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A human and ecological
approach to chemistry
PROVIPLAST® PLS GREEN
An innovative way to use epoxidized fatty acid alkyl esters as
primary plasticizers for PVC
Biobased content
Proviplast® PLS Green 5 Iso-amyl epoxy stearate 100 % MW: 365
Proviplast® PLS Green 8 2-ethylhexyl epoxy stearate 68 % MW: 407
- Partnership between Petrom and Proviron
- Introduction on the European market
- Bio-based plasticisers based on green resources
- No direct competition with feed and food resources
PROVIPLAST® PLS GREEN : Introduction
2
Petrom – Petroquímica Mogi das Cruzes S.A.
History:
1953 Start of phthalic anhydride production
1964 Start of plasticiser production
1970 Start of fumaric acid production
1998 Formation of Petrom (MBO)
• Production of plasticisers (>100kt)
• 200 FTE
Incorporation of bio-based products:
Iso-amyl alcohol, and more recently PLS Green
3
Proviron
• Process Engineering and Environment
• Belgium based Company
• Independent Chemical Company
• Founded in 1977
3 Production sites (Belgium and US)
Sales office in China
• 150m€ turnover (2012)
• 300 FTE
4
Proviron
5
Surfactants
Niche Plasticisers
Specialty Esters
Functional Chemicals
Polymer Additives
Water Borne Systems
Feed Additives
Bio Energy
Focus on three business lines and five markets
• Customer oriented approach
• Joint development programmes
• Close follow-up of trials
• Technical advise
• Tailor made solutions
• Focus on biobased raw materials
• Work under confidentiality
Gelation behaviour Transparant Paste PVC
6
Rheology and paste aging (viscosity Pa.s)
0
5
10
15
20
25
30
35
DEHP DINP DIDP PLS GREEN 5 PLS GREEN 8 PLS GREEN 9
To
To+24h
7
Plasticiser efficiency (Shore A hardness)
8
83 85
90
85 84
81
78 80
84
80 78
76
65
70
75
80
85
90
PLS GREEN 5 PLS GREEN 8 ESBO DOP ATBC DOA
Immediate After 15 seconds
Thermal stability transparant paste PVC 50phr
9
Mass loss at 105°C (ASTM 2115)
1.4 0.7
0.2
1.2
3.6 3
5.2
1.8
0.3
5.4
15.6
11.9
0
2
4
6
8
10
12
14
16
18
PLS GREEN 5 PLS GREEN 8 ESBO DOP ATBC DOA
24 h
168 h
10
Extraction tests ASTM D1239
Soapy water 40°C (%)
11
0.8
1.2
0.2 0.2
0.6 0.5
2.6
2.4
0.7
0.9
2
2.4
0
0.5
1
1.5
2
2.5
3
PLS GREEN 5 PLS GREEN 8 ESBO DOP ATBC DOA
24 h
168 h
Extraction tests ASTM D1239 Vegetable oil 40°C (%)
12
5.7 6.3
1.1
2.5
1.6
5.4
12.6 12.7
2.6
6.7
4
13.9
0
2
4
6
8
10
12
14
16
PLS GREEN 5 PLS GREEN 8 ESBO DOP ATBC DOA
24 h
168 h
Extraction tests ASTM D1239 Heptane 40°C (%)
13
12.8 13.1
5.5
9.4
8.4
15.8 15.4 15.6
14.4
12.8 13.7
18.1
0
2
4
6
8
10
12
14
16
18
20
PLS GREEN 5 PLS GREEN 8 ESBO DOP ATBC DOA
24 h
168 h
Mechanical properties and ageing
Tensile strenght (N)
0
50
100
150
200
250
PLS GREEN 5 PLS GREEN 8 ESBO DOP ATBC DOA
fresh
aged
14
Mechanical properties and ageing
Strain at break (%)
0
100
200
300
400
500
600
700
PLS GREEN 5 PLS GREEN 8 ESBO DOP ATBC DOA
fresh
aged
15
Mechanical properties and ageing
Stress at break (Mpa)
0
5
10
15
20
25
PLS GREEN 5 PLS GREEN 8 ESBO DOP ATBC DOA
fresh
aged
16
Proviplast® PLS Green
Evaluation Summary (Solvay)
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TRANSPARANT PASTE PVC SUMMARY
Plasticiser Rheology P. ageing Gelation Air Release T. Stability Colour Transp Gloss W Loss Score
DEHP 0/- + + 0 0 0 0/- 0 -- -1
DINP 0 0 0 0 0 0 0 0 0 0
DIDP 0/- + - 0/+ 0 0 0/- 0/- + 0
DEHA + + 0 + 0 0 0 0/- --- -1
PLS GREEN 5 + ++ -- ++ +++ - - 0 - 3
PLS GREEN 8 + ++ -- + ++ - - 0/+ 0 2,5
PLS GREEN 9 + ++ -- - ++ - - 0/+ + 1,5
FOAMY PASTE PVC
SUMMARY
Plasticiser Rheology P. ageing Color Density Exp Rate Cell Quality Score
DEHP 0/- 0 0/+ 0 - 0 -1
DINP 0 0 0 0 0 0 0
DIDP 0/+ - 0/+ 0/- 0/- 0 -1
DEHA ++ 0 0/- 0/+ 0/+ 0/- 1,5
PLS GREEN 5 + 0 - 0/+ + 0 1,5
PLS GREEN 8 + 0 - 0/+ + - 0,5
PLE GREEN 9 + 0 - + ++ - 2
Commercial examples of the use of
Proviplast® PLS Green
Experiences – Uses – Product Replacement - Limitations – Advantages
1. Proviplast® PLS Green in artificial leather
2. Phthalate free textile coatings
3. Food wrapping films
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CASE 1: Duvinil: artificial leather
• Proviplast® PLS Green 8 in artificial leather
• Coated high quality materials for sportshoes
• Replacement of DEHP in phthalate-free applications
• 30 % of total production phthalate free
• PVC plastisol application
• 1:1 replacement
• 70 phr loading
19
CASE 1: Duvinil: artificial leather
“PROJETO FTALATO FREE”
• Project started in November 2011 (pilot run)
• Approved for use in January 2012
• Large scale production started March 2012
2 routes for phthalate free
1. polyurethane (complete plasticiser free)
Non-recyclable / more production waste
Very expensive
Toxic chemicals / safety risks
2. Phthalate free plasticiser
Cheaper
DOA, DOTP, PLS Green 5, 8 and 9 tested
PLS Green 8 best choice
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CASE 1: Duvinil: artificial leather
ADVANTAGES PROVIPLAST® PLS GREEN 8
• Same plasticiser efficiency as DEHP / same surface properties
• No exudation (humidity / temperature) / no smell
• Less fumes in production compared to DOP
• No need for a PVC / PU top coating
• No problems with adhesion / printing on the artifical leather surface
• Better siliconated paper release and reuse (50% more)
• Better overall economics
21
CASE 2: Cipatex
• Coating, adhesives, synthetic laminates,
calandering and coagulated substrates based on
PVC and PU
• Applications in automotive, graphical, footware,
• Specialised in post-treatment (coating,
embossing, printing, laminating, …)
• Extensive development center
• Search for phthalate free, more sustainability,
• Total cost of products
22
Project phthalate-free plasticiser for coated materials
• Until 2009, DOP was the standard plasticiser
• Then changed to DINP
• In 2011 question from customers for phthalate free material
• Different products tested for both standard and foam layer
70% DOTP, DINCH® and 30% PLS Green 9
• Formulation tested, approved and in use for already 2 years
CASE 2: Cipatex
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Experience with PLS Green
• No exudation
• Good paste ageing, very good thermal stability
• No influence on printing and adhesion properties
• Higher amounts of PLS Green 9 give some cloudiness
• Current tests to increase PLS Green 9 to 50% based on experience
with the product.
• Current tests to use PLS Green 5 and PLS Green 8
CASE 2: Cipatex
24
CASE 3: Goodfilm
• Producer of PVC stretch film
• Produces 150 kilometer / day
• Different food applications
Bio-based phthalate-free formulation
• PVC resin with 40 phr plasticiser
• 55% epoxidized methyl soyate
• 45% PLS Green 5
• Anti-fogging aid
• ESBO
• Lubricant
25
CASE 3: Goodfilm
Experience with PLS Green:
• PLS Green is a replacement for Unimoll AGF (bio-based product)
• PLS Green gives a lower total cost
• Color and transparency are better
• Film used for refrigerated and room temperature applications
26
Conclusions – Proviplast® PLS Green
• Functions as a primary plasticiser
• Well suited for low viscosity plastisol formulations
• High bio-based content (100% for Proviplast® PLS Green 5)
• Excellent photo-thermal stability
• Good properties at low temperature, better than GP phthalates
• Proven applications
• Artificial leather
• PVC laminates
• Toys and highly flexible objects
• Coated materials
• Food-wrapping films
27
Our commitment
• To promote and support the product in different applications
• We will provide all the needed technical information
• Improve product characteristics if needed
• Help customers in technical development and recipe transition
• Apply for Reach and all needed approvals
28
Acknowledgements
• THANKS TO
– Duvinil, Fabiano André Trein
– Cipatex, Fernando Brandão
– Goodfilm, Furlan
– Solvay, Daniel Ortiz Martinz, for product evaluation
PROVIRON Functional Chemicals
Oudenburgsesteenweg 100
8400 Oostende, Belgium
+3259562100
[email protected] (R&D)
[email protected] (sales)
PETROM
Petroquimica Mogi das Cruzes S/A
Rod. Dom Paulo Rolim Loureiro
08766-500 – Mogi das Cruzes, SP – Br
+551147987600
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