Side Chain Crystallization of n-Alkyl Polymethacrylates and Polyacrylates<sup>1</sup>

Greenberg, S. A.; Alfrey, Turner

doi:10.1021/ja01653a015

Cited by 135 publications

(90 citation statements)

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“…The diagrams show that most of the characteristic peaks of the monomer disappear rapidly as the irradiation dose increases, but a broad weak peak at 28= 6.8° and a sharp intense peak at 28 = 21.4 o, which correspond to the spacings of 13.0 and 4.2 A, respectively, remain even after the monomer is converted almost completely to polymer. Since the single intense line corresponding to a spacing of 4.2 A, is similar to that observed in vinyl stearate 5 and also in polymers derived from the vinyl stearate 14 and long-chain alcohol esters of acrylic and methacrylic acid, 15 the irradiated ODMA which has been converted to poly(ODMA) is considered to maintain an ordered structure due to paraffin-like crystallites. The diffuse 13 A reflection is not so easily interpreted.…”

Section: X-ray Diffraction Studiesmentioning

confidence: 56%

Cyclopolymerization. IX. Radiation-Induced Solid-State Polymerization of N-Octadecyldimethacrylainide

Kodaira

Sakai

1979

Polym J

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ABSTRACT:Solid-state cyclopolymerization of N-octadecyldimethacrylamide(ODMA) has been investigated in an attempt to clarify the effect of its long-chain substituent on the polymerization, as compared with the reported polymerization of N-substituted dimethacrylamides(RDMA) which have small substituents. The polymerizability ofODMA has been found to be higher than that of RD MA in the solid state, especially in the postirradiation polymerization, though the former is comparable with the latter in the solution polymerization. Xray diffraction studies have revealed that poly(ODMA) is a partially crystalline polymer, in contrast to the poly(RDMA) which is amorphous. However, the other results are similar to those obtained in the polymerization ofRDMA, viz., the sigmoid time-<:onversion curve, higher polymerizability in the liquid state than in the solid state, structural characteristics of the polymer, and the fact that the ratedetermining step of the solid-state polymerization of ODMA is an intramolecular cyclization reaction. Consequently, it has been suggested that the polymerization ofODMA proceeds under the influence of crystalline structure, probably due to the ordered arrangement originating from its long octadecyl group, but some destruction of the structure is necessary for the polymerization.The effect of a long alkyl chain in the solid-state polymerization of a homologous series of compounds has been investigated by several authors. A high rate of the solid-state polymerization is observed in long-chain alcohol esters of methacrylicl. 2 and acrylic 3 acid. The dependence of the polymerization behavior of maleimide derivatives 4 on the length of N-alkyl substituents in the solid state has been found. Both results suggest the fundamental role of the ordered structure, which originates from the long alkyl chain, in the polymerization of these monomers. Further, the formation of partially crystalline polymers has been reported in the case of the polymerization of vinyl stearate 5 in the solid state, where vinyl monomers usually afford amorphous polymers.is slightly different from that formed in the liquid state, 7 10 though the crystallographic study showed that the polymers are amorphous. In addition, the rate-determining step of the solid-state polymerization of RDMA has been determined to be an intramolecular cyclization reaction irrespective of the substituents on nitrogen. 8 • 11 Since the reported results on the monomers having a long alkyl chain mentioned above show that they have quite different polymerization behaviors from their homologues, the polymerization of N-octadecyldimethacrylamide(ODMA) in the solid state has been undertaken in an attempt to clarify the effect of its longThe solid-statepolymerization of N-substituted dimethacrylamides(RDMA) which have smaller groups, e.g., methyi(MDMA), propyl(PrDMA), benzyi(BDMA), and phenyl(PhDMA) groups, as substituents has already been reported. 6 The structure ofpoly(RDMA) formed in the solid state 7 • 8 ODMA 595

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Section: X-ray Diffraction Studiesmentioning

confidence: 56%

Cyclopolymerization. IX. Radiation-Induced Solid-State Polymerization of N-Octadecyldimethacrylainide

Kodaira

Sakai

1979

Polym J

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“…In both cases a reversible change in the spectra was observed at about 35°C to 40 0c. This temperature corresponds to the melting of the side chains in the bulk material 13)• The rather broad feature between 3 500 cm -1 and 3 000 cm -1 seen in some IR spectra is due to water which condenses on the cold MCT-B detector element. …”

Section: Interesting Phenomenamentioning

confidence: 99%

Langmuir‐Blodgett mono‐ and multilayers of preformed poly(octadecyl methacrylate)s, 2. Structural studies by IR spectroscopy and small‐angle X‐ray scattering

Arndt¹,

Schouten²,

Schmidt³

et al. 1991

Makromol. Chem.

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Langmuir‐Blodgett (LB) mono‐ and multilayers of preformed atactic and isotactic poly(octadecyl methacrylate)s were studied on gold surfaces and silicon wafers. The average orientation of the carbonyl bond of the ester group was found to be about 50° with respect to the normal to the substrate, and the side chains were concluded to be oriented perpendicular to the substrate. Furthermore, the degree of side chain orientation increased on going from a single monolayer to a multilayer. This is explained by an interdigitation of the side chains during or after the transfer process. A peculiar transfer behavior of the atactic samples is discussed in terms of the effect of disorder of the first layer on the transfer process. On heating multilayers of the polymers, melting of the crystalline domains formed by the side chains was observed at temperatures of about 35°C to 40°C. However, the layer structure appeared to be stable up to 100°C. The oriented structure was completely recovered after cooling down to room temperature.

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“…Rehberg and Fisher studied the brittle points of polyacrylates and poly(methacrylates) and found that upon an increase in carbons within the alkyl side chain the brittle points decrease up to 8 carbons for acrylates and 12 carbons for methacrylates, above which the brittle points increased. 13 This was attributed to the increase in the melting point of the side chains 14,15 Jordan et al investigated the crystallinity of the alkyl side chains in poly(n-alkyl acrylates) and they established that only the outer methylene units contributed to the crystal lattice. 16,17 This was also independently confirmed by several other investigators, it was proposed that the 8-9 methylene units closest to the polymer backbone do not contribute to the side chain crystallinity.…”

Section: Introductionmentioning

confidence: 99%

“…16,17 This was also independently confirmed by several other investigators, it was proposed that the 8-9 methylene units closest to the polymer backbone do not contribute to the side chain crystallinity. 15,18,19 Thus for both semi-crystalline poly(alkyl acrylate)s and poly(alkyl methacrylate)s the longer the side chain the higher the Tm of the poly(alkyl(meth)acrylate). 15,16 Furthermore it has been demonstrated that by copolymerising (meth)acrylate monomers the Tm of the resultant statistical copolymers can be manipulated to occur within a given range typically between the Tm values of the two homopolymers, with the exact value dependent upon the ratio of monomers within the structure.…”

Section: Introductionmentioning

confidence: 99%

“…15,18,19 Thus for both semi-crystalline poly(alkyl acrylate)s and poly(alkyl methacrylate)s the longer the side chain the higher the Tm of the poly(alkyl(meth)acrylate). 15,16 Furthermore it has been demonstrated that by copolymerising (meth)acrylate monomers the Tm of the resultant statistical copolymers can be manipulated to occur within a given range typically between the Tm values of the two homopolymers, with the exact value dependent upon the ratio of monomers within the structure. [20][21][22][23] By copolymerising ODMA with an alkyl methacrylate monomer with a higher melting transition temperature it should therefore be possible to manipulate the melting transition of the alkyl methacrylate block of a PEO-bpoly(alkyl methacrylate) copolymer and thereby the melting transition of the aggregates formed.…”

Section: Introductionmentioning

confidence: 99%

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Controlling the melting transition of semi-crystalline self-assembled block copolymer aggregates: controlling release rates of ibuprofen

et al. 2017

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. (2017) Controlling the melting transition of semi-crystalline self-assembled block copolymer aggregates: controlling release rates of ibuprofen. Polymer Chemistry, 8 (35 where PEO is the hydrophilic block (25 wt%) and PODMA/PDSMA is the semi-crystalline hydrophobic block (75 wt%) that gives a thermoresponsive component to the self-assembled aggregates. By varying the relative molar proportion of DSMA to ODMA (from 0:1 to 1:0) in the synthesis of the copolymers by atom transfer radical polymerisation, the melting transition of the hydrophobic block could be varied from 21.5 to 41.1°C in the solid state. When self-assembled in aqueous dispersions the Tm range was 23.4 to 41.3°C, closely matching that of the solid samples. Preliminary analysis of the rate of release of ibuprofen from three of the block copolymer aggregates demonstrated that the rate of release was correlated with the degree of crystallinity of the hydrophobic block and that increasing temperature causes melting and a significantly enhanced release rate.

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Side Chain Crystallization of n-Alkyl Polymethacrylates and Polyacrylates¹

Cited by 135 publications

References 1 publication

Cyclopolymerization. IX. Radiation-Induced Solid-State Polymerization of N-Octadecyldimethacrylainide

Cyclopolymerization. IX. Radiation-Induced Solid-State Polymerization of N-Octadecyldimethacrylainide

Langmuir‐Blodgett mono‐ and multilayers of preformed poly(octadecyl methacrylate)s, 2. Structural studies by IR spectroscopy and small‐angle X‐ray scattering

Controlling the melting transition of semi-crystalline self-assembled block copolymer aggregates: controlling release rates of ibuprofen

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Side Chain Crystallization of n-Alkyl Polymethacrylates and Polyacrylates1

Cited by 135 publications

References 1 publication

Cyclopolymerization. IX. Radiation-Induced Solid-State Polymerization of N-Octadecyldimethacrylainide

Cyclopolymerization. IX. Radiation-Induced Solid-State Polymerization of N-Octadecyldimethacrylainide

Langmuir‐Blodgett mono‐ and multilayers of preformed poly(octadecyl methacrylate)s, 2. Structural studies by IR spectroscopy and small‐angle X‐ray scattering

Controlling the melting transition of semi-crystalline self-assembled block copolymer aggregates: controlling release rates of ibuprofen

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Side Chain Crystallization of n-Alkyl Polymethacrylates and Polyacrylates¹