Segmented copolymers of uniform tetra-amide units and poly(phenylene oxide): 1. Synthesis and thermal-mechanical properties

Copolymers of telechelic poly(2,6-dimethyl-1,4-phenylene ether) segments with terephthalic methyl ester endgroups (PPE-2T), 13 wt% crystallisable tetra-amide segments of uniform length (two-and-a-half repeating unit of nylon-6,T) and dodecanediol (C12) as an extender were made via a polycondensation reaction in the melt. The maximum reaction temperature was 280 °C. The PPE-2T/C12/T6T6T copolymers are semi-crystalline materials with a T_g around 170 °C, a melting temperature of 264-270 °C and a T_g/T_m ratio of above 0.8. The modulus is high up to the T_g, which is not achievable in a blend of PPE and polyamide. The most probable morphology is that of long crystalline nano-ribbons in the amorphous matrix. The materials are slightly transparent and have good solvent resistance, low water absorption and good processability.     

Segmented copolymers of uniform tetra-amide units and poly(phenylene oxide). Part 4. Influence of the extender

Copolymers of telechelic poly(2,6-dimethyl-1,4-phenylene ether) (PPE) segments, uniform crystallisable tetra-amide units (T6T6T, 6-15 wt%) and different diols (C2-C36, polytetramethylene oxide) as an extender were synthesised. The telechelic PPE segment was end-functionalised with terephthalic ester groups and had a molecular weight of 3100 g/mol. The coupling between the PPE segment and the T6T6T unit was made with diols. The influence of the length and flexibility of the diol-extender and the concentration of the T6T6T units were studied on the thermal (DSC) and thermal-mechanical (DMA) properties of the copolymers. A crystalline T6T6T phase in the copolymers was evident from 9 wt% onwards. The length of diol extender had an effect on the glass transition temperature of the PPE phase, the crystallinity of the T6T6T segments and modulus above the glass transition temperature. With ethylene glycol the T_g of the copolymer was high but the crystallinity of the T6T6T rather low. With dodecanediol or hexanediol as an extender the T_gs of the PPE phase were somewhat lower, but the crystallinities of the T6T6T segments higher. With C36 and polytetramethylene oxide diols, the T_g were strongly decreased and broad and the modulus above the glass transition temperature not so high.     

Segmented copolymers of uniform tetra-amide units and poly(phenylene oxide): 3. Influence of tetra-amide content

Copolymers of telechelic poly(2,6-dimethyl-1,4-phenylene ether) (PPE) segments and crystallisable T6T6T units (two-and-a-half repeating unit of nylon-6,T) of uniform length were synthesised. The influence of the T6T6T content (0-20 wt%), the purity of the telechelic PPE and uniformity of the T6T6T segment length on the thermal mechanical (DMA) properties were studied. The polymers are semi-crystalline materials with a high T_g/T_m ratio of above 0.8. Increasing the T6T6T content (0-20 wt%) has little effect on the T_g transition region, but the modulus of the rubbery plateau increases strongly (0-13 MPa) and the flow temperature increases slightly as well (260-275 °C). The materials are transparent when the T6T6T content is below 10 wt%. Surprisingly copolymers based on telechelic PPE of narrow molecular weight distribution had lower crystallinity. The uniformity of the T6T6T segment length seems to have little effect on the properties of the copolymer, as long as at least 70% of the units are of one length.     

Segmented blockcopolymers with uniform amide segments

Segmented blockcopolymers based on poly(tetramethylene oxide) (PTMO) soft segments and uniform crystallisable tetra-amide segments (TxTxT) are made via polycondensation. The PTMO soft segments, with a molecular weight of 1000 g/mol, are extended with terephthalic groups to a molecular weight of 6000 g/mol. The crystallisable segment is uniform of length and is based on a tetra-amide with terephthalamide groups. The length of the aliphatic diamine (x) in the tetra-amide segment is varied from x=2 to 8. The thermal properties of the blockcopolymers were studied with dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). Due to the use of uniform TxTxT segments a fast and almost complete crystallization of the hard segments is obtained. The melting temperature of the blockpolymers increases with decreasing diamine length and the well-known odd-even effect is observed. The elastic behavior of the blockcopolymer was studied by compression set. All the blockcopolymers had a low compression set and were highly elastic.     

Segmented copolymers of uniform tetra‐amide units and poly(phenylene oxide) by direct coupling

Segmented copolymers with telechelic poly(2,6‐dimethyl‐1,4‐phenylene ether) (PPE) segments and crystallizable bisester tetra‐amide units (two‐and‐a‐half repeating unit of nylon‐6,T) were studied. The copolymers were synthesized by reacting bifunctional PPE with hydroxylic end groups with an average molecular weight of 3500 g/mol and bisester tetra‐amide units via an ester polycondensation reaction. The bisester tetra‐amide units had phenolic ester groups. By replacing part of the bisester tetra‐amide units with diphenyl terephthalate units (DPT), the concentration of tetra‐amide units in the copolymer was varied from 0 to 11 wt%. Polymers were also prepared from bifunctional PPE, DPT, and a diaminediamide (6T6‐diamine). The thermal and thermal mechanical properties were studied by DSC and DMA and compared with a copolymer with flexible spacer groups between the PPE and the T6T6T. The copolymers had a high T_g of 180–200°C and a melting temperature that increased with amide content of 220–265°C. The melting temperature was sharp with monodisperse amide segments. The T_m – T_c was 39°C, which suggests a fast, but not very fast, crystallization. The crystallinity of the amide was ～ 20%. The copolymers are semicrystalline materials with a high T_g and a high T_g/T_m ratio (> 0.8). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 512–518, 2007     

Influence of alternating sequential fraction on the melting and glass transition temperatures of ethylene-tetrafluoroethylene copolymer

The melting (T_m) and glass transition (T_g) temperatures of a series of ethylene (E)-tetrafluoroethylene (TFE) copolymer (ETFE) have been found to show unique dependence on the TFE content with the minimal and maximal points. These behaviors have been interpreted successfully on the basis of the degree of alternation of E and TFE monomeric units along the skeletal chain. The melting point of a perfectly alternating copolymer is estimated to be 295 °C on the basis of the dependence of T_m using a modified Flory’s equation. The corresponding T_g was estimated as 145 °C by applying a modified Gibbs-Damnation’s equation.     

Ionene segmented block copolymers containing imidazolium cations: Structure-property relationships as a function of hard segment content

Imidazolium ionene segmented block copolymers were synthesized from 1,1′-(1,4-butanediyl)bis(imidazole) and 1,12-dibromododecane hard segments and 2000 g/mol PTMO dibromide soft segments. The polymeric structures were confirmed using ¹H NMR spectroscopy, and resonances associated with methylene spacers from 1,12-dibromododecane became more apparent as the hard segment content increased. TGA revealed thermal stabilities ≥250 °C for all imidazolium ionene segmented block copolymers. These ionene segmented block copolymers containing imidazolium cations showed evidence of microphase separation when the hard segment was 6-38 wt%. The thermal transitions found by DSC and DMA analysis found that the T_g and T_m of the PTMO segments were comparable to PTMO polymers, namely approximately −80 °C and 22 °C, respectively. In the absence of PTMO soft segments the T_g increased to 27 °C The crystallinity of the PTMO segments was further evidence of microphase separation and was particularly evident at 6, 9 and 20 wt% hard segment, as indicated in X-ray scattering. The periodicity of the microphase separation was well-defined at 20 and 38 wt% hard segment and found to be approximately 10.5 and 13.0 nm, respectively, for these ionenes wherein the PTMO soft segment is 2000 g/mol. Finally, the 38 and 100 wt% hard segment ionenes exhibited scattering from correlations within the hard segment on a length scale of approximately 2-2.3 nm. These new materials present structure on a variety of length scales and thereby provide various routes to controlling mechanical and transport properties.     

Synthesis and characterisation of uniform bisester tetra-amide segments

The synthesis and characterisation of a new type of high melting and fast crystallising amide units that can be used for copolymerisation have been studied. These bisester tetra-amide or TxTxT-dimethyl segments (T is a terephthalic unit and x=(CH₂)_n (n=2-8)) can be synthesised in a two-step reaction. These segments are based on two-and-a-half repeating units of nylon-x,T. The structure of the products was confirmed by NMR. The melting temperature and enthalpy of xTx-diamine and TxTxT-dimethyl and -diphenyl were determined by DSC. The melting temperature increases with decreasing length of x. For odd x the melting temperature is lower. The melting temperature and enthalpy of the products decrease with decreasing purity.     

Influence of copolymerisation on fracture behaviour of aliphatic polyketones

High strain rate tensile impact properties of aliphatic polyketone terpolymers were investigated and related to the polymer chain structure. Aliphatic polyketones were used as a model system, by changing the termonomer content and type. Aliphatic polyketone is a perfectly alternating copolymer and the structure was changed with the addition of a few mol% of termonomer: propylene, hexylene and dodecene. Studied were the thermal properties with DSC and DMTA, tensile behaviour, notched tensile impact behaviour, notched Izod properties and the temperature development during deformation. The perfectly alternating copolymer had a melting point of 257 °C, a T_g at 15 °C, a high crystallinity (48%), a high yield stress (77 MPa) and yield strain (31%) but a relatively low fracture strain (85%) and an impact strength (notched Izod) of 13 kJ/m². Increasing the propylene content to 6%, lowered the melting temperature to 224 °C, without changing the T_g. The modulus and yield stress were lowered but the impact strength improved. Increasing the length of the termonomer while keeping the T_m at 224 °C lowered the T_g, the modulus, the yield stress but strongly improved the impact resistance. The longer termonomers, with a lower yield stress, reduced the necking behaviour. The temperature increase in front of the notch was about 85 °C. By adding termonomers to aliphatic ketones, the notched impact behaviour improved significantly at the cost of modulus and yield stress.     

Structure and properties of highly stereoregular isotactic poly(methyl methacrylate) and syndiotactic poly(methyl methacrylate) blends treated with supercritical CO2

The structure and properties of highly stereoregular isotactic poly(methyl methacrylate) (it-PMMA) and syndiotactic poly(methyl methacrylate) (st-PMMA) blends with crystalline stereocomplex formed by supercritical CO₂ treatment at temperatures ranging from 35 to 130 °C were investigated by means of differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), and dynamic mechanical analysis (DMA) measurements. The melting temperature, T_m, and the heat of fusion, ΔH_m, had maximum values at about 200 °C and 25 J/g, respectively. The degree of crystallinity evaluated by WAXD ranged in value from 32 to 38%. The fringed-micellar stereocomplex crystallites were formed in case of treatment temperatures below 90 °C, and the orderliness perpendicular to the helix axis of the fringed-micellar crystallites was considered to be increased with increasing treatment temperature. In case of treatment temperature of 130 °C, the fringed-micellar crystallites and the lamellar crystallites with high orderliness parallel to the helix axis coupled with the perpendicular orderliness were formed, and the respective double endothermic peaks, T_m¹ and T_m³, were observed in DSC due to the melting of the two kinds of stereocomplex crystallites. The it-PMMA/st-PMMA blends containing the fringed-micellar crystallites maintained high values of storage modulus, E′, up to higher temperature compared with the amorphous blends. The E′ of the blend treated with CO₂ at 130 °C decreased twice at temperatures corresponding to T_m¹ and T_m³.     

The polydispersity of ethylene sequence in metallocene ethylene/α-olefin copolymers III: crystallization and melting behavior of short ethylene sequence

Crystallization and melting behavior of short ethylene sequence of metallocene ethylene/α-olefin copolymer with high comonomer content have been studied by standard DSC and modulated-temperature differential scanning calorimetry (M-TDSC) technique. In addition to high temperature endotherm around 120°C, a low temperature endotherm is observed at lower temperatures (40-80°C), depending on time and temperature of isothermal crystallization. The peak position of the low temperature endotherm T_m^low varies linearly with the logarithm of crystallization time and the slope, D, decreases with increasing crystallization temperature T_c. The T_m^low also depends on the thermal history before the crystallization at T_c, and an extrapolation of T_m^low (30.6°C) to a few seconds has been obtained after two step isothermal crystallization before the crystallization at 30°C. The T_m^low is nearly equal to T_c, and it indicates that the initial crystallization at low temperature is nearly reversible. Direct evidence of conformational entropy change of secondary crystallization has been obtained by using M-TDSC technique. Both the M-TDSC result and the activation energy analysis of temperature dependence suggest that crystal perfection process and conformational entropy decreasing in residual amorphous co-exist during secondary crystallization.     

Synthesis and characterisation of copolyesters from poly(ethylene terephthalate) and poly(hexamethylene terephthalate)

Copolyesters containing poly(ethylene terephthalate) and poly(hexamethylene terephthalate) (PHT) were prepared by a melt condensation reaction. The copolymers were characterised by infrared spectroscopy and intrinsic viscosity measurements. The density of the copolyesters decreased with increasing percentage of PHT segments in the backbone. Glass transition temperatures (T_g). melting points (T_m) and crystallisation temperatures (T_c) were determined by differential scanning calorimetry. An increase in the percentage of PHT resulted in decrease in T_g, T_m and T_c. The as-prepared copolyesters were crystalline in nature and no exotherm indicative of cold crystallisation was observed. The relative thermal stability of the polymers was evaluated by dynamic thermogravimetry in a nitrogen atmosphere. An increase in percentage of PHT resulted in a decrease in initial decomposition temperature. The rate of crystallisation of the copolymers was studied by small angle light scattering. An increase in percentage of PHT resulted in an increase in the rate of crystallisation.     

Reversible thickness control of polymer thin films containing photoreactive coumarin derivative units

The reversible control of the thickness of polymer thin films was investigated using (meth)acrylic polymers containing photoreactive coumarin derivative units in the side chain. Coumarin derivative units underwent dimerization and the reverse-dimerization by photoirradiation and were used as a reversible cross-linking point. The homopolymer of 7-methacryloyloxy-4-methylcoumarin (T_g = 194 °C) did not cause changes in film thickness after photoreactions. The homopolymer of 7-(2′-acryloyloxyethoxy)-4-methylcoumarin (AEMC) (T_g = 89 °C) decreased 19% of film thickness by photodimerization and 73% of the decreased thickness was recovered after the reverse-dimerization and the subsequent thermal annealing at 130 °C. The reverse-dimerization of the copolymer of AEMC and n-butyl acrylate (AEMC content = 19 mol%, T_g = 11 °C) resulted in 53% of recovery from the decreased film thickness without annealing. The mobility of polymer main-chain was revealed to be essential factor to change film thickness by photoreactions. Photodimerization of coumarin derivative units in low glass transition temperature (T_g) tended to proceed faster than in high T_g polymers and resulted in larger decrease in film thickness.     

Isothermal crystallization kinetics of nylon 6, blends and copolymers using simultaneous small and wide-angle X-ray measurements

Crystallization behavior in a number of blends and copolymers of nylons (polyamides) was investigated using time-resolved X-ray scattering data obtained simultaneously in the small- and wide-angle regimes. The following samples studied were: nylon 6 homopolymers (N6) of different molecular weights, copolymers of N6 and nylon 6,6 (N6/66), and blends of these with an amorphous nylon (N6I/T), which is a 70:30 random copolymer of poly(hexamethylene isophthalamide) and poly(hexamethylene terephthalamide). Addition of comonomers and blending with the N6I/T reduces the crystallinity of N6. Isothermal crystallization data obtained at several temperatures showed the expected faster crystallization kinetics at higher degrees of supercooling. Comonomer units in the N6 backbone reduce the rate of crystallization. N6I/T affects the crystallization (lamellar growth) behavior of N6/N66: the rate is higher at temperatures above the T_g of N6I/T (120 °C) where the crystallization is nucleation-driven, and lower below the T_g of N6I/T where it is growth-driven. Lamellar spacing decreases with an increase in the degree of supercooling, and this decrease is smaller in the blends than in the homopolymer. Larger lamellar spacing in N6I/T blends is due not to the insertion of N6I/T segments into the interlamellar regions but to an increase in the lamellar thickness. Blending seems to change the morphology by affecting the crystallization behavior rather than by thermodynamic phase separation. Residual monomers, which act as plasticizers, dramatically reduce the crystallization rate, whereas shear or similar mechanical history of the resin considerably accelerate the crystallization rate.     

Soft matter electrolytes based on polymethylmetacrylate dispersions in lithium bis(trifluoromethanesulfonyl)imide/1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquids

Ion transport in a polymer-ionic liquid (IL) soft matter composite electrolyte is discussed here in detail in the context of polymer-ionic liquid interaction and glass transition temperature. The dispersion of polymethylmetacrylate (PMMA) in 1-butyl-3-methylimidazolium hexafluorophosphate (BMIPF₆) and 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMITFSI) resulted in transparent composite electrolytes with a “jelly-like” consistency. The composite ionic conductivity measured over the range −30 °C to 60 °C was always lower than that of the neat BMITFSI/BMIPF₆ and LiTFSI-BMITFSI/LiTFSI-BMIPF₆ electrolytes but still very high (>1 mS/cm at 25 °C up to 50 wt% PMMA). While addition of LiTFSI to IL does not influence the glass T_g and T_m melting temperature significantly, dispersion of PMMA (especially at higher contents) resulted in increase in T_g and disappearance of T_m. In general, the profile of temperature-dependent ionic conductivity could be fitted to Vogel-Tamman-Fulcher (VTF) suggesting a solvent assisted ion transport. However, for higher PMMA concentration sharp demarcation of temperature regimes between thermally activated and solvent assisted ion transport were observed with the glass transition temperature acting as the reference point for transformation from one form of transport mechanism to the other. Because of the beneficial physico-chemical properties and interesting ion transport mechanism, we envisage the present soft matter electrolytes to be promising for application in electrochromic devices.     

High thermal stable thermoplastic-thermosetting polyimide film by use of asymmetric dianhydride (a-BPDA)

In order to obtain thermoplastic (before curing) and thermosetting (after curing) polyimides with high T_g for adhesive film, we prepared novel polyimides having phenylethynyl group in the side chain (44% of concentration of curing group) from asymmetric 2,3,3′,4′-biphenyltetracarboxylic dianhydride (a-BPDA), 3,4′-oxydianiline (3,4′-ODA) or 1,3-bis(4-aminophenoxy)benzene (1,3,4-APB) or 1,3-bis(3-aminophenoxy)benzene (1,3,3-APB), and 2,4-diamino-1-(4-phenylethynylphenoxy)benzene (mPDAp). Among three kinds of polymer, uncured polyimide of a-BPDA/1,3,4-APB; mPDAp had rather high T_g (265 °C, DMA) and thermoplasticity (E′ drop>10³ at T_g). After curing reaction of phenylethynyl group, the T_g of the polyimide was increased dramatically (364 °C, DMA). The polyimide derived from 1,3,4-APB having less concentration of curing group (20%) was also prepared to improve further film flexibility and toughness.     

Thermal, spectroscopy, and morphological studies on polymorphic crystals in poly(heptamethylene terephthalate)

Polymorphism and its influential factors in poly(heptamethylene terephthalate) (PHepT) were probed using differential scanning calorimetry (DSC), Fourier-transform infrared (FTIR) spectroscopy, and wide angle X-ray diffraction (WAXD). PHepT exhibits two crystal types (α and β) upon crystallization at various isothermal melt-crystallization temperatures (T_cs) by quenching from different T_maxs (maximum temperature above T_m for melting the original crystals). Melt-crystallized PHepT with either initial α- or β-crystal by quenching from T_max lower than 110 °C leads to higher fractions of α-crystal, but crystallization from T_max higher than 140 °C leads to higher fractions of β-crystal. In addition to T_max, polymorphism in PHepT is also influenced by crystallization temperature (T_c = 25-75 °C). When PHepT is melt-crystallized from a high T_max = 150 °C (completely isotropic melt), it shows solely β crystal for higher T_c, and solely the α-crystal for T_c < 25 °C; in-between T_c = 25 and 35 °C, mixed fractions of both α- and β-crystals. However, by contrast, when PHepT is melt-crystallized from a lower T_max = 110 °C, it shows α-crystal only at all T_cs, high or low.     

Polyether‐amide segmented copolymers based on ethylene terephthalamide units of uniform length

Segmented copolymers were synthesized using the crystallizable bisesterdiamide segment (N,N′‐bis(p‐carbomethoxybenzoyl)ethanediamine) T2T‐dimethyl (a one‐and‐a‐half repeating unit of nylon 2,T) and poly(tetramethyleneoxide) segments. Poly(tetramethyleneoxide) (PTMO) is amorphous and has a low T_g. The segment length was varied from 650 to 2800 g/mol by extending PTMO₆₅₀ using dimethyl isophthalate. The polymers were synthesized in the melt, and test samples were prepared by injection molding. The melting behavior, as well as the torsion modulus spectrum as a function of temperature, were studied using DSC and DMA, respectively. The T2T‐PTMO polymers were found to have sharp glass (T_g) and flow transitions (T_fl), and the modulus at the rubbery plateau appeared to be virtually temperature independent. The T_g value was found to be independent of the diamide concentration, thus indicating that the T2T segments were fully crystallized. The T_fl was found to decrease with increasing soft segment length; this was ascribed to a “solvent” effect of the amorphous phase of the crystalline T2T units. The difference between the melting and crystallization temperatures was found to be low, thus suggesting that on cooling, there is a high rate of crystallization. When ethanediol was added as a T2T segment extender, amide‐ester‐amide segments were introduced. These amide‐ester‐amide segments form a separate lamellar phase with a much higher melting temperature (>300°C). It was found that the crystallization rate of the T2T units was enhanced by the presence of the amide‐ester‐amide segments, indicating that upon cooling, the crystallized amide‐ester‐amide segments form the nucleation sites for the nonextended T2T segments. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1173–1180, 2001     

Real-time investigation of crystallization in nylon 6-clay nano-composite probed by infrared spectroscopy

Via time-resolved FTIR, we examined the real-time investigation of the structural change in molecular chain of nylon 6 during crystallization of neat nylon 6 and the corresponding nano-composite (N6C3.7) having fully exfoliated structure. The neat nylon 6 predominantly formed α-phase in the crystallization temperature (T_c) range of 155-195 °C. For N6C3.7 crystallization at low T_c range of 150-168 °C, where the network structure formed by the dispersed clay particles still affected chain folding of nylon 6, the formation of the γ-phase was dominant. The crystallization took place so rapidly (less than 1 s) without induction time of crystallization. At high T_c range (=177-191 °C), the stable growth of the α-phase crystal coexisting with γ-phase occurred in N6C3.7 crystallization. The growth mechanism in the subsequent crystallization processes (amides IIIα and IIIγ) was virtually the same in both N6C3.7 and neat nylon 6.     

Isotactic polymerization of propylene with zirconocene catalysts in the presence of a lewis base

Summary Polymerization of propylene was carried out at 0°C in the presence of methyl methacrylate(MMA) or ethyl benzoate(EB) using rac-Et(Ind)₂ZrMe₂ or rac-Me₂Si(Ind)₂ZrMe₂/Ph₃CB(C₆F₅)₄ as catalyst, which resulted in highly isotactic poly(propylene) with [mmmm]>98%, T_m=160–161°C and very few 1,3- or 2,1 regioirregular units. With the use of an achiral zirconocene Cp₂ZrMe₂, a polymer with T_m=139°C was resulted as well. Base on these experimental fact that the zirconocene can form a C₁-symmetrical complex with a Lewis base.