Network formation during styrene-divinylbenzene copolymerization investigated by the fluorescence polarization method

Leicht, R.; Fuhrmann, Jürgen

doi:10.1007/bf01045252

Cited by 31 publications

(18 citation statements)

References 13 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In 1935, Staudinger et al 8) reported the formation of styrene-divinylbenzene microgel. Thereafter, numerous reports on microgel formation in the homopolymerizations of multivinyl compounds and their copolymerizations with monovinyl monomers were published 7,[9][10][11][12] . However, no microgelation was observed in the bulk polymerization of diallyl phthalate (DAP) 13) giving a quite low primary chain length as a characteristic feature of allyl polymerization 14) , although Erath et al 1) observed directly the DAP cured resin as the agglomerate of colloidal particles by electron microscopy.…”

Section: Introductionmentioning

confidence: 99%

ESR spectroscopic evaluation of void parts in microheterogeneously crosslinked monomethacrylate/dimethacrylate resins by using copper(II) tetraphenylporphyrin spin probe

Aota

Nishizawa

Matsumoto

2000

Macromol. Mater. Eng.

View full text Add to dashboard Cite

Section: Introductionmentioning

confidence: 99%

ESR spectroscopic evaluation of void parts in microheterogeneously crosslinked monomethacrylate/dimethacrylate resins by using copper(II) tetraphenylporphyrin spin probe

Aota

Nishizawa

Matsumoto

2000

Macromol. Mater. Eng.

View full text Add to dashboard Cite

“…[37][38][39] As the latter case of controlling intramolecular crosslinking in the free-radical crosslinking monovinyl/divinyl copolymerization, we pursued the intramolecular crosslinking reaction to generate the net or loop structure as an origin of CSM, although the locally extensive occurrence of intramolecular crosslinking leads to microgelation. [3,[40][41][42][43][44] Eventually, we reached the preparation of novel loopstructures containing net polymers as the ultimate precursors of CSM consisting of microgel-like NPPs. Here it should be noted that the new term, i.e., net polymer, was proposed by us; [12] thus, it is necessary to demonstrate the definition of the term ''net polymer'', being different from ordinary branched polymers.…”

Section: Molecular Design Of Npps As Modules Of Csm Based On Crosslinmentioning

confidence: 99%

Construction of Crosslink‐System‐Materials Utilizing Designed Network‐Polymer‐Precursor Modules

Matsumoto

2011

Macromolecular Symposia

View full text Add to dashboard Cite

Summary: For a long time, we have been concerned with the elucidation of network formation mechanism of free-radical crosslinking (co)polymerization of multivinyl monomers. We have pursued two extreme network structures formation such as ideal and nanogel-like NPP formation. During the course of these investigations, we recognized that a network polymer may be reconsidered as a crosslink-systemmaterial (CSM) or a giant system consisting of network polymer precursor (NPP) modules. The network polymer is not a giant molecule as a smallest unit of matter which could behave as one molecule. According to this definition, our subject may be changed from the molecular design of network polymer to the molecular design of NPP based on the free-radical crosslinking multivinyl polymerization mechanism. Then, we could construct a variety of CSMs utilizing designed NPP modules. A variety of CSM constructions are exemplified.

show abstract

mentioning

confidence: 99%

“…It should be recalled that we have been concerned with crosslinking multiallyl polymerization 7,8 as compared with that of the opposite case of multivinyl systems, in which numerous reports about microgel formation were published on the homopolymerization of common multivinyl monomers and their copolymerization with common monovinyl monomers. [9][10][11][12][13] In our previous investigation, 14 we tried to clarify the inhomogeneous cross-link structure formation or the microgelation in the bulk polymerization of DAP because the cross-linked DAP resin consisted of colloidal particles when observed using electron microscopy. 15 However, our results clearly demonstrated that any microgelation leading to the formation of colloidal particles did not occur before the gel point.…”

mentioning

confidence: 99%

Microgel-like network polymer precursor formation in free-radical cross-linking multiallyl polymerization

Hamamoto

Himei

Inoue

et al. 2010

Polym J

View full text Add to dashboard Cite

The present study is an extension of our preceding work on gelation behavior. We observed no substantial difference in the actual gel points among three isomeric diallyl phthalates: diallyl phthalate, diallyl isophthalate and diallyl terephthalate. The resulting network polymer precursors (NPPs) were characterized by size-exclusion chromatography with both multiangle laser light scattering and viscometry. It is of note that the structure of NPP, consisting of oligomeric primary polymer chains, becomes core-shell type dendritic or nanogel-like with the progress of polymerization. The nanogel-like NPPs can then collide with one another to form cross-links, eventually leading to gelation. Although the concentration of NPP should be high at the conversion close to the gel point, the dilution of NPP by adding monomer could prevent the cross-link formation among NPPs, and consequently lead to the successive growth of high-molecular-weight NPP from a nanogel to a microgel. The further growth of the microgel as an inhomogeneous NPP with high cross-link density could eventually reach an extremely inhomogeneous network polymer. These processes were pursued as typical examples using the bulk polymerization of DAT. Polymer Journal ( Keywords: cross-linking; gelation; microgel; multiallyl polymerization; nanogel; network polymer precursorIn our previous work, 1 the gel points in the free-radical polymerizations of diallyl aromatic dicarboxylates-including three isomeric diallyl phthalates: diallyl phthalate (DAP), diallyl isophthalate (DAI) and diallyl terephthalate (DAT)-were experimentally reexamined in detail and discussed according to Gordon's theory. 2 Although the discrepancy between actual and theoretical gel-point conversions was quite large and, moreover, it was enhanced in the order DAP o DAI o DAT, no substantial difference in the actual gel points was observed between the three isomeric DAPs. This interesting gelation behavior was discussed in detail 3 in terms of the correlation between gelation and the difference in cyclization modes, 4 as well as the difference in reactivity between the uncyclized and cyclized radicals for cross-linking. Conclusively, the nonconsecutive addition in DAT polymerization led to a delayed gelation, and the cyclized radical in DAP polymerization showed an enhanced reactivity for cross-linking.Then, we tried to extend our previous discussion 3 to the polymerization of triallyl trimellitate (TAT) because the chemical structure of TAT essentially exhibits the characteristics of three isomeric DAPs (Figure 1). Therefore, the enhanced gelation was expected in TAT polymerization, involving both abundant unreacted pendant double bonds and cyclized radicals as two significant factors responsible for an enhanced intermolecular cross-linking. However, no promoted gelation was observed in TAT polymerization when compared with DAP, DAI and DAT polymerizations.For a full understanding of the gelation behavior in cross-linking multiallyl polymerization, our preceding work 5 was focused on the cha...

show abstract

Network formation during styrene-divinylbenzene copolymerization investigated by the fluorescence polarization method

Cited by 31 publications

References 13 publications

ESR spectroscopic evaluation of void parts in microheterogeneously crosslinked monomethacrylate/dimethacrylate resins by using copper(II) tetraphenylporphyrin spin probe

ESR spectroscopic evaluation of void parts in microheterogeneously crosslinked monomethacrylate/dimethacrylate resins by using copper(II) tetraphenylporphyrin spin probe

Construction of Crosslink‐System‐Materials Utilizing Designed Network‐Polymer‐Precursor Modules

Microgel-like network polymer precursor formation in free-radical cross-linking multiallyl polymerization

Contact Info

Product

Resources

About