Mathematical Relations Correlating Pluronics Properties with their Chemical Structure

Statistically valid equations correlating properties of ethylene and propylene oxides block copolymers of Pluronic type with molecular mass of polyoxybutylene chain, the content of ethylene oxide and concentration are given. The following properties are considered: density, viscosity, melting point, cloud point, surface and interfacial tension, foaming, wetting and washing ability.     

Laundry Detergency of Solid Nonparticulate Soil or Waxy Solids: Part II. Effect of the Surfactant Type

In this work, methyl palmitate with a melting point around 30°C was used as a model of waxy soil. Its detergency was evaluated with a hydrophilic surface (cotton) or a hydrophobic surface (polyester) using different surfactants: alcohol ethoxylate (EO9), sodium dodecyl sulfate (SDS), methyl ester sulfonate (MES), methyl ester ethoxylate (MEE), and two extended surfactants (C_12,14-10PO-2EO-SO₄Na and C_12,14-16PO-2EO-SO₄Na). The detergency efficiency at a 0.2 wt.% surfactant and 5 wt.% NaCl gradually increased while redeposition gradually decreased with increasing washing temperature in most studied surfactant solutions; this was observed both above and below the melting point of methyl palmitate on both studied fabrics. If the methyl palmitate was heated above the melting point when deposited on the fabric, it was better able to penetrate into the fabric matrix as compared to deposition below the melting point, resulting in poorer detergency for heated deposition, particularly for washing temperatures lower than the melting point. Among the surfactants studied, the nonionic surfactant (EO9) showed the highest detergency efficiency (73–94%) at any washing temperature especially on the polyester fabric. For washing temperatures below the melting point, detergency performance correlated well with the contact angle of surfactant solution on the solid methyl palmitate surface for all studied surfactants when salinity was varied. In this work, conditions resulting in the highest detergency below the melting point corresponded to the highest detergency above the melting point, suggesting this as a systematic approach to formulating below the melting point of the soil. Charge of particles or fabric was not observed to be important to the detergency mechanism, but steric factors resulting from surfactant adsorption were observed to be important mechanistic factors in waxy solid detergency.     

Thermorheological and mechanical behavior of polylactide and its enantiomeric diblock copolymers and blends

In this study, different compositions of nearly monodispersed diblock copolymers of dl-lactide or d-lactide and l-lactide were synthesized by living ring-opening polymerization with a dinuclear indium catalyst. The effects of molecular weight and block length ratio on the rheological behavior of dl and l-lactide diblock copolymers in the disordered state were investigated. For comparison, blends of PDLLA and PLLA homopolymers of equivalent molecular weights to the diblock copolymers were prepared. We found that the time–temperature (t–T) superposition principle is applicable to the diblock copolymers PLLA-b-PDLLA and blends in the disordered state. However, the t–T superposition failed at low temperatures close to the temperature of crystallization. In contrast, diblock copolymers PLLA-b-PDLA formed stereocomplex crystallites of high melting point (slightly above 200 °C) that causes a viscosity enhancement. The failure of t–T superposition was found due to existing of micro homo or stereocomplex crystallites. The non-isothermal crystallization behavior was investigated using differential scanning calorimetry (DSC). The DSC thermograms of blends exhibited a single glass transition at 50–60 °C followed by melting point of PLLA at 177 °C. With decreasing of the PLLA content in the blends, the intensity of the melting peak decreased. In addition, different crystallization behavior was observed for diblock copolymers compared to their equivalent blends. Specifically, low temperatures and enthalpies of melting peaks were observed for diblock copolymers. These also show improvement in elongation at break and tensile strength as compared to their counterpart homopolymer blends.     

Polyamide4‐block‐poly(vinyl acetate) via a polyamide4 azo macromolecular initiator: Thermal and mechanical behavior,biodegradation, and morphology

A series of polyamide4‐block‐poly(vinyl acetate)s were synthesized by the radical polymerization of vinyl acetate (VAc) using an azo macromolecular initiator composed of polyamide4 (PA4). The block copolymers were investigated by examining their molecular weight, structure, thermal and mechanical properties, biodegradation, and the morphology of the film surface. The compositions and molecular weights (Mw) ranging from 46,800 to 163,700 g mol^?1 of the block copolymers varied linearly with increasing molar ratio of VAc to azo‐PA4. The block copolymers have high melting points of 248.2–262.5°C owing to PA4 blocks and heats of fusion, which were linearly dependent on the PA4 content. The mechanical properties of the block copolymers were monotonically dependent on the composition, i.e., increasing the PA4 content increased the tensile strength, whereas increasing the poly(vinyl acetate) content increased the elongation at break. The morphology of the block copolymers suggested the appearance of microphase separation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42466.     

Polymerization of α, α-disubstituted-β-propiolactones and lactams. 9. ABA block copolymers of α-methyl-α-butyl-β-propiolactone and pivalolactone

ABA block copolymers were prepared by the anionic polymerization of α-methyl-α-butyl-β-propiolactone, MBPL (B block), and pivalolactone, PL (A blocks). The MBPL block had a very low decree of crystallinity and a glass temperature of ? 13°C, so phase separation with extensive crystallization of the PL blocks gave thermoplastic elastomers when the MBPL block constituted the principal and continuous phase. The observed crystallinity and melting point of 40–45°C in the MBPL homopolymer have not been previously reported. Measurements were obtained by electron microscopy of the initial size distribution of the PL domains as a function of copolymer composition and degree of polymerization, and on the effect of annealing on this parameter. Tensile strengths and elongations at break were both less than those previously observed for equivalent ABA block copolymers of PL and α-methyl-α-propyl-β-propiolactone.     

Block polymers from isocyanate-terminated intermediates. IV. Properties of cured butadiene–ε-caprolactam block polymers

Butadiene–ε-caprolactam block polymers containing a high proporation of 1,2 units in the butadiene-segments were synthesized and physical properties were measured on the cured copolymers. Flexural strength and impact resistance both increase regularly with increasing ε-caprolactam content in peroxide cured copolymers. This behavior is explained by the higher values of flexural modulus and impact resistance for poly(ε-caprolactam) compared with peroxide-cured polybutadiene resins. Copolymers reinforced with silica showed higher heat distortion temperatures but lower impact resistance than corresponding unfilled samples. Arrhenius plots of flexural properties at various test temperatures were linear. Both flexural modulus and strength decreased regularly with increasing test temperature. Flexural properties of filled copolymers were relatively unaffected by heat aging up to 204°C for several weeks, however, dramatic decreases in these properties were noted in a matter of days when heat aging was done at 260–316°C. These results are explained by the rapid degradation of poly(ε-caprolactam) above its melting point. Block polymers whose butadiene segments contained a high proportion of 1,4 units were also synthesized. These copolymers were elastomeric when cured with either sulfur or peroxide.     

Novel ternary block copolymerization of carbon dioxide with cyclohexene oxide and propylene oxide using zinc complex catalyst

Block copolymers of poly (propylene carbonate—cyclohexyl carbonate) (PPC-PCHC) were successfully synthesized by a one-pot method with the zinc complex catalyst (Zn2G). The IR and ¹H-NMR and ¹³C-NMR spectra verified the introducing of PCHC segments in the copolymers. The GPC curves of the copolymers appeared only one peak and the DSC results showed three glass transition temperatures at 40 °C, 66 °C and 115 °C, indicating the three-block copolymer structure. TGA tests revealed that the thermal decomposition temperature of the synthesized block copolymers increased up to about 300 °C. The mechanical properties proved to be also enhanced greatly as evidenced by static and dynamic mechanical tests. The thermal and mechanical properties of the resultant block copolymers lay between those of PPC and PCHC, demonstrating the desired properties of a polymer can be achieved via block copolymerization.     

Preparation and properties of poly(ether‐ester‐amide)/poly(acrylonitrile‐co‐butadiene‐co‐styrene) antistatic blends

A novel antistatic agent poly(ether‐ester‐amide) (PEEA) based on caprolactam, polyethylene glycol, and 6‐aminocaproic acid was successfully synthesized by melting polycondensation. The structure, thermal properties, and antistatic ability of the copolymer were characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analyses, and ZC36 megohmmeter. Test results show that PEEA is a block copolymer with a melting point of 217°C and a thermal decomposition temperature of 409°C, together with a surface resistivity of 10⁸ Ω/sq. Antistatic poly(acrylonitrile‐co‐butadiene‐co‐styrene) (ABS) materials were prepared by blending different content of PEEA to ABS resin. The antistatic performances, morphology, and mechanical properties were investigated. It is indicated that the surface resistivity of PEEA/ABS blends decrease with the increasing PEEA content, and the excellent antistatic performance is obtained when the antistatic agent is up to 10–15%. The antistatic performance is hardly influenced by water‐washing and relative humidity, and a permanent antistatic performance is available. The antistatic mechanism is investigated. The compatibility of the blends was studied by scanning electron microscopy images. The ladder distribution of antistatic agent is formed, and a rich phase of antistatic agent can be found in the surface layer. The elongations at break of the blend are improved with the increasing antistatic agent; the tensile strength and the notched impact strength kept almost the same. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Characterization of block copolymers based on poly[3,3-bis(ethoxymethyl)oxetane] and other novel polyethers

Diblock, triblock, and alternating block copolymers based on poly[3,3-bis(ethoxymethyl) oxetane] [poly(BEMO)] and a random copolymer center block poly(BMMO-co-THF) composed of poly[3,3-bis(methoxymethyl)oxetane] [poly(BMMO)], and poly(tetrahydrofuran) [poly(THF)] were synthesized and characterized with respect to molecular weight. Glass transition temperatures T_g and melting temperatures T_m were characterized via DSC, modulus–temperature, and dynamic mechanical spectroscopy (DMS). These polyethers had T_m between 70°C and 90°C, and T_g between ?55°C and ?30°C. The degree of crystallinity of poly(BEMO) was found to be 65% by X-ray powder diffraction. Tensile properties of the triblock copolymer, poly(BEMO-block-BMMO-co-THF-block-BEMO) were also studied. A yield point was found at 4.1 × 10⁷ dyn/cm² and 10% elongation and failure at 3.8 × 10⁷ dyn/cm² and 760 % elongation. Morphological features were examined by reflected light microscopy and the kinetics of crystallization were studied. Poly(BEMO) and its block copolymers were found to form spherulites of 2–10 μm in diameter. Crystallization was complete after 2–5 min.     

Investigations on the morphology and melt crystallization of poly(L‐lactide)‐poly(ethylene glycol) diblock copolymers

Ring opening polymerization of L ‐lactide was realized in the presence of monomethoxy poly(ethylene glycol), using zinc lactate as catalyst. The resulting PLLA‐PEG diblock copolymers were characterized by using ¹H‐NMR, SEC, WAXD, and DSC. All the copolymers were semicrystalline, one or two melting peaks being detected depending on the composition. Equilibrium melting temperature (T_m⁰) of PLLA blocks was determined for three copolymers with different EO/LA molar ratios. T_m⁰ decreased with decreasing PLLA block length. A copolymer with equivalent PLLA and PEG block lengths was selected for melt crystallization studies and the resulting data were analyzed with Avrami equation. The obtained Avrami exponent is equal to 2.6 ± 0.2 in the crystallization temperature range from 80 to 100°C. In addition, the spherulite growth rate of PLLA‐PEG was analyzed by using Lauritzen‐Hoffmann theory in comparison with PLLA homopolymers. The nucleation constant was found to be 2.39 × 10⁵ K² and the free energy of folding equal to 53.8 erg/cm² in the range of 70–94°C, both higher than those of PLLA homopolymers, while the spherulite growth rate of the diblock copolymer was lower. POLYM. ENG. SCI., 2008. © 2007 Society of Plastics Engineers     

Unbiased evaluation of literature data on equilibrium melting temperature and enthalpy of fusion of perfectly syndiotactic polypropylene

The thermodynamic properties of highly syndiotactic polypropylene (PP) were reevaluated based on the data taken from the literature. The thermodynamic equilibrium melting temperature of a perfectly syndiotactic PP, which was estimated based on the Flory theory for the depression of the melting point in random copolymers, was 168.0°C. However, it was found to be 174.2°C when a linear extrapolation was attempted on a plot of the observed equilibrium melting temperature against the syndiotacticity level. The thermodynamic enthalpy of fusion of a perfect crystal of fully syndiotactic PP was estimated to be 8.7 kJ mol⁻¹, and the average value of the literature data was 7.8 kJ mol⁻¹. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1603–1609, 2001     

Thermal properties of poly(tetramethyl-p-silphenylene siloxane) and (tetramethyl-p-silphenylene siloxane-dimethyl siloxane) copolymers

Some physical properties of poly(tetramethyl-p-silphenylene siloxane) homopolymer and random block copolymers of tetramethyl-p-silphenylene siloxane-dimethyl siloxane have been determined and correlated with polymer structure. Differential scanning calorimetry (d.s.c.), differential thermal analysis (d.t.a.), density gradient column measurements and optical hot stage melting point determination and diluent techniques were used. The thermodynamic melting temperature of the homopolymer was estimated to be 160°C and its heat of fusion, ΔH_u, found to be 54.4 J/g (13 cal/g or 2710 cal/mol of monomer repeat units). Its limiting glass transition temperature, T_g, was ?20°C. T_g of the copolymer was found to vary almost monotonically with increasing dimethyl siloxane (DMS) content ranging from ?20° (0% DMS) to just above ?123°C, for pure DMS polymer. The copolymer melting temperature was found to increase as the fraction of the crystalline (hard) TMPS constituent was increased. Based upon copolymer theory and extrapolated melting point data, it was estimated that the block size of soft DMS component in the copolymer most probably consists of twelve monomer units distributed amongst TMPS sequences of varying length.     

Silicone Macroinitiator in Atom Transfer Radical Polymerization of Styrene and Vinyl Acetate: Synthesis and Characterization of Pentablock Copolymers

Poly(dimethylsiloxane) (PDMS) based pentablock copolymers has been synthesized via atom transfer radical polymerization (ATRP) of styrene (St) and vinyl acetate (VAc) telomer at 60 °C in the presence of CuCl/PMDETA as a catalyst system. Vinyl acetate telomer was prepared from controlled radical telomerization with Co(acac)₂/DMF with PDI ≈ 1.3. Poly(vinyl acetate-b-styrene-b- dimethylsiloxane- b- styrene-b-vinyl acetate) (PVAc-b-PSt-b-PDMS-b-PSt-b-PVAc) pentablock copolymers provided a method to design block copolymer with PDMS segment, allowing us for the adjustments in the flexibility by PDMS with a large effect from its softening point (T_g), or rigidity of styrene monomer and a higher melting temperature (T_m). Penta-block copolymers were characterized by FTIR, ¹HNMR, DSC, and GPC techniques. Meanwhile, the number-average molecular weights calculated from ¹HNMR spectra were in very good agreement with the theoretically calculated value. It could be concluded from the ¹HNMR and DSC spectrum that the pentablock copolymers of PVAc-b-PSt-b-PDMS-b-PSt-b-PVAc consisting of a PDMS center block and PSt and PVAc terminal blocks were synthesized.     

Synthesis and characterization of poly(ε‐caprolactone)‐b‐poly(ethylene glycol)‐b‐poly(ε‐caprolactone) triblock copolymers with dibutylmagnesium as catalyst

Two series of poly(ε‐caprolactone)‐b‐poly(ethylene glycol)‐b‐poly(ε‐caprolactone) triblock copolymers were prepared by the ring opening polymerization of ε‐caprolactone in the presence of poly(ethylene glycol) and dibutylmagnesium in 1,4‐dioxane solution at 70°C. The triblock structure and molecular weight of the copolymers were analyzed and confirmed by ¹H NMR, ¹³C NMR, FTIR, and gel permeation chromatography. The crystallization and thermal properties of the copolymers were investigated by wide‐angle X‐ray diffraction (WAXD) and differential scanning calorimetry (DSC). The results illustrated that the crystallization and melting behaviors of the copolymers were depended on the copolymer composition and the relative length of each block in copolymers. Crystallization exothermal peaks (T_c) and melting endothermic peaks (T_m) of PEG block were significantly influenced by the relative length of PCL blocks, due to the hindrance of the lateral PCL blocks. With increasing of the length of PCL blocks, the diffraction and the melting peak of PEG block disappeared gradually in the WAXD patterns and DSC curves, respectively. In contrast, the crystallization of PCL blocks was not suppressed by the middle PEG block. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Modification of vegetable oils. XIV. Properties of aceto-oleins

Summary Pure 1,2-diaceto-3-olein was prepared by acetylating mono-olein. A mixture of aceto-oleins was prepared by acetylating a mixture of mono-, di-, and trioleins derived from commercial oleic acid. Several natural oils were acetylated either by ester-ester interchange with triacetin or by glycerolysis followed by acetylation. The various products were examined for cloud and solid points, point of complete melting, and consistency. The 1,2-diaceto-3-olein, which contains 19.5% of acetyl group on a weight basis, has a melting point of −18.3°C. while the mixture of aceto-oleins, which contained 14.3% of acetyl on a weight basis, melted at −24°C. Acetylation of the natural oils raises in most instances their cloud and solid points and point of complete melting, but it also greatly increases their plasticity at lower temperatures. Aceto-compounds were used to plasticize highly hydrogenated cottonseed oil. These mixtures were prepared so that they possessed the consistency of margarine oil at room temperature. These mixtures, when compared with partially hydrogenated oil, butterfat, or a mixture of cottonseed oil and hydrogenated cottonseed oil, were softer below room temperature and firmer above room temperature. A margarine-like product containing 79% of aceto-olein and 18.5% of highly hydrogenated cottonseed oil had a practically constant consistency over the temperature range of −15° to 49°C. (5° to 120°F.). Presented at the 26th Fall Meeting of the American Oil Chemists' Society, Cincinnati, O., Oct. 20–22, 1952. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture.     

Micelle formation of polyoxyethylene-polyoxypropylene surfactants

Contradictory literature references on their micelle formation led to an investigation of block copolymers of ethylene and propylene oxides. By means of differential absorbance measurements of the dye-surfactant complex, critical micelle concentrations (CMC’s) for these polyols were determined. CMC values for surfactants with a molecular weight range of 1,100 to over 15,000 varied from 3.0 to 11.1 μmoles per liter, which are much lower than for other nonionics normally encountered. Corroborative data were obtained by the surface tension depression method. An increase in temperature below the cloud point or the addition of sodium chloride resulted in an increase in the CMC, which is not usual for many nonionics. Presented at the AOCS meeting, Houston, April, 1965.     

Stereocomplex formation in enantiomeric diblock and triblock copolymers of poly (ɛ-caprolactone) and polylactide

Summary Enantiomeric diblock and triblock copolymers from caprolactone and lactide with various compositions were synthesized using alcohol/tin octoate as initiator system. Stereocomplexes were formed between pairs of enantiomeric block copolymers and their thermal properties examined. The melting temperatures of the crystalline PCL and PLA phases are depending on the composition of block copolymers. A raise of approximately 55°C of the temperature of PLA phase is observed in the blends as a consequence of stereocomplex formation as well in diblock as in triblock copolymers. Received: 31 July 2000/Revised version: 11 October 2000/Accepted: 26 October 2000     

Studies on crystallization kinetics of nylon 6-polyoxypropylene-nylon 6 copolymers

The crystllization kinetics of anionic-prepared nylon6-poly(oxypropylene) 1000-nylon 6 (NPN) block copolymers containing 1.20 to 8.76 wt% poly(oxypropylene)(POP) were studied. The thermograms of isothermal and nonisothermal differential scanning calorimetry of NPN block copolymers obtained were used for the study. The Avrami equation was used to analyze the isothermal crystallization of NPN nylon block copolymers. The Avrami exponent n obtained in the temperature range of 180 to 200 °C was 2.0 to 2.5. It was not similar to that for nylon 6 reported in literature. The activation energies of crystallization for the nylon block copolymers were smaller than that of nylon 6, and showed a minimum with POP content. The equilibrium melting point increased as the POP content decreased. For the nylon block copolymers with lower POP content, the slopes of T_c vs. T_m plots were higher than the values reported elsewhere. The Ozawa plot was used to analyze the data of nonisothermal crystallization. The obvious curvature in the plot indicated that the Ozawa model could not fit our system well, and there was an abrupt change of the slope in the Ozawa plot at a critical cooling rate.     

Thermal and mechanical properties of tetramethyl-p-silphenylenesiloxanedimethylsiloxane block copolymer

Several kinds of $\text{tetramethyl}\text{-p-}\text{silphenylenesiloxane}\text{dimethylsiloxane}$ (TMPS/DMS) block copolymers having various compositions and segment lengths were synthesized by the polycondensation of p-bis(dimethylhydroxysilyl)benzene and silanol-terminated DMS oligomers of different degrees of polymerization, which were 19, 43, 300, 380 and 540 DMS monomer units. The compositions ranged from TMPS/DMS wt% ratio of 100/0 to 24/76. For these copolymers, differential scanning calorimetry was carried out to determine the melting temperatures, the heat of fusion and the crystallinities. The melting temperatures and the crystallinities of the block copolymers were found to decrease as DMS contents were increased from 11 to 76 wt% and as DMS segment lengths were decreased from 540 to 19. The crystalline parts of TMPS segment would be increased according to the long TMPS sequences which were obtained from the copolymerizations by using DMS oligomers with high degrees of polymerization such as 300, 380 and 540. The stress-strain behaviour and the dynamic mechanical behaviour were also investigated for these copolymers. The tensile strength was decreased and the percentage elongation was increased with increasing DMS content and segment length. In the case of the copolymers for which the DMS contents remained constant at 26 wt%, two major transitions were observed at around ?120° and ?10°C for the copolymers having DMS block sizes of 300, 380 and 540. But for the copolymers having those of 19 and 43 the two transitions merged together at ?50°C. The relaxations at ?120°C corresponding to the glass transition of DMS component and those at ?10°C are due to the amorphous TMPS phase which is separated from the DMS phase owing to the longer sequence length. The relaxation observed around ?50°C is due to the shorter sequence length of TMPS in the main chain plus the presence of more flexible DMS component. It may be suggested that the long sequence length causes large domains of hard and soft phases which consist of TMPS and DMS blocks respectively.     

Characterization of poly(3,3-bisethoxymethyl oxetane) and poly(3,3-bisazidomethyl oxetane) and their block copolymers

The homopolymers, poly(3,3-bisethoxymethyl oxetane) (polyBEMO), poly(3,3-bisazidomethyl oxetane) (polyBAMO), and triblock copolymers based on these homopolymers and a statistical copolymer center block composed of BAMO and 3-azidomethyl-3-methyl oxetane AMMO were synthesized and characterized by differential scanning calorimetry, modulus-temperature, optical microscopy, membrane osmometry, and solution and melt viscosity. The values of K and a for the Mark-Houwink equation were found to be 7.29 × 10^?3 mL/g and 0.80, respectively, for polyBEMO at 25°C using number-average molecular weights. Glass transition temperatures were in the range ?25 to ?40°C and melting temperatures were between 65 and 90°C for all polymers. The melting temperature was found to increase as expected with molecular weight. Melt viscosities of triblock copolymers with polyBAMO end blocks were at least an order of magnitude lower than those with polyBEMO end blocks and clear optically, suggesting that the polyBAMO-based triblock copolymers formed one phase in the melt, while the polyBEMO-based triblock materials (milk white) phase separated. The addition of filler raised the melt viscosity to a level between that predicted by the Guth-Smallwood and the Mooney equations.