1	"Chemistry" Chemistry
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3	Eugene G. Rochow Father of Modern Silicone Chemistry Eugene Rochow has made some of the most significant contributions to the study and commercialization of silicon compounds. The “Direct Process” allowed for commercial usage over the older “Gringnard Process”. The “Direct Process now bears Rochow’s name. Chemistry of Silicones (John Wiley) by Rochow published in 1946 is not only an extremely interesting historical work, but still contains some very enlightening data.
4	Quartz
5	Silicon
6	Hydrolysate Chlorosilanes Si + CH₃Cl ------> Chlorosilanes Mixture
7	Hydrolysate Hydrolysis of Rochow Chlorosilanes Rochow Process Products + Water ---> Hydrolyzate and HCl
8	Silicone Compounds Performance is dictated by 1. Construction, 2. Functionalization and 3. Derivatization
9	Silicone Compounds Construction relates to the make up of the silicone backbone. Functionalization relates to the groups that are on the silicone backbone. Derivatization relates to chemistry conducted on the groups added by Functionalization.
10	Silicone Compounds The “Construction” relates to the polymer backbone. It is prepared by reacting various silicone precursors to make the “silicone backbone”. The “M”, “D”, “T” are part of the construction. The “Functionalization” relates to the functional groups that are present. They are generally a direct consequence of Si-H groups reacted with unsaturated groups in a process called “Hydrosilylation”. “Construction” “Functionalization” and “Derivatization ” result in the properties of the compound. Both are rarely disclosed making proper selection of a product difficult.
11	Construction Polymer Backbone Preparation
12	Construction (Silicone Portion) “M unit” is monosubstituted “D unit” is disubstituted
13	Construction (Silicone Portion) “T unit” is trisubstituted “Q unit” is Quadsubstituted
14	Construction (Silicone Portion) If organofunctional groups other than carbon are introduced, an “” is added to its designation. “M unit” is monosubstituted “D* unit” is disubstituted with organofunctionality
15	Construction (Silicone Portion) “T* unit” is trisubstituted with organofunctionality There is no “Q* unit” since there is no possibility of functional groups.
16	Construction There are three types of construction of silicone polymers. They are:
17	Construction
18	Functionalization Hydrosilylation
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20	Just a Few Hydrosilylatable Olefins Alkoxylated allyl alcohol CH₂=CH-CH₂-O-(EO)_a-(PO)_b-(EO)_cH Alpha olefin CH₂=CH- (CH₂)_n CH₃ Fluoro alpha olefin CH₂=CH-CH₂- (CF₂)_n CF₃ Ester CH₂=CH-(CH₂)_8-C(O)-OCH₃ Combinations Multifunctionals
21	Construction / Functionalization The “construction” is the molecular knitting machine that makes the silicone backbone. The “Functionalization” is the “Lego Set” of appendages that provide additional functionality. “Construction” without “Functionalization” results in silicone homopolymers like fluids. “Functionalization” is not possible without “Construction”.
22	Group Opposites Hydrophilic (water loving) Hydrophobic (water hating) Oleophilic (oil loving) Oleophobic (oil hating) Siliphilic (silicone loving) Siliphobic (silicone hating) Hydrophobic (water hating) materials can be either oleophilic or siliphilic. Oleophobic (oil hating) materials may be either hydrophilic or siliphilic. Siliphobic (silicone hating) materials may be either oleophilic or hydrophilic. This means that a hydrophobic fiber can be treated with silicone or with hydrocarbon. If treated with silicone, the fiber will also be oleophobic. If treated with oil, the fiber will also be siliphobic. For application in waterproofing fibers, selection of the proper molecule is critical. Improper selection will result in unacceptable oil staining.