IP Library Granted Patent US 9,023,953
Granted Patent B2
US 9,023,953 · App. 13/825,992 · Granted May 5, 2015

Process for production of poly(lactic acid)-type resin, and poly(lactic acid)-type prepolymer

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Quick Facts
Patent No.
US 9,023,953
App. No.
13/825,992
Granted
May 5, 2015
Kind
B2
Abstract

A method of producing a poly(lactic acid) resin includes carrying out direct polycondensation using lactic acid as a main raw material to prepare a crystallized prepolymer having a weight average molecular weight of 5,000 to 25,000, an enthalpy of fusion ΔHm of 50 to 65 J/g and an acid value A mol/ton satisfying (1) below: 450/(Mw/10,000−0.14)< A <950/(Mw/10,000−0.14)  (1) (wherein Mw represents weight average molecular weight of the crystallized prepolymer); and subjecting the crystallized prepolymer to solid-phase polymerization.

Claims (23)

1. A method of producing a poly(lactic acid) resin comprising:

carrying out direct polycondensation using lactic acid as a main raw material with a tin organic carboxylate and methanesulfonic acid to prepare a crystallized prepolymer having a weight average molecular weight of 5,000 to 25,000, an enthalpy of fusion ΔHm of 50 to 65 J/g and an acid value A mol/ton satisfying (1):

450/(Mw/10,000−0.14)< A< 950/(Mw/10,000−0.14)  (1)

wherein Mw represents weight average molecular weight of said crystallized prepolymer and said crystallized prepolymer is a pellet having a maximum diameter of about 1.5 to 6 mm; and

subjecting said crystallized prepolymer to solid-phase polymerization.

2. The method according to claim 1 , wherein lactide content L of said crystallized prepolymer is 0.1 to 3.0 wt %.

3. The method according to claim 1 , wherein said crystallized prepolymer is poly-L-lactic acid or poly-D-lactic acid, and, in the poly-L-lactic acid, D-lactic acid content d is 0.2 to 2.0 mol %, and in the poly-D-lactic acid, L-lactic acid content 1 is 0.2 to 2.0 mol %.

4. The method according to claim 1 , wherein enthalpy of fusion ΔHm of said crystallized prepolymer is not less than 53 J/g.

5. The method according to claim 1 , wherein acid value A mol/ton of said crystallized prepolymer satisfies (2):

550/(Mw/10,000−0.14)< A< 850/(Mw/10,000−0.14)  (2).

6. The method according to claim 1 , wherein a temperature increasing rate in said solid-phase polymerization is not more than 10° C. per hour.

7. The method according to claim 1 , wherein final temperature in said solid-phase polymerization is 155 to 165° C.

8. A crystallized poly(lactic acid) prepolymer pellet containing a tin organic carboxylate and methanesulfonic acid having a maximum diameter of about 1.5 to 6 mm, a weight average molecular weight of 5,000 to 25,000, an enthalpy of fusion ΔHm of 50 to 65 J/g and an acid value A mol/ton satisfying (1):

450/(Mw/10,000−0.14)< A< 950/(Mw/10,000−0.14)  (1)

(wherein Mw represents weight average molecular weight of said crystallized prepolymer).

9. The crystallized poly(lactic acid) prepolymer pellet according to claim 8 , wherein said crystallized poly(lactic acid) prepolymer is prepared by carrying out direct polycondensation using lactic acid as a main raw material to obtain a prepolymer, and crystallizing said prepolymer.

10. The method according to claim 2 , wherein said crystallized prepolymer is poly-L-lactic acid or poly-D-lactic acid, and, in the poly-L-lactic acid, D-lactic acid content d is 0.2 to 2.0 mol %, and in the poly-D-lactic acid, L-lactic acid content 1 is 0.2 to 2.0 mol %.

11. The method according to claim 1 , wherein enthalpy of fusion ΔHm of said crystallized prepolymer is not less than 53 μg.

12. The method according to claim 3 , wherein enthalpy of fusion ΔHm of said crystallized prepolymer is not less than 53 J/g.

13. The method according to claim 2 , wherein acid value A mol/ton of said crystallized prepolymer satisfies the (2) below:

550/(Mw/10,000−0.14)< A< 850/(Mw/10,000−0.14)  (2).

14. The method according to claim 3 , wherein acid value A mol/ton of said crystallized prepolymer satisfies the (2) below:

550/(Mw/10,000−0.14)< A< 850/(Mw/10,000−0.14)  (2).

Assignments (5)
RELEASE OF SECURITY INTEREST Recorded Aug 11, 2025
From: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT
To: NATUREWORKS, LLC
Reel/Frame 072412/0844 →
TERMINATION AND RELEASE OF SECURITY INTEREST IN PATENTS Recorded Oct 20, 2021
From: BANK OF AMERICA, N.A., AS ADMINISTRATIVE AGENT
To: NATUREWORKS LLC
Reel/Frame 057873/0985 →
SECURITY INTEREST Recorded Oct 20, 2021
From: NATUREWORKS LLC
To: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT
Reel/Frame 057879/0338 →
NOTICE OF GRANT OF SECURITY INTEREST IN PATENTS Recorded Jan 16, 2018
From: NATUREWORKS LLC
To: BANK OF AMERICA, N.A., AS ADMINISTRATIVE AGENT
Reel/Frame 045075/0556 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 6, 2017
From: TORAY INDUSTRIES, INC.
To: NATUREWORKS LLC
Reel/Frame 044321/0242 →