Aliphatic Polycarbonates Produced from the Coupling of Carbon Dioxide and Oxetanes and Their Depolymerization via Cyclic Carbonate Formation

Darensbourg, Donald J.; Moncada, Adriana I.; Wei, Sheng-Hsuan

doi:10.1021/ma2002323

Cited by 66 publications

(59 citation statements)

References 32 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…This behavior has been ascribed to an increased steric hindrance of the substituents at 3-position. 72 Similar reactivity behavior was also noted by Kleij and co-workers for the substrates 3,3-dimethyloxetane and 3-methyl-3-methoxymethyloxirane using Al(III) or Fe(III) aminotriphenolate based catalysts (Entries 2 and 11-12, Table 3). 42,58 In general, more sterically hindered substrates such as the 3,3-disubstituted oxetanes require increased reaction times and give modest results in terms of conversion and selectivity towards the corresponding COCs.…”

Section: 71supporting

confidence: 77%

Recent Advances in the Catalytic Preparation of Cyclic Organic Carbonates

2015

View full text Add to dashboard Cite

ABSTRACT:The catalytic formation of cyclic organic carbonates (COCs) using carbon dioxide (CO 2 ) as a renewable carbon feed stock is a highly vibrant area of research with an increasing amount of researchers focusing on this thematic investigation. These organic carbonates are highly useful building blocks and nontoxic reagents, and are most commonly derived from CO 2 coupling reactions with oxirane and di-alcohol precursors using homogeneous catalysis methodologies. The activation of suitable reaction partners using catalysis as a key technology is a requisite for efficient CO 2 conversion as its high kinetic stability poses a barrier to access functional organic molecules with added value in both academic and industrial laboratories. Though this area of science has been flourishing for at least a decade, in the last 2−3 years significant advancements have been made to address the general reactivity and selectivity issues that are associated with the formation of COCs. Here we present a concise overview of these activities with a primary focus to highlight the most important progress made and the opportunities that catalysis can bring about when the synthesis of these intermediates is optimized to a higher level of sophistication. The attention will be limited to those cases where homogeneous metal-containing systems have been employed as they possess the highest potential for directed organic synthesis using CO 2 as molecular building block. This review discusses examples of exceptional reactivity and selectivity taking into account the challenging nature of the substrates that were involved, and mechanistic understanding guiding the optimization of these protocols is also highlighted.

show abstract

Section: 71supporting

confidence: 77%

Recent Advances in the Catalytic Preparation of Cyclic Organic Carbonates

2015

View full text Add to dashboard Cite

show abstract

“…Oxetanes a , b , n , and p – u are commercially available and were used as received. Oxetanes e ,11 h , [24 l ,24 and j 25 were prepared according to modified literature procedures. Oxetanes c 11 and d 26 were prepared according to previously reported procedures.…”

Section: Methodsmentioning

confidence: 99%

“…5‐((Benzyloxy)methyl)‐5‐methyl‐1,3‐dioxan‐2‐one (5) :11 Conditions: [ Al t Bu ]: 2.5 mol %; [TBAB]: 5 mol %; T : 75 °C, p (CO 2 ): 10 bar, time: 24 h; conversion: 99 %. Isolated by column chromatography (EtOAc/hexane 1:8 to 1:1 v/v) in 92 % yield.…”

Section: Methodsmentioning

confidence: 99%

“…The group of Darensbourg has extensively studied the metal‐catalyzed formation of polycarbonates derived from oxetane10 and a limited number of 3,3′‐disubstituted oxetanes;11 their work demonstrated that poly(carbonate) formation may (partially) result from the ring‐opening polymerization (ROP) of a pre‐formed six‐membered cyclic carbonate (6MCC), a process being more pronounced when using more substituted oxetanes giving the thermodynamically favored polycarbonates as end‐products. Therefore, new catalytic methods are still required to favor chemoselectivity towards the cyclic carbonate product.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Highly Chemoselective Catalytic Coupling of Substituted Oxetanes and Carbon Dioxide

Rintjema

Guo

Martín

et al. 2015

Chemistry A European J

View full text Add to dashboard Cite

Abstract:The chemo--selective coupling of oxetanes and carbon dioxide to afford functional, heterocyclic organic compounds known as six--membered cyclic carbonates remains a challenging topic. Here we describe an effective method for their synthesis relying on the use of Al--catalysis. The catalytic reactions can be carried out with excellent selectivity for the cyclic carbonate product tolerating various (functional) groups present in the 2--and 3--position(s) of the oxetane ring, and the presented methodology is the first general approach towards the formation of six--membered cyclic carbonates (6MCCs) through oxetane/CO 2 coupling chemistry. Apart from a series of substituted six--membered cyclic carbonates, also the unprecedented room temperature coupling of oxetanes and CO 2 is disclosed giving, depending on the structural features of the substrate, a variety of five--and six--membered heterocyclic products. A mechanistic rationale is presented for their formation and support for the intermediary presence of a carbonic acid derivative is given. The presented functional carbonates may hold great promise as building blocks in organic synthesis and the development of new, biodegradable polymers.

show abstract

“…Inoue first reported in 1969 that the copolymerization of carbon dioxide with epoxides could form aliphatic polycarbonates using organometallic compounds as catalysts [1,2], since then much progress has been made to synthesize various carbon dioxide based copolymers [3][4][5][6][7][8], among which poly(propylene carbonate) (PPC), theoretically the alternating copolymer of CO 2 and propylene oxide (PO), have been reported as good gas barrier with potential wide range applications [9,10].…”

Section: Introductionmentioning

confidence: 99%

Ether linkage in poly(1,2-propylene carbonate), a key structure factor to tune its performances

et al. 2012

View full text Add to dashboard Cite

As an alternating copolymer of CO 2 and propylene oxide, poly(1,2-propylene carbonate) (PPC) should be composed of fully carbonate structure, whereas it generally contains certain ether linkage due to the existence of competitive formation of ether linkage by consecutive epoxide enchainment. Though the ether linkage was not always the dominant structure in PPC, a new understanding was provided in that the ether linkage was crucial structure factor on the PPC performances, especially for oxygen barrier property, transparency, thermal and mechanical properties. The gas barrier properties and transparency of PPC film became worse with increasing ether linkages, the oxygen, nitrogen and carbon dioxide permeability of PPC with ether linkage of 0.6 % were 14 cm 3 /m 2 /24 h/0.1 MPa, 11 cm 3 /m 2 /24 h/ 0.1 MPa and 220 cm 3 /m 2 /24 h/0.1 MPa, respectively, while for PPC with ether linkage of 54.1 %, they became 116 cm 3 / m 2 /24 h/0.1 MPa, 108 cm 3 /m 2 /24 h/0.1 MPa and 599 cm 3 / m 2 /24 h/0.1 MPa, respectively. When the ether linkage in PPC increased from 0.6 % to 54.1 %, the thermal decomposition temperature at 5 wt% loss(T d-5% ) increased from 218.6°C to 241.0°C, while the glass-transition temperature (T g ) decreased from 45.2°C to 11.1°C, meanwhile, the room temperature tensile strength decreased from 55.4 MPa to 2.3 MPa, and the elongation at break increased from 8.5 % to 1558.2 %.

show abstract

Aliphatic Polycarbonates Produced from the Coupling of Carbon Dioxide and Oxetanes and Their Depolymerization via Cyclic Carbonate Formation

Cited by 66 publications

References 32 publications

Recent Advances in the Catalytic Preparation of Cyclic Organic Carbonates

Recent Advances in the Catalytic Preparation of Cyclic Organic Carbonates

Highly Chemoselective Catalytic Coupling of Substituted Oxetanes and Carbon Dioxide

Ether linkage in poly(1,2-propylene carbonate), a key structure factor to tune its performances

Contact Info

Product

Resources

About