1

Outline

1.Introduction
2.PVC Production Process
3.Suspension Polymerization Process
4.R/Ms for Suspension polymerization
5.Quality of S- PVC
6.Factors Affecting S-PVC Quality

2
Outline

1.Introduction
2.PVC Production Process
3.Suspension Polymerization Process
4.R/Ms for Suspension polymerization
5.Quality of S- PVC
6.Factors Affecting S-PVC Quality

3
Polyvinyl Chloride; PVC

Vinyl Chloride Monomer; VCM

Radical Polymerization of Vinyl Chloride Monomer

Thermo plastic resin produced by the Radical polymerization of vinyl chloride monomer
57% of the molecular weight derived from salt
43% derived from hyrdocarbon feedstocks
Never used alone (always mixed with heat stabilizers, lubricants,
plasticizers, fillers, and other additives to make processing possible,
all of which can influence its physical and mechanical properties)

4
PVC Producer

World Capacity = 53.9 Million Metric Tons

Source: CMAI 2012, Solvay

1. Includes Shintech and CIRES

2. Including The Limburgse Vinyl Maatschappij (LVM)

5
World PVC Demand FY2012

Demand = 37.5 Million Metric Tons

Source: IHS Chemical World Analysis – Vinyls 2013

6
Outline

1.Introduction
2.PVC Production Process
3.Suspension Polymerization Process
4.R/Ms for Suspension polymerization
5.Quality of S- PVC
6.Factors Affecting S-PVC Quality

7
PVC Production Process

1.Bulk or Mass polymerization process

2.Solution polymerization process
3.Emulsion polymerization process
4.Suspension polymerization process

Source: CMAI, 2012

8
Bulk or Mass polymerization process

Pre-polymerization Post-polymerization
VCM + Initiator Continue polymerization Classification Silo & Packing
(Conversion 10%) (Conversion up to 80%)

9
Solution polymerization process

VCM
Solvent
Initiators

PVC
Powder
Reactor Precipitation Wash Dry

Polymerization in Solvent
Multi Step
Solvent Distillation

10
Emulsion polymerization process

Particle size 0.1-3.0 micron

PVC Emulsion Particle Growth
Water soluble initiator
Emulsifier Sodium or ammonium salt of alcohol sulfate ,alkyl
sulphonates , sulphosuccinate and fatty acid

11
Suspension polymerization process

PVC Resin
(size 100-150 micron)

+ Initiator Polymerization

12
Outline

1.Introduction
2.PVC Production Process
3.Suspension Polymerization Process
4.R/Ms for Suspension polymerization
5.Quality of S- PVC
6.Factors Affecting S-PVC Quality

13
Suspension Polymerization Process

AFA Coating

R/M Charging

Heat up

Reaction

Termination RVCM Recovery Centrifuge Drying

Storage & Packing

14
Typical Reaction Profile of Suspension polymerization

Heat up Reaction Termination

15
PVC Morphology

PVC Particle PVC Particle Cross Section

PVC Particle Model

16
PVC Grain Formation

VCM Droplet
Water

Reactor
Reactor pressure and PVC morphology

“Control of the morphology of each PVC grain

is the main parameter controlling the quality
of PVC resin”

After Xie, T. Y. et al. (1991)

17
Outline

1.Introduction
2.PVC Production Process
3.Suspension Polymerization Process
4.R/Ms for Suspension polymerization
5.Quality of S- PVC
6.Factors Affecting S-PVC Quality

18
R/Ms for Suspension polymerization

1. Vinyl Chloride Monomer; VCM

2. Process Water (De-mineralized Water); PW
3. Suspending Agent
4. Initiator
5. Antioxidant & Heat Stabilizer
6. Anti Fouling Agent ; AFA (Anti Scaling, Built up suppressant)
7. Buffer & Neutralizer

19
Vinyl Chloride Monomer; VCM

Physical properties
Unit Quantity / Description
Appearance - Colorless Gas
Molecular weight g/mol 62.5
B.P. at 1.0 atm °C -13.8
Freezing point °C -158.8
Heat of polymerization Cal./g 405

20
Process Water (De-mineralized Water); PW
Function
Continuous Phase
Heat transfer
Protective Colloid carrier
Reduce viscosity of reaction mixture

Qualities
Unit Spec.
pH - 6-7
SiO2 ppm. 1.0 max.
Conductivity Ohm/cm 2.0 max.
Iron ppm 0.05 max.

21
Suspending Agent

Function : Prevent the coalescence of the individual VCM

droplets during polymerization (protective colloid)
Suspending Agent : Water-soluble polymers
- Partially hydrolyzed polyvinyl acetate (PVA)

- Cellulose derivatives

- Other polymer ; Polyvinyl Pyrrolidone, Ethylene/Maleic Anhydride

Copolymer, Polyacrylates, Naturally Occurring Material eg. Gelatin

22
Initiator
Substances that can produce radical species under mild conditions and
promote radical reactions
Generally possess weak bonds—bonds that have small bond dissociation
energies eg. Azo cpd. (R-N=N-R'), Organic peroxide (R-O-O-R')
Used monomer soluble initiators
Initiator Physical form
1. Solid Form
2. Liquid Form
3. Water – Based
- Suspension
- Emulsion
- Frozen Emulsion (Non Anti-freezing Agent)
Initiator Selection
1. Depend on reaction temperature (Half Life)
2. Required polymerization rate
High K Low polymerization temp. Fast initiator
Used Mixed type
Low K High polymerization temp. Slow initiator

23
Initiator (Cont.)

Type Structure
Hydroperoxides
Dialkylperoxides

Peroxyesters

Diacylperoxides

Peroxydicarbonates

Peroxy ketals

24
Antioxidants & Heat Stabilizer
Antioxidants retard the oxidative degradation of plastics which is
initiated when free radicals are created in the polymer by heat, UV,
mechanical shear, or metallic impurities

Antioxidant & Heat stabilizer Type

1. Hindered Phenol derivatives
2. Thioester
3. Phosphite
4. Epoxidized Soya bean Oil

25
Anti Fouling Agent; AFA
PVC Scale
PVC build up on reactor wall, agitator etc. that is non granular and non –
porous
PVC Scale Problem

Efficiency of heat transfer of the reactor wall decreases

Scale formation on the reactor internal parts (Agitator)

affects the agitation regime negatively

Block reflux condensers, transfer nozzles, etc.

Contamination with product

During clean scale Downtime and exposure of workers

to high levels of VCM

26
Anti Fouling Agent; AFA (Cont.)
Anti Fouling Agent (AFA) or build up suppressant
Chemical (substance) that eliminates build up (scale) on the reactor’s wall
leading to a higher number of batch productions, easy to clean and better
quality of PVC resin. Reactor Wall

VCM Droplet
Ideal Anti Fouling Agent

Adhesion to reactor surface PVC scale

Radical trap
Insolubility in water Non AFA Coat
Insolubility in VCM
VCM Droplet
Stability during storage
No effect on polymerization reaction
No effect on resin properties -Radical trap
-Inhibit VCM deposit
AFA Layer

27
Buffer & Neutralizer

pH adjustment in suspension polymerization

Protect corrosion
Prevent PVC degradation during storage
Buffer & Neutralizer ; Sodium bicarbonate, Sodium hydroxide,
Sodium carbonate, Tetrasodium pyrophosphate, Calcium hydroxide
Buffer and Neutralizer Selection
O Base on application SC grade VR concern (non Na+)
O Calcium hydroxide pH > 7 FE. (Film app.)

28
Outline

1.Introduction
2.PVC Production Process
3.Suspension Polymerization Process
4.R/Ms for Suspension polymerization
5.Quality of S- PVC
6.Factors Affecting S-PVC Quality

29
Quality of S-PVC
PVC Particle Morphology
o Particle size
o Porosity (Plasticizer Take Up, Plasticizer Absorption Time)
o Bulk density
K-value (Molecular weight)
Residual VCM (RVCM)
Volatile Matter (VM)
Fish Eye (F.E.)
Yellow Index (YI)
Fusion time (Brabender, HAAKE)
Thermal Stability
o Color changes
o Metrastat
o Sticky test
o Oil bath
o Gear Oven test
o Dynamic Test
Other (Out put, Strip test, Melt Index, Biological Test ,conductivity, Impact etc.)

30
Outline

1.Introduction
2.PVC Production Process
3.Suspension Polymerization Process
4.R/Ms for Suspension polymerization
5.Quality of S- PVC
6.Factors Affecting S-PVC Quality

31
Factors Affecting PVC Quality

1. R/M quality
2. Suspending Agent
3. Initiator
4. Oxygen content
5. Reaction Temperature
6. Agitation
7. PW/VCM Ratio
8. Charging Sequence

32
R/M quality

Control impurity and consistency of quality

VCM; Alkalinity/Acidity Particle size, Porosity
Soluble Iron Particle size, Porosity, Color
Process Water; Soluble Iron Particle size, Porosity, Color
Select R/M quality related to regulation and customer requirement

33
Suspending Agent
Suspending Agent Type :
1. Primary Suspending Agent
- Protective colloid and control mainly particle size
- High degree of hydrolysis partial hydrolyzed polyvinyl acetate (PVA)
(~70-98%) and hydroxypropyl methylcellulose (HPMC)
2. Secondary Suspending Agent 1°SA
Water
- Increase the porosity of PVC particle
VCM Droplet
- Lower degree of hydrolysis, less than 60%,

2°SA

34
Suspending Agent (Cont.)
“Selection of suspending agent route Control PVC morphology”
Primary Suspending Agents

Cellulose Derivatives
PVA
P = > 2000
DH > 90 mole% Control grain size & Bulk density
PVA
P = 2000
DH = 80mol%
PVA
P = 700
DH = 70mol%

Secondary Suspending Agents

PVA
P = 300 - 500
Improve Porosity
DH = 30 - 55mol%

35
Initiator
- Fish eye (FE.)
Solid Form High F.E.

- Bulk Density (B.D)

High reactivity Initiator High BD

- Scale
Low Mw. High vaporized Scale (Vapor Phase)
High Water solubility Scale (Liquid phase)

- Initial Color (YI, Pressed sheet color)

High reactivity (H-Attraction) High color of PVC (Pereoxydicarbonate type)

Peroxyester Peroxydicarbonate

36
Oxygen Content

o PS trend small, reduce PTU

o Induce thermo-Oxidative degradation (Chain scission)

37
Reaction Temperature
Control K-Value (Molecular Weight)

Polymerization Temp (oC)

Porosity

Polymerization Temp (oC)

38
Agitation

Continuous stirred during polymerization

Breaking VCM to VCM droplet
Heat transfer between the reaction medium and cooled vessel walls
Stirrer type & Agitation speed Grain size and morphology of the PVC
particles
PS & Weber Number BD & Weber Number
We = ρN2D3
σgc
ρ = Average density of total disperse mass
N = Agitator speed
D = Impeller diameter
σ = Interfacial tension
gc = Gravitational constance

39
PW / VCM Ratio

PW/VCM Advantage Disadvantage

1. Low BD
2. High Porosity If too high
High Ratio 3. Good PS distribution 1. Low BD Bad processing
4. Good heat transfer 2. Lost
5. Small PS

40
Charging Sequence
Cold Charge
Step Sequence
Charging
- Cold PW
- Suspending Agent
- Initiator
- Other R/M
- VCM
Heat up
Reaction

Hot Charge
Step Sequence
Charging
- Cold PW
- Suspending Agent
- Initiator
- Other R/M
- VCM
- Hot PW Short cycle time
Heat up
Reaction

41