Temperature‐responsive Catalyst for the Coupling Reaction of Carbon Dioxide and Propylene Oxide

The selective synthesis of polypropylene carbonate (PPC) and cyclic propylene carbonate (CPC) from coupling reaction of CO₂ and propylene oxide (PO) is a long term pursuing target. Here we report that a temperature controllable porphyrin aluminum catalyst using 5,10,15,20‐tetra(1,2,3,4,5,6, 7,8‐octahydro‐1,4:5,8‐dimethanoanthracen‐9‐yl)porphyrin as ligand, once in conjunction with suitable onium salt, achieved single cycloaddition or copolymerization reaction. Only cycloaddition reaction happened at temperature above 75 °C to produce 100% CPC, whereas copolymerization became dominant to afford PPC with selectivity over 99% at 25 °C, and the obtained PPC showed over 99% carbonate linkage and 92% head‐to‐tail structure. Based on systematic analysis of the electronic and steric feature in the porphyrin ligand, it was found that the electronic feature of the substituent in porphyrin ligand was decisive for PPC selectivity, porphyrin ligand bearing strong electron‐donating substituents displayed a significantly reduced tolerance towards increased temperature with respect to PPC formation. Therefore, temperature‐responsive catalyst could be designed by suitable modification in porphyrin ligand, and such accurate synthesis of target product by one catalyst may create a useful and facile platform for selective PPC or CPC production.     

Concerning the Deactivation of Cobalt(III)‐Based Porphyrin and Salen Catalysts in Epoxide/CO2 Copolymerization

Functioning as active catalysts for propylene oxide (PO) and carbon dioxide copolymerization, cobalt(III)‐based salen and porphyrin complexes have drawn great attention owing to their readily modifiable nature and promising catalytic behavior, such as high selectivity for the copolymer formation and good regioselectivity with respect to the polymer microstructure. Both cobalt(III)–salen and porphyrin catalysts have been found to undergo reduction reactions to their corresponding catalytically inactive cobalt(II) species in the presence of propylene oxide, as evidenced by UV/Vis and NMR spectroscopies and X‐ray crystallography (for cobalt(II)–salen). Further investigations on a TPPCoCl (TPP=tetraphenylporphyrin) and NaOMe system reveal that such a catalyst reduction is attributed to the presence of alkoxide anions. Kinetic studies of the redox reaction of TPPCoCl with NaOMe suggests a pseudo‐first order in cobalt(III)–porphyrin. The addition of a co‐catalyst, namely bis(triphenylphosphine)iminium chloride (PPNCl), into the reaction system of cobalt(III)–salen/porphyrin and PO shows no direct stabilizing effect. However, the results of PO/CO₂ copolymerization by cobalt(III)–salen/porphyrin with PPNCl suggest a suppressed catalyst reduction. This phenomenon is explained by a rapid transformation of the alkoxide into the carbonate chain end in the course of the polymer formation, greatly shortening the lifetime of the autoreducible PO‐ring‐opening intermediates, cobalt(III)–salen/porphyrin alkoxides.     

Regarding Initial Ring Opening of Propylene Oxide in its Copolymerization with CO2 Catalyzed by a Cobalt(III) Porphyrin Complex

Cobalt(III) tetraphenylporphyrin chloride (TPPCoCl) was experimentally proved to be an active catalyst for poly(propylene carbonate) production. It was chosen as a model catalyst in the present work to investigate the initiation step of propylene oxide (PO)/CO₂ copolymerization, which is supposed to be the ring opening of the epoxide. Ring‐opening intermediates ( 1 – 7 ) were detected by using ¹H NMR spectroscopy. A first‐order reaction in TPPCoCl was determined. A combination of monometallic and bimetallic ring‐opening pathways is proposed according to kinetics experiments. Addition of onium salts (e.g., bis(triphenylphosphine)iminium chloride, PPNCl) efficiently promoted the PO ring‐opening rate. The existence of axial ligand exchange in the cobalt porphyrin complex in the presence of onium salts was suggested by analyzing collected ¹H NMR spectra.     

The influence of the metal (Al, Cr, and Co) and the substituents of the porphyrin in controlling the reactions involved in the copolymerization of propylene oxide and carbon dioxide by porphyrin metal(III) complexes. 1. Aluminum chemistry

The reactivities of aluminum(III) complexes LAlX, where L = 5,10,15,20-tetraphenylporphyrin (TPP), 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (TFPP), and 2,3,7,8,12,13,17,18-octaethylporphyirn (OEP) and X = Cl or OEt, have been studied with respect to their ability to homopolymerize propylene oxide (PO) and copolymerize PO and CO(2) to yield polypropylene oxide (PPO) and polypropylene carbonate (PPC), respectively, with and without the presence of a cocatalyst, namely, 4-dimethylaminopyridine (DMAP) or a PPN(+) salt where the anion is Cl(-) or N(3)(-). In the presence of a cocatalyst (0.5 equiv), the TFPP complex is the most active in copolymerization to yield PPC, with the latter being effective even at 10 bar CO(2). An increase in the PPN(+)X(-)/[Al] ratio decreases the rate of PPC formation and favors the formation of propylene carbonate, (PC). Studies of the polymers formed in reactions involving Al-alkoxide initiators and PPN(+) salts by mass spectrometry indicate that one chain is grown per Al center. These results are compared with earlier studies where the reactions display first order kinetics in the metal complex.     

Bifunctional aluminum porphyrin complex: Soil tolerant catalyst for copolymerization of 2 and propylene oxide

Due to the concern on residue toxic metal in biodegradable poly(propylene carbonate) (PPC), soil tolerant and heavy metal free aluminum complexes, that is, bifunctional aluminum porphyrin catalysts bearing quaternary ammonium salts on the ligand framework were prepared. Variation of the quaternary ammonium anion and the axial ligand had dramatic effects on the catalytic activity of resultant complex, among which complex 3b yielded perfectly alternative PPC with high molecular weight and relatively narrow polydispersity, and its TOF reached 3,407 h^?1 at [PO]/[cat.] ratio of 20,000 at 110 °C, although the PPC selectivity was 71%. By introducing specific substituent on the ligand framework, the electronic environment at the active center can be changed, among which complex 5b bearing tertiary butyl‐functionalized aryl substituents exhibited a TOF of 449 h^?1 at [PO]/[cat.] ratio of 5,000 at 70 °C, with PPC selectivity of 92% and number average molecular weight of 36 kg mol^?1. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2346–2355     

Study of electronic effect in bifunctional catalysts for the copolymerization of CO2 and PO/CHO

Carbon dioxide (CO₂) is an easily available renewable carbon source that can be used as a comonomer in the catalytic ring-opening polymerization of epoxides to form aliphatic polycarbonates. Herein, a series of new Salen-Co(III) bifunctional catalysts were synthesized for the first time, and they were studied to catalyze the copolymerization of CO₂ and propylene oxide (PO)/cyclohexene oxide (CHO). At the same time, the effects of reaction conditions (electronic effect, temperature, time) on catalytic activity and selectivity were investigated. The results show that the Salen-Co(III) complexes with electron-withdrawing groups have higher selectivity and activity for propylene carbonate (PPC)/cyclohexylene carbonate (PCHC). At the same time, the Salen-Co(III) complexes can better catalyze the copolymerization of CHO and CO₂ than that of PO and CO₂. The catalytic efficiency of the four complexes increased with increasing temperature, and the best reaction condition is 80°C, 30 min and 2 MPa of CO₂.     

铝卟啉配合物催化二氧化碳与环氧丙烷共聚反应

铝卟啉是一类土壤环境友好的金属卟啉,尽管早在1978年Inoue就已经发现它可以催化CO₂和环氧丙烷的共聚反应,但是该催化体系一直面临催化活性低、聚合物相对分子质量低等难题。 本文通过改变铝卟啉催化剂配体中苯环上取代基的种类和位置,制备出中心金属电子环境差异化的铝卟啉,并以双三苯基膦氯化铵(PPNCl)为助催化剂,探讨其对CO₂与环氧丙烷的共聚反应的催化行为。 结果表明,当铝卟啉中苯环上2,4位同时被Cl^-取代后,在90 ℃和3 MPa压力下,转化频率(TOF)达到2672 h^-1。 当利用离去能力较强的对甲苯磺酸基团(OTs^-)作为铝卟啉的轴向配体,可以合成出数均相对分子质量达1.84×10⁵的脂肪族聚碳酸酯。     

Correlating Metal Redox Potentials to Co(III)K(I) Catalyst Performances in Carbon Dioxide and Propene Oxide Ring Opening Copolymerization

Carbon dioxide copolymerization is a front-runner CO₂ utilization strategy but its viability depends on improving the catalysis. So far, catalyst structure-performance correlations have not been straightforward, limiting the ability to predict how to improve both catalytic activity and selectivity. Here, a simple measure of a catalyst ground-state parameter, metal reduction potential, directly correlates with both polymerization activity and selectivity. It is applied to compare performances of 6 new heterodinuclear Co(III)K(I) catalysts for propene oxide (PO)/CO₂ ring opening copolymerization (ROCOP) producing poly(propene carbonate) (PPC). The best catalyst shows an excellent turnover frequency of 389 h⁻¹ and high PPC selectivity of >99 % (50 °C, 20 bar, 0.025 mol% catalyst). As demonstration of its utility, neither DFT calculations nor ligand Hammett parameter analyses are viable predictors. It is proposed that the cobalt redox potential informs upon the active site electron density with a more electron rich cobalt centre showing better performances. The method may be widely applicable and is recommended to guide future catalyst discovery for other (co)polymerizations and carbon dioxide utilizations.     

Xphos ligand and platinum catalysts: A versatile catalyst for the synthesis of functionalized β-(E)-vinylsilanes from terminal alkynes

Hydrosilylation of functionalized terminal arylalkynes with a variety of silanes catalyzed by PtCl₂ or PtO₂ in the presence of the air-stable and bulky Xphos ligand was investigated. Regardless of the electronic nature (electron withdrawing or donating group) and the position (o, m, p) of the substituents on the aromatic ring, a single β-(E)-styrylsilanes was obtained in good to excellent yields. The regioselectivity of the H-Si bond addition was found to be governed by steric effects induced by the bulky Xphos ligand. A dramatic regioselectivity was also observed when functionalized terminal aliphatic alkynes were employed as a substrate and in these cases regioisomeric β-(E)-vinylsilanes were generated with excellent selectivity.     

Cobalt catalysts for the alternating copolymerization of propylene oxide and carbon dioxide: combining high activity and selectivity

Synthetic pathways to (salcy)CoX (salcy = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-diaminocyclohexane; X = halide or carboxylate) complexes are described. Complexes (R,R)-(salcy)CoCl, (R,R)-(salcy)CoBr, (R,R)-(salcy)CoOAc, and (R,R)-(salcy)CoOBzF(5) (OBzF(5) = pentafluorobenzoate) are highly active catalysts for the living, alternating copolymerization of propylene oxide (PO) and CO(2), yielding poly(propylene carbonate) (PPC) with no detectable byproducts. The PPC generated using these catalyst systems is highly regioregular and has up to 99% carbonate linkages with a narrow molecular weight distribution (MWD). Inclusion of the cocatalysts [PPN]Cl or [PPN][OBzF(5)] ([PPN] = bis(triphenylphosphine)iminium) with complex (R,R)-(salcy)CoCl, (R,R)-(salcy)CoBr, or (R,R)-(salcy)CoOBzF(5) results in remarkable activity enhancement of the copolymerization as well as improved stereoselectivity and regioselectivity with maximized reactivity at low CO(2) pressures. In the case of [PPN]Cl with (R,R)-(salcy)CoOBzF(5), an unprecedented catalytic activity of 620 turnovers per hour is achieved for the copolymerization of rac-PO and CO(2), yielding iso-enriched PPC with 94% head-to-tail connectivity. The stereochemistry of the monomer and catalyst used in the copolymerization has dramatic effects on catalytic activity and the PPC microstructure. Using catalyst (R,R)-(salcy)CoBr with (S)-PO/CO(2) generates highly regioregular PPC, whereas using (R)-PO/CO(2) with the same catalyst gives an almost completely regiorandom copolymer. The rac-PO/CO(2) copolymerization with catalyst rac-(salcy)CoBr yields syndio-enriched PPC, an unreported PPC microstructure. In addition, (R,R)-(salcy)CoOBzF(5)/[PPN]Cl copolymerizes (S)-PO and CO(2) with a turnover frequency of 1100 h(-1), an activity surpassing that observed in any previously reported system.     

Preparation of poly(propylene‐co‐γ‐butyrolactone carbonate) and release profiles of drug‐loaded microcapsules

A new aliphatic poly(propylene‐co‐γ‐butyrolactone carbonate) (PPCG) was successfully synthesized through the copolymerization of carbon dioxide, propylene oxide (PO), and γ‐butyrolactone (GBL). GBL was inserted into the backbone of PO–CO₂. The glass transition of PPCG was as high as 16 °C, far higher than that (?1.5 °C) of poly(propylene carbonate) (PPC). The decomposition temperatures of PPCG and PPC were only slightly different. Because of the existence of the GBL ester unit, PPCG had stronger degradability than PPC in a pH 7.4 phosphate‐buffered solution. However, when the PO/GBL ratio increased beyond 5:2, the excessive amount of GBL was not added to the polymerization. PPCG and PPC microcapsules were prepared by the water‐in‐oil‐in‐water multiple‐emulsion method. Glucose was encapsulated. The PPCG microcapsules, about 2 μm in diameter, had smooth and spherical surfaces. The glucose release test revealed that the glucose release speed of the PPCG–glucose microcapsules was more than eight times faster than that of the PPC–glucose microcapsules in a pH 7.4 phosphate‐buffered solution. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2468–2475, 2005     

稀土三元催化体系ZnO/SiO2负载化及季铵盐催化CO2与环氧丙烷合成高分子量聚碳酸酯

由环氧丙烷(PO)和CO2交替共聚合成脂肪族聚碳酸亚丙酯,CO2利用率高, 所得产物具有一定的力学性能和生物降解性能, 具有广泛应用前景. 目前, 用于CO2和环氧化合物共聚的催化体系主要包含锌、钴、镉、铬、铝和稀土等金属活性中心, 结构、活性各异的催化剂体系, 其催化性能和产物性能也各具特色. 其中, 稀土三元催化剂(ZnEt2-甘油-三氯乙酸钇)因合成聚碳酸酯产物的分子量高、碳酸酯单元含量高、聚醚及环碳酸酯副产物少的特点而受到关注. 但是由于催化剂催化效率低, 聚合时间长, 产品成本高, 使得工业化规模生产受到限制.本文基于稀土三元催化体系, 将催化剂负载于硅胶及锌改性硅胶, 优化了其制备条件, 同时考察了添加季铵盐对催化CO2/环氧丙烷共聚合成聚碳酸酯性能的影响. 结果表明, 在1 L聚合釜中, 于3.5 MPa和70 oC反应条件下, ZnO担载量及ZnO/SiO2添加量对反应性能均有影响. 当3 wt% ZnO/SiO2的添加量为5 g时, 稀土三元催化体系的活性为4845.2 g/molZn..所得聚合物经过多次纯化处理后, 能够有效提高材料的热学性能, 即有效除去产物中的ZnO对聚合物的热稳定性有重要作用. 添加含有不同阴离子(F- , Cl- 和Br- )的季铵盐可显著影响稀土三元催化剂的活性. 其中, 仅四甲基氟化铵可以明显提高反应活性乃至聚合物分子量. 在3 wt% ZnO/SiO2载体和四甲基氟化铵的协同作用下, 稀土三元催化体系的共聚性能明显提 升, 活性最高可达5223.0 g/molZn. 聚合物结构分析表明, 在载体和四甲基氟化铵存在下, 聚合物分子量明显提高, 可达到20万以上, 分子量分布明显变窄, 且聚合物结构如碳酸酯的单元含量、副产物含量以及聚合物产品玻璃化温度基本不变, 后者均保持在40-41 ?C. 基于此, 我们提出了在ZnO改性硅胶载体及四甲基氟化铵存在下稀土三元催化体系催化CO2/环氧丙烷共聚的反应机理: ZnO/SiO2载体有利于稀土三元催化体系的分散, 而四甲基氟化铵则有利于吸附在ZnEt2上的环氧丙烷开环.     

Asymmetric,regio‐ and stereo‐selective alternating copolymerization of CO2 and propylene oxide catalyzed by chiral chromium Salan complexes

Chiral chromium complexes of tetradentate N,N′‐disubstituted bis(aminophenoxide) (designated as Salan, a saturated version of Schiff‐base Salen ligand) in conjunction with an ionic quaternary ammonium salt can efficiently catalyze the copolymerization of CO₂ with racemic propylene oxide (rac‐PO) at mild conditions to selectively afford completely alternating poly(propylene carbonate) (PPC) with ～ 95% head‐to‐tail linkages and moderate enantioselectivity. These new catalyst systems predominantly exceed the previously much‐studied SalenCr(III) systems in catalytic activity, polymer enantioselectivity, and stereochemistry control. The chiral diamine backbone, sterically hindered substitute groups on the aromatic rings, and the presence of sp³‐hydridized amino donors and its N,N′‐disubstituted groups in chiral SalanCr(III) complexes all play significant roles in controlling polymer stereochemistry and enantioselectivity. Furthermore, a relationship between polycarbonate enantioselectivity and its head‐to‐tail linkages in relation to regioselective ring‐opening of the epoxide was also discussed on the basis of stereochemical studies of PPCs derived from the copolymerization of CO₂ with chiral PO at various conditions. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6102–6113, 2008     

Fixation of carbon dioxide into aliphatic polycarbonate,cobalt porphyrin catalyzed regio‐specific poly(propylene carbonate) with high molecular weight

Cobalt porphyrin complex (TPPCo^IIIX) (TPP = 5, 10, 15, 20‐Tetraphenyl‐ porphyrin; X = halide) in combination with ionic organic ammonium salt was used for the regio‐specific copolymerization of propylene oxide and carbon dioxide. A turnover frequency of 188 h^?1 was achieved after 5 h, and the byproduct propylene carbonate was successfully controlled to below 1%, where the obtained poly(propylene carbonate) (PPC) showed number average molecular weight (M_n) of 48 kg/mol, head‐to‐tail content of 93%, and carbonate linkage of over 99%. When the polymerization time was prolonged to 24 h, PPC with M_n over 115 kg/mol and head‐to‐tail linkage maintaining 90% was prepared, whose glass transition temperature reached 44.5 °C. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5959–5967, 2008     

Effects of the structure and morphology of zinc glutarate on the fixation of carbon dioxide into polymer

Zinc glutarates were synthesized from zinc oxides with varying purities via different stirring routes. The particle size and structure of these zinc glutarates were determined by wide‐angle X‐ray diffraction, transmission electron microscopy, and the laser particle size analyzer technique. The results demonstrated that the crystallinity and crystalline perfectness of zinc glutarate are the crucial factors that affect the catalytic activity for the copolymerization of carbon dioxide (CO₂) and propylene oxide (PO). Additionally, the catalyst with a small particle size dramatically increased the yield of the copolymerization between CO₂ and PO. High‐molecular‐weight and regular molecular structure poly(propylene carbonate)s (PPC)s were obtained from CO₂ and PO with the synthesized zinc glutarates. Very high catalytic activity of 160.4 g polymer/g catalyst was afforded. The NMR technique revealed that the PPC copolymer exhibits an exact alternating copolymer structure. The relationships between the crystallinity and the particle size of catalyst with the catalytic activity are correlated and discussed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3579–3591, 2002     

Bifunctional cobalt Salen complex: a highly selective catalyst for the coupling of CO2 and epoxides under mild conditions

A bifunctional cobalt Salen complex containing a Lewis acid metal center and two covalent bonded Lewis bases on the ligand was designed and used for the coupling of CO₂ and epoxides under mild conditions. The complex exhibited excellent activity (turnover frequency = 673/h) and selectivity (no less than 97%) for polymer formation in the copolymerization of propylene oxide (PO) and CO₂ at an appropriate combination of all variables. High molecular weight of 110 200 and yield 99% were achieved at a higher [PO]/[complex] ratio of 6000:1. The complex also worked satisfactorily for the terpolymerization of CO₂, PO and cyclohexene oxide (CHO), without formation of cyclic carbonate or ether linkages to give the polycarbonate. High cyclohexene carbonate unit content in the CO₂/PO/CHO terpolymers resulted in enhanced thermal stability. Copyright © 2011 John Wiley & Sons, Ltd.     

Regio‐regular structure high molecular weight poly(propylene carbonate) by rare earth ternary catalyst and Lewis base cocatalyst

Lewis base modification strategy on rare earth ternary catalyst was disclosed to enhance nucleophilic ability of active center during copolymerization of carbon dioxide and propylene oxide (PO), poly(propylene carbonate) (PPC) with H‐T linkages over 83%, and number–average molecular weight (M_n) up to 100 kg/mol was synthesized at room temperature using Y(CCl₃OO)₃‐ZnEt₂‐glycerine catalyst and 1,10‐phenanthroline (PHEN) cocatalyst. Coordination of PHEN with active Zinc center enhanced the nucleophilic ability of the metal carbonate, which became more regio‐specific in attacking carbon in PO, leading to PPC with improved H‐T linkages. Moreover, the binding of PHEN to active Zinc center also raised the carbonate content of PPC to over 99%, whereas the PPC from common rare earth ternary catalyst was about 96%. Unlike the highly regio‐regular structure PPC but with relatively low molecular weight recently reported in the literature, our high molecular weight regio‐regular PPC did show significant improvement in thermal and mechanical performances. PPC with H‐T linkages up to 83.2% showed glass transition temperature (T_g) of 43.3 °C, while T_g of PPC with H‐T linkages of 69.7% was only 36.1 °C. When H‐T connectivity was raised from 69.7 to 83.2%, the modulus of PPC showed a 78% increase. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4451–4458, 2008     

Crosslinkable poly(propylene carbonate): High‐yield synthesis and performance improvement

A crosslinking strategy was used to improve the thermal and mechanical performance of poly(propylene carbonate) (PPC): PPC bearing a small moiety of pendant C?C groups was synthesized by the terpolymerization of allyl glycidyl ether (AGE), propylene oxide (PO), and carbon dioxide (CO₂). Almost no yield loss was found in comparison with that of the PO and CO₂ copolymer when the concentration of AGE units in the terpolymer was less than 5 mol %. Once subjected to UV‐radiation crosslinking, the crosslinked PPC film showed an elastic modulus 1 order of magnitude higher than that of the uncrosslinked one. Moreover, crosslinked PPC showed hot‐set elongation at 65 °C of 17.2% and permanent deformation approaching 0, whereas they were 35.3 and 17.2% for uncrosslinked PPC, respectively. Therefore, the PPC application window was enlarged to a higher temperature zone by the crosslinking strategy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5329–5336, 2006     

聚己内酯、聚环氧丙烷大单体制备及其与甲基丙烯酸正丁酯共聚合

聚己内酯、聚环氧丙烷大单体制备及其与甲基丙烯酸正丁酯共聚合曹维孝，管治斌，江必旺，冯新德（北京大学化学系北京１００８７１）关键词大单体，聚己内酯，聚环氧丙烷以四苯基卟啉氯化铝（ＴＰＰＡＩ－Ｃｌ）与甲基丙烯酸－β－羟基两酯（ＨＰＭＡ）制备的活性开环催化...     

A one‐step strategy for aliphatic poly(carbonate‐ester)s with high performance derived from CO2, propylene oxide and l‐lactide

To improve the performance of PPC, aliphatic poly(carbonate‐ester)s were prepared in one‐step strategy from the terpolymerization of CO₂, propylene oxide (PO), and l ‐lactide (L ‐LA) catalyzed by zinc glutarate. Consequently giving high‐molecular weight terpolymers (PPCLAs) in a very high yield (8450.8–9435.8 g mol^?1 of Zn). The resulting terpolymers PPCLAs were characterized by ¹H NMR, showing that PPCLAs had an almost alternating structure for the components of CO₂, PO, and L‐LA. The influence of molecular weight and L‐LA content on the properties of PPCLAs was also investigated. Differential scanning calorimetry and thermogravimetric analysis (measurements revealed that the glass transition temperature (T _g) and thermal decomposition temperature (T _d) of PPCLAs are all much higher than those of PPC and increased with increasing molecular weight and L‐LA content. Tensile tests showed that the high mechanical properties of PPCLAs are due to the introduction of L‐LA into the copolymerization of CO₂ and PO. Furthermore, PPCLA4 exhibits high degradability, and after 10 weeks, the weight loss increases up to 6.58%, which is significantly higher than that of PPC of 4.58%. Copyright © 2016 John Wiley & Sons, Ltd.