Isopoly-molybdic acid coordination polymer catalyst, method of manufacturing the same and application thereof

Patent metadata

Field	Value
Publication number	US-11878288-B2
Application number	US-202217872021-A
Country	US
Kind code	B2
Filing date	Jul 25, 2022
Priority date	Dec 3, 2021
Publication date	Jan 23, 2024
Grant date	Jan 23, 2024

Abstract

An isopoly-molybdic acid coordination polymer catalyst for manufacturing polycaprolactone and method of manufacturing the same are provided. It relates to a field of catalysts from polycaprolactone. The chemical formula of the isopoly-molybdic acid coordination polymer catalyst is [Cu2(trz)2(γ-Mo8O26)0.5(H2O)2]. In the chemical formula, trz is 1,2,4-triazole negative monovalent anion, and [γ-Mo8O26] is a γ type octamolybdate anion. This synthesis method offers higher yield with strong reproducibility. The resulting crystal products have higher purity. The isopoly-molybdic acid coordination polymer catalyst shows high catalytic activity towards the bulk ring-opening polymerization of caprolactone. The resulting polycaprolactone has a weight average molecular weight exceeding 50,000 and a narrow molecular distribution. The polycaprolactone has great potential in the application of low- to medium-temperature thermoplastic medical materials.

First claim

The invention claimed is:

1. An isopoly-molybdic acid coordination polymer catalyst, having a chemical formula of [Cu 2 (trz) 2 (γ-Mo 8 O 26 ) 0.5 (H 2 O) 2 ], wherein trz is a negative monovalent anion of 1,2,4-triazole, and [γ-Mo 8 O 26 ] is a γ type octamolybdate anion.

2. The isopoly-molybdic acid coordination polymer catalyst of claim 1 , wherein a secondary structure unit of the isopoly-molybdic acid coordination polymer catalyst is a crystal of monoclinic crystal system, the isopoly-molybdic acid coordination polymer catalyst has a space group of P2 1 /c, a molecular formula of C 4 H 8 Cu 2 Mo 4 N 6 O 15 , and a molecular weight of 891.00, the isopoly-molybdic acid coordination polymer has cell parameters of a=13.674(5)Å, b=7.811(3)Å, c=21.980(6)Å, α=90°, β=128.321(15°), γ=90°, cell volume of 1841.8(11)Å 3 , z=4, and a basic structure of the isopoly-molybdic acid coordination polymer catalyst is a three-dimensional network structure coordinated by copper ions, 1,2,4-triazole negative monovalent anions and molybdate[γ-Mo 8 O 26 ] radicals.

3. A method of manufacturing an isopoly-molybdic acid coordination polymer catalyst comprising:
providing a composition, comprising copper salt, sodium molybdate dihydrate, 1,2,4-triazole and distilled water;
adding the composition to a closed reactor and heating the reactor in an oven;
cooling the reactor to a room temperature after a reaction being completed in the reactor;
performing centrifugal drying to the composition to obtain a product;
rinsing the product with deionized water and ethanol; and
drying the product to obtain purified isopoly-molybdic acid coordination polymer catalyst.

4. The method of claim 3 , wherein the heating the reactor in the oven has an oven temperature ranging between 160 and 200° C. and a heating time ranging between 48 and 96 hours.

5. The method of claim 3 , wherein the providing the composition includes a copper salt being selected from the group consisting of copper nitrate trihydrate, copper acetate monohydrate, anhydrous copper chloride, or a combination thereof, a mass ratio between the copper salt and sodium molybdate dihydrate ranges between 1:1 and 1:3, a mass ratio between the copper salt and 1,2,4-triazole ranges between 1:1 and 1:3, and a mass ratio between the sodium molybdate dihydrate and 1,2,4-triazole ranges between 1:1 and 1:2.

6. The method of claim 3 , wherein the providing the composition includes a molar amount and volume ratio between the 1,2,3-triazole and deionized water ranging between 3:10 and 3:40.

7. An application of an isopoly-molybdic acid coordination polymer catalyst comprising:
mixing and heating the isopoly-molybdic acid coordination polymer catalyst and a caprolactone in a dry container.

8. The application of claim 7 , wherein the mixing and heating the isopoly-molybdic acid coordination polymer catalyst and caprolactone has a heating temperature ranging between 120 and 160° C., and a heating time ranging between 1 and 8 hours.

9. The application of claim 7 , wherein the mixing and heating the isopoly-molybdic acid coordination polymer catalyst and caprolactone includes a mass ratio between the isopoly-molybdic acid coordination polymer catalyst and caprolactone ranging between 1:500 and 1:10000.

10. The application of claim 7 , wherein a polycaprolactone obtained by mixing and heating the isopoly-molybdic acid coordination polymer catalyst and caprolactone has a weight average molecular weight ranging between 30,000 and 60,000 and a molecular weight distribution index ranging between 1.2 and 1.5.

Assignees

• Univ Changzhou

Inventors

• Chen Shengchun
• Zhang Qitao
• Chen Qun
• Qian Junfeng
• He Mingyang
• Wei Meijun

Classifications

• B01J23/88 Primary

  Molybdenum · CPC title

• B01J37/04

  Mixing {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• B01J37/08

  Heat treatment {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• C08G63/823

  for the preparation of polylactones or polylactides · CPC title

• C08G83/008 Primary

  Supramolecular polymers · CPC title