Polymerization of glycolide promoted by ω-Al-alkoxide poly(ϵ-caprolactone) macro-initiators and formation of stable colloidal dispersions

Block polymerization of glycolide (GA) and ϵ-caprolactone (ϵ-CL) has been initiated with aluminum alkoxides, such as Al(OⁱPr)₃ and Et₂AlOCH₂X (where X = -CH₂-Br and -CH₂O-C(O)-C(Me)=CH₂), in THF at 40°C. Structure and composition of block copolyesters have been characterized with respect to the molecular weight by NMR spectroscopy and thermal analysis. Copolymerization is typically living, so that block copolyesters have been synthesized with predictable molecular weight and composition. The inherent insolubility of polyglycolide block is responsible for the heterogeneity of the polymerization medium and formation of stable, non-aqueous colloidal dispersions. This effect is especially pronounced at high GA/ϵ-CL molar ratios. Colloidal dispersions have been analyzed by transmission electron microscopy (TEM) and photocorrelation spectroscopy (PCS).     

Thermally induced cationic polymerization of divinyl ethers using iodonium and sulfonium salts

Cationic polymerization of diethyleneglycoldivinyl ether was thermally induced by diphenyliodonium, alkylbenzylsulfonium, and phenacyltetramethylenesulfonium salts. The reactivity was enhanced by using free radical sources in combination with diphenyliodonium or phenacyltetramethylenesulfonium salts. Even at low onium salt concentrations extremely reactive formulations could be obtained, e.g., the polymerization was complete within 1 minute at 100°C when using the most reactive salts. Polymerizations were induced at temperatures ranging from 50 to 180°C. The Counterion, Supplied by the onium salts, strongly influenced the appearance of the resulting crosslinked polymer: salts containing SbF⁻₆ usually gave highly discolored samples due to the large heat evolution during polymerization whereas polymerization with PF⁻₆ proceeded smoother resulting in transparent, uncolored polymers. The purity of the monomer greatly affected the initiation by the diphenyliodonium and phenacyltetramethylenesulfonium salts. Adventitious radical sources, e. g., hydroperoxides on oxidized monomer, lowered the activation temperature but also led to poor storage stability of these formulations.     

Synthesis and characterization of biodegradable homopolymers and block copolymers based on adipic anhydride

Homopolymers of adipic anhydride (AA) and block copolymers of ϵ-caprolactone (ϵ-CL) and AA have been synthesized with aluminum triisopropoxide as an initiator. Homopolymerization was studied at 20°C in toluene and methylene chloride (CH₂Cl₂). The end-group analysis agrees with a coordination insertion mechanism based on the acyl-oxygen cleavage of the AA ring. Living poly(ϵ-caprolactone) (PCL) chains are very efficient macro-initiators for the polymerization of AA, with formation of diblock copolymers of a narrow molecular weight distribution. At our best knowledge, low molecular weight ω-aluminum alkoxide PCL macroinitiators (M_n < 1000) allow the first valuable synthesis of PAA with a molecular weight as high as 58,000 and a quite narrow polydispersity (M_w/M_n = 1.2). Size-exclusion chromatography (SEC) and ¹³C NMR confirm the blocky structure of the copolymers, in agreement with DSC that shows two melting endotherms and two glass transitions characteristic of the crystalline and amorphous phases of PCL and PAA, respectively. Block copolymers of ϵ-CL and AA are also sensitive to hydrolysis, which makes them possible candidates for biomedical applications. Initiation of the AA polymerization in bulk with aluminum triisopropoxide in the presence of various ligands is also discussed. © 1997 John Wiley & Sons, Inc.     

Soluble polymer-supported catalysts containing pendant quaternary onium salts for the addition reaction of oxiranes with carbon dioxide

The addition reaction of oxiranes ( 15a-d ) with carbon dioxide (CO₂) was carried out using 1 mol % of soluble polymer-supported quaternary onium salts as catalysts under atmospheric pressure. The reaction of 15a-d with CO₂ proceeded very smoothly to give the corresponding five-membered cyclic carbonates ( 16a-d ) in high yields at 90-100°C. The catalytic activity of the soluble polymer-supported quaternary onium salts was strongly affected by the following factors: kind of reaction solvent, degree of introduction of the pendant onium salt residues in the polymer chain, and type of alkyl group on the onium salts due to the balance between lipophilicity and steric hindrance of the onium salt residue. Furthermore, these soluble polymer-supported quaternary onium salts were found ordinarily to have higher catalytic activity than low molecular weight quaternary onium salts under the same reaction conditions. It was also found that the rate of reaction was proportional both to catalyst concentration and to oxirane concentration. © 1995 John Wiley & Sons, Inc.     

Insoluble polystyrene-bound quaternary onium salt catalysts for the synthesis of cyclic carbonates by the reaction of oxiranes with carbon dioxide

The addition reaction of oxiranes ( 26a—e ) with carbon dioxide (CO₂) was performed using insoluble polystyrene beads containing pendant quaternary ammonium or phosphonium salts as catalysts under atmospheric pressure. The reaction of 26a—e with CO₂ proceeded smoothly catalyzed by 1–2 mol % of the polymer-supported quaternary onium salts to give the corresponding cyclic carbonates ( 27a—e ) in high yields at 80–90°C. In this reaction system, the catalytic activity of the polymer-supported quaternary onium salts was strongly affected by the following factors: degree of ring substitution (DRS) of the onium salt residues to the polymer, degree of crosslinking (DC) of the polystyrene beads, chain length of the alkylene spacer between the polymer back-bone and the onium salt, hydrophobicity of the alkyl group on the onium salts, and kind of onium salts. That is, the polymer-supported quaternary phosphonium salts with low DRS and DC and with long alkylene spacer chain were found to have higher catalytic activity than low molecualr weight quaternary onium salts. The above polymer-supported catalysts can easily be separated at the end of a reaction by filtration and can be reused for at least seven runs. It was also found that the rate of reaction was proportional to the products of catalyst concentration and oxirane concentration. © 1993 John Wiley & Sons, Inc.     

Photoinitiated Cationic Polymerization of Unconventional Monomers

Photoinitiated cationic polymerization of unconventional monomers namely, benzoxazines, monothiocarbonates and macromonomers of poly(ε-caprolactone) and poly(ethylene oxide) is described. Ring opening polymerization of benzoxazines and thiocarbonates by direct and sensitized photoinitiation using onium salts was studied. The structures of the resulting polybenzoxazine were complex and related to the ring opening process of the protanated monomer either at through oxygen or nitrogen atoms. In the case of monothiocarbonate, the polymerization was accompanied with isomerization of thiocarbonate group. The potential use of macromonomers in photoiniated cationic polymerization to design complex macromolecular structures such as graft copolymers, water-borne photoresist materials and networks with dangling chains was presented. Photoinduced oxidative polymerization of thiophene, precursor for conducting polymers, using onium salts was also demonstrated.     

Cationic photopolymerization with the aid of pyridinium‐type salts

Pyridinium‐type salts containing an N‐ethoxy group belong to the family of onium salts and are photoinitiators appropriate for the polymerization of monomers such as oxiranes and vinyl ethers which are not polymerizable by a free radical mechanism. The initiation is accomplished by direct or indirect (sensitized) photolysis of the onium ion, with the former being restricted to the wavelength range of self absorption, the latter being applicable at wavelengths of visible light. An additionally useful tool, namely free radical‐mediated generation of initiating species enlarges the versatility of pyridinium salts as photoinitiators. In this connection, the oxidation of free radicals by pyridinium‐type ions and the free radical‐induced fragmentation of alkoxy pyridinium ions are addressed in this article. Moreover, an interesting application is noted concerning the synthesis of novel block copolymers with the aid of the onium salt‐based photopolymerization technique.     

Copolymer of lactide and ε-caprolactone catalyzed by bimetallic Schiff base aluminum complexes

A series of copolymers of lactide(LA) and e-caprolactone(ε-CL) with different monomer feed ratios were achieved using three kinds of bimetallic Schiff aluminum complexes as catalysts. The ratios of LA and ε-CL units in different copolymers and the average segments length were determined by NMR analysis. The comparative kinetic study of L-LA/ε-CL and rac-LA/ε-CL copolymerization systems showed that the polymerization rate of LA was faster than ε-CL, and L-LA showed polymerization rate slightly faster than rac-LA. It was inferred that the copolymers achieved by these complexes were gradient copolymers with gradual change in distribution of LA and e-CL units. The thermal properties of these copolymers were characterized by DSC analysis, which showed that the glass transition temperature(Tg) of these copolymers changed regularly according to the pro-portion change of two structural units.     

The discovery and development of onium salt cationic photoinitiators

The story of the discovery and development of onium salt photoinitiators for cationic polymerization is chronicled. The chemistry of the synthesis of these compounds is outlined, and the mechanisms of their initiation are discussed briefly. Among the most useful of these types of photoinitiators are diaryliodonium and triarylsulfonium salts, which are used widely for photoinduced cationic crosslinking reactions. From the very beginning, onium salt photoinitiated cationic polymerizations have found use in a multitude of practical applications. Specifically discussed in this article are the use of onium salts in coatings, adhesives, printing inks, release coatings, stereolithography, holographic recording, photocurable composites, and microelectronic photoresists. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4241–4254, 1999     

Redox initiated cationic polymerization: Silane‐N‐aryl heteroaromatic onium salt redox couples

In this article, a new route for the synthesis of N‐aryl heteroaromatic onium salts by the direct copper catalyzed arylation of pyridine, substituted pyridines, isoquinoline, and acridine with diaryliodonium salts is described. It was demonstrated that these N‐aryl heteroaromatic onium salts undergo facile platinum or rhodium‐catalyzed reduction by silanes bearing Si? H groups. The reduction of N‐aryl heteroaromatic onium salts generates Brønsted acids. When this redox reaction was carried out in situ in the presence of an appropriate monomer, cationic polymerization was observed. Using this approach, the cationic polymerizations of epoxides, oxetanes, 1,3,5‐trioxane, styrene, and vinyl ethers were carried out. The use of optical pyrometry to monitor the redox initiated cationic polymerizations of some representative multifunctional monomers is described. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Structural Effects in the Addition–Fragmentation Reaction of Allylic Onium Salts

Allylic onium salts with different hetero‐atoms and various substituent groups at the allylic double bond have been shown to be very efficient initiators for cationic polymerization. When attacked by a radical, they become radical cations, which are highly unstable species, and undergo fragmentation into smaller radical cations called onium radical cations. The reaction mechanism involves radical formation, addition and fragmentation. In our previous work, radical initiators generated in the same way and under the same conditions are studied experimentally for their ability to affect the polymerization efficiency. Here, the factors affecting the polymerization efficiency are discussed theoretically using semi‐empirical quantum mechanical techniques. The type of radical species, substituent group at the allylic side, the heteroatom at the onium side and the onium group itself are analyzed separately. For this purpose, the geometries of different onium radical cations to be fragmented are optimized and the strength of the C–heteroatom bond to be broken and the size of the radical cations after fragmentation are considered.     

Effect of microwave energy on chain propagation of poly(ε-caprolactone) in benzoic acid-initiated ring opening polymerization of ε-caprolactone

Microwave-assisted ring opening polymerization of ε-caprolactone (ε-CL) initiated by benzoic acid was investigated. The molar ratio of ε-CL to benzoic acid was 5, 15 and 25. The mixtures of ε-CL/benzoic acid were heated under microwave irradiation and the temperatures were self-regulated to equilibrium from 204 to 240 °C with microwave power ranging from 340 to 680 W. The polymer chain propagated fast between 160 and 230 °C, within which the higher the temperature, the faster the propagation. However, when the temperature was over 230 °C, the resultant poly-(ε-caprolactone) (PCL) degraded. The advantage of microwave-assisted polymerization was that the propagation of PCL chain was significantly enhanced but the formation of growing center at the beginning stage of the polymerization was greatly inhibited. With this metal-free method, PCL with weight-average molar mass (M_w) over 4×10⁴ g/mol was prepared.     

Synthesis of degradable copolymers by ring-opening polymerization

Hydrolysable copolymers made from different cyclic monomers have been studied. The monomers involved are 1,5-dioxepan-2-one (DXO), L-dilactide, 1,3-dioxan-2-one (TMC), oxepan-2,7-dione (AA) and oxepan-2-one (ϵ-CL). The hydrolysis of the DXO/L-dilactide copolymer showed great differences in degradation rate depending on composition. A statistical copolymer made from TMC and ϵ-CL was amorphous with a glass transition temperature of −48°C. TMC and AA could form a blockcopolymer with n-BuLi as initiator in toluene, 0°C.     

Anionic polymerization of lactones initiated by alkali graphitides. IV. Copolymerization of ε-caprolactone initiated by KC24

The copolymerization of ε-caprolactone (ε-CL) with octamethylcyclotetrasiloxane (D₄) and styrene (St) under the action of the second-stage potassium graphitide KC₂₄ was investigated. The copolymerizations were carried out in bulk or in xylene at 20°C. The content of the block copolymer ε-CL/D₄ in the polymerization mixture was 60–95%, the molecular weight ranging between 150,000 and 300,000. The data for the copolymers' composition obtained by ¹H-NMR and GPC showed 14–20% of D₄-units in the copolymer. The amount of the block copolymer ε-CL/St in the polymerization products was 0–87%, and the molecular weights in the case of copolymer formation were between 100,000 and 500,000. The content of St-units in the copolymers was from 10 to 75% as shown by GPC and ¹H-NMR. The mechanism of action of the initiator is discussed.     

New alternating poly(amide-ester)S: Synthesis and properties

New alternating poly(amide-ester)s derived from β-hydroxy acids and α-amino acids 3a,b or ϵ-aminocaproic acid 4a-c were prepared. Two approaches were considered: (i) polycondensation of N-(β-hydroxyacyl)-amino acids 1a,b and 2b,c and (ii) ring-opening polymerization of cyclic amide-esters 5a-c and 6a-c . For all the linear precursors polycondensation reactions result in oligomers with number average molecular weights lower than 5000. The ring-opening polymerization of the cyclic precursors is substrate specific and is sensitive to changes in the polymerization conditions. For N-(3-hydroxybutyroyl)-ϵ-aminocaproic acid lactone [c(3HB-ϵAC); 5b ] (IUPAC nomenclature: 2-methyl-5-aza-1-oxa-cycloundecan-4,11-dione) bulk and solution polymerizations result in oligomers with an alternating ester amide microstructure. Polymerization of N-(3-hydroxypropionyl)-ϵ-aminocaproic acid lactone [c(3HP-ϵAC); 5a ] (IUPAC nomenclature: 5-aza-1-oxa-cycloundecan-4-11-dione) in dimethylformamide solution and with Bu₂Sn(OMe)₂ as initiator high molecular weight linear, semi-crystalline polymers were obtained (T_m = 145.9°C). Polymerization of N-(hydroxypivaloyl)-ϵ-aminocaproic acid lactone [c(HPv-ϵAC); 5c ] (IUPAC nomenclature: 3,3-dimethyl-5-aza-1-oxa-cycloundecan-4-11-dione) in bulk results in amorphous alternating poly(amide-ester)s with cyclic structure (T_g = 6.8°C). The fourteen membered cyclo(diamide-diester)s 6a-c (IUPAC nomenclatures:: 4,11-diaza-1,8-dioxa-cyclotetradecan-2,5,9,12-tetraone ( 6a ), 7,14 dimethyl-4,11-diaza-1,8-dioxa-cyclotetradecan-2,5,9,12-tetraone ( 6b ), 3,10-dimethyl-4,11-diaza-1,8-dioxa-cyclotetradecan-2,5,9,12-tetraone ( 6c ) based on β-hydroxy acids and α-aminoacids could not be polymerized.     

Ring-opening polymerization of ε-caprolactone initiated by diphenylzinc

In the present work the polymerization of ε-caprolactone (ε-CL) using Ph₂Zn as initiator is reported. The effects of reaction temperature, molar ratio of monomer/initiator and reaction time on the yield and the molecular weight are investigated. The temperature is varied between 20 and 120 °C and the molar ratio of monomer to initiator between 200 and 800 mol/mol. The results indicate that the Ph₂Zn induces the polymerization of ε-CL to high conversion and produces polymer with high molecular weight at temperatures around 40-60 °C.     

Propenyl ethers. III. Study of the photoinitiated cationic polymerization of propenyl ether monomers

The effects of photoinitiator structure and variations in the experimental parameters on the rate and extent of the photoinitiated cationic polymerization of propenyl ether monomers were studied. It was found that the photoinitiators can be divided into two classes: those which exhibit an induction period and those which do not. It was demonstrated that in those propenyl ether polymerizations using iodonium salts and certain sulfonium salts which do not have an induction period, a free radical chain-induced decomposition of the onium salt takes place. The reactivity of a particular onium salt photoinitiator was shown to be related to its reduction potential. It was also shown that the structure of the monomer plays a major role in the free radical induced decomposition reaction. © 1993 John Wiley & Sons, Inc.     

Ring-Opening Polymerization of Lactones Initiated with Metal Hydroxide-Activated Macrocyclic Ligands: Determination of Mechanism and Structure of Polymers

Anhydrous alkali metal hydroxide (KOH, NaOH, and LiOH)-activated macrocyclic ligand complexing metal cations, i.e., coronands 12C4, 15C5, 18C6, DCH24C8, and cryptand C222, were selected for initiation of β-butyrolactone (β-BL) and ε-caprolactone (ε-CL) polymerization. It was found that β-BL polymerizes in the presence of KOH/18C6, KOH/C222, and NaOH/C222 systems. The real initiators in this case are two salts, potassium 3-hydroxybutyrate and potassium trans-crotonate, which are responsible for the formation of two fractions of the obtained polymer. ε-CL underwent polymerization with KOH or NaOH activated by all ligands used or without the ligand but with LiOH/12C4. Using KOH-activated strong ligands, i.e., 15C5, 18C6, or C222, two polymer fractions were generated containing linear and, unexpectedly, also cyclic macromolecules. The mechanism of the studied processes is discussed.     

Decomposition mechanism of dinitramide onium salts

Thermal decomposition of dinitramide onium salts proceedsvia the dissociative mechanism when pK _a of the base is lower than 5.0 andvia the monomolecular decay of the anion at pK _a>7.0. On going from the melt to the solid state, the reaction mechanism does not change, and the rate decreases by 1–2 orders of magnitude. No anomalous effects inherent in dinitramide metal salts in the solid phase are observed during decomposition of onium salts. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1951–1953, November, 1997     

Photoinitiation of cationic polymerization. III. Photosensitization of diphenyliodonium and triphenylsulfonium salts

Photoinitiated cationic polymerization by photosensitization of diphenyliodonium and triphenylsulfonium salts is shown to proceed by two distinct electron transfer process: (1) direct electron transfer from excited-state photosensitizers and (2) indirect electron transfer from photogenerated radicals. The efficiency of the former process is attributed to the instability of the reduction products (from diphenyliodonium and triphenylsulfonium salts), which dissociate in competition with undergoing energy-wastage reverse electron transfer. Amplification of photons in the production of protons (or other reactive cations) is postulated to account for the high quantum yields observed in the latter process. Potential advantages of utilizing the indirect redox process in the design of UV curable hybrid systems, which contain functionality for both radical and cationic polymerization, are noted. The results also provide evidence against the importance of triplet states of the onium salts in photoinitiator activity.