Synthesis, Characterization, and Epoxidation of an Aliphatic Polycarbonate from 2,2-(2-Pentene-1,5-diyl)trimethylene Carbonate (^cHTC) Ring-Opening Polymerization

Abstract

2,2-(2-Pentene-1,5-diyl)trimethylene carbonate ( c HTC) was synthesized from cyclohexene-4,4-dimethanol in high yield (>80%). This new carbonate monomer was successfully ring-open polymerized to form P( c HTC) in bulk at 90 °C using various organometallic catalysts including aluminoxanes (methyl and isobutyl), BunSnCl4-n (n ) 1, 2, 3), BunSn(OMe)4-n (n ) 2, 3), ZnEt2, and ZnEt2-H2O. Comparison of these systems showed that the Zn-and Al-based catalysts were preferred for the preparation of high molecular weight polymers in yields g89% and reaction times of e8 h. For the BunSnX4-n catalysts investigated, values of n ) 1 when X is Cl and n ) 2 when X is OMe resulted in relatively greater polymerization rates and higher polymer molecular weights. The effects of reaction time and monomer/ catalyst molar ratio were investigated for the Al and Zn catalysts. An outcome of this study was determining that the ZnEt2-H2O (1/0.5) catalyst for a monomer/catalyst (M/C) molar ratio of 400 and a 2 h reaction time gave a product with Mn ) 276 000 in 98% yield. The P( c HTC) products were characterized by FTIR, 1 H-NMR, 13 C-NMR, DSC, TGA, and GPC. NMR results showed that c HTC decarboxylation did not occur during chain propagation. P( c HTC) has a moderate glass transition temperature (Tg ) 30 °C) with high thermal stability. 13 C NMR at 62.5 MHz did not resolve chain diad sequences although the polymers are likely atactic. Epoxidation of P( c HTC) vinyl side groups was carried out to various extents by using 3-chloroperoxybenzoic acid at room temperature.

Nucleophile-initiated and thermal bulk polymerizations of cyclic trimethylene carbonate in the absence of added catalysts

“…The polymerization can be achieved using a large variety of intiators: anionic, [1][2][3][4][5][6][7] cationic [4,[8][9][10] and of coordination-insertion type. [11][12][13][14][15][16][17] Very recently the enzymatic polymerization has also been developed. [18][19][20] The continuous interest in aliphatic polycarbonates results from their potential applications in several attractive domains.…”

Synthesis, Modification, and Characterization of l-Lactide/2,2-[2-Pentene-1,5-diyl]trimethylene Carbonate Copolymers

“…For example, P( c HTC) CdC groups were converted to epoxides with little molecular weight decrease. 22 The copolymerizations of cyclic carbonates with lactide have been explored. 18,19,23,24 Specifically, 2,2-dimethyltrimethylene carbonate L-LA (DTC/L-LA) copolymerizations were conducted using various catalysts including Al(O-sec-Bu) 3 and ZnEt 2 at reaction temperatures from 100 to 130°C.…”

Preparation and Properties of Poly(l-lactide)-block-poly(trimethylenecarbonate) as Biodegradable Thermoplastic Elastomer

“…PTMC with the reported glass transition temperature of −25 • C, is rubbery at room temperature and biodegradable both in vivo and in vitro, and hence, possesses potential applications in medical and environmental areas. [11][12][13] Here we report the preparation and chain extension of P(LLA-b-TMC-b-LLA) triblock copolymers. Also the basic tensile properties as thermoplastic elastomer along with the phase-separated morphology will be discussed.…”