Method for preparing polylactone by ring opening

Patent metadata

Field	Value
Publication number	US-11149115-B2
Application number	US-201816607654-A
Country	US
Kind code	B2
Filing date	Apr 24, 2018
Priority date	May 19, 2017
Publication date	Oct 19, 2021
Grant date	Oct 19, 2021

Abstract

Disclosed is a method for preparing polylactone by ring opening, belonging to the technical fields of organic catalysis and polymer materials. The invention proposes a new catalytic mechanism, wherein an organic alcohol is used as an initiator to initiate ring opening polymerization of a cyclic monomer under the catalysis of an organic catalyst to obtain a polylactone; and the catalyst is a pyridinium salt. The present invention has the advantages of non-toxic reaction, simple conditions and controllable process; further, the invention can obtain a narrow molecular weight distribution in the absence of solution polymerization, and can effectively inhibit the occurrence of the transesterification compared with the catalysis of 4-(N,N-dimethylamino)pyridine.

First claim

The invention claimed is:

1. A method for preparing polylactone carrying out a ring opening polymerization of a cyclic monomer in the presence of an organic catalyst and an organic alcohol as an initiator to obtain a polylactone,
wherein the organic catalyst is a pyridinium salt shown as formula I:

wherein:
when R 5 is hydrogen, R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen, methyl, ethyl, isopropyl, and C1-C4 alkyls substituted by one or more substituents selected from hydroxyl, phenyl, and cyano; X is one selected from fluorine, chlorine, bromine, iodine, methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid, trifluoroacetic acid, trichloroacetic acid, and benzenesulfonic acid;
when R 5 is selected from N,N-dimethylamino, R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, sec-butyl, and C1-C10 alkyls substituted by one or more substituents selected from hydroxyl, phenyl, and cyano, with the proviso that R 1 , R 2 , R 3 , and R 4 are not simultaneously hydrogen; X is one selected from fluoro, chloro, bromo, iodo, methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid, trifluoroacetic acid, trichloroacetic acid and benzenesulfonic acid; and
when R 5 is selected from N-pyrrolidinyl, R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, sec-butyl, and C1-C10 alkyls substituted by one or more substituents selected from hydroxyl, phenyl, and cyano; X is one selected from fluoro, chloro, bromo, iodo, methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid, trifluoroacetic acid, trichloroacetic acid and benzenesulfonic acid.

2. The preparation method of claim 1 , wherein the organic catalyst is selected from

3. The preparation method of claim 1 , wherein R in the initiator organic alcohol ROH is an alkyl or a phenyl group, and the alkyl is a linear, branched or cyclic chain having 1 to 22 carbon atoms.

4. The preparation method of claim 3 , wherein the organic alcohol is methanol, ethanol, pentaerythritol, butynol, phenylpropanol, or benzyl alcohol.

5. The preparation method of claim 1 , wherein the cyclic monomer is one of lactones of formula (II), carbonates of formula (III), and lactides of formula (IV),

wherein, in formula (II), A is [—(CR 1 R 2 )—] n , n is an integer from 2 to 10; R 1 and R 2 are independently selected from H, unsubstituted C1-C5 alkyls, and C1-C5 alkyls substituted with a halogen or a hydroxyl group;
wherein, in formula (III), A and B are [—(CR 1 R 2 )—], n is an integer from 1 to 10, and A and B are the same or different; R 1 and R 2 are independently selected from H, C1-C5 alkyls, and C1-C5 substituted with a halogen atom or a hydroxyl group;
Wherein, in formula (IV), A is [—(CR 1 R 2 )—] n , n is an integer from 1 to 10; R 1 and R 2 are independently selected from H, C1-C5 alkyls, and C1-C5 alkyls substituted with a halogen atom or a hydroxyl group.

6. The preparation method of claim 5 , wherein the lactone cyclic monomer is butyrolactone, valerolactone, or caprolactone; the carbonate cyclic monomer is trimethylene carbonate, dimethyl carbonate and diethyl carbonate; and the lactide cyclic monomer is glycolide or lactide.

7. The preparation method of claim 1 , wherein a molar ratio of the cyclic monomer, the organic catalyst, and the organic alcohol is (30:1:1)-(120:1:1).

8. The preparation method of claim 1 , wherein further comprising adding a terminator to the reaction mixture, and precipitating a polymer in a precipitation solvent that is methanol, diethyl ether, n-hexane, or n-pentane.

9. The preparation method of claim 1 , wherein the ring opening polymerization is carried out at a temperature of 30-140° C. for 1-48 hours.

Assignees

• Nanjing University Of Technology

Inventors

• Guo Kai
• Zhu Hui
• Li Zhenjiang
• Wei Fulan
• Chen Siming
• Gao Yu

Classifications

• C08G63/87

  Non-metals or inter-compounds thereof (boron C08G63/84) · CPC title

• C08G63/823 Primary

  for the preparation of polylactones or polylactides · CPC title

• C08G63/08 Primary

  Lactones or lactides · CPC title

• B01J31/0237

  Amines · CPC title

• C08G64/30 Primary

  using carbonates · CPC title