Method for producing aliphatic polyester resin, and an aliphatic polyester resin composition
A method for producing an aliphatic polyester resin including a melt polymerization step and a subsequent solid phase polymerization step, using a sulfonic acid group-containing compound as a catalyst, wherein the addition amount of the sulfonic acid group-containing compound during melt polymerization is 300 to 3000 ppm with respect to a raw material monomer calculated as sulfur atoms, the content of the sulfonic acid group-containing compound during melt polymerization is 300 to 3000 ppm with respect to a produced polymer calculated as sulfer atoms, and a residual rate of the sulfonic acid group-containing compound after solid phase at polymerization is more than 50.
1. A method for producing an aliphatic polyester resin using a sulfonic acid group-containing compound as a catalyst, comprising:
melt polymerizing a raw material monomer, wherein an addition amount of the sulfonic acid group-containing compound during melt polymerization is 300 to 3000 ppm with respect to the raw material monomer calculated as sulfur atoms; and
solid phase polymerizing a resulting melt polymer, wherein the content of the sulfonic acid group-containing compound after solid phase polymerization is 300 to 3000 ppm with respect to a produced aliphatic polyester resin calculated as sulfur atoms, and a residual rate of the sulfonic acid group-containing compound after solid phase polymerization is more than 50% wherein the melt polymerization is continuously performed under a condition including at least 2 stages, and the solid phase polymerization is continuously performed under the condition including at least the 2 stages:
Melt polymerization: Condition 1 140° C. to 160° C., 13.3 to 66.6 kPa;
Condition 2 160° C. to 180° C., 1.3 to 6.5 kPa,
Solid phase polymerization: Condition 1 130° C. to 150° C.;
Condition 2 higher than 150° C. to 165° C.
2. The method according to claim 1 , wherein the content of the sulfonic acid group-containing compound after solid phase polymerization is 350 to 2500 ppm with respect to the produced aliphatic polyester resin calculated as sulfur atoms, and a residual rate of the sulfonic acid group-containing compound after solid phase polymerization is 80% or more.
3. The method according to claim 1 , wherein the sulfonic acid group-containing compound has 2 or more sulfonic acid groups in one molecule.
4. The method according to claim 3 , wherein the sulfonic acid group-containing compound having 2 or more sulfonic acid groups in one molecule is one or more kinds selected from the group consisting of methanedisulfonic acid, ethanedisulfonic acid, propanedisulfonic acid, butanedisulfonic acid, benzenedisulfonic acid, naphthalenedisulfonic acid, biphenyldisulfonic acid, phenoldisulfonic acid, catecholdisulfonic acid, benzidinedisulfonic acid, naphtholdisulfonic acid, and benzene-trisulfonic acid.
5. The method according to claim 1 , wherein the sulfonic acid group-containing compound is added at any time from before initiation of melt polymerization to before completion of melt polymerization.
6. The method according to claim 1 , wherein one or more kinds of compounds selected from the group consisting of a nitrogen-containing organic compound, an alkali metal compound, and an alkaline earth metal compound are further added.
7. The method according to claim 6 , wherein the nitrogen-containing organic compound is one or more selected from the group consisting of an aromatic amine compound, an alkylamine compound having 4 or more carbon atoms, and a compound having a pyrimidine skeleton, the alkali metal compound is one or more kinds selected from an organic carboxylic acid alkali metal compound having 4 or more carbon atoms, and the alkaline earth metal compound is one or more kinds selected from the group consisting of an organic carboxylic acid alkaline earth metal compound having 4 or more carbon atoms.
8. The method according claim 6 , wherein one or more compounds selected from the group consisting of the nitrogen-containing organic compound, the alkali metal compound and the alkaline earth metal compound are added after addition of the sulfonic acid group-containing compound.
9. The method according to claim 1 , wherein one or more metal compounds selected from the group consisting of a tin compound, a titanium compound, a lead compound, a zinc compound, a cobalt compound, an iron compound, a lithium compound, and a rare earth compound are further added.
10. The method according to claim 9 , wherein the ratio of a sulfur atom molar amount of the sulfonic acid group-containing compound with respect to a total metal molar amount of the tin compound, the titanium compound, the lead compound, the zinc compound, the cobalt compound, the iron compound, the lithium compound, and the rare earth compound after solid phase polymerization is 3.0 to 50.
11. The method according to claim 1 , wherein a stabilizer is added at any time from before initiation of melt polymerization to after completion of solid phase polymerization.
12. The method according to claim 1 , wherein each polymerization reaction of melt polymerization and solid phase polymerization is performed continuously.
13. The method according to claim 1 , wherein the aliphatic polyester resin is a polylactic acid-based resin.