Side-chain crystallinity. I. Heats of fusion and melting transitions on selected homopolymers having long side chains

Heats of fusion, melting transitions, and the derived entropies of fusion were obtained by differential scanning calorimetry for examples from three homologous series of homopolymers having long side chains. Homopolymers having side-chain lengths between 12 and 22 carbon atoms were chosen from the poly(n-alkyl acrylates), the poly(N-n-alkyl-acrylamides) and the poly(vinyl esters). The data demonstrated that only the outer paraffinic methylene groups were present in the crystal lattice. This was concluded because phase diagrams obtained for mixtures of structurally different monomers and homopolymers, as well as for selected copolymers, showed only isomorphism in the polymeric examples. In addition, scanning curves, reflecting the distribution of crystallite sizes, became narrower as the side chains became longer. The critical chain length required to maintain a stable nucleus in the bulk homopolymers was a constant value for each homologous series. It varied between 9 to 12 carbon atoms. When heats of fusion were determined in the presence of methanol, main-chain restraints were freed, thus permitting more methylene groups to enter the crystal lattice. Hence, the heats of fusion, the crystallinity, and melting points increased above that of the bulk state. The magnitude of the contribution to the heats of fusion by each methylene group indicated that the hexagonal paraffin crystal modification prevailed in these homopolymers, in agreement with x-ray data from the literature.     

Side-chain crystallinity. IV. Mechanical properties and transition temperatures of copolymers of methyl methacrylate with higher n-alkyl acrylates and N-n-alkylacrylamides

Mechanical properties were correlated with glass transition temperatures for a series of random copolymers of methyl methacrylate with comonomers selected from the higher n-alkyl acrylates and N-n-alkylacrylamides. The plasticizing comonomers were the n-butyl, 2-ethylhexyl, n-octadecyl, and oleyl acrylates, and the N-n-butyl-, N-n-octyl-, N-n-octadecyl-, and N-oleylacrylamides. The complete range of compositions was investigated. However, the bulk of the data was obtained on compositions in the glassy region below the onset of the vitreous transition. In this region it was found that the decrease in tensile and flexural moduli and strengths with increase in internal plasticizer for all of the systems was directly proportional to the decrease in T_g. It was concluded that the additive contribution to the free volume made by each side-chain methylene group was alone responsible for the magnitude of the rate of change of properties. However, polar contributions of the amide group to stiffening the main chain exceeded those of the ester, so that the amides were less efficient plasticizers. An empirical equation was derived which described, with fair accuracy, the decrease in the mechanical parameters with composition for the amorphous copolymers. It was reasonably successful in predicting properties even into the composition range where the ambient testing temperature corresponded to or exceeded the transition temperature. In this transition region an accelerated decrease in the magnitude of the physical properties was observed. All samples exhibited brittle fracture except those tested in the transition region. Here the strain was largely irrecoverable flow. Side-chain crystallinity did not interfere significantly with the mechanical properties because moduli and strengths had already decayed to small values near the compositions where crystallinity commenced. Non-random copolymers of vinyl stearate and methyl methacrylate showed no internal plasticization, apparently because of macrophase aggregation.     

Side-chain crystallinity. III. Influence of side-chain crystallinity on the glass transition temperatures of selected copolymers incorporating n-octadecyl acrylate or vinyl stearate

The influence of side-chain crystallinity on the glass transition temperatures of selected copolymers was investigated. The copolymers were selected, in part, from those whose crystallinity was treated in the preceding paper. These included the lower amorphous acrylate esters, such as methyl, ethyl, n-butyl, and 2-ethylhexyl acrylates, together with methyl methacrylate and acrylonitrile, each copolymerized with n-octadecyl acrylate over the range of composition. The decline in the glass transition temperature was linear with increasing weight fraction of n-octadecyl acrylate for all systems in the composition range where the copolymers were essentially amorphous. The extrapolated T_g for the amorphous state of poly(n-octadecyl acrylate), and for amorphous poly(oleyl acrylate), was close to ?111°C. This coincided with a value previously obtained by an extrapolation of data on homologs. Beyond a critical fraction of octadecyl acrylate (0.3 to 0.5), developing side-chain crystallinity in n-octadecyl acrylate raised the glass temperature steadily for all systems, up to a value of 17-C, obtained for the crystalline homopolymer. Crystallinity did not develop in stiff copolymers until T_g was about 30°C below the melting point of the most perfect crystals. In compositionally heterogeneous copolymers incorporating vinyl stearate, blocks of crystalline units appeared to be dispersed in a glassy matrix of amorphous co-units. An empirical equation was derived which fitted the experimental data for random copolymers, over all composition ranges, with fair accuracy.     

Liquid crystal polymers. 15. Synthesis and liquid crystalline properties of alkyl-substituted polyesters

Alkyl substitution in a series of main chain, liquid crystal polyesters strongly depressed their glass temperatures, melting points, clearing points, and mesophase thermal stabilities. Polymers with pendant n-alkyl substituents eight carbon atoms or longer did not form a liquid crystal phase.     

Mechanical properties and transition temperatures for copolymers of N-n-alkylacrylamides and acrylonitrile

Random copolymers of N-n-butyl-, N-n-octyl-, or N-n-octadecylacrylamide with acrylonitrile were prepared in tert-butanol at 60°C. to test the effect of amide homologs as internal plasticizers. At room temperature under high deformations all samples showed brittle failure; at 100°C. flexible and resilient copolymers were obtained. At low deformations, torsional stiffness values T_f followed the equations of Wood, Fox, and Dimarzio and Gibbs, the latter two modified by use of mole fraction instead of weight fraction. Mole fraction appeared to function better than weight fraction for these special cases where w_i > 2m_i and where modulus-temperature curves were broad. Because literature values for the glass (or brittle) temperatures of homologs of poly-n-alkyl acrylates, methacrylates, n-alkyl styrenes and alkenes, and estimated values for poly-N-n-alkylacrylamides, plotted as a function of the logarithm of the number of single bonds in repeat units, extrapolate to an average value of ?111°C. at a chain length of eighteen carbon atoms, and because side-chain melting points of linear eighteen carbon side-chain homologs appear to have a common value of 48–50°C. regardless of structure, it was concluded that similar glass and melting transitions are obtained when the side chain reaches eighteen carbon atoms in any series of homologs. Transitions for longer side-chain lengths then approach the limit of a polyethylene graft, where T_g is ?81°C. and T_m is 137°C.     

Structure of crystalline polymers with unbranched long side chains

The structure and thermodynamic properties of atactic and isotactic acrylic and methacrylic polymers containing 16–18 carbon atoms in the n-aliphatic side chains, and of copolymers of hexadecyl acrylate with isopropyl acrylate were studied by means of x-ray and differential thermal analysis. The crystallization of branched acrylic and methacrylic polymers and of acrylic copolymers proceeds in the form of a hexagonal crystal, regardless of the configuration of the backbone chain. Methods of ordering branched macromolecules are proposed, and the melting points, heats and entropies of fusion determined. The role of flexibility of the backbone chains in ordering and the crystallization processes was determined. In the case of poly(n-alkyl acrylates) the backbone chain is involved in the crystalline lattice; this is not the case in methacrylates and copolymers of hexadecyl acrylate with isopropyl acrylate. Some similarity was assumed between the structure of biopolymers and synthetic branched polymers.     

Rigid backbone polymers. X. Transitions in bulk polyisocyanates

Data obtained by hot-stage cross-polarized light microscopy and thermogravimetric analysis were used to plot a transition map for the poly(n-alkylisocyanate) homologous family. Most members had a low-temperature transition (or relaxation). The middle members of the family, with side-chain length of 4 ≤ n < 13 carbon atoms, exhibit a mesomorphic range of temperatures. Members with sidechains of n ≥ 13 in length, go directly from the low-temperature transition to the melting point without passage through a liquid crystalline state. A transition map for two homopolymers and a series of their copolymers, poly[x mol% n-butyl + (100-x)mol% p-anisole-3-propyl]isocyanate, was also prepared. The range of mesomorphicity as a function of composition and temperature is clearly indicated.     

Poly(γ-alkyl glutamates). I

Good yields of some crystalline γ-alkyl esters of L -glutamic acid were obtained by carrying out the esterfication with a small (20–50 mole-%) excess of alcohol in aqueous hydrochloric acid or 60–80% sulfuric acid followed by neutralization with an alkaline solution. This new method made it possible to synthesize various γ-alkyl L -glutamates, including those higher than ethyl, and consequently, various poly(γ-alkyl L -glutamates) such as methyl, ethyl, n-propyl, n-butyl, isobutyl, and isoamyl. The conformation of these poly-L -glutamates in the solid state was determined by the infrared absorption method. The molecular motions of the polymers of γ-methyl, -ethyl, -n-propyl, -n-butyl, and-isoamyl L -glutamates and poly(γ-methyl-D -glutamate) in the solid state were studied by NMR, and dielectric and mechanical measurements. At temperatures up to 400°K., the NMR spectra of poly(γ-methyl D -glutamate) can be explained only by rotational motion of the side chain. Also, from NMR results, rotational motion of C?O groups in the side chain of poly(γ-methyl D -glutamate) is expected near room temperature, and such a motion was examined by dielectric measurements. Rotation of C?O groups in the side chains of polymers of γ-methyl, γ-ethyl, γ-n-propyl, γ-n-butyl, and γ-isoamyl L -glutamate was also observed near room temperature by dielectric measurements in the frequency range from 10² to 10⁶ cps. Activation energies obtained by dielectric and mechanical measurements were similar to those for the side chain motions of the corresponding esters of poly(methacrylic acid). Although it has been noted that the molecular motion of poly(γ-benzyl L -glutamate) in the solid state at room temperature may be related to the motion of its back bone, the molecular motion in these poly-L -glutamates at these temperatures can be explained only in terms of side-chain rotation.     

Enthalpy relaxation in polymethyl(α-n-alkyl)acrylates: Effect of length of alkyl chain

In this work, we have investigated by DSC the structural relaxation of amorphous polymethyl(α-n-alkyl)acrylates in which it is possible to change the length of the alkyl chain. We have evaluated the Narayanaswamy parameter, x, which controls the relative contribution of temperature and of structure to the relaxation time, the apparent activation energy, Δh*, and the nonexponentiality parameter, β, of the stretched exponential response function. The results suggest that x increases while Δh* decreases and β remains constant as the length of the side chain increases. This allows us to comment on the effect of chemical modification on the relaxation kinetics. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 583–593, 1998     

Head-to-head vinyl polymers. V. Preparation and characterization of alternating head-to-head copolymers of alkyl acrylates with alkyl methacrylates

Alternating head-to-head (h-h) copolymers of methyl or n-butyl acrylates with the corresponding methacrylates were synthesized by alternating copolymerization of ethylene with citraconic anhydride, followed by esterification and Characterization. The respective equimolar (1:) head-to-tail (h-t) copolymers were also prepared by conventional radical copolymerization as comparison. The alternating, relatively low molecular weight h-h copolymers obtained showed softening, glass transition, and degradation temperatures somewhat higher than those displayed by the 1:1 h-t copolymers. After pyrolysis the main decomposition products from both h-h and h-t copolymers were alcohols, acrylates, and methacrylates. Furthermore, the ratios of alcohols to acrylates were larger for the h-h than for the h-t copolymers and smaller for the methyl than for the n-butyl esters.     

Preparation of syndiotacticity-rich high molecular weight poly(vinyl alcohol) microfibrillar fiber by photoinitiated bulk polymerization and saponification

Vinyl pivalate (VPi) was polymerized in bulk by ultraviolet-ray initiation at low temperatures using 2,2′-azobis(2,4-dimethylvaleronitrile) (ADMVN) and 2,2'-azobis(isobutyronitrile) (AIBN) as photoinitiators. High molecular weight (HMW) poly(vinyl pivalate) (PVPi), having a number-average degree of polymerization (P_n) of 13,000–28,000, was obtained at conversions below 30% and converted by saponification to a syndiotacticity-rich HMW poly(vinyl alcohol) (PVA) microfibrillar fiber with P_n of 7300–18,300, syndiotactic diad (S-diad) and triad contents of ∼ 64% and ∼ 39%, respectively, and crystal melting temperature (T_m) of ∼ 249°C. ADMVN gave higher P_n than AIBN. On the other hand, conversion was smaller with the former than with the latter, and it was found that the initiation rate of ADMVN was lower than that of AIBN. P_n of PVA was constant while P_n of the precursor PVPi increased with increasing conversion. The syndiotacticity, T_m and thermal stability of PVA obtained from PVPi were much superior to those of PVA derived from poly(vinyl acetate) prepared under the same polymerization conditions. Polymerization of VPi at lower temperatures gave PVA with higher syndiotacticity. © 1997 John Wiley & Sons, Inc.     

Glass transition temperatures of some linear polymers containing phenyl side groups

The glass transition temperatures of a number of poly(vinyl phenyl ketones), poly-(vinyl benzoates), and poly(phenyl acrylates) have been measured by a refractometric method. The effects exerted on T_g by the nature and position of the ring substituents and by the different groups binding the pendant phenyl rings to the polyvinyl chain are discussed. The importance of knowledge of the side-group motions in the glassy state for the interpretation of glass temperature data is emphasized.     

Cobalt‐mediated radical polymerization routes to poly(vinyl ester) block copolymers

Cobalt‐mediated radical polymerizations (CMRPs) utilizing redox initiation are demonstrated to produce poly(vinyl ester) homopolymers derived from vinyl pivalate (VPv) and vinyl benzoate (VBz), and their block copolymers with vinyl acetate (VAc). Combining anhydrous Co(acac)₂, lauroyl peroxide, citric acid trisodium salt, and VPv at 30 °C results in controlled polymerizations that yield homopolymers with M_n = 2.5–27 kg/mol with M_w/M_n = 1.20–1.30. Homopolymerizations of scrupulously purified VBz proceed with lower levels of control as evidenced by broader polydispersities over a range of molecular weights (M_n = 4–16 kg/mol; M_w/M_n = 1.34–1.65), which may be interpreted in terms of the decreased nucleophilicity of these less electron donating propagating polymer chain ends. Based on these results, we demonstrate that sequential CMRP reactions present a viable route to microphase separated poly(vinyl ester) block copolymers as shown by small‐angle X‐ray scattering analyses. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

A crystal transition in poly(γ-n-alkyl L-glutamate)s

A thermally reversible crystal transition was found for γ-helical poly(γ-n-alkyl L -glutamate)s (alkyl = ethyl, propyl, butyl, and amyl). The transition temperature is higher than that of the side-chain mechanical dispersion, and decreases from 115 to ?5°C, as the alkyl groups become longer. The transition in poly(γ-n-propyl L -glutamate) is clearly first order. The structures were analyzed by x-ray diffraction at various temperatures. It is noteworthy that the pseudohexagonal form observed below the transition temperature is less ordered than the hexagonal form at higher temperatures. The mechanism of this transition is discussed.     

Thermal stability of copolymers of vinyl acetate and methyl acrylate

The thermal degradation of a series of copolymers of vinyl acetate and methyl acrylate and the two homopolymers poly(vinyl acetate) and poly(methyl acrylate) obtained using Ce(IV) as initiator has been investigated using differential thermal analysis (DTA) and thermogravimetry (TGA) in dynamic nitrogen. The kinetic parameters E, n, and A have been obtained following several methods of thermogravimetric analyses. The stability increases as the methyl acrylate content in the copolymer composition increases. The incorporation of 5 mol % of vinyl acetate in the copolymer produces a marked decrease in stability compared to the homopolymer poly(methyl acrylate). There is evidence for an intramolecular lactonization process in vinyl acetate—methyl acrylate copolymers.     

Gas chromatography of homologous esters : XXVIII. Retention increments of aliphatic C1---C18n-alkyl esters of butanoic acid and its monochloro derivatives on SE-30 and OV-351 capillary columns

The retention behaviour of C₁---C₁₈n-alkyl esters of butanoic 2-, 3- and 4-chlorobutanoic acids was examined isothermally at several temperatures on SE-30 and OV-351 capillary columns. Retention increments showing the effects of each position of chlorine substitution are presented. The considerable enhancement of terminal chlorine substitution is discussed together with the corresponding behaviour of the monochloropropanoate esters.     

Tough photopolymers based on vinyl esters for biomedical applications

Photocurable vinyl esters have recently been introduced as suitable alternatives to (meth)acrylates in biomedical applications. While (meth)acrylates exhibit good mechanical properties, their cytotoxicity and degradation products principally disqualify them from medical use. Vinyl esters exhibit much lower cytotoxicity and give biocompatible degradation products, but their disadvantage are relatively low mechanical properties, particularly brittleness. This study focuses on the identification of suitable functional groups that are capable of introducing enhanced impact strength into the vinyl ester network, for example, cyclic structures or urethane groups. A new pathway for the synthesis of vinyl esters carrying these groups was established and resulting monomers were tested regarding their photoreactivity and cytotoxicity. Mechanical properties and degradation behavior of the new materials were investigated as well. In addition, the thiol‐ene reaction was utilized to enhance photoreactivity and tune hydrolytical degradation. The new vinyl esters exhibit excellent biocompatibility and good photoreactivity that can be significantly enhanced with thiols on to the level of highly photoreactive acrylates. Ultimately, the impact strength was improved by a factor of more than ten compared to commercial vinyl esters. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1987–1997     

Higher aliphatic polyaldehydes. IV. Transitions in poly(n-valeraldehyde), poly(n-hexaldehyde), poly(n-heptaldehyde), and poly(n-octaldehyde)

Crystalline polymers of n-valeraldehyde, n-hexaldehyde, n-heptaldehyde, and n-octaldehyde were prepared by anionic polymerization with lithium tertiary butoxide as the initiator at low temperatures. The polymers were end-capped with acetic anhydride, and their thermal stability was studied primarily by DTG. It was found that all polymers degrade rapidly above 150°C. All polymers show a dual melting-point behavior. The first melting region, which is associated with the melting of the side chain, is 80–85°C for poly(n-valeraldehyde); 87–90°C for poly(n-hexaldehyde); 78–101°C for poly(n-heptaldehyde); and 41–69°C for poly(n-octaldehyde). Annealing and quenching of the samples showed that this melting-point region consisted of several endotherm peaks whose intensity changed according to the thermal history of the sample. Although the samples are apparently highly crystalline, the side-chain crystallinity is apparently only in the 20% range.     

Radical block polymerization of vinyl chloride. II. Synthesis and characterization of vinyl chloride block copolymers

Peroxidized polypropylene has been used as a heterofunctional initiator for a two-step emulsion polymerization of a vinyl monomer (M₁) and vinyl chloride with the production of vinyl chloride block copolymers. Styrene, methyl-, and n-butyl methacrylate and methyl-, ethyl-, n-butyl-, and 2-ethyl-hexyl acrylate have been used as M₁ and polymerized at 30–40°C. In the second step vinyl chloride was polymerized at 50°C. The range of chemical composition of the block copolymers depends on the rate of the first-step polymerization of M₁ and the duration of the second step; e.g., with 2-ethyl-hexyl acrylate block copolymers could be obtained with a vinyl chloride content of 25–90%. The block copolymers have been submitted to precipitation fractionation and GPC analysis. Noteworthy is the absence of any significant amount of homopolymers, as well as poly(M₁)n as PVC. The absence of homo-PVC was interpreted by an intra- and intermolecular tertiary hydrogen atom transfer from polypropylene residue to growing PVC sequences. The presence of saturated end groups on the PVC chains is responsible for the improved thermal stability of these block polymers, as well as their low rate of dehydrochlorination (180°C). Molecular aggregation in solution has been shown by molecular weight determination in benzene and tetrahydrofuran.     

Domino meta-C−H Ethyl Glycosylation by Ruthenium(II/III) Catalysis: Modular Assembly of meta-C-Alkyl Glycosides

Glycosyl anomeric radical addition reactions have been well-explored and proved efficient for the C-alkyl glycosides synthesis, but multicomponent Domino transformations for the rapid and controllable construction of structurally diversified C-alkyl glycosides in a single step are still rare. In contrast, we, herein, report a ruthenium(II)-catalyzed Domino meta-C−H ethyl glycosylation, enabling the construction of challenging meta-C-alkyl glycosides. Our ruthenium(II) catalysis was reflected by the mild reaction condition, exclusive meta-site selectivity and high levels of anomeric selectivity. In addition, the ruthenium(II)-catalyzed Domino meta-C−H glycosylation allowed for the synthesis of versatile 1,2-trans-C-alkyl glycosides with commercially available vinyl arenes, acrylates and easily accessible glycosyl bromides.