Copolymerization Modification and Properties of Poly（butylene succinate） by 2，2'-Bithiazole-4，4'-Dicarboxylic Acid

doi:10.19894/j.issn.1000-0518.240098

Chinese Journal of Applied Chemistry ›› 2024, Vol. 41 ›› Issue (11): 1565-1571.DOI: 10.19894/j.issn.1000-0518.240098

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Copolymerization Modification and Properties of Poly（butylene succinate） by 2，2'-Bithiazole-4，4'-Dicarboxylic Acid

Yu-Song LUO¹^,², Rui WANG¹()

^1.Dalian Institute of Chemical Physics，Chinese Academy of Sciences，High Performance Polymer Materials Research Center，Dalian 116023，China
^2.University of Chinese Academy of Sciences，Beijing 100049，China

Received:2024-03-26 Accepted:2024-10-23 Published:2024-11-01 Online:2024-12-04
Contact: Rui WANG
About author:wangrui87@dicp.ac.cn
Supported by:
the Young Scientist Project of the National Key R&D Program(2022YFC2105800)

Abstract

Abstract:

A series of poly（butylene succinate-co-ethylene 2，2'-bisthiazole-4，4'-dicarboxylate）（PBEBS） were synthesized by melt polycondensation using 1，4-butanedioic acid （SA）， 1，4-butanediol （BDO） and diethyl 2，2'-bisthiazole-4，4'-dicarboxylate （BTDC-Et） as raw materials. In order to further understand its structure and properties， nuclear magnetic resonance （NMR）， differential scanning calorimeter （DSC）， gel permeation chromatography （GPC）， fourier transform infrared spectrometer （FT-IR） and gas barrier tester were used for detailed characterization. The experimental results showed that when the feed molar ratio of SA∶BDO∶BTDC-Et was 1∶2.5∶0.1， the number average molecular mass of PBEBS reached 41000 and the material changed from brittle to ductile plastic. At the same time， compared with polybutylene succinate （PBS）， the carbon dioxide gas_{barrier performance is improved by 80 times. In addition， the thermal stability of PBEBS copolyesters increased with the increase of BTDC-Et feed ratio， and the decomposition temperature T_d，5% increased from 295 to 346 ℃.}

Key words: Diethyl 2, 2'-bisthiazole-4, 4'-dicarboxylic acid, Polybutylene succinate, Barrier performance

CLC Number:

O633.4

Yu-Song LUO, Rui WANG. Copolymerization Modification and Properties of Poly（butylene succinate） by 2，2'-Bithiazole-4，4'-Dicarboxylic Acid[J]. Chinese Journal of Applied Chemistry, 2024, 41(11): 1565-1571.

Figures/Tables 10

Fig.1 Synthesis of PBEBS

Fig.4 Three polymerization sequences of the ester group in PBEBS and 1H NMR spectra of PB80EBS20 （c）

Table 1 Atructure analyse of PBEBS copolyesters

Sample	x（BTDC-Et）/% in feed	x（BTDC-Et）/% in coploymer	¹H NMR
Sample	x（BTDC-Et）/% in feed	x（BTDC-Et）/% in coploymer	R	L_EBE	L_SBS	10^-4M_n
PB₉₀EBS₁₀	10	9.5	1.04	1.08	8.77	4.1
PB₈₅EBS₁₅	15	14.5	1.02	1.16	6.52	3.3
PB₈₀EBS₂₀	20	19	0.99	1.24	5.13	3.0

Fig.5 DSC second heating curves of PB90EBS10 （a）， PB85EBS15 （b） and PB80EBS20 （c）（A） and relationship between mass ratio of BTDC-Et and Tg of PBEBS （B）

Fig.6 XRD patterns of PB90EBS10 （a） and PB80EBS20 （b）

Fig.7 TGA curves of PB90EBS10 （a）， PB85EBS15 （b） and PB80EBS20 （c）

Fig.8 Stress-strain curves of the PB90EBS10 （a）， PB85EBS15 （b） and PB80EBS20 （c）

Table 2 CO2 gas barrier properties of PBEBS

Sample	CO₂ gas permeability/（cm³·cm·cm^-2·s^-1·Pa^-1）	BIFp
PBS^［20］	3.3×10^-14	1
PB₉₀EBS₁₀	4.3×10^-15	7.8
PB₈₅EBS₁₅	4.1×10^-16	80
PB₈₀EBS₂₀	1.6×10^-14	2.1
PET	8.6×10^-15	3.8

References 20

1	WANG H， LIU K， CHEN X， et al. Thermal properties and enzymatic degradation of PBS copolyesters containing dl-malic acid units［J］. Chemosphere， 2021， 272： 129543.
2	VYTEJČKOVÁ S， VÁPENKA L， HRADECKÝ J， et al. Testing of polybutylene succinate based films for poultry meat packaging［J］. Polym Test， 2017， 60： 357-364.
3	BARLETTA M， AVERSA C， AYYOOB M， et al. Poly（butylene succinate）（PBS）： materials， processing， and industrial applications［J］. Prog Polym Sci， 2022， 132： 101579.
4	RAJGOND V， MOHITE A， MORE N， et al. Biodegradable polyester-polybutylene succinate （PBS）： a review［J］. Polym Bull， 2023， 81（7）： 5703-5752.
5	ANANKAPHONG H， PENTRAKOON D， JUNKASEM J. Effect of rubberwood content on biodegradability of poly（butylene succinate） biocomposites［J］. Int J Polym Sci， 2015， 2015： 1-9.
6	KIM H S， KIM H J， LEE J W， et al. Biodegradability of bio-flour filled biodegradable poly（butylene succinate） bio-composites in natural and compost soil［J］. Polym Degrad Stab， 2006， 91（5）： 1117-1127.
7	WANG J， ZHENG L， LI C， et al. Synthesis and properties of biodegradable poly（ester-co-carbonate） multiblock copolymers comprising of poly（butylene succinate） and poly（butylene carbonate） by chain extension［J］. Ind Eng Chem Res， 2012， 51（33）： 10785-10792.
8	YU Y， LIU Y， WEI Z. Trans-2-butene-1，4-diol as an olefinic building block to prepare biobased unsaturated copolyesters with high molecular weight： synthesis， characterization， and physical properties［J］. ACS Sustainable Chem Eng， 2021， 9（49）： 16699-16708.
9	GUIDOTTI G， SOCCIO M， GAZZANO M， et al. Biocompatible PBS-based copolymer for soft tissue engineering： introduction of disulfide bonds as winning tool to tune the final properties［J］. Polym Degrad Stab， 2020， 182： 109403.
10	XU P Y， LIU T Y， HUANG D， et al. Degradation performances of CL-modified PBSCL copolyesters in different environments［J］. Eur Polym J， 2022， 174： 111322.
11	JIN C， WANG B， LIU L， et al. Biodegradable poly（butylene succinate） copolyesters modified by bioresoured 2，5-tetrahydrofurandimethanol［J］. ACS Sustainable Chem Eng， 2022， 10（34）： 11203-11214.
12	HU H， LIN C， LUAN Q， et al. Synergistic modification of PBT with diglycolic acid and succinic acid： fast crystallization and high strength-toughness copolyesters for environmentally degradable packaging［J］. ACS Sustainable Chem Eng， 2023， 11（38）： 14068-14080.
13	TACHIBANA Y， YAMAHATA M， KIMURA S， et al. Synthesis， physical properties， and biodegradability of biobased poly（butylene succinate-co-butylene oxabicyclate）［J］. ACS Sustainable Chem Eng， 2018， 6（8）： 10806-10814.
14	ZHANG H， JIANG M， WU Y， et al. Development of completely furfural-based renewable polyesters with controllable properties［J］. Green Chem， 2021， 23（6）： 2437-2448.
15	QI J， WU J， CHEN J， et al. An investigation of the thermal and （bio） degradability of PBS copolyesters based on isosorbide［J］. Polym Degrad Stab， 2019， 160： 229-241.
16	TESHIMA Y， SAITO M， MIKIE T， et al. Bithiazole dicarboxylate ester： an easily accessible electron-deficient building unit for π-conjugated polymers enabling electron transport［J］. Macromolecules， 2021， 54（7）： 3489-3497.
17	JIANG X， YU Y， GUAN Y， et al. Random and multiblock PBS copolyesters based on a rigid diol derived from naturally occurring camphor： influence of chemical microstructure on thermal and mechanical properties‍［J］. ACS Sustainable Chem Eng， 2020， 8（9）： 3626-3636.
18	CHEN X， CHEN W， ZHU G， et al. Synthesis， ¹H‐NMR characterization， and biodegradation behavior of aliphatic-aromatic random copolyester［J］. J Appl Polym Sci， 2007， 104（4）： 2643-2649.
19	WANG Q， LI J， WANG J， et al. Biobased biodegradable copolyesters from 2，5-thiophenedicarboxylic acid： effect of aliphatic diols on barrier properties and degradation［J］. Biomacromolecules， 2023， 24（12）： 5884-5897.
20	SIRACUSA V， LOTTI N， MUNARI A， et al. Poly（butylene succinate） and poly（butylene succinate-co-adipate） for food packaging applications： gas barrier properties after stressed treatments［J］. Polym Degrad Stab， 2015， 119： 35-45.

Copolymerization Modification and Properties of Poly（butylene succinate） by 2，2'-Bithiazole-4，4'-Dicarboxylic Acid

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