Crystal Structure Effect in Radiation Induced Solid State Polymerization of Methacrylamide

Usanmaz, Ali; Kafadar, Aylin Beycar

doi:10.1081/ma-120028474

“…The resulting sheets, stacked along the a axis, interact via van der Waals forces (see Figure 1). While polymerization of acrylamide has been extensively investigated, [51][52][53][54][55][56][57][58][59][60] only a few studies of hydrostatic pressure induced solid state polymerization exist. Polymerization in solid acyrlamide has been reported in the range of 1-5 GPa after successive compressiondecompression cycles.…”

Section: Introductionmentioning

confidence: 99%

Pressure Induced Topochemical Polymerizationof Solid Acryalmide Facilitated by Anisotropic Response of Hydrogen Bond Network

Maiti¹,

Gangan²,

Anshu³

et al. 2020

Preprint

0

View full text Add to dashboard Cite

The pressure induced polymerization of molecular solids is an appealing route to obtain pure, crystalline polymers without the need for radical initiators. Here, we report a detailed density functional theory (DFT) based study of the structural and chemical changes that occur in defect free solid acrylamide, a hydrogen bonded crystal, when it is subjected to hydrostatic pressures. Our calculations predict a polymerization pressure of 94 GPa, in contrast to experimental estimates of 17 GPa, while being able to reproduce the experimentally measured pressure dependent spectroscopic features. Interestingly, we find that the two-dimensional hydrogen bond network templates a topochemical polymerization by aligning the atoms through an anisotropic response at low pressures. This results not only in conventional C-C, but also unusual C-O polymeric linkages, as well as a new hydrogen bonded framework, with both NH... O and C-H...O bonds.

show abstract

“…53 At ambient conditions, solid acrylamide exists in an 8-membered centro-symmetric dimeric form, with 4 formula units in a monoclinic unit cell with space group P2 1 /c. [54][55][56] The hydrogen bonded dimers are arranged along two rows that make an angle of 115 • with each other. These rows are further connected by inter-dimer H-bonds, thus forming a 2-dimensional N-H ... O H-bond network.…”

Section: Introductionmentioning

confidence: 99%

“…The resulting sheets, stacked along the a axis, interact via van der Waals forces (see Figure 1). While polymerization of acrylamide has been extensively investigated, [57][58][59][60][61][62][63][64][65][66] only a few studies of hydrostatic pressure induced solid state polymerization exist. Polymerization in solid acyrlamide has been reported in the range of 1-5 GPa after successive compressiondecompression cycles.…”

Section: Introductionmentioning

confidence: 99%

Pressure Induced Topochemical Polymerizationof Solid Acryalmide Facilitated by Anisotropic Response of Hydrogen Bond Network

Maiti¹,

Gangan²,

Anshu³

et al. 2020

Preprint

0

View full text Add to dashboard Cite

The pressure induced polymerization of molecular solids is an appealing route to obtain pure, crystalline polymers without the need for radical initiators. Here, we report a detailed density functional theory (DFT) based study of the structural and chemical changes that occur in defect free solid acrylamide, a hydrogen bonded crystal, when it is subjected to hydrostatic pressures. Our calculations predict a polymerization pressure of 94 GPa, in contrast to experimental estimates of 17 GPa, while being able to reproduce the experimentally measured pressure dependent spectroscopic features. Interestingly, we find that the two-dimensional hydrogen bond network templates a topochemical polymerization by aligning the atoms through an anisotropic response at low pressures. This results not only in conventional C-C, but also unusual C-O polymeric linkages, as well as a new hydrogen bonded framework, with both NH... O and C-H...O bonds.

show abstract

“…47 At ambient conditions, solid acrylamide exists in an 8-membered centro-symmetric dimeric form, with 4 formula units in a mono- clinic unit cell with space group P2 1 /c. [48][49][50] The hydrogen bonded dimers are arranged along two rows that make an angle of 115 • with each other. These rows are further connected by inter-dimer H-bonds, thus forming a 2-dimensional N-H ... O H-bond network.…”

Section: Introductionmentioning

confidence: 99%

“…The resulting sheets, stacked along the a axis, interact via van der Waals forces (see Figure 1). While polymerization of acrylamide has been extensively investigated, [51][52][53][54][55][56][57][58][59][60] only a few studies of hydrostatic pressure induced solid state polymerization exist. Polymerization in solid acyrlamide has been reported in the range of 1-5 GPa after successive compressiondecompression cycles.…”

Section: Introductionmentioning

confidence: 99%

Pressure Induced Topochemical Polymerizationof Solid Acryalmide Facilitated by Anisotropic Response of Hydrogen Bond Network

Maiti¹,

Gangan²,

Anshu³

et al. 2020

Preprint

0

View full text Add to dashboard Cite

The pressure induced polymerization of molecular solids is an appealing route to obtain pure, crystalline polymers without the need for radical initiators. Here, we report a detailed density functional theory (DFT) based study of the structural and chemical changes that occur in defect free solid acrylamide, a hydrogen bonded crystal, when it is subjected to hydrostatic pressures. Our calculations predict a polymerization pressure of 94 GPa, in contrast to experimental estimates of 17 GPa, while being able to reproduce the experimentally measured pressure dependent spectroscopic features. Interestingly, we find that the two-dimensional hydrogen bond network templates a topochemical polymerization by aligning the atoms through an anisotropic response at low pressures. This results not only in conventional C-C, but also unusual C-O polymeric linkages, as well as a new hydrogen bonded framework, with both NH... O and C-H...O bonds.

show abstract

Crystal Structure Effect in Radiation Induced Solid State Polymerization of Methacrylamide

Cited by 8 publications

References 9 publications

Pressure Induced Topochemical Polymerizationof Solid Acryalmide Facilitated by Anisotropic Response of Hydrogen Bond Network

Pressure Induced Topochemical Polymerizationof Solid Acryalmide Facilitated by Anisotropic Response of Hydrogen Bond Network

Pressure Induced Topochemical Polymerizationof Solid Acryalmide Facilitated by Anisotropic Response of Hydrogen Bond Network

Pressure Induced Topochemical Polymerizationof Solid Acryalmide Facilitated by Anisotropic Response of Hydrogen Bond Network

Contact Info

Product

Resources

About