Preparation and Properties of Poly（L-lactide-p-dioxocyclohexanone）

doi:10.19894/j.issn.1000-0518.250265

Chinese Journal of Applied Chemistry ›› 2025, Vol. 42 ›› Issue (12): 1629-1635.DOI: 10.19894/j.issn.1000-0518.250265

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Preparation and Properties of Poly（L-lactide-p-dioxocyclohexanone）

Shu-Ming DAI¹, Jia-Yue LI¹, Yu CHENG², Kun-Yu ZHANG², Zhe MA¹, Zi-He ZHAO²(), Bin WANG¹

^1.School of Materials Science and Engineering，Tianjin University，Tianjin 300350，China
^2.Advanced Materials Research Center，Petrochemical Research Institute，Petro China Company Limited，Beijing 102206，China

Received:2025-07-01 Accepted:2025-09-09 Published:2025-12-01 Online:2025-12-30
Contact: Zi-He ZHAO

Abstract

Abstract:

A multinuclear β-ketoimine zinc metal complex was used as a catalyst to catalyze the ring-opening copolymerization of levulinic acid ester （L-LA） and p-dioxocyclohexanone （PDO） into a series of polymers P（L-LA-co-PDO） with different ratios of compositions， and the thermal and mechanical properties of the polymers were investigated. The results showed that the polynuclear β-ketoimine zinc complex catalyst exhibited better catalytic activity than commercial stannous octoate. The relative molecular mass of the polymer obtained was above 200×10³ and the relative molecular mass distribution was between 1.4 and 1.7. L-LA exhibited higher reactivity than PDO during copolymerization. The introduction of PDO units with different contents had a significant effect on the thermal and mechanical properties of the polymers. With the increase of PDO content， the polymer changed from crystalline state to amorphous state， and its toughness was greatly improved. Compared with traditional PLLA materials， the elongation at break was increased by 704%. This kind of chemical copolymerization is expected to broaden the application range of PLLA materials.

Key words: Polylactide, Dioxanone, β-Ketoimide zinc complexes, Ring-opening copolymerization, Toughening

CLC Number:

O631.5

Shu-Ming DAI, Jia-Yue LI, Yu CHENG, Kun-Yu ZHANG, Zhe MA, Zi-He ZHAO, Bin WANG. Preparation and Properties of Poly（L-lactide-p-dioxocyclohexanone）[J]. Chinese Journal of Applied Chemistry, 2025, 42(12): 1629-1635.

Figures/Tables 8

References 22

[1]	HU C， ZHANG Y， PANG X， et al. Poly（lactic acid）： recent stereochemical advances and new materials engineering［J］. Adv Mater， 2024， 37（22）： 2412185.
[2]	CASTRO-AGUIRRE E， IÑIGUEZ-FRANCO F， SAMSUDIN H， et al. Poly（lactic acid）-mass production， processing， industrial applications， and end of life［J］. Adv Drug Deliv Rev， 2016， 107： 333-366.
[3]	XUE Y， FENG J， MA Z， et al. Advances and challenges in eco-benign fire-retardant polylactide［J］. Mater Today Phys， 2021， 21： 100568.
[4]	LI X， YANG Q， ZHANG K， et al. Property improvement and compatibilization mechanism of biodegradable polylactic acid/maleic anhydride-based/polypropylene spunbonded nonwoven slices［J］. J Clean Prod， 2022， 375： 134097.
[5]	ALI W， ALI H， GILLANI S， et al. Polylactic acid synthesis， biodegradability， conversion to microplastics and toxicity： a review［J］. Environ Chem Lett， 2023， 21（3）： 1761-1786.
[6]	DE ALBUQUERQUE T L， MARQUES JUNIOR J E， DE QUEIROZ L P， et al. Polylactic acid production from biotechnological routes： a review［J］. Int J Biol Macromol， 2021， 186： 933-951.
[7]	SUN C， WEI S， TAN H， et al. Progress in upcycling polylactic acid waste as an alternative carbon source： a review［J］. Chem Eng J， 2022， 446： 136881.
[8]	LI Z， SHANG J， ABDUREXIT A， et al. Improving the performance of polylactic acid/polypropylene/cotton stalk fiber composites with epoxidized soybean oil as a high efficiency plasticizer［J］. Int J Biol Macromol， 2024， 283： 137814.
[9]	ASHOTHAMAN A， SUDHA J， SENTHILKUMAR N. A comprehensive review on biodegradable polylactic acid polymer matrix composite material reinforced with synthetic and natural fibers［J］. Mater Today Proc， 2023， 80： 2829-2839.
[10]	HUA X， LIU X， CUI D. Degradation behavior of poly（lactide-co-carbonate）s controlled by chain sequences［J］. Macromolecules， 2020， 53（13）： 5289-5296.
[11]	SANCHEZ L A H， WOROCH C P， DUMAS D M， et al. Toughening poly（lactic acid） without compromise-statistical copolymerization with a bioderived bicyclic lactone［J］. J Am Chem Soc， 2025， 147（6）： 5212-5219.
[12]	LEI J， GUI Z X， XIONG W T， et al. Boosting thermal stability and crystallization of closed-loop-recyclable biodegradable poly（p-dioxanone） by end-group regulation［J］. Sci China Chem， 2023， 67（2）： 642-651.
[13]	FAN T， QIN J， DONG F， et al. Effects on the crystallization behavior and biocompatibility of poly（LLA-ran-PDO-ran-GA） with poly（D-lactide） as nucleating agents［J］. RSC Adv， 2022， 12（17）： 10711-10724.
[14]	YIN J， ZHAO Q， SHEN Y， et al. P（LLA‐co‐PDO） copolymers with random and block architectures： synthesis and characterizations［J］. J Appl Polym Sci， 2022， 139（25）： e52140.
[15]	李斌. 聚对二氧环己酮与聚乳酸嵌段共聚物的合成［D］. 成都：四川大学， 2007.
	LI B. Synthesis of block copolymers of poly（p-dioxocyclohexanone） and polylactic acid［D］. Chengdu： Sichuan University， 2007.
[16]	李佳岳，王明倩，丁志强，等. 苯基亚胺基吡啶酚锌配合物用于聚乳酸合成及化学回收为单体［J］. 中国高分子科学杂志， 2025， 43： 914-923.
	LI J Y， WANG M Q， DING Z Q， et al. Phenylimino-pyridine-phenolate zinc complexes for polylactide synthesis and chemical recycling to monomers［J］. Chin J Polym Sci， 2025， 43： 914-923.
[17]	WANG Z B， WANG M， DING Z， et al. Robust， thermally stable and impurity-tolerant aluminum-based catalyst system for polylactide production under industrial conditions［J］. Polym Sci Technol， 2025， 1（6）： 541-550.
[18]	KREMER A B， MEHRKHODAVANDI P. Dinuclear catalysts for the ring opening polymerization of lactide［J］. Coord Chem Rev， 2019， 380： 35-57.
[19]	WANG R， ZHANG J， YIN Q， et al. Controlled ring‐opening polymerization of o‐carboxyanhydrides using a β‐diiminate zinc catalyst［J］. Angew Chem Int Ed， 2016， 55（42）： 13010-13014.
[20]	SANTULLI F， PAPPALARDO D， LAMBERTI M， et al. Simple and efficient zinc catalysts for synthesis and chemical degradation of polyesters［J］. ACS Sustainable Chem Eng， 2023， 11（43）： 15699-15709.
[21]	CHENG Y， ZHAO Z， XU X， et al. Efficient synthesis of polylactide and copolymers under industrial conditions by multinuclear β-ketoimide zinc complexes［J］. Polym Chem， 2025， 16： 3030-3040.
[22]	秦凡，车晶，杨荣杰，等. 对二氧环己酮与丙交酯共聚反应的¹H-NMR分析［J］. 高分子材料科学与工程， 2011， 27（8）： 118-125.
	QIN F， CHE J， YANG R J， et al. Analysis on copolymerization of dioxanone with lactide by ¹H-NMR［J］. Polym Mater Sci Eng， 2011， 27（8）： 118-125.

Entry	Sample	n（L-LA）∶n（PDO）∶n（Zn）∶n（BnOH）	T/℃	Reaction time/h	Conv.L-LA/（PDO）/%	10^-3M_n，calc	10^-3M_n，GPC	D
1	-	1 400∶600∶1∶1	100	20	26.0/15.0	61.6	59.5	1.45
2	PLDO-21%	1 400∶600∶1∶1	120	20	98.3/61.2	235.7	259.3	1.41
3	-	1 400∶600∶1∶1	140	20	97.5/52.3	228.6	164.6	1.47
4	PLLA	2 000∶0∶1∶1	120	0.75	96.2/-	276.9	225.3	1.52
5	PLDO-5%	1 800∶200∶1∶1	120	20	98.5/40.8	263.7	239.6	1.67
6	PLDO-13%	1 600∶400∶1∶1	120	20	99.0/53.7	250.1	197.6	1.55
7	PLDO-17%-Sn	1 400∶600∶1∶1	120	20	97.0/47.9	224.9	117.6	1.58
8	PLDO-21%-Sn	1 400∶600∶1∶1	120	30	97.1/60.2	232.7	145.6	1.76

Entry	Sample	n（L-LA）∶n（PDO）∶n（Zn）∶n（BnOH）	T/℃	Reaction time/h	Conv.L-LA/（PDO）/%	10^-3M_n，calc	10^-3M_n，GPC	D
1	-	1 400∶600∶1∶1	100	20	26.0/15.0	61.6	59.5	1.45
2	PLDO-21%	1 400∶600∶1∶1	120	20	98.3/61.2	235.7	259.3	1.41
3	-	1 400∶600∶1∶1	140	20	97.5/52.3	228.6	164.6	1.47
4	PLLA	2 000∶0∶1∶1	120	0.75	96.2/-	276.9	225.3	1.52
5	PLDO-5%	1 800∶200∶1∶1	120	20	98.5/40.8	263.7	239.6	1.67
6	PLDO-13%	1 600∶400∶1∶1	120	20	99.0/53.7	250.1	197.6	1.55
7	PLDO-17%-Sn	1 400∶600∶1∶1	120	20	97.0/47.9	224.9	117.6	1.58
8	PLDO-21%-Sn	1 400∶600∶1∶1	120	30	97.1/60.2	232.7	145.6	1.76

Preparation and Properties of Poly（L-lactide-p-dioxocyclohexanone）

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