SYNOPSISLinear ABA triblock and ( AB ), segmented block copolymers of energetic monomers have been synthesized. The rigid and soft blocks are prepared from 3,3-bis( azidomethyl) oxetane (BAMO) and 3-nitratomethyl-3-methyloxetane (NMMO) , respectively. Polymerization of BAMO initiated by triethyloxonium tetrafluoroborate and by spiro (benzoxasilole) /propanediol produced a-monohydroxy-PBAMO ( 3) and a,w-dihydroxy-PBAMO ( 4 ) of @" 16,000 and 2,000, respectively, and a,w-dihydroxy-PNMMO ( 5 ) of M,, = 13,000 was synthesized by the latter method. The block copolymers were prepared from the appropriate telechelic polymers and toluene diisocyanate. The PBAMO-PNMMO-PBAMO copolymer 6 has T , = 8Z°C, T, = -3"C, and is strongly phase separated even in the melt. It decomposes sharply within 1°C a t 224OC evolving 0.69 kJ/g of heat. Copolymer 6 has excellent mechanical properties with elongation of 683% at break, 5.25 MPa stress, and 82% recovery.The ( PBAMO-PNMMO ), , copolymer 7 has similar thermal properties and spectroscopic characteristic, but is inferior to copolymer 6 in all rheological and mechanical properties. INTRODUCTIONThermoplastic elastomers (TPE) are useful materials.' They can be prepared from any combination of low Tg building block with high Tg or crystalline ones. Segmented TPE is prepared by coupling the appropriate telechelic prepolymer in equal molar ratio. Linear ABA triblock copolymer can be elegantly synthesized by sequential polymerization if living propagation of all the constituent monomers can be achieved. It is more readily prepared by coupling telechelic low Tg prepolymer with monofunctional high Tg/ crystalline prepolymer as the terminal hard blocks. The synthesis of these functional prepolymers are prerequisite for this route. TPE containing energetic groups have been considered to be binder for propellent. The central purpose of this research is to synthesize both segmented and ABA TPE's from energetic monomers.It has been reported that 3,3,3',3'-tetrakis- Though living polymerization was not achieved for these oxetanes, a,w-dihydroxypolymer was obtained with 1 /propandiol. Furthermore, a-monohydroxypolyoxetanes was synthesized using either the 1 / benzyl alcohol catalyst or the Et30+BF; initiator.We present here the synthesis of TPE from these prepolymers and their properties.* To whom correspondence should be addressed. Polymerization and block coupling reactions were performed using dry argon purged Schlenk type apparatus. The crystalline block 3 was synthesized by BAMO, catalyst 2, and methylene chloride in the desired ratios were mixed and stirred at 25°C. The polymerization was quenched with water and the white powdery polymer 3 was precipitated with tenfold excess of aqueous NH3 in methanol. a,w-Dihydroxy PoIy(NMM0) (5)The telechelic amorphous block 5 was also prepared using catalyst 1 and propanediol: NMMO (9.9 g, 67 mmol), propanediol (0.5 g, 7 mmol), and 1 (0.3 g, 0.59 mmol) were combined and reacted for 3 days. The product was washed with an equal volume of aqueous methanol th...
The interfacial properties of a new family of lauryl trimethyl ammonium salts of the general formula CH3(CH2)11N+(CH3)3X− (X = CH3OCOO, HCOO, CH3COO, CH3CHOHCOO) were studied. The physicochemical parameters of these quaternary ammonium salts were discussed. The effect of the counteranion on the behavior of these surfactants was analyzed.
The kinetics of ethylene (E)/propene (P) copolymerization by heterogeneous Ziegler-Natta catalysts have characteristic rE * rp (product of monomer reactivity ratios) and p (persistence ratio) both greater than unity. The resulting E/P copolymers tend to contain short blocks of E. Therefore, uniform E/P copolymers and terpolymers are manufactured with homogeneous vanadium catalysts. The vanadium catalysts, however, have low productivity, require halogen-containing modifiers, and the high catalyst residue needs to be removed. The new zirconocene/MAO (methylaluminoxane) catalyst is superior'-9) to the above catalyst in most respects. It exhibits very high activity (> lo7 g E/P (mol Zr * h * bar)-') for random copolymerization of E and P (rE * rp < 1; p < 1). By proper choice of the hapto ligand, catalysts can be prepared which have rE and rp values different by orders of magnitudel9). At one time the zirconocene/MAO catalyst suffered an economical handicap because it requires MA0 in amount as high 0,l M. It also had apparent limitation for fluidized bed application because MA0 is essentially nonvolatile. Recently, the zirconocenium ion, produced by the reaction between rac-ethylenebis(indeny1)diethylzirconium (1) with triphenylcarbenium tetrakis(pentafluoropheny1)borate (2), has been found to be an exceedingly active and stereoselective propene polymerization catalyst 'O), especially at low polymerization temperatures ( T J . We now report that this system is a very efficient catalyst for E/P copolymerization and terpolymerizations.The metallocenium species (tetravalent, group 4, 3d O, 14 electrons) is commmonly prepared by the following method: Metallocene dichloride was converted to the dimethyl derivative, then a methyl anion is removed by a variety of reagents discussed in Jordan's review 'I). However, metallocene alkyls are unstable to heat, light, moisture and air and have short storage lives. We have developed an economical and efficient synthesis of zirconocenium species from stable precursors, such as rac-ethylenebis(in-deny1)dichlorozirconium (Et [Ind],ZrCI,, 3). The Zr compound is alkylated by triethylaluminium (TEA) which in turn reacts with 2 12) to produce the corresponding ruc-ethylenebis(indeny1)ethylzirconocenium species (Et[Ind],Zr + (C,H,), 4).
A spiro(benzoxasilole) catalyst, 3,3,3′,3′‐tetrakis(trifluoromethyl)‐1,1′‐(3H,3H′)‐spirobis(1,2‐benzoxasilole) was used to polymerize 3,3‐R,R′‐oxetanes: BEMO (R, R′ = ethoxymethyl), AMMO (R = azidomethyl, R′ = methyl), NMMO (R = nitratomethyl, R′ = methyl), BAMO (R, R′ = azidomethyl), and BCMO (R, R′ = chloromethyl) with descending rates in this order. 31P‐NMR of polymerization mixtures quenched using Bu3P are consistent with an oxonium ion propagating species. Water is not a cocatalyst because it increases the induction period which is not eliminated by the proton trap 2,6‐di‐t‐bu‐tylpyridine. The propagating chains were terminated by transfer with the ether oxygen of the polymer either intermolecularly or intramolecularly. The index of propagation to chain transfer, Kkikp/ktr, varies over more than three orders of magnitude for BEMO > AMMO > NMMO > BAMO. However, kp/ktr for the four monomers differ by less than a factor of five indicating the same factors are affecting propagation and chain transfer. Addition of benzyl alcohol and propandiol produced poly(BEMO) having one and two hydroxyl termini, respectively. These telechelic polymers can be used to synthesize linear triblock or multiblock copolymers of oxetane derivatives. © 1992 John Wiley & Sons, Inc.
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