NDLI: On the Role of Tin Catalysts in Step-Growth Polymerization Reactions

Content Provider	Springer Nature Link
Author	Kuo, Chung Mien Clarson, Stephen John
Copyright Year	2012
Abstract	Organotin compounds have been used to catalyze the condensation of various α,ω-dihydroxyl terminated organosiloxane diols. This tin catalyzed reaction extends the length of siloxane chains and it also produces narrow molar mass distribution polyorganodisilanols (M$_{w}$/M$_{n}$ = 1.4). The reaction occurs between a variety of siloxanes that are terminated with hydroxyl groups and it does not depend on the organic side groups connected to silicon for the systems studied here. These systems include silicon atoms bearing dimethyl, methylphenyl or methyl 1,1,1 trifluoropropyl substituents. The organotin catalyst in the reaction facilitates the organosilanol condensation releasing water as a byproduct. However it does not appear to facilitate the opening of siloxane bonds nor the redistribution of siloxane bonds under the conditions employed here. Copolymerization of linear oligomeric dimethylsiloxane diol and linear oligomeric methylphenylsiloxanediol was found to give a relatively equal reactivity of homo polymerization and hetro polymerization in the condensation and randomly alternating segmented block copolymers that were formed. The reaction kinetics of the polymerization was used to experimentally verify the fact that there is a chain length dependence of the reacting silanol end-groups. The molar mass values during the polymerizations were determined using gel permeation chromatography. The chromatography, viscosity and FTIR results demonstrate that the reactivity of the hydroxyl end-groups in the polycondensation reaction decreases upon increasing the chain length of the siloxane. It therefore appears that these tin catalyzed siloxane systems deviate from the widely demonstrated hypothesis of Paul Flory on the “equal reactivity of functional groups” for step-growth polymerizations.
Starting Page	577
Ending Page	587
Page Count	11
File Format	PDF
ISSN	15741443
Journal	Journal of Inorganic and Organometallic Polymers and Materials
Volume Number	22
Issue Number	3
e-ISSN	15741451
Language	English
Publisher	Springer US
Publisher Date	2012-04-19
Publisher Place	Boston
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Silicone Polyorganosiloxane Organotin Step-growth Polycondensation Block copolymers Inorganic Chemistry Polymer Sciences Organic Chemistry
Content Type	Text
Resource Type	Article
Subject	Materials Chemistry Polymers and Plastics

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