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PROCESS ECONOMICS
PROGRAM SRI INTERNATIONAL
Menlo Park, California
94925
Abstract
Process Economics Program Report No. 160
SILICONES
(June 1983)
Silicones comprise a broad group of polymers classified as fluids,
elastomers, and resins based on chains or networks of alternating sili-
con and oxygen atoms with pendant organic groups. They are stable, non-
sticking, and inert. They also have good low temperature properties
and are good electrical insulators. In 1981, over 250,000 metric tons
of silicones were produced in the free world; demand has been increas-
ing at 8 to 10% per year.
A silicone plant usually produces a broad range of products, in-
cluding many kinds of fluids, elastomers, and resins. These products
are obtained from different proportions of various organohalosilane
monomers, principal among which are methylchlorosilanes, phenylchloro-
silanes, and vinylchlorosilanes. This report discusses the technology
and economics of producing organohalosilanes and their conversion to
silicone polymers.
PEP'82 HWS/DC
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Report No. 160
SILICONES
by HAROLD W. SCHEELINE
DILIP CHANDWANI
June 1963
A private report by the
PROCESS ECONOMICS PROGRAM
Menlo Park, California 94025
I
l
For detailed marketing data and information, the reader is
referred to one of the SRI programs specializing in marketing
research. The CHEMICAL ECONOMICS HANDBOOK Program covers
most major chemicals and chemical products produced in the
United States and the WORLD PETROCHEMICALS Program covers
major hydrocarbons and their derivatives on a worldwide basis.
In addition, the SRI DIRECTORY OF CHEMICAL PRODUCERS services
provide detailed lists of chemical producers by company, prod-
uct, and plant for the United States and Western Europe.
ii
CONTENTS
1 INTRODUCTION. . . . . . . . . . . . . . . . . . . . . . . . . 1
2 SUMMARY ........................... 3
Methylchlorosilanes by Direct Synthesis ........... 6 Trichlorosilane by Direct Synthesis ............. 7 Phenylchlorosilanes ..................... 8 Vinylchlorosilanes ...................... 9 Silicone Fluids Silicone Elastomers ...........................................
9 11
Silicone Resins ....................... 12
3 INDUSTRY STATUS ....................... 13
Production .......................... 14 Uses ............................. 19 Fluids ........................... 20 Elastomers ......................... 23 Resins ........................... 24
4 SILICONES--AN OVERALL PERSPECTIVE . . . . . . . . I . . . . . 27
Organosilicon Monomers . . . . . . . . . . . . . . . . . . . . 27 Methylchlorosilanes . . . . . . . . . . . . . . , . . . . . 28 Trichlorosilane . . . . . . . . . . . . . . . . , . . . , . 28 Phenylchlorosilanes and Vinylchlorosilanes . . . . . . . . . 29
Silicone Polymers . . . . . . . . . . . . . . . . . . . . . . 30 Hydrolysis of Dimethyldichlorosilane . . . . . . . . . . . . 30 Cyclic Separation . . . . . . . . . . . . . . . , . . . . . 31 Equilibration . . . . . . . . . . . . . . . . . . . . . . . 31 Polymerization of Cyclic8 . . , . . . . . . . . . . . . . . 31
Silicone Elastomers . . . . . . . . . . . . . . . . . . . . . 32 Heat Curing Elastomers . . . . . . . . . . . . . . . . . . . 32 Room Temperature Vulcanizing Elastomers . . . . . . . . . . 33
5 METHYLCHLOROSILANES BY DIRECT SYNTHESIS ........... 35
Chemistry .......................... 35 Reaction Mechanism ..................... 38 Reaction Kinetics ..................... 39
Review of Processes ..................... 40 Synthesis of Methylchlorosilanes .............. 41 Catalyst and the Contact Mixture ............. 41
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CONTENTS
5 METHYLCHLOROSILANES BY DIRECT SYNTHESIS (Continued)
Purity of Raw Materials and Effect of Cocatalysts ... Temperature. ..................... Pressure ....................... Type of Reactor. ................... Silicon Conversion .................. Product Separation ...................
Auxiliary Processes ................... Process Description .................... Process Discussion .................... Cost Estimates ......................
6 TRICHLOROSILANE BY DIRECT SYNTHESIS ............
Chemistry ......................... Reaction Mechanism ................... Reaction Kinetics ....................
Review of Processes .................... Silicon Purity ..................... Catalyst ........................ Type of Reactor and Operating Conditions ........ Product Separation and Purification ...........
Process Description .................... Process Discussion .................... Cost Estimates ......................
7 PHENYLCHLOROSILANES ...................
Review of Processes .................... Direct Synthesis of Phenylchlorosilanes ......... Synthesis of Phenylchlorosilanes by Organometallic Methods Using Grignard Reactions ............ Synthesis of Phenylchlorosilanes by Reactions of Hydrosilanes with Benzene ................ Synthesis of Phenylchlorosilanes by the Reactions of Hydrosilanes with Chlorobenzene .............
Process Description .................... Process Discussion .................... Cost Estimates ......................
22 44 46 46 47 49 50 59 59
65
65 66 67 68 68 69 69 71 73 81 81
89
89 89
91
92
95 98 106 106
CONTENTS
8 VINYLCRLOROSILANES .................... 111
Review of Processes ................... 111 Direct Synthesis of Vinylchlorosilanes ......... 111 Chlorination and Dehydrochlorination of Ethyltrichlorosilane .................. 112 Addition of Hydrosilanes to Acetylene ......... 112 High Temperature Condensation of Vinyl Chloride with Hydrosilanes ................... 114
Process Description ................... 117 Process Discussion .................... 123 Cost Estimates ...................... 123
9 SILICONE FLUIDS ..................... 129
Chemistry ........................ 129 Review of Processes ................... 133 Hydrolysis of Dimethyldichlorosilane .......... 134 Hydrolysis Processes .................. 137 Isolation of Cyclics .................. 139 Production of Silicone Fluids ............. 140 Polymerization of Cyclics ............... 142
Process Description ................... 144 Hexamethyldisiloxane Preparation ............ 146 Dimethyldichlorosilane Hydrolysis ........... 146 Cyclics Separation ................... 148 Equilibration Section ................. 148 Polymerization Section ................. 149 Materials of Construction ............... 150
Process Discussion .................... 156 Cost Estimates ...................... 156
10 SILICONE GUMS AND ELASTOMERS ............... 165
Chemistry ........................ 165 Heat Cured Elastomers ................. 167 Room Temperature Vulcanizing Elastomers ........ 169
Review of Processes ................... 171 Polymerization ..................... 171 Heat Curing Elastomers ................. 175 Fillers ........................ 175 Reinforcing Fillers .................. 176 Extending Fillers ................... 179
V
CONTENTS
10 SILICONE GUMS AND ELASTOMERS (Continued)
Curing Agents. ..................... 181 Additives for Silicone Elastomers ............ 182
Compounding of Silicone Elastomers ........... 185 Room Temperature Vulcanizing (RTV) Elastomers in General .................. 187 Two-Package RTV Elastomers ............... 187 Single-Package RTV Elastomers .............. 188 Compounding of RTV Elastomers .............. 192 Hydroxylated Polysiloxanes ............... 192 Multifunctional Cross-Linking Agents .......... 193
Process Description .................... 194 Process Discussion .................... 199 Cost Estimates ...................... 199
11 SILICONE RESINS ..................... 203
Chemistry ......................... 203 Review of Processes .................... 207
Process Description .................... 209
PATENT SUMMARY TABLES . . . . . . . . . . . . . . . . . . . . . . 213
CITED REFERENCES . . . . . . . . . . . . . . . . . . . . . . 247
PATENT REFERENCES . . . . . . . . . . . . . . . . . . . . . . 263
Vi
4.1
5.1
5.2
6.1
7.1
7.2
8.1
8.2
8.3
8.4
8.5
9.1
9.2
9.3
10.1
11.1
ILLUSTRATIONS
Overall Block Diagram of Silicone Plant FlowSheet........................
Composition of Direct Synthesis Product . . . . . . . . .
Methylchlorosilanes by Direct Synthesis FlowSheet........................
Trichlorosilane by Direct Synthesis FlowSheet........................
267
45
269
273
Phenyltrichlorosilane Yield as a Function of Temperature and Catalyst . . . . . . . . . . . . . . .
Phenylchlorosilanes from Hydrosilanes and Benzene Flowsheet........................
96
277
Methylvinyldichlorosilane Yield as a Function of Temperature . . . . . . . . . . . . . . .
Methylvinyldichlorosilane Yield as a Function of Contact Time . . . . . . . . . . . . . .
115
115
Vinyltrichlorosilane Yield as a Function of Temperature . . . . . . . . . . . . . . .
Vinyltrichlorosilane Yield as a Function of Molar Ratio of Trichlorosilane to Vinylchloride . . . . .
Vinylchlorosilanes from Vinyl Chloride and Hydrosilanes Flowsheet........................
Kinematic Viscosity of Silicone Fluids as a Function of Feed Monomer Concentrations . . . . . . . . . . . . . .
Block Diagram of Silicone Fluids Plant . . . . . . . . . .
Manufacture of Silicone Fluids FlowSheet........................
116
116
279
141
145
281
Silicone Gums and Elastomers Flowsheet........................ 285
Silicone Resins Flowsheet................. . . . . . . . 287
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TABLES
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2.1 Summary of Cost Estimates for Organohalosilanes ...... 4
2.2 Summary of Cost Estimates for Silicones .......... 5
3.1 Basic Producers of Silicones and Related Chemicals .... 16
3.2 Silicone Processors .................... 17
3.3 Silicone Production and Sales Statistics for the United States ................... 18
3.4 Production of Silicones in Japan ............. 19
3.5 Silicone Consumption by Major Market - 1981 ........ 20
3.6 U.S. Consumption of Silicone Fluids by Application .... 22
5.1 Low Boiling Silanes Formed in the Reaction of Methyl Chloride with Silicon ......... 36
5.2 Some High Boiling Products Formed in the Reaction of Methyl Chloride with Silicon ......... 37
5.3 Kinetic Data for the Reaction of Methyl Chloride with Silicon ............... 40
5.4 Methylchlorosilanes by Direct Synthesis Patent Summary ...................... 215
5.5 Selective Synthesis of Methylchlorosilanes ........ 42
5.6 Azeotropes Between 54.7' and 63.2OC ............ 48
5.7 Azeotrope Boiling Points ................. 48
5.8 Product Pattern ...................... 50
5.9 Methylchlorosilanes by Direct Synthesis Design Bases and Assumptions . . . . . . . . . . . . . . . 51
5.10 Methylchlorosilanes by Direct Synthesis StreamFlows . . . . . . . . . . . . . . . . . . . . . . . 54
5.11 Methylchlorosilanes by Direct Synthesis Major Equipment . . . . . . . . . . . . . . . . . . . . . . 56
5.12 Methylchlorosilanes by Direct Synthesis Utilities Summary . . . . . . . . . . . . . . . . . . . . . 58
5.13 Methylchlorosilanes by Direct Synthesis Total Capital Investment . . . . . . . . . . . . . . . . . 61
IX
5.14
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.1
7.2
7.3
7.4A
7.4B
7.5
7.6
TABLES
Methylchlorosilanes by Direct Synthesis Production Costs . . . . . . . . . . . . . , , . . . . . . .
Trichlorosilane by Direct Synthesis Patent Summary, Product Formation . . . . . . . . . . . . .
Trichlorosilane by Direct Synthesis Patent Summary, Product Separation and Purification . . . .
Trichlorosilane by Direct Synthesis Design Bases and Assumptions . . . . . . . . . . . . . . . .
Trichlorosilane by Direct Synthesis Stream Flows . . . . . . . . . . . . . . . . . . . . . . . .
Trichlorosilane by Direct Synthesis Major Equipment . . . . . . . . . . . . . . . . . . . . . .
Trichlorosilane by Direct Synthesis Utilities Summary . . . . . . . . . . . . . . . . . . . . .
Trichlorosilane by Direct Synthesis Total Capital Investment . . . . . . . . . . . . . . . . . .
Trichlorosilane by Direct Synthesis Production Costs . . . . . . . . . . . . . . . . . . . . . .
Trichlorosilane by Direct Synthesis Direct Operating Costs by Section . . . . . . . . . . . . .
Direct Synthesis of Phenylchlorosilanes . . . . . . . . . .
Yields of Arylchlorosilanes Obtained by Organomagnesium Synthesis in Tetrahydrofuran . . . . . . . .
Phenylchlorosilanes Design Bases and Assumptions . . . . . . . . . . . . . . . .
Phenylchlorosilanes from Hydrosilanes and Benzene Stream Flows, Phenyltrichlorosilane . . . . . . . . . . . .
Phenylchlorosilanes from Hydrosilanes and Benzene Stream Flows, Phenylmethyldichlorosilane . . . . . . . . . .
Phenylchlorosilanes from Hydrosilanes and Benzene Major Equipment . . . . . . . . . . . . . . . . . . . . . .
Phenylchlorosilanes from Hydrosilanes and Benzene Utilities Summary . . . . . . . . . . . . . . . . . . . . .
63
224
226
75
77
78
80
83
85
87
90
92
99
102
103
104
105
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TABLES
7.7 Phenylchlorosilanes from Hydrosilanes and Benzene Total Capital Investment . . . . . , . . . . , . . . . . . . 108
7.8 Phenylchlorosilanes from Hydrosilanes and Benzene Production Costs . . . . . . . . . . . . . . . . . . . . . . 109
7.9 Phenylchlorosilanes from Hydrosilanes and Benzene Direct Operating Costs by Section . . . . . . . . . . . . . 110
8.1 Vinylchlorosilanes Patent Summary. . . . . . . . . . . . . . . . . . . . . . . 232
8.2 Direct Synthesis of Vinylchlorosilanes . . . . . . . . . . . 112
8.3 Vinylchlorosilanes Design Bases and Assumptions . . . . . . . . . . . . , . . . 118
8.4A Vinylchlorosilanes from Vinyl Chloride and Hydrosilanes Stream Flows, Vinyltrichlorosilane . . . . . . . . . . . . . 119
8.4B Vinylchlorosilanes from Vinyl Chloride and Hydrosilanes Stream Flows, Methylvinyldichlorosilane . . . . . . . . . . 120
8.5 Vinylchlorosilanes from Vinyl Chloride and Hydrosilanes Major Equipment . . . . . . . . . . . . . . . . . . . . . . 121
8.6 Vinylchlorosilanes from Vinyl Chloride and Hydrosilanes Utilities Summary . . . . . . . . . . . . , . . . . . . . . 122
8.7 Vinylchlorosilanes from Vinyl Chloride and Hydrosilanes Total Capital Investment . . . . . . . . . . . . . . . . . . 124
8.8 Vinylchlorosilanes from Vinyl Chloride and Hydrosilanes Production Costs . . . . . , . . . . . . . . . . . . . . . . 125
9.1 Survey of the Products of the Hydrolysis of Dimethyldichlorosilane, Dimethyldimethoxysilane, and Dimethyldiethoxysilane, under Different Conditions . . . . . 137
9.2 Silicone Fluids PatentSummary....................... 234
9.3 Silicone Fluids Design Bases and Assumptions . . . . . . . . . . . . . . . . 147
9.4 Silicone Fluids StreamFlows. . . . . . . . . . . . . . . . . . . . . . l , 151
9.5 Silicone Fluids Major Equipment . . . . . . . . . . . . . . . . . . . . . . 153
Xi
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TABLES
9.6 Silicone Fluids Utilities Summary . . . . . . . . . . . . . . . . . . . . . 155
9.7 Silicone Fluids Total Capital Investment . . . . . , . . , . . . . . . . . 158
9.8 Silicone Fluids Production Costs . . . . . . . . . . . . . . . . . . . . . 161
9.9 Silicone Fluids Direct Operating Costs by Section . . , . . . . . . . . . . 163
10.1 Silicone Gums and Elastomers Patent Summary, Polymerization of Low Molecular Weight Siloxanes . . . . . . . . . . . . . . , . . . . . . 237
10.2 Reinforcing Fillers . . . . . . . . . . . . . . . . . . . . 177
10.3 Extending Fillers . . . . . . . . . . . . . . . . . . . . . 180
10.4 Curing Agents. . . . . . . . . . . . . . . . . . . . . . . 183
10.5 Recommended Vulcanizing Agents for Various Vulcanizing and Processing Methods . . . . . . 184
10.6 Silicone Gums and Elastomers Patent Summary, Room Temperature Vulcanizing Elastomers . . 239
10.7 Silicone Gums and Elastomers Patent Summary, Hydroxylated Siloxanes and Multifunctional Cross-Linking Agents . . . . . . . . . . . 240
10.8 Silicone Elastomers Design Basis and Assumptions . . . . . . . . . . . . . . . 196
10.9 Silicone Elastomers Stream Flows . . . . . . . . . . . . . . . . . . . . . . . 197
10.10 Silicone Gums and Elastomers Major Equipment . . . . . . . . . . . . . . . . . . . . . . 198
10.11 Silicone Gums and Elastomers Utilities Summary . . . . . . . . . . . . . . . . . . . . . 198
10.12 Silicone Gums and Elastomers Total Capital Investment . . . . . . . . . . . . . . . . . 200
10.13 Silicone Gums and Elastomers Production Costs . . . . . . . . . . . . . . . . . . . . . 201
11.1 Silicone Resins PatentSummary . . . . . . . . . . . . . . . . . . . . . . 241
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