Ring-opening polymerization of ɛ-caprolactone by base catalyst for synthesis of grafted polysilsesquioxane

Kashio, Mikihiro; Sugizaki, Toshio; Yamamoto, Shinichi; Matsuoka, Tomonori; Moriya, Osamu

doi:10.1016/j.polymer.2008.05.031

Cited by 9 publications

(12 citation statements)

References 24 publications

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“…The PSQ grafted poly(CL) (CLPSQ), APSQ and the base catalyst (1), obtained from TBD and allyl isocyanate, were prepared in the previous work. 22 The analytical data of APSQ and CLPSQs were as follows. APSQ: aminopropyl group = 2.29 mmol eq./g, phenyl group = 5.16 mmol eq./g, M n ¼ 2300 g/mol, M w =M n ¼ 1:52; CLPSQ1: M n ¼ 12900 g/mol, M w =M n ¼ 1:54, phenyl group = 1.03 mmol eq./g, aminopropyl group = 0.46 mmol equiv./g, CL unit = 6.44 mmol equiv./g; CLPSQ2: M n ¼ 18200 g/mol, M w =M n ¼ 1:71, phenyl group = 0.62 mmol eq./g, aminopropyl group = 0.28 mmol equiv./g, CL unit = 8.08 mmol equiv./g.…”

Section: Generalmentioning

confidence: 99%

“…Next, CLPSQ1, the M n of which was estimated to be 12900 by GPC, 22 was employed as the macroinitiator for the incorporation of poly(LA). In the grafting, the content of the end hydroxyl group in CLPSQ1 was thought to be 0.46 mmol eq./g.…”

Section: Preparation Of Grafted Psqmentioning

confidence: 99%

“…The results of our previous examination demonstrated that the procedure was applicable to the graft ring-opening polymerization of CL from the polysilsesquioxane having phenyl and amino groups (APSQ). 22 Along with the investigations concerning the utilization of the ring-opening polymerization, the graftings of L-(À)-lactide (LA) and the block copolymer of LA and CL from APSQ were mentioned in this report. The introduction of polymeric LA component besides CL units is expected to change the properties of the graft chains such as grass transition temperature (T g ) and melting point (T m ) of the resulting PSQ derivative.…”

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confidence: 99%

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Synthesis of Grafted Polysilsesquioxane by Ring-Opening Polymerization of Lactide

et al. 2009

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Section: Generalmentioning

confidence: 99%

Section: Preparation Of Grafted Psqmentioning

confidence: 99%

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confidence: 99%

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Synthesis of Grafted Polysilsesquioxane by Ring-Opening Polymerization of Lactide

et al. 2009

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“…[8][9][10][11][12] We have previously investigated the grafting of the biodegradable polymers e-caprolactone (CL) and L-(-)-lactide (LA) from the PSQ main chain containing phenyl and aminopropyl groups (APSQ). 13,14 In thermal analyses of the resultant PSQs, low crystallinity of the polymeric components seems to be induced by the presence of the polysiloxane structure. This property is favorable for the use of grafted PSQs as practical hybrids.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of grafted polysilsesquioxane by ring-opening polymerization of lactide and trimethylene carbonate

Kashio

Sugizaki

Tanaka

et al. 2011

Polym J

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The polysilsesquioxane (PSQ) containing 3-aminopropyl and phenyl groups (APSQ) was prepared from the corresponding trimethoxysilanes by co-condensation under basic conditions. The amino groups on APSQ were used as the initiator species for the graft polymerization of 1,3-trimethylene carbonate (TMC) and L-(-)-lactide (LA). The ring-opening polymerization of TMC and LA in the presence of the catalytic 1-trimethylsilylimidazole proceeded effectively to afford the PSQ with poly(TMC) and/or poly(LA) as the graft chains. The grafted PSQ containing poly(LA) showed the heat durability as an advantage of the hybrid polymer. In differential scanning calorimetry analysis, the grafted random copolymer of TMC and LA showed no clear endotherm corresponding to melting point (T m ). For the poly(LA)-grafted PSQ, the peak indicating T m was observed in the first heating run, but the corresponding peak was very small in the second run.

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“…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.…”

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Graft polymerization of acrylamide monomers from polysilsesquioxane containing xanthate groups

Kashio

Sugizaki

Miyasaka

et al. 2012

Polym J

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Polysilsesquioxanes (PSQs) containing 4-chloromethylphenyl groups were prepared and used for introducing ethylxanthate groups. The obtained PSQs that contained benzyl xanthate structures (XAPSQs) were employed as macroinitiators for grafting acrylamide monomers. The use of XAPSQs for the radical polymerization with acryloylmorpholine (ACMO), N,Ndimethylacrylamide (DMAA) or N-isopropylacrylamide enabled the preparation of the respective grafted PSQ, in which no cross-linked product was formed. The results of the graft polymerizations from XAPSQs supported the interpretation that the reversible addition-fragmentation chain transfer polymerization progressed effectively using the technique known as macromolecular design via the interchange of xanthate. The introduction of polymerized ACMO and DMAA units provided an amphiphilic property to the grafted PSQ. In addition, the PSQs containing poly(ACMO) components showed reversible hydrophobic aggregation behavior at approximately 801C in aqueous solution. Polymer Journal ( The graft polymerization from the silsesquioxane backbone is an effective method for transforming the silsesquioxanes into practical and useful materials. [13][14][15][16][17][18][19][20] Grafted silsesquioxanes are expected to show functions based on the incorporated polymeric components without losing the essential properties of the inorganic polysiloxane structure, such as durability against heat and weatherability. 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. 24 The use of the DTC group was appropriate for designing the sequence and number of monomer units of the graft chains that were the important factors for extending grafted PSQ to a high performance hybrid material. However, in a few examples, the formation of a small amount of by-product that showed unexpectedly high number average molecular weights (M n s) was observed.

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Ring-opening polymerization of ɛ-caprolactone by base catalyst for synthesis of grafted polysilsesquioxane

Cited by 9 publications

References 24 publications

Synthesis of Grafted Polysilsesquioxane by Ring-Opening Polymerization of Lactide

Synthesis of Grafted Polysilsesquioxane by Ring-Opening Polymerization of Lactide

Synthesis of grafted polysilsesquioxane by ring-opening polymerization of lactide and trimethylene carbonate

Graft polymerization of acrylamide monomers from polysilsesquioxane containing xanthate groups

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