Thermal response poly-(carbonate-ether) capable of being biologically degraded and preparation method thereof

A biodegradable and carbonated technology, applied in the field of poly(carbonate-ether), can solve the problems of limited application and non-biodegradable polymers

Active Publication Date: 2012-09-19
CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the polymer is not biodegradable, which limits its applicat

Method used

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  • Thermal response poly-(carbonate-ether) capable of being biologically degraded and preparation method thereof
  • Thermal response poly-(carbonate-ether) capable of being biologically degraded and preparation method thereof
  • Thermal response poly-(carbonate-ether) capable of being biologically degraded and preparation method thereof

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[0035] Correspondingly, the present invention also provides a method for preparing the above-mentioned poly(carbonate-ether), which includes the following steps: copolymerizing carbon dioxide and ethylene oxide on the double metal cyanide-rare earth complex catalyst by the catalytic action , Get poly(carbonate-ether). The reaction formula is as follows:

[0036]

[0037] The poly(carbonate-ether) prepared above has the structural unit shown in formula I:

[0038]

[0039] Formula I,

[0040] Wherein, n is the ratio of the structural unit represented by formula II to the structural unit represented by formula I, and n is 4%-45%.

[0041]

[0042] Formula II.

[0043] The number average molecular weight of poly(carbonate-ether) is 70 to 250 kg / mol, preferably 70 to 247 kg / mol; the transition temperature is 10 to 90°C, preferably 35 to 37°C.

[0044] According to the present invention, the double metal cyanide-rare earth complex composite catalyst is an important factor affecting the prop...

Example Embodiment

[0053] Example 1

[0054] Preparation of double metal cyanide-rare earth complex composite catalyst

[0055] The double metal cyanide catalyst is prepared with reference to the method of Eur.Polym.J.,47(11),2152,2011:

[0056] 11.42g (0.084mol) ZnCl 2 Dissolve in a mixed solution of 60mL deionized water and 30mL tert-butanol (TBA). The resulting solution is heated to 50°C and kept at a constant temperature for 20min, and then added dropwise to the solution with a dropping funnel under stirring (300rpm) 1.32g (0.004mol) analytically pure K 3 [Co(CN) 6 ] And 20mL of deionized water. It takes 45 minutes to add dropwise to keep the reaction constant at 50°C. After the dropwise addition, continue to stir at 50°C for 1 hour; the resulting suspension is centrifuged for 10 minutes with a centrifuge (5000rpm), decanted and separated Use 60mL 50℃ TBA / H 2 The mixed solution of O is washed 5 times with chemical slurry, and finally with TBA chemical slurry once, the mixed solution TBA / H 2 O (V / V...

Example Embodiment

[0059] Example 2

[0060] 5mg Zn 3 [Co(CN) 6 ] 2 ·0.92ZnCl 2 ·2.05t-BuOH·1.93H 2 A composite catalyst composed of O, 8mg yttrium trichloroacetate and 10mL 1,3-dioxolane in CO 2 Add under protection, pump down at 80°C (20~40Pa), charge CO 2 Processing for 2 hours (charge CO 2 10 times) and cooled to 0°C in the autoclave, while adding 100 mL of ethylene oxide into the autoclave, and quickly pass the carbon dioxide pressure regulator to make the carbon dioxide pressure in the autoclave reach 4.0 MPa. The polymerization temperature was 90°C, the reaction time was 6 hours, and the stirring speed was 500 rpm. After the polymerization, the autoclave was cooled to 0°C with a cold water bath, the residual carbon dioxide in the autoclave was slowly removed, and dichloromethane was added to the autoclave until the polymer was diluted to facilitate the passage of the G2 glass sand core funnel, with G2 glass The diluent was filtered through a sand core funnel to remove the catalyst, and then ...

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Abstract

The invention discloses thermal response poly-(carbonate-ether) capable of being biologically degraded and a preparation method thereof. The method comprises a step of implementing co-polymerization reaction for carbon dioxide and ethylene oxide under a catalytic action of a composite catalyst of a duplex-metal-cyanide-rare-earth complex to obtain the poly-(carbonate-ether). Because the rare earth complex can accelerate the ring-opening reaction of the ethylene oxide, so that the method can adopt the composite catalyst of the duplex-metal-cyanide-rare-earth complex to accelerate the co-polymerization reaction, can ensure that the contents of the carbonic ester of the poly-(carbonate-ether) can be adjusted within 4% and 45%, and can ensure that the prepared poly-(carbonate-ether) has thermal response performance while being biologically degraded. The test result shows that the poly-(carbonate-ether) prepared by using the method has a thermal response behavior in water liquid and can be dissolved in water at low temperature. The polymer cannot be dissolved and separated out from water while the temperature is higher than the critical dissolving temperature. The transition temperature is 10 DEG C to 90 DEG C. Especially the poly-(carbonate-ether) has the thermal response behavior at 35 DEG C to 37 DEG C.

Description

technical field [0001] The invention relates to the technical field of poly(carbonate-ether), and more specifically, relates to a biodegradable heat-responsive poly(carbonate-ether) and a preparation method thereof. Background technique [0002] As a room temperature gas, the greenhouse effect produced by carbon dioxide has constituted increasingly serious environmental pollution, so reducing carbon dioxide emissions has become a focus of attention of countries all over the world. But on the other hand, carbon dioxide is an inexhaustible raw material. One of the main directions of using carbon dioxide is to use it as a raw material to synthesize polymer materials. For example, carbon dioxide and 2-methylaziridine can be used as raw materials to copolymerize aliphatic poly(urethane-amine) with thermally responsive carbon dioxide-based copolymers. . Due to the presence of hydrophobic urethane units and hydrophilic amine units in the main chain, the polymer exhibits thermores...

Claims

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Application Information

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IPC IPC(8): C08G64/34
Inventor 顾林周庆海王献红王佛松
Owner CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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