From Silicon To Silicones
From silicon to silicones
Introduction to the chemistry
Geir J Andersen
17.04.2012
Introduction Simple Chemistry
Simple Chemistry
• Direct Process
• Direct Process
M2
Methyl Chloride + Silicon ===== Dimethyldichlorosilane
Methyl Chloride + Silicon ===== Dimethyldichlorosilane
2MeCl
2MeCl+ Si =====
+ Si ===== Me22SiCl2
Me2SiCl
In the presence of a Copper Catalyst
In the presence of a Copper Catalyst
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Simple Chemistry
• Hydrolysis
Dimethyldichlorosilane + Water = Polydimethylsiloxane + HCl
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Simple Chemistry
• Hydrolysis
Dimethyldichlorosilane + Water = Polydimethylsiloxane + HCl
• Methyl Chloride
HCl + MeOH == MeCl + H20
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Linear PDMS
Me Me Me Me Me
(Cl) – Si – O – Si – O – Si – O – Si – O – Si – (OH)
Me Me Me Me Me
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Cyclic PDMS
Me
Si
Me
O O
Me - Si - Me Me - Si - Me
O O
Me
Si
Me
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What is silicon?
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Differentiation to Carbon Chemistry
Andreas Ruff
• In the differentiation to the Carbon chemistry lies the destinct behaviour of
Silicones. Carbon is able to form rather stable molecules in chain or ring
form, each connected via a C-C bondage.
• Chains or even rings consisting of Si-Si are instable and rather unknown
• This can be seen when comparing the binding energy:
C-C: 347,36 kJ/mol Si-Si: 176,4 kJ/mol
• This is due to the different electro negativities (EN) of the two Elements
EN of C: 2,50 EN of Si: 1,74 EN of O: 3,5
• The molecular binding length (respectively strength) depends on the
combination of elements with different EN:
C-O: 358 kJ/mol Si-O: 444 kJ/mol
• Carbon forms single and double bonding with Oxygen. These often are
the active centres of organic chemistry.
• The Si-O bond is very strong and serves as the backbone of any Silicone
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Products of the of
Products Direct
the Process
Direct Process
- Si -
Me Cl H Si
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Products of the Direct Process
M2
Me
Cl - Si - Cl
Me
Dimethyldichlorosilane
Me2SiCl2
“Di”
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Products of the Direct Process
M1
Me
Cl - Si - Cl
Cl
Monomethyltrichlorosilane
MeSiCl3
“Tri”
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Products of the Direct Process
M3
Me
Me - Si - Cl
Me
Trimethylmonochlorosilane
Me3SiCl
“Mono”
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Products of the Direct Process
MH
Me
H - Si - Cl
Cl
Methylhydrogendichlorosilane
MeHSiCl2
“Methyl hydrogen”
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Products of the Direct Process
M2H
Me
H - Si - Cl
Me
Dimethylhydrogenchlorosilane
Me2HSiCl
“Dimethyl hydrogen”
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Products of the Direct Process
Me Me
Cl - Si – Si - Cl
Me Me
A typical disilane
“High Boilers”
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Product Distribution
Product Wt % Value
Di 80 - 90 +++
Tri 5 – 10 +
Mono 1–3 ++
Methyl Hydrogen 1–3 +
Dimethyl Hydrogen <0.5 +++
Tetramethyl <0.5 ?
High Boilers 3 – 5% ---
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By-product Uses
Tri Fume Silica
Mono Internal + Pharma
MeH H-siloxane
Me2H Specialities
Me4 Redistribution
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Challenges
Andreas Ruff
Chemical Name Chem. Formula Boiling Point
Dichlordimethylsilan (CH3)2SiCl2 70°C
Trichlormethylsilan CH3SiCl3 66°C
Chlortrimethylsilan (CH3)3SiCl 57°C
Trichlortrimethyldisilan (CH3)3Si2Cl3 152-156°C
• Fractional Distillation of M2 and M1
• Multi-stage columns (high reflux) with high energy consumption
• Azeotrope of CH3Cl and inert (N2, hydrocarbons)
• Loss of product (CH3 & Cl) due to bleed off
• Formation of Polysilanes (cleavable and non-cleavable)
• Loss of product (Si, CH3 & Cl) due to bleed off
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Processing of Dimethyldichlorosilanes
Andreas Ruff
Polykondensation (Hydrolysis) of M2 with H2O or CH3OH
+ H2O
• Intermediate formation of Silanol (OH-Si-OH)
• Polykondensation to Siloxane either in chain or ring form
• If n ≤ 8 then a ringstructure is energetic
advanced over linear chains
• Recovery of Chlorine either as HCl
or CH3Cl (feed)
• Octamethylcyclotetrasiloxan (D4)
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Chemistry of by-products
Andreas Ruff
• Chemistry of monofunctional Silane:
Application: Chainstopper
• Chemistry of trifunctional Silane:
Application: Crosslinker & Filler
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Silicone-Rubber - Chemistry
Andreas Ruff
The addition of silicone-vinyl end stopped polymer with a base silicon
(e.g. D4) relates back to simple organic chemistry. In this case a Pt
catalysed addition reaction.
Alternative reaction mechanism are possible with peroxides or free
radical initiated. Reaction can starts @ high temperature or is induced by
UV radiation. Self curing shall be avoided.
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Properties and Applications
Andreas Ruff
• Silicone Rubber
There are some incredible qualities to silicone rubber that make it a
superior product all around, and these include:
• Retention of flexibility and resilience across a wide range of environments,
exposure and temperatures
• Providing a much longer life to the product(s) using it
• High temperature resistibility
• Offering a large range of hardness, which means it can be fabricated into an
enormous number of shapes, sizes and styles
• High electrical insulation properties
• Unaffected by weather conditions
• Having no taste or smell, and an extremely low toxicity range making it
perfectly acceptable for direct food contact
• Low interaction with other chemicals
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Differentiation of Polymer and Elastomer
Andreas Ruff
Property Polymer Elastomer
Bonding type only chemical chemical and physical
Additives none Silica, Chalk, Carbon etc.
Deformation remains deformed formes back
Hardness ≤ ~ 30 shore A up to 90 shore A
Structure
Shore A hardness: Measured material deformation when penetrated with a
steel ball @ 12.5N. Scale from 0 Shore (2,5 mm) - 100 Shore (0 mm) depth.
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Typical Fillers used
Andreas Ruff
Black
Carbon paste, etc.
Non black
The non-black fillers for rubber are calcium carbonate, kaolin clay, precipitated
silica, talc, barite, wollastonite, mica, precipitated silicates, fumed silica and
diatomite. Of these, the three most widely used, by volume and by functionality, are
calcium carbonate, kaolin clay and precipitated silica Source: http://www.rtvanderbilt.com/NonBlackFillers.pdf
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The Effect of Fillers
Andreas Ruff
Source: http://www.rtvanderbilt.com/NonBlackFillers.pdf
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Filler Surface Activity
Andreas Ruff
A filler can offer high surface area, high aspect ratio and small particle size, but still provide relatively poor
reinforcement if it has low specific surface activity. In the simplest terms, this means the affinity for and ability to
bond to the matrix. The non-black fillers generally offer less affinity and less surface activity toward the common
elastomers.
Source: http://www.rtvanderbilt.com/NonBlackFillers.pdf
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Mechanical Properties of Elastomers
Andreas Ruff
The force required to stretch a defined specimen of Tear resistance is essentially a measure of resistance to the
rubber to a given percent elongation is measured as propagation of a crack or slit under tension. Large or poorly
modulus. Most often, modulus is reported at 300% bound fillers will act as flaws and initiate or
elongation (four times the original length). This can be propagate cracks under test conditions. Small particle size, high
alternatively viewed as the resistance to a given surface area, high surface activity and high aspect ratio allow the
elongating force. filler particles to act as barriers to the propagation of
microcracks, in addition to providing the higher tensile strength
required to resist failure.
Source: http://www.rtvanderbilt.com/NonBlackFillers.pdf
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What is the ideal mix of products from the Direct Process?
CH3
CH3
CH3 Si Cl M3
H Si Cl
CH3
MH
Cl
CH3
Cu, Zn, Sn
Si (s) + 2CH3Cl (g) Si(CH3)2Cl2 (g) Cl Si Cl M2
250-350oC
CH3
CH3 CH3
Disilanes (Cleavable)
Polysilanes (Non cleavable) CH3 Si Cl Cl Si Cl
M2H M1
H Cl
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Key to Performance
Andreas Ruff
Base Raw Materials
Business Strategy
Operating Conditions
