Terpolymerization Of Propylene Oxide Research Articles

Low molar mass polycarbonate diols from degradation of terpolymers obtained by epoxide/o-phthalaldehyde/CO2 copolymerization

In this manuscript, we describe the synthesis of low molar mass polycarbonate diols by acid cleavage of labile acetal linkages included in high molar mass poly(ether-co-carbonate-co-acetal) terpolymers. These copolymers were prepared by terpolymerization of propylene oxide (PO) with o-phthalaldehyde (OPA) and carbon dioxide (CO2), using triethyl borane (TEB) as activator and an onium salt as initiator. The advantage of this strategy of synthesis of poly(propylene carbonate) diols (PPC-diols) lies in the minute amounts of TEB and initiator required. Moreover, OPA could be isolated through post-hydrolysis of the terpolymers and recycled for subsequent use. We also demonstrated that this strategy works for the synthesis of low molar mass poly(ethylene carbonate) diols (PEC-diols). The structural integrity of the terpolymers before and after acid treatment, the characterization of low molar mass PPC-diols, and recycling process of OPA were carried out by 1H NMR spectroscopy, gel permeation chromatography, and matrix-assisted laser desorption ionization time of flight (MALDI-TOF) MS.

Synthesis of high-toughness waterborne polyurethane utilizing self-emulsifying CO2-based polyols

In this work, a self-emulsifying CO2-based polyol (LAPEC) was prepared by the terpolymerization of propylene oxide, allyl glycidyl ether and CO2, followed by thiol-ene click reaction with mercaptopropionic acid. And the carboxyl group was successfully introduced into LAPEC verified in 1H NMR. LAPEC was served as both soft segments and internal emulsifiers for WPU. Meanwhile, γ-aminopropylmethyldiethoxysilane (KH902) was also employed to improve the mechanical properties of WPU. Compared to dimethylol propionic acid (DMPA), WPU emulsion prepared by LAPEC had smaller particle size and higher emulsification efficiency. And the performance differences between LAPEC-based WPU films (LWPUs) and DMPA-based WPU films (DWPUs) with different hard segment contents were studied. The stronger hydrogen-bonding interactions improved the tensile strength, toughness and thermal stability. Compared with DWPU, the tensile strength and the elongation at break of LWPU respectively increased from 17.8 to 21.1 MPa and from 302.3 % to 356.5 %, when their hard segment content was both maintained around 37 wt%. Meanwhile, due to rougher surfaces and more hydrophobic silicon clusters, LWPU had stronger surface hydrophobicity. Therefore, LAPEC can provide a new way to synthesize WPU with high toughness and can be potentially used for flexible substrate coatings in the future.

Terpolymerization of propylene oxide, carbon dioxide, and trimethylene carbonate

Terpolymerization of propylene oxide, carbon dioxide, and trimethylene carbonate

Metal‐free terpolymerization of propylene oxide, carbon dioxide, and carbonyl sulfide: A facile route to sulfur‐containing polycarbonates with gradient sequences

AbstractIntroducing sulfur atoms into polycarbonate can improve its optical properties, but is limited by the lack of efficient synthetic methods. Here we develop a facile method to achieve the one‐pot/one‐step incorporation of sulfur atoms into polycarbonate chains using raw chemicals of propylene oxide (PO), carbon dioxide (CO2), and carbonyl sulfide (COS). The metal‐free Lewis acid–base pair composed of N, N‐dimethylcyclohexylamine combined with triethyl borane can effectively catalyze the terpolymerization of PO, CO2, and COS, affording a sulfur‐containing polycarbonate with high molecular weight (Mn) up to 58.4 kDa and narrow dispersity (Đ = 1.24–1.56). The obtained terpolymers display gradient sequence with tunable thiocarbonate units (27%–81%) upon simply varying the feed ratio of COS. The refractive indices of the terpolymers can be enhanced up to 1.55 at high thiocarbonate content, suggesting promising applications of the terpolymer in optical materials.

Sustainable polycarbonate adhesives for dry and aqueous conditions with thermoresponsive properties

Pressure sensitive adhesives are ubiquitous in commodity products such as tapes, bandages, labels, packaging, and insulation. With single use plastics comprising almost half of yearly plastic production, it is essential that the design, synthesis, and decomposition products of future materials, including polymer adhesives, are within the context of a healthy ecosystem along with comparable or superior performance to conventional materials. Here we show a series of sustainable polymeric adhesives, with an eco-design, that perform in both dry and wet environments. The terpolymerization of propylene oxide, glycidyl butyrate, and CO2, catalyzed by a cobalt salen complex bearing a quaternary ammonium salt, yields the poly(propylene-co-glycidyl butyrate carbonate)s (PPGBC)s. This polymeric adhesive system, composed of environmentally benign building blocks, implements carbon dioxide sequestration techniques, poses minimal environmental hazards, exhibits varied peel strengths from scotch tape to hot-melt wood-glue, and adheres to metal, glass, wood, and Teflon® surfaces.

A Zn-MOF-Catalyzed Terpolymerization of Propylene Oxide, CO2, and β-butyrolactone

The terpolymerization of propylene oxide (PO), CO2, and a lactone is one of the prominent sustainable procedures for synthesizing thermoplastic materials at an industrial scale. Herein, the one-pot terpolymerization of PO, CO2, and β-butyrolactone (BBL) was achieved for the first time using a heterogeneous nano-sized catalyst: zinc glutarate (ZnGA-20). The reactivity of both PO and BBL increased with the CO2 pressure, and the polyester content of the terpolymer poly (carbonate-co-ester) could be tuned by controlling the infeed ratio of PO to BBL. When the polyester content increased, the thermal stability of the polymers increased, whereas the glass transition temperature (Tg) decreased.

Terpolymerization of propylene oxide and vinyl oxides with CO2: copolymer cross-linking and surface modification via thiol–ene click chemistry

Terpolymerization of epoxides containing vinyl pendant groups, propylene oxide, and carbon dioxide afforded polycarbonates which were cross-linked and surface modified via thiol–ene chemistry.

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 cyclic anhydrides by porphyrin metal(III) complexes

A series of porphyrin metal(III) complexes of general formula LMX (L = tetraphenylporphyrin (TPP), octaethylporphyrin (OEP), tetrakispentafluorophenylporphyrin (TFPP), M = Al, Cr, Co, X = Cl, OH or OEt); has been investigated as catalyst systems for the copolymerization of propylene oxide (PO) and cyclic anhydrides to produce polypropylene carboxylates, with and without a Lewis base cocatalyst: bis(triphenylphosphine)iminium chloride (PPN+Cl−). The highest rate of copolymerization was observed with 1.0 equiv. cocatalyst and the use of phthalic anhydride (PA) monomer allowed the formation of higher molecular weight polyesters. The terpolymerization of PO, cyclic anhydride and CO2 produced poly(ester-b-carbonates). With PPN+Cl− cocatalyst, TPPCrCl catalyst system produced two polymer chains per metal. The polymerization processes were followed by 1H NMR spectroscopy and polymer samples were characterized by GPC, Mass (ESI and MALDI TOF) and NMR (1H, 13C{1H}) spectroscopy. The observed results are compared with earlier studies of salen and related complexes.

Alternating copolymerization of CO2 with propylene oxide and terpolymerization with aliphatic epoxides by bifunctional cobalt Salen complex

A novel N,N′-[2,2′-bis(nitrilomethylidyne)]bis[α-methyl-4-(morpholin-1-ylmethyl)-6-tert-butyl phenolato]-1,2-diaminocyclohexane CoIII (2,4-dinitrophenoxy) complex (complex 1) was designed and used to couple carbon dioxide (CO2) and propylene oxide (PO) as a single-component catalyst. Systematic investigation revealed that complex 1 was highly active and selective in the coupling of CO2/PO and that complete consumption of PO was accomplished with high copolymer selectivity. A high molecular weight of up to 108.6 kg mol−1 was achieved with an appropriate combination of all variables. Matrix-assisted laser desorption ionization–time-of-flight mass spectrometer analysis implied that a chain-end control mechanism controls the copolymerization. In addition, complex 1 could operate very efficiently in the terpolymerization of PO and cyclohexene oxide (CHO) with CO2 to provide polycarbonates with a narrow polydispersity. The Tg of the PO/CHO/CO2 terpolymer can be easily adjusted between 40 and 118.9 °C. A bifunctional cobalt Salen complex containing a Lewis acid metal center and two covalent bonded Lewis base units on the ligand was designed and used for the coupling of carbon dioxide (CO2) and epoxides at mild conditions. The Tg of the propylene oxide/cyclohexene oxide/CO2 terpolymer can be easily adjusted between 40 and 118.9 °C.

Synthesis, characterization and hydrolysis of an aliphatic polycarbonate by terpolymerization of carbon dioxide, propylene oxide and maleic anhydride

Terpolymerization of propylene oxide (PO), carbon dioxide (CO 2) and maleic anhydride (MA) was carried out by using a polymer-supported bimetallic complex (PBM) as a catalyst. A degradable aliphatic poly(propylene carbonate maleate) (PPCM) was synthesized, and determined by FT-IR, 1H NMR, 13C NMR, DSC, TGA and WAXD measurements. The influences of various reaction conditions such as molar ratio of the monomers, reaction time and reaction temperature on the terpolymerization progress were investigated. The results showed that MA was inserted into the backbone of CO 2–PO successfully. The viscosity, glass transition temperature and decomposition temperature of the terpolymers were much higher than those of poly(propylene carbonate) (PPC). Because of the existence of the MA ester unit, PPCM had stronger degradability than PPC in a pH 7.4 phosphate-buffered solution. MA offered an ester structural unit that gave the terpolymers remarkable degradability. And the degradation rate of the backbone increased with the insertion of MA into the terpolymers.