Composite catalyst for preparing polyether-polylactide-aliphatic polycarbonate ternary block copolymer and application of composite catalyst

A technology of composite catalyst and polylactide, which is applied in the polymer field to achieve good catalytic effect, narrow molecular weight distribution and high catalytic efficiency

Inactive Publication Date: 2016-09-21
WUHAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Metalloporphyrin and metallosalen catalysts are catalysts with definite structure and good modifiability, which can be applied to the living three-way copolymerization of carbon dioxide, propylene oxide and lactide, but the method of adding monomers step by step The preparation of polyether-polylactide-polycarbonate block copolymers has not been reported in the literature,

Method used

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  • Composite catalyst for preparing polyether-polylactide-aliphatic polycarbonate ternary block copolymer and application of composite catalyst
  • Composite catalyst for preparing polyether-polylactide-aliphatic polycarbonate ternary block copolymer and application of composite catalyst
  • Composite catalyst for preparing polyether-polylactide-aliphatic polycarbonate ternary block copolymer and application of composite catalyst

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026]

[0027]Add 22.7mg (0.036mmol) of the SalenCrCl catalyst shown in the above formula, 8.78mg (0.072mmol) of the promoter DMAP and 0.5mL of propylene oxide into the autoclave respectively (SalenCrCl catalyst: promoter: propylene oxide=1:2 :200 (molar ratio)), the polymerization reaction temperature is 60 ℃, after reacting for 12 hours, add lactide 1.037g (the molar ratio of lactide and propylene oxide is 1:1) and solvent dioxane 5mL After reacting for 2 hours, feed carbon dioxide into the autoclave to maintain the pressure in the kettle at 3MPa, and the reaction time was 18 hours. After the reaction, 100mL of methanol hydrochloride (HCl mass percentage concentration was 1%) was added to terminate the reaction, and the obtained The product was washed with a large amount of methanol, and dried in vacuum to obtain 1.6 g of white polyether-polylactide-aliphatic polycarbonate ternary block copolymer with a number-average molecular weight of 10,000 and a molecular weight dist...

Embodiment 2

[0030]

[0031] The SalenCo(OC shown in the above formula 6 h 3 (NO 2 ) 2 ) catalyst 29mg (0.035mmol), co-catalyst 2,6-lutidine 7.58mg (0.07mmol) and propylene oxide 12.2mL (175mmol) were added in the autoclave respectively (molar ratio SalenCo(OC 6 h 3 (NO 2 ) 2 ) Catalyst: co-catalyst: propylene oxide=1:2:5000), polymerization reaction temperature is 25 ℃, after reacting for 24 hours, add lactide 2.52g again (the mol ratio of lactide and propylene oxide is 1: 10) and solvent dichloromethane 10mL, after reacting for 6 hours, then rapidly charge carbon dioxide in the autoclave, the pressure in the autoclave is maintained at 1.5MPa, and the reaction time is 22 hours, add 100mL hydrochloric acid methanol (HCl mass hundred concentration is 1%) to terminate the reaction, the resulting product is washed with a large amount of methanol, and vacuum-dried to obtain 3.3 g of white polyether-polylactide-aliphatic polycarbonate ternary block copolymer, its number-average molecul...

Embodiment 3

[0033]

[0034] The SalenCr (OOCCF shown in the above formula 3 ) catalyst 23mg (0.035mmol), bis-(triphenylphosphoryl) ammonium chloride PPNCl 10mg (0.0175mmol) and propylene oxide 12.2mL (175mmol) were added in the autoclave respectively (molar ratio SalenCr(OOCCF 3 ) Catalyst: cocatalyst: propylene oxide=1:0.5:5000), polymerization reaction temperature is 60 ℃, after reacting for 10 hours, add lactide 0.504g again (the mol ratio of lactide and propylene oxide is 1: 50) of propylene oxide 5mL solution, after reacting for 6 hours, then quickly charge carbon dioxide in the autoclave, the pressure in the autoclave was maintained at 4.5MPa, and the reaction time was 22 hours. Add 100mL of methanol hydrochloride (HCl mass hundred concentration is 1%) to terminate the reaction, the resulting product is washed with a large amount of methanol, and vacuum-dried to obtain 0.6g of white polyether-polylactide-aliphatic polycarbonate ternary block copolymer, its number-average molecula...

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Abstract

The invention relates to a composite catalyst for preparing a polyether-polylactide-aliphatic polycarbonate ternary block copolymer and an application of the composite catalyst. The composite catalyst comprises a metal Salen catalyst and a cocatalyst in a molar ratio of 1: (0.5-2), wherein the cocatalyst is bis-(triphenylphosphine)iminium chloride, 4-dimethylaminopyridine or 2,6-lutidine. The composite catalyst has the following beneficial effects: 1, The catalysis effect of the composite catalyst is good, the catalysis efficiency is high, the obtained ternary copolymer has larger number-average molecular weight and narrow molecular weight distribution; 2, composition of a polyether segment, a polylactide segment and a PPC (poly(propylene carbonate)) segment in the copolymer can be effectively controlled through regulation of step reaction time and monomer ratio, the glass transition temperature of the copolymer is 2-42 DEG C, the elongation at break is 55%-331%, and the tensile strength is 6-39 MPa.

Description

technical field [0001] The invention relates to the technical field of macromolecules, in particular to a composite catalyst for preparing polyether-polylactide-aliphatic polycarbonate ternary block copolymer and its application. Background technique [0002] Carbon dioxide is considered to be the main gas responsible for the "greenhouse effect", leading to climate changes such as global warming, melting of glaciers, and extreme weather. Therefore, the utilization and fixation of carbon dioxide has attracted great attention. One way to solve this problem is to turn this abundant and cheap source of carbon dioxide into polymer products. Since 1969, Inoue Shohei et al.'s pioneering work, using carbon dioxide and epoxy compounds to synthesize aliphatic polycarbonate, has become a potentially important way to effectively utilize carbon dioxide. Carbon dioxide copolymer (polypropylene carbonate PPC) with high alternating structure can be synthesized by using carbon dioxide and p...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G63/82C08G63/84C08G64/34
CPCC08G63/823C08G64/34
Inventor 谢东刘军吟李昱浩孙娜
Owner WUHAN UNIV OF TECH
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