Synthesis of Photosensitive and Thermosetting Poly(phenylene ether) Containing Butenyl Groups (original) (raw)
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Journal of Polymer Science Part A: Polymer Chemistry, 2005
A chemically amplified photosensitive and thermosetting polymer based on poly[2,6-di(3-methyl-2-butenyl)phenol (15 mol %)-co-2,6-dimethylphenol (85 mol %)] (3c) and a photoacid generator [(5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2methylphenyl)acetonitrile] was developed. Poly[2,6-bis(3-methyl-2-butenyl)phenol]-co-2,6-dimethylphenol)] (3) with high molecular weights (number-average molecular weight ϳ 24,000) was prepared by the oxidative coupling copolymerization of 2,6-di(3methyl-2-butenyl)phenol with 2,6-dimethylphenol in the presence of copper(I) chloride and pyridine as the catalyst under a stream of oxygen. The structures of 3 were characterized with IR, 1 H NMR, and 13 C NMR spectroscopy. 3 was crosslinked by a thermal treatment at 300°C for 1 h under N 2. The 5% weight loss temperatures and glass-transition temperatures of the cured copolymers reached around 420°C in nitrogen and 300°C, respectively. The average refractive index of the cured copolymer (3c) film was 1.5452, from which the dielectric constant at 1 MHz was estimated to be 2.6. The resist showed a sensitivity of 35 mJ cm Ϫ2 and a contrast of 1.6 when it was exposed to 436-nm light, postexposure-baked at 145°C for 5 min, and developed with toluene at 25°C. A fine negative image featuring 8-m line-and-space patterns was obtained on a film exposed to 100 mJ cm Ϫ2 with 436-nm light in the contact-printed mode.
Synthesis of thermosetting poly(phenylene ether) containing allyl groups
Polymer, 2004
New thermosetting poly(2-allyl-6-methylphenol-co-2,6-dimethylphenol)s (3) have been developed by oxidative coupling copolymerization of 2-allyl-6-methylphenol (1) with 2,6-dimethylphenol (2), followed by thermal curing. Copolymerization was conducted in nitrobenzene in the presence of copper(I) chloride and pyridine as the catalyst under a stream of oxygen, producing high molecular weight copolymers ðM n , 50; 000Þ with broad molecular weight distributions ðM w =M n , 35Þ: The structure of resulting copolymers 3 was characterized by IR, 1 H, and 13 C NMR spectroscopy. Cross-linking reactions of copolymers were carried out by thermal treatment in the absence or presence of a peroxide (3 wt%, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-butane). The 10% weight loss and glass transition temperatures of the cured copolymers were 436 8C in nitrogen and 235 8C, respectively after curing at 70 8C for 1 h and 300 8C for 1 h. The average refractive index of the cured copolymer (3b) film was 1.5407, from which the dielectric constant ð1Þ at 1 MHz was estimated as 2.6. The 1 and dissipation factor of copolymer-films at 1 MHz were directly measured from their capacitances as 2.5 -2.6 and 0.0015 -0.0019, respectively. q
Polymer, 2004
A positive working and chemically amplified photosensitive polymer based on partially (30%) O-methylated poly(2,6-dihydroxy-1,5naphthylene) [PMPDHN (30)], 1,3,5-tris[(2-vinyloxy)ethoxy]benzene (TVEB) as an acidolytic de-cross-linker, and a photoacid generator (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile (PTMA) has been developed. Poly(2,6-dihydroxy-1,5naphthylene) (PDHN) with a number-average molecular weight of 33,000 was prepared by oxidative coupling polymerization of 2,6dihydroxynaphthalene (2,6-DHN) using dim -hydroxo-bis-[(N,N,N 0 ,N 0-tetramethylethylenediamine)copper(II)] chloride [CuCl(OH)TMEDA] as the catalyst in 2-methoxyethanol at room temperature. PDHN was converted to PMPDHN by treating with iodomethane. The resist showed a sensitivity of 19.4 mJ cm K2 and a contrast of 7.5 when it was exposed to 436 nm light, followed by post-baking at 120 8C for 5 min and developing with 2.38 wt% aqueous tetramethylammonium hydroxide (TMAH) solution at 25 8C. A fine positive image featuring 6 mm line and space patterns was obtained on the film exposed to 20 mJ cm K2 of UV-light at 436 nm by the contact-printed mode. The optically estimated dielectric constants (at 1 MHz) of PMPDHN (30) with and without TVEB and PTMA are 3.03 and 3.01, respectively. The moisture absorption (1.7 wt%) of the resist system based on PMPDHN (30) and TVEB is very low compared to that (4.3%) of the resist system consisting of PDHN and 4,4 0methylenebis[2,6-bis(hydroxymethyl)]phenol (MBHP).
Journal of Polymer Science Part A: Polymer Chemistry, 1996
A new monomer, methyl 4-(2-methyl-l-oxoprop-2-en-l-yl)benzoate (p-(methoxycar-bony1)phenyl isopropenyl ketone, MeOCO-PIPK), was synthesized and copolymerized with styrene and methyl methacrylate (MMA). The copolymers of MeOCO-PIPK and 2-methyl-1-phenylprop-2-en-1-one (phenyl isopropenyl ketone, PIPK) with styrene and MMA were photoIyzed by deep-, mid-and near-UV light in dilute solution; and the quantum yields of scission, &, and the UV absorption spectra were measured. The p-methoxycarbonyl substitution increased the molar extinction coefficients of the ketone monomer units extensively, but slightly lowered the 4s values in styrene and MMA copolymers. This is expected to increase the net sensitivity of solid films of the polymers. The was found independent of the wavelength, despite the concurrent absorption by styrene units in the styrene copolymers. Larger & values were obtained for the MMA copolymers than the corresponding styrene copolymers. Solvents with larger dielectric constants gave larger & for the copolymer of MMA with PIPK; but when the dielectric constants were similar, lower 4s values were observed in the solvents with more easily abstractable hydrogens. A large bleaching effect was seen in MMA copolymers, which should make possible the formation of resist patterns with steep profiles when used in photolithography. 0 1996 John Wiley & Sons, Inc.
Journal of Photopolymer Science and Technology
A positive working thermally stable and photosensitive polymer based on poly(2-hydroxy-6-methylphenol-co-2,6-dimethylphenol)(PHP-MP) and 2,3,4-tris[2-diazo-1(2H)naphthalenone-4-sulfonyloxy] benzophenone (D4SB) as a photoreactive compound has been developed. The copolymer PHP-MP was prepared by oxidative coupling polymerization of 2-(tetrahydropyran-2-yl)oxy-6-methylphenol with 2,6-dimethylphenol, followed by acid treatment. The PHP-MP film showed excellent transparency above 300 nm. The dissolution behaviour of the PHP-MP film containing 30 wt% of D4SB after exposure and post exposure bake (PEB) has been studied and it has been found that the dissolution rate of an exposed area was 200 times faster than that of an unexposed area, due to the photochemical reaction of D4SB in the polymer film. This system containing 25 wt% of D4SB showed a sensitivity of 75 mJ/cm2 and a contrast of 1.5 with 365 nm light, when it was post-exposure baked at 100 °C for 3 min, followed by developing with a 2.38 wt% aqueous tetramethylammonium hydroxide solution at 25 °C.
Polymer Journal, 2007
A novel negative-working thermally stable photosensitive polymer based on poly(naphthylene ether), a cross-linker hexa(methoxymethyl)melamine, and a photoacid generator (5-propylsulfonyl-oxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile. Poly(naphthylene ether) was prepared via the oxidative coupling polymerization of 4,4 0-bis(1-naphthyloxy)-2,2 0-dimethylbiphenyl. This photosensitive polymer showed a high sensitivity (D 0:5) of 6.0 mJ cm À2 and a high contrast (0:5) of 5.2, when it was exposed to a 436 nm light, post-exposure baked at 140 C for 5 min, and developed with toluene. A negative image featuring 20 mm line and space patterns was obtained on a film exposed to 20 mJ cm À2 of visible light at 436 nm by the contact-printed mode. The resulting polymer film had the low dielectric constant of 2.8 and high thermal stability.
Journal of Polymer Science Part A: Polymer Chemistry, 2008
A negative-type photosensitive poly(phenylene ether) (PSPPE) based on poly(2,6-dimethyl-1,4-phenylene ether) (PPE), a novel crosslinker 4,4 0-methylene-bis [2,6-bis(methoxymethyl)phenol] (MBMP) having good compatibility with PPE, and diphenylidonium 9,10-dimethoxy anthracene-2-sulfonate (DIAS) as a photoacid generator (PAG) has been developed. This resist consisting of PPE (73 wt %), MBMP (20 wt %) and DIAS (7 wt %) showed a high sensitivity (D 0.5) of 58 mJ/cm 2 and a contrast (c 0.5) of 9.5 when it was exposed to i-line (365 nm wavelength light), postexposure baked at 145 8C for 10 min, and developed with toluene at 25 8C. A fine negative image featuring 6 lm line-and-space pattern was obtained on the film exposed to 300 mJ/cm 2 of i-line by a contact-printed mode. The resulting polymer film cured at 300 8C for 1 h under nitrogen had a low dielectric constant (e ¼ 2.46) comparable to that of PPE and a higher T g than that of PPE. In addition, the cured PSPPE film was pretty low water absorption (<0.05%) as same as PPE. V
European Polymer Journal, 2001
The objective of the present work, described in this paper, is to synthesize and characterize new conjugated materials with tunable properties, as well as to contribute to a better understanding of their structure and physical properties. This copolymer, derived from poly-phenylene-vinylene (PPV), denoted PPV±ether is amorphous and insoluble in common solvents. It was characterized by infrared absorption (IR), Raman scattering, optical density (OD), gravimetric thermal analysis (GTA), dierential thermal analysis (DTA), X-ray photoelectron spectroscopy (XPS) and photoluminescence. After synthesis and puri®cation the copolymer PPV±ether is obtained with oligomer (F3), a fraction of copolymer, which is soluble. The results of GTA and DTA show that this copolymer is very stable. The IR, Raman scattering, and XPS studies show the good purity of the materials and con®rm the proposed structure. The OD and photoluminescence (PL) measurements show that this copolymer can be exploited in optoelectronic applications. Ó