Method for preparing polycaprolactone polyol by using enzymatic catalysis method

A technology of polycaprolactone and enzymatic catalysis, which is applied in the field of preparation of polycaprolactone polyols and polyester polyols by enzymatic catalysis, and can solve the problem of uncontrollable content, complexity, polymer metal compound residue synthesis methods, etc. problems, to achieve the effect of improving thermodynamic properties and hydrophilic properties

Active Publication Date: 2018-08-21
EAST CHINA UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the above-mentioned synthesis route of polyester polyol often requires the use of organometallic catalysts or cumbersome procedures such as protection and deprotection of the hydroxyl groups of polyols. These steps are usually accompanied by the disadvantages of polymer metal compound residues and complex synthesis methods.
[0004] In the prior art, the invention patent CN1572851A discloses a method for preparing an enzyme-catalyzed polyester and polyol polymer, but the method uses polyol (polyhydric small molecule) as an initiator to initiate the ring-opening polymerization of lactone or Polycondensation with polybasic acid / anhydride, the hydroxyl group of the obtained polyester polyol is located at the end of the molecular chain, and its number is consistent with the number of hydroxyl groups contained in the initiator (for example: the product obtained by ring opening / polycondensation initiated by diol is polyester binary Alcohol), there is a small number of hydroxyl groups and the inability to control its content, etc.

Method used

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  • Method for preparing polycaprolactone polyol by using enzymatic catalysis method
  • Method for preparing polycaprolactone polyol by using enzymatic catalysis method
  • Method for preparing polycaprolactone polyol by using enzymatic catalysis method

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Effect test

Embodiment 1

[0048] Connect a 25mL reaction flask with a magnetic stirrer to the double-row tube, and use a gas lamp to bake the tube 3 times to remove the residual moisture in the flask. Under the condition of argon gas, caprolactone monomer (1.03g, 9mmol), N-phenyldiethanolamine (1.631g, 9mmol), catalyst N435 (450mg) and solvent diphenyl ether (9.0g) were sequentially added. The argon gas was used to ventilate 3 times, and the reaction temperature was set to 70°C. After 24 hours of reaction at this temperature, the reaction can be stopped to obtain polycaprolactone prepolymer (PCL 1 ), its structural formula is shown in formula V, where n 1 +n 2 = 1.

Embodiment 2

[0050] Connect a 25mL reaction flask with a magnetic stirrer to the double-row tube, and use a gas lamp to bake the tube 3 times to remove the residual moisture in the flask. Under argon, add caprolactone monomer (3.078g, 27mmol), N-phenyldiethanolamine (0.979g, 5.4mmol), catalyst N435 (510mg) and solvent diphenyl ether (10.32g) in sequence . The argon gas was used to ventilate 3 times, and the reaction temperature was set to 70°C. After 24 hours of reaction at this temperature, the reaction can be stopped to obtain polycaprolactone prepolymer (PCL 5 ), its structural formula is shown in formula V, where n 1 +n 2 = 5.

Embodiment 3

[0052] Connect a 25mL reaction flask with a magnetic stirrer to the double-row tube, and use a gas lamp to bake the tube 3 times to remove the residual moisture in the flask. Under the condition of argon gas, caprolactone monomer (3.42g, 30mmol), N-phenyldiethanolamine (0.381g, 2mmol), catalyst N435 (430mg) and solvent diphenyl ether (8.42g) were sequentially added. The argon gas was used to ventilate 3 times, and the reaction temperature was set to 70°C. After 24 hours of reaction at this temperature, the reaction can be stopped to obtain polycaprolactone prepolymer (PCL 15 ), its structural formula is shown in formula V, where n 1 +n 2 = 15.

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Abstract

The invention discloses a method for preparing polycaprolactone polyol by using an enzymatic catalysis method. The method comprises: S1, under a solvent condition, carrying out ring opening polymerization by using N-phenyldiethanolamine or binary primary alcohol as an initiator, using caprolactone as a monomer and using immobilized enzyme as catalyst to obtain a prepolymer with a structure represented by a formula V defined in the specification, wherein the sum of n1 and n2 is 1-50; and S2, carrying out a reaction on the prepolymer prepared in the step S1 and D-diethyl tartrate to obtain a compound represented by a formula IV defined in the specification, wherein the sum of n1 and n2 is 1-50. According to the present invention, the product can improve the thermodynamic property and the hydrophilic property of the polycaprolactone material to a certain extent, can introduce a certain amount of hydroxyl groups into the side chain of the polymer, and can be used for post-modification of the polymer or other applications.

Description

Technical field [0001] The invention belongs to the technical field of polyester polyol preparation, and relates to a preparation method of polyester polyol, and specifically relates to a method for preparing polycaprolactone polyol by an enzyme catalysis method. Background technique [0002] Due to the unique biocompatibility, biodegradability, and good permeability of polyvinyl lactone (PCL), it is widely used in the fields of biomaterials and medicine. Polycaprolactone is a semi-crystalline hydrophobic polymer whose crystallinity decreases with increasing molecular weight. Its hydrophobicity leads to a long degradation cycle, which is often difficult to meet the diverse needs of biomedicine. Therefore, the introduction of hydrophilic groups on the polycaprolactone chain can effectively improve this shortcoming, and can also provide potential applications for polymer post-modification. [0003] Polyester polyol materials are usually formed by condensation (or transesterificatio...

Claims

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Application Information

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IPC IPC(8): C08G63/685C12P7/62
CPCC08G63/6852C12P7/625
Inventor 肖艳潘景浩
Owner EAST CHINA UNIV OF SCI & TECH
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