Membrane Materials for Gas and Separation: Synthesis and Application fo Silicon–Containing Polymers

The key to the successful development of separation membrane materials is finding and elaborating convenient methods for the synthesis of appropriate monomers and the determination of their optimal polymerization conditions, resulting in polymers with good gas transport and film–forming properties. This book discusses the chemistry and synthesis of silicon–containing polymers, and gas permeation and separation properties of the prepared polymers. Topics include

monomer synthesis polymerization processes catalyst selection physicochemical properties parameters of permeability diffusivity sorption thermodynamics computer modeling free volume practical applications

Aimed at researchers and advanced students working in membrane science, organosilicon chemistry, polymer science and physical chemistry as well as those in related areas such as materials science, this volume combines membrane science, organosilicon chemistry, polymer science, materials science and physical chemistry.

1. Permeability of polymers
Yu.Yampolskii

1.1 Introduction

1.2 Detailed mechanism of sorption and transport

1.2.1 Transition state model

1.2.2 Free volume model

1.2.3 Sorption isotherms

1.3 Concentration dependence of coefficients of permeability and diffusion

1.4 Effects of properties of gases and polymers on permeation parameters

References

2. Organosiloxanes (Silicones), Polyorganosiloxane Block Copolymers: Synthesis, Properties, and Gas Permeation Membranes Based On Them
I.Raigorodskii, V.Kopylov, and A.V. Kovyazin

2.1 Introduction

2.2 Synthesis and transformations of organosiloxanes

2.2.1 Polyorganosiloxanes with Aminoalkyl Groups at Silicon

2.2.2 Organosilicon alcohols and phenols

2.3 Synthesis of polyorganosiloxane block copolymers

2.3.1 Polyester(ether)–polyorganosiloxane block copolymers

2.3.2 Synthesis of polyurethane–, polyurea–, polyamide–, polyimide–organosiloxane POBC

2.4 Properties of polyorganosiloxane block copolymers

2.4.1. Phase state of polyblock organosiloxane copolymers

2.5. Morphology of POB and its effects on their diffusion properties

2.6 Some representatives of POBC as membrane materials and their properties

2.6.1 Polycarbonate–polysiloxanes

2.6.2 Polyurethane(urea) polysiloxanes

2.6.3 Polyimide(amide) polysiloxanes

2.7 Conclusions

References

3. Polysilalkylenes
N.V. Ushakov, S.L. Guselnikov, and E.Sh Finkelshtein

4. Polyvinylorganosilanes: the materials for membrane gas separation
N.Ushakov

4.1 Introduction: historical background

4.2 Syntheses and polymerization of vinyltriorganosilanes

4.2.1 Syntheses of vinyltriorganosilanes.

4.2.2. Vinyltriorganosilanes (VTOS) polymerization.

4.2.2.1. VTOS homopolymerizaiton.

4.2.2.2. Statistical copolymerization of VTOS with other monomers

4.2.2.3. Block–copolymerization of VTOS with monomers of other types.

4.3 Properties of polymer materials based on polyvinyltriorganosilanes.

4.4 Concluding remarks

References

5. Substituted Polyacetylenes
T. Sakaguchi, Y. Hu, and T.Masuda

5.1 Introduction

5.2 Poly(1–trimethylsilyl–1–propyne) and related polymers

5.2.1 Synthesis and general properties

5.2.2 Permeation of gases and liquids

5.2.3 Aging effect and cross–linking

5.2.4 Free volume

5.2.5 Nanocomposites and hybrids

5.3 Poly[1–phenyl–2–(p–trimethylsilylphenyl)acetylene] and related polymers

5.3.1 Polymer synthesis

5.3.2 Gas separation

5.4 Desilylated polyacetylenes

5.4.1 Desilylation of poly[1(p–trimethylsilylphenyl)–2–phenylacetylene]

5.4.2 PDPAs from precursor polymers with various silyl groups

5.4.3 Soluble poly(diphenylacetylene)s obtained by desilylation

5.4.4 Poly(diarylacetylene)s

5.5 Polar group–containing polyacetylenes

5.5.1 Hydroxy group

5.5.2 Sulfonated and nitrated poly(diphenylacetylene)s

5.5.3 Other polar groups

5.6 Concluding remarks

References

6. Polynorbornenes
E.Finkelshtein, M.Gringolts, M.Bermeshev, P.Chapala, and Yu. Rogan

6.1. Introduction

6.2. Monomers synthesis

6.3. Metathesis polynorbornenes

6.4. Addition polynorbornenes

6.6. Conclusions

References

7. Polycondensation materials containing bulky side groups: synthesis and transport properties
S.Banerjee and D. Bera,

7.1. Introduction

7.2. Synthesis of the polymers

7.2.1. Polyimides

7.2.1.1. One step polymerization

7.2.1.2. Two step polymerization

7.2.1.2.1. Thermal imidization of poly(amic acid)

7.2.1.2.2. Chemical imidization of poly(amic acid)

7.2.2. Poly(arylene ether)s (PAEs)

7.2.3. Aromatic Polyamides (PAs)

7.2.3.1. Low temperature polymerization

7.2.3.2. High temperature polymerization

7.3.Effect of different bulky groups on polymers gas transport properties

7.3.1. Gas transport properties of the polyimides containing different bulky groups

7.3.2. Gas transport properties of the polyamides containing different bulky groups

7.3.3. Gas transport properties of the poly(arylene ether)s containing different bulky groups

7.3.4. Summary

References

8. Gas and vapor transport properties and free volume of Si–containing and related polymers
Yu.Yampolskii

8.1.Introduction

8.2. Rubbery Si–containing polymers

8.2.1 Polysiloxanes

8.2.2 Siloxane–containing copolymers (block copolymers, random copolymers and graft copolymers)

8.2.3 Polysilmethylenes

8.3. Glassy Si–containing polymers

8.3.1. Polymers with Si–O bonds in side chains

8.3.2 Poly(vinyltrimethyl silane) and related vinylic polymers

8.3.3 Metathesis norbornene polymers

8.3.4 Additive norbornene polymers

8.3.5 Polyacetylenes

8.3.6 Other glassy Si–Containing polymers.

8.4. Free volume in Si–containing polymers

References

9. Modeling of Si–containing polymers
J. R. Fried, T. Dubbs M. Azizi

9.1 Introduction

9.2 Main–Chain Silicon–Containing Polymers

9.2.1 Polysiloxanes

9.2.2 Polysilanes And Silalkylene Polymers

9.3. Side–Chain Silicon–Containing Polymers

9.3.1. Polyvinyltrimethylsilane

9.3.2. Poly[1–(Trimethylsilyl)–1–Propyne]

9.4 Conclusions

Appendices

References

10. Pervaporation and Evapomeation with Si Containing Polymers
T. Uragami

10.1. Introduction

10.2. Structural Design of Si Containing Polymer Membranes

10.2.1 Chemical Design of Si Polymer Membrane Materials

10.2.2 Physical Construction of Si Containing Polymer Membranes

10.3 Pervaporation

10.3.1 Principle of Pervaporation

10.3.2 Fundamentals of Pervaporation

10.3.3 Solution–Diffusion Model in Pervaporation

10.4. Evapomeation

10.4.1 Principle of Evapomeation

10.4.2 Principle of Temperature–Difference Controlled Evapomeation

10.5. Technology of Pervaporation with Si Containing Polymer Membranes

10.5.1 Alcohol Permselective Membranes

10.5.2 Hydrocarbon Permselecive Membranes

10.5.2.1 Aromatic Hydrocarbon Removal

10.5.2.2 Chlorinated Hydrocarbon Removal

10.5.3 Organic Permselecive Membranes

10.5.4 Membranes for Separation of Organic/Organic Mixture

10.5.5 Membranes for Optical Resolution

10.6.      Technology of Evapomiation with Si Containing Polymer Membranes

10.6.1 Permeation and Separation by Evapomeation

10.6.2 Concentration of Ethanol by Temperature–Difference Controlled Evapomeation

10.7. Conclusions

References

11. Si–containing polymers in membrane gas separation
Adele Brunetti, Leonardo Melone, Enrico Drioli, and Giuseppe Barbieri

Executive Summary

11.9.1. Introduction

11.9.2. Si–containing polymer membranes used in gas separation

Silicon rubber polymer membranes

Polyacetylene polymer membranes

Polynorbornene polymer membranes

Other polymer membranes

11.9.3. Separations

11.9.4. Membrane Modules

11.9.5. Competing technologies for separation of gases

11.9.6. Applications

Air separation

Hydrogen separation

Hydrocarbons separation

VOCs separation

References

Editors
Yuri Yampolskii
Eugene Finkelshtein
A.V. Topchiev Institute of Petrochemical Synthesis, RAS, Moscow, Russia