Polymeric Lewis acid-catalyst

Cationic polymerization of coal-tar fractions has been commercially achieved through the use of strong protic acids, as well as various Lewis acids. Sulfuric acid was the first polymerization catalyst (11). More recent technology has focused on the Friedel-Crafts polymerization of coal fractions to yield resins with higher softening points and better color. Typical Lewis acid catalysts used in these processes are aluminum chloride, boron trifluoride, and various boron trifluoride complexes (12). Cmde feedstocks typically contain 25—75% reactive components and may be refined prior to polymerization (eg, acid or alkali treatment) to remove sulfur and other undesired components. Table 1 illustrates the typical components found in coal-tar fractions and their corresponding properties. 

Benzyl chloride reacts with benzene in the presence of a Lewis acid catalyst to give dipbenylmetbane [101 -81-5]. It undergoes self-condensation to form polymeric oils and soHds (21). With phenol, benzyl chloride produces a mixture of o- andp-her zylpbeno1. 

The use of catalysts for a Diels-Alder reaction is often not necessary, since in many cases the product is obtained in high yield in a reasonable reaction time. In order to increase the regioselectivity and stereoselectivity (e.g. to obtain a particular endo- or exo-product), Lewis acids as catalysts (e.g. TiCU, AICI3, BF3-etherate) have been successfully employed." The usefulness of strong Lewis acids as catalysts may however be limited, because they may also catalyze polymerization reactions of the reactants. Chiral Lewis acid catalysts are used for catalytic enantioselective Diels-Alder reactions. ... 

Step-growth polymerization processes must be carefully designed in order to avoid reaction conditions that promote deleterious side reactions that may result in the loss of monomer functionality or the volatilization of monomers. For example, initial transesterification between DMT and EG is conducted in the presence of Lewis acid catalysts at temperatures (200°C) that do not result in the premature volatilization of EG (neat EG boiling point 197°C). In addition, polyurethane formation requires the absence of protic impurities such as water to avoid the premature formation of carbamic acids followed by decarboxylation and formation of the reactive amine.50 Thus, reaction conditions must be carefully chosen to avoid undesirable consumption of the functional groups, and 1 1 stoichiometry must be maintained throughout the polymerization process. 

Homogeneous catalysts are also often used in cationic and anionic polymerization processes. Lewis acid catalysts, such as boron trifluoride and stannic chloride, accept protons from co-... 

The controlled polymerization of (meth)acrylates was achieved by anionic polymerization. However, special bulky initiators and very low temperatures (- 78 °C) must be employed in order to avoid side reactions. An alternative procedure for achieving the same results by conducting the polymerization at room temperature was proposed by Webster and Sogah [84], The technique, called group transfer polymerization, involves a catalyzed silicon-mediated sequential Michael addition of a, /f-unsaluralcd esters using silyl ketene acetals as initiators. Nucleophilic (anionic) or Lewis acid catalysts are necessary for the polymerization. Nucleophilic catalysts activate the initiator and are usually employed for the polymerization of methacrylates, whereas Lewis acids activate the monomer and are more suitable for the polymerization of acrylates [85,86]. 

The incorporation of comonomers into PET and other polyesters, with the intent that these comonomers would then serve as the site for additional, postpolymerization reactions, has not been widely explored. A potential difficulty in such an approach is that the reactive comonomer cannot react under PET synthesis conditions of ca. 285 °C/2h/Lewis acid catalyst if the modification is to be effective. Two such systems, stable under PET synthesis, and then subjected to post-polymerization reactions, have been recently reported. 

Two different mechanisms have been proposed for the ROP of (di)lactones depending on the nature of the organometalhc derivatives. Metal halides, oxides, and carboxylates would act as Lewis acid catalysts in an ROP actually initiated with a hydroxyl-containing compound, such as water, alcohol, or co-hydroxy acid the later would result more hkely from the in-situ hydrolysis of the (di)lac-tone [11]. Polymerization is assumed to proceed through an insertion mechanism, the details of which depends on the metal compound (Scheme la). The most frequently encountered Lewis acid catalyst is undoubtedly the stannous 2-ethylhexanoate, currently referred to as stannous octoate (Sn(Oct)2). On the other hand, when metal alkoxides containing free p-, d-, or f- orbitals of a favo-... 

Group transfer polymerization (GTP) requires either a nucleophilic or Lewis acid catalyst. Bifluoride (HF2) and fluoride ions, supplied by soluble reagents such as tris(dimethylamino)-sulfonium bifluoride, [(CH3)2N]3SHF2, and (w-C NF, are the most effective nucleophilic catalysts, although other nucleophiles (CN , acetate, p-nitrophenolate) are also useful. Zinc... 

For the anionic polymerization of methacrylonitrile (MAN), many initiators have been developed, which include alkali-metal alkyls such as butyllithium [42], triphenylmethylsodium [43], phenylisopropylpotassium [43], the disodium salt of living a-methylstyrene tetramer [44], alkali-metal amides [45], alkoxides [46], and hydroxide [47], alkali metal in liquid NH3 [48], quaternary ammonium hydroxide [49], and a silyl ketene acetal coupled with nucleophilic or Lewis acidic catalysts [50]. However, only a single example of the synthesis of PMAN with narrow molecular-weight distribution can be cited, and the reported number-average molecular weights were much higher than those calculated from the stoichiometry of the butyllithium initiator [42]. 

In an effort to prepare a stereospecifically (1—>6)-linked glucan, the polymerizatioii of l,6-anhydro-2,3,4-tri-O-benzyl-0-D-glucopyranose (tri-O-benzylievoglucosan) has been studied. Polymerization of this monomer in dichloromethane at —78°, using the Lewis acid catalyst, phosphorus... 

Diels-Alder Polymerization Diels-Alder type polymerization of a bisdienophile monomer (30) and bisdiene monomers (31, 32a,b) by using chiral Lewis acidic catalysts (33-35) affords optically active polymers [68]. For instance, the polymerization of 30 in CH2C12 with 32b by using 33 as a catalyst at -30°C gives a polymer with structure 36 showing molecular rotation of [ ]D +243°. When CHC13 or tetrahydrofuran is used as solvent, the polymers with only low optical activity are produced. 

As outlined earlier, three methods of polymerization have been established for the preparation of thiophenes, viz. electrochemical polymerization [189, 190], oxidative chemical polymerization using Lewis acid catalysts such as FeCl3 [191,192], and step-growth condensation polymerization using transition metal-catalyzed coupling reactions [lj]. 

Diels-Alder catalyst.2 The acrylates (4) of three chiral alcohols (1-3) have been found to undergo asymmetric Diels-Alder reactions with cyclopentadiene (equation I) in the presence of a Lewis acid catalyst. For this purpose, catalysts of the type TiCl2(X2) are superior to TiCl4 because they do not promote polymerization of the acrylate. The final products (6) all have the enrfo-orientation the configuration (R) or (S) depends upon the chiral alcohols. Those derived from 1 all have (S)-configuration ... 

Homopolymerization, epoxides aluminate-Lewis acid catalyst system, 11, 602 via aluminum-porphyrin-Lewis acid catalysts, 11, 599 aluminum-tetradentate ligand catalyst system, 11, 601 anionic polymerization, 11, 598 cationic aluminum catalyst system, 11, 603 cationic polymerization, 11, 598 characteristics, 11, 597 zinc-based catalyst system, 11, 605 Homopolymers, cyclic olefins, 11, 716... 

In a process related to GTP, aldehydes initiate the polymerization of silyl vinyl ethers and silyl diene ethers. Here the silyl group is present in the monomer and transfers to the aldehyde ended chains regenerating aldehyde ends [17] (Scheme 8). A Lewis acid catalyst is required. terf-Butyldimethylsilyl works best as a transfer group for vinyl ether while trimethylsilyl is suitable for diene ethers [18]. Even though aldol GTP provides a route to polyvinyl alcohol segments in the subsequent block polymer synthesis, the projected cost of the monomers discouraged further research aimed at commercialization. 

The stereochemistry of GTP of MMA polymerization was measured for Lewis acid as well as for bifluoride catalysis. Lewis acid catalysts gave a ratio of syndiotactic heterotactic triads of 2 1 while bifluoride catalysis gave ratios near 1 1 [9, 41]. The amount of isotactic triads was about 5%. The effect of temperature on triad and diad composition provided data to calculate the difference in activation enthalpy (AAH ) and activation entropy (AAS ) for... 

Inoue [56] has developed a method similar to GTP for polymerization of acrylic monomers. A methylaluminum porphyrin (MeAlTPP) is converted to a ketene acetal by in situ reaction of MMA and used to polymerize MMA (Scheme 24). A hindered Lewis acid catalyst is needed to activate the MMA. 

The presence of these cyclic esters in the crude polycondensation reaction product was found to be unavoidable indeed some evidence was developed that the polycondensation at least in part proceeds via these cyclic esters. Considerable effort was expended to find means for eliminating these cyclic five-membered esters from our polycondensation products. The cyclic esters can be eliminated by either inducing them to polymerize by use of Lewis acid catalysts such as stannous octoate, or by subjecting them to ring opening by means of an alcohol or water (7). 

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