Separation of poly(methyl methacrylate)s according to their tacticity

Summary The unconventional liquid chromatography of polymers under limiting conditions of their solubility was applied to poly(methyl methacrylate)s differing in their tacticity. The polymers were dissolved in thermodynamically good solvents and injected into an appropriate size exclusion chromatographic (SEC) column flushed with matched, moderately strong nonsolvents. The set of (limiting) conditions was found under which less soluble syndiotactic poly(methyl, methacrylate) moved along the column together with the zone of its initial solvent while better soluble isotactic poly(methyl methacrylate) was eluted according to the SEC mechanism. This indicates the potential of liquid chromatography under limiting conditions to characterize the tacticity of poly(methyl methacrylate)s.     

Relation between the repulsion of incompatible and compatible polymers in solution and their degree of mixing in the solid state: the memory effect

The incompatible polymer pairs polystyrene (PS)/poly(methyl methacrylate) (PMMA) and polystyrene (PS)/poly(oxyethylene) (POE) and the compatible polymer pair POE/PMMA have been studied in solution and in the solid state. A close relation is observed between the behaviour in solution and in the solid state for both incompatible and compatible polymer mixtures. When we use a selective solvent and when the molecular masses of the polymers of the mixture are different, even compatible polymers behave like incompatible polymers; the obtained films present an important demixing. The opposite is observed when the films are obtained by casting from a common solvent and when the two polymers possess similar molecular masses. In this case, even incompatible polymers behave like compatible polymers. These results confirm the already reported memory effect when we go from the solution to the solid state. © 2000 Society of Chemical Industry     

Glass transition behavior of emulsion-polymerized polymer films containing a surface-active agent

The glass transition behavior of emulsion-polymerized poly(methyl methacrylate) and polystyrene films containing sodium laurylsulfate as emulsifier was studied by measurements of dynamic mechanical properties and thermal depolarization current. The film specimens of the emulsion-polymerized polymers were prepared by casting from their benzene solutions. The glass transition temperatures of the emulsion-polymerized films are higher than those of the bulk-polymerized films. The higher glass transition temperature of the emulsion-polymerized films is attributed to the colloidal properties of sodium laurylsulfate in the process of the film formation. The restriction of the molecular chains in the emulsion-polymerized films is attributed to the interaction between the hydrophobic groups of sodium laurylsulfate and the polymer molecules.     

Structural changes in glassy polymers

It has previously been shown that glassy poly(ethylene terephthalate) gives rise to endothermal peaks in DTA when annealed at temperatures near to the glass temperature. The present work describes results obtained from DTA and DSC on annealing a number of glassy polymers which have been rapidly cooled from above the glass temperature and on slowly cooled samples of the same polymers. The polymers which have been studied are: poly(ethylene terephthalate), poly(methyl methacrylate), atactic and isotactic polystyrene, bisphenol-A polycarbonate, poly(ethyl methacrylate) and poly(vinyl acetate). In every case, evidence of structural reorganization is observed, and the rate at which this takes place is reported. Separate studies on poly(ethylene terephthalate) reflect density changes which also take place upon annealing. These results are discussed in the context of the calorimetric observations.     

Dissolution dynamics of some polymers: Solvent-polymer boundaries

A critical angle illumination microscopy technique was used to study the in situ dissolution dynamics of polystyrene, poly (α-methylstyrene) and the two tactic forms of poly (methyl methacrylate), (PMMA), in several solvents. The dissolution characteristics; of polymers were found to be greatly influenced by several factors: type of polymer, processing condition of the sample, type of solvent, and tacticity, Polystyrene was found to exhibit extensive swelling in several solvents while atactic PMMA exhibited extensive cracking on dissolution. Isotactic PMMA, which has a glass temperature of about 70°C lower than the atactic PMMA, showed swelling behavior similar to atactic polystyrene, while the α-methylstyrene showed the cracking phenomena exhibited by atactic PMMA.     

Modulus reinforcement in elastomer composites. II. Polymeric fillers

Blends were prepared with high-modulus “filler polymers,” polystyrene, polyamide, and poly(methyl methacrylate) dispersed in a low modulus matrix of ethylene/vinyl acetate copolymer. The modified Kerner equation was applied to dynamic mechanical data obtained on these blends, which may be considered to be model systems for thermoplastic elastomer block polymers. The implication of the interaction parameter, B, in terms of the reinforcing capability of each polymer as well as its optimum volume fraction in the blend, is discussed.     

Stereoregular poly(alkyl methacrylate)s: polymer-polymer and copolymer-polymer blends

Amorphous blends of isotactic and syndiotactic poly(methyl methacrylate) were found to be compatible. To evaluate the interaction between these tactic polymers, random copolymers of isotactic poly(methyl/ethyl methacrylate) were blended with syndiotactic poly(methyl methacrylate). Only the copolymers with an ethyl methacrylate content below 45% were compatible with syndiotactic poly(methyl methacrylate). Using a Flory-Huggins type treatment of copolymer mixtures, the segmental interaction parameters for poly(methyl methacrylate) with poly(ethyl methacrylate) and for isotactic with syndiotactic poly(methyl methacrylate) were calculated. The interaction parameter for the tactic poly(methyl methacrylate) pair was found to be small and negative.     

Ellipsometric determination of Flory-Huggins interaction parameters in solution

We have used spectroscopic ellipsometry to determine the Flory-Huggins parameters in thin films of polystyrene, poly(2vinyl pyridine), and poly(tert butyl methacrylate) swollen in controlled atmosphere of various common solvents. From the experimental data the concentration dependent Flory-Huggins interaction parameters between the homopolymers and the different solvents are revealed. Similar experiments were performed on binary copolymers of the three components. From the comparison between the degree of swelling of the homopolymers and the copolymers, respectively, the polymer/polymer Flory-Huggins interactions parameters are determined as a function of solvent content as well.     

Compatibility of polyacrylates and polymethacrylates with poly(vinyl chloride): 1. Compatibility and temperature variation

Mixtures of a series of polymethacrylates and polyacrylates with PVC were prepared by solvent casting from methyl ethyl ketone. Some mixtures were also prepared by mechanical mixing and in situ polymerization (polymerization of vinyl chloride monomer in the presence of the other polymer). The mixtures were assessed for compatibility by dynamic mechanical measurements and optical clarity. It was found that all polymethacrylates from poly(methyl methacrylate) to poly(n-hexyl methacrylate) were compatible with PVC as were poly(n-propyl acrylate) and poly(n-butyl acrylate). Higher chain polyacrylates are incompatible. Poly(methyl acrylate) and poly(ethyl acrylate) appear incompatible with PVC when mixtures are prepared by solvent casting, but compatible when prepared by in situ polymerization, and mechanical mixtures show some sign of compatibility. It seems possible that in this case the solvent interferes with the compatibility. Mixtures of PVC with poly(n-hexyl methacrylate), poly(n-butyl acrylate) and poly(n-propyl acrylate) phase separate when heated in the region between 100°C and 160°C indicating the existence of a lower critical solution temperature.     

Thermal Decomposition of Polymer Mixtures Containing Poly(vinyl chloride)

Thermal decomposition of a series of 1 : 1 mixtures of typical polymer waste materials [polyethylene (PE), poly(propylene) (PP), polystyrene (PS), polyacrylonitrile (PAN), polyisoprene, poly(methyl methacrylate) (PMMA), polyamide‐6 (PA‐6), polyamide‐12 (PA‐12), polyamide‐6,6 (PA‐6,6), and poly(1,4‐phenylene terephthalamide) (Kevlar)] with poly(vinyl chloride) (PVC) was examined using thermal analysis and analytical pyrolysis techniques. It was found that the presence of polyamides and PAN promotes the dehydrochlorination of PVC, but PVC has no effect on the main decomposition temperature of polyamides. The hydrogen chloride evolution from PVC is not altered when other vinyl polymers or polyolefins are present. The thermal degradation of PAN is retarded significantly, whereas that of the other vinyl polymers is shifted to a slightly higher temperature in the presence of PVC. Among the pyrolysis products of PAN‐PVC mixture methyl chloride was found in comparable amount to the other gaseous products at 500°C pyrolysis temperature.     

Effect of solvent balance on the surface properties of poly(vinyl chloride)

Films of poly(vinyl chloride) have been cast from solutions of varying thermodynamic quality and the film properties studied by inverse phase gas chromatography. The solvents included tetrahydrofuran, cyclohexanone, and mixtures of toluene with both tetrahydrofuran and cyclohexanone. The solvent composition was followed during evaporation and film formation for the mixed solvents, and it was shown that the slower evaporating solvent component has the greatest effect on the surface properties of the films. The porosity of the polymer film surfaces is interpreted in terms of the mobility of the polymer chains during film formation. At high concentrations, polymer chain–polymer chain interactions become stronger when thermodynamically less powerful solvents are used or are last to leave during film formation; therefore, the solvent balance has a critical influence on the film surface properties. Annealing the poly(vinyl chloride) above the glass transition temperature reduces the surface porosity of the cast polymer.     

Polymer sorbents for phosphorus esters: I. Selection of polymers by analog calorimetry

Heats of mixing of a variety of solvents with dimethyl methyl phosphonate, DMMP, are presented. A qualitative correlation between the exothermicity of the heat of mixing of DMMP with a particular solvent and sorption of DMMP by polymers containing structural units analogous to the solvent is observed. By this approach, polymers containing acidic hydroxyl functionality, such as phenol-formaldehyde condensation products and poly(styrene-co-vinyl benzyl hexafluorodimethyl carbinol), were identified as good sorbents for DMMP. Sorption isotherms, measured for these materials by the piezoelectric method, show enhanced sorption at low vapor activity and 135°C compared to polystyrene and poly(vinyl chloride) which lack these acidic sites and whose solvent analogs mix more endothermically with DMMP.     

碳纳米管/PMMA/PVAC复合膜气敏性能研究(英文)

本文将一定量的PMMA、PVAc和碳纳米管在四氢呋喃溶剂中混合,通过超声分散和溶液浇铸工艺制备了碳纳米管/PMMA/PVAc复合膜.研究了在0.4-4.1ppt乙酸乙酯气氛下,碳纳米管/PMMA/PVAc复合膜电阻与气氛浓度的变化关系.研究表明:在0.4-4.1ppt气氛下,碳纳米管/PMMA/PVAc复合膜电阻随着乙酸乙酯气氛浓度的增大而增大,复合膜对乙酸乙酯气氛具有较优的敏感性,且同时随着复合膜中PMMA含量增加,复合膜电阻增加,即气敏性增加.因此,PMMA/PVAC共混物在气敏材料的应用领域上具有潜在的价值.     

利用规整接枝共聚物作为增容剂制备耐油热塑性弹性体

通过大单体技术合成了三种现整接校共聚物；主链为聚甲基丙烯酸及支链为甲基丙烯酸甲酯的接枝共聚物（ＰＭＡＡ－ｇ－ＰＭＭＡ）可用作氨醇橡胶与聚氯乙烯的熔融共混的增容剂，而主链为聚丙烯酰胺、支链为聚苯乙烯的接校共聚物（ＰＡＭ—ｇ－ＰＳ）及主链为聚甲基丙烯酸甲酯、支链为聚苯乙烯的接枝共聚物都能作为氯化聚乙烯与聚苯乙烯共混的增容剂。用量仅占２％即可制得耐油的热塑性共混物弹性体。     

Microindentation studies at the near surface of glassy polymers: Influence of molecular weight

The viscoelastic‐plastic properties of various amorphous, glassy polymers [polystyrene (PS), poly(styrene‐acrylonitrile) copolymer (SAN), poly(methyl methacrylate) (PMMA), poly(vinyl chloride) (PVC), polycarbonate (PC)] in the micron and submicron range were investigated by means of load‐displacement analysis from depth‐sensing experiments. Hardness and Young's modulus values decrease rapidly with increasing depth up to a few microns. New data on the glass transition temperature correlation with microhardness are presented. The influence of annealing below the glass transition temperature upon the microhardness for various glassy polymers is pointed out. For PS, the influence of the molecular weight variation and molecular weight distribution on the microhardness is reported. Results are discussed on the basis of an entanglement network model, recently developed to explain the fine structure of crazes in amorphous polymers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1951–1956, 2004     

Applicability of the two-dimensional approach to polymer miscibility in pure and mixed organic liquids

Previously it was proposed that the solvent power of a pure or mixed organic liquid for a given polymer can be characterized by two parameters δ_h and χ_H. Using these two parameters, a two-dimensional (2D) solubility diagram can be constructed to predict solubility or insolubility. In the investigation only the polymers, poly(methyl methacrylate), polystyrene, and poly(vinyl acetate), were used to demonstrate the applicability of the 2D method. In this note, applicability of the 2D method to the 33 polymers investigated in Hansen's works is presented.     

Viscoelastic properties of stereocomplex polymers

Sterecomplex polymers were synthesized by radical polymerization of mixtures of isotactic and syndiotactic poly(methyl methacrylate) (PMMA) in some vinyl monomers under the conditions of stereocomplex formation. The viscoelastic properties of stereocomplex polymers were studied by a sinusoidal vibration method and compared with those of the usual blended polymers. It was found that the network structure resulting from the stereocomplex association between isotactic and syndiotactic PMMA prevents a phase separation of the newly created polymers from the matrix of PMMA during the polymerization process, and that makes the viscoelastic properties and optical transparency of stereocomplex polymers very different from those of the usual blended polymers without stereocomplex formation.     

Correlating miscibility of PVC/PMMA blend with polymer chain orientation

Blends of poly (vinyl chloride) (PVC) and poly (methyl methacrylate) (PMMA) with varying concentrations of the polymers were prepared in a film form by standard solution casting method, using methyl ethyl ketone (MEK) as a common solvent. The miscibility of the blend was studied by dynamic mechanical analysis. The chain orientation behaviors of PVC and PMMA in the stretched blend films were studied by infrared dichroism method. Up to 60 wt % PVC concentration in the blend, PVC showed negative values for orientation function whereas PMMA showed independent positive values for its orientation function. On further increasing PVC concentration in the blend, the orientation function of PVC flipped to positive values, and both PVC and PMMA showed same magnitude and trend in orientation behavior. The chain orientation behavior of individual polymers in the immiscible compositions of the blend was observed to be independent, while there was a high degree of cooperation for chain orientation in the miscible composition. Change in the miscibility of the blend was simultaneously accompanied by conformational changes in PVC. The change in orientation behavior is interpreted in terms of curling of polymer chains in the immiscible phase. The polymer chain curling hypothesis used here is applicable independent of the type of polymers in the blend. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 624–630, 2006