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Thermoplastic copolyester composition with thermally reversible chemical crosslinking properties and preparation method and application thereof

A thermoplastic copolyester and chemical crosslinking technology, which is applied to thermoplastic copolyester compositions with thermally reversible chemical crosslinking properties and their preparation and application fields, can solve the problem of affecting the secondary processing and utilization of polymer recycling and restricting applications. It can achieve the effect of excellent thermo-mechanical properties, favorable material properties, and commercialization.

Active Publication Date: 2015-12-16
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Chemically crosslinked thermosetting polymers, the most common such as vulcanized rubber, have excellent mechanical properties and heat resistance, but the existence of chemically crosslinked structures makes it difficult to carry out secondary processing, which makes a large number of Scraps and waste products generated during use are difficult to be reused and wasted through thermoplastic processing; thermoplastic elastomers have good thermoplasticity and are easy to process and recycle, but their thermo-mechanical properties are often not as good as chemical crosslinking Thermosetting polymers, thus limiting its application and scope to a certain extent
[0003] At this stage, some research has been devoted to the preparation of thermally reversible chemically crosslinked polymers, but due to the limitation of direct selection of commercialized polymers or the lack of its own molecular structure design, the final crosslinked polymers The main chain still contains a large number of unsaturated carbon-carbon double bonds, and the presence of unsaturated carbon-carbon double bonds makes the cross-linked polymer prone to produce a large number of irreversible cross-linked structures under thermal processing and long-term use of natural light.
Therefore, even if the polymer itself has a thermally reversible cross-linked structure, the irreversible cross-linked structure produced by unsaturated bonds in the later stage will inevitably greatly affect the recovery and secondary processing of the polymer.

Method used

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  • Thermoplastic copolyester composition with thermally reversible chemical crosslinking properties and preparation method and application thereof
  • Thermoplastic copolyester composition with thermally reversible chemical crosslinking properties and preparation method and application thereof
  • Thermoplastic copolyester composition with thermally reversible chemical crosslinking properties and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0075] Embodiment 1: the preparation of PBASf-BMI composition

[0076] (1) In a 250mL flask, add adipic acid (0.5mol, 73g), 1,4-butanediol (1.0mol, 90.1g), functional monomer DMF-FM containing 2-furfurylsulfanyl side group (the amount is 5mol%, 10mol%, 15mol%, 20mol% of the total acid feed) and n-butyl titanate (the amount is 0.2mol% of the total acid), the alkyd ratio is 2, and the reaction 6- After 7 hours, an esterified product was obtained with an esterification rate of 98%; n-butyl titanate was added to the esterified product (the amount used was 0.1 mol% of the total acid), and the melt polycondensation reaction was carried out at 190-220°C and about 100Pa. -6 hours, the copolyester PBASf having 2-furfurylthio side groups was prepared.

[0077] (2) A mold for mixing the copolyester PBASf prepared in step (1) and bismaleimide (the molar ratio of furan and maleimide groups is 1:1.1 to 1.1:1) The method of thermocompression molding, prepares the thermoplastic copolyester ...

Embodiment 2

[0081] Embodiment 2: the preparation of PBSf-BMI composition

[0082] (1) In a 250mL flask, add succinic acid (0.5mol, 59g), 1,4-butanediol (1.0mol, 90.1g), functional monomer DMF-FM containing 2-furfurylsulfanyl side group (the amount is 5mol%, 10mol%, 15mol%, 20mol% of the total acid feed) and n-butyl titanate (the amount is 0.2mol% of the total acid), the alkyd ratio is 2, and the reaction 3- 6h, the esterification product was obtained, and the esterification rate reached 98%; n-butyl titanate was added to the esterification product (the amount used was 0.1mol% of the total acid), and the melt polycondensation reaction was carried out at 190-220°C and about 100Pa. -6 hours, the copolyester PBSf having 2-furfurylthio side groups was prepared.

[0083] (2) Mix the copolyester PBSf prepared in step (1) with bismaleimide BMI (the molar ratio of furan and maleimide groups is 1:1.1~1.1:1) A thermoplastic copolyester composition PBSf-BMI with thermally reversible crosslinking pr...

Embodiment 3

[0084] Embodiment 3: the preparation of PBSASf-BMI composition

[0085] (1) Add succinic acid (0.25mol, 59g), adipic acid (0.25mol, 36.5g) 1,4-butanediol (1.0mol, 90.1g) and 2-furfurylsulfanyl in a 250mL flask The functional monomer DMF-FM of the side group (the amount is 5mol%, 10mol%, 15mol%, 20mol% of the total acid feed) and n-butyl titanate (the amount is 0.2mol% of the total acid), the alkyd ratio is 2 , react at 160-190°C for 4-7h to obtain an esterified product with an esterification rate of 98%; add n-butyl titanate (0.1mol% of total acid) to the esterified product, The melt polycondensation reaction is carried out under the conditions of ℃ and about 100 Pa for 4-6 hours, and the copolyester PBSASf with 2-furfurylsulfanyl side groups is prepared.

[0086] (2) Mix the copolyester PBSASf prepared in step (1) with bismaleimide (the molar ratio of furan and maleimide groups is 1:1.1 to 1.1:1) with a mold A thermoplastic copolyester composition PBSASf-BMI with thermoreve...

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Abstract

The invention discloses a thermoplastic copolyester composition with thermally reversible chemical crosslinking properties and a preparation method and application thereof. The copolyester contains a side functional group, namely 2-furfuryl sulfenyl, and is prepared from dibasic acid or dibasic acid ester containing 2-furfuryl sulfenyl, dibasic acid and dibasic alcohol by a melting copolycondensation method. The 2-furfuryl sulfenyl of the copolyester and a crosslinking agent containing maleimide can carry out Diels-Alder cycloaddition reaction at 50-70 DEG C to realize chemical crosslinking and can realize decrosslinking at high temperature, thereby being convenient for recovery and secondary processing and utilization of the materials and realizing a self-repairing or shape memory function of the materials. The thermally reversible crosslinking copolyester designed in the invention has a saturated main chain structure, has excellent thermal stability and mechanical properties, is not easy to generate an irreversible crosslinking structure in thermal processing and life-time service processes of the materials, and can realize thermoplastic processing many times and keep the mechanical properties unchanged.

Description

technical field [0001] The present invention relates to a thermoplastic copolyester composition with thermally reversible chemical crosslinking properties and its preparation method and application, especially relates to utilizing the thermally reversible properties of Diels-Alder cycloaddition reaction to realize 2-furfurylsulfanyl side groups Thermally reversible crosslinking between the copolyester and the crosslinking agent containing maleimide groups to prepare a thermally reversible chemically crosslinked thermoplastic with good mechanical properties, recyclable reprocessing and self-healing Copolyester compositions. Background technique [0002] For polymers, chemical crosslinking structure and thermoplasticity are often a pair of contradictions, and it is difficult to coexist. Chemically crosslinked thermosetting polymers, the most common such as vulcanized rubber, have excellent mechanical properties and heat resistance, but the existence of chemically crosslinked ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G63/688C08G63/78C08J3/24C08L67/02C08K5/3415
Inventor 吴林波李琴琴
Owner ZHEJIANG UNIV
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