Chemistry of Polymers

Chemistry and Technology of Polymers (CHIM-9319)
1. General Introduction on Polymers

2. Chemistry of Polymers
2.1. Polymer Structure
2.2. Polymer properties
2.2.1. Polymer classes
2.2.2. Thermal properties
2.2.3. Mechanical properties
2.3. Polymer synthesis
2.3.1.Chain growth vs step growth
2.3.2. Polycondensation and polyaddition
2.3.3. Ionic polymerization
2.3.4. Radical polymerization
2.3.5. Coordination polymerization
I 3-1
Petroleum and gas Biosources

Chemistry of Polymers (A. Debuigne)
Structure
Energy recovery
Landfill
Bio-refinery Extraction Properties Compost
Extraction
Natural Polymers
Products Use
Raw materials Monomers Synthetic Polymers
Processing
Refinery Polymerization Fabrication
Chemical production reuse
Purification
Depolymerization
Technology of Polymers (K. Keck)

I 3-2
Technology versus Chemistry of Polymers
• Chemistry of polymerisation visualizes the principle chemical reactions to build a
synthetic macromolecule
 “Aufbaureaktion” (“(molecular weight) build-up reaction” by Karl Ziegler)
 Broad range
• Technology of polymerization narrows the above mentioned chemical

possibilities of polymerisation due to
 Reactor mode (continuous versus batch)
 Reactor type (tubular, autoclave, extruder, steam bath, UV-radiation, …)
 Polymerization medium
 Mass (bulk)
 Precipitation from mass
 Solution
 Slurry
 Emulsion
 Suspension
• In a 2D grid chemistry versus technology of polymerisation, not every

combination is possible, but some are strongly preferred
 Certain combinations are as well commercially strongly preferred
March 2023 I 3-3

Technology versus Chemistry of Polymers
• Technology of polymerization enlarges the chemisrty of polymerisation via
 Polymer alloys
 Orientation of macromolecules
 Addition of chemicals (initially not bound to the macromolecule; so-called additives)
 Composites
 “Processing”
 Modification of molecular weight during “processing” (various mechanisms including &
beyond chain & step reactions)
 Crosslinking outside polymerization (various mechanisms beyond chain & step reactions)
 Polymer chain “endcapping”
• Most polymers are not used as initially polymerized

 Design of molecular structure done more than once
 Significant “post-synthesis” modifications
March 2023 I 3-4

3. Technology of Polymers
3.1. Introduction & Terminology
3.2. Industrial Considerations
3.3. Polymerization Technology
3.4. Modifications during Polymerization
3.5. Mixing & Homogenization
3.6. Shaping & Orientation
3.7. Modification with Additives
4. End-of-Live Options
4.2. Routes to Recycling
4.3. Requirements for Recycling
4.4. Outlook on Energy & Resource Management
I 3-5
I 3-5
Use of Polymers in Various End Applications & Industry Segments
„Monomer“
Synthesis
Polymer Life Science

Mainly natural polymers
Preparation / Compound
Plastic (Synthetic) Fiber „Coating“ Functional

Additive
(Thermo) Plastic Textile Topical
Processing Processing Application Incorporation
Plastic Articles Textile Semi – Surface of Into Other

finished Goods Substrates Substrates
Plastic Industry Textile Industry Coating / Paint Leather

Leather Plastic
Paper Textile
Plastic
Textile
Source: C. Bonten; Kunststofftechnik; Hanser Publishers (2016); page 50

March 2023 I 3-6
„Monomer“
Synthesis
Polymer Life Science

Mainly natural polymers

Additive
o Dimensional stability at operating o Dimensional stability at operating (use) o Initially low dimensional stability o Various
(use) temperature temperature o Low Tg o Polymer alloy
o Minimum “constant” o Minimum “constant” temperature o Cold flow (“creep”) o In general not compatible with
temperature range range o Adhesion matrix
o Allignment of macromolecules o Paints, varnishes & adhesives (glue)
o Elongation

March 2023 I 3-7
Example of …
„Monomer“
Synthesis
Polymer
Broad enough temperature range with

(more or less) „constant“ properties
Plastic (Synthetic) Fiber
o Dimensional stability at operating o Dimensional stability at operating (use)

(use) temperature temperature
o Minimum “constant” o Minimum “constant” temperature
temperature range range
o Allignment of macromolecules
o Elongation

March 2023 I 3-8
POLYESTER … as example

Additive
o Terephthalic acid (increase of Tg) o Terephthalic acid (increase of Tg)

o “High” MW o Lower MW & elongation
o (Mainly) blow moulded PET o Oriented Polyester fiber
(thermoplastic processing)
o Adipic acid (decrease of Tg)
o MW depending on crosslinking
o (Mainly) Saturated aliphatic PES
(Unsaturated) PES resin
85% Polyester fiber + 15% Elasthan fiber

o (Mainly) Unsaturated PES (unsaturated
dicarboxylic acid (e.g. fumaric acid)
March 2023 I 3-9

Routes to the Formation of Thermoplastics, Elastomers & Thermosets
Raw materials with partially a functionality > 2

„Monomer“
Many raw materials are low viscous materials at room
LMW Raw Material Synthesis temperature.
Direct formation of a 3-dimensional network During polymer (network) growth mobility via thermal
Raw materials with 2 functionalities Synthesis energy and solvent decreases. The effect is irreversible.
Moderate temperatures required.
Polymer synthesis, mixing & shaping of the final article
„Linear“ Polymer must occur at the same moment.
Linear polymers even with a high degree of branching can

in general be mobilized (processed) via the incorporation
Thermoplastic Synthesis
of thermal energy and subsequent melting. Processing Subsequent Crosslinking
Polymer melts have generally a high viscosity. Many suitable chemical mechanisms
Linear polymers can as well be mobilized via solvents.
The mobilization/solidification behaviour is revesible and Low Crosslinking High Crosslinking
can be several times repeated. Density Density
Relatively high temperatures (up to 350°C) required for
processing.
Thermoplast Elastomer Duromer
March 2023 I 3-10

Life Cycle of Thermoplastics
Petrol
Synthesis of polymer Shaping of granules

& 1st melt conversion by fabricator & 2nd Endarticle Waste
(disposal or burning)
melt conversion
Compounding Recycling
Masterbatch
• Thermoplastics can undergo various melt-conversion steps

• The melt conversion steps can be separated in time & geography
• Often concentration of huge synthesis units at locations with easy access to feedstock
March 2023 I 3-11
Life Cycle of Thermosets
Petrol
Synthesis of polymer, 1st and only processing step & Waste

Endarticle
shaping (form giving) (disposal or burning)
• Thermosets can undergo only one processing & shaping step

• During "processing" ,the polymer is formed (synthesis) and shaped into the final article (or at least
semi-finished good)
• Geographically fragmented, local manufacturing
March 2023 I 3-12
Life Cycle of (Selected) Elastomers
2.2.1. Polymer classes
Petrol
(Polymer made by individual macromolecules) (Polymer made by one « Giant macromolecules »)
Synthesis of polymer Shaping of granules & Linear or branched

macromolecules lightly crosslinked Highly crosslinked
polymer polymers
& 1st melt conversion 2nd melt conversion amorphous polymers
semi-crystalline
polymers (including elastomer) thermosets
thermoplastics Crosslinked networks

Polymer-based materials that can be melted (reshaped) Crosslinked polymer-based materials
above a certain temperature and can be solubilized. that are insoluble and non-melting.
2nd or 3rd processing step & shaping (form giving) & Waste
Endarticle
vulcanisation (disposal or burning)
• Scheme only valide for rubbers (elastomers) with unsaruration in the backbone; so-called "butadiene
rubbers" (e.g. NR, BR, SBR, NBR, …)
• Elastomer formation as well possible via "Thermoset scheme" (but with lower crosslinking density)
• "Butadiene rubbers" are first processing as thermoplastics and only crosslinked (vulcanized) at the last
moment
• As exception, butadiene rubbers can be highly crosslinked an behave like thermosets
March 2023 Ebonit I 3-13

Temperature Ranges
Biosynthesis
of Polymers
Synthesis & "Processing"

of Thermosets
Synthesis
of Thermoplastics
0 100 200 300 400 500 600
Degree Centigrade °C
Processing
of Thermoplastics
Processing of Lead Pb
Mp ~328
Selected Melting Ranges
Aluminium Al ~ 660
Brass (Copper Cu + Zinc Zn) ~ 900-940
Iron Fe ~ 1540
Steel (Iron Fe + < 2% C) ~ 1370
Glass ~1400-1600
March 2023 I 3-14
Temperature Ranges
Biosynthesis
of Polymers
Synthesis & "Processing"

of Thermosets
Synthesis
of Thermoplastics
0 100 200 300 400 500 600
Degree Centigrade °C
Processing
of Thermoplastics
~ Minus 50-75°C
Maximum Solid State Temperature of Thermoplastics
VICAT softening temperature

> Minus 100°C
Actual maximum service life temperature
March 2023 I 3-15
Terminology
• Polymer
 Polymer (Greek origin) derived from “poly” (many) and “meros” (parts)
 Macromolecule
 Mainly organic material with high molecular weight being composed of many small molecules
(monomers)
 Repeating sub-units
 Monomers are connected (in most cases) via covalent bonds
 Approx. 8 000 to 6 000 000 Dalton (general)
 Approx. 30 000 to 1 000 000 Dalton for technical polymers
• Compound
 Technical material which comprises one or more polymers as well as all processing auxiliaries,
preservatives & modifiers at final concentration
 Solid or liquid
 Example: Solvent-based paint (coating) compound
March 2023 I 3-16

Terminology
• Compound (cont.)
 Technical material which comprises one or more polymers as well as all processing auxiliaries,
preservatives & modifiers at final concentration
 Solid or liquid
 Example: Polypropylene PP for automotive applications, comprising
 Polypropylene PP (brittle thermoplastic as matrix)
 Ethylene-Propylene-Diene Monomer EPDM crosslinked elastomer for impact resistance
 Inorganic filler (e.g. talc) to improve stiffness
 Pigment
 Preservatives for thermoplastic processing, thermal durability & UV resistance
March 2023 I 3-17

Terminology
• Masterbatch
 Pre-dispersion of additives in a polymeric matrix
 10 % active (in extreme cases up to 70 %)
 Required especially for thermoplastics in case processing equipment has limitation in mixing (homogenization)
 Solid or liquid
 Very common for pigments, but as well used for additives (preservant & modifier) which are difficult to
disperse
 Example: Solid pigment masterbatch, comprising
 Polypropylene PP (or PP wax)
 20% pigment
 Pre-dispersed
March 2023 I 3-18

Terminology
• "Processing"
 Mixing & homogenization (different polymer batches and/or additives)
 Shaping of final article and/or prior the semi-finished good
 Orientation of macro-molecules
 Mixing operation for thermoplastic (high viscous melt) and low viscous pre-cursors of thermosets are
significantly different
 Distributive mixing less sophisticated than dispersive mixing (specifically for additives)
 Very common for pigments, but as well used for additives (preservant & modifier) which are difficult to
disperse
 Examples: Solid polypropylene PP compound or masterbatch
Shaped PP/TPO car bumper
PP long fibers (unpigmented)
March 2023 I 3-19

Terminology
• "Processing" (cont.)
 On the example of plastics
 Preparation of a plastic (compound) and processing of plastics to form a plastic article
Polymer Plastic Produced Article
Preparation Processing Processing

Create "Compound"
Mixing Injection moulding IM Orientation
(Mixing of various batches of the same polymer)
Exrusion …
Distributive
Dispersive Additive dispersion Blow moulding BM
Filler Thermoforming
Reinforcement …
Degassing
Filter (& screen)
…
Source: A. Franck, B. Herr, H. Ruse & G. Schulz; Kunststoff Kompendium; (2011) page 147
C. Bonten; Kunststofftechnik; Hanser Publishers (2016); page 176
March 2023 I 3-20
Terminology
• Rubber ("R") versus Elastomer
 The term “rubber” is generally used for butadiene based rubbers and describes the not yet crosslinked
linear polymer with unsaturation in the backbone
 The term “elastomer” describes networks wit low crosslinking density
 In the case of “butadiene rubbers”, the term “elastomer” is used to describe the state after crosslinking
(vulcanization)
 Unfortunately, this terminology is not used in a systematic manner
 Examples: Polymers made from 1,4-Butadiene
Polybutadiene Butadiene Elastomer

Butadiene Rubber BR
March 2023 I 3-21

Terminology
Source: A. Franck & K. Biederbick; Kunststoff Kompendium (1988); pages 298 & 299
March 2023 I 3-22
Terminology
Source: A. Franck & K. Biederbick; Kunststoff Kompendium (1988); pages 298 & 299
March 2023 I 3-23
Genesis of Polymer Alloys
1920 Hermann Staudinger

“Macromolecules”
1940 1960 1980 2000
1920
PVC Polyvinylchloride SI Silicon PEI Polyetherimid LCP Liquid Crystal Polymers

PS Polystyrene PBT Polybutylene terephtalate PI Polyimide …
BR Butadiene Rubber EP Epoxy resin PESU Polyethersulfon
PMMA Polymethy methacrylate PAN Polyacrylonitrile PEEK Polyetherketone COC
LDPE Low Density Polyethylene ABS Acrylonitrile Butadiene Styrene … PBT / LCP
SBR Styrene Butadiene Rubber HDPE High Density Polyethelene PC / ASA
PA Polyamide PP Isotactic Polypropylene PC / ABS PP / PA
PET Polyethylene terephtalate EPDM Ethylene Propylene Diene Elast. PC / PBT PVC/ CPE
PIB Polyisobutylene EPM Ethylene Propylene Elastomer PET / EPDM PA / PPO / PS
PUR Polyurethane PTFE Polytetrafluoroethylene PET / EPDM PA / HDPE
PEOX Polyethylene oxide POM Polyacetal PP / EPDM SMA / ABS
… PPS Polyphenylenesulfid PVC / ABS POM / PUR
… PVC / EVA PBT / EPDM
PS / PPO …
SAN / NBR GFK Glassfiber reinforced plastic
PS / BR …
PVC / NBR
…
• Initial polymer material development based on new monomers and rawmaterials

• Since late 1980s sifted to polymer alloys (polymer blends) and composites
• Manufactyring of polymer alloys is partially decentralized
Source: Myung Kim; MKExtrusions (general service brochure); (2016)
March 2023 I 3-24
Terminology
• Composite
 Assembly or heterogenous mix of at least 2 materials which are not miscible
 In general complementation of (often but not exclusively mechanical) properties
 Maximization of synergistic effect & minimization of antagonistic effects
 Examples:
Steel fiber reinforced (mixture of) elastomers Carbon-fiber "glued together" with epoxy resin EP
Inorganic filler containing linseed oil
March 2023 I 3-25

I 3-26
Fundamental Industrial Considerations
• Industrial manufacturing of polymer compounds (for all end applications) comprises always
commercial considerations
• Selected commercial considerations
 Cost of raw material
 Cost of manufacturing
 Cost of sales & distribution
 "Fit-for-purpose“
• "Fit-for-purpose" is benchmarked against technical specifications ("technical standards") for a
plastic part (or paint, adhesive, etc.). The target is to meet such a technical specification with as
low cost as possible (including a potential safety marging).
• The target is not to create a plastic part (or paint, adhesive, etc) with superior properaties &
characteristic than those specified in the technical specifications
Tin Lizzy (Henry Ford)
First assembly line manufactured car
• This approach has 3 fundamental consequences

 In general various polymers of different natures (but requiring different modification after synthesis) can
compete for the same end application … Inter-polymer competition (e.g. talc-filled PP versus PA6)
 In general various materials of different natures can compete for the same end application … Inter-material
competition (e.g. plastic versus paper, glass & metal)
 Significant problems in the recycling of polymer based packaging material (short or even one-time use)
March 2023 I 3-27
Places of Synthesis
• Wide definition of synthesis (polymerisation) … design of molecular architecture
• Various different routes for initially linear polymers
Dedicated (Industrial)
Synthesis Reactor
Post synthesis
Reactive Extrusion Crosslinking
Initial „Molecular Architecture“ (excluding Orientation & Additives)
March 2023 I 3-28

Places of Synthesis (2)
Initial „Molecular Architecture“
Incorporation of Orientation of
Chemicals Macromolecules
Polymer Alloys
Final „Molecular Architecture“
March 2023 I 3-29

Size of Polymer Synthesis
Shellac Syndetikon
(secret from insects) (glue based on fishbone) Caoutchouc plantation
Size (Capacity) of Polymerization "Reactor"

< 100 mg
< 0.1 kg 1 to 25 kg
< 0.0001 tons 0.001 to 0.025 tons 2 000 000 tons/a
Modern synthesis plants for

thermoplastics
Fast drying, rigid glue 2-Component epoxy paint > 100 000 tons/a
(cyano-acrylate monomer)
Golden Triangle Polymers

2 polymerization trains of 1 000 000 tons/a each
Location: Orange (Texs, USA)
Polymerization Technology: Cr Loop Slurry (CPCHEM)
2-Component PUR adhesive Feedstock: Qatar Energy
IOL Intraocular lense implant based
on acrylic polymers
March 2023 I 3-30
Classification of (Thermo-) Plastics
Source: M. Loubry; Plastics – Intelligent materials; Bandol Conferences; Bandol (F), (2016)
March 2023 I 3-31
Classification of (Thermo-) Plastics
Source: M. Loubry; Plastics – Intelligent materials; Bandol Conferences; Bandol (F), (2016)
March 2023 I 3-32
Physical Form of Polymers
• Physical form of polymers (after synthesis) varies significantly
• In general, the particle size is not suitable for industrial "processing"
• In particular fine powder increases the risk of dust explosion
 Unfovourable dust explosion classification Polyethylene PE powder
• Particle size adjustment required (slurry process)
 Particle size enlargement to avoid (fine) dust explosion Cotton field (cellulose C)
 Regular particle size & dimension
 Good flow properties of particles
Carbon-fiber (carbonized
polyacylonitrile PAN fiber)
prepreg with epoxy resin EP
Extruded & granulated PE Spherical P-polypropylene PP Smoked natural rubber NR sheets

(morphology- controlled)
Fast drying, rigid glue Solvent based paint Polyurethane PUR foam Styrene-butadiene rubber SBR crumps after
(cyano-acrylate monomer) sheet (mattress) coaggulation & drying
March 2023 I 3-33
The Physical Form of Polymer (Compounds)
• Polymer (compounds) can be classified according to their physical form
• The physical form determines which "processing & conversion" operations are suitable
• Not every "processing & conversion" operation is suitable for every type of polymer
 Differentiation of thermoplastics from thermosets & elastomer
• Many polymers exist in various physical forms
Physical Form
Dissolved or Liquid Plastic Softelastic Solid

Emulsified
o Striking / brushing o Striking / brushing o Extrusion o Thermoforming o Mechanical
o Casting o Casting o Moulding
o Lamination o Blowing
o Pressing o Calandering
o Foaming o Pressing
o Gluing o Foaming
o Spinning
o Welding
Increased Viscosity
March 2023 I 3-34
Examples of Industrial Polymer (Article) Manufacturing
• C4 (Butene)-Linear Low Density Polyethylene LLDPE blown film grade
• Standard ("commodity") grade
Monomer(s)
Synthesis
AO (Processing, Storage & Servicelife + Modifier)

(Stereo-regular) chain addition reaction of ethylene AO (Processing, Storage & Servicelife)
Fluidized bed gas phase Physical Form Adjustment
Z/N catalyst
Reactor dimension: ~400 000 tons/a
Dedicated Grade
Erucamide
Oleamide
Silica
Conversion / Reactive Extrusion / Crosslinking
Endproduct
March 2023 I 3-35
• Durable thermoplastic polyurethane applications TPU
• Liquid system
Monomer(s) AO (Polymer Stabilization for enduse)
Synthesis
Modifier
Reactive Extrusion
Physical Form Adjustment
Dedicated Grade
Conversion / Reactive Extrusion / Crosslinking
Endproduct
March 2023 I 3-36
• Acrylonitrile-Butadiene-Styrene ABS
• Graft copolymer via emulsion polymerization (as major option)
Source: N. Niessner; ABS and styrene copolymers – an overview; (2002)

March 2023 I 3-37
Petrochemical Feedstock Operations
Oil refining (distillation)
ExxonMobil, Oil refining comprising distillation & steam cracking Baton Rouge (Lousiana, USA)
Source: Internet (2019)

March 2023 I 3-38
Petrochemical Feedstock Operations
Basic fractions of crude oil distillation with hydrocarbon classification Feedstock for steam cracker

March 2023 I 3-39
Ethylene & Propylene Feedstock
Naphtha
Ethylene Mix of Aromats Propylene Methane Butene

29.1 % 19.1 % 16.1 % 15.4 % 5.5 %
Main product Side products Side product
1,3-Butadiene Ethane Hydrogene Propane Residues and

4.3 % 3.9 % 2.0 % 1.9 % Traces of CO, CO2, H2S

March 2023 I 3-40
Ethylene-based manufacturing stream Propylene-based manufacturing stream
NaCl

March 2023 I 3-41
European ethylene & propylene pipelines as well as steam crackers

Source: K. Keck; Industrial polymerization procedures (Ulg), (2015)
March 2023 I 3-42
Feedstock for Aromatics

March 2023 I 3-43
Feedstock
• Not every raw material for polymerization is available in every part of the world
 Different polymers produced (for commercial consideratons)
• Occassionaly shortage of "non-target" raw materials
 E.g. propylene shortage (side product from naphtha-cracking) due to lower demand of ethylene (main product
of naphtha cracking)
• Unique situation of polyvinylchloride PVC
 By weight only 65 % dependance on petrochemical feedstock & 35 % dependance on inorganic minerals
 Simiar situation for all halogenated polymer
March 2023 I 3-44

I 3-45
Polymerization Technology
• Technology of polymerization narrows the chemical possibilities of polymerization due to
 Reactor mode (continuous versus batch)
 Reactor type (tubular, autoclave, extruder, steam bath, UV-radiation, …)
 Polymerization medium
 Mass (bulk)
 Solution
 Precipitation from mass
 Precipitation from solution
 Slurry
 Emulsion
 (Precipitation from) Suspension
 Finishing operations
• Size (and sophistication) of the "polymerization reactor" can vary significantly … which affects the
transfer of polymerization heat
• Focus on primary location of synthesis
 Post reactor modifications (at this point) excluded
 See chapter 3.5 & 3.6
April 2023 I 3-46

Industrial Pre-Treatments
• Purification of monomer
• Deactivation or elimination of monomer polymerization inhibitors
 Sometimes required during storage & transport of highly reactive monomers
 Dangeous goods
• "Dimer" formation
 E.g. AH salt formation in the case of PA 6 Polyamide 6
• Prepolymerization
 "Baby loop"
 E. g. in many case for polypropylene
• Dissolution of selected additive in the monomer (or reaction medium)
 For easy incorporation
 Excellent homogenization
April 2023 I 3-47

Mass Polymerization
• Other terminology
 Bulk polymerization
 Liquid pool polymeriztion
 Polymerization in substance
Reaction Chemicals Reaction System Physical Form Example
Monomer Compact (solid) PS Polystyrene

Homogenous reaction system Compact melt (T > Tg or Tm)
Initiator or catalyst Solution in monomer
Monomer Reaction medium
Polymer Solution in monomer
Incorrect tacticity (illustration purpose only)
• Consequences
 Monomer(s) present in liquid or gasous form
 Pure polymerisate, but removal of unreacted monomer necessary (degassing)
 Very broad molecular weight distribution
 Very high molecular weight obtainable
 Transfer of polymerization heat difficult
 Low polymerization speed
April 2023 I 3-48

Mass Polymerization of PS Polystyrene
• Early processes
Early tower process

(Continuous mass polymerisation
BASF; 1930’s)
Can process
(mass polymerisation; Dow; 1938)
Improved tower process

(Continuous mass polymerisation Tube tank process
BASF; 1936) (Continuous mass polymerisation
Dow; late 1940’s)
Source: J. Schiers; Historical overview of styrene polymers; in Modern Styrenic Copolymers, Wiley Publishers (2003); page 5ff
April 2023 I 3-49
Mass Polymerization of PS Polystyrene
Continuous mass process
Source: E. Martin; Procédés de polymérisation; ULg (2012)

April 2023 I 3-50
Mass Polymerization
Chemistry Additional Examples Remark
Radical PS Polystyrene (Standard) Amorphous thermoplast
Radical PMMA Polymethylmethacrylate Amorphous thermoplast

"Plexiglass"
Anionic PCYA Polycyanoacrylate 1K glue

H20 (moisture) as initiator
April 2023 I 3-51

Mass Polymerization
Ionic Polymerization PA 6 Polyamide 6 HMW engineering thermoplast

of Heterocycles HMW Cast applications High stiffness & tensile strength for
(Hydrolytic-cationic) technical parts
April 2023 I 3-52

Chemistry vs. Technology of Polymerization
Chemistry Technology
Homogenous Heterogenous
Mass Solution Precipitation Precipitation Emulsion Suspension Precipitation
from from from
Mass Solution Suspension
Radical PS, PMMA
Anionic PCYA Selected Examples Only

Chain Reaction
Cationic
Stereo-regular
(Heterocycles) PA 6 (cast)
April 2023 I 3-53

from from from
Radical PS, PMMA
Anionic PCYA
Chain Reaction
Cationic
Stereo-regular
PA 6 Polyamide 6 (HMW for cast applications) PMMA Polymethylmethacrylate

PCYA Polycyanoacrylate PS Polystyrene
April 2023 I 3-53

Mass Polymerization
Addition EP Epoxy resin Family of EP resins

Step reaction [1-chloro-2,3-epoxypropane + Dihydroxy compound]
[1-chloro-2,3-epoxypropane + Bisphenol A]
Condensation UPES Unsaturated polyester Family of UPES resins

Copolymers
[Saturated Diacid + Unsaturated Diacid + Aliphatic Diol]
[Maleinic acid + Phthalic acid + Propyleneglycol]
April 2023 I 3-54

from from from
Addition EP
Step Reaction
Condensation UPES (linear PES)
EP Epoxy resin
UPES Unsaturated poyester
• (As drawn) Both resisn (EO & UPES) are linear molecules and hence thermoplastics
• Conversion to duromers (thermosets) will be discussed in chapter 3.6
 Crosslinking (X-linking, hardening) of UPES via radical mechanism … no chain reaction
 X-linking of EP via addition step reaction (more than bi-functional co-monomers)
April 2023 I 3-55

Solution Polymerization
 No other terminology
 In many cases not specifically indicated
 Important differenciation (vs. emulsion polymerization) for butadiene and styrene copolymers
Solvent Solution PVAC Polyvinylacetate

Often low boiling hydrocarbon High concentrated solutions (~50%)
Homogenous reaction system No solvent stripping required for glue and coating
Initiator or catalyst Solution in solvent or
Dispersion in solvent
Monomer Solution in solvent
Polymer Solution in solvent
• Consequences
 Excellent heat transfer
 Low viscosity (even at high monomer conversion rate)
 Often operated at higher temperatures (to maintain forming polymer in solution)
 Relatively pure polymerisate, but removal of solvent (and unreacted monomer necessary)
 Temperature decrease in case polymer has limited solubility
April 2023
 Temperature increase (stripping or flushing) to volatilize low boiling hydrocarbon solvent I 3-56
(Generic) Solution Polymerization
April 2023 I 3-57

(Generic) Solution Polymerization
Evaporation of solvet via temperature increase

Need for oxidative protection of organic subsrate
April 2023 I 3-57

from from from
Radical PS, PMMA PVAC coatings
Anionic PCYA
Chain Reaction
Cationic PIB
Stereo-regular HDPE, (LLDPE)

BR
BR Polybutadiene (rubber) PIB Polyisobutylene

HDPE High denity polyethylene PMMA Polymethylmethacrylate
LLDPE Linear low density polyethylene PS Polystyrene
PA 6 Polyamide 6 (HMW for cast applications) PVAC Polyvinylacetate
PCYA Polycyanoacrylate
April 2023 I 3-58
from from from
Radical PS, PMMA PVAC coatings

HIPS (PS+BR)
Anionic PCYA
Chain Reaction
Cationic PIB
Stereo-regular HDPE, (LLDPE)

BR
BR Polybutadiene (rubber) PIB Polyisobutylene

HDPE High denity polyethylene PMMA Polymethylmethacrylate
LLDPE Linear low density polyethylene PS Polystyrene
PA 6 Polyamide 6 (HMW for cast applications) PVAC Polyvinylacetate
PCYA Polycyanoacrylate
April 2023 I 3-58
Synthesis of HIPS in Modified Mass Polymerization
• 2 independant synthesis reactions

 Poymerization of 1,4-butadiene monomer in solution via metalorganic catalyst to form polybutadiene BR
 Dissolution of BR in syyrene monomer
 Polymerization of styrene monomer in mass via free radical mechanism
 Polymerisation of PS around "BR particles"
 Due to high viscosity, 5-15 % ethylbenzene as solvent added, resulting in modified mass polymerization
April 2023 I 3-59
Radical PVAC Polyvinylacetate Thermoplastic binder & adhesive
Cationic PIB Polyisobutylene Viscous & sticky thermoplast

LMW: impregnation & plasticing
n
HMW: weather-resistant films
Stereo-regular BR Polybutadiene (Rubber) Raw material for butadiene elastomer

Not yet x-linked
April 2023 I 3-60

Condensation PC Polycarbonate Family of PC (amorphous) thermoplastics

[Dioxuidiphenylalkene + phosgen or carbonic acid]
[Bisphenol A + Phosgen ]
April 2023 I 3-61

from from from
Addition EP
Step Reaction
Condensation UPES (linear PES) PC
EP Epoxy resin
PC Plycarbonate
April 2023 I 3-62

Polymerization via Precipitation from Mass
 Precipitation from substance
Monomer Powder PP Polypropylene

Beginning: Homogenous Particle size < 2 mm
End: Heterogenous
Initiator or catalyst Solution in monomer
Monomer Reaction medium
Polymer Dispersion in monomer
• Consequences
 Towards the end of the synthesis developes a heterogenous reaction system (starting from a certain molecular
weight range) the growing polymer is not anymore soluble in the monomer
 Separation of polymer from reaction medium very easy
 Low viscosity
 Relatively good heat transfer
 Increased polymerization speed relative to mass polymerization
April 2023 I 3-63

Polypropylene PP – Precipitation from Mass
• Evolution of polypropylene synthesis (version 1)
Source: H. Sato & H. Ogawa; Review on development of polypropylene manufacturing proces; Sumitomo R&D report (2009)
April 2023 I 3-64
• Evolution of polypropylene synthesis (version 1)
Source: H. Sato & H. Ogawa; Review on development of polypropylene manufacturing proces; Sumitomo R&D report (2009)
April 2023 I 3-64
• Evolution of
polypropylene
synthesis (version 2)
Source: M. Covezzi; Ethics shoud be intrinsic to industrial research; Ethics and science for the environment (2007)
April 2023 I 3-65
• Evolution of
polypropylene
synthesis (version 2)
Source: M. Covezzi; Ethics shoud be intrinsic to industrial research; Ethics and science for the environment (2007)
April 2023 I 3-65
• GRACE UNIPOL PP process as an example of a very simple polymerization technology
 Fluidized bed gasphase polymerization of propylene
 Precipitation of formed polypropylene PP from gasous propylene

April 2023 I 3-66
Polymerization via Precipitation from Mass
Stereo-regular PP Polypropylene (Standard) semi-crystalline thermoplast

Precipitation from liquid or gasous propylene
Radical LDPE Low density polyethylene (Standard) low crystalline thermoplast

Precipitation from liquid ethylene
Radical SAN Styrene-Acrylonitile x y n Mainly captive use for the manufacturing

Statistic co-polymerization Composition: = ~70% Styrene + ~30% Acrylonitrile
of ABS
Source: D. Malpass; Industrial polyethylene; Wiley Publishers (2010)

April 2023 I 3-67
from from from
Radical PS, PMMA PVAC coatings SAN, LDPE
Anionic PCYA
Chain Reaction
Cationic PIB
Stereo-regular HDPE, (LLDPE) PP

BR
BR Polybutadiene (rubber) PCYA Polycyanoacrylate SAN Styrene-Acrylonitrile (Co-polymer)

HDPE High denity polyethylene PIB Polyisobutylene
LD Low density polyethylene PMMA Polymethylmethacrylate
LLDPE Linear low density polyethylene PP Polypropylene
PA 6 Polyamide 6 (HMW for cast applications) PS Polystyrene
April 2023 PVAC Polyvinylacetate I 3-68
Polymerization via Precipitation from Solution
 None
Solvent (Fine) powder PAN Polyacrylonitrile

Often low boiling hydrocarbon Finely dispersed powder
Initiator or catalyst Dispersion or solution in N N N N
solvent
Monomer Solution in solvent
Polymer Dispersion in solvent
• Consequences
 Separation of polymer from reaction medium very easy
 Low viscosity
April 2023 I 3-69

Polymerization via Precipitation from Solution
Radical PAN Polyacrylonitrile Linear polymer, but no thermoplast

Precipitation from water-based solution Softening & decomposition 225 to 250°C
No melting
N N N N
Dissolution in DMF Dimethymformamide
Solution-dry spinning of PAN fiber
Highly resistant fiber
1
Mainly captive use for synthesis of
carbon fibers
1 Spinning of PAN fiber
2 Low tempertature treatment for cyclization
3 High temperature oxidation for carbonization
2 (hydrogen removal) and subsequent formation of
graphite planes
Source: Internet download (2023)

April 2023 I 3-70
from from from
Radical PS, PMMA PVAC coatings SAN, LDPE PAN
Anionic PCYA
Chain Reaction
Cationic PIB
Stereo-regular HDPE, (LLDPE) PP

BR
BR Polybutadiene (rubber) PAN Polyacrylonitrile PVAC Polyvinylacetate

HDPE High denity polyethylene PCYA Polycyanoacrylate SAN Styrene-Acrylonitrile (Co-polymer)
LD Low density polyethylene PIB Polyisobutylene
LLDPE Linear low density polyethylene PMMA Polymethylmethacrylate
PA 6 Polyamide 6 (HMW for cast applications) PP Polypropylene
April 2023 PS Polystyrene I 3-71
PVAC Polyvinylacetate
Emuslion Polymerization
 Often the prefix "E" is used before the polymer, such as E-ABS, E-SBR
Water (Very) fine powder SBR Styrene-Butadiene rubber

Initiator or catalyst Solution in water 0.05 to 0.1 mm diameter
Monomer Emulsion in water Finely dispersed powder
Polymer Dispersion in water
Emulsifier required
• Consequences
 Low viscosity
 High polymerisation speed possible
 No metal-organic (stereo-regular) catalyst suitable due to polarity of
reaction medium (catalyst poison)
 Lower purity of polymerisate … containing up to 5% of "polymerization
aids", such as emulsifiers
 Fouling possible
 Lower electrical properties & Lower long term oxidative stability
April 2023 I 3-72
Emulsion Polymerization of SBR
April 2023 I 3-73

Termination of growing free radical

(Molecular weight control)
April 2023 I 3-73


Addition of antioxidant before
coagulation (to protect substrate during
drying)
April 2023 I 3-73


Addition of antioxidant before
coagulation (to protect substrate during
drying)
Coagulation (various coagulation
systems)
April 2023 I 3-73

Emulsion Polymerization of SBR (2
nd Illustration)
Source: Internet download (2018)

April 2023 I 3-74
Copolymerization of Styrene & Butadiene
(Styrene + Butadiene)n
Emulsion Solution
Cold Hot
 5°C  50°C
 ~60% conversion after 8 hours  70 – 75% conversion aftre 12 hours
 Shortstopp  Gel formation (x-linking)
 Shortstopp
SBR Latex S/B Latex

 23-25% styrene content  48-80% styrene content
 Vulcanized  Not vulcanized
 Elastomer  Thermoplast
 Carboxylated (copolymerisation with acrylic, methacrylic or itaconic acid)
April 2023 I 3-75

SBR via Emulsion or Solution Polymerization
Criterion Emulsion E-SBR Solution S-SBR
Genesis Original process

Main process (82% of SBR production)
„Workhorse“ of the rubber industry
Catalyst / Initiator Free radical Alkyl lithium
Reactive Medium Water Hexane / Cyclohexane
Conversion 60-65% 100%
Molecular Architecture Broad to very broad MWD Narrow to broad MWD

Very low & very high MW fractions Normally no chain branching
Chain branching Chain branching can be introduced
Greater contol of process
Tailoring of polymer (properties)
None-rubber Antioxidants Antioxidants

Initiater Traces of Li
constituents Emulsifier
Shortstop
Colour Opac, yellow, amber, dark Transparent, colourless
Application Multi-purpose Specialty
April 2023 I 3-76

SBR via Emulsion or Solution Polymerization
Criterion Emulsion E-SBR Solution S-SBR
International 1500 – Discolouring, not oil-extended, cold polymerised

1502 – Non staining, not oil-extended, cold polymerised
Classification 1700 – Oil-extended, cold polymerised
…
Remark Main rubber components are defined …

Styrene content
Coagulation system
AO (stabiliser) system
Emulsifier system
Oil type & content
Carbon black type & content
April 2023 I 3-77

Emulsion (& Suspension) Rubbers (Polymers) in General
• Fundamental decision to treat emulsion polymers as emulsions (liquid form) or as dry
(thermoplastic) polymer
• Low viscosity emulsion from requires less sophisticated mixing equipment
Emulsion
Emulsion Solid Rubber
1. Incorporation of finely ground vulkanisation additives 1. Coagulation (e.g. with acetic or formic acid)
2. Form giving & coagulation 2. Drying
2.1 Dipping 3. Mastication (incl. incorporation of other
2.2 Cast process ingredients)
2.3 Foam process 4. Vulcanisation
2.4 Spinning
2.5 Topical application onto textile
3. Vulcanisation via steam, boiling water or hot air
April 2023 I 3-78

(Solid) OE-E-SBR
• E-SBR latex is coagulated & de-watered to obtain thermoplastic (solid) SBR
• Solid SBR is often oil-extended
 Addition of 25-50% of (extender) oil
 Aromatic (staining) or alternatively naphtenic (none-staining) oils
• Addition at the end of synthesis (before coagulation); optionally during compounding
• Technical effect
 Plasticizing & lubrication effects allows better processability
 Cost dilution
• (Future) oil-extended SBR is polymerized to higher MW to counter balance LMW oils
April 2023 I 3-79

from from from
Radical PS, PMMA PVAC coatings SAN, LDPE PAN E-SBR, E-ABS
E-PVC, NBR
Anionic PCYA
Chain Reaction
Cationic PIB
Stereo-regular HDPE, (LLDPE) PP Not possible

BR, S-SBR
BR Polybutadiene (rubber) PA 6 Polyamide 6 (HMW for cast applications) PP Polypropylene

HDPE High denity polyethylene PAN Polyacrylonitrile PS Polystyrene
LDPE Low density polyethylene PCYA Polycyanoacrylate PVAC Polyvinylacetate
LLDPE Linear low density polyethylene PIB Polyisobutylene PVC Polyvinylchloride
NBR Acrylonitrile-Butabiene Rubber PMMA Polymethylmethacrylate SAN Styrene-Acrylonitrile (Co-polymer)
April 2023 SBR Styrene-Butadiene Rubber I 3-80
Emulsion Polymerization
Radical E-SBR Styrene-Butadiene Rubber (Standard) synthetic rubber

Statistical copolymer
Not yet x-linked
Radical NBR Acrylonitril-Butadiene Rubber Synthetic rubber

Statistical copolymer Resistant to gasoline, oil & fats
Not yet x-linked
April 2023 I 3-81

Classification of Rubbers
Rubber
Synthetic Natural
Unsaturated Saturated
Diene based
 Styrene-Butadiene Rubber SBR
 Butadiuene Rubber BR
 Acrylonitril-Butadiene Rubber NBR
 Isoprene Rubber IR (NR)
 Butyl Rubber (Isoprene-Isobutylene Copolymer) IIR
Vinylelastomers Elastomers based on Siloxan

polycondensation or
polyaddition products
Caoutchouc
 Sulfochlorinated polyethylene CSM
SI
 Ethylene-Propylene Copolymer EPM
 Ethylene-Vinylacetate Copolymer EVA
 Fluorocarbon Caoutchouc FCM  Polysulfid Caoutchouc (Thioplasts)
 Acrylat rubber ACM  Urethane Caoutchouc PUR
 Polyisobutylene PIB  Chloepoxy Caoutchouc CO
April 2023 I 3-82

Classification of Rubbers
Source: W. Hofmann; Rubber technology handbook; Hanser Publishers, page 38 (1989)

April 2023 I 3-83
Suspension Polymerization
 Sometimes the prefix "S" is used before the polymer, such as S-PVC
 Attention to not confuse with the "S" indicating solution polymer
Water Fine powder PS Polystyrene (foam)

Initiator or catalyst Solution in monomer 1 mm diameter
Monomer Suspension in water Finely dispersed powder
Polymer Suspension in water
Some colloids required
• Consequences
 Low viscosity
 No metal-organic (stereo-regular) catalyst suitable due to polarity of reaction medium (catalyst poison)
 Purity of polymerisate between emulsion and mass polymerization
 Reactor design identical to emulsion polymerization, but yielding larger particles
 Different solutility requirement for initiator
April 2023 I 3-84
Suspension Polymerization of PS Foam (EPS)

April 2023 I 3-85
Monomer activation

April 2023 I 3-85
Monomer activation
Addition of blowing agent into synthesis reactor

April 2023 I 3-85
Monomer activation
Addition of blowing agent into synthesis reactor
PS beads (no extrusion)

April 2023 I 3-85
Polymerization of PS
Criterion Mass Solution Suspension
Genesis Original process Mainly discontinued
Grade Range Main process

Standard grades Medium MW PS HMW PS
Expandable PS beads
Block copolymers (SB) HIPS (based on EPDM)
Solvent --- Toluene Water

Ethylbenzene (up to 25%)
5-15% ethylbenzene = modified mass process
Prepolymerisation 80°C No No
48 hours
Up to 35% conversion
Initiator Peroxide Butyl Lithium Peroxide
Operating Continuous Batch Batch

100-180°C (gradient) CSTR reactor CSTR reactors
Conditions High conversion rates 90-175°C 80-100°C
5 to 9 hours [styrene:H2O] [50:50] to [20:80]
Desactivation of initiator by polar substances Suarface active suspending agents
Blowing agent (n-pentane) for EPS
April 2023 I 3-86

Polymerization of PS
Criterion Mass Solution Suspension
Other Advantages Simple & economic Easy heat transfer PS beads (0,1 to 1 mm)
PS of high purity & constant quality Temperature control Good heat transfer
Evaporation of residual styrene monomer in No solvent issues
reaction tower Can be modified for mass polymerisation (less
Continuous operation solvent) EPS production in same reactor
High capacities
Investment cost
Operating cost
No solvent recovery
Other Difficult control of viscosity & temperature Solvent Lower purity PS

Lower purity PS No particle size advantage in case of post
Disadvantage reactor extrusion
Investment cost
Operating cost
Other Remarks TDrying must vaporise blowing agent (EPS)
April 2023 I 3-87

PS – Downstream Aspect of Foam Production
EPS beads, expanded beads & EPS foam XEPS foam
EPS foam XPS foam

Source: H. Kwon; XPS project – Stabilization of Emerald Innovation 3000; Songwon (2015)
April 2023 I 3-88
EPS
Suspension Blowing agent

Polymerization
Beads
Steam
Pre-Expansion 90-100°C
Air
Equilibrium Storage
Room temperature
Steam
90-120°C
Molding
April 2023 I 3-89

XEPS EPS
GPPS Suspension Blowing agent

Mass Polymerization GeneralPurpose Polystyrene Polymerization
Either GPPS Beads
or PS Beads
Blowing agent Beads
Extrusion
EPS: Tm 110-120°C
GPPS: Tm 160-180°C
Steam
Air
Equilibrium Storage
Room temperature
Steam
90-120°C
Molding
April 2023 I 3-89

XPS XEPS EPS
GPPS Suspension Blowing agent

Mass Polymerization GeneralPurpose Polystyrene Polymerization
Either GPPS Beads
or PS Beads
Blowing agent Beads
Sheet Extrusion Extrusion
Tm 180-230°C EPS: Tm 110-120°C
GPPS: Tm 160-180°C
Steam
Air
Equilibrium Storage
Room temperature
Steam
90-120°C
Molding
April 2023 I 3-89

from from from
Radical PS, PMMA PVAC coatings SAN, LDPE PAN E-SBR, E-ABS PS, PMMA
E-PVC, NBR PVAC
Anionic PCYA
Chain Reaction
Cationic PIB
Stereo-regular HDPE, (LLDPE) PP Not possible HDPE

BR, S-SBR

LDPE Low density polyethylene PCYA Polycyanoacrylate PVAC Polyvinylacetate
Polymerization via Precipitation in Suspension
 Sometimes the prefix "S" is used before the polymer, such as S-PVC
 Attention to not confuse with the "S" indicating solution polymer
Water Fine powder PVC Polyvinylchloride

Initiator or catalyst Solution in water 1 mm diameter
Monomer Suspension in monomer Finely dispersed powder
Polymer Dispersion in monomer
Suspension in water (end)
Some colloids required
• Consequences
 Low viscosity
 No metal-organic (stereo-regular) catalyst suitable due to polarity of reaction medium (catalyst poison)
 Purity of polymerisate between emulsion and mass polymerization
 Similar process diagram than (Suspension) S-PS
 VCM vinyl chloride monomer is highly reactive (inhibition) & carcinogenic (closed loop required)
April 2023 I 3-91
Polymerization of Vinylchloride VCM
Criterion Mass Suspension Microsuspension Emulsion
Genesis ~ 5-10% of global production ~ 90% of global production
Grade Range Main process

Standard grades Standard grades Specialty grades Specialty grades
Rigid & flexible (plasticized) Thin films (w/o fisheyes) Thin films (w/o fisheyes)
grades Plastisol Plasticized PVC
Thin film Plastisol (paste)
Thin film
Physical Form 100-200 micron 100-200 micron Fine powder (~ 1 micron) Fine powder (~ 1 micron)
Porous Porous Broad PSD Narrow PSD
Excellent flow Excellent flow Non porous Non porous
Poor flow Poor flow
Solvent --- Water Water Water
Prepolymerisation Up to 12% conversion No No No
Initiator Peroxide Peroxide Peroxide Peroxide
April 2023 I 3-92

Synthesis of Polyvinylchloride PVC
• Polymerization procedure required closed loop due to carcinogenic effect of VCM
 Suspension process due to more efficient work-up preferred over mass polymerization
• PVC as synthecised is rigid and very difficult to process in the melt
• Suspension poymerization yields porous particles
• High importance of plasticizer addition to rigid PVC
 External plasticization
 20-50 % plasticizer addition
 > 50% plasticizer is used as paste (plastisol)
• PVC paste
 Plastisol … PVC dissolved in plasticizer
 < 35 °C, no reaction (no dissolution of PVC particle in plasticizer, hence processable
 Degree of swelling of PVC from plasticizer and dissolution in plasticizer is temperature dependant
PVC with liquid plasticizer Swelling of PVC due to Further swelling of PVC at At 100 to 120°C solid At 160 to 180°C (flow range
(up to 50%) immediately migration of pasticizer into 60°C. consistency of PVC of amorphous PVC)
after mixing at RT. PVC. In parallel, start of plastigel; including still soft formation of homogenous
dissolution of PVC in Formation of still in homo- areas at the contact edges. plastigel.
PVC can still be filtered & plasticizer. genous plastigel.
separated. . Soft-elastic solid at RT.
Max. 40°C. PVC cannot be . .
separated anymore.
Plastisol.
Source: A. Franck, B. Herr, H. Kruse &G. Schulz; Kunststoff Kompendium; Vogel Publishers , page 191 (2011)
March 2023 I 3-93
from from from
Radical PS, PMMA PVAC coatings SAN, LDPE PAN E-SBR, E-ABS PS, PMMA S-PVC
E-PVC, NBR PVAC
Anionic PCYA
Chain Reaction
Cationic PIB

BR, S-SBR

LD Low density polyethylene PCYA Polycyanoacrylate PVAC Polyvinylacetate
from from from
Radical PS, PMMA PVAC coatings SAN, LDPE PAN E-SBR, E-ABS PS, PMMA S-PVC
E-PVC, NBR PVAC
Anionic PCYA
Chain Reaction
Cationic PIB

BR, S-SBR

LD Low density polyethylene PCYA Polycyanoacrylate PVAC Polyvinylacetate
from from from
Addition EP
Step Reaction
Condensation UPES (linear PES) PC
EP Epoxy resin
PC Plycarbonate
April 2023 I 3-95

I 3-96
"Synthesis" of Polymers
• Various places / "occasions" for synthesis during life cycle of a polymer
• Dedicated synthesis reactor mainly for standard ("commodity grades")
• Monomer selection mainly (but not exclusively) determines
 Chemistry & technology of polymerization
 Properties of polymer (chapters 2.1 & 2.2)
 Possibility for further MW design (branching, x-linking)
• Purity level of polymers can vary
 Complete removal of impurities & polymerization aids in technologies where work-
up is required
 Up to 5% impurities at the end of emulsion polymerization
 Impurities generally have negative effect on the properties of polymers in use
• For addition and/or kondenstation chain reaction, often the reactivity
of the chain ends is adjusted at the end of synthesis
 Complete pasification (no reactivity anymore)
 Covalent bonding of stabilizers (or modifiers)
• Lot-to-lot variation possible on industrial scale
April 2023 I 3-97

Chemistry vs. Technology of Polymerization of Styrene & Butadiene
• Examples of possibilities for co-polymerization on top of the polymer alloy [PS+ BR]
from from from
Radical PS E-BR (for ABS) PS foam

E-SBR (latex)
S/B (hot)
BS in Styrene
Chain Reaction
Anionic SBS
Cationic
Stereo-regular BR (for HIPS) Not possible

S-SBR
(Heterocycles)
April 2023 I 3-98
I 3-99
Mixing & Homogenization
• Different procedures for thermoplastics vs. Duromers
manufactured from LMW raw materials
• For duromers, mixing & homogenization as well as shaping must
happen at the same moment in time
• Thermoplastics
 Particle size adjustment
 Homogenization of lot-to-lot variations of the polymer
 Accommodation of “wide-spec” material
 Mixing operation for thermoplastic (high viscous melt) and low viscous
pre-cursors of thermosets are significantly different
 Addition of stabilizers often necessary (organic materials are in general
very sensitive to “aging”)
 Addition of modifiers possible
March 2023 I 3-100

• Processing often used as general term for all operations (of chapters 3.5 & 3.6 as well as for the
activity of incorporation the chemicals of chapter 3.7)

Create "Compound"
Exrusion …
Distributive
Reinforcement …
Degassing
Filter (& screen)
…
March 2023 I 3-101
• Processing often used as general term for all operations (of chapters 3.5 & 3.6 as well as for the
activity of incorporation the chemicals of chapter 3.7)

Create "Compound"
Exrusion …
Distributive
Reinforcement …
Degassing
Filter (& screen)
…
March 2023 I 3-101
• Dispersive mixing strongly preferred
• No conveying or shaping required
• Desing of mixing equipment depending on

 Viscosity of polymer compound at operating conditions
 Continuous or batch operation (productivity versus flexibility)
Viscosity
Batch Low High
Kneader
Continuous
Twin Screw Extruder
April 2023 I 3-102

Continuous Mixing in the Melt
• Process scheme of a continuous (twin screw) extruder
Source: C. Bonten; Kunststofftechnik; Hanser Publishers, page 270ff (2016)

April 2023 I 3-103
• Process scheme of a continuous twin screw extruder
Atmspheric Vacuum
Polymer
Degassing Degassing
Additive or Filler
Plastification Conveying Mix

Degassing Homogeni Degassing Pressure
Entry Zone Increase
Zone zation Zone
Co-Rotation Counter-Rotation
High shear forces Low shear forces
Mixing Forced, but soft conveying

October 2020 I 3-104
• Process scheme of a continuous twin screw extruder
• Example of particle size adjustment
Die with exiting strand Granulation

Air drying
Waterbath

Internet download (2020)
I 3-106
The Physical Form of Polymer (Compounds) vs. "Shaping Operations"
Physical Form

Emulsified
o Gluing o Foaming
o Spinning
o Welding
Increased Viscosity old I 3-34

March 2023 I 3-107
Polymer Processing Cathegories
• Illustration of major polymer processing technologies
• The capability for dispersive mixing is limited in many polymer processing operations
(Flow-based) Shaping Coating
Thermoforming Orientation
Welding, Glueing, Screwing &

Mechnical
Riveting
Source: A. Franck, B. Herr, H. Ruse & G. Schulz; Kunststoff Kompendium; Vogel Publishers, page 147 (2011)
Flow-Based Shaping Technologies
Mixing
Sheet
Film
Pipe & tube
Extrusion Fibers
Continuos Flow Process

Cable coating
Sintering
Coextrusion
Continuous
Mixing
Sheet formation
Calandering Coating
(Flow-based)
Shaping Compression moulding CM
GMT
Principal Processes
Compression Moulding SMC
CM
Batch Process (Production of Individual Pieces)

Batch
Injection mulding IM
Cascade IM
2 component IM
Injection IM & Blow Moulding BM Sandwich IM
Extrusion blow moulding
Strecth blow moulding
…
Rotational Moulding RM
Extrusion
• Continuous process for the manufacture of semi-finished goods
• Design of die determines the dimensions & shape of the semi-finished good
• Extrusion temperature & speed can vary signigficantly (and hence influences orientation of macromolecules)
Extrusion
Slit Fiber Pipe Cable Coating Co-Extrusion

Sheet BCF Pipe Composite
Cast film Meltblown Tube
Tape Spunbond
Profile RAM Extrusion Coating

Complex profile Sintering of PTFE & Composite
UHMWPE
Crosslinking
(Optional)
Fiber Extrusion ("Spinning")
• High degree of orientation of macromolecules
• 3 fundamental technologies
 Melt spinning
 Solution dry spinning
 Solution wet spinning
Source: A. Thurmer; Polymer properties and processing technologies; page 18 (2011)

Moulding Operations
• Batch or semi-batch operation
• Thermoplastics (major operation)
• Molten polymer is injected into cooled mold
• Mould consists of 2 pieces (one fixed with injection canal and one retractable)
• Manufacturing of detailed, none-hollow articles
• Cooling operation determines cycle time

Further Processing & Finishing Operations
• Thermoplastic only
• Softelastic state (around Tg or slightly below Mp)
• Deformation & subsequent cooling
Further Processing & Finishing
Elevated Temperature Ambient Temperature
Folding & Stretching & Thermoforming Embossing Welding

Bending Shrinking

Processing at Ambient Temperature
• Mainly for duromers & thermoplastics … limited suitability for elastomers
• Similar behaviour than wood or light metal
• Attention to heat transfer (as many polymers are thermal insulators)
• Heated tools are possible for thermoplastics
• Possible operations …
 Cutting
 Punching
 Sawing
 Drilling
 Grindingor sanding (duromers only)

Surface Treatment of Polymers
Surface Treatment
Polishing Flocking Surface Embossing Various modifications

Decoration with auxilliary products
Surface Polarisation
Gloss
(if needed)
Coefficient of friction
Electrostatic propertied
Colour
Coating / Metallisation
Varnish
Source: A. Franck & K. Biederbick; Kunststoff Kompendium; Vogel Publishers, page 102 (1988)
Shaping & Orientation of Elastomers
• Different of procedures depending on thickness of final article
• Linear rubber molecules can be processed as thermoplastics until the moment of x-linking
• Various x-linking mechanisms (vulcanization)
Emulsion (& Suspension) Rubbers (Polymers) in General

• Fundamental decision to treat emulsion polymers as emulsions (liquid form) or as dry
(thermoplastic) polymer
• Low viscosity emulsion from requires less sophisticated mixing equipment
Emulsion
Emulsion Solid Rubber
1. Incorporation of finely ground vulkanisation additives 1. Coagulation (e.g. with acetic or formic acid)
2. Form giving & coagulation 2. Drying
2.1 Dipping 3. Mastication (incl. incorporation of other
2.2 Cast process ingredients)
2.3 Foam process 4. Vulcanisation
2.4 Spinning
2.5 Topical application onto textile
3. Vulcanisation via steam, boiling water or hot air
April 2023 I 3-78
April 2023 I 3-116

X-Linking Procedures for Rubber
• X-linking of rubber to form elastomers, so-called vulcanization, is one of several technologies to create
3 dimensional networks
• Vulcanization of unsaturated rubber
Sulphur Metal Oxide Peroxide Radiation
Cold Hot
 Thin-walled elastomer articles  Sulphur compounded into rubber
 Dipping into 2 to 4% S2Cl2 solution in petrol  125 to 170°C
 Immediate x-linking at room temperature  Accelerator
 Activator (for accelerator)
 Filler and/or reinforcing agents
 Plasticizer
 Stabiliser
 Oil-extension
April 2023 I 3-117

Shaping of Thick-Walled Elastomers
• 6 processing steps to manufacture a car tire
 Mixing of carbon black, elastomer and chemicals in a Banbury mixer to form the rubber compound
 Calandering the fabrics and steel cord and coating them with rubber
 Extruding the treads and sidewall components
 Manual assembly of the tire components on tire building machines
 Vulcanizing or curing the tire with heat and pressure
 Finishing

Shaping of Thin-Walled Elastomers
• Dipping

(Synthesis) & Shaping of Duromers
• Synthesis of polymer and shaping of (finished or semi-finished) good must occur at the same moment
• Role of temperature (increase) is different to thermoplastics
 Initial decrease of viscosity of LMW raw materials
 Acceleration of viscosity increase (accelerated x-linking)
 Dimensional stability even at elevated temperature
• Various technologies available appart from simple topical applications …
The Physical Form of Polymer (Compounds)
Physical Form

Emulsified
o Gluing o Foaming
o Spinning
o Welding
Increased Viscosity
March 2023 I 3-34
April 2023 I 3-120

(Synthesis &) Shaping Technologies for Duromers
Simple geometries
Extrusion
Continuos Flow Process

Continuous
Calandering
(Flow-based)
Shaping Compression moulding CM
GMT
Principal Processes
Compression Moulding SMC
CM
Batch Process (Production of Individual Pieces)

Batch
Injection moulding IM
Injection IM & Blow Moulding BM
Rotational Moulding RM
RIM
Reactive Injection Moulding
Hand Lamination
Tumbling
Spray Lamination
Continuous Sheet
Duromer
Injection Lamination often fiber-reinforced
Pultrusion
SMC
Sheet Moulding Compound
3D-Winding
BMC
Bulk Moulding Compound
Source: A. Franck, B. Herr, H. Ruse & G. Schulz; Kunststoff Kompendium; Vogel Publishers, page 194 & 195 (2011)
April 2023 I 3-122
• Slapstock foam
• Mechanical finishing
1. raw material 2. mixing head 3. trough 4. creaming
5. operators platform 6. bottom paper feed 7. fall plates 8. horizontal conveyor

I 3-124
Additives
• Chemicals with a broad range of characteristics
• Physical dispersion in the polymer matrix
 Dispersive mixing required
 However, many additives are not soluble and/or not meltable in the polymer matrix
 Physico-chemical aspects of the additive are important
• (Initially) No covalent bond between the additive and the polymer
• Broad concentration range from 10 ppm (optical brightener) to > 50 % (500 000 ppm for plasticizers)
• Concentration often below 1% (10 000 ppm)
• The perfect additive does not exist

 There are always drawbacks
• Gain of essential properties
• Sacrifice none-essential properties
 Accept drawbacks & disadvantages
• Priority list of required properties

The Chemical Aspect of Additives
• Main effect
 … which property needs to be improved?
• Many chemical classes of additives exist which have more than one effect on the polymer
 Effects can be positive or negative
• Technical selection of additive class(es) based on main effect
• Technical selection of an individual molecule within a chemical class based on
 Desired strength of the effect
 (Acceptable) secondary effects
 Physico-chemical properties
 Physical form
• Regulatory status
• "Philosophical" selection of an individual molecule (additive)

 Taylor-made solutions versus multi-purpose compromise

The Physico-Chemical Aspect of Additives
• Efficacy of additives on an industrial scale us governed (beyond the chemical aspect) as well by
physico-chemical aspects & properties
• Scale-up required
• Fundamental physico-chemical requirements for additives which modify bulk properties
 High solubility
 Low diffusion rate
 High degree of homogeniety
• Low solubility and/or high diffusion rate will lead to significant loss of the performane (scale of the
effect)
 Accurate dosing required
• Fundamental physico-chemical requirements for additives which modify surface properties
 Designed incompatibility
 Sufficiently high rate of diffusion to the surface without (excessive) physical loss
 Incorportation into polymer matrix via mixing versus topical application

Physical Form of Additives
Partially contradicting requirements

Handling / Dosing /
Conveying Homogenisation
 Good flow behaviour  ʻEqual mixes best with equalʼ

 Flow behaviour similar to substrate
 Robust  Easy dispersable
 Avoidance of dust (explosion risk)  Good flow behaviour
 Avoidance of high viscous materials  Flow behaviour similar to substrate
 Avoidance of low melting, sticky materials
 Often particle size enlargement  Often small prticle size (molecular level)
• Addition point determines optimum physical form during dosing & homogenisation
• Various alternative addition points are often possible
December 2017 I 3-128

Modification of Polymers via Additives
Mandatory Optional
Stabilizers Modifiers
Antioxidants Stabilizers against other Scavengers

Degradation Patterns of Degradation Products
Reinforcing Functional
Agents Fillers
Additives

Aging & Stabilizers
• Stabilizers or preservants
• Preservation of organic substrates (not just polymers) from un-intentional & hence un-wanted changes
due to aging
• Preservation of initial molecular architecture
• Slow down only of aging processes
• Chemistry of stabilizers (chemical class) depending on aging mechanism(s)
• Many organic substrates age after more than 1 mechanism
 Simple understanding for homopolymers
 Complex situation for copolymers, polymer alloys & compounds
 Organic additives age as well
 Aging of one chemical can spark the onset of aging of additional organic chemicals

General Mechanisms of Aging
Aging
Mechanical Physical Chemical
Static Heat
Dynamic Contact with media
Usage Separation
Agglomeration
Secondary valences Covalent level

Partially reversible In general not reversible
March 2019 I 3-131

Mechanisms of Chemical Aging
Chemical Aging
Oxidation Thermal Solvolysis Mechanical Biological
Auto-oxidation Depolymerisation Hydrolysis Shear (molten state) Indirect degradation

Thermo-oxidation Chain cleavage … Mechanical load (solid Direct degradation
state)
Photo-oxidation (Crosslinking) (Effects w/o
degradation)
Side group cleavage
(Extraction of additives)
Changes in molecular structure

Formation of functional groups
Cleavage of low-molecular weight products
March 2019 I 3-132

Chemical Aging

state)
degradation)
Side group cleavage

The same chemical mechanisms can be exploited for intentional chemical recycling of polymers
March 2019 I 3-132

(Intentional) Modification of Polymers
Functional Additives
Bulk Properties Surface Properties

Controlled Rheology Antistatic Agent
Crosslinking Slip Agents
Chain Extention Antiblocking Agent
Oxo-Degradability Mould Release
Anti Scratch Agent
Plasticizer Surface Improvement (gloss)
Lubricant Lubricant
Thixtropy Agent Antifogging Agent
Rheopexy Agent
Nucleating Agent Biocide
Impact Modifier Emulsifier
Odor Modification
Pigment & Dye ...
Fluorescent Whitening Agent
Blowing Agent
Copatibilizer
Flame Retardant
...
Fillers
• High concentration (up to 50%)
• Inorganic & organic nature
• Inactive (extenders) and active (functional) fillers
• Improved mechanical properties (for standard polymers)
• Cost dilution without loss of mechanical properties (for ETP)
• Filler surface must be in close contact with polymer matrix
• Sophisticated homogenisation operations required Grey talc
Wood flour Carbon fiber
Glass fiber

Fillers
Cubic & Spheroidal Platy Acicular & Fiberous Others
Natural CaCO3 Talc Wollastonite Conductive fillers

Precipitated CaCO3 Mica Wiskers Lubricating fillers1
Dolomite Kaolin Glass fibers (chopped strands) Organic fillers2
Magnesium carbonate Clay Aramid fibers Nanofillers
Calcium sulfate Graphite Carbon fibers ...
Barium sulfate ... ... 1 Graphite, molybdenium disulfide, PTFE powder
Glass beads 2 Bark flour, lignine, nut shell flour, starch, jute, ...
Ceramic beads
Synthetic silica
Natural silica
Feldspar
Aluminium trihydroxide
Aluminium hydroxide
Wood flour
...
I 3-136
Natural Polymeric Materials
• Occure in nature
• Derived from "living organisms"
• Not designed, hence significant "lot-to-lot" variations
• Often need to modify for use in technical applications
 Semi-synthetic or modified natural polymers
• Regenerated
Regenerated raw material
Natural Polymers
None biodegradable
Biodegradable
Conventional
Plastics
Petrochemical raw material
Source: H. Enders & A. Siebert-Raths; Technische Biopolymere; Hanser Publishers, page 6 (2009)
March 2016 I 3-137
Natural Polymeric Materials
Natural Polymer
Proteins Polysaccarides Sequences of Polymerisates of Polyprenes

Nucleic Acids Unsaturated
Natural Oils
(Amino acid)n (Sugar)n (Nucleic acid)n X-linked natural oil ~ (Terpene)n

(Glucose)n
Carbohydrates
Collagen Cellulose DNA (deoxyribonucleic acid) Linseed oil (Linoleum) Natural rubber
Albumin Lignin ... Faktis Guttapercha
Fibrin Starch ... Amber
Gelatine Chitosan ...
Silk Dextran
Wool Chitin
... Pektin
Agar
Enzymes Shellac
March 2016 I 3-138

The Need for Packaging Materials
• Use of polymers (plastics) deried from material properties
March 2016 I 3-139

March 2016 I 3-139

chemistries) as coatings & adhesives

Main use of polymers (of various
March 2016 I 3-139

Packaging Materials
Source: National Geographic (French edition, 2018)

March 2016 I 3-140
• Destiny of mainly packaging material & general waste …
Waste along street in India Illegal waste accumulation in Qingdao, China
Illegal waste accumulation in Germany

I 3-142
Real Mechanical Recycling of Plastics

Real Mechanical Recycling of Metals from Plastics Cables

Concept for Plastics Recycling
Source: Chemical recycling; Positioning paper of PlasticsEurope for a meeting with the European Commission on 2011-08-29 (2011)
Concept for Plastics Recycling
Source: Chemical recycling; Positioning paper of PlasticsEurope for a meeting with the European Commission on 2011-08-29 (2011)
I 3-146
Chemical Aging

state)
degradation)
Side group cleavage

The same chemical mechanisms can be exploited for intentional chemical recycling of polymers
old I 3-132
March 2019 I 3-147
Recycling of Plastic Waste
Recycling Waste Stream
Post Consumer Post Industrial Post Production
Mix Single Collection

(High volume items)

Post Consumer Post Industrial Post Production
Mix Single Collection

(High volume items)
Increased Homogeniety & Purity
Increased „Heterogenous“ Impurities

Sorting Increased Need for Cleaning
(Plastics vs. Other materials
Plastics vs; plastics)

Physical Chemical
Fedstock Recycling
Mechanical Thermo Gasification Biodegradation
Physical Solvolysis
Solvent-Based
Depolymerisation Pyrolysis

Physical Chemical
Fedstock Recycling
Physical Solvolysis
Solvent-Based
Polymer structure retained
(to a high degree)

Physical Chemical
Fedstock Recycling
Physical Solvolysis Polymer structure destroyed

Solvent-Based
Polymer structure retained Monomers &
Undefined (petro-) chemical feedstock
(to a high degree) defined rawmaterials

Physical Chemical
Fedstock Recycling
Physical Solvolysis Polymer structure destroyed

Solvent-Based
Polymer structure retained Monomers &
Undefined (petro-) chemical feedstock
(to a high degree) defined rawmaterials
Re-melting & re-shaping Selective somubility of different Hydrolysis (PET, PC, (PA), (PUR)) Polyolefins No recycling Interfacial process
Down-cycling polymers in multi-layer No circular ecomomy Polymers with high N & O
Re-cycling structures Depolymerisation (PMMA, PS, …) content
Hybride –compounds
Up-cycling Fuels All carbon-based recycling streams CO2
Waxes Small gaseous products CH4
Co-feed into General chemical feedstock Biomass
petrochemical refinery Synthesis gases

Pyrolysis (of Polyolefins)
Source: US 2021/0301210 A1 (Chevron USA Inc.; 2020)

I 3-151

Chemistry of Polymers

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Chemistry of Polymers

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Chemistry and Technology of Polymers (CHIM-9319)

1. General Introduction on Polymers

Petroleum and gas Biosources

Technology of Polymers (K. Keck)

• Technology of polymerization narrows the above mentioned chemical

• In a 2D grid chemistry versus technology of polymerisation, not every

March 2023 I 3-3

• Most polymers are not used as initially polymerized

March 2023 I 3-4

Polymer Life Science

Plastic (Synthetic) Fiber „Coating“ Functional

Plastic Articles Textile Semi – Surface of Into Other

Plastic Industry Textile Industry Coating / Paint Leather

Source: C. Bonten; Kunststofftechnik; Hanser Publishers (2016); page 50

Polymer Life Science

Plastic (Synthetic) Fiber „Coating“ Functional

Source: C. Bonten; Kunststofftechnik; Hanser Publishers (2016); page 50

Broad enough temperature range with

o Dimensional stability at operating o Dimensional stability at operating (use)

Source: C. Bonten; Kunststofftechnik; Hanser Publishers (2016); page 56

Plastic (Synthetic) Fiber „Coating“ Functional

o Terephthalic acid (increase of Tg) o Terephthalic acid (increase of Tg)

(Unsaturated) PES resin

85% Polyester fiber + 15% Elasthan fiber

March 2023 I 3-9

Raw materials with partially a functionality > 2

Linear polymers even with a high degree of branching can

Thermoplast Elastomer Duromer

March 2023 I 3-10

Synthesis of polymer Shaping of granules

• Thermoplastics can undergo various melt-conversion steps

Synthesis of polymer, 1st and only processing step & Waste

• Thermosets can undergo only one processing & shaping step

Synthesis of polymer Shaping of granules & Linear or branched

thermoplastics Crosslinked networks

March 2023 Ebonit I 3-13

Synthesis & "Processing"

0 100 200 300 400 500 600

Synthesis & "Processing"

0 100 200 300 400 500 600

Maximum Solid State Temperature of Thermoplastics

VICAT softening temperature

March 2023 I 3-16

March 2023 I 3-17

March 2023 I 3-18

Shaped PP/TPO car bumper

PP long fibers (unpigmented)

March 2023 I 3-19

Polymer Plastic Produced Article

Preparation Processing Processing

Polybutadiene Butadiene Elastomer

March 2023 I 3-21

1920 Hermann Staudinger

PVC Polyvinylchloride SI Silicon PEI Polyetherimid LCP Liquid Crystal Polymers

• Initial polymer material development based on new monomers and rawmaterials

Inorganic filler containing linseed oil

March 2023 I 3-25

• This approach has 3 fundamental consequences

Initial „Molecular Architecture“ (excluding Orientation & Additives)

March 2023 I 3-28

Initial „Molecular Architecture“

Final „Molecular Architecture“

March 2023 I 3-29