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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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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the polymer is not biodegradable, which limits its application in some biomedical applications, especially in vivo applications

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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preparation example Construction

[0035] Correspondingly, the present invention also provides a preparation method of the above-mentioned poly(carbonate-ether), comprising the following steps: carrying out a copolymerization reaction of carbon dioxide and ethylene oxide under the catalysis of a double metal cyanide-rare earth complex composite catalyst , to give poly(carbonate-ether). The reaction formula is as follows:

[0036]

[0037] The poly(carbonate-ether) prepared above has a 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 the poly(carbonate-ether) is 70~250kg / mol, preferably 70~247kg / mol; the transition temperature is 10~90°C, preferably 35~37°C.

[0044] According to the present invention, the double metal cyanide-rare earth complex composite cataly...

Embodiment 1

[0054] Preparation of Double Metal Cyanide-Rare Earth Complex Composite Catalyst

[0055] 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 formed by 60mL deionized water and 30mL tert-butanol (TBA), heat the formed solution to 50°C and keep the temperature for 20min, then add 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, the dropwise addition takes 45min, keeping the reaction constant at 50°C, and continuing to stir at 50°C for 1h after the dropwise addition; the obtained suspension is centrifuged with a centrifuge (5000rpm) for 10min, poured out and separated The supernatant and the sediment were successively washed with 60mL 50℃ TBA / H 2 The mixed solution of O was pulped and washed 5 times, and finally washed once with TBA pulp, and the mixed solu...

Embodiment 2

[0060] 5mg Zn 3 [Co(CN) 6 ] 2 0.92ZnCl 2 2.05t-BuOH 1.93H 2 O, the composite catalyst of 8mg trichloroacetate yttrium and 10mL 1,3-dioxane composition is in CO 2 Under protection, add in evacuation (20~40Pa) at 80°C, fill with CO 2 Treat for 2 hours (filled with CO 2 10 times), and cooled to 0°C in the autoclave, at the same time, 100mL of ethylene oxide was added into the autoclave, and the pressure of carbon dioxide in the autoclave reached 4.0MPa quickly through the carbon dioxide pressure regulator. The polymerization reaction 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, and the residual carbon dioxide in the autoclave was slowly removed, and dichloromethane was added into the autoclave until the polymer was diluted to facilitate passing through the G2 glass sand core funnel. Filter the diluent through a sand core funnel to remove the catal...

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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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