Studies in ring-opening polymerization. II. Cyclohexane spiro-5-1,3,2-dioxathiolan-4-one 2-oxide

The effect of spiro cyclohexane substitution on the polymerizability of the 1,3,2-dioxathiolan-4-one-2-oxide ring in various solvents has been examined. The steric hindrance of the cyclohexane ring inhibits the bimolecular chain propagation reaction which involves direct attack by a terminal hydroxyl group on the ring and which has been shown to occur in simpler dioxathiolan systems. The conjoined cyclohexane ring does not, however, markedly affect the “thermal” polymerization which occurs in nonhydroxylic solvents and in which chain propagation is thought to involve a reactive α-lactone intermediate. The rate-determining step in the sequence of reaction leading to polymer formation is a ring-scission process in which sulfur dioxide is evolved and the α-lactone intermediate formed. The values of the activation energy (25–30 kcal/mole) and frequency factor (10¹¹–10¹³sec^?1) associated with this reaction are, therefore, those which govern the the overall polymerization, since the subsequent steps are sensibly instantaneous. In the presence of adventitious traces of water the resultant polymer, poly(1-hydroxycyclohexanecarboxylic acid) has one carboxyl and one hydroxyl endgroup per chain. Polymers having M?_n ～ 15,000 are readily obtained; these are amorphous materials, in contrast to the analogous poly-β-ester and dialkyl-substituted poly-α-esters which are crystalline. At temperatures in excess of 120°C a competitive first-order fragmentation reaction leading to the formation of cyclohexanone, carbon monoxide, and sulfur dioxide was observed. Kinetic studies demonstrated that this reaction, which is characterized by an activation energy of ～40 kcal/mole is unimportant, in the sense that it does not interfere with polymer formation at temperatures below 100°C.     

Radical polymerization of methyl methacrylate in the presence of stereoregular poly(methyl methacrylate). V. Kinetics of initial template polymerization

The influence of stereoregular poly(methyl methacrylate) (PMMA) as a polymer matrix on the initial rate of radical polymerization of methyl methacrylate (MMA) has been measured between ?11 and +60°C using a dilatometric technique. Under proper conditions an increase in the relative initial rate of template polymerization with respect to a blank polymerization was observed. Viscometric studies showed that the observed effect could be related to the extent of complex formation between the polymer matrix and the growing chain radical. The initial rate was dependent on tacticity and molecular weight of the matrix polymer, solvent type and polymerization temperature. The accelerating effect was most pronounced (a fivefold increase in rate) at the lowest polymerization temperature with the highest molecular weight isotactic PMMA as a matrix in a solvent like dimethylformamide (DMF), which is known to be a good medium for complex formation between isotactic and syndiotactic PMMA. The acceleration of the polymerization below 25°C appeared to be accompanied by a large decrease in the overall energy and entropy of activation. It is suggested that the observed template effects are mainly due to the stereoselection in the propagation step (lower activation entropy Δ S_p^?) and the hindrance of segmental diffusion in the termination step (higher activation energy Δ E_t^?) of complexed growing chain radicals.     

Surface‐initiated ring‐opening polymerization of p‐dioxanone on Wang resin bead

Biodegradable poly(p‐dioxanone) (PPDO) was formed on Wang resin surface by surface‐initiated ring‐opening polymerization (SI‐ROP). The SI‐ROP of p‐dioxanone (PDO) was achieved by heating a mixture of Tin(II) bis(2‐ethylhexanoate) [Sn(Oct)₂], hydroxyl functionalized Wang resin, and PDO in anhydrous toluene at 80 °C. The resultant polymer‐grafted Wang resin (Wang‐g‐PPDO) was characterized by fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), optical microscopy (OM), and field‐emission scanning electron microscopy (FE‐SEM). The FTIR spectra of Wang‐g‐PPDO show peak characteristic of PPDO at 2943 cm^?1 (? C? H stretch), at 1741 cm^?1 (? C?O stretch), and 1136 cm^?1 (C? O? C stretch) indicating the formation of ester linkage between PPDO and hydroxyl terminated Wang resin. The DSC thermogram show melting peak corresponding to PPDO polymer on Wang resin surface. Thermogravimetric investigation shows increase in PPDO content on the Wang resin surface in terms of percentage of weight loss with increase in reaction time. The OM and SEM photographs clearly show the formation of PPDO polymer on the Wang resin surface without altering the spherical nature of Wang resin bead. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1178–1184, 2008     

Influence of catalyst depletion or deactivation on polymerization kinetics. III. Solution polymerization of acrylonitrile in N,N-dimethylformamide at −30°C.

The experimental results on homogeneous polymerization of acrylonitrile initiated with the sodium triethylthioisopropoxyaluminate, NaAlEt₃S(i-Pr), catalyst in DMF at ?30°C. are compared with the prediction of equations based on a postulated mechanism. The agreement between the calculated and observed number-average molecular weight combined with the kinetic data and the relationship between the conversion and the initial catalyst concentration provides a rigorous test concerning the validity of the equations and the mechanism of the polymerization. A plausible mechanism is postulated as follows: The initiation must be relatively fast in accordance with the rate equations and the growing polymer undergoes propagation, transfer (to monomer), and deactivation simultaneously. The infrared spectrum of the low molecular weight polymer prepared at a high catalyst concentration showed strong absorption at 2337, 2205, and 1620 cm.^?1 but no absorption at 900 cm.^?1, indicating that there are two nitriles in the polymer, one of which is conjugated. The possibility of having ? CH?CH₂ groups in the polymer is ruled out by the absence of the band at 900 cm.^?1. In view of these facts, it is concluded that the polymer has a ? CH?CHCN endgroup resulting from the transfer reaction.     

Synthesis and characterization of poly(ethylene oxide‐co‐ethylene carbonate) macromonomers and their use in the preparation of crosslinked polymer electrolytes

Methacrylate‐functionalized poly(ethylene oxide‐co‐ethylene carbonate) macromonomers were prepared in two steps by the anionic ring‐opening polymerization of ethylene carbonate at 180 °C, with potassium methoxide as the initiator, followed by the reaction of the terminal hydroxyl groups of the polymers with methacryloyl chloride. The molecular weight of the polymer went through a maximum after approximately 45 min of polymerization, and the content of ethylene carbonate units in the polymer decreased with the reaction time. A polymer having a number‐average molecular weight of 2650 g mol^?1 and an ethylene carbonate content of 28 mol % was selected and used to prepare a macromonomer, which was subsequently polymerized by UV irradiation in the presence of different concentrations of lithium bis(trifluoromethanesulfonyl)imide salt. The resulting self‐supportive crosslinked polymer electrolyte membranes reached ionic conductivities of 6.3 × 10^?6 S cm^?1 at 20 °C. The coordination of the lithium ions by both the ether and carbonate oxygens in the polymer structure was indicated by Fourier transform infrared spectroscopy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2195–2205, 2006     

Ring‐opening metathesis polymerization of cyclododecene using an electrochemically reduced tungsten‐based catalyst

The ring‐opening metathesis polymerization of cyclododecene using an electrochemically reduced tungsten‐based catalyst (WCl₆? e^?? Al? CH₂Cl₂) is described. In addition, the influence of reaction conditions on the polymerization yield was determined. The resulting polymer has been characterized by NMR, IR, gel permeation chromatography and differential scanning calorimetry. The glass transition temperature and melting point of the polydodecenamer are 19.6°C and 70.0°C respectively. Furthermore, cyclododecene has been polymerized into a low‐molecular‐weight polymer (12.0 × 10³) with a polydispersity of 2.06 in high yields (94%). IR and NMR analysis indicate that the polydodecenamer has a high trans content (60%). Copyright © 2004 John Wiley & Sons, Ltd.     

Studies in ring-opening polymerization. III. 5-methyl-5-propyl and 5-methyl-5-isopropyl-1,3,2-dioxathiolan-4-one 2-oxide

5-Methyl-5-propyl-1,3,2-dioxathiolan-4-one 2-oxide (MPAS) and 5-methyl-5-isopropyl-1,3,2-dioxathiolan-4-one 2-oxide (MiPAS), which are isomers of the previously studied 5,5-diethyl-1,3,2-dioxathiolan-4-one 2-oxide (DEAS), have been synthesized and their polymerizability compared with that of the last compound. The two unsymmetrically substituted monomers polymerize by a mechanism which is substantially identical to that of their symmetrically substituted counterpart. In dry nonhydroxylic solvents the rate-determining process is the primary scission of the ring, which takes place with elimination of sulfur dioxide and concurrent ring contraction to form an α-lactone intermediate. In this reaction, the parent acid, produced by reaction of the monomer with adventitious traces of moisture, acts as the initiating species. The resultant polymers are all hydroxyl/carboxyl-terminated, but, whereas those derived from the two unsymmetrically substituted monomers are amorphous and readily soluble in a variety of organic solvents, those derived from the diethyl-substituted ring have been shown to be highly crystalline materials which dissolve in very few solvents. The relative polymerization rates are illustrated by the first-order rate constants for decomposition in nitrobenzene at 90°C: DEAS, 20.1 × 10^?5 sec^?1; MiPAS, 11.0 × 10^?5 sec^?1; MPAS, 9.7 × 10^?5 sec^?1. The role of the substituents in determining the magnitude of these constants is discussed in terms of both the Thorpe-Ingold effect and electron donation at C-5.     

Direct functionalization of polyisobutylene by living initiation with α‐methylstyrene epoxide

This article describes the synthesis and characterization of polyisobutylene (PIB) carrying one primary hydroxyl head group and a tertiary chloride end group, [Ph? C(CH₃)(CH₂OH)–PIB–CH₂? C(CH₃)₂Cl] prepared with direct functionalization via initiation. The polymerization of isobutylene was initiated with the α‐methylstyrene epoxide/titanium tetrachloride system. Living conditions were obtained from ?75 to ?50 °C (198–223 K). Low molecular weight samples (number‐average molecular weight ～ 4000 g/mol) were prepared under suitable conditions and characterized by Fourier transform infrared and ¹H NMR spectroscopy. The presence of primary hydroxyl head groups in PIB was verified by both methods. Quantitative Fourier transform infrared with 2‐phenyl‐1‐propanol calibration and ¹H NMR performed on both the hydroxyl‐functionalized PIB and its reaction product with trimethylchlorosilane showed that each polymer chain carried one primary hydroxyl head group. The synthetic methodology presented here is an effective and simple route for the direct functionalization of PIB. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1005–1015, 2002     

Synthesis of thermally-induced phase separating polymer with well-defined polymer structure by living cationic polymerization. I. Synthesis of poly(vinyl ether)s with oxyethylene units in the pendant and its phase separation behavior in aqueous solution

Living cationic polymerization of alkoxyethyl vinyl ether [CH₂?CHOCH₂CH₂OR; R: CH₃ (MOVE), C₂H₅ (EOVE)] and related vinyl ethers with oxyethylene units in the pendant was achieved by 1-(isobutoxy)ethyl acetate ( 1 )/Et_1.5AlCl_1.5 initiating system in the presence of an added base (ethyl acetate or THF) in toluene at 0°C. The polymers had a very narrow molecular weight distribution (M?_w/M?_n = 1.1–1.2) and the M?_n proportionally increased with the progress of the polymerization reaction. On the other hand, the polymerization by 1 /EtAlCl₂ initiating system in the presence of ethyl acetate, which produces living polymer of isobutyl vinyl ether, yielded the nonliving polymer. When an aqueous solution of the polymers thus obtained was heated, the phase separation phenomenon was clearly observed in each polymer at a definite critical temperature (T_ps). For example, T_ps was 70°C for poly(MOVE), and 20°C for poly(EOVE) (1 wt % aqueous solution, M?_n ～ 2 × 10⁴). The phase separation for each case was quite sensitive (ΔT_ps = 0.3–0.5°C) and reversible on heating and cooling. The T_ps or ΔT_ps was clearly dependent not only on the structure of polymer side chains (oxyethylene chain length and ω-alkyl group), but also on the molecular weight (M?_n = 5 × 10³-7 × 10⁴) and its distribution. © 1992 John Wiley & Sons, Inc.     

Radiation-induced heterogeneous polymerization of ethylene in the presence of ethyl alcohol

The radiation-induced heterogeneous polymerization of ethylene in ethyl alcohol was carried out in a reactor with a capacity of 100 ml under the following reaction conditions: temperature, 24 ± 3°C; pressure, 200–400 kg/cm²; amount of ethyl alcohol, 30–70 ml; dose rate, 3.7 × 10⁴?1.05 × 10⁵ rad hr. The effects of amount of ethyl alcohol, pressure, and dose rate on the rate of polymerization at the steady state, the amount of polymerized monomer, the molecular weight of polymer, and the number of polymer chains were studied compared with the results obtained in the polymerization in tert-butyl alcohol. It was found that there is an acceleration period in the early stage of reaction followed by a steady state. The rate of polymerization was maximum when about 50 ml of ethyl alcohol was used. The molecular weight of polymer increased with a decrease in the amount of ethyl alcohol. The dependences of pressure (p) and dose rate (I) on the rate of polymerization at steady state (R_s) and the molecular weight of polymer (M?_n) were expressed as follows; R_s ∝ p^0.74, M?_n ∝ p^0.3?0.4, R_s ∝ I^0.9 and M?_n ∝ I^{?0.1 ?0.0}. The results were analyzed by a kinetic treatment based on a reaction mechanism containing both first-and second-order terminations. The rate constant of first-order termination by radical occlusion was considerably larger than that in the polymerization in tert-butyl alcohol, because the affinity of ethyl alcohol for polyethylene is smaller than that of tert-butyl alcohol. It was found that chain transfer to ethyl alcohol takes place easily and the G value of ethyl alcohol for initiation is larger than 1.5.     

Living carbocationic polymerization. IV. Living polymerization of isobutylene

Truly living polymerization of isobutylene (IB) has been achieved for the first time by the use of new initiating systems comprising organic acetate-BCl₃ complexes under conventional laboratory conditions in various solvents from ?10 to ?50°C. The overall rates of polymerization are very high, which necessitated the development of the incremental monomer addition (IMA) technique to demonstrate living systems. The living nature of the polymerizations was demonstrated by linear M _n versus grams polyisobutylene (PIB) formed plots starting at the origin and horizontal number of polymer molecules formed versus amount of polymer formed plots. DP _n obeys [IB]/[CH₃COOR^t · BCl₃]. Molecular weight distributions (MWD) are very narrow in homogeneous systems (M _w/M _n = 1.2–1.3) whereas somewhat broader values are obtained when the polymer precipitates out of solution (M _w/M _n = 1.4–3.0). The MWDs tend to narrow with increasing molecular weights, i.e., with the accumulation of precipitated polymer in the reactor. Traces of moisture do not affect the outcome of living polymerizations. In the presence of monomer both first and second order chain transfer to monomer are avoided even at ?10°C. The diagnosis of first and second order chain transfer has been accomplished, and the first order process seems to dominate. Forced termination can be effected either by thermally decomposing the propagating complexes or by nucleophiles. In either case the end groups will be tertiary chlorides. The living polymerization of isobutylene initiated by ester. BCl₃ complexes most likely proceeds by a two-component group transfer polymerization.     

Synthesis of polyacetals with various main‐chain structures by the self‐polyaddition of vinyl ethers with a hydroxyl function

To establish the optimum conditions for obtaining high molecular weight polyacetals by the self‐polyaddition of vinyl ethers with a hydroxyl group, we performed the polymerization of 4‐hydroxybutyl vinyl ether (CH₂?CH? O? CH₂CH₂CH₂CH₂? OH) with various acidic catalysts [p‐toluene sulfonic acid monohydrate, p‐toluene sulfonic anhydride (TSAA), pyridinium p‐toluene sulfonate, HCl, and BF₃OEt₂] in different solvents (tetrahydrofuran and toluene) at 0 °C. All the polymerizations proceeded exclusively via the polyaddition mechanism to give polyacetals of the structure [? CH(CH₃)? O? CH₂CH₂CH₂CH₂? O? ]_n quantitatively. The reaction with TSAA in tetrahydrofuran led to the highest molecular weight polymers (number‐average molecular weight = 110,000, weight‐average molecular weight/number‐average molecular weight = 1.59). 2‐Hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, cyclohexane dimethanol monovinyl ether, and tricyclodecane dimethanol monovinyl ether were also employed as monomers, and polyacetals with various main‐chain structures were obtained. This structural variety of the main chain changed the glass‐transition temperature of the polyacetals from approximately ?70 °C to room temperature. These polyacetals were thermally stable but exhibited smooth degradation with a treatment of aqueous acid to give the corresponding diol compounds in quantitative yields. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4053–4064, 2002     

Low‐temperature controlled free‐radical polymerization of vinyl monomers in the presence of a novel cyclic dixanthate under γ‐ray irradiation

The free‐radical polymerization of methyl acrylate (MA) has been studied in the presence of a novel cyclic dixanthate under γ‐ray irradiation (80 Gy min^?1) at room temperature (～28 °C), ?30 °C, and ?76 °C respectively. The resultant polymers have controlled molecular weights and relatively narrow molecular weight distributions, especially at low temperatures (i.e., ?30 and ?76 °C). The polymerization control may be associated with the temperature: the lower the temperature is, the more control there is. Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry analysis of poly(methyl acrylate) (PMA) samples shows that there are at least three distributions: [3‐(MA)_n‐H]⁺ cyclic polymers, [3‐(MA)_n‐THF‐H]⁺, and [3‐(MA)_n‐(THF)₂‐H]⁺ linear PMAs. The relative content of the cyclic polymers markedly increases at a lower temperature, and this may be related to the reduced diffusion rate and the suppressed chain‐transfer reaction at the low temperature. It is evidenced that the good control of the polymerization at the low temperature may be associated with the suppressed chain‐transfer reaction, unlike reversible addition–fragmentation chain transfer polymerization. In addition, styrene bulk polymerizations have been performed, and gel permeation chromatography traces show that there is only one cyclic dixanthate moiety in the polymer chain. This article is the first to report the influence of a low temperature on controlled free‐radical polymerizations. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2847–2854, 2007     

Molecular weight distribution studies. I. Radiation-induced polymerization of liquid α-methylstyrene

The concentration of water in purified and BaO-dried α-methylstyrene was found to be 1.1 × 10^?4M. The radiation-induced bulk polymerization of the α-methylstyrene thus prepared was studied in the temperature range of ?20°C to 35°C. The polymerization rate varied as the 0.55 power of the dose rate. The theoretical molecular weights and molecular weight distribution were calculated from a proposed kinetic scheme and these values were then compared with those found experimentally. The agreement between these two was reasonably close, and therefore it was concluded that, from the molecular weight distribution point of view, the proposed kinetic scheme for the cationic polymerization of α-methylstyrene is an acceptable one. The rate constant for chain transfer to monomer k_f changed with temperature and was found to be responsible for the decrease in the molecular weight of the polymer with increase in temperature. k_f and k_p at 20°C were found to be 0.95 × 10⁴ l./mole-sec and 0.99 × 10⁶ l./mole-sec, respectively.     

Anomalous solubility of polyacrylamide prepared by dispersion (precipitation) polymerization in aqueous tert‐butyl alcohol

Polyacrylamide prepared by dispersion (precipitation) polymerization in an aqueous t‐butyl alcohol (TBA) medium is only partially soluble when the TBA concentrations in the polymerization media are in the range 82 vol % < TBA < 95 vol %. Independent experiments with a soluble (linear) sample of polyacrylamide show that the polymer swells sufficiently in the aforementioned media to lower the glass‐transition temperature of the polymer below the polymerization temperature (50 °C). The anomalous solubility has been attributed to the crosslinking of polymer chains that occurs during the solid‐phase polymerization of acrylamide in the swollen polymer particles. It is postulated that some of the radical centers shift from the chain end to the chain backbone during solid‐phase polymerization by chain transfer to neighboring polymer molecules, and when pairs of such radicals come into close vicinity, crosslinking occurs. However, dispersion (precipitation) polymerization in other media such as aqueous methanol and aqueous acetone yields polymers that are soluble. This result has been attributed to the fact that the polymer radical undergoes a chain‐transfer reaction with these solvents at a much faster rate than with TBA, which overcomes the effect of the polymer‐transfer reaction. Even the addition of as little as 5% methanol to a TBA–water mixture (TBA:water = 85:10) gives rise to a soluble polymer. The chain‐transfer constants for acetone, methanol, and TBA have been determined to be 9.0 × 10^?6, 6.9 × 10^?6, and 1.48 × 10^?6, respectively, at 50 °C. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3434–3442, 2001     

Transfer reactions in radical polymerization of styrene in acetone–chloroform mixture

The study of chain-transfer reactions in thermal and AIBN-initiated polymerization of styrene is aimed at the determination of transfer constants to the solvents at 60°C. For thermal polymerization the transfer constants C_s to acetone, chloroform, and chloroform mixed with acetone are 3.2 × 10^?5, 4.1 × 10^?5, and 4.4 × 10^?5, respectively. In the case of AIBN-initiated polymerization, the transfer constant of chloroform in the mixture acetone–chloroform is C_s = 3.3 × 10^?4. All these transfer constants are average values. It has been found that neither acetone nor chloroform satisfies the Mayo equation in the presence of transfer agent very well. These anomalies can be explained by assuming a complexation phenomenon. The changes in the polarity and resonance are taken into account. It is considered that in the chain-transfer reactions under investigation, the association or complex-forming ability of solvent and monomer or polymer play a role. In studying the chain-transfer reaction in the acetone–chloroform solvent mixture another phenomenon affecting the determination of the chain transfer constant is assumed. This phenomenon consists in formation of associates in which both solvents participate.     

Polymerization of N-vinylcarbazole by transition metal salts

The polymerization of N-vinylcarbazole (NVC) in the presence of transition metal salts such as WCI₆, MoCI₅, TaCl₅ and NbCl₅ under different reaction conditions was studied. In general, aromatic solvents were found to be superior to aliphatic solvents in the polymerization of NVC, i. e., both conversion and molecular weight were higher in aromatic solvents. It was observed that the polymerization reaction proceeds rapidly and almost quantitatively, even at low monomer concentration (< 5 × 10^?2M) and at low catalyst to monomer mole ratio (10^?5) in aromatic solvents. The copolymerization of NVC with acenaphthylene (ACN) was also investigated in solution at room temperature. The resulting homo- and copolymer were characterized by IR, NMR, x-ray diffraction, and elemental analysis. Thermal and photophysical properties are also reported. From the spectral data, the polymerization solvent was found to have a strong influence upon the polymer stereoregularity.     

Some studies on a polymer from urea

A polymer having the structure of guanidinopolyhydroxynitrile has been produced by heating an equimolar mixture of urea and anhydrous ZnCl₂ in nitrogen at 300°C and 27 atm. The structure has been established from elemental analysis, percentage of nitrogen as primary amine, and ultraviolet and infrared spectra of the polymer and its derivatives. A mechanism of the polymerization based on some experimental evidence has been suggested. Its physical properties have been attributed to its skeletal structure and ring closure by hydrogen bonding. Thermograms reveal that it is stable to 150°C, after which it decomposes slowly till a 75% weight residue is obtained at 575°C with a constant weight plateau extended to 680°C. In acid solvents, protonation occurs at the ? NH₂ group or the azomethine nitrogen atoms, producing polycations. The polyelectrolytic character in acids has been confirmed by viscometric and osmotic studies and the molecules tend to be both coiled up and associated in solutions. [n] in anhydrous formic acid is 0.3636 dl/g. The molecular weights of the polymer and its various fractions range between 39,500 and 25,900. Dielectric constants, dielectric losses, and conductivities of the polymer have also been measured as functions of frequency and temperature and it has been proved that the dispersion is due to dipole polarization. The average energy of the dipole is 1.73 × 10^?2 eV/°K, the intrinsic activation energy for conduction is 0.186 eV, the conductivities being of the order of 2 × 10^?6 to 7 × 10^?7 mho-cm^?1. The polymer is therefore a semiconductor. The number of charge carriers is 2.12 × 10¹⁶/cm², which agrees reasonably well with the value, 6.66 × 10¹⁶, obtained from spin-density calculations from ESR signals.     

Raman spectral changes during the solid-state polymerization of diacetylenes

Raman spectral changes resulting from the solid-state 1,4-addition polymerization of conjugated diacetylenes are reported. The monomers show an intense C?C stretching frequency near 2260 cm^?1, where as the polymers showed two strong bands, a C?C vibration near 2100 cm^?1 and a C?C vibration near 1500 cm^?1. The presence of both double and triple bonds in the polymers suggests the backbone structure (?C? C?C? C?)_n. The alternate mesomeric structure (? C?C?C?C? )_n can be eliminated as a possibility by the presence of the strong C?C vibration in the polymer. Sequential Raman spectra obtained during radiation-induced polymerization revealed intermediate spectral states between the initial monomer and final polymer. Intermediate-state vibrations first increase and then decrease in intensity as polymerization proceeds. However, the observed vibtrational frequencies of intermediate states were not dependent upon the extent of polymerization. Whether polymerization occurred thermally or as a result of radiation did not appear to influence the spectrum of the final polymer, but the observed number of intermediate states differed. Polymerization mechanisms, required molecular motions, and resulting structural changes are discussed.     

Ring-opening polymerization of ethylene organophosphorothioates: Stereoregular polymerization involving asymmetry at phosphorus

Stereoregular polymerization involving asymmetry at phosphorus has been obtained from ethylene methyl or phenyl phosphorothioate with R₂Mg? NH₃ catalysts, or, in some cases, with R₂Mg alone. The methyl ester gave two types of polymer: an amorphous rubber and a low-melting (75°C) crystalline polymer. The phenyl ester gave mainly a low-melting (68°C) crystalline polymer of 2.2 inherent viscosity. Proton and ³¹P NMR and infrared spectra of these polymers are in accord with the expected chain unit, ? CH₂CH₂? O? P(S)(OR)? O? . The polymerization mechanism probably involves an anionic ring-opening step with P? O cleavage. Ring opening with C? O cleavage appears to be largely excluded. This conclusion is based on the expectation that anionic ring opening with C? O cleavage should lead to a rearranged chain unit, ? CH₂CH₂? O? P(O)? (OR)? S? , because of the high nucleophilicity of sulfur as compared with oxygen. Proton and ³¹P NMR spectra give no evidence for the rearranged unit within the limit of detection (ca. 3%). However, on aging, the methyl ester polymer changes drastically to form up to 40% CH₂SP groups. Presumably, the polymer undergoes the well-known thiono-thiolo rearrangement characteristic of simple phosphorothioate esters to form ? CH₂CH₂? O? P(O)(SCH₃)? O? chain units. The phenyl ester polymer is stable under the same aging conditions.