Ring-opening polymerization of cyclic carbonates by alcohol–acid catalyst

Ring-opening reactions of 1,3-dioxepan-2-one ( 1 ) and 1,3-dioxan- 2 -one (2) with several alcohols were examined. The reactions proceeded without trifluoroacetic acid (TFA) in low conversions, while they proceeded smoothly with TFA to afford the ring-opened adducts and oligomers. Ring-opening polymerizations of 1 and 2 were also carried out by alcohol–acid catalysts to afford the corresponding polycarbonates (M _n = 2500−6800). The molecular weights increased with increase of the conversions of 1 and 2. The observed polymerization rates of 1 and 2 were determined as 24.4 × 10⁻⁶ and 0.8 × 10⁻⁶ s⁻¹, respectively. Mechanistic aspects were studied by NMR spectroscopy. The methylene protons α and β to the carbonate moieties shifted to lower fields in 0.06–0.11 ppm in the ¹H-NMR spectra by the addition of TFA. Downfield shifts of the carbonyl carbon signals of 1 and 2 were observed in 3.94–4.15 ppm in the ¹³C-NMR spectra. These results strongly suggest that the cyclic carbonates are activated by TFA. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2463–2471, 1998     

Reaction of anthranilic acid amides with cyclic anhydrides

Anthranilic acid amide reacts with cyclic anhydrides to give the corresponding N-acyl derivatives at the amino group, while analogous reactions of o-aminobenzohydroxamic acid lead lead to formation of 3-hydroxy-quinazolin-4-ones under mild conditions. N-Acyl derivatives of anthranilic acid amide undergo intramolecular cyclization to imides on microwave irradiation or on melting, and their treatment with acetic anhydride in the presence of sodium acetate on heating yields quinazolin-4-ones.     

Bifunctional organocatalyst for methanolytic desymmetrization of cyclic anhydrides: increasing enantioselectivity by catalyst dilution

Highly enantioselective methanolysis of meso-cyclic anhydride was achieved with bifunctional organocatalyst containing a quinine-thiourea moiety; unusual concentration, temperature and solvent effects on the enantioselectivity can be explained in terms of a mechanism involving monomer-dimer equilibration of the catalyst.     

Regioselective polymerization of divinyl sebacate and triols using lipase catalyst

The lipase‐catalyzed regioselective polymerization of divinyl sebacate and triols has been carried out. Immobilized lipase derived from Candida antarctica induces the polymerization of divinyl sebacate and glycerol, yielding a soluble polymer of relatively high molecular weight. NMR analysis showed that 1,3‐diglyceride is a main unit and the branching unit (triglyceride) is contained in the resulting polymer. These data indicate that the polymerization proceeds regioselectively to give the reactive polyester having a pendant hydroxy group.     

Highly efficient heterogeneous acylations of aromatic compounds with acid anhydrides and carboxylic acids by montmorillonite-enwrapped titanium as a solid acid catalyst

Montmorillonite-enwrapped titanium hydroxide species (Ti⁴⁺-mont) acted as a highly efficient heterogeneous acid catalyst for the acylation of aromatic compounds with acid anhydrides or carboxylic acids. The catalytic activity of the Ti⁴⁺-mont was higher than those of other acid catalysts such as zeolites, SO ₄ ²⁻ /ZrO₂ and p-toluenesulfonic acid. For example, the reaction of anisole with dodecanoic acid in the presence of the Ti⁴⁺-mont catalyst gave 1-(4-methoxyphenyl)-1-dodecanone in 97% yield. Furthermore, the Ti⁴⁺-mont catalyst was easily separated from the reaction mixture and was recyclable.     

Highly efficient heterogeneous acylations of aromatic compounds with acid anhydrides and carboxylic acids by montmorillonite-enwrapped titanium as a solid acid catalyst

Montmorillonite-enwrapped titanium hydroxide species (Ti⁴⁺-mont) acted as a highly efficient heterogeneous acid catalyst for the acylation of aromatic compounds with acid anhydrides or carboxylic acids. The catalytic activity of the Ti⁴⁺-mont was higher than those of other acid catalysts such as zeolites, SO ₄ ^2? /ZrO₂ and p-toluenesulfonic acid. For example, the reaction of anisole with dodecanoic acid in the presence of the Ti⁴⁺-mont catalyst gave 1-(4-methoxyphenyl)-1-dodecanone in 97% yield. Furthermore, the Ti⁴⁺-mont catalyst was easily separated from the reaction mixture and was recyclable.     

Enzymatic silicone oligomerization catalyzed by a lipid-coated lipase

A lipid (1)-coated lipase can catalyze the oligomerization of diethoxydimethylsilane (DEDMS) in isooctane containing 2wt% water, where the polymerization occurs at the OH group of the coating lipid (1) in the enzyme cavity.     

p-Chlorophenyldiazonium hexafluorophosphate as a catalyst in the polymerization of tetrahydrofuran and other cyclic ethers

p-Chlorophenyldiazonium hexafluorophosphate is shown to be a convenient and effective catalyst for initiating the polymerization of tetrahydrofuran (TH) and other cyclic ethers. The polymerizations apparently proceed without any significant termination or transfer reactions (i.e., “living” polymers result), and materials of very high molecular weight can be obtained. A mobile monomer-polymer equilibrium for THF was obtained during polymerization and equilibrium conversions were determined at a number of temperatures. The ceiling temperature derived from these data was 84°C., the heat of polymerization was ?4.58 kcal./mole and the corresponding entropy change was ? 17.7 cal./°C.-mole. Hydrocarbons are suitable inert solvents for these polymerizations, but concentrated solutions must be used at ambient temperatures in order to stay above the required equilibrium monomer conceiitration and also to dissolve the catalyst which is insoluble in hydrocarbons. It was shown that acyclic ethers act as transfer agents in these polymerizations and that transfer with consequent reduction of molecular weight continues even after monomer-polymer equilibrium is reached. Cyclic ethers do not act as transfer agents but only copolymerize. Trimethyl orthoformate was shown to be a particularly effective transfer agent; it resulted in a polymer with methoxy endgroups and produced methyl formate as a by-product. The data obtained are consistent with a mechanism involving initiation by hydrogen abstraction and polymerization via tertiary oxonium ions associated with PF^?₆ gegenions. This gegenion is thought to be responsible for the “living” nature of the system.     

Controllable polymerization of N-carboxy anhydrides in a microreaction system

We have developed a microfluidic system for polymerization of amino acid N-carboxyanhydride and compared the properties of the products with those obtained by batchwise system under various experimental conditions. It was found that the microreactor produced polymers with narrower molecular weight distribution compared with polymers obtained by the batchwise system. Also, the molecular mass of the polymer produced using the microreactor was simply governed by the flow (pumping) rate. These results indicated that the microreactor could be a model for synthesis of amino acid polymer with highly controllable average molecular weight and molecular weight distribution.     

Tungsten hexachloride alone as a catalyst for the metathetic polymerization of cyclic olefins

The polymerization of cyclic olefins may be initiated by tungsten hexachloride alone. The rate of polymerization is less than that normally obtained with bimetallic catalysts but the equilibrium conversion monomer is of the same order.     

The first example of the copolymerization of cyclic acid anhydrides with oxetane by bulky titanium bisphenolates

The copolymerization of oxetane with glutaric anhydride was found to proceed with bulky titanium bisphenolate ( 1 ) as the initiator. The ¹H NMR spectrum of the produced copolymer shows that the copolymer contains both alternating units and oxytrimethylene units in the polymer main chain. 1 was also effective for the copolymerization of oxetane with other cyclic acid anhydrides, affording the corresponding copolymers. With the titanium bisalkolate complex ( 4 ), a copolymer rich in alternating sequences was obtained.     

Synthesis of cyclic methacrylic acid oligomers by atom transfer radical polymerization

Poly(methacrylic acid) (PMAA) oligomers were synthesized by combining template polymerization and copper‐mediated atom transfer polymerization with multivinyl monomer of β‐cyclodextrin (CD) having 20.4 methacryloyl groups on both primary and secondary hydroxyl group sides of CD scaffold, with 1,3‐dibromobutane as an initiator. The initiation and propagation sites of polymerized sequence of β‐CD were connected by postpolymerization of polymerized products with CuBr and tris[(2‐dimethylamino)ethyl]amine (Me₆TREN) in a methanol/water mixture of 10 wt % of water. Polymerized and cyclized sequences, PMAA oligomers formed on the primary and the secondary hydroxyl group sides, were detached from β‐CD scaffold by hydrolysis. Molecular weights of PMAA oligomers were measured by GPC and matrix assisted laser desorption ionization time‐of‐flight mass measurement. By ¹H NMR measurements, it was found that three types of cyclic PMAA were obtained by postpolymerization. The cyclization preferentially occurred on the secondary hydroxyl group side than on the primary hydroxyl group side. From the structures of cyclic PMAA, two reaction positions were proposed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6262–6271, 2005     

Investigation of the reaction of some unsaturated dicarboxylic acid anhydrides with cyclic carbonates

This work reports attempts to extend to unsaturated anhydrides the rapid reaction of dicarboxylic acid anhydrides with ethylene carbonate to form polymer directly. The reaction of unsaturated diacid anhydrides with two cyclic carbonates, ethylene and propylene carbonate, leads to gelled products whenever the anhydride is capable of Michael addition, while an anhydride without such unsaturation gave linear polymer in- stead. The GC/MS results, along with efforts to trap radical reactions, support Michael addition as an explanation of gelation in these systems.     

Novel ring-opening polymerization of lactide by lipase

Six-membered D,L-, L,L- and D,D-lactides were polymerized by lipase over a temperature range of 80 to 130 °C to yield the polylactide with a molecular weight (M_w) of greater than 270000. Among the lipases tested, lipase PS gave the greatest molecular weight of polylactide. The polymerization of D,L-lactide by lipase was better than that of L,L- and D,D-lactides. The polymerization of lactide by lipase showed the characteristic features, such as induction period for the initiation of polymerization, formation of oligomer and subsequent formation of high molecular weight polylactide, which may imply the characteristic polymerization by lipase. Immobilization of lipase on celite significantly enhanced the polymerization of lactide particularly with respect to the low concentration of the enzyme and the M_w of the resultant polymer. It was found that there is no clear relationship between enzymatic polymerizability and enzymatic degradability with respect to the enzyme origin and the stereochemistry of lactide.     

Enzymatic polymerization to artificial hyaluronic acid using a transition state analogue monomer

Artificial hyaluronic acid has been synthesized in vitro via enzymatic polymerization catalyzed by testicular hyaluronidases, which is the first successful example of the hyaluronic acid synthesis via non-biosynthetic pathways. The novel GlcAβ(1→3)GlcNAc oxazoline derivative was designed and synthesized as a transition state analogue monomer for the hyaluronidase catalysis. The oxazoline monomer was efficiently recognized by the enzymes at pH 7.1 to 9.0 and the polymerization reaction proceeded in a regio- and stereo-selective manner to give rise to artificial hyaluronic acid with molecular weight higher than 15000. These results strongly suggest that the transition state of these testicular hyaluronidases catalysis corresponds to a sugar oxazolinium ion.     

Mechanism of olefin polymerization by a soluble zirconium catalyst

A mechanistic study has been carried out on the homogeneous olefin polymerization/oligomerization catalyst formed from Cp₂ZrMe₂ and methylaluminoxane, (MeAlO)_x, in toluene. Formal transfer of CH₃ from Zr to Al yields low concentrations of Cp₂ZrMe⁺ solvated by [(Me₂AlO)_y(MeAlO)_x−y]_y. The cationic Zr species initiates ethylene oligomerization by olefin coordination followed by insertion into the Zr–CH₃ bond. Chain transfer occurs by one of two competing pathways. The predominant one involves exchange of Cp₂Zr–P⁺ (P=growing ethylene oligomer) with Al–CH₃ to produce another Cp₂ZrMe⁺ initiator plus an Al-bound oligomer. Terminal Al–C bonds in the latter are ultimately cleaved on hydrolytic workup to produce materials with saturated end groups. Concomitant chain transfer occurs by sigma bond metathesis of Cp₂Zr–P⁺ with ethylene. Metathesis results in cleavage of the Zr–C bond of the growing oligomer to produce materials also having saturated end groups; and a new initiating species, Cp₂Zr-CHCH₂⁺. The two chain transfer pathways afford structurally different oligomers distinguishable by carbon number and end group structure. Oligomers derived from the Cp₂ZrMe⁺ channel are C_n (n=odd) alkanes; those derived from Cp₂Zr–CHCH₂⁺ are terminally mono-unsaturated C_n (n=even) alkenes. Chain transfer by beta hydride elimination is detectable but relatively insignificant under the conditions employed. Propylene and 1-hexene react similarly but beta hydride elimination is the predominant chain transfer step. The initial Zr-alkyl species produces a Cp₂ZrH⁺ complex that is the principle chain initiator. Chain transfer is fast relative to propagation and the products are low molecular weight oligomers.