introducing polyolefins³l_roviden... · content . synthetic polymers – classification – global...
TRANSCRIPT
![Page 1: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/1.jpg)
Introducing Polyolefins
1
![Page 2: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/2.jpg)
Content
Synthetic polymers – Classification
– Global production
Polyolefins – Polyolefins family
– PE classification
– PP structures
– Key properties
– Additivation
– Application
– Global consumption
– Domestic production and consumption
2
![Page 3: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/3.jpg)
Synthetic Polymers Classification by
Plastics Europe
Standard Plastics PE, PP, PVC, PS, EPS, PET (Bottle grade)
Engineering Plastics ABS, SAN, PA, PC, PBT, POM, PMMA, Other High Performance Polymers
PUR Polyurethanes
Thermoplastics Standard Plastics + Engineering Plastics
Plastic Materials Standard Plastics + Engineering Plastics + PUR
Plastics Plastic Materials + Others (Thermosets, Adhesives, Coatings, Sealants)
Elastomers Synthetic Elastomers (SBR, IR, IIR, BR, NBR, CR, Others)
Fibres PA, Polyester, Acrylic, Other Synthetic Fibres
Synthetic Polymers Plastic Materials + Fibres + Elastomers + Others (Thermosets, Adhesives, Coatings, Sealants)
3
![Page 4: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/4.jpg)
World Synthetic Polymers Production 2007
PUR Polyurethanes
Thermoplastics Standard Plastics+ Engineering Plastics
Others Thermosets, Adhesives, Coatings, Sealants
Elastomers Synthetic Elastomers (SBR, IR, IIR, BR, NBR, CR, Others)
Fibres PA, Polyester, Acrylic, Other Synthetic Fibres
Elastomers
4%
Others
14%
Fibres
13%
PUR
4%
Thermoplastics
65%
Polyolefins (PE+PP)
36%
Synthetic Polymers
production in 2007
approximately
315 million t globally
PE+PP represents
114 million t or 36%
of global Synthetic
Polymers production
4
![Page 5: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/5.jpg)
World Plastics Production 1950 – 2011
Plastics=Synthetic Polymers less Elastomers and Fibres
1,7
47
99
204
245
280
14,5
41
90
115128
0
50
100
150
200
250
300
1950 1960 1970 1980 1990 2000 2010
Mil
lio
n t
Plastics
Polyolefins
5
![Page 6: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/6.jpg)
Polyolefins
PE and PP
6
![Page 7: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/7.jpg)
The Polyolefins Family
Polyethylene - PE
– LDPE
– Linear PE
HDPE/MDPE
LLDPE
Polypropylene - PP
– Homopolymers
– Copolymers
Random copolymers
Block copolymers (impact copolymers, heterophasic
copolymers)
7
![Page 8: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/8.jpg)
PE Classification by Density
HDPE/MDPE
LLDPE
LDPE
Schematic representation of various PE structures
8
DENSITY COMONOMER PE GRADE
0,926-0,970 –/alfa-Olefins HDPE
0,926-0,940 alfa-Olefins MDPE
0,915-0,935 –/Acrylates/VA LDPE
0,915-0,926 alfa-Olefins LLDPE
PE grades by density
![Page 9: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/9.jpg)
HDPE Chain Segments
9
![Page 10: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/10.jpg)
LLDPE Chain Segment
10
![Page 11: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/11.jpg)
LDPE Chain Segment
11
![Page 12: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/12.jpg)
PP Structures
12
Isotactic homopolymer Atactic homopolymer
Syndiotactic homopolymer
Block copolymer
PPPEEEEEEEPPPPPPEEEEEEEEPPP
Random copolymer
PPPPPEPPEPEPPEPPPPEPPPEPPPP
![Page 13: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/13.jpg)
Isotactic PP Chain Segment
13
![Page 14: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/14.jpg)
Atactic PP
14
![Page 15: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/15.jpg)
Syndiotactic PP
15
![Page 16: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/16.jpg)
PP Homopolymer and Random Copolymer
16
![Page 17: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/17.jpg)
PP Block Copolymer
17
![Page 18: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/18.jpg)
18
Connection between properties
18
Secondary or end use properties -melt index -mechanicals
• tensile strength • flexural modulus • impact strength
-ESCR
Primary properties -molecular weight -molecular weight distribution -comonomer content -stereoregularity (PP)
![Page 19: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/19.jpg)
Molecular weight
Number average
• 𝑀𝑛 = 𝛴𝑁𝑖𝑀𝑖/𝛴𝑁𝑖
Weight average
• 𝑀w=ΣNiMi2/Σ(NiMi)
Polydispersity
• P=Mw/Mn
19
![Page 20: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/20.jpg)
Molecular weight distribution
number average
molecular weightweight average
molecular weight Mn
Mw
molecular weight
number of
molecules
20
![Page 21: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/21.jpg)
Bimodal Polymer Molecular structure vs. properties
21
R1 R2
Mw
N
Low Mw homopolymer:
- increased crystallinity →
higher stifness
- good processability
high Mw copolymer:
- tie chains between crsytals
- elastic properties
- high mechanical strength
- high toughness
- excellent ESCR
SC
B/1
00
0C
Comonomer built into
high Mw molecules:
- impact strength
- ESCR
tie molecules
Crystalinelayers
m(lo
g M
)
log M
Crystaline layers: Stiffness
Tie Molecules: ESCR, Impact Strength
SCB
Crystallite
![Page 22: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/22.jpg)
Melt Index
Melt index – measure of ease of flow of polymer melt One kind of reciprocal viscosity
Instead of determination of molecular weight
Fast standard method to
control quality
compare products
Melt index and molecular weight High melt index=low viscosity=low molecular weight
Low melt index=high viscosity=high molecular weight
Non Newtonian behaviour Melt index (viscosity) depends on load
Melt indices measured at different loads give indication on molecular weight distribution
22
![Page 23: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/23.jpg)
Density (D)
– Important for PE - strong influence on properties
– Depends on comonomer content (SCB=short chain
branching): more SCB = lower D
– Longer comonomer chain = lower D
– Comonomers tend to incorporate into lower Mw
molecules deteriorating organoleptic properties
23
tie molecules
Crystalinelayers
m(l
og
M)
log M
Crystaline layers: Stiffness
Tie Molecules: ESCR, Impact Strength
SCB
Crystallite
Crystalline layers: stiffness
Tie molecules: ESCR, impact strength
![Page 24: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/24.jpg)
Mechanical Properties 1
Tensile strength (TS)
– Higher crystallinity results on higher TS
– TSPP>TSHDPE>TSLDPE
– TS measured on both machine (MD) and transversal direction (TD) on film
24
![Page 25: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/25.jpg)
Mechanical Properties 2
Impact strength (IS)
– Ability to withstand shock loading
– Higher Mw = higher IS
– Lower D = higher IS
– Dart drop: special impact test for film grades
25
![Page 26: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/26.jpg)
Mechanical Properties 2
Flexural modulus (FM)
– Measure of stiffness – higher FM means higher stiffness
– Higher D = higher FM
– FMPPHOMO>FMPPHECO>FMPPRACO
26
![Page 27: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/27.jpg)
ESCR – Environmental Stress
Cracking Resistance
– Ability to withstand cracking under load in chemicals
– Mainly used for PE - very important for blow moulding and pipe grades
– Lower D = higher ESCR
– Higher MW = higher ESCR
– Role of comonomer distribution – comonomers built into high MW molecules give very good ESCR
27
![Page 28: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/28.jpg)
Additivation
Polyolefins mainly PP and HDPE need different additives to meet end use requirements. Typical concentration: some hundreds through some thousands ppm (1 ppm=1 g/t)
Typical polyolefins additives
– Stabilizers – to protect polymer from oxidative degradation during
Processing – melt stabilization (high temperature, short time + oxygen)
Long term use
– thermal stabilization (low temperature, long time + oxygen)
– UV stabilization – ( low temperature, long time, UV light + oxygen)
– Processing aids and property modifiers
Slip agents – to reduce friction during processing
Antistatic agent – to prevent build up of electrostatic charging
Antiblocking agent – to avoid sticking of film layers
Nucleating agents – to improve stiffness
Clarifying agents – to increase product transparency
28
![Page 29: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/29.jpg)
Application
0%
20%
40%
60%
80%
100%
LDPE LLDPE HDPE PP
others
pipe and conduit
extrusion coating
injection moulding
blow moulding
fibre
film
29
![Page 30: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/30.jpg)
Global Consumption
0
10
20
30
40
50
60
70
80
90
1975
1977
1979
1981
1983
1985
1987
1989
1991
1993
1995
1997
1999
2001
2003
2005
2007
2009
2011
mil
lió
to
nn
a
PE
PP
30
![Page 31: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/31.jpg)
Per Capita Consumption
0
5
10
15
20
25
30
35
North
America
South
America
Western
Europe
Africa Asia Global
kg
per c
ap
ita
PE
PP
31
![Page 32: Introducing Polyolefins³l_roviden... · Content . Synthetic polymers – Classification – Global production . Polyolefins – Polyolefins family – PE classification – PP structures](https://reader034.vdocuments.net/reader034/viewer/2022042318/5f07eec87e708231d41f7c37/html5/thumbnails/32.jpg)
Domestic Production and
Consumption
55
105
155
205
255
305
355
405
455
505
2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012
PE production
PE consumption
PP production
PP consumption
32