Ring-opening polymerization of isopropylglycidyl ether (IPGE) with new catalysts of Ti, Sn, Al-alkoxides and comparison of its reactivity

Abstract

The polymerization reactions of isopropylglycidyl ether (IPGE) were carried out by various catalysts potassium hydroxide, potassium tert-butoxide, tetrafluorophthalate aluminum secbutoxide, tetrafluorophthalate tin tert-butoxide, and tetrafluorophthalate-titanium isopropoxide complexes. Tetrafluorophthalate-aluminum, tin, and titanium have been prepared from aluminum sec-butoxide, tin tert-butoxide, and titanium isopropoxide in alcohol and tetrafluorophthalic acid. Poly-IPGE and catalysts were characterized by 1 H, 13 C NMR, FTIR spectroscopy, elemental analysis, and gel permeation chromatography. IPGE is less reactive toward OH À nucleophiles than 3-glycidyloxypropyltrimethoxysilane and propylene oxide.Keywords: polymer; catalyst; synthesis; NMR; ring opening IntroductionRing-opening polymerization of epoxide monomers has been gaining attention in both academic and industrial circles due to its wide range of applications such as production of detergents, nonionic surfactants, washing agents, the heavy metal-free coating, filler, extenders, in drinking water distribution systems, antireflective composition for photoresists, reinforced plastics, adhesives, and polyurethane production process [1][2][3][4][5][6]. Propylene oxide (PO), styrene oxide (SO), 3-glycidyloxypropyltrimethoxysilane (GPTS), and phenylglycidyl ether (PGE) of cyclic ethers have been polymerized by both anionic and cationic catalysts and also by more selective catalyst system and their products characterized by different spectroscopic techniques [6][7][8][9][10][11][12][13]. As in the mechanism of ring-opening polymerization of PO initiated with porphyrin aluminum chloro complex [9,10], I have recently suggested that the polymerization of GPTS initiated with tetrafluorophthalate zirconium complex proceeds as follows [13].Although there is some spectroscopic evidence ( 1 H NMR) for the formation of polyisopropylglycidyl ether (IPGE) [14][15][16], nothing is known about the effect of different catalysts on the epoxide ring-opening and polymerization degree of IPGE in polymerization reactions. The first purpose was to prepare and use new catalysts in the ring-opening polymerization of IPGE. The second purpose of this study was to synthesize and characterize the polymers of IPGE prepared with various catalysts. The third purpose was to see whether the side isopropoxymethyl group (CH 2 OC 3 H 7 ) of oxirane will affect both the reactivity toward basic catalysts and the regioselectivity and stereoselectivity of polymerization when compared with other groups such as methyl, phenoxymethyl, and trimethoxysilylpropoxymethyl on epoxides.

Graft polymerization of p-dioxanone onto polyhydroxyethylaspartamide through ring-opening polymerization using organometallic and enzyme catalysts

“…However, high cost and discontinuous degradation rate are the key factors limiting wider applications of PPDO, for example, controlled release of drug. Graft copolymerization [13][14][15][16][17][18][19] is a versatile method to modify the PPDO for providing functionality to the resulting polymers, and for regulating polymer properties. However, there are few reports about graft copolymerization of PPDO with other polymers [20][21][22].…”

Advances in cyclic ester ring‐opening polymerization using heterogeneous catalysts

“…As a result, many studies have reported creating effective metal-based initiators (Figure 2) and their re-activities. 10 Metallic alkoxides such as Sn, 42,43 Al, 44,45 Zn, 46 Ti, 47 Sc, 48 enzyme, 49 and other catalysts have made significant contributions to the ROP of cyclic esters.…”

“…As a result, many studies have reported creating effective metal‐based initiators (Figure 2) and their re‐activities 10 . Metallic alkoxides such as Sn, 42,43 Al, 44,45 Zn, 46 Ti, 47 Sc, 48 enzyme, 49 and other catalysts have made significant contributions to the ROP of cyclic esters. Metal‐based complexes show a greater ability to manipulate the polymer's properties like molecular weight, PDI, and microstructure than aforementioned catalysts 26 .…”

Synthesis of poly(styrene oxide) with different molecular weights using tin catalysts

“…The reactions were carried out similarly to the preparations of β-diketonate tin(IV) propoxide and tetrafluorophthalate tin(IV) butoxide complexes. [10,11] The formulations of compounds were determined by elemental analysis, FTIR, and NMR measurements. The number of oxo group was one for both compounds.…”