Lactide copolymer, method for preparing same, and resin composition comprising same

Patent metadata

Field	Value
Publication number	US-9382386-B2
Application number	US-201314434613-A
Country	US
Kind code	B2
Filing date	Dec 4, 2013
Priority date	Dec 6, 2012
Publication date	Jul 5, 2016
Grant date	Jul 5, 2016

Abstract

The present invention relates to a lactide copolymer having excellent general physical properties such as mechanical physical properties, processability, and the like, and having excellent flexibility to be effectively usable as a packaging material, and the like, a preparing method thereof, and a resin composition including the same, wherein the lactide copolymer includes: two or more block copolymer repeating units in which hard segments of polylactide repeating units are bound to both ends of soft segments of polyether polyol repeating units, the block copolymer repeating units are linked with each other via a urethane linking group induced from a polyvalent isocyanate compound having more than 2 to less than 3 equivalents of an isocyanate group per a molecule, and the polyether polyol repeating unit has a number average molecular weight of 1000 to 10000.

First claim

The invention claimed is:

1. A lactide copolymer comprising:
two or more block copolymer repeating units in which hard segments of polylactide repeating units are bound to both ends of soft segments of polyether polyol repeating units, the block copolymer repeating unit being represented by Formula 1,
wherein the block copolymer repeating units are linked with each other via a urethane linking group induced from a polyvalent isocyanate compound having more than 2 to less than 3 equivalents of an isocyanate group per molecule, and
the polyether polyol repeating unit has a number average molecular weight (Mn) of 1000 to 10000:

and wherein in Formula 1, D is a C2 to C10 linear or branched alkylene group, x is each independently an integer of 30 to 500, and n is an integer of 30 to 1000.

2. The lactide copolymer of claim 1 , wherein it has a weight average molecular weight (Mw) of 100,000 to 1,000,000.

3. The lactide copolymer of claim 1 , wherein each of the block copolymer repeating units has a weight average molecular weight (Mw) of 50,000 to 300,000.

4. The lactide copolymer of claim 1 , wherein the polyvalent isocyanate compound includes a mixture of a diisocyanate compound and a polyvalent isocyanate compound having 3 or more equivalents of an isocyanate group.

5. The lactide copolymer of claim 4 , wherein the diisocyanate compound is selected from the group consisting of ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 1,2-dodecane diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 2,4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate, hexahydro-1,3-phenylene diisocyanate, hexahydro-1,4-phenylene diisocyanate, perhydro-2,4-diphenylmethane diisocyanate, perhydro-4,4′-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,4-stilbene diisocyanate, 3,3′-dimethyl-4,4′-diphenylene diisocyanate, toluene 2,4-diisocyanate (TDI), toluene 2,6-diisocyanate, diphenylmethane-2,4′-diisocyanate (MDI), diphenylmethane-2,2′-diisocyanate, diphenylmethane-4,4′-diisocyanate and naphthylene-1,5-diisocyanate, and the polyvalent isocyanate compound having 3 or more equivalents of the isocyanate group is selected from the group consisting of an oligomer of the diisocyanate compound, a polymer of the diisocyanate compound, a cyclic polymer of the diisocyanate compound, hexamethylene diisocyanate isocyanurate, a triisocyanate compound and isomers thereof.

6. The lactide copolymer of claim 1 , wherein the urethane linking group includes urethane bonds obtained by a reaction of a terminal hydroxy group derived from the polylactide repeating unit and the isocyanate group derived from the polyvalent isocyanate compound.

7. The lactide copolymer of claim 1 , wherein two or more block copolymer repeating units include 50 to 95 wt % of the hard segment and 5 to 50 wt % of the soft segment with respect to the total weight.

8. A preparing method of the lactide copolymer of claim 1 , comprising:
forming a block copolymer represented by Formula 1a by ring opening polymerization of a lactide monomer in the presence of a tin- or zinc-containing catalyst and an initiator including a polyether polyol polymer having a number average molecular weight (Mn) of 1000 to 10000; and
reacting the block copolymer represented by Formula 1a with a polyvalent isocyanate compound having more than 2 to less than 3 equivalents of an isocyanate group per a molecule:

and wherein in Formula 1a, D is a C2 to C10 linear or branched alkylene group, x is each independently an integer of 30 to 500, and n is an integer of 30 to 1000.

9. The preparing method of claim 8 , wherein the tin- or zinc-containing catalyst includes an organic metal composite represented by Formula 2 or a mixture of a compound represented by Formula 3 and a compound represented by Formula 4:

and wherein in Formula 2 to 4, 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 which may be the same as or different from each other are each hydrogen, substituted or unsubstituted C3 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C6 to C10 aryl, R 2 is substituted or unsubstituted C3 to C10 alkylene, substituted or unsubstituted C3 to C10 cycloalkylene, substituted or unsubstituted C6 to C10 arylene, and X and Y are each independently an alkoxy group or a carboxyl group.

10. The preparing method of claim 8 , wherein the ring opening polymerization is performed at a temperature of 120 to 200° C. for 0.5 to 8 hours.

11. The preparing method of claim 8 , wherein the polyvalent isocyanate compound is used in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the block copolymer represented by Formula 1a.

12. The preparing method of claim 8 , wherein the reacting of the block copolymer with a polyvalent isocyanate compound is performed at a temperature of 100 to 190° C. for 0.001 to 1 hour.

13. The preparing method of claim 8 , wherein the reacting of the block copolymer with a polyvalent isocyanate compound is performed in the presence of a tin-based catalyst.

14. A resin composition comprising the lactide copolymer of claim 1 .

15. A film comprising the lactide copolymer of claim 1 .

16. The film of claim 15 , wherein it is used as a packaging film.

Assignees

• Lg Chemical Ltd
• Lg Chemical Ltd

Inventors

• Sohn Jung Min
• Park Seung Young
• Youk Kyung Seog
• Choi Seung Ho

Classifications

• C08J5/18

  Manufacture of films or sheets · CPC title

• C08L75/04

  Polyurethanes · CPC title

• C08G63/664

  derived from hydroxy carboxylic acids · CPC title

• C08J2387/00

  Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds · CPC title

• C08G81/00 Primary

  Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers (involving only carbon-to-carbon unsaturated bond reactions C08F299/00 {; polyester-amides C08G69/44; polyester-imides C08G73/16; polyamides-imides C08G73/14; block- or graft polymers containing polysiloxane sequences C08G77/42}) · CPC title