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Triblock copolymer using furandicarboxylic acid flexible random copolyester as soft block and preparation method thereof

A technology of furandicarboxylic acid and copolyester, which is applied in the field of triblock copolymer and its preparation, can solve the problems of decreased environmental protection significance, loss of properties of bio-based materials, etc., and achieves commercialization, reduced dependence, and simple process. Effect

Active Publication Date: 2015-02-11
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The block copolymer exhibits good mechanical properties, but because this method uses a large amount of petroleum-based monomer terephthalic acid, it loses the properties of bio-based materials, and the significance of environmental protection is greatly reduced

Method used

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  • Triblock copolymer using furandicarboxylic acid flexible random copolyester as soft block and preparation method thereof
  • Triblock copolymer using furandicarboxylic acid flexible random copolyester as soft block and preparation method thereof
  • Triblock copolymer using furandicarboxylic acid flexible random copolyester as soft block and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0068] (1) Add 31.2 grams (0.2mol) of 2,5-furandicarboxylic acid, 35.4 grams (0.3mol) of succinic acid, 90 grams (1mol, alkyd-acid molar ratio) of butanediol, and titanic acid into the reactor. 85 milligrams of butyl esters (accounting for 0.05mol% of the total amount of dibasic acid monomers) were subjected to an esterification reaction at 160-200°C for 4 hours (this process is a temperature-programmed process) to obtain an esterified product; 85 mg of n-butyl titanate (accounting for 0.05 mol% of the total amount of dibasic acid monomers), at 200-240°C and 10-500Pa pressure (during the reaction, the pressure is gradually reduced from 500Pa to 10Pa), the melt polycondensation reaction After 5 hours, the flexible random copolyester-poly(butylene succinate-co-2,5-butylene furandicarboxylate) of hydroxyl-terminated furandicarboxylic acid was obtained, denoted as PBS 60 f 40 ;

[0069] (2) Add 113.4 grams of L-lactide to the product of step 1, and add 0.113 grams of stannous oc...

Embodiment 2

[0071] (1) Add 23.4 grams (0.15mol) of 2,5-furandicarboxylic acid, 33.2 grams (0.2mol) of terephthalic acid, 21.9 grams (0.15mol) of adipic acid, and 135 grams (1.5 mol, alkyd acid molar ratio 3), add 170 mg of n-butyl titanate (accounting for 0.1 mol% of the total amount of dibasic acid monomers), and perform an esterification reaction at 190-230° C. for 1 hour to obtain an esterified product; Add catalyst, melt polycondensation reaction at 200-250°C, 50-500Pa pressure for 8 hours, and prepare flexible random copolyester-poly(butylene adipate-co-2) of hydroxyl-terminated furandicarboxylic acid , 5-butanediol furandicarboxylate-co-butylene terephthalate), denoted as PBA 30 f 30 T 40 ;

[0072] (2) Add 10.6 grams of D-lactide to the product of step 1, and add 53 mg of stannous octoate (0.5wt% of D-lactide), and react at 160-180°C for 0.5 hours to obtain PBA 30 f 30 T 40 A triblock copolymer PDLA-b-PBA with soft segment and poly(D-lactide) as hard segment 30 f 30 T 40 ...

Embodiment 3

[0074](1) Add 23.4 grams (0.15mol) of 2,5-furandicarboxylic acid, 21.9 grams (0.15mol) of adipic acid, 11.8 grams (0.1mol) of succinic acid, and 20.2 grams (0.1mol) of sebacic acid into the reactor ), 67.5 grams of butanediol (0.75mol, alkyd molar ratio 1.5), 142 mg of isopropyl titanate (accounting for 0.1mol% of the total amount of dibasic acid monomers), esterification reaction at 190-220°C for 1 After 1 hour, an esterification product was obtained; 110 mg of lanthanum acetylacetonate (accounting for 0.05mol% of the total amount of dibasic acid monomers) was added to the esterification product, and the melt polycondensation reaction was carried out at 220~250°C and 100~500Pa pressure for 8 hours, the flexible random copolyester of furandicarboxylic acid with terminal hydroxyl group—poly(butylene succinate-co-butylene adipate-co-butylene sebacate-co-2 , 5-butylene furandicarboxylate), recorded as PBS 20 A 30 Se 20 f 30 ;

[0075] (2) Add 40.8 grams of glycolide to the p...

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Abstract

The invention discloses a triblock copolymer using furandicarboxylic acid flexible random copolyester as a soft block and a preparation method thereof. The triblock copolymer is of a hard-soft-hard structure, the mass ratio of the soft block to the hard block is (10:90)-(90:10); the hard block is polylactic acid, polyglycolide or poly (p-dioxanone); and the soft block is a random copolyester composed of a furandicarboxylic acid dibasic alcohol ester chain element and at least one aliphatic dibasic acid dibasic alcohol ester chain element. The triblock copolymer is obtained by firstly carrying out copolycondensation on furandicarboxylic acid, at least one aliphatic dibasic acid and aliphatic dibasic alcohol to obtain a hydroxyl-terminated furandicarboxylic acid copolyester soft block and then initiating ring-opening polymerization of lactide, glycolide or p-dioxanone. The triblock copolymer is a partial or complete bio-based polymer, the hard block is crystallizable and the soft block has weak crystallinity or is close to be amorphous and has excellent comprehensive performances. The preparation method disclosed by the invention has the advantages of simple process, no application of organic solvents and environmental friendliness and is conductive to commercialization.

Description

technical field [0001] The invention relates to a three-block copolymer and a preparation method thereof, in particular to a three-block copolymer with furandicarboxylic acid flexible random copolyester as a soft segment and a preparation method thereof. Background technique [0002] As an environmentally friendly material prepared from renewable resources, bio-based polymers, as a substitute for traditional non-renewable petroleum-based polymers, are becoming more and more popular when the environment is deteriorating and petroleum resources are becoming increasingly tense. Pay attention to. However, due to the unsatisfactory mechanical properties of existing bio-based polymers, their application range is limited. Therefore, how to improve the mechanical properties of bio-based polymers is one of the research priorities that people are facing. [0003] Polylactic acid (polylactic acid produced by ring-opening polymerization of lactide is also commonly referred to as polyl...

Claims

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Application Information

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IPC IPC(8): C08G63/672C08G63/664C08G63/78
Inventor 吴林波徐煜韬
Owner ZHEJIANG UNIV
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