Inorganic Material chemistry
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1 Inorganic Material chemistry
2 Silicone -Inorganic Polymer
3 Polymer poly + mer many units Basic unit is called repeat unit (monomer) A polymer is a large molecule (macro molecule) composed of repeating structural units. These sub-units are typically connected by covalent chemical bonds Normally has high molecular weight
4 Silicon (Si) Silicone is not to be confused with the chemical element silicon, a crystalline metalloid widely used in computers and other electronic equipment.
5 What are Silicones? Are synthetic polymers with a repeating silicon-oxygen backbone with a variety of forms and uses Silicone polymers do not have carbon as a part of the backbone structure They look like this.
6 Silicones Name was derived from the word ketone
7 Preparation From Sand to Silicones Silicone polymers are obtained by a three-step synthesis: Chlorosilane synthesis : Chlorosilane hydrolysis Polycondensation and Polymerization
8 1 st step -Chlorosilane synthesis 1. Direct process of Rochow 2. Grignard reaction (i) Direct process of Rochow Today, silicones are obtained commercially ( 850,000 t/y) from chlorosilanes prepared following the direct process of Rochow Eugene George Rochow (October 4, 1909 March 21, 2002)
9 Direct process of Rochow -A mixture of different silanes is obtained containing mainly the dimethyldichlorosilane, Me 2 SiCl 2 -Separation of each component is carried out by distillation
10 Chlorosilane synthesis Grignard reaction SiCl 4 + CH 3 MgCl CH 3 SiCl 3 + MgCl 2 CH 3 SiCl 3 + CH 3 MgCl (CH 3 ) 2 SiCl 2 + MgCl 2 -carry. out distillation in order to separate the each components -Can be used to prepare mixed alkyl/aryl silanes by selecting appropriate components CH 3 SiCl 3 + C 6 H 5 MgBr (CH 3 )(C 6 H 5 )SiCl 2 + MgBrCl
11 Preparation From Sand to Silicones Silicone polymers are obtained by a three-step synthesis: Chlorosilane synthesis : Chlorosilane hydrolysis Polycondensation and Polymerization
12 2 nd step - Chlorosilane hydrolysis
13 3 rd step condensation and polymerization (CH 3 ) 2 Si(OH) 2 disilanol - H 2 O Polymer
14 Eg. -Hydrolysis of dimethyldichorosilane (CH 3 ) 2 SiCl 2 gives rise to straight chain polymers and as an active OH group is left at each end of the chain, polymerization continuous and the chain increases in length -(CH 3 ) 2 SiCl 2 is therefore a chain building unit -So the starting materials for the manufacture of silicones are alkyl or aryl substituted chlorosilanes
15 -Hydrolysis under carefully controlled conditions can produce cyclic structures with rings containing 3,4,5, or 6 Si atoms Tris cyclo-dimethylsiloxane tetrakis cyclodimethylsiloxane
16 -HCl is recycled and reacted with methanol to -give CH 3 Cl used in the direct process
17 Ring opening polymerization -Cyclic, (SiR 2 O) 3, 4 can be opened and polymerized to form long linear chains -The reaction being catalyzed by many base or acid compounds -Growing chain is called a living polymer
18 Most useful properties of silicones -Odorless and colorless -Thermal stability/heat resistant -good electrical insulators -Low chemical reactivity -Low toxicity -High flexibility of the siloxane chain -Oxidation resistant -Low surface tension -The ability to repel water (and form watertight seals) -Does not support microbial growth -Biocompatible
19 Origin of the properties -Odorless and colorless -Thermal stability/heat resistant -good electrical insulators -Low chemical reactivity -Low toxicity -High flexibility of the siloxane chain -Oxidation resistant -Low surface tension -The ability to repel water and form watertight seals -Does not support microbiological growth -Biocompatible inert
20 Their strength and inertness are related to Very high Si-O bond energy The siloxane bond is longer, more polar, more ionic and has a higher bond energy than a C-C bond.
21 The ability to repel water (water repellent) A Silicone chain surrounded by organic side groups looks like an alkane from the outside
22 High flexibility of the siloxane chain 1. Low Si-O rotational barrier -Corresponding to a nearly free rotation -siloxane backbone will be able to adopt various conformtions/orientations
23 High flexibility of the siloxane chain 2. The bonds between a silicon atom and the two oxygen atoms attached to it are very flexible.
24 High flexibility of the siloxane chain 3. Long Si-O skeletal bond length Bond Length (A 0 ) Si-O skeletal bond length 1.65 C-C bond length in most Organic polymers Steric interferences or intra-molecular congestion are diminished
25 High flexibility of the siloxane chain 4. Methyl groups (alkyl) shield the main chain
26 Silicone Products Sealants Adhesives Lubricants Medical applications (catheters) Cookware (non-stick coating) Electrical insulators can be found in products such as cosmetics, deodorant, defoamers
27 Zeolites
28 Zeolites -Zeolites (aluminosilicate minerals), are microporous crystalline solids with well-defined structures
29 . Mordenite Chabazite Heulandite Analcime Gmelinite
30 -This gives an infinite 3D lattice
31 Crystals are highly porous and are veined with submicroscopic channels
32 -Have internal cavities and channels of discrete sizes ( in the range Å) and shapes depending on the chemical composition and crystal structure sodalite faujasite
33 Uses Water purification As an adsorbent as catalysts, for the preparation of advanced materials Laundry detergents They are also used in medicine and in agriculture
34 Conventional water softening
35
36 4. Shape selective catalysis Product selectivity : Synthesis of p-xylene
37 Shape selective catalysis + CH 3 OH wider cages narrow channels Product selectivity
38 Reactant selectivity Shape selective catalysis
39 Shape selective catalysis Transition state selectivity -Reactions requiring smaller transition states proceed unhindered
40 Hydrothermal Synthesis of Zeolite -Hydrothermal synthesis can be defined as a method of crystallizing substances from aqueous solutions at hightemperature and high vapor pressures
41 Hydrothermal synthesis of zeolites
42 Templating Agents Pore sizeand shapecan be controlled by growing the zeolite around templates, R 4 N + may be used as a template around which the aluminosilicate framework crystallizes with large cavities to accommodate the ion -Later, upon heating the cation is pyrolyzed, but the structure retains the cavities
43
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