Side‐chain crystallinity. II. Heats of fusion and melting transitions on selected copolymers incorporating <i>n</i>‐octadecyl acrylate or vinyl stearate

Jordan, Edmund F.; Artymyshyn, Bohdan; SPECA, A. N.; Wrigley, A. N.

doi:10.1002/pol.1971.150091121

Cited by 99 publications

(84 citation statements)

References 31 publications

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“…This tendency has been explained by difference in the mobility of the segmental motion of the main chain. 8 Melting temperature of the hexagonally-packed n-alkyl side chain is 10-40°C, which is higher and lower than the glass transition temperature, Tg, ofpoly(methyl acrylate) and poly(methyl methacrylate), respectively. Thus, the segmental motion of the main chain of PMx may be considerably restricted at the crystallization temperature of n-alkyl side chain.…”

Section: Effect Of Main-chain Structurementioning

confidence: 95%

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Solid-State Structure of Comb-Like Polymers Having n-Octadecyl Side Chains I. Cocrystallization of Side Chain with n-Octadecanoic Acid

Inomata

Sakamaki

Nose

et al. 1996

Polym J

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ABSTRACT:Solid-state structures of comb-like polyacrylates (PAx) and polymethacrylates (PMx) having crystallizable n-octadecyl side chains and their blends with n-octadecanoic acid (Cl8) have been investigated by means of differential scanning calorimetry and X-ray diffraction methods. It is concluded that n-alkyl side chains of comb-like polymer cocrystallize with low-molecular-weight Cl8 by incorporation of Cl8 into hexagonal crystalline lattice. In the case of amorphous PMx, the addition of Cl8 can induce a formation of crystalline domain by the cocrystallization with the side chain. Differences in the crystallization behavior, such as fractions of crystallized methylene units and effects of thermal history, between PAx and PMx are found to be considerably large. These results are explained by the difference in the segmental mobility of main chain.KEY WORDS Comb-Like Polymer/ n-Octadecanoic Acid/ Cocrystallization / X-Ray Diffraction/ DSC Measurement / n-Alkyl Side Chain / Differences in solid-state nature between side chain and main chain in comb-like polymers are anticipated to give a wide variety of phases, structures, and morphologies, for example, those in side-chain liquid crystalline polymers 1 and rigid-rod polymer with flexible side chains. 2 -4 Comb-like polymers, which have crystallizable long n-alkyl side chains being attached to amorphous main chain, are known to pack into layered structure with alternating crystalline side-chain region and amorphous main-chain region in the solid state. 5 -13 Plate and Shibaev 6 studied these comb-like polymers extensively. X-Ray diffraction profile for such polymer has an intense reflection corresponding to the Bragg spacing d of 4.2 A, which suggests a formation of hexagonal crystalline lattice of n-alkyl side chain. There also exists a reflection in smaller angle region, which is considered to originate from the layered structure. The repeating distance of crystalline-amorphous layer can be obtained by the diffraction angle of this reflection. Plate et al. 6 observed striking difference in the diffraction patterns and layer spacings between comb-like polyacrylates and polymethacrylates. In order to interpret this difference, they proposed two models for chain packing: two-layer structure and one-layer structure for respective polymers. In the former model, the side chains are extended on both side of the main chain and these polymers pack closely because of the flexibility of the main chain. In the latter structure, the disordered packing of the end groups of side chains occurs because of the increased bulkiness of the main chain, and the polymer chains are arranged with a shift toward the extended side-chain axis. Later, Hsieh et al. 9 proposed a new structural model for the solid state poly(n-octadecyl methacrylate), where the side-chain crystallites are formed by intercalating side chains pointing in opposite directions. Although the detailed solid-state structures of these comb-like polymers have not been clarified as yet, the layered structure with the...

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Section: Effect Of Main-chain Structurementioning

confidence: 95%

“…Heat of melting for the hexagonal modification of the n-alkane has been reported as 0. 73 kcal per mole of methylene unit, 8 • 2 5 then heat of transition for sixteen methylenes can be calculated as 11. 7 kcal mol -1 , which is comparable with the extrapolated value of !…”

Section: Effect Of Main-chain Structurementioning

confidence: 99%

Solid-State Structure of Comb-Like Polymers Having n-Octadecyl Side Chains I. Cocrystallization of Side Chain with n-Octadecanoic Acid

Inomata

Sakamaki

Nose

et al. 1996

Polym J

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“…22, No. 11,1990 St or MMA. 18 -22 Tgs increased almost linearly with the content of isopropenyltriazines in the copolymers.…”

Section: Glass Transition Temperaturesmentioning

confidence: 99%

“…11 Hirabayashi et al found the values of alternating comb-like copolymers to be 5.0 for OA-St, 2.7 for octadecyl methacrylate (OMA)-St, and 2.6 for OA-a-methylstyrene, respectively. 15 The copoylmers in this work gave Ne, smaller than those 982 of the conventional comb-like copolymers.…”

Section: (A)mentioning

confidence: 99%

“…8 Furthermore, comb-like copolymers prepared by the copolymerization of long-chain monomers with common comonomers have been studied to improve solubility and to increase flexibility by internal plasticization. [9][10][11][12][13][14][15] and property of the copolymers. 1 7 -22 As a part of these studies, this paper deals with copolymerization parameters of isopropenyl-1,3,5-triazines containing long alkyl groups, and with the T 8 s and the side-chain crystallization of the resulting comb-like copolymers.…”

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confidence: 99%

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Comb-Like Copolymers Obtained by Copolymerization of 2-Amino-4-(N-alkylanilino)-6-isopropenyl-1,3,5-triazines

Kunisada

Yuki

Kondo

et al. 1990

Polym J

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ABSTRACT:Copolymerizations of 2-amino-4-(N-alkylanilino )-6-isopropenyl-1,3,5-triazines with styrene, methyl methacrylate and methyl acrylate were carried out using azobisisobutyronitrile as an initiator. Alkyl groups were propyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and docosyl. Copolymerization parameters (ri, r2, Q, and e) were determined for these monomers. No significant effect of alkyl chain length on the copolymrization parameters could be observed. Relationships between glass transition temperatures and composition of the copolymers were investigated. Crystallization exothermic and melting endothermic peaks due to the side-chains were observed in the DSC thermograms of the comb-like copolymers containing octadecyl and docosyl groups. The crystallinity of the side-chains decreased with increasing content of styrene or methyl methacrylate in the copolymers. KEY WORDSIsopropenyltriazines / Long Alkyl Group / Copolymerization Parameters / Glass Transition Temperature / Comb-Like Copolymer / Side-Chain Crystallization / Polymers containing long alkyl side-chains, so-called comb-like polymers, have attracted much attention due to specific properties such as side-chain crystallization, 1 -3 peculiar mechanical properties, 3 ability of liquid crystal formation,4-7 and formation of LangmuirBlodgett film. 8 Furthermore, comb-like copolymers prepared by the copolymerization of long-chain monomers with common comonomers have been studied to improve solubility and to increase flexibility by internal plasticization. [9][10][11][12][13][14][15] and property of the copolymers. 1 7 -22 As a part of these studies, this paper deals with copolymerization parameters of isopropenyl-1,3,5-triazines containing long alkyl groups, and with the T 8 s and the side-chain crystallization of the resulting comb-like copolymers.In a previous paper, 16 we reported the synthesis and polymerization of 2-amino-4-(Nn-alkylanilino )-6-isopropenyl-1,3,5-triazines, and found that long alkyl side-chains in the resulting comb-like polymers could be crystallized below the glass transition temperature (T 8 ) of the main-chain. On the other hand, we have studied substituent effects of isopropenyl-1,3,5-triazines on copolymerization behaviorThe structures and abbreviations of isopropenyl-1,3,5-triazines used in this study are shown in Figure 1.

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A study of blends of poly(n‐octadecyl methacrylate) with n‐dodecane and n‐octadecane

Rubin¹,

Pugliese²

1989

Angew. Makromol. Chem.

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DSC and X-ray diffraction analysis were used to study blends of poly(n-octadecyl methacrylate) with n-dodecane and n-octadecane crystallized from the melt to gain a better understanding of the interaction of comb-like polymethacrylates with paraffin waxes. In both sets of blends both components could crystallize in separate lattices. However, the polymer interfered with the crystallization of the n-paraffin, resulting in less crystalline paraffin than expected on the basis of blend composition. In the blends with n-dodecane, evidence was found for partial cocrystallization of the paraffin and the polymer side chains. No cocrystallization was observed in the blends with n-octadecane. ZUSAMMENFASSUNG:Mit Hilfe der Differential-Scanning-Calorirnetrie und RiSntgenbeugung wurde das Kristallisationsverhalten von Mischungen aus Poly(n-octadecylmethacry1at)en rnit n-Dodekan und n-Oktadekan bei der Kristallisation aus der Schmelze untersucht. Hierbei sollten bessere Erkenntnisse uber die Wechselwirkungen von kamm2hnlich strukturierten Polymethacrylaten rnit paraffinischen Kohlenwasserstoffen gewonnen werden. In beiden Mischungen war ein Auskristallisieren der beiden Komponenten in verschiedenen Gittern mtiglich. Es wurde jedoch gefunden, da8 das Polymere die Kristallisation der n-Paraffine beeinflufit rnit dem Ergebnis, da13 weniger Paraffin kristallisierte, als vom Paraffinanteil in der Mischung zu envarten war.In Mischungen rnit n-Dodekan wurden Anhaltspunkte fur eine teilweise Cokristallisation des Paraffins rnit den Seitenketten des Polymeren gefunden. In Mischungen rnit n-Oktadekan wurde keine Cokristallisation beobachtet.

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Side‐chain crystallinity. II. Heats of fusion and melting transitions on selected copolymers incorporating n‐octadecyl acrylate or vinyl stearate

Cited by 99 publications

References 31 publications

Solid-State Structure of Comb-Like Polymers Having n-Octadecyl Side Chains I. Cocrystallization of Side Chain with n-Octadecanoic Acid

Solid-State Structure of Comb-Like Polymers Having n-Octadecyl Side Chains I. Cocrystallization of Side Chain with n-Octadecanoic Acid

Comb-Like Copolymers Obtained by Copolymerization of 2-Amino-4-(N-alkylanilino)-6-isopropenyl-1,3,5-triazines

A study of blends of poly(n‐octadecyl methacrylate) with n‐dodecane and n‐octadecane

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