Silicone Resins and their Combinations

1 Introduction 11
1.1 Organo-siloxanes and organo-polysiloxanes 11
1.2 Chlorosilanes – the building blocks for silicone resins 17
1.3 Manufacture of the resin intermediates 20
2 Silicone resins 23
2.1 Pure silicone resins 23
2.1.1 Methyl-silicone resins 26
2.1.2 Methyl/phenyl-silicone resins 28
2.2 Silicone combination resins/silicone resin hybrids 29
2.2.1 Silicone-modified polyester resins 31
2.2.2 Silicone-modified alkyd resins 31
2.2.3 Silicone-modified epoxy resins 34
2.2.4 Silicone-modified polyacrylate resins 38
2.3 Alkoxy-silyl modified resins and alkoxy-silyl modified isocyanate crosslinkers 39
2.4 Radiation-curable silicone resins 41
2.4.1 Acrylic-functional silicone resins 41
2.4.2 Epoxy-functional silicone resins 45
2.5 Room temperature vulcanizing silicone resins (RTV resins) 46
2.6 Waterborne silicone resins 48
3 Examples of applications of silicone resins 51
3.1 Silicone resins for heat resistant coatings
and corrosion protection above 300 °C 51
3.2 Silicone-modified aromatic polyester resins for heat
resistant coatings up to 250 °C for decorative coatings 56
3.3 Applications at normal temperatures 59
3.3.1 Silicone-modified aliphatic epoxy resin
for versatile coating applications 59
3.3.2 Acrylic- and epoxy-functional silicone resins
as UV-cured release coatings 65
3.4 Silicones and silicone resins in building conservation 69
3.4.1 External water repellency 69
3.4.2 Internal water repellency 75
3.4.3 Architectural coatings 77
3.4.4 Silicate emulsion coatings and renderings 78
3.4.5 Emulsion based coatings with silicate character
(SIL coatings) 80
3.4.6 Siloxane architectural coatings
with strong water-beading effect 81
3.4.7 Silicone resin coatings and renderings 82
3.4.8 Below-critical PVC formulated exterior coatings 87
3.4.9 Photocatalytic architectural coatings 87
4 Outlook 91
5 Glossary 93
5.1 Façade protection theory according to Künzel 93
5.2 sd-value 93
5.3 w-value 95
5.4 Definitions of PVC and CPVC 97
6 Analysis of silicone polymers 99
6.1 NMR spectroscopy 99
6.2 IR spectroscopy 103
6.3 Wet analysis 103
7 Literature 105
Authors 108
Index 109

Foreword Because of their molecular structure, silicone resins and silicone combination resins are used in numerous industrial applications, particularly as binders, for formulating coatings. The linking of silicon and oxygen atoms to form a stable basic framework, in which the free valencies of the silicon are saturated by hydrocarbon groups, results in outstanding properties which cannot be achieved with other products. The many possible combinations of the silicone building blocks are reflected in the impressive diversity of silicone chemistry and the resultant products. The present book (2nd edition) is intended to provide a concentrated overview of the chemistry and technology of silicone resins and their use from an industrial viewpoint. It aims to report on current developments in the field of silicones for coatings and gives those approaching the subject an overview of the most important areas of application. Since publication of the 1st edition of this book almost ten years ago, some areas of application have seen further technological developments and these have driven significant advances. For example, silicone combination resins are being increasingly used in anti-corrosion coatings to cope with extreme weather conditions and temperatures. Alkoxy-silyl functional urethane resins are used in high-tech coatings to increase scratch resistance. New types of acrylic dispersions in combination with functional polysiloxanes enable the formulation of “below-critical” emulsion coatings with similar properties to “above-critical” silicone resin coatings. These and further innovations are described in the 2nd edition of this book and reflect the current state of the art in this field. Since this field will continue to develop, I am pleased that I have been able to win my colleague Dr. Sascha Herrwerth to join me as co-author for this new edition. I would like to thank our colleagues Dr. Michael Ferenz, Dirk Hinzmann and Dr. Berendjan de Gans for numerous technical discussions. Thanks are also due to Evonik for making available company literature and permission to reprint extracts as well as for technical and material resources. Wernfried Heilen Essen, July 2014

Foreword
Because of their molecular structure, silicone resins and silicone combination resins are used in numerous industrial applications, particularly as binders, for formulating coatings. The linking of silicon and oxygen atoms to form a stable basic framework, in which the free valencies of the silicon are saturated by hydrocarbon groups, results in outstanding properties which cannot be achieved with other products. The many possible combinations of the silicone building blocks are reflected in the impressive diversity of silicone chemistry and the resultant products.
The present book (2nd edition) is intended to provide a concentrated overview of the chemistry and technology of silicone resins and their use from an industrial viewpoint.
It aims to report on current developments in the field of silicones for coatings and gives those approaching the subject an overview of the most important areas of application.
Since publication of the 1st edition of this book almost ten years ago, some areas of application have seen further technological developments and these have driven significant advances.
For example, silicone combination resins are being increasingly used in anti-corrosion coatings to cope with extreme weather conditions and temperatures.
Alkoxy-silyl functional urethane resins are used in high-tech coatings to increase scratch resistance.
New types of acrylic dispersions in combination with functional polysiloxanes enable the formulation of below-critical emulsion coatings with similar properties to above-critical silicone resin coatings.
These and further innovations are described in the 2nd edition of this book and reflect the current state of the art in this field.
Since this field will continue to develop, I am pleased that I have been able to win my colleague Dr. Sascha Herrwerth to join me as co-author for this new edition.
I would like to thank our colleagues Dr. Michael Ferenz, Dirk Hinzmann and
Dr. Berendjan de Gans for numerous technical discussions.
Thanks are also due to Evonik for making available company literature and permission to reprint extracts as well as for technical and material resources.
Wernfried Heilen
Essen, July 2014