Graft polymerization of polysilsesquioxane containing chloromethylphenyl groups by atom transfer radical polymerization

Abstract

Polysilsesquioxane with phenyl and chloromethylphenyl groups (PCPSQ) was prepared readily from phenyltrimethoxysilane and [2‐(chloromethylphenyl)ethyl]trimethoxysilane under acidic conditions. Polymerization with chloromethylphenyl groups on PCPSQ with methyl methacrylate (MMA) was conducted in the presence of a catalytic amount of copper(I) bromide and (−)‐sparteine. Atom transfer radical polymerization yielded a graft polymer (PCPSQ‐g‐MMA) efficiently, and no gelation was observed. The process was also applied to the preparation of graft block copolymers on PCPSQ with several methacrylate monomers. An advantage of the graft hybrid polymers was shown in improved thermal behavior. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4212–4221, 2004

Graft polymerization of acrylamide monomers from polysilsesquioxane containing xanthate groups

“…22 CPTMS (12.30 g, 49.84 mmol), PTMS (9.91 g, 49.98 mmol) and methanesulfonic acid (0.48 g, 5.00 mmol) were added to the mixed solvent of toluene (100 ml) and water (50 ml). The solution was stirred at ambient temperature for 16 h and then distilled under reduced pressure to remove the solvents.…”

“…The spectral data and solubility in the usual organic solvents seemed to indicate that the obtained CPPSQs and XAPSQs were constructed by incomplete ladder-and cage-like polysiloxane structures, but not, at least, by a randomly cross-linked structure. 22 The introduction of the xanthate group could be readily achieved using a simple substitution reaction with benzylchloride structures in the CPPSQs. In addition, the signals of the methylene and methyl protons from this group were distinguishable in the 1 H NMR spectrum of the grafted product.…”

“…With the regard to this expectation, we also tried to develop new multifunctional hybrid materials using acrylamide monomers by the graft polymerizations from polysilsesquioxane (PSQ). [21][22][23][24][25][26] In fact, the graftings of polymeric N,N-dimethylacrylamide (DMAA) and N-isopropylacrylamide (NIPAM) successfully produced amphiphilic and thermoresponsive PSQs. 23,24 For the graft polymerizations, the reversible addition-fragmentation chain transfer (RAFT) process was utilized, in which the N,Ndimethyldithiocarbamate (DTC) group was chosen as the chain transfer species.…”

Preparation of Stimuli-responsive Polysilsesquioxane Grafted Block Copolymer of Acrylamide Monomers

“…[10][11][12][13][14][15][16] In the previous works, we also have investigated concerning the graft polymerizations from polysilsesquioxane backbone, which intended to develop the new multi-functional hybrid materials. [17][18][19][20][21] As an example of such graftings, the introduction of block copolymer of N,N-dimethylacrylamide (DMAA) and N-isopropylacrylamide (NIPAM) by the living polymerization technique, reversible addition-fragmentation chain transfer (RAFT) process, was reported. 21 In the graft polymerization, the PSQ having chloromethylphenyl groups (CPPSQ) was prepared from the corresponding trimethoxysilane and, then, N,N-dimethyldithiocarbamate (DTC) group was introduced as a chain transfer specie for RAFT process.…”

Preparation of Thermoresponsive Grafted Polysilsesquioxane from Polyacrylamides Having Methoxysilyl End Group

“…[10][11][12][13][14] We also presented several reports concerning the grafted PSQ which intended to prepare a new multi-functional hybrid material. [15][16][17] The synthesis of thermoresponsive PSQs, grafted the copolymer of N,N-dimethylacrylamide (DMAA) and Nisopropylacrylamide (NIPAM), was an example utilizing the modification method. [18][19][20] The PSQ, showing the stimuliresponsive property, has potential to be used in the practical material scenes of microencapsulation, biosensor, and drug delivery as postulated in the investigations concerning poly-(NIPAM).…”