Performance tailorable terpolymers synthesized from carbon dioxide, phthalic anhydride and propylene oxide using Lewis acid-base dual catalysts

Liang, Jian; Ye, Shuxian; Wang, Wenjing; Fan, Congxiao; Wang, Shuanjin; Han, Dongmei; Liu, Wei; Cui, Yan; Hao, Limin; Xiao, Min; Ye, Meng

doi:10.1016/j.jcou.2021.101558

Cited by 36 publications

(17 citation statements)

References 58 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In 2020, Meng reported the quadripolymerization of CO 2 with PA, PO and CHO in the presence of TEB and PPNCl, resulting in the formation of the copolymer (pCO 2 = 1 MPa, T = 70 • C, t = 24-96 h) with good selectivity (94%) with respect to the cyclic product [34,35]. The microstructure of the resulting quadripolymer was clarified by 1 H and 13 C NMR showing the presence of four main blocks, i.e., poly(PA-alt-CHO), poly(PA-alt-PO), poly(propylene carbonate) (PPC), and poly(cyclohexene carbonate) (PCHC), and a very low amount of polyether linkages (<1%).…”

Section: Metal-free Catalystsmentioning

confidence: 99%

Terpolymerization of CO2 with Epoxides and Cyclic Organic Anhydrides or Cyclic Esters

Lamparelli

Capacchione

2021

Catalysts

View full text Add to dashboard Cite

The synthesis of polymeric materials starting from CO2 as a feedstock is an active task of research. In particular, the copolymerization of CO2 with epoxides via ring-opening copolymerization (ROCOP) offers a simple, efficient route to synthesize aliphatic polycarbonates (APC). In many cases, APC display poor physical and chemical properties, limiting their range of application. The terpolymerization of CO2 with epoxides and organic anhydrides or cyclic esters offers the possibility, combining the ROCOP with ring-opening polymerization (ROP), to access a wide range of materials containing polycarbonate and polyester segments along the polymer chain, showing enhanced properties with respect to the simple APC. This review will cover the last advancements in the field, evidencing the crucial role of the catalytic system in determining the microstructural features of the final polymer.

show abstract

Section: Metal-free Catalystsmentioning

confidence: 99%

Terpolymerization of CO2 with Epoxides and Cyclic Organic Anhydrides or Cyclic Esters

Lamparelli

Capacchione

2021

Catalysts

View full text Add to dashboard Cite

show abstract

“…With the goal of exploring the monomer enchainment order in the TEB/TEA (1/1) pair-catalyzed PO/PA/CO 2 copolymerization, the monomer conversion and polymer composition were monitored at different reaction times via 1 H NMR analysis (Figure 1 and Table S4). Referring to the reported studies, 28,46 the peak emerging at 5.4 (marked as 2) and 5.0 ppm (marked as 4) evidenced the coexistence of polyester units from PO/PA ROCOP and polycarbonate segments from PO/CO 2 ROCOP, respectively. Moreover, abundant junction units can be detected from the comparable areas of peaks 2' (5.3 ppm) and 2'' (5.1 ppm) even when only 23% of PA was conversed after 1h reaction.…”

Section: Macromolecules Pubsacsorg/macromoleculesmentioning

confidence: 59%

“…Unexpectedly, a slight decrease in the TOF value occurred when increasing the CO 2 pressure from 1.0 to 1.5 MPa, which can be explained by the slower PA conversion under higher CO 2 pressure. 46 Hence, the equivalent TEB and TEA as well as a 1.0 MPa CO 2 pressure are enough for the efficient and selective PO/PA/CO 2 copolymerization. S4).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…45−48 Notably, the most widely studied systems are Lewis pairs consisting of TEB and onium salts, which require excess TEB loadings and display high activity with a TOF value up to 185 h −1 , but the highest productivity did not exceed 250 g polymer/g catalyst. 46 Other organic bases including guanidine and phosphazene bases were also applied and displayed medium/high activity (76−191 h −1 ).…”

Section: ■ Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Biodegradable Copolymers from CO₂, Epoxides, and Anhydrides Catalyzed by Organoborane/Tertiary Amine Pairs: High Selectivity and Productivity

Liang

Wang

et al. 2022

Macromolecules

Self Cite

View full text Add to dashboard Cite

Copolymerization of epoxides and carbon dioxide (CO2) with cyclic anhydrides has been developed to be a facile route to obtain biodegradable poly(ester-co-carbonate)s with diversified structures. Metal-free Lewis acid–base pairs emerging in recent years have offered great opportunities for preparing polymers without metal residuals. Herein, the scope of Lewis bases is extended to the tertiary amines with different pK a values and steric hindrances. Especially, the simplest Lewis pair composed of triethylborane (TEB) and triethylamine (TEA) exhibits high catalytic activity even at very low catalyst loadings in the copolymerization of propylene oxide (PO), CO2, and phthalic anhydride (PA). With a PO/PA/TEB/TEA feeding ratio of 16,000/2000/4/1, a low cyclic carbonate content not exceeding 5.0 wt % and a high productivity up to 1.2 kg polymer/g catalyst have been realized at 65 °C. Moreover, the molecular weight of the resultant copolymer climbs to 131 kg/mol with a relatively narrow polymer dispersity index (PDI = 1.31), which is the highest record among the results catalyzed by the homogenous binary catalyst systems. Furthermore, the TEB/TEA (1/1) pair is applicable to provide random copolymers from CO2 with various epoxides and anhydrides, while quasi-block copolymers are yielded with inferior selectivity by replacing TEA with onium salt. Interestingly, the low activity in cyclohexene oxide (CHO) involving copolymerization with PA and CO2 can be dramatically boosted upon adding a small amount of PO (1 mol % of CHO), which can be attributed to the stronger ring-opening ability of PO during the initiation period. The glass transition temperatures of the resultant polymers are adjustable in the range of 34–131 °C by applying different epoxides and anhydrides.

show abstract

“…[16][17][18] For example, (AB) n (CB) m type block terpolymers have been one-step synthesized from mixtures containing an epoxide, a cyclic anhydride (CA), and CO 2 or dihydrocoumarin (DHC). [19][20][21][22][23][24][25][26][27][28] The adequately higher electrophilicity of CA, as compared with CO 2 or DHC, ensures that the alkoxide species on the initiator or at the propagating copolymer chain end (derived from the epoxide) react exclusively with it before reaching high or complete conversion (mostly ≥95%). Then, CAderived terminal carboxylate species can only react with the epoxide to accomplish the growth of the first block.…”

Section: Introductionmentioning

confidence: 99%

One‐Step Sequence‐Selective Synthesis of Block Copolyester from Mixed Phthalic Anhydride, Cyclohexene Oxide, and δ‐Valerolactone

Zhao

2021

Macro Chemistry & Physics

View full text Add to dashboard Cite

One-step synthesis of well-defined block copolymer is of great fundamental and practical values. Here, an aromatic-aliphatic block copolyester is one-step synthesized from the mixture of phthalic anhydride (PA), cyclohexene oxide (CHO), and 𝜹-valerolactone (𝜹-VL) at room temperature in the presence of a metal-free Lewis pair catalyst consisting of triethylborane and excess phosphazene base. Alcohol-initiated ring-opening alternating copolymerization of PA and CHO occurs first and selectively because of the overwhelmingly higher activity of PA than CHO and 𝜹-VL toward the reaction with base-activated hydroxy species. Only after full conversion of PA is reached can ring-opening polymerization of 𝜹-VL occur from the terminus of the aromatic polyester so that a well-defined (AB) n C m type block copolyester is formed. The two polymerizations are both highly chemoselective without homopolymerization of CHO or extensive transesterification reactions. Owing to the sequence-selective and living characteristics of the terpolymerization, hepta-and undecablock copolyesters with controlled molar mass and low dispersity are obtained through addition of the three-component monomer mixture in batches. Applicability of the method to propylene oxide and 𝝐-caprolactone is also examined.

show abstract

Performance tailorable terpolymers synthesized from carbon dioxide, phthalic anhydride and propylene oxide using Lewis acid-base dual catalysts

Cited by 36 publications

References 58 publications

Terpolymerization of CO2 with Epoxides and Cyclic Organic Anhydrides or Cyclic Esters

Terpolymerization of CO2 with Epoxides and Cyclic Organic Anhydrides or Cyclic Esters

Biodegradable Copolymers from CO₂, Epoxides, and Anhydrides Catalyzed by Organoborane/Tertiary Amine Pairs: High Selectivity and Productivity

One‐Step Sequence‐Selective Synthesis of Block Copolyester from Mixed Phthalic Anhydride, Cyclohexene Oxide, and δ‐Valerolactone

Contact Info

Product

Resources

About

Performance tailorable terpolymers synthesized from carbon dioxide, phthalic anhydride and propylene oxide using Lewis acid-base dual catalysts

Cited by 36 publications

References 58 publications

Terpolymerization of CO2 with Epoxides and Cyclic Organic Anhydrides or Cyclic Esters

Terpolymerization of CO2 with Epoxides and Cyclic Organic Anhydrides or Cyclic Esters

Biodegradable Copolymers from CO2, Epoxides, and Anhydrides Catalyzed by Organoborane/Tertiary Amine Pairs: High Selectivity and Productivity

One‐Step Sequence‐Selective Synthesis of Block Copolyester from Mixed Phthalic Anhydride, Cyclohexene Oxide, and δ‐Valerolactone

Contact Info

Product

Resources

About

Biodegradable Copolymers from CO₂, Epoxides, and Anhydrides Catalyzed by Organoborane/Tertiary Amine Pairs: High Selectivity and Productivity