POLYLACTIDE RESIN AND PREPARATION METHOD THEREOF
The present invention is directed to an organometallic complex and a catalyst composition capable of producing polylactide resins with improved properties at a higher conversion rate, a method of producing the organometallic complex, polylactide resins having enhanced hydrolysis resistance and heat resistance together with superior mechanical properties, a preparation process therefor, and polylactide resin compositions including the same.
1 . An organometallic complex of Chemical Formula 1:
wherein n is an integer of 0 to 15, p is an integer of 0 to 2, a is 0 or 1, M is Sn or Zn, R 1 and R 3 are the same as or different from each other, and each of them is hydrogen, a substituted or unsubstituted C3 to C10 alkyl, a substituted or unsubstituted C3 to C10 cycloalkyl, or a substituted or unsubstituted C6 to C10 aryl, R 2 is a substituted or unsubstituted C3 to C10 alkylene, a substituted or unsubstituted C3 to C10 cycloalkylene, or a substituted or unsubstituted C6 to C10 arylene, and each of X and Y is independently an alkoxy group or a carboxyl group.
2 . The organometallic complex according to claim 1 , wherein each of R 1 and R 3 is a monovalent phenyl group substituted with a C1 to C10 alkyl group, or a C3 to C10 alkyl group or cycloalkyl group, R 2 is a divalent phenylene group substituted with a C1 to C10 alkyl group, or a C3 to C10 alkylene group or cycloalkylene group.
3 . The organometallic complex according to claim 1 , wherein the MX p Y 2-p is tin(II) 2-ethylhexanoate (Sn(Oct) 2 ).
4 . A method of producing a organometallic complex of claim 1 , which comprises a step of subjecting a compound of Chemical Formula 2 and a compound of Chemical Formula 3 to a reaction:
wherein n is an integer of 0 to 15, p is an integer of 0 to 2, M is Sn or Zn, R 1 and R 3 are the same as or different from each other, and each of them is hydrogen, a substituted or unsubstituted C3 to C10 alkyl, a substituted or unsubstituted C3 to C10 cycloalkyl, or a substituted or unsubstituted C6 to C10 aryl, R 2 is a substituted or unsubstituted C3 to C10 alkylene, a substituted or unsubstituted C3 to C10 cycloalkylene, or a substituted or unsubstituted C6 to C10 arylene, and each of X and Y is independently an alkoxy group or a carboxyl group.
5 . A catalyst composition comprising a compound of Chemical Formula 2 and a compound of Chemical Formula 3:
wherein n is an integer of 0 to 15, p is an integer of 0 to 2, M is Sn or Zn, R 1 and R 3 are the same as or different from each other, and each of them is hydrogen, a substituted or unsubstituted C3 to C10 alkyl, a substituted or unsubstituted C3 to C10 cycloalkyl, or a substituted or unsubstituted C6 to C10 aryl, R 2 is a substituted or unsubstituted C3 to C10 alkylene, a substituted or unsubstituted C3 to C10 cycloalkylene, or a substituted or unsubstituted C6 to C10 arylene, and each of X and Y is independently an alkoxy group or a carboxyl group.
6 . The catalyst composition according to claim 5 , wherein each of R 1 and R 3 is a monovalent phenyl group substituted with a C1 to C10 alkyl group, or a C3 to C10 alkyl group or cycloalkyl group, and R 2 is a divalent phenylene group substituted with a C1 to C10 alkyl group, or a C3 to C10 alkylene group or cycloalkylene group.
7 . The catalyst composition according to claim 5 , wherein the compound of Chemical Formula 3 is tin(II) 2-ethylhexanoate (Sn(Oct) 2 ).
8 . A polylactide resin which has an acidity of 10 meq/kg or less and a weight average molecular weight of 100,000 to 1,000,000.
9 . The polylactide resin according to claim 8 , which has acidity of 3 to 10 meq/kg and a weight average molecular weight of 200,000 to 1,000,000.
10 . The polylactide resin according to claim 8 , which comprises a catalyst residue including an organometallic complex of Chemical Formula 1 or a compound of Chemical Formula 2 and a compound of Chemical Formula 3:
wherein n is an integer of 0 to 15, p is an integer of 0 to 2, a is 0 or 1, M is Sn or Zn, R 1 and R 3 are the same as or different from each other, and each of them is hydrogen, a substituted or unsubstituted C3 to C10 alkyl, a substituted or unsubstituted C3 to C10 cycloalkyl, or a substituted or unsubstituted C6 to C10 aryl, R 2 is a substituted or unsubstituted C3 to C10 alkylene, a substituted or unsubstituted C3 to C10 cycloalkylene, or a substituted or unsubstituted C6 to C10 arylene, and each of X and Y is independently an alkoxy group or a carboxyl group.
11 . The polylactide resin according to claim 10 , wherein the amount of the catalyst residue is no more than 15 ppm.
12 . The polylactide resin according to claim 8 , which shows a weight loss of less than 20 wt % when heated from room temperature to 300° C. during thermal gravimetric analysis (TGA).
13 . A process for preparing a polylactide resin, which comprises a step of subjecting lactide monomers to ring opening polymerization in the presence of an organometallic complex of claim 1 .
14 . A process for preparing a polylactide resin, which comprises a step of subjecting lactide monomers to ring opening polymerization in the presence of a catalyst composition of claim 5 .
15 . The process for preparing a polylactide resin according to claim 13 or claim 14 , wherein the MX p Y 2-p is tin(II) 2-ethylhexanoate (Sn(Oct) 2 ).
16 . The process for preparing a polylactide resin according to claim 13 or claim 14 , wherein R 1 is a monovalent phenyl group substituted with a C1 to C10 alkyl group or a C3 to C10 alkyl group or cycloalkyl group, and R 2 is a divalent phenylene group substituted with a C1 to C10 alkyl group, or a C3 to C10 alkylene group or cycloalkylene group.
17 . The process for preparing a polylactide resin according to claim 13 , wherein the organometallic complex is prepared by a method comprising a step of subjecting a compound of Chemical Formula 2 and a compound of Chemical Formula 3 to a reaction:
wherein n is an integer of 0 to 15, p is an integer of 0 to 2, M is Sn or Zn, R 1 and R 3 are the same as or different from each other, and each of them is hydrogen, a substituted or unsubstituted C3 to C10 alkyl, a substituted or unsubstituted C3 to C10 cycloalkyl, or a substituted or unsubstituted C6 to C10 aryl, R 2 is a substituted or unsubstituted C3 to C10 alkylene, a substituted or unsubstituted C3 to C10 cycloalkylene, or a substituted or unsubstituted C6 to C10 arylene, and each of X and Y is independently an alkoxy group or a carboxyl group.
18 . The process for preparing a polylactide resin according to claim 13 , wherein the organometallic complex is added at a ratio of 0.001 to 0.1 moles with respect to 100 moles of the lactide monomers.
19 . The process for preparing a polylactide resin according to claim 14 , wherein the compounds of Chemical Formula 2 and Chemical Formula 3 are added at a ratio of 0.001 to 0.1 moles with respect to 100 moles of the lactide monomers, respectively.
20 . The process for preparing a polylactide resin according to claim 13 or claim 14 , wherein the ring opening polymerization is carried out in the presence of an initiator comprising a compound with a hydroxy group.
21 . The process for preparing a polylactide resin according to claim 20 , wherein the compound with a hydroxy group has 8 or more carbon atoms.
22 . The process for preparing a polylactide resin according to claim 20 , wherein the initiator is added at a ratio of 0.001 to 1 mole with respect to 100 moles of the lactide monomers.
23 . The process for preparing a polylactide resin according to claim 13 or claim 14 , wherein the ring opening polymerization is carried out in a manner of a bulk polymerization.
24 . The process for preparing a polylactide resin according to claim 13 or claim 14 , wherein the ring opening polymerization is carried out at a temperature of 120 to 200° C. for 0.5 to 8 hours.
25 . A polylactide resin composition comprising a polylactide resin of claim 8 .