Solid-phase polymerization method for preparing high-molecular-weight aliphatic polyester
View Patent ↗A solid-phase polymerization method of high-molecular-weight aliphatic polyester conducts the solid-phase polymerization of aliphatic polyester prepolymer under a gas stream containing sulfonic acid catalyst. The method features preparing metal free aliphatic polyester with high molecular weight, good color and luster and perfect thermal stability efficiently. The non-metal-ion aliphatic polyester is not only applicable to common use, but is also suitable as high value-added medical material and packing material which contacts with food directly than other metal-containing polyester.
1. A solid-phase polymerization method of preparing aliphatic polyester comprising a gas stream containing a sulfonic acid catalyst, then flowing the gas stream containing sulfonic acid catalyst into a reactor, and then carrying out solid-phase polymerization of aliphatic polyester prepolymer in the reactor, wherein a concentration Cg of said sulfonic acid catalyst in the gas stream is 0.0001 mmol/L to 1 mmol/L.
2. The method according to claim 1 , wherein said sulfonic acid catalyst is one or multiple of monosulfonic acid of C1-C20 and monosulfonic acid of C1-C20 substituted by halogen.
3. The method according to claim 1 , wherein the concentration Cg of said sulfonic acid catalyst in the gas stream is 0.0005 mmol/L to 0.2 mmol/L.
4. The method according to claim 3 , wherein the concentration Cg of said sulfonic acid catalyst in the gas stream is 0.001 mmol/L to 0.1 mmol/L.
5. The method according to claim 1 , wherein during the solid-phase polymerization, concentration Cp of sulfonic acid catalyst in aliphatic polyester prepolymer is 10 mmol/L to 350 mmol/L.
6. The method according to claim 5 , wherein during the solid-phase polymerization, concentration Cp of sulfonic acid catalyst in aliphatic polyester prepolymer is 20 mmol/L to 150 mmol/L.
7. The method according to claim 1 , wherein concentration Cg of sulfonic acid catalyst in the gas stream during the solid-phase polymerization, concentration Cp of sulfonic acid catalyst in aliphatic polyester prepolymer and partition coefficient Kgp of sulfonic acid catalyst in gas stream and aliphatic polyester prepolymer at a temperature for solid-phase polymerization meet formula (1):
0.1
≤
Cg
CpKgp
≤
10.
(
1
)
8. The method according to claim 1 , wherein linear velocity of the gas stream during solid-phase polymerization is 1 cm/s to 200 cm/s.
9. The method according to claim 1 , wherein the aliphatic polyester prepolymer contains more than 50 mol % of hydroxy carboxylic acid units.
10. The method according to claim 9 , wherein the aliphatic polyester prepolymer is polylactic acid or polyglycolic acid.
11. The method according to claim 1 , wherein weight-average molecular weight Mw of said aliphatic polyester prepolymer before and after solid-phase polymerization respectively is 8000 to 30000 and 100000 to 500000; average growth speed of Mw in solid-phase polymerization is greater than or equal to 3500/h.