Synthesis of polymers with pendant hydroxyl groups by polyaddition of bis(oxetane)s with dithiols

Nishikubo

2004

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ABSTRACT:The anionic ring-opening polymerization of 3,3-bis(hydroxymethyl)oxetane (BHO) was carried out using t-BuOK as an initiator in the presence of 18-crown-6-ether (18-C-6) in NMP at 180 C, affording the corresponding hyperbranched polyethers, poly(BHO)s containing an oxetanyl group and many hydroxyl groups at the ends in 83-98% yields. Since the resulting poly(BHO)s were insoluble in common organic solvents, the poly(BHO)s were treated with acetic anhydride to obtain poly(BHO-Ac)s containing acetyl groups at the ends. The M n s and degree of branching (DB) of poly(BHO-Ac)s were in the range of 2600-4400 estimated by SEC and 0.09-0.55 calculated by 13 C NMR spectroscopy, respectively. The cationic copolymerization of poly(BHO-Ac) and 3-ethyl-3-phenoxymethyloxetane (EPO) was examined using BF 3 reported the synthesis of hyperbranched polyethers by the cationic ring-opening polymerization of EHO using various cationic initiators. Penczek et al. 4 reported that the cationic ring-opening polymerizations of 3,3-bis(hydroxymethyl)oxetane (BHO), and the copolymerization of BHO with EHO were performed to give medium molecular-weight polymers in good yields.Meanwhile, we have developed many new reactions of oxetanes with various protonic reagents such as phenols, 5 thiophenols, 6 carboxylic acids, 7 and thioesters 8 in the presence of quaternary onium salts or crown ether complexes as catalysts. These new reactions have been applied to the synthesis of polymers such as polyethers, 5 polyesters, 7,9 polyphosphonates, 10 and poly(silyl ether)s. 11 Furthermore, we have found anionic alternating ring-opening copolymerization of oxetanes with carboxylic anhydrides in the presence of the quaternary onium salts as initiators.12 Inoue and Endo et al. preformed the living anionic polymerization of oxetanes using metal complexes as catalysts. [13][14][15][16][17] More recently, we reported a new anionic ringopening polymerization of EHO and 3-methyl-3-hydroxymethyloxetane (MHO) containing hydroxyl groups using potassium tert-butoxide (t-BuOK) and 18-crown-6-ether (18-C-6), affording the hyperbranched polyether containing an oxetanyl group and many hydroxyl groups at the end (Scheme 1).18,19 Furthermore, we achieved the synthesis of a pseudo dendritic polymer with many pendant hydroxyl groups by the cationic ring-opening polymerization of the poly(EHO) derivative.19 These synthesized polymers poly(EHO), poly(MHO), and pseudo dendritic polymers are expected as useful functional materials, because they have many hydroxyl groups at the ends.In a series of the study for the synthesis of hyperbranched polyether by the anionic ring-opening polymerization of the oxetane with hydroxyl groups in this article, we examined the reaction of BHO containing two hydroxyl groups in the presence of t-BuOK in several conditions in detail. Furthermore, we also examined the reaction of the resulting polymers for the synthesis of new branched polymers containing pendant many hydroxyl groups. EXPERIMENTAL MaterialsThe solvents, chloroform (CHCl 3 ...

Section: Synthesis Of 33-bis(hydroxymethyl)oxetane (Bho)mentioning

confidence: 99%

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confidence: 99%

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confidence: 99%

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Synthesis of Hyperbranched Polymers by the Anionic Ring-Opening Polymerization of 3,3-Bis(hydroxymethyl)oxetane

Morita

Nishikubo

2004

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“…On the other hand, we have recently found a new polyaddition reactions of bis(oxetane)s with dicarboxylic acids 14 or bisphenols [15][16][17] to produce the high molecular weight polyesters and polyethers with pendant primary hydroxy groups which can be use as the reactive groups for the introduction of functional groups, respectively. Given these background, we designed 18 new hyperbranched poly(ester)s with pendant primary hydroxy groups as reactive groups by the polyaddition reaction of bis(oxetane)s with 1,3,5-benzenetricarboxylic acid (TMA).…”

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confidence: 99%

Synthesis of Photocrosslinkable Hyperbranched Polyesters with Terminal Methacryloyl Groups by the One-pot Polyaddition of Bis(oxetane)s with 1,3,5-Benzenetricarboxylic Acid and Methacrylic Acid

Nishikubo

Maruyama

et al. 2006

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ABSTRACT:The hyperbranched poly(ester)s with pendant primary hydroxy, methacryloyl, and oxetanyl groups were synthesized by the one-pot method for the polyaddition of bis(oxetane)s with 1,3,5-benzenetricarboxylic acid (TMA) and methacrylic acid (MA) in the presence of tetraphenylphosphonium chloride (TPPC) as a catalyst. A alkaline-developable photo-reactive hyperbranched polymer (P-4b) was prepared by the addition reaction of the synthesized hyperbranched poly(ester) P-4a with cis-1,2,3,6-tetrahydrophthalic anhydride (THPA). A resist composed of 58 wt % P-4b, 12 wt % dilute monomer, 5 wt % Irgacure907Ò as a photo-initiator, 24 wt % epoxy resin, and 1 wt % dicyandiamide achieved a resolution of a 55 mm line pattern and a 27 mm space pattern by UV irradiation (1000 mJ) when 6 mm thick film is used. 1,2 such as coatings, printing inks, adhesives, photo-resists, and solder masks, because of their low volatile organic compound (VOC), high productivity, excellent physical properties, and energy saving. Recently, these systems have also been applied to electronics and information technology fields 3 such as display, CD, DVD, optical-fiber, and opticaldevice. In these curing systems, acrylate monomers and oligomers are mainly used due to their high reactivity. Most of acrylate oligomers such as acrylated epoxy resins, poly(urethane)s, poly(ester)s, and poly-(ether)s have relatively high viscosity, because these oligomers were composed from linear polymer chains in general.More than 30 years ago, we 4,5 reported the synthesis of polyesters with pendant hydroxy groups and (meth)acrylate groups by the addition reaction of epoxy resins with (meth)acrylic acid, which have been used as main resins in the fields of coatings and printing inks due to their high photochemical reactivity and excellent mechanical property. Furthermore, these oligomers were modified 6 with cyclic carboxylic anhydride to form photo-curable oligomer with alkaline developable property. These (meth)acrylated epoxy resin derivatives have been widely used as main resin in solder masks in the world.Meanwhile, hyperbranched polymers (HBPs) containing a large number of terminal groups possess a randomly branched structure 7 and have recently attracted a great deal of attention for their unique properties such as lower viscosity, good solubility and many reactive terminal groups compared with the corresponding linear ones. Condensation polymers with hyperbranched structure are mainly synthesized 8,9 by the one-step self-polycondensation of an AB m type monomer which has one 'A' functional group and multiple 'B' functional groups. However, these monomers are generally required to process tedious multistep organic synthesis and are unsuitable for industrial application on a large scale synthesis. To overcome this technical problem, Kakimoto and his co-workers 10 substituted a new method by conventional combination of A 2 and B 3 monomers. Since the reaction system between A 2 þ B 3 monomers produced gel products in general, the control of the reaction conditio...

“…In addition, it was found that fluorine-containing poly(ether)s with pendant hydroxyl groups are highly transparent at 157 nm, and transmittance of poly(ether)s were determined to be 14-75 % at 157 nm for 0.1 mm thickness. 9 Meanwhile, our research group previously reported the polyaddition of bis(oxetane)s with various protonic reagents such as dicarboxylic acids, 10 dithiols, 11 and bis(phenol)s 12 proceeded smoothly in the presence of quaternary onium salts and crown ether complexes as catalysts to give corresponding soluble polymers with pendant primary hydroxyl groups. The pendant primary hydroxyl groups seemed to be useful reactive groups for chemical modification.…”

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Synthesis and Properties of Fluorine-containing Poly(ether)s with Pendant Hydroxyl Groups by the Polyaddition of Bis(oxetane)s and Bisphenol AF

Konno

Suzuki

et al. 2004

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ABSTRACT:Fluorine-containing poly(ether)s with pendant primary hydroxyl groups were synthesized by the polyaddition of bisphenol AF di(3-ethyl-3-oxetanylmethyl ether) (BPAFEO) with bisphenol AF (BPAF) using quaternary onium salts, crown ether complexes or organic bases as catalysts. When the polyaddition was performed with co-catalysts such as tetraphenylphosphonium chloride (TPPC) and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) without solvent at 190C for 120 h, the corresponding poly(ether)s pendant primary hydroxyl groups were successfully obtained in good yield. The polyaddition of various bis(oxetane)s with BPAF also proceeded in bulk to provide the corresponding poly(ether)s. It was found that these poly(ether)s are highly transparent at 157 nm, and transmittance of poly(ether)s were determined to be 34-55 % at 157 nm for 0.1 mm thickness.KEY WORDS Polyaddition / Bis(oxetane) / Synthesis / Fluorine-containing Poly(ether)s / High Transparency at 157 nm / It is well known that fluorine-containing polymers exhibit high thermal stability, excellent chemical resistance, and many other special properties. Therefore, fluoropolymers have been investigated as high performance materials for application of optical and microelectronics derivatives. Recently, most research groups investigated fluoropolymers as photoresist materials for F 2 lithography because they are fairly transparent in the vacuum ultraviolet (VUV). [1][2][3][4][5][6] In our recent paper, we demonstrated the synthesis and characterization of fluorine-containing polymers by the polyaddition of fluorine-containing bis(epoxide)s with fluorine-containing dicarboxylic acids, diols, 7 and active diesters. 8 The refractive indices of the obtained polymers decreased when the fluorine contents increased. In addition, it was found that fluorine-containing poly(ether)s with pendant hydroxyl groups are highly transparent at 157 nm, and transmittance of poly(ether)s were determined to be 14-75 % at 157 nm for 0.1 mm thickness.