This document summarizes the synthesis of a well-defined alternating copolymer of 1,1-diphenylethylene (DPE) and tert-butyldimethylsilyloxymethyl substituted styrene (St-TBS) by anionic copolymerization. The temperature and monomer ratio were important in controlling the copolymer structure and suppressing homopolymerization of the styrene derivatives. Various graft copolymers with controlled side chain densities were then synthesized using the alternating copolymer backbone and both "grafting from" and "grafting onto" methodologies. Characterization techniques like MALDI-TOF-MS, SEC, NMR and DSC confirmed the

1. Synthesis of a well-defined alternating copolymer
of 1,1-diphenylethylene and tert-
butyldimethylsilyloxymethyl substituted styrene
by anionic copolymerization: toward tailored
graft copolymers with controlled side chain
densities
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Raita Goseki, Fan Zhang, Kazuki Takahata, Satoshi Uchida and Takashi Ishizone; Polym. Chem.; 2019
CH 601-Coursework Presentation
Subham Sahoo & Rohit Kumar
1921CH01 & 1921CH09
Department of Chemistry
Indian Institute Of Technology Patna

2. Contents
1. Introduction
2. Synthesis
3. Characterization
4. Conclusion
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3. Introduction
◦ Living anionic alternating copolymerization of 1,1-
diphenylethylene and styrene derivatives
◦ Suppressed the formation of a defect structure comprising
consecutive styrene–styrene repeating
◦ Synthesis of side-chain-density-controlled graft copolymers
by using both “grafting from” and “grafting onto”
methodologies.
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4. Anionic polymerization
◦ For initiation to be successful, the free energy of the
initiation step must be favorable. Therefore, it is necessary
to match the monomer with initiator.
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5. Grafting copolymerization
◦ Graft polymerization is a process in which monomers
are covalently bonded and polymerized as side chains
onto the main polymer chain (the backbone).
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6. Grafting types
◦ Grafting onto- attaching a pre-synthesized polymer to a
polymer backbone
◦ Grafting from- growing polymers from a polymer backbone
bearing pendant functionality
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7. Synthesis
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• Synthesis of monomer
• Main reaction

8. Characterization
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9. 9
MALDI-TOF-MS

10. MALDI-TOF-MS
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11. Deprotection determined by SEC
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12. NMR
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13. DSC curves
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14. Scheme for poly(DPE-alt-St-BMS)-g-PS by
grafting onto
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15. Scheme for poly(DPE-alt-HBS)-g-PCL
by grafting from
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16. DSC
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17. Conclusion
◦ Successful synthesis controlled alternating copolymers
◦ The temperature and monomer ratio of [DPE]/[St-TBS] are
important factors for controlling the resulting structure.
◦ The bulky TBS functionality efficiently suppressed the
formation of St–St homopolymerization.
◦ With the help of Grafting the group synthesize a wide
variety of side-chain-density-controlled graft copolymers
as model compounds.
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18. Thank You
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19. Supporting data
◦ St-TBS = meta-Tertbutyldimethylsilyloxymethylstyrene
◦ DPE = 1,1-Diphenylethylene
◦ -HMS = Hydroymethylstyrene
◦ -BMS = Bromomethylstyrene
◦ -g-PS = grafting with polystyrene
◦ -g-PCL = grafting with polycaprolactam
◦ -g-PMMA = grafting with polymethylmethacrylate
◦ MALDI-TOF-MS = Matrix-Assisted Laser Desorption-Time Of Flight- Mass Spectroscopy
◦ SEC = Size Exclusion Chromatography
◦ DSC = Differential Scanning Calorimetry
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