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Metal complex for catalyzing cycloate polymerization and application of metal complex for catalyzing cycloate polymerization

A technology of metal complexes and catalyzed cyclic esters, which is used in metal catalysts coordinated by phosphate esters and pyrophosphoric acid to catalyze the ring-opening polymerization of cyclic esters. It can solve the problems of narrow molecular weight distribution, narrow activity, and metal catalysts that have not been reported. Achieve narrow molecular weight distribution and high catalytic activity

Active Publication Date: 2015-11-18
NANJING COSTAR BIOTECHNOLOGY RES INST CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the above catalyst systems either have high activity but wide product molecular weight distribution, or narrow molecular weight distribution but low activity, and it is difficult to balance the characteristics of high activity and narrow molecular weight distribution.
Toyoji Kakuchi of Japan studied the bifunctional activation mechanism of phosphoric acid catalysts, which can effectively control the molecular weight distribution of polymers and have no metal residues in the product, but the catalysts have poor reactivity [Macromolecules, 2011, 44(7), 1999–2005 ]
[0005] It can be seen that the catalysts of the existing cyclic ester coordination ring-opening polymerization cannot take into account the characteristics of catalytic activity and narrow molecular weight distribution, and the present invention provides a phosphate metal complex catalyst, which has high catalytic activity and a wide range of Adaptability to the catalytic environment, that is, the metal complex exhibits strong catalytic activity no matter in bulk polymerization or solution polymerization, and the catalytic polymerization product has the characteristics of narrow molecular weight distribution
So far, such phosphate and pyrophosphate coordinated metal catalysts have not been reported.

Method used

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  • Metal complex for catalyzing cycloate polymerization and application of metal complex for catalyzing cycloate polymerization
  • Metal complex for catalyzing cycloate polymerization and application of metal complex for catalyzing cycloate polymerization
  • Metal complex for catalyzing cycloate polymerization and application of metal complex for catalyzing cycloate polymerization

Examples

Experimental program
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Embodiment 1

[0032]In Examples 11-15, the metal complexes in the above-mentioned Example 1 were used as catalysts, and bulk polymerization was carried out under different temperature conditions. 5.7 g (50 mmol) of ε-caprolactone were respectively placed in a 50 mL flask, and 0.2 mmol of the metal complex in Example 1 and 0.1 mmol of benzyl alcohol were added. Heating in an oil bath at 5 temperatures, reacting at a constant temperature for 2 hours, cooling, sampling and analysis, the conversion rate was measured by liquid chromatography, and the molecular weight was measured by GPC (polystyrene as a standard sample). The experimental results of Examples 11-15 are shown in Table 2.

[0033] The ε-caprolactone monomer described in Examples 11-15 is a product with higher purity after rectification in the production process of caprolactone.

[0034] Polymerization results at different temperatures in table 2

[0035]

[0036] Examples 16–20

[0037] In Examples 16-20, the metal complexes ...

Embodiment 3

[0048] Examples 31-34 use the metal complex of the above-mentioned Example 3 as a catalyst to catalyze the bulk polymerization of 4 different cyclic esters. , 4 kinds, 5g of cyclic esters were respectively placed in 50mL flasks, and 1mg of the polymerization inhibitor in Example 3 was added, heated in an oil bath at 120°C, reacted for 4 hours, cooled, and sampled for analysis of the cyclic ester content. Based on this, the conversion rate of cyclic ester (ie polymerization rate) is calculated, and the experimental results of Examples 31-34 are shown in Table 5.

[0049] Polymerization of different cyclic ester monomers in table 5

[0050]

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Abstract

The invention relates to the technical field of catalyzing of organic chemistry, and provides a metal complex for catalyzing cycloate polymerization and the application of the metal complex for catalyzing the cycloate polymerization. The molecular formula of the metal complex is as shown in the description, wherein R1, R2, R3 and R4 are separately and independently selected from C1-C30 chain alkane groups, C3 -C8 cycloalkyl groups, C2 -C8 alkylene , C2 -C5 alkyne groups, or as shown in the description; R5 and R6 are separately and independently selected from C1 -C5 alkane groups and C1 -C5 alkoxyl groups or hydrogen atoms; M is Sn, Mg, Ca or Zn. The metal complex is suitable for the ring-opening polymerization of a cycloate compound, and besides, a coinitiator can be added. The metal complex disclosed by the invention has high catalytic activity for epsilon-caprolactone and other lactone and lactide monomers, the molecular weight distribution of polyreacted products is narrow in range, the molecular weight size can be regulated, and the metal complex has the characteristics of living polymerization.

Description

technical field [0001] The invention relates to the technical field of organic chemical catalysis, in particular to a metal catalyst coordinated by phosphoric acid ester and pyrophosphoric acid and its use in catalyzing ring-opening polymerization of cyclic esters. Background technique [0002] In the context of serious environmental problems and shortage of petroleum resources, biodegradable plastics have received widespread attention. Among them, polycaprolactone has become a hot spot for research and development. Polycaprolactone is a hydrophobic, semi-crystalline polymer whose crystallinity decreases with the molecular weight of the polymer, and the polymer can be degraded by microorganisms. The raw materials of polycaprolactone industry are renewable biological materials, and the final products of its degradation are also water and carbon dioxide, which can be completely biodegraded and are one of the most competitive biodegradable materials. [0003] The synthesis of...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/30C07F9/32C08G63/08C08G63/85C08G63/83
Inventor 芮桂生唐定良李健葛九敢吴华冯玉军林鸿飞
Owner NANJING COSTAR BIOTECHNOLOGY RES INST CO LTD