Stereocomplex formation between isotactic PMMA and syndiotactic polymers of methacrylates of straight-chain alcohols

Summary Stereocomplex formation between isotactic (iso-) poly(methyl methacrylate) (PMMA) and syndiotactic (syn-) polymers of methacrylates of straight-chain alcohols such as ethyl, propyl, butyl and allyl alcohols was found to occur in acetone to form gel. The solid complexes recovered from the gels in acetone showed endotherms in their DSC thermograms due to the melting of the complexes. The melting points of the complexes are 143.0°C, 125.4°C, 101.5°C and 141.5°C, respectively. The X-ray powder patterns of these complexes showed reflection peaks at 2=4.3–4.4° and 6.8–10.6°. The former reflections are commonly observed for all stereocomplexes including PMMA stereocomplex and should correspond to the fiber period. The degree of the latter decreased as the size of ester group increased corresponding to the increasing distances between two double-stranded helices, if we adopt the Challa's double-stranded helical model for the stereocomplex.     

Preparation of PMMA macromers by o-vinylbenzylmagnesium chloride and their polymerization

Summary Polymerization of MMA with o-vinylbenzylmagnesium chloride was examined in toluene and in tetrahydrofuran (THF) at various temperatures. The polymer formed in toluene at –78°C was highly isotactic (mm=94%) and containing one vinylbenzyl group at the -end of the chain, although the methanol-soluble fraction concomitantly formed in an appreciable amount was less isotactic. The PMMAs formed in THF at –78 and –98°C were mostly methanol-soluble and highly syndiotactic (rr=88% at –78°C and 96% at –98°C), and also contained one vinylbenzyl group. The methanol-soluble, isotactic and syndiotactic PMMA macromers were polymerized or copolymerized with styrene by AIBN in toluene at 60°C. The isotactic macromer exhibited slightly higher reactivity than the syndiotactic one.     

Highly syndiotactic poly(methyl methacrylate) with narrow molecular weight distribution formed by tert-butyllithium-trialkylaluminium in toluene

Summary Polymerization of MMA with t-C₄H₉Li in toluene in the presence of trialkylaluminum(alkyl=methyl, ethyl, butyl, isobutyl, and octyl) was examined at various Al/Li ratios. Triethyl-, tributyl and trioctylaluminums worked quite effectively in the polymerization to give highly syndiotactic PMMA with narrow molecular weight distribution (MWD) at the Al/Li ratio of 3 and higher than 3. The highest syndiotacticity of 96% was attained with t-C₄H₉Li/(n-C₈H₁₇)₃Al (1/3) at –93°C. The polymerization was initiated by t-C₄H₉ anion and proceeded in a living manner. The structure of the syndiotactic PMMA is chemically identical to that of isotactic PMMA prepared with t-C₄H₉MgBr. Consequently, highly isotactic and syndiotactic PMMAs with narrow MWD and with the same chemical structure from -end to -end were obtained.     

Preparation of stereoregular block copolymer comprising isotactic PMMA and polyisobutylene blocks and its characterization

Summary A triblock copolymer of isotactic(it)-poly(methyl methacrylate) (PMMA) and polyisobutylene (PIB), it-PMMA-block-PIB-block-it-PMMA, was prepared by anionic polymerization of triphenylmethyl methacrylate initiated with , -dilithiated PIB diisobutyrate in tetrahydrofuran at -78°C, and subsequntt hydrolysis and methylation with diazomethane. Molecular weight distribution of the triblock copolymer was narrow, and the stereoregularity of the PMMA block was highly isotactic. Proton spin-lattice relaxation times of the block copolymer in acetone-d₆, which is non-solvent for PIB but dissolves the block copolymer, indicate the aggregation of the copolymer through PIB block. Stereocomplex formation between the it-block copolymer and syndiotactic(st)-PMMA-block-PIB-block-st-PMMA was also studied.     

Segmental motion of stereoregular poly(methyl methacrylates) in a homologous series of n-alkyl acetate solvents by nmr relaxation measurements

The ¹³C spin-lattice relaxation times, T₁s, of both stereoregular poly(methyl methacrylates) (PMMA) and homologous series of n-alkyl acetate solvents in solution have been measured at 40°C. It was observed that the motion of polar side-chains was highly affected by the degree of interaction with solvent molecules. The stronger polymer-solvent interactions in predominantly syndiotactic PMMA solutions than in isotactic PMMA solutions were shown from the T₁ values for the carbonyl, methoxy, and quaternary carbons in polymer segments and also from the carbonyl T₁s of solvent molecules. By relating the solvent dependences of the T₁ data in syndiotactic polymer solutions to that of the known dissolution rate data of atactic PMMA, it was found that the solvent dependences of the T₁ values of those carbon groups in which the polymer-solvent interaction is not significant, e.g., methylene and α-methyl carbon groups, were consistent with the solvent dependence of the dissolution rate of polymer. This result suggested that the dissolution of polymer is mainly governed not by the sorption process related to the polymer-solvent interaction but by the transport process related to the local motions of polymer segments and solvent molecules.     

Wettability and microstructure of polymer surfaces: stereochemical and conformational aspects

Stereoregular poly(methyl methacrylates) (PMMAs) solvent-cast in the form of films against a glass substrate were employed as model systems for a systematic study of the relationship between the molecular structure (as characterized by the stereochemistry and conformations of macromolecules), the functional-group composition, and the wettability of polymer surfaces. The water wettability of a syndiotactic surface was found to be highly sensitive to the polarity of the adjacent phase in the film-casting process, whereas the wettability of an isotactic surface was invariant to the polarity of the contacting medium. The tacticity-dependent wetting behavior arises from the difference in the extent of functional-group surface segregation or, in other words, from the different surface activity of the different tactic versions of the polymer. This difference, in turn, is associated with fundamental distinctions in the conformational structures energetically allowed for the isotactic and syndiotactic configurations of the polymer chain; the syndiotactic macromolecule is capable of adopting an amphiphilic surface conformation, whereas the energetically allowed conformational structures of the isotactic macromolecule do not possess amphiphilic character. In view of these findings, the isotactic surfaces can be regarded as 'ideal' model surfaces for research on the fundamentals of wetting phenomena. In addition, there is evidence for failure of the basic assumption of the Cassie approach, i.e. the assumption of macroscopic chemical heterogeneity, to describe adequately the wetting behavior of isotactic PMMA surfaces.     

PMMA-block-polyisobutylene-block-PMMA prepared with α,ω-dilithiated polyisobutylene and its characterization

Summary A triblock copolymer of PMMA and polyisobutylene(PIB), PMMA-block-PIB-block-PMMA, was prepared by anionic polymerization of methyl methacrylate initiated with , -dilithiated poly(isobutylene) diisobutylate in tetrahydrofuran at -60°C. The molecular weight distribution of the block copolymer was close to that of the starting PIB. The stereoregularity of PMMA block was predominantly syndiotactic. Proton spin-lattice relaxation time and solution viscosity of the block copolymer in acetone, which is non-solvent for PIB, indicate that the block copolymer forms rigid spherical particles. Stereocomplex formation with isotactic PMMA was also studied.     

Preparation of highly isotactic and syndiotactic poly(methyl methacrylate) macromonomers having the same chemical structure and their polymerization

Summary Highly isotactic living poly(methyl methacrylate) (PMMA) anion prepared with t-C₄H₉MgBr in toluene at –78°C reacted quantitatively with p-bromomethylstyrene (p-BMST) in the presence of hexamethylphosphoramide or 1,8-diazabicyclo[5.4.0]-undec-7-ene to give the PMMA macromonomer with narrow molecular weight distribution. Highly syndiotactic PMMA macromonomer was also prepared by the reaction of p-BMST and the living PMMA anion formed by t-C₄H₉Li-(n-C₄H₉),Al (Al/Li=3) initiation in the presence of tetramethylethylenediamine. Radical polymerization and copolymerization of these macromonomers were studied in some detail. The results showed the higher reactivity of the isotactic PMMA macromonomer than the syndiotactic one.     

Influence of the tacticity of poly(methyl methacrylate) on the miscibility with poly(vinyl chloride)

It can be concluded from the work of Schurer et al.¹⁰ that poly(vinyl chloride) (PVC) is more miscible with syndiotactic than with isotactic poly(methyl methacrylate) (PMMA). By choosing different molar masses for the various tactic forms of PMMA it is possible to obtain blends with PVC with similar phase behaviour, i.e. in all cases a cloud-point curve with a minimum in the vicinity of 190°C. In this way a more quantitative statement about the influence of the tacticity of PMMA on its miscibility with PVC can be made. One of the principal differences between syndiotactic or atactic PMMA and isotactic PMMA is the higher flexibility of the latter. Using Flory's equation of state theory it will be shown that the effect of this difference is large enough to explain the difference in phase behaviour observed. Heats of mixing of low molar mass analogues were also measured and found to be negative.     

Effect of the tacticity of poly(methyl methacrylate) on the phase diagram of its ternary blends

Previously, isotactic and atactic poly(methyl methacrylates) (PMMAs) were found to be miscible with poly(vinyl phenol) (PVPh) and poly(hydroxy ether of bisphenol‐A) (phenoxy) because all the prepared films were transparent and showed composition‐dependent glass transition temperatures (T_g's). However, syndiotactic PMMA was immiscible with PVPh because most of the cast films had two T_g's. On the contrary, syndiotactic PMMA was still miscible with phenoxy. According to our preliminary results, PVPh and phenoxy are not miscible. Also to our knowledge, nobody has reported any results concerning the effect of the tacticity of PMMA on its ternary blend containing PVPh and phenoxy. The miscibility of a ternary blend consisting of PVPh, phenoxy, and tactic PMMA was thus investigated and reported in this article. Calorimetry was used as the principal tool to study miscibility. An approximate phase diagram of the ternary blends containing different tactic PMMA was established, probably for the first time, based on differential scanning calorimetry data. Immiscibility was found in most of the studied ternaries but a slight difference due to the effect of tacticity of PMMA was definitely observed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2720–2726, 2002     

Copolymerisation of 1,9-decadiene and propylene with binary and isolated metallocene systems

1,9-Decadiene/propylene copolymers were obtained with isolated metallocenes and with a binary metallocene catalyst system activated by methylaluminoxane. The metallocenes under investigation were syndiospecific diphenylmethyl(cyclopentadienyl)(9-fluorenyl)zirconium dichloride (1) and isospecific rac-dimethylsilylbis(4-tert-butyl-2-methyl-cyclopentadienyl)zirconium dichloride (2). A copolymer structure, in which 1,9-decadiene linked isotactic and syndiotactic polymer chains, was obtained when copolymerisation was started with catalyst 2 at 80 °C followed by injection of catalyst 1 and instantaneous lowering of polymerisation temperature to 40 °C after 15 min of polymerisation. The copolymer was also shown to work as a compatibiliser in a blend of syndiotactic and isotactic polypropylene. We propose that catalyst 2 incorporates 1,9-decadiene into the isotactic main chain without any significant crosslinking within the first 15 min of polymerisation at 80 °C and the produced isotactic macromonomers are further incorporated at 40 °C into the syndiotactic main chain in polymerisation with catalyst 1.     

Synthesis of stereoblock poly(methyl methacrylate) via transformation of isotactic-specific living polymer anion to syndiotactic-specific anion

Polymerization of methyl methacrylate (MMA) by isotactic poly(methyl methacrylate) (PMMA) living anion, prepared with t-C₄H₉MgBr in toluene at ?60°C, was carried out at ?78°C in the presence of trialkylaluminiums (R₃Al; R = CH₃, C₂H₅, and n-C₄H₉) to obtain a stereoblock PMMA, isotactic PMMA-block-syndiotactic PMMA. Among the R₃Als, (CH₃)₃Al gave most effectively the steroblock PMMA with narrow molecular weight distribution. The fraction of rr triad in the syndiotactic PMMA block increased with increase in the ratio of Al/Mg and reached about 76% at a ratio of Al/Mg ≥ 6. The method was also used to prepare stereoblock copolymer comprising isotactic PMMA block and syndiotactic block of butyl methacrylate. Stereocomplex formation and solution viscosity of the stereoblock PMMA were also studied.     

NMR-study of structure and dynamics of associates of syndiotactic poly(methyl methacrylate) in toluene

Summary High-resolution ¹H NMR spectra (¹H HR-NMR) of solutions of isotactic (i) and syndiotactic (s) poly(methyl methacrylate) (PMMA) in toluene-d₈ were measured in the concentration range 0.2 to 10% w/v; for solutions of s-PMMA (10% w/v), ¹H NMR spectra with magic angle rotation (MAR-NMR) at various temperatures and ¹³C NMR spectra with strong proton decoupling were also measured. It was found that even in very dilute solutions of s-PMMA in toluene-d₈ a considerable portion (76%) of polymer segments are associated: association is of intramolecular origin and is due to interaction of long syndiotactic sequences. Prom NMR spectra the motion of associated segments appears as isotropic with and effective correlation frequency 10⁶ – 10⁷ Hz. A globular structure of the associates of s-PMMA is proposed.     

Measurement of the unperturbed dimensions of stereoregular poly(methyl methacrylate)

The results of measurements of unperturbed dimensions for a series of stereoregular poly(methyl methacrylates) are reported. The measurements were made by a recently developed method involving a gel permeation chromatograph coupled with an on-line low angle laser light scattering photometer. Measurements were performed in a thermodynamically good solvent, tetrahydrofuran at 25°C. The unperturbed dimensions were obtained by means of viscosity plots. Comparison of the results obtained by this method with those currently available in the literature, as well as with values predicted by statistical calculations, show good agreement. It was determined that a measurable difference occurs in the Mark-Houwink relationship between isotactic and syndiotactic poly(methyl methacrylate); isotactic poly(methyl methacrylate) is 30% more extended than syndiotactic poly(methyl methacrylate) in its unperturbed state; and isotactic poly(methyl methacrylate) exhibits a smaller degree of polymer solvent interaction than the syndiotactic form.     

Syndiotactic poly[(R,S)-β-hydroxybutyrate]isolated from methylaluminoxane-catalyzed polymerization

Summary Poly[(R,S)--hydroxybutyrate] was prepared via the methylaluminoxane-catalyzed polymerization of (R,S)--butyrolactone, fractionated, and characterized by ¹H and ¹³C nmr, gel permeation chromatography, differential scanning calorimetry, and x-ray diffraction. All the material isolated from these reactions was identified by nmr as poly(-hydroxybutyrate), but in each case, ¹³C nmr showed that a portion of the material contained more syndiotactic than isotactic diads. Although this new syndiotactic material was low in molecular weight, it showed crystallinity by differential scanning calorimetry and x-ray diffraction, with d-spacings different in value and relative intensity from those of the isotactic polymer.     

Preparation of heterotactic-rich poly(methyl methacrylate) with narrow molecular weight distribution bytert-butyllithium/bis(2,6-di-tert-butylphenoxy)methylaluminum

Summary Polymerization of methyl methacrylate (MMA) withtert-butyllithium (t-C₄H₉Li) in toluene in the presence of aluminum alkoxides such as ethoxide,tert-butoxide and 2,6-di-tert-butylphenoxide, were examined at various Al/Li ratios. In the cases of ethoxide andtert-butoxide, predominantly isotactic polymers with broad molecular weight distribution were obtained. Combinations oft-C₄H₉Li and bis(2,6-ditert-butylphenoxy)methylaluminum [MeAl(ODBP)₂] were found to be an efficient initiating system for heterotactic polymerization of MMA, which gives PMMA rich in heterotactic triads up to 68% with narrow molecular weight distribution (Mw/Mn=1.09–1.17). End group analysis by¹H NMR indicated thatt-C₄H₉Li initiates the polymerization and MeAl(ODBP)₂ works as a stereospecific modifier. From stereosequence analysis of the heterotactic PMMA by¹³C NMR, it was found that the calculated pentad fractions from the first-order Markovian statistics (Pm/r=0.742, Pr/m=0.627) fitted the observed ones better than those from Bernoullian statistics. The glass transition temperature of the heterotactic PMMA was 13°C lower than that of syndiotactic PMMA, and the intrinsic viscosity in tetrahydrofuran was close to that of isotactic PMMA with a similar molecular weight but higher than that of syndiotactic PMMA.     

Effect of tacticity of poly(methyl methacrylate) on the miscibility with poly(vinyl pyrrolidone)

Isotactic, atactic, and syndiotactic poly(methyl methacrylates) (PMMA) (designated iPMMA, aPMMA, and sPMMA) with approximately the same molecular weight were mixed separately with poly(vinyl pyrrolidone) (PVP) primarily in chloroform to make three polymer blend systems. Differential scanning calorimetry (DSC) was used to study the miscibility of these blends. The results showed that the tacticity of PMMA has a definite impact on its miscibility with PVP. The aPMMA/PVP and sPMMA/PVP blends were found to be miscible because all the prepared films showed composition-dependent glass-transition temperatures (T_g). The glass-transition temperatures of the aPMMA/PVP blends are equal to or lower than weight average and can be qualitatively described by the Gordon–Taylor equation. The glass-transition temperatures of the other miscible blends (i.e., sPMMA/PVP blends) are mostly higher than weight average and can be approximately fitted by the simplified Kwei equation. The iPMMA/PVP blends were found to be immiscible or partially miscible based on the observation of two glass-transition temperatures. The immiscibility is probably attributable to a stronger interaction among isotactic MMA segments because its ordination and molecular packing contribute to form a rigid domain. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3190–3197, 2001     

Synthesis and characterization of poly(methyl methacrylate) nanoparticles by emulsifier‐free emulsion polymerization with a redox‐initiated system

In this study, the emulsifier‐free emulsion polymerization of methyl methacrylate (MMA) was initiated directly by a Cu²⁺/HSO redox system. Latex particles with negative charge due to the bonded anionic sulfite ion were successfully synthesized after 2 h of reaction at 40–60°C. Scanning electron microscopy pictures showed a uniform particle size distribution, and the average size decreased from 223 to 165 nm wit increasing reaction temperature from 40 to 60°C. The initiation step in the polymerization mechanism was proven to be a redox reaction, in which Cu²⁺ oxidized the bisulfite ion to produce an anionic sulfite radical and proton. The produced anionic sulfite radical then initiated the polymerization of MMA. Moreover, Cu²⁺ not only served as one component in the redox initiator system but also as a chain‐transfer agent that terminated growing polymer chains to produce chains with unsaturated end groups [poly(methyl methacrylate) (PMMA)? CH?CH₂]. For this system, about 17% PMMA? CH?CH₂ was produced. The tacticities of the PMMA latex prepared at 40–60°C were almost the same, about 62–64% syndiotactic, 33–35% heterotactic, and 3% isotactic. These PMMA latexes had almost the same glass‐transition temperature, 125–127°C, regardless of the reaction temperatures, and their weight‐average molecular weights were in the range between 254,000 and 315,000. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Poly(methyl methacrylate) membranes

Uniform and symmetric membranes were formed from poly(methyl methacrylate) (PMMA) by making use of the stereocomplex phenomenon which characteristically occurs in the solution of a mixture of isotactic PMMA and syndiotactic PMMA. The water permeability of the membrane was very high compared to a commercially available cellulosic membrane, whereas their NaCl permeabilities were the same. The permeabilities of the membranes are explained by a simple capillary model. By varying the tacticity of the polymer it was found that the finest membrane structure is formed at the isotactic polymer ratio of ca. 30%. This shows the close relationship between complex formation and membrane permeability.     

Heterogeneous polymerization of some methacrylate monomers

It has been found that sodium metabisulphite failed to initiate the polymerization of methyl and butyl acrylates but succeeded in polymerizing methyl, ethyl, and hydroxy propyl methacrylates. All the samples of the poly(hydroxypropyl methacrylates) were crosslinked, even those prepared at low conversions. Gel permeation chromatographic analysis indicated a multinodal molecular weight distribution, suggesting the existence of more than one mechanism occurring in such a heterogeneous system. It has also been proved by electron spin resonance that the polymerization process, using sodium bisulphite as the initiator in such a system, is a radical mechanism. The use of substances such as quartz, glass powder, and kaoline powder enabled the detection of the bisulphite radicals by trapping them. Using ¹³C NMR spectroscopy, the estimated triad fractions from α-methyl peaks and from quaternary carbon peaks of the poly(methyl methacrylates) and poly(ethyl methacrylates) showed that the polymers obtained were all predominantly syndiotactic in structure, as expected. The poly(ethyl methacrylate) samples were found to have a slightly higher syndiotacticity than the poly(methyl methacrylates), also as expected. The greater bulk of the ethyl ester group relative to that of the methyl ester group probably leads to greater steric hindrance in the isotactic and heterotactic triad (i.e., in a mesodyad).