5 -C 20  heteroarylene or a combination of two or more substituted or unsubstituted C 5 -C 20  heteroarylenes. 
     
     
         17 . The method according to  claim 16 , wherein the base catalyst is composed of a lithium, sodium or potassium cation and an alkoxy anion formed by deprotonation of the HO-A-OH and is used in an amount of 0.01 mol % to 0.1 mol %, based on the HO-A-OH.