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Preparation method of crystalline/amorphous triblock copolymer

A tri-block, amorphous technology, applied in the field of block copolymer preparation, can solve problems such as lack of PHA

Active Publication Date: 2012-11-21
DONGHUA UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, there is still a lack of synthesis and theoretical studies of PHA-based crystalline-amorphous block polymers, how does the amorphous component in crystalline-amorphous block polymers affect the crystallization behavior of PHA, and how does it cause thermal degradation of the block copolymer? Performance changes, these are of great significance to the modification and processing of PHA

Method used

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  • Preparation method of crystalline/amorphous triblock copolymer
  • Preparation method of crystalline/amorphous triblock copolymer
  • Preparation method of crystalline/amorphous triblock copolymer

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Under nitrogen protection, add chloroform (ρ=1.48g / cm 3 ) 118ml, macromer PHBV-diol 5mmol, acid-binding agent triethylamine 3.333mmol, slowly drop 10mmol of 2-bromoisobutyryl bromide, warm up to room temperature, react for 24h, ether precipitates to obtain 2-bromo Substituted isobutyryl-based PHBV macroinitiator (PHBV-diBr).

[0024] Under the protection of nitrogen, add 1,4-dioxane (2.550ml) 29.028mmol, PHBV-diBr0.354mmol, methyl acrylate MMA monomer 5.664mmol, PMDETA0.708mmol, cuprous bromide 0.708mmol to the reaction eggplant bottle successively mmol, mix well, heat up to 70°C for 8h, and then quench the reaction with liquid nitrogen. Add 1,4-dioxane (15ml) to the reaction flask to dilute the reaction product, use a 200-mesh neutral alumina column to remove unreacted initiators, catalysts and ligands, distill the concentrated solution under reduced pressure, and use glacial ether to The product was precipitated to obtain the triblock copolymer PMMA-b-PHBV-b-PMMA. ...

Embodiment 2

[0030] Under nitrogen protection, add chloroform (ρ=1.48g / cm 3 ) 130ml, macromonomer PHB-diol 5mmol, acid-binding agent triethylamine 3.333mmol, slowly drop 10mmol of 2-bromoisobutyryl bromide, warm to room temperature, react for 4h, ether precipitates to obtain 2- Bromoisobutyryl-based PHB macroinitiator (PHB-diBr).

[0031] Under the protection of nitrogen, add 29.028mmol of 1,4-dioxane (2.550ml), 0.354mmol of PHB-diBr, 67.968mmol of MMA, 0.708mmol of PMDETA, and 0.708mmol of cuprous chloride in the reaction eggplant bottle, and mix well , after the temperature was raised to 70° C. for 6 h, the reaction was quenched with liquid nitrogen. Add 1,4-dioxane (15ml) to the reaction flask to dilute the reaction product, use a 200-mesh neutral alumina column to remove unreacted initiators, catalysts and ligands, distill the concentrated solution under reduced pressure, and use glacial ether to The product was precipitated to obtain the triblock copolymer PMMA-b-PHB-b-PMMA.

Embodiment 3

[0033] Under nitrogen protection, add chloroform (ρ=1.48g / cm 3) 172.50ml, macromonomer P(3HB-co-4HB)-diol5 mmol, acid-binding agent triethylamine 3.333mmol, slowly drop 10mmol of 2-bromoisobutyryl bromide, warm to room temperature, react for 36h, diethyl ether The P(3HB-co-4HB) macroinitiator (P(3HB-co-4HB)-diBr) with 2-bromoisobutyryl at both ends was obtained by precipitation.

[0034] Under nitrogen protection, 1,4-dioxane (2.550ml) 29.028mmol, P(3HB-co-4HB)-diBr0.354mmol, MMA 11.328mmol, bpy0.708mmol, Copper 0.708mmol, fully mix uniformly, be heated up to 70 ℃ of reaction 8h, adopt liquid nitrogen to quench the reaction. Add 1,4-dioxane (15ml) to the reaction flask to dilute the reaction product, use a 200-mesh neutral alumina column to remove unreacted initiators, catalysts and ligands, distill the concentrated solution under reduced pressure, and use glacial ether to The product was precipitated to obtain the triblock copolymer PMMA-b-P(3HB-co-4HB)-b-PMMA.

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Abstract

The invention relates to a preparation method of a crystalline / amorphous triblock copolymer, which comprises the steps of: (1) using poly-hydroxy fatty acid ester macromer PHA-diol with hydroxyl groups at the two ends as a matrix in chloroform solution in the nitrogen atmosphere, adding a modifier and an acid binding agent, and performing reaction for 4-36 hours at room temperature to obtain a PHA macroinitiator PHA-diBr with 2-bromoisobutyryl groups at the two ends; and (2) adding PHA-diBr, a methacrylate ester monomer, a catalyst and ligand into 1, 4-dioxane solution in the nitrogen atmosphere, mixing well, heating to 70-100 DEG C, performing reaction for 6-8 hours, stopping reaction with liquid nitrogen, separating, and purifying, thereby obtaining the crystalline / amorphous triblock copolymer. The molecular weight and the length of block components of the prepared triblock copolymer are controllable. Changes in the thermal performance of PHA crystalline and block copolymers can be affected by amorphous components in the triblock copolymer, and important significance can be achieved for modification and processing of PHA.

Description

technical field [0001] The invention belongs to the field of preparation of block copolymers, in particular to a preparation method of crystalline / amorphous tri-block copolymers. Background technique [0002] Polyhydroxyalkanoate (PHA) is a non-petroleum-based polyester material produced by microbial fermentation of polysaccharide-containing plants, and its resources are renewable and biodegradable. The PHA molecular chain has high stereoregularity and a large crystallization tendency; the molecular chain is flexible, and its glass transition temperature Tg is lower than room temperature. At around 0°C, secondary crystallization will occur during storage, and because of its small nucleation density , the spherulites will develop to super large sizes visible to the naked eye. There are many defects and voids in the large spherulites, and the mutual extrusion between spherulites will cause cracks in the spherulites, resulting in poor toughness of the material. [0003] Peopl...

Claims

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Application Information

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IPC IPC(8): C08F293/00
Inventor 朱美芳相恒学王世超江晓泽王仁林
Owner DONGHUA UNIV