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- Herausgeber: Wiley-VCH Verlag GmbH & Co. KGaA
- Kategorie: Fachliteratur
- Sprache: Englisch
This first comprehensive overview of reactive extrusion technology for over a decade combines the views of contributors from both academia and industry who share their experiences and highlight possible applications and markets. They also provide updated information on the underlying chemical and physical concepts, summarizing recent developments in terms of the material and machinery used.
As a result, readers will find here a compilation of potential applications for reactive extrusion to access new and cost-effective polymeric materials, while using existing compounding machines.
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Veröffentlichungsjahr: 2017
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Table of Contents
Cover
Title Page
Copyright
Preface
List of Contributors
Part I: Introduction
Chapter 1: Introduction to Reactive Extrusion
References
Part II: Introduction to Twin-Screw Extruder for Reactive Extrusion
Chapter 2: The Co-rotating Twin-Screw Extruder for Reactive Extrusion
2.1 Introduction
2.2 Development and Key Figures of the Co-rotating Twin-Screw Extruder
2.3 Screw Elements
2.4 Co-rotating Twin-Screw Extruder – Unit Operations
2.5 Suitability of Twin-Screw Extruders for Chemical Reactions
2.6 Processing of TPE-V
2.7 Polymerization of Thermoplastic Polyurethane (TPU)
2.8 Grafting of Maleic Anhydride on Polyolefines
2.9 Partial Glycolysis of PET
2.10 Peroxide Break-Down of Polypropylene
2.11 Summary
References
Part III: Simulation and Modeling
Chapter 3: Modeling of Twin Screw Reactive Extrusion: Challenges and Applications
3.1 Introduction
3.2 Principles and Challenges of the Modeling
3.3 Examples of Modeling
3.4 Conclusion
References
Chapter 4: Measurement and Modeling of Local Residence Time Distributions in a Twin-Screw Extruder
4.1 Introduction
4.2 Measurement of the Global and Local RTD
4.3 Residence Time, Residence Revolution, and Residence Volume Distributions
4.4 Modeling of Local Residence Time Distributions
4.5 Summary
References
Chapter 5: In-process Measurements for Reactive Extrusion Monitoring and Control
5.1 Introduction
5.2 Requirements of In-process Monitoring of Reactive Extrusion
5.3 In-process Optical Spectroscopy
5.4 In-process Rheometry
5.5 Conclusions
Acknowledgment
References
Part IV: Synthesis Concepts
Chapter 6: Exchange Reaction Mechanisms in the Reactive Extrusion of Condensation Polymers
6.1 Introduction
6.2 Interchange Reaction in Polyester/Polyester Blends
6.3 Interchange Reaction in Polycarbonate/Polyester Blends
6.4 Interchange Reaction in Polyester/Polyamide Blends
6.5 Interchange Reaction in Polycarbonate/Polyamide Blends
6.6 Interchange Reaction in Polyamide/Polyamide Blends
6.7 Conclusions
References
Chapter 7: In situ Synthesis of Inorganic and/or Organic Phases in Thermoplastic Polymers by Reactive Extrusion
7.1 Introduction
7.2 Nanocomposites
7.3 Polymerization of a Thermoplastic Minor Phase: Toward Blend Nanostructuration
7.4 Polymerization of a Thermoset Minor Phase Under Shear
7.5 Conclusion
References
Chapter 8: Concept of (Reactive) Compatibilizer-Tracer for Emulsification Curve Build-up, Compatibilizer Selection, and Process Optimization of Immiscible Polymer Blends
8.1 Introduction
8.2 Emulsification Curves of Immiscible Polymer Blends in a Batch Mixer
8.3 Emulsification Curves of Immiscible Polymer Blends in a Twin-Screw Extruder Using the Concept of (Reactive) Compatibilizer
8.4 Emulsification Curves of Reactive Immiscible Polymer Blends in a Twin-Screw Exturder
8.5 Conclusion
References
Part V: Selected Examples of Synthesis
Chapter 9: Nano-structuring of Polymer Blends by in situ Polymerization and in situ Compatibilization Processes
9.1 Introduction
9.2 Morphology Development of Classical Immiscible Polymer Blending Processes
9.3
In situ
Polymerization and
in situ
Compatibilization of Polymer Blends
9.4 Summary
References
Chapter 10: Reactive Comb Compatibilizers for Immiscible Polymer Blends
10.1 Introduction
10.2 Synthesis of Reactive Comb Polymers
10.3 Reactive Compatibilization of Immiscible Polymer Blends by Reactive Comb Polymers
10.4 Immiscible Polymer Blends Compatiblized by Janus Nanomicelles
10.5 Conclusions and Further Remarks
References
Chapter 11: Reactive Compounding of Highly Filled Flame Retardant Wire and Cable Compounds
11.1 Introduction
11.2 Formulations and Ingredients
11.3 Processing
11.4 Evaluation and Results on the Compound
11.5 Cable Trials
11.6 Conclusions
References
Chapter 12: Thermoplastic Vulcanizates (TPVs) by the Dynamic Vulcanization of Miscible or Highly Compatible Plastic/Rubber Blends
12.1 Introduction
12.2 Morphological Development of TPVs from Immiscible Polymer Blends
12.3 TPVs from Miscible PVDF/ACM Blends
12.4 TPVs from Highly Compatible EVA/EVM Blends
12.5 Conclusions and Future Remarks
References
Part VI: Selected Examples of Processing
Chapter 13: Reactive Extrusion of Polyamide 6 with Integrated Multiple Melt Degassing
13.1 Introduction
13.2 Synthesis of Polyamide 6
13.3 Review of Reactive Extrusion of Polyamide 6 in Twin-Screw Extruders
13.4 Recent Developments in Reactive Extrusion of Polyamide 6 in Twin-Screw Extruders
13.5 Conclusion
References
Chapter 14: Industrial Production and Use of Grafted Polyolefins
14.1 Grafted Polymers
14.2 Industrial Synthesis of Grafted Polymers
14.3 Main Applications
14.4 Conclusion and Outlook
References
Index
End User License Agreement
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Guide
Cover
Table of Contents
Preface
Part I: Introduction
Begin Reading
List of Illustrations
Chapter 1: Introduction to Reactive Extrusion
Figure 1.1 Simplified process chain from monomer to the final plastics product [11].
Figure 1.2 Modification of PP with MAH and glass fibers [4].
Figure 1.3 Reactions to extend PET chains [4].
Chapter 2: The Co-rotating Twin-Screw Extruder for Reactive Extrusion
Figure 2.1 Character dimensions of twin-screw extruder. (Reproduced with permission of Coperion GmbH.)
Figure 2.2 Development of the ZSK design parameters diameter ratio and specific torque. (Reproduced with permission of Coperion GmbH.)
Figure 2.3 Modular design for ZSK barrels and screw elements. (Reproduced with permission of Coperion GmbH.)
Figure 2.4 Types of screw elements. (Reproduced with permission of Coperion GmbH.)
Figure 2.5 One- and two-flighted conveying screws. (Reproduced with permission of Coperion GmbH.)
Figure 2.6 Working principle of kneading blocks. (Reproduced with permission of Coperion GmbH.)
Figure 2.7 Three-lobed kneading blocks. (Reproduced with permission of Coperion GmbH.)
Figure 2.8 Operating principle of three-lobed kneading blocks. (Reproduced with permission of Coperion GmbH.)
Figure 2.9 Schematic of radial pressure profile in two-lobed kneading disks. (Reproduced with permission of Coperion GmbH.)
Figure 2.10 Radial pressure profile comparison between two- and three-lobed kneading disks. (Reproduced with permission of Coperion GmbH.)
Figure 2.11 Low shear (SAM) kneading blocks. (Reproduced with permission of Coperion GmbH.)
Figure 2.12 Tapered kneading blocks (TKB). (Reproduced with permission of Coperion GmbH.)
Figure 2.13 ZME and TME mixing elements. (Reproduced with permission of Coperion GmbH.)
Figure 2.14 SME mixing element. (Reproduced with permission of Coperion GmbH.)
Figure 2.15 Typical unit operations. (Reproduced with permission of Coperion GmbH.)
Figure 2.16 Time–temperature curves for discontinuous and continuous kneading. (Reproduced with permission of Coperion GmbH.)
Figure 2.17 Typical setup for TPE-V. (Reproduced with permission of Coperion GmbH.)
Figure 2.18 Productivity improvement with increased machine torque capacity. (Reproduced with permission of Coperion GmbH.)
Figure 2.19 Typical setup for polymerization of TPU. (Reproduced with permission of Coperion GmbH.)
Figure 2.20 Schematic of process configuration for grafting MAH onto a polyolefin polymer. (Reproduced with permission of Coperion GmbH.)
Figure 2.21 Schematic of process configuration for partial glycolysis on ZSK. (Reproduced with permission of Coperion GmbH.)
Figure 2.22 Diverse product range after partial glycolysis of PET. (Reproduced with permission of Coperion GmbH.)
Figure 2.23 ZSK extruder layout: Compounding of PP. (Reproduced with permission of Coperion GmbH.)
Chapter 3: Modeling of Twin Screw Reactive Extrusion: Challenges and Applications
Figure 3.1 Diagram of the interactions between the process parameters in the case of the polymerization of PMMA in a twin-screw extruder; the signs + or − indicate an increase or a decrease in the considered parameter.
Figure 3.2 Transesterification reaction of EVA copolymer.
Figure 3.3 Screw profile used for the esterification of EVA.
Figure 3.4 Esterification of EVA; change along the screws of the mean temperature, the cumulative residence time, and the conversion.
Figure 3.5 Esterification of EVA; evolution of the conversion with the flow rate. Symbols: experimental points, lines: theoretical model.
Figure 3.6 Esterification of an EVA; evolution of the conversion with the screw speed. Symbols: experimental points, lines: theoretical model.
Figure 3.7 Peroxide-controlled degradation of PP; screw profile used in the experiments.
Figure 3.8 Peroxide-controlled degradation of PP; example of calculated results; evolution of weight average molecular weight
M
w
, cumulative residence time
t
r
, and temperature
T
along the screws. Full lines correspond to first calculation and dotted lines to the final result, after coupling between reaction extent and viscosity.
Figure 3.9 Peroxide degradation of polypropylene; changes in the average molecular weight along the screws for various peroxide contents. Symbols are experimental points, lines are the results of the model
Figure 3.10 Peroxide degradation of polypropylene; changes in peroxide efficiency with peroxide concentration.
Figure 3.11 Peroxide degradation of polypropylene. Influence of feed rate on average molecular weight at constant screw speed (225 rpm, 170 °C, 0.1 wt%). Symbols are experimental points, lines are the results of the model.
Figure 3.12 Peroxide degradation of polypropylene. Influence of screw speed on average molecular weight at constant feed rate (10 kg h
−1
, 170 °C, 0.1 wt%). Symbols are experimental points, lines are the results of the model.
Figure 3.13 Peroxide degradation of polypropylene; change in average molecular weight along the screws with screw speed (a) and barrel temperature (b). Symbols are experimental points, lines are the results of the model.
Figure 3.14 Chemical mechanism of ϵ-caprolactone polymerization initiated by tetrapropoxy-titanium.
Figure 3.15 Polymerization of ϵ-caprolactone; evolution of conversion rate (CR) (--) and viscosity (−) along the screws.
Figure 3.16 Polymerization of ϵ-caprolactone; influence of feed rate on CR at constant screw speed. Symbols (•: 1.5 kg h
−1
; ○: 2.4 kg h
−1
; ▪: 3 kg h
−1
) represent experimental measurements by
1
H NMR.
Figure 3.17 General comparison between computed and measured CRs.
Figure 3.18 Reaction scheme of starch cationization.
Figure 3.19 Starch cationization; variation of degree of substitution along the screws with feed rate at constant screw speed (400 rpm, 80 °C,
DS
th
= 0.04).
Figure 3.20 Starch cationization; comparison between computed and experimental efficiency (• Quab 151®; ○ Quab 188®).
Figure 3.21 Polymerization of ϵ-caprolactone; changes in the CR with flow rate and barrel temperature.
Figure 3.22 Laboratory machine; variation of reaction efficiency with screw profile and flow rate (○ 2.5 kg h
−1
, • 5 kg h
−1
, □ 10 kg h
−1
, ▪ 20 kg h
−1
, □ 40 kg h
−1
).
Figure 3.23 Production machine; variation of reaction efficiency with screw profile and flow rate (•: 90 kg h
−1
, ○: 180 kg h
−1
, ▪: 360 kg h
−1
, □: 720 kg h
−1
).
Chapter 4: Measurement and Modeling of Local Residence Time Distributions in a Twin-Screw Extruder
Figure 4.1 Diagram of the in-line RTD measuring system involving three main parts: a fluorescent light generating source, fluorescent light detection and signal processing.
Figure 4.2 A picture and a schematic diagram of the optical probe.
Figure 4.3 (a) Three locations (three test points) where the RTD probes are placed; (b) details of the screw profile of the kneading zone between probes 1 and 2; (c) details of the three different types of kneading disks used for the kneading zone. A kneading block
x
/
y
/
z
is one which has a length of
z
mm and
y
disks. The latter are assembled
x
degrees one with respect to the other. The processing temperature is set at 220 °C.
Figure 4.4 Variation of the viscosity of the polystyrene as a function of shear rate at 220 °C.
Figure 4.5 Raw analog signal (relative voltage) versus time curves for three repeated experiments carried out under the following conditions: screw configuration 3; screw speed = 90 rpm, feed rate = 8 kg h
−1
; tracer = masterbatch containing 5% anthracene by mass; amount of the tracer = three pellets.
Figure 4.6 (a) Effect of the concentration of the tracer (anthracene) in the masterbatch on the raw analog signal at probe 3; (b) Normalized relative voltage versus time curves based on Figure 4.6a. Screw configuration 1; screw speed = 60 rpm; feed rate = 10.7 kg h
−1
; amount of the tracer masterbatch = 0.1 g (four pellets); concentration of the tracer in the masterbatch varying from 1% to 10% by mass. The baselines of the raw analog signal are scaled to zero.
Figure 4.7 (a) Effect of the amount of the masterbatch (number of pellets) on the raw analog signal at probe 3; (b) Normalized relative voltage versus time curves based on Figure 4.7a. Screw configuration 1; screw speed = 60 rpm; feed rate = 10.7 kg h
−1
. The baselines of the raw analog signal are scaled to zero.
Figure 4.8 Effect of screw speed on the RTD. (a) screw configuration 3 and probe 1; (b) screw configuration 3 and probe 2.
Figure 4.9 Effect of feed rate on the RTD. (a) screw configuration 3 and probe 1; (b) screw configuration 3 and probe 2.
Figure 4.10 Effect of the staggering angle of the kneading disks on the partial RTDs. (a) Probe 1 (b) Probe 2 (c) Probe 3. Screw speed = 120 rpm; feed rate = 15.5 kg h
−1
.
Figure 4.11 Effect of the staggering angle on the RTD over the kneading zone between probes 1 and 2. See Figure 4.10 for the screw configurations and the operating conditions.
Figure 4.12 Effect of the staggering angle on the RTD between probes 2 and 3. See Figure 4.10 for the operating conditions.
Figure 4.13 Effect of the staggering angle on the RTD between probes 1 and 3. The deconvolution results of
E
3
(
t
) and
E
1
(
t
) agree with the convolution results of
E
12
(
t
) and
E
23
(
t
) corresponding to Figure 4.11 and 4.12 well. See Figure 4.10 for the operating conditions.
Figure 4.14 Geometries of the three different types of kneading blocks and one type of gear blocks used for the test zone. A kneading block
x
/
y
/
z
has a length of
z
mm and
y
disks. The latter are assembled
x
degrees one with respect to the adjacent one. A gear block has two rows of gears along its length of 32 mm. There are 10 gears per row.
Figure 4.15 Effect of increasing screw speed and throughput on the RTD for a of 1.53 × 10
−3
liter/revolution. (a) Probe 1; (b) Probe 2. Screw configuration 1.
Figure 4.16 Dimensionless residence time distribution density function
E
(τ) versus τ curves corresponding to the
E
(
t
) versus
t
curves in Figure 4.15. (a) Probe 1; (b) Probe 2. Screw configuration 1, = 1.53 × 10
−3
liter/revolution. Note that all the
E
(τ) versus τ curves fall on a single curve.
Figure 4.17 RRD corresponding to probes 1 and 2, respectively. (a) Probe 1; (b) probe 2; screw configuration 1; = 1.53 × 10
−3
liter/revolution. Note that all the RRD curves overlap.
Figure 4.18 RVD corresponding to probes 1 and 2, respectively. (a) Probe 1; (b) probe 2; screw configuration 1; = 1.53 × 10
−3
liter/revolution. Note that all the RVD curves overlap.
Figure 4.19 Effects of the screw speed (a) and throughput (b) on the local RTD of the test zone of screw configuration 1.
Figure 4.20 Local RTD (a), RRD (b), and RVD (c) curves between probes 1 and 2 for screw configuration 3 at a given (2.04 × 10
−3
liter/revolution). They are obtained by deconvolution. Note that all the local RTD, RRD, and RVD curves fall on single master curves, respectively.
Figure 4.21 Effect of screw configuration on the local RRD and RVD for screw speed: 150 rpm, feed rate: 17.8 kg h
−1
. (a) RTD, (b) RRD, and (c) RVD.
Figure 4.22 Geometries of the kneading disks and flow channels for simulation.
Figure 4.23 Top view of (a) KD6 with gaps and (b) KD7 without gap.
Figure 4.24 Streamlines of two particles for KD3. Screw speed = 150 rpm; feed rate = 17.8 kg h
−1
.
Figure 4.25 Comparison of the local RTD between the numerical and experimental results for different feed rates.
Figure 4.26 Comparison of the local RTD between numerical and experimental results for different screw configurations.
Figure 4.27 Effect of stagger angle on the local RTD.
Figure 4.28 Effects of the disk gap (a) and disk width (b) on the local RTD.
Figure 4.29 Axial evolution of log η: (a) arithmetic mean of log η, (b) critical value of log η for given percentiles of marker particles. Screw speed: 150 rpm, feed rate: 17.8 kg h
−1
.
Figure 4.30 Effects of the disk gap and disk width on the axial evolution of log η: (a) arithmetic mean of log η, (b) log η for given percentiles of marker particles. Screw speed: 150 rpm, feed rate: 17.8 kg h
−1
. The vertical lines in Figure 4.34 a correspond to the locations of the disk gaps of KD6 of Figure 4.23.
Figure 4.31 Axial evolution of time-average efficiency ⟨
e
η
⟩: (a) arithmetic mean of ⟨
e
η
⟩, (b) ⟨
e
η
⟩ for given percentiles of marker particles. Screw speed: 150 rpm, feed rate: 17.8 kg h
−1
.
Figure 4.32 Axial evolution of time-average efficiency ⟨
e
η
⟩: (a) arithmetic mean of ⟨
e
η
⟩, (b) ⟨
e
η
⟩ for different percentiles of marker particles. Screw speed: 150 rpm, feed rate: 17.8 kg h
−1
.
Figure 4.33 Axial evolution of (a) the arithmetic mean of and (b) that of (
D
:
D
)
1/2
. Screw speed: 150 rpm, feed rate: 17.8 kg h
−1
.
Chapter 5: In-process Measurements for Reactive Extrusion Monitoring and Control
Figure 5.1 Effect of screw speed on the evolution of melt temperature along the screw axis and die of a co-rotating twin-screw extruder, upon compounding of PLA with a chain extender (unpublished data).
Figure 5.2 Set-up for in-process measurement of the average residence time and residence time distribution at a specific location of the extruder. The measuring probe sits in a modified barrel segment. It contacts the melt stream on one end and contains a bifurcated optical fiber bundle that transfers the light emitted by a mercury lamp source and modulated by an optical chopper, while simultaneously carrying the light emitted by the fluorescent tracer to a photodetector that converts it into a voltage signal (for details and results see [19]). (Carneiro
et al
. 2004 19]. Reproduced with permission of Elsevier.)
Figure 5.3 Effect of screw speed on the evolution of the minimum (a) and maximum (b) residence time along the screw axis and die of a co-rotating twin-screw extruder, upon compounding of PLA with a chain extender (unpublished data).
Figure 5.4 Temperature change of melt samples collected from various locations along the extruder axis (
v
3
to
v
6
) and deposited in the reservoir of an on-line rheometer set to 200°C prior to testing. (a) extruder set-up and locations for melt sampling/measurements; (b) results for PP with extruder barrel set to 210°C; (c) results for HDPE with extruder barrel set to 230°C [39].
Figure 5.5 In-line monitoring of polymerization of ϵ-caprolactam in a twin-screw extruder by means of FTIR. Sensitivity of the measured absorbance to changes in time of the monomer/polymer ratio (a) and screw speed (b). (Haberstroh
et al
. 2002 [56]. Reproduced with permission of Wiley.)
Figure 5.6 NIR set-up developed to monitor reactive extrusion in a co-rotating twin-screw extruder using commercial reflectance and transmission probes (Axiom Analytical, Inc., USA ) and NIR spectrometer (Bruker Optics, Bruker Corporation). (Barbas
et al
. 2012 [43]. Reproduced with permission of Wiley.)
Figure 5.7 Steps for developing a chemometrical model for NIR.
Figure 5.8 Viscosity curves of reactively degraded PP with increasing initiator concentration (curves 1–4) measured off-line (dashed lines) and in-line (solid lines) with a tapered slit. (Pabedinskas
et al
. 1991 [83]. Reproduced with permission of Wiley.)
Figure 5.9 On-line capillary rheometers from GÖTTFERT Werkstoff-Prüfmaschinen GmbH, Germany. (a) Compact on-line rheometer without melt return into the process (note also the purge valve); (b) on-line instrument with melt return and bypass with continuous circulating volume stream.
Figure 5.10 On-line capillary rheometer with modified barrel element to be inserted in between standard elements of a twin-screw extruder.
Figure 5.11 Effect of peroxide concentration on shear viscosity of PP + DHDP along a co-rotating twin-screw extruder. (Adapted from Machado
et al
. 2004 [97]. Reproduced with permission of Wiley.)
Figure 5.12 On-line rotational rheometer. From A to C: global set-up for measurements along the extruder; configuration adopted for coupling to the flow channel between extruder and die; operating sequence. (Mould
et al
. 2012 [100]. Reproduced with permission of Carl Hanser Verlag GmbH & Co. KG.)
Figure 5.13 Evolution of
G
′ and
G
″ (at 1 s
−1
) of a PA6/PE/PE-
g
-MA (70/15/15 w/w%) blend along the axis of a co-rotating twin-screw extruder, measured off-line and on-line. (Covas
et al
. 2008 [39]. Reproduced with permission of Elsevier.)
Figure 5.14 Evolution of the linear viscoelastic response of a PLA and chain extender system along the axis of a co-rotating twin-screw extruder (unpublished data).
Chapter 6: Exchange Reaction Mechanisms in the Reactive Extrusion of Condensation Polymers
Figure 6.1 Schematic representation of the interchange reaction mechanisms that can occur in polymers containing reactive functional groups: (a) the interchange involves the inner functional groups of the same chain, (b) the interchange involves the inner functional groups of two chains, (c) the interchange involves the outer and inner reactive groups of the same chain, and (d) the interchange involves the outer and inner reactive groups of different chains.
Scheme 6.1 Interchange reactions that occur in the melt mixing of PEs/PEs blends.
Scheme 6.2 Formation of acetaldehyde from 2-hydroxyethyl end groups of PET during processing [83].
Figure 6.2 Section of the
1
H NMR spectra of PET/PEN (bottom) and PET-Bz/PEN (upper) blends melt mixed for: (a) 30 min, (b) 60 min, and (c) 120 min.
Figure 6.3 Section of
1
H NMR spectra of all capped PET/PEN (50/50 w/w) melt mixed at 285 °C for 60 min without (a) and with (b) Ti(isopropoxide)
4
as catalyst.
Scheme 6.3 Schematic representation of the reaction that occurs during the melt mixing of PC/PBT blends in the presence of Ti(OBu)
4
as catalyst at processing temperature >300 °C.
Scheme 6.4 Schematic representation of the reaction that occurs during the melt mixing of PC/PEN blends [6].
Figure 6.4 Molar amount (mol%) of structural units in the copolymers formed by reactive blending of PC/PEN (1 : 1 mol/mol with respect to the repeat units) at different reaction time.
Figure 6.5 DSC traces of the initial PC/PEN blend and of all copolymers formed.
Scheme 6.5 Sequence of reactions responsible for the formation of copoly(ester-amide) by melt mixing of PBT-COOH/PA6 blends at 280 °C [49].
Figure 6.6 A cycle that depicts the regeneration of reactive −COOH end chains [49].
Figure 6.6 Normalized intensity/temperature profiles of the species
II
,
III
,
IV
, and
V
in Scheme 6.5, characterized by MALDI-TOF MS spectra of the PBT-COOH/PA6 blend melt mixed for 60 min at different temperatures.
Scheme 6.7 Thermal-degradation mechanism of PET heated at 285 °C in the presence of 0.5 wt% of TsOH [50].
Scheme 6.8 Reactions occurring by melt mixing (285 °C) of PET/MXD6 in the presence of terephthalic acid [51].
Scheme 6.9 Formation of cyclopentanone end groups during the melt mixing of MXD6 [51].
Figure 6.7 DSC trace in the
T
g
region for the PET/MXD6 melt mixed for different times in the presence of terephthalic acid.
Figure 6.8 SEM images (magnification 5000×) of PBT/PA6 blends (25/75 w/w): (a) binary, (b) added with CP-2EPOX.
Scheme 6.10 Aminolysis interchange reaction that occurs in the PC/PA6 blends [120].
Figure 6.9 Mol% of PA6 units versus processing time in: (a) TFE-soluble fractions and (b) insoluble fractions of melt-mixed PC/PA6 (1 : 1 mol/mol) blends. PA6
M
w
: (▴) 7930, (○) 50 000 g mol
−1
.
Scheme 6.11 Hydrolyis reaction of high molar mass PA-6 and consecutive reaction of amino end groups with the inner carbonate groups of PC [120].
Figure 6.10 SEM images of a PC/PA6 blend (25/75 w/w) melt mixed at 240 °C for 5 min (a) without and (b) 2wt% of PC-PA6 di-block copolymer.
Scheme 6.12 Formation of (a) secondary amino groups and (b) branching along the PA66 chains during the processing [115].
Scheme 6.13 Acidolysis interchange reactions that occur during the melt mixing of the aliphatic polyamide blends such as PA6,6/PA6,10 [52].
Figure 6.11 Sections of the
13
C NNR spectra of the PA6-COOH/PA4,6 melt mixed blends at 310 °C for (a) 0 min, (b) 30 min, (c) 60 min, and (d) 120 min.
Figure 6.12 Types of carbonyl resonance signals due to the dyads and triads sequences in the PA6/PA6,10, PA6/PA6,6, and PA6/PA4,6 copolyamides.
Figure 6.13 (a) Experimental and calculated
13
C NMR spectra of PA6-COOH/PA6,10 blends reacted at 310 °C (a) for 30 min and (b) for 60 min.
Figure 6.14 MALDI-TOF mass spectra, in the mass range of 850–1850 Da, of equimolar PA66-COOH/PA6,10 blend melt mixed at 290 °C for (a) 10 min, (b) 15 min, and (c) 30 min. Labels A and B indicate the PA6,6 and PA6,10 repeat units, respectively.
Chapter 7: In situ Synthesis of Inorganic and/or Organic Phases in Thermoplastic Polymers by Reactive Extrusion
Figure 7.1 Hydrolysis–condensations reactions of a tetraalkoxysilane (M = Si, R is an alkyl group).
Figure 7.2 Screw profile and injection point of titanium
n
-butoxide precursor for the processing of PP/TiO
2
nanocomposite. Extruder: Leistritz LSM 30–34, screw diameter
D
= 34 mm, length to diameter ratio
L/D
= 34.5. (Bahloul
et al
. 2011 [7]. Reproduced with permission of Wiley.)
Figure 7.3 Prediction of the conversion compared with experimental data for different concentrations (12%, 20%, and 30% of inorganic precursors) under different processing conditions (screw speed and flow rate). (Bahloul
et al
. 2011 [7]. Reproduced with permission of Wiley.)
Figure 7.4 TEM image of PP/TiO
2
nanocomposite materials: (a)
in situ
PP/TiO
2
and
(
b
)
melt blended PP/TiO
2
(anatase). (Bahloul
et al
. 2010 [15]. Reproduced with permission of Wiley.)
Figure 7.5 Heat release rate curves for pure PA 6 and
in situ
nanocomposites versus time at 35 kW m
−2
. (Theil-Van Nieuwenhuyse
et al
. 2013 [18]. Reproduced with permission of Elsevier.)
Figure 7.6 (a) Structure of the SiDOPO and (b) Heat release rate versus time for the copolymer PA66/PA6, and nanocomposites based on SiP and SiDOPO for a heat flux of 35 kW m
−2
. (Sahyoun
et al
. 2015 [20]. Reproduced with permission of Elsevier.)
Figure 7.7 Variation of the normal force versus mixing time. PVDF-HFP/Silica-SH nanocomposite (
R
0
= 0.5) for different
R
1
ratio. Time
t
= 0 s corresponding to the injection of the pre-hydrolyzed inorganic solution. (
R
1
= 0.2 curve on the left,
R
1
= 1.6 curve on the right). (Seck
et al
. 2015 [21]. Reproduced with permission of Elsevier.)
Figure 7.8 SEM images of extruded nanocomposites. Effect of
R
1
ratio on the morphology: From left to right
R
1
= 0.2; 0.4; 0.8; 1.6. The last image was magnified due to a change of scale in the particle size. (Seck
et al
. 2015 [21]. Reproduced with permission of Elsevier.)
Figure 7.9 Principle of reactive extrusion for designing nanoblends from the
in situ
synthesis of grafted copolymers. (Ruzette and Leibler 2002 [25]. Reproduced with permission of Nature Publishing Group.)
Figure 7.10 Reaction of PBT
100
grafting resulting in the EVA-
g
-PBT
100
copolymer synthesis. (Bahloul
et al
. 2009 [32]. Reproduced with permission of Elsevier.)
Figure 7.11 Morphology of the blend obtained from the
in situ
CBT polymerization in the presence of (EVA28 800/cBT
100
/Ti(OPh)
4
). (Bahloul
et al
. 2009 [32]. Reproduced with permission of Elsevier.)
Figure 7.12 Mechanical properties of EVA28 800/cBT
100
/Ti(OPh)
4
compared to EVA alone and to the blend obtained with another cyclic monomer (cBT
160
). (Bahloul
et al
. 2009 [32]. Reproduced with permission of Elsevier.)
Figure 7.13 Reactional scheme leading to PC–PCL copolymers formation under molten conditions during reactive extrusion.
Figure 7.14 Synthesis by reactive extrusion of PC/PCL copolymers. The table shows the different temperature profiles used in this work.
Figure 7.15 TEM images of the morphology of engage (70%)/PMMA blends by
in situ
synthesis of MMA. (Badel
et al
. 2012 [39]. Reproduced with permission of Wiley.)
Figure 7.16 Reaction scheme for the poly(ethylene-
co
-1-octene) functionalization with PMMA in the presence of DEPN. (Badel
et al
. 2012 [39]. Reproduced with permission of Wiley.)
Figure 7.17 DGEBA/IPD particles after crosslinking of a PS/25% DGEBA + IPD blend (SEM images). (a) The blend was mixed and crosslinked at 180 °C in the internal mixer at 64 rpm. Large irregular shape particles of DGEBA/IPD were obtained. (b) The blend was mixed at 180 °C in an internal mixer and then crosslinked in static conditions in a compression press. 1.4 µm spherical particles were formed [51].
Figure 7.18 PS/40 wt% DGEBA–MDEA blend cured at 177 °C. Transmission electron microscopy images of the blend crosslinked in dynamic conditions inside the internal mixer during (a)
t
= 30 min, (b)
t
= 43 min, (c)
t
= 80 min. (d) Same blend cured in static conditions during 6 h. DGEBA–MDEA appears in light gray. (Meynié
et al
. 2004 [53]. Reproduced with permission of Elsevier.)
Figure 7.19 Scheme of the proposed mechanism for morphology evolution of initially miscible epoxy/amine crosslinked under shear in a thermoplastic matrix. (Meynié
et al
. 2004 [53]. Reproduced with permission of Elsevier.)
Figure 7.20 PS/40 wt% DGEBA–MDEA blend cured at 177 °C. (a) Epoxy conversion of the blend (□) crosslinked in dynamic condition inside the internal mixer (▪) cured in static condition in a hot press [53]. (Reproduced with permission of Elsevier.) (b)
T
g
data of PS-rich phase (
T
gα
) and of the epoxy-rich phase (
T
gβ
) compared to data obtained from simulation as a function of epoxy conversion
p
. (Riccardi 2004 [54]. Reproduced with permission of Wiley.)
Figure 7.21 (a) Screw and temperature profile of the twin-screw extruder used to prepare PS/DGEBA-AEP oriented blends. The two injection zones of the amine, Z5 and Z8 are indicated. (b) Morphology of PS/DGEBA, no amine, draw ratio = 3 (c) Morphology of PS/DGEBA-AEP, amine injected in zone 8 of the extruder, draw ratio = 3, conversion of the epoxy = 71 wt%. (Fenouillot and Perier-Camby 2004 [56]. Reproduced with permission of Wiley.)
Figure 7.22 PS/40 wt% DGEBA–MDEA with 15 wt% SMX reactive copolymer cured at 177 °C in the internal mixer. Transmission electron microscopy image where DGEBA–MDEA appears in light gray. (Meynié
et al
. 2005 [58]. Reproduced with permission of Wiley.)
Figure 7.23 PS + 25 wt% trimethylol propane triacrylate + initiator cured at 130 °C in the internal mixer [51].
Chapter 8: Concept of (Reactive) Compatibilizer-Tracer for Emulsification Curve Build-up, Compatibilizer Selection, and Process Optimization of Immiscible Polymer Blends
Figure 8.1 SEM images of microtomed surfaces of various PS/PA6 (80/20 by mass) blends: (a) without PS-
g
-PA6, (b) PS-
g
-PA6a (5 wt%), (c) PS-
g
-PA6a (10 wt%), (d) PS-
g
-PA6a (15 wt%), (e) PS-
g
-PA6b (5 wt%), (f) PS-
g
-PA6b (10 wt%), (g) PS-
g
-PA6b (15 wt%), (h) PS-
g
-PA6c (5 wt%), (i) PS-
g
-PA6c (10 wt%), (j) PS-
g
-PA6c (15 wt%), (k) PS-
g
-PA6d (5 wt%), (l) PS-
g
-PA6d (10 wt%), and (m) PS-
g
-PA6d (15 wt%). PS-
g
-PA6 concentration is based on the mass of the dispersed phase. Mixing temperature: 230 °C; mixing time: 8.5 min and rotation speed: 65 rpm.
Figure 8.2 Effect of the molecular architecture of PS-
g
-PA6 as a compatibilizer on the emulsification curve of the PS/PA6 (80/20 by mass) blend. The PS-
g
-PA6 concentration is based on the mass of the dispersed phase. Mixing temperature: 230 °C; mixing time: 8.5 min; rotation speed: 65 rpm. Symbols: experimental data; curves: trends.
Figure 8.3 Schematic of the structure of PS-
g
-PA6-MAMA compatibilizer-tracer.
Figure 8.4 (a) Diagram of the in-line fluorescence measuring device involving three main parts: a fluorescent light generating source, fluorescent light detection and signal processing; (b) a photo of a bifurcated optical probe, which has the same dimensions as a pressure transducer mounted on a screw extruder; (c) a schematic of a bifurcated optical probe.
Figure 8.5 Screw configuration of the twin-screw extruder [17–19].
Figure 8.6 Geometry of the extrusion die used to install a bifurcated optical probe in the side hole (unit: mm).
Figure 8.7 Effect of the amount of the compatibilizer-tracer on the CCD and the corresponding DDD of the PS/PA6 (80/20 by mass) blend. Feed rate: 13 kg h
−1
; screw speed: 100 rpm. The amount of the PS-
g
-PA6-MAMA-1 compatibilizer-tracer is obtained from the anthracene concentration by the in-line fluorescent measuring device. The initial mass of the compatibilizer-tracer is 1.6, 3.2, or 4.8 g.
Figure 8.8 Emulsification curves obtained from the CCD and DDD curves illustrated in Figure 8.7 for the PS/PA6 (80/20 by mass) blend.
Figure 8.9 CCD and DDD curves of the PS/PA6 (80/20 by mass) blend compatibilized by PS-
g
-PA6-MAMA-1 and PS-
g
-PA6-MAMA-2, respectively. Die width: 5 mm; feed rate: 13 kg h
−1
; mass of the compatibilizer-tracer: 4.8 g; screw speed: 100 rpm.
Figure 8.10 Effect of the molecular architecture of the compatibilizer-tracer on the emulsification curve of the PS/PA6 (80/20 by mass) blend. Die width: 5 mm; feed rate: 13 kg h
−1
; mass of the compatibilizer-tracer: 4.8 g; screw speed: 100 rpm.
Figure 8.11 Effect of screw speed on the CCD and DDD curves of the PS/PA6 (80/20 by mass) blend. Die width: 5 mm; feed rate: 13 kg h
−1
; mass of the compatibilizer-tracer PS-
g
-PA6-MAMA-1: 3.2 g.
Figure 8.12 Effect of screw speed on the emulsification curves of the PS/PA6 (80/20 by mass) blend. Die width: 5 mm; feed rate: 13 kg h
−1
; mass of the compatibilizer-tracer PS-
g
-PA6-MAMA-1: 3.2 g.
Figure 8.13 Effect of the type of mixer on the emulsification curves of the PS/PA6 blends. The data for the short time domain and long time domain are obtained from the twin-screw extruder, whereas those for a batch mixer are obtained from a Haake torque rheometer. Blending conditions in the twin-screw extruder are: die width: 5 mm; feed rate: 13 kg mol
−1
; mass of PS-
g
-PA6-MAMA-1: 1.6 g for PS/PA6 (90/10 by mass) and 3.2 g for PS/PA6 (80/20 by mass); screw speed: 100 rpm. Blending conditions in the batch mixer are: screw speed: 65 rpm; mixing time: 8 min.
Figure 8.14 Common chemical reactions between functional groups: (a) acid/amine reaction to form an amide; (b) amine/epoxy reactions; (c) carboxylic acid/oxazoline; (d) carboxylic acid/epoxy; (e) two-step reaction to form an imide from amines and cyclic anhydrides [22].
Figure 8.15 Schematic of the structure of PS-
co
-TMI-MAMA reactive compatibilizer-tracer.
Figure 8.16 Formation of the PS-
g
-PA6-MAMA graft copolymer by the interfacial reaction between the PS-
co
-TMI-MAMA and PA6.
Figure 8.17 Two mixing modes for reactive blending of PS and PA6 using PS-
co
-TMI-MAMA as a reactive compatibilizer-tracer: continuous mixing and stepwise mixing.
Figure 8.18 Evolution of the percentage of the reacted PS-TMI-MAMA (a) and that of the DD of the PA6 (b) of the PS/PA6/PS-TMI-MAMA reactive blends as a function of mixing time for the continuous mixing case. The PS/PA6 (80/20 by mass) non-reactive blend in terms of
d
v
is shown as a reference. (c) Evolution of the DD of the PA6 of the PS/PA6/PS-TMI-MAMA reactive blends as a function of the percentage of the reacted PS-TMI-MAMA for the continuous mixing case.
Figure 8.19 (a) Evolution of the percentage of the reacted PS-TMI-MAMA (a) and that of the DD (b) of the PS/PA6/PS-TMI-MAMA (80/20/1.5 by mass) reactive blends as a function of mixing time for the stepwise mixing case. The continuous mixing case and the PS/PA6 (80/20 by mass) non-reactive blend are shown as references. (c) Comparison between the continuous and stepwise mixing cases for the PS/PA6/PS-TMI-MAMA (80/20/1.5 by mass) reactive blend in terms of
d
v
as a function of the percentage of the reacted PS-TMI-MAMA.
Figure 8.20 (a) and (b) confocal fluorescent spectroscopy images of the PS/PA6/PS-
co
-TMI-MAMA (80/20/3 by mass) reactive blend after 2 and 10 min of continuous mixing, respectively. (c) Confocal spectroscopy image of the PS/PS-TMI-MAMA (80/3) control system after 10 min of continuous mixing. Turquoise dots correspond to the PS-
g
-PA6-MAMA graft copolymer micelles whose
d
n
and
d
v
are about 200 and 300 nm, respectively.
Figure 8.21 Screw configuration of the twin-screw extruder used.
Figure 8.22 CCD, DDD, and RCCD of the PS/PA6 (80/20 by mass) blend with PS-TMI-MAMA as a reactive compatibilizer-tracer, which is injected as a pulse (3.2 g) at port 1. Feed rate: 13 kg h
−1
; screw speed: 100 rpm.
Figure 8.23 Emulsification curve of the PS/PA6 (80/20 by mass) blend using PS-TMI-MAMA as the reactive compatibilizer-tracer (data from Figure 8.21).
Figure 8.24 RCC versus CC of the PS-TMI-MAMA compatibilized PS/PA6 (80/20 by mass) blend (data from Figure 8.23).
Figure 8.25 Effective emulsification curve of the PS/PA6 (80/20) blend using PS-
co
-TMI-MAMA as the reactive compatibilizer-tracer (data from Figure 8.23).
Figure 8.26 Effects of the reactive compatibilizer-tracer injection location (port 1 or port 2) on the CCD (a), DDD (b), and RCCD (c) for the PS/PA6 (80/20 by mass) blend. Feed rate: 13 kg h
−1
; screw speed: 100 rpm; amount of PS-
co
-TMI-MAMA reactive compatibilizer-tracer: 3.2 g.
Figure 8.27 Effect of the reactive compatibilizer-tracer injection location on the emulsification curve (a), RCC as a function of CC (b), and the effective emulsification curve (c) of PS/PA6 (80/20 by mass) system. Feed rate: 13 kg h
−1
; screw speed: 100 rpm; amount of the reactive compatibilizer-tracer PS-
co
-TMI-MAMA: 3.2 g.
Figure 8.28 Effect of the PS/PA6 blend composition on the CCD, DDD, and RCCD using PS-
co
-TMI-MAMA as a reactive compatibilizer-tracer. Feed rate: 13 kg h
−1
; screw speed: 100 rpm; amount of the PS-TMI-MAMA reactive compatibilizer-tracer: 3.2 g. The reactive compatibilizer-tracer is injected at port 1 or port 2.
Figure 8.29 Effect of the PS/PA6 blend composition on the emulsification curves (a,b), the RCC versus CC (c,d), and the effective emulsification curves (e,f) using PS-
co
-TMI-MAMA as a reactive compatibilizer-tracer. Feed rate: 13 kg h
−1
; screw speed: 100 rpm; amount of tracer-compatibilizer: 3.2 g.
Figure 8.30 A schematic of the development of the interfacial reaction and morphology of the PS/PA6 (80/20 by mass) and PS/PA6 (95/5 by mass) blends using a reactive compatibilizer-tracer of type PS-TMI-MAMA.
Figure 8.31 Screw elements used in the experiments. (a) 30° kneading block and (b) 90° kneading block.
Figure 8.32 Effects of the geometry of the kneading block (30° vs 90°) on the CCD, DDD, and RCCD of the PS/PA6 (95/5 by mass) blend using the PS-
co
-TMI-MAMA as a reactive compatibilizer-tracer. Feed rate: 13 kg h
−1
; screw speed: 100 rpm; amount of compatibilizer-tracer: 3.2 g; reactive compatibilizer-tracer injection location: port 1.
Figure 8.33 Effect of the geometry of the kneading zone on the emulsification curve (a), RCC versus CC (b), and effective emulsification curve (c) using PS-
co
-TMI-MAMA as a reactive compatibilizer-tracer of the PS/PA6 (95/5 by mass) blend. Feed rate: 13 kg h
−1
; screw speed: 100 rpm; amount of tracer-compatibilizer: 3.2 g. The reactive compatibilizer-tracer is injected at port 1.
Chapter 9: Nano-structuring of Polymer Blends by in situ Polymerization and in situ Compatibilization Processes
Figure 9.1 Different steps involved in the morphology development of an immiscible polymer blend starting from solid pellets: melting of solid pellets (S); stretching/deformation of the molten polymer (M) to slender threads (T); breakup of slender threads to small particles (P); and coalescence of small particles to larger ones (C). (Li and Hu 2001 [5]. Reproduced with permission of Wiley.)
Figure 9.2 Mechanism proposed for the initial morphology development in polymer blending. (Sundararaj
et al
. 1995 [8]. Reproduced with permission of Elsevier.)
Figure 9.3 Morphology development for a polyamide (PA)/maleic anhydride modified ethylene–propylene rubber (EP-MA) blend system with 20 wt% EP-MA in a batch intensive mixer. The rotation speed of the rotors is fixed at 50 rpm. Volume average diameter can be statistically characterized by the following equation: . (Scott and Macosko 1994 [12]. Reproduced with permission of Elsevier.)
Figure 9.4 Torque as a function of mixing time for: (O) polystyrene (PS)/polyamide66 (PA66) blends (data from seven runs are overlaid); (+) vinyl oxazoline-modified polystyrene (PS-Ox)/PA66 blend (data from two runs are overlaid). (Scott and Macosko 1995 [7]. Reproduced with permission of Elsevier.)
Figure 9.5 Evolution of the radius of PA6 particles in the PP matrix for PP/PA6 (100/0.5 by mass) blend with and without a graft copolymer of PP and PA6 as a compatibilizer as a function of mixing time in an internal batch mixer of type Haake Rheocord. (Li and Hu 2001 [5]. Reproduced with permission of Wiley.)
Figure 9.6 Two mechanisms proposed for the suppression of coalescence by copolymers: (a) surface tension gradient (Marangoni) force and (b) steric repulsion. (Lyu
et al
. 2002 [19]. Reproduced with permission of American Chemical Society.)
Figure 9.7 Schematic description of the
in situ
polymerization and
in situ
compatibilization methodology for preparing (nano-)blends of polymer A and polymer B. A′: polymer A chain bears initiating sites either at the chain end(s) or along the chain; MB: the monomer of polymer B; A–B: copolymer of polymer A and polymer B.
Figure 9.8 Schematic representation of the mechanisms of the morphology development of two different systems subjected to a flow field. (a) An immiscible mixture of polymer A and polymer B; (b) a homogeneous mixture of polymer A and a polymerizable monomer of polymer B (MB). (Hu and Cartier 1999 [27]. Reproduced with permission of American Chemical Society.)
Figure 9.9 Schematic description of the activated anionic polymerization of ϵ-caprolactam (CL).
Figure 9.10 Mechanism of formation of a graft copolymer of PP and PA6, denoted as PP-
g
-PA6, using an isocyanate-bearing PP as a macromolecular activator [27].
Figure 9.11 Molecular structure of TMI [27, 32].
Figure 9.12 Reaction between PP-
g
-TMI (75 wt%) and CL (25 wt%) at 180 and 200 °C. The TMI content of the PP-
g
-TMI is 0.4 wt%. (Zhang
et al
. 2011 [30]. Reproduced with permission of Wiley.)
Figure 9.13 Evolution of the torque and temperature during the
in situ
polymerization of CL in a batch mixer in the presence of PP or PP-
g
-TMI. NaCL/micro-activator = 3.0/100 g of CL/PP or CL/PP/PP-
g
-TMI. All the polymerizing systems have almost the same temperature profiles, as shown by the single temperature–time curve. (Zhang
et al
. 2011 [30]. Reproduced with permission of Wiley.)
Figure 9.14 Morphologies of the
in situ
polymerized blends from the PP/CL/NaCL/micro-activator (50/50/3/3 by mass) system (a) and the PP-
g
-TMI/CL/NaCL/micro-activator (50/50/3/3 by mass) system (b), respectively. (Hu and Cartier 1999 [27]. Reproduced with permission of American Chemical Society.)
Figure 9.15 Comparison of the DSC thermograms of the polymerized material from the CL/NaCL/micro-activator (100/3/3 by mass), PP/CL/NaCL/micro-activator (50/50/3/3 by mass), and PP-
g
-TMI/CL/NaCL/micro-activator (50/50/3/3 by mass) during heating (a) and cooling (b). Heating and cooling rates are 10 °C min
−1
. (Zhang
et al
. 2011 [30]. Reproduced with permission of Wiley.)
Figure 9.16 Stress–strain traces of the PP/PA6 blends prepared from the PP-
g
-TMI/CL/NaCL/micro-activator (50/50/3/3 by mass) system at different testing speeds. Tensile speed = 50 (solid line), 150 (dashed line), and 500 mm min
−1
(dotted line). The stress–strain curve for the blend prepared from the PP/CL/NaCL/micro-activator (50/50/3/3 by mass) system is also shown for comparison; tensile speed = 50 mm min
−1
(solid line). (Zhang
et al
. 2011 [30]. Reproduced with permission of Wiley.)
Figure 9.17 Reaction mechanism of
in situ
polymerization and
in situ
compatibilization to prepare a compatibilized PPO/PA6 blend [34].
Figure 9.18 Effect of the PPO/PPO-
g
-MPAA/CL mass ratio on the morphology of the polymerized PPO/PPO-
g
-MPAA/CL system. (a) 30/0/70 by mass, (b) 15/15/70 by mass, (c) 0/30/70 by mass, and (d) 0/40/60 by mass. (Ji
et al
. 2005 [34]. Reproduced with permission of Elsevier.)
Figure 9.19 Schematic diagram of the formation of PA6/core–shell blends. (Yan
et al
. 2013 [35]. Reproduced with permission of Wiley.)
Figure 9.20 TEM images of PA6 (a and b), PA6/SEBS-
g
-MA/PS (85/5/10 by mass) blends (c and d), PA6/SEBS-
g
-MA/PS (85/7.5/7.5 by mass) blends (e and f), and PA6/SEBS-
g
-MA/PS (85/10/5 by mass) blends (g and h) prepared by reactive extrusion of PA6. (Yan
et al
. 2013 [35]. Reproduced with permission of Wiley.)
Chapter 10: Reactive Comb Compatibilizers for Immiscible Polymer Blends
Figure 10.1 Compatibilization by Reactive Linear polymers and the formation of micelles (a); by Reactive Comb polymers (b).
Figure 10.2 Schematic diagram of the molecular structure of Reactive Comb polymers.
Scheme 10.1 Synthesis of the Reactive Comb and Reactive Linear polymers.
Figure 10.3 SEM (a) and TEM (b) images of uncompatibilized PLLA/PVDF (50/50, w/w) blend (marrix: PLLA, particle: PVDF). All blends were prepared by melt mixing at 190 °C for 10 min using a batch mixer (Haake Polylab QC), with a rotation speed of 50 rpm.
Figure 10.4 SEM images of PLLA/PVDF blends compatibilized by RL (L-M-0-1-9) or RC (C-M-1-1-8(S-2400)) at different weight ratios; (a) PLLA/PVDF/RL (50/50/1), (b) PLLA/PVDF/RC (50/50/1), (c) PLLA/PVDF/RL (50/50/3), (d) PLLA/PVDF/RC (50/50/3), (e) PLLA/PVDF/RL (50/50/5), and (f) PLLA/PVDF/RC (50/50/5). The number average diameter (
d
n
) of the dispersed phase in PLLA/PVDF (50/50) blends versus wt% of L-M-0-1-9 (g) and C-M-1-1-8(S-2400) (h).
Figure 10.5 Stress–strain curves of PLLA/PVDF blends compatibilized by RL (L-M-0-1-9) (A) or RC(C-M-1-1-8(S-2400)) (B) polymers. The weight ratio of PLLA/PVDF/RL or RC was (a) 50/50/1, (b) 50/50/3 and (c) 50/50/5.
Figure 10.6 TEM images of PLLA/PVDF blends compatibilized by RL (L-M-0-1-9) or RC (C-M-1-1-8(S-2400)) at different weight ratios; (a) PLLA/PVDF/RL (50/50/3), (b) PLLA/PVDF/RC (50/50/3), (c) PLLA/PVDF/RL (50/50/5), and (d) PLLA/PVDF/RC (50/50/5). The scale bar was 1 µm.
Figure 10.7 AFM images of PLLA/PVDF (50/50) blends uncompatibilized (a) and compatibilized by 3 wt% of (b) L-M-0-2-8; (c) C-M-1-2-7(S-2400); (d, e) C-M-1-2-7(S-4800); and (f) C-M-1-2-7(S-6300).
Figure 10.8 Representative stress–strain curves of (a) PLLA/PVDF (50/50), (b) PLLA/PVDF/L-M-0-2-8 (50/50/3), (c) PVDF, and (d) PLLA/PVDF/C-M-1-2-7(S-4800) (50/50/3).
Figure 10.9 High-magnification TEM images of PLLA/PVDF (50/50) blends compatibilized by 3 wt% of (a) RL, (b) RC (C-M-1-2-7(S-2400)), (c) RC (C-M-1-2-7(S-4800)), and (d) RC C-M-1-2-7(S-6300). The scale bar was 200 nm.
Figure 10.10 The micelles formed by pull-in have a core of PLLA (light) and a shell of PMMA (dark gray); those by pull-out have an inverse inversion phase.
Figure 10.11 TEM images of PLLA/ABS blends compatibilized by RC (C-M-2-2-6(S-4800)) polymers at different compositions; (a) PLLA/ABS/RC = 90/10/3, (b) PLLA/ABS/RC = 70/30/3, (c) PLLA/ABS/RC = 50/50/3, and (d) PLLA/ABS/RC = 30/70/3. The scale bar was 5 µm.
Scheme 10.2 Reaction scheme between the carboxyl groups in PLLA with epoxy groups in RC polymer.
Figure 10.12 (A) Tensile stress–strain curves of neat components and compatibilized blends by RC (C-M-2-2-6(S-4800)) polymers; (a) PLLA, (b) PLLA/ABS/RC=90/10/3, (c) PLLA/ABS/RC = 70/30/3, (d) PLLA/ABS/RC = 50/50/3, (e) PLLA/ABS/RC = 30/70/3, and (f) ABS. (B) Effect of the ABS content on the energy to break and the ductility in the compatibilized blends.
Figure 10.13 SEM images of the tensile fracture surfaces of (a, b) uncompatibilized PLLA/ABS = 50/50 and (c, d) compatibilized PLLA/ABS/RC(C-M-2-2-6(S-4800)) = 50/50/3 blend. The scale bar was 2 µm in (a, c) and 1 µm in (b, d).
Figure 10.14 TEM images of the uncompatibilized blends and compatibilized PLLA/ABS by RC (C-M-2-2-6(S-4800)) polymers; (a) PLLA/ABS = 70/30, (b) PLLA/ABS/RC = 70/30/3, (c) PLLA/ABS = 50/50, and (d) PLLA/ABS/RC = 50/50/3. The scale bar was 500 nm.
Scheme 10.3 Schematic of the generation of the internal pressure and the enlargement of the free volume in the compatibilized blend.
Figure 10.17 Tan δ-temperature curves of neat components and compatibilized blends by RC (C-M-2-2-6(S-4800)) polymers; (a) PLLA, (b) PLLA/ABS/RC = 90/10/3, (c) PLLA/ABS/RC = 70/30/3, (d) PLLA/ABS/RC = 50/50/3, (e) PLLA/ABS/RC = 30/70/3, and (f) ABS.
Scheme 10.4 Proposed mechanism of
in situ
formed JNMs as compatibilizers in immiscible polymer blends.
Figure 10.16 PLLA/PVDF blends uncompatibilized and compatibilized by JNMs. SEM images of (a) PVDF/PLLA (50/50), (b) and (c) PLLA/PVDF/C-St-1-2-7(S-6300) (50/50/3); TEM images of (d) PLLA/PVDF (50/50), (e) and (f) PLLA/PVDF/C-St-1-2-7(S-6300) (50/50/3). The blend samples were ultramicrotomed to a thickness of 80–90 nm and then stained by RuO
4
for 4 h in order to selectively stain the PVDF phase as well as the JNMs (the white phase was PLLA, the black phase was JNMs and the gray phase was PVDF).
Figure 10.17 Tensile stress–strain curves of PLLA/PVDF (50/50) blends uncompatibilized (a) and compatibilized at a weight ratio of PLLA/PVDF/C-St-1-2-7(S-6300) = 50/50/3 for (b) 0.1 min, (c) 10 min, and (d) 15 min.
Scheme 10.5 Schematic view of the
in situ
formation of JNMs and the morphology development of binary blends from “droplet stacks domains” to “co-continuous phase encapsulated by nanomicelles” via reactive blending.
Chapter 11: Reactive Compounding of Highly Filled Flame Retardant Wire and Cable Compounds
Figure 11.1 Wire and cable market outlook 2015 Q4 [1].
Figure 11.2 Formulations tested (polar and non-polar polymer base).
Figure 11.3 Principles of silane grafting.
Figure 11.4 Simplified description of the Bayer process.
Figure 11.5 Endothermic decomposition of ATH.
Figure 11.6 Technical data of different fine precipitated ATH grades.
Figure 11.7 TGA at 1 K min
−1
of fine precipitated Martinal® grades.
Figure 11.8 Isothermal TGA of fine precipitated Martinal® grades.
Figure 11.9 Impact of specific surface area on compound properties.
Figure 11.10 Mixing/shearing mechanism on Kneaders [9, 10].
Figure 11.11 Details of the screw geometry on latest generation of Kneaders [13, 14]. (Reproduced with permission of Buss AG.)
Figure 11.12 Injection nozzle for liquid components [15]. (Reproduced with permission of Buss AG.)
Figure 11.13 Buss Kneader with 15
L
/
D
configuration for the second step of the two-step process [15]. (Reproduced with permission of Buss AG.)
Figure 11.14 Flowchart of two-step process versus one-step process.
Figure 11.15 Buss Kneader with 22
L
/
D
configuration for the one-step process [15]. (Reproduced with permission of Buss AG.)
Figure 11.16 Observed (intermediate product conditions after a forced emergency stop along the processing zones (flow direction from right to left) [4, 15]. (Reproduced with permission of Buss AG.)
Figure 11.17 Thermocouple installed in a hollow kneading tooth at selected position along the process length [4]. (Reproduced with permission of Buss AG.)
Figure 11.18 Example of the melt temperature at different points in a Kneader at various throughputs.
Figure 11.19 Impact of silane addition level on hot-set and melt flow of a polar compound.
Figure 11.20 Impact of silane addition level on hot-set and extrusion pressure of a polar compound.
Figure 11.21 Impact of specific surface area and loading on tensile strength.
Figure 11.22 Impact of specific surface area and loading on elongation at break.
Figure 11.23 Change of mechanical properties after aging at 135 °C.
Figure 11.24 Burning chamber of a cone calorimeter [18].
Figure 11.25 Heat release rate (HRR) over the time of cross-linked compounds according to Figure 11.2.
Figure 11.26 Heat release rate (HRR) measurement according to Figure 11.2.
Figure 11.27 Impact of silane addition level on hot-set and melt flow of a non-polar compound.
Figure 11.28 Mechanical properties of crosslinked non-polar compounds.
Figure 11.29 Char of the polar compound.
Figure 11.30 Char of the non-polar compound.
Figure 11.31 Cone performance of Martinal® OL-104 LEO filled cross-linked compounds in polar and non-polar polymer systems.
Figure 11.32 Standard crosshead [20].
Figure 11.33 Final cable construction [21]. (Reproduced with permission of Buss AG.)
Figure 11.34 Mounting of the cables in the burning chamber.
Figure 11.35 Cables mounted in the burning chamber according to EN 50399 [21]. (Reproduced with permission of Buss AG.)
Figure 11.36 Classification of cables according to the construction products regulation.
Figure 11.37 Additional criteria for the classification of cables.
Figure 11.38 Burning test according to EN 50399; sheathing material flame retarded with 160 phr Martinal® OL-104 LEO (formulation according to Figure 11.2).
Figure 11.39 Burning test according to EN 50399; sheathing material flame retarded with 160 phr Martinal® OL-104 LEO (formulation according to Figure 11.2) [21]. (Reproduced with permission of Buss AG.)
Figure 11.40 Comparison of the key properties measured according to EN 50399.
Figure 11.41 Burning test according to EN 50399; sheathing material flame retarded with 187.5 phr Martinal® OL-104 LEO (formulation according to Figure 11.2).
Figure 11.42 Burning test according to EN 50399; sheathing material flame retarded with 187.5 phr Martinal® OL-104 LEO [21]. (Reproduced with permission of Buss AG.)
Figure 11.43 Flame spread at different loading [21]. (Reproduced with permission of Buss AG.)
Chapter 12: Thermoplastic Vulcanizates (TPVs) by the Dynamic Vulcanization of Miscible or Highly Compatible Plastic/Rubber Blends
Figure 12.1 Schematic of thermal reversibility of copolymer TPEs.
Figure 12.2 Schematic illustration of the transformation from blend to TPV in morphology.
Figure 12.3 Sketch illustrating the deformation and recovery of dynamically vulcanized blends.
Figure 12.4 Tan δ versus temperature for the PVDF/ACM blends with various composition ratios: (a) neat PVDF, (b) PVDF/ACM 95/5, (c) PVDF/ACM 90/10, (d) PVDF/ACM 80/20, (e) PVDF/ACM 70/30, (f) PVDF/ACM 60/40, (g) PVDF/ACM 50/50, (h) PVDF/ACM 40/60, (i) PVDF/ACM 20/80, and (j) neat ACM.
Figure 12.5 TEM images of the PVDF/ACM blends dynamically vulcanized with (a) 0 wt%, (b) 0.8 wt% curative (HMDC).
Figure 12.6 Schematic diagram of dynamic vulcanization induced phase decomposition and the phase structure for the TPVs (dark gray part indicates ACM and light gray part indicates PVDF).
Figure 12.7 Photograph of the injection molded dumbbell-shaped and tube-shaped TPV samples.
Figure 12.8 Strain–stress curves and strain recovery curves for the PVDF/ACM TPVs dynamically vulcanized with (a) 0 wt%, (b) 0.2 wt%, (c) 0.4 wt%, and (d) 0.8 wt% curative (HMDC).
Figure 12.9 SEM images of blends based on (a) EVM/EVA9, (b) EVM/EVA28, and (c) EVM/EVA40 at the constant ratio of 50/50. The dark regions represent the EVM phase and the light regions the EVA phase.
Figure 12.10 DMA–tanδ as a function of temperature for neat EVM, neat EVA28, and the EVM/EVA28 (50/50) blend.
Figure 12.11 Vulcanization curves of (a) pure EVA28, (b) pure EVM, and (c) the EVM/EVA28 (50/50) blends containing 0.2 wt% DCP.
Figure 12.12 Morphology transition of the EVM/EVA28 (50/50, wt/wt) after dynamic vulcanization. Panel (a) is the SEM image of non-vulcanized blend and (b) is the TEM image of dynamically vulcanized blend with 0.1 wt% DCP.
Figure 12.13 (a) Strain–stress curves for the EVM/EVA28 (50/50) blends with addition of the indicated DCP content. (b) Strain–stress curves of EPDM/PP (60/40) TPV samples A, B, C, D with same degree of resol and SnCl
2
with 3, 10, 15, 20 min dynamic vulcanization time.
Figure 12.14 Strain recovery curves for the EVM/EVA28 (50/50) TPVs with 0.1 wt% DCP at the indicated stretching.
Chapter 13: Reactive Extrusion of Polyamide 6 with Integrated Multiple Melt Degassing
Figure 13.1 Reaction scheme of anionic polymerization of PA6.
Figure 13.2 Conversion as a function of time for the polymerization of ϵ-caprolactame [61].
Figure 13.3 Inhibition of active catalyst by addition of water.
Figure 13.4 Schematic process set-up for the continuous anionic polymerization of polyamide 6 and multiple degassing of residual monomer in a twin-screw extruder.
Figure 13.5 Screw configurations for multiple melt degassing.
Figure 13.6 Residual monomer content for vacuum degassing without an entrainer (amount of activator: 2 wt%, polymer throughput: 10 kg h
−1
, screw speed: 400 rpm).
Figure 13.7 Residual monomer content for atmospheric degassing using an entrainer (amount of activator: 2 wt%, polymer throughput: 10 kg h
−1
, screw speed: 400 rpm).
Figure 13.8 Residual monomer content depending on number of degassing steps for 2 wt% activator and use of an entrainer in each degassing zone (polymer throughput: 10 kg h
−1
, screw speed: 400 rpm).
Figure 13.9 Residual monomer content and resulting mass temperature depending on number of degassing steps for different amounts of activator (polymer throughput: 10 kg h
−1
, screw speed: 400 rpm).
Figure 13.10 Assumed trend of mass temperature along the multiple degassing process depending on amount of activator.
Figure 13.11 Relative viscosity and resulting mass temperature depending on number of degassing steps for 2 wt% activator (polymer throughput: 10 kg h
−1
, screw speed: 400 rpm).
Figure 13.12 Relative viscosity and resulting mass temperature depending on number of vacuum degassing steps for 0.5 wt% activator (polymer throughput: 10 kg h
−1
, screw speed: 400 rpm).
Figure 13.13 Thermal degradation of polyamide 6 with 2 wt% activator based on anionic polymerization depending on temperature and time.
Figure 13.14 Change of molecular weight distribution for low amount of activator due to monomer degassing (polymer throughput: 10 kg h
−1
, screw speed: 400 rpm).
Figure 13.15 Change of molecular weight distribution for high amount of activator due to monomer degassing (polymer throughput: 10 kg h
−1
, screw speed: 400 rpm).
Figure 13.16 Change of molecular weight due to triple degassing for different contents of activator (polymer throughput: 10 kg h
−1
, screw speed: 400 rpm).
Figure 13.17 Influence of amount of water as entrainer on residual monomer content for the two-step degassing of PA6 based on 0.5 wt% activator (polymer throughput: 10 kg h
−1
, screw speed: 400 rpm).
Figure 13.18 Influence of amount of water as entrainer on relative viscosity for the two-step degassing of PA6 based on 0.5 wt% activator (polymer throughput: 10 kg h
−1
, screw speed: 400 rpm)
Figure 13.19 Influence of different entrainers on residual monomer content, relative viscosity and mass temperature for PA6 based on 0.5 wt% activator and two-step degassing (polymer throughput: 10 kg h
−1
, screw speed: 400 rpm).
Figure 13.20 Residual monomer content depending on polymer throughput (screw speed: 400 rpm).
Chapter 14: Industrial Production and Use of Grafted Polyolefins
Figure 14.1 Chemical process of synthesis (a) and possible structures of grafted polymers achievable by grafting polar monomers onto a non-polar backbone (b).
Figure 14.2 General principle of melt grafting via extrusion.
Figure 14.3 Working steps of solid state grafting in an industrial scale.
Figure 14.4 The principle of solid state grafting.
Figure 14.5 Comparison of melt grafted and solid state grafted polypropylene types (a) and reaction mechanism of grafting polypropylene with maleic acid anhydride using different reaction conditions (b).
Figure 14.6 Improvement of properties of PP GF compound by using a coupling additive (a) and REM-Figure of a polypropylene glass fiber compound without coupling agent (b) and with a solid state grafted polypropylene containing maleic acid anhydride groups (SCONA TPPP 9012 FA) as coupling agent (c). (Reproduced with permission of BYK-Chemie GmbH.)
Figure 14.7 Exemplary screw design used for compounding of glass in polyolefins.
Figure 14.8 Reaction of the coupling agent with the sized glass fiber. (The black square illustrates a sized glass fiber containing primary amine groups.)
Figure 14.9 Comparison of performance of two grafted polyolefins with different grafting levels regarding impact strength.
Figure 14.10 Influence of increasing coupling agent quantity on the properties of the PP/GF compound.
Figure 14.11 Processing temperatures for commonly used thermoplastics compared to the temperature of wood degradation [19].
Figure 14.12 Influence of wood flour content on basic mechanical properties of PP-based WPC.
Figure 14.13 Bending strength and Charpy impact strength for PP/wood flour (60/40 wt%) with and without a coupling agent.
Figure 14.14 Comparison of the influence of coupling agents with different grafting levels onto bending strength of WPC based on polypropylene with 40 wt% wood flour [22].
Figure 14.15 Coupling mechanism of maleic acid anhydride grafted polypropylene on wood (fibers).
Figure 14.16 Example for search of optimal dosage of a coupling agent at various grafting levels.
Figure 14.17 Improving the level of grafting by combining solid phase grafting with melt grafting in a two-step synthesis.
Figure 14.18 Comparison of properties of HDPE wood compounds using various coupling agents based on maleic acid anhydride grafted polyethylene (SCONA TSPE 1112 GALL: LLDPE-
g
-MSA, SCONA TSPE 2102 GAHD: HDPE-
g
-MSA).
Figure 14.19 Mechanism of
in situ
production of compatibilizer for modified PA during extrusion.
Figure 14.20 Typical screw design for toughness modifying of polyamides.
Figure 14.21 Dispersion of polyolefins (immiscible polymers or polymer-elastomer-blend) during reactive compounding.
Figure 14.22 Polyamide blended with sPS, TEM-Figure Ultra-thin cut, contrast with RuO
4
-formalin solution. The lighter spots show the sPS finer distributed (a) or worse distributed (b). (Seydewitz
et al
. 2004 [27]. Reproduced with permission of Carl Hanser Verlag GmbH & Co. KG.)
Figure 14.23 Building of cracks during stretching of a polyamide blend with sPS, TEM-Figure Ultra-thin cut, contrast with RuO
4
. (Seydewitz
et al
. 2004 [27]. Reproduced with permission of Carl Hanser Verlag GmbH & Co. KG.)
Figure 14.24 Results for testing maleic acid anhydride grafted POE modifier (different SCONA TSPOE 1002-Types) regarding toughness and MVR.
Figure 14.25 Results for testing a maleic acid anhydride grafted polypropylene (SCONA TPPP 2112 GA) (in a mixture 70 % PA, X % SCONA TPP 2112 GA, 30-X % PP) regarding bending strength and Charpy impact strength (notched).
Figure 14.26 Reaction of acrylic acid grafted polyolefins with polyamides.
Figure 14.27 Viscosity regulation of PA 6 by using acrylic acid grafted HDPE (AA: acrylic acid).
Figure 14.28 Comparison of polyamide 6 blended with maleic acid anhydride grafted POE and acrylic acid grafted EVA regarding toughness and melt flow of the blends.
Figure 14.29 Reaction mechanism of PET with maleic acid anhydride grafted polyolefins.
Figure 14.30 Comparison of neat PET and recycling PET compounds with 12% maleic acid anhydride grafted POE.
Figure 14.31 Possible structures of TPEs [32].
Figure 14.32 Compression set values of commercially available SEBS-based compounds (SEPTON: trade name for SEEPS polymers from Kuraray; with high viscosity oil) [32].
