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Polyisocyanathärter
für umweltfreundliche Beschichtungen
für die Anwendung in der Bauchemie
Worlee Kunden Seminar – 28. und 29. November 2017
Presented by: Marc Cornick, Market Development Manager (DACH, CEE & UK)
Acknowledgements to P. Barbeau, R. Klucker, P. Olier and N. Resham
1
Vencorex
• Vencorex: a JV formed in 2012 between: PTT Global Chemical and Perstorp
• Company history much longer, French site established in 1916, production of aromatic isocynates since 1962, aliphatic isocyanates since 1978
• Over 600 employees globally
• Vencorex is a worldwide leader in aliphatic isocyanate monomers and derivatives
• Manufacturing sites at Pont-de-Claix (France) and Freeport (USA), Rayong (Thailand)
• R&D centres in Europe (France) and in Asia (China)
• Well established product brands - Tolonate™, Easaqua™ and
Scuranate™
2
Content
This presentation is in two parts:
o First part: an ‘AGBB-friendly’ self-emulsifying
hardener for 2K waterborne PU coatings
o Second part: a low viscosity polyisocyanate
hardener, as a reactive diluent and internal
flexibiliser in solvent-free polyurea coatings
3
Content
This presentation is in two parts:
o First part: an ‘AGBB-friendly’ self-emulsifying
hardener for 2K waterborne PU coatings
o Second part: a low viscosity polyisocyanate
hardener, as a reactive diluent and internal
flexibiliser in solvent-free polyurea coatings
4
AGBB
5
• System to evaluate / restrict VOC in building products
• Total VOC of interest but limits set (LCI / NIK) for individual
components also
• Low LCI / NIK is bad, (no value is even worse), high is good*
• Solvents often included in 2K WB PU to help: • Compatibility / miscibility
• Optimise drying and open time
• Film formation
• Improve and film appearance
• Vencorex fast drying Easaqua grades use IPDI trimer, which
requires solvent in order to be incorporated, also can give
‘ready to use’ grades
Easaqua Range
Easaqua™ L series
Glossy finish, High chemical resistance, Low viscosity, DTM
Easaqua™ M series Easy mixing, Primers, Matt to
Glossy finish, Flexibility of Application
Easaqua™ D series
Fast drying, Ready to use , High gloss, Long pot life
• Easaqua™ X D 401
• Easaqua™ X D 803
• Easaqua™ L 600
• Easaqua™ M 501
• Easaqua™ M 502
• Easaqua™ X D 870
New Easaqua™ X D 870
• Easy mixing
• Environment friendly Easaqua™
technology
• Fast drying
• Long pot life
• Good chemical resistance
Based on HDI/IPDI derivatives
• Low odor, suitable for low VOC emission regulations
• Ready to use
• Nice flow, Superior film aspect
Diluted in PGDA
• NCO (%) : 12.4
• Viscosity (mPa.s @ 25°C) : 380
• Solid content (%) : 69
Targeted characteristics
New Easaqua™ X D 870
PGDA is a low odor solvent, suitable to comply with VOC emissions regulations
(high LCI value 5300 µg/m3)
PGDA
PGDA
0
200
400
600
800
1000
1200
1400
1600
1800
2000
3 days 28 days
PG
DA
em
issi
on
(µ
g/m
3)
TVOC limit AgBB scheme
PGDA emission of a 2 K PUD formulation for parquet
3 layers 105 g/ m2 wet on oak ,24 h drying between layers, no sanding, 48 h conditioning at 23°C and 50 % RH
The limit of 1000 μg / m3 in order to comply with the AgBB scheme can be respected
depending on A part
• 2 K Parquet formulation based on Alberdingk® U 9150 (Alberdingk Boley) A/B = 9/1
• 2 K Furniture formulation based on Setaqua™ 6522/6516 (Allnex) NCO/OH =1,3
Flooring
Kitchen & office
furniture and joinery
New Easaqua™ X D 870
Reduction of drying times thanks to IPDI derivatives
New Easaqua™ X D 870
According to ISO 1517
Formulation based on Alberdingk ® U 9150 Formulation based on Setaqua™ 6522/6516
Ready to use, excellent dispersability in PUD and 2K PU waterborne formulations
Formulation based on Alberdingk ® U 9150
New Easaqua™ X D 870
Formulation based on Setaqua™ 6522/6516
Anfeuerung : Easaqua™ X D 870 closer to the “wet look”
New Easaqua™ X D 870
Easaqua™ X D 870
Easaqua™ M 502 70% PGDA
Easaqua™ X D 803
Formulation based on Alberdingk ® U 9150, average on 5 panels
Excellent TABER abrasion and good stackability
New Easaqua™ X D 870
0
5
10
15
20
25
30
mg
Easaqua™ X D 870
Easaqua™ X D 803
Easaqua™ M 502 (70 % PGDA)
Formulation based on Alberdingk ® U 9150 (1 Kg, 1000 rotations, CS 10 wheels)
Formulation based on Setaqua™ 6522/6516, 100 µm wet on Leneta chart, curing at 50°C, Contact black
on white1h, 50°C,150 g/cm2
Curing time
Easaqua™ X D 870
Easaqua™ X D 803
Easaqua™ M 502
30’ Pass Pass Fail
45’ Pass Pass Pass
Pass Fail
While keeping a good chemical resistance
New Easaqua™ X D 870
Formulation based on Setaqua™ 6522/6516, 200µm wet film on glass panels According to EN 12720, 0 = bad, 5 = good
New Easaqua™ X D 870
Recommended for on site application, also suitable for industrial
applications
Flooring,
Anti-graffiti
Metal,
Transportation
0 = bad, 5 = good
Marine &
Protective
XD 870 was also tested by Worlee together with some of their resin grades.
With WorléeCryl A 1241 W and WorléeCryl A 2441 W, XD 870 gave the
same high level of performance as seen with XD 803.
Results with WorléeCryl A 2441 W:
XD 870 XD 803
New Easaqua™ X D 870
We have tested XD 870 also in one concrete flooring formulation.
We have no comparative data but the XD 870 gave rise to some
promising results:
New Easaqua™ X D 870
Properties/Characteristics NCO/OH 1.7 Pot life at 23°C 3 hours Gloss at 60° ~ 80 GU Gloss at 85° ~ 95 GU Persoz hardness ~ 300 s Drying times (23°C/50% r.h)
T1 (dust free time): 1 hour T2 (touch dry time) : 3 hours T3 (through cure time) : 6 hours
Chemical/stain resistance* (0 : excellent, 5 : bad)
Sulfuric acid: 1 Acetic acid : 4 Ammoniac : 1 Ethanol 96° : 4 Skydrol : 0 Wine : 1 Coffee : 1 Ketchup : 0
Content
This presentation is in two parts:
o First part: an ‘AGBB-friendly’ self-emulsifying
hardener for 2K waterborne PU coatings
o Second part: a low viscosity polyisocyanate
hardener, as a reactive diluent and internal
flexibiliser in solvent-free polyurea coatings
18
• A polyurea is formed by reacting a polyisocyanate and a polyamine
• Of increasing interest in various application areas, and specifically in
flooring due to very fast curing speeds, therefore surfaces can be brought
back into use very quickly
• There are however some disadvantages to this technology:
• Films can be brittle
• Coatings can be quite viscous if solvent-free (flow / overlap issues)
• Open time can be short
Polyurea Overview
However: Tolonate™ X FLO 100 can help here!
Putting the care
into chemicals
• Partially bio-based, Tolonate™ X FLO 100 is an aliphatic isocyanate polymer
• 25% of renewable material certified via. external analsyis (ACDV). Weight of all
atoms of renewable part vs total weight of molecule
• Product based on Hexamethylene Diisocyanate (HDI), with high flexibility due to R
group
• 100% solids, extremely low viscosity
• R group is also hydrophobic, so can help to improve the corrosion resistance of
coatings
• Functionality = 2, so cannot be used by itself but should be combined with other
hardeners (can also be used as a building block for resin manufacture)
Tolonate™ X FLO 100 :
characteristics
20
Low viscosity grades
Tolonate™ XFLO 100 Ultra Low viscosity grade for VOC reduction, Functionality is 2, not suitable as such for coating
Also building block for resins Brings flexibility and hydrophobicity
Tolonate™ technology :
Low viscosity range
0
500
1000
1500
2000
2500
Tolonate™
HDT
Tolonate™
HDB-LV
Tolonate™
HDT-LV
Tolonate™
HDT-LV2
Tolonate™
X FLO 100
2400 2000
1200
600
140
Vis
co
sity
(m
Pa
.s à
25
°C)
Partially bio based
0
10
20
30
40
50
60
70
80
90
100
100/0 60/40
Impact Resistance of Polyaspartic Coating as a Function of X FLO 100 Content
AFNOR
ASTM
Tolonate™ X FLO 100
as Internal Flexibiliser
Tolonate™ X FLO 100 Can Improve Flexibility
Blend viscosity (A+B part)
Initial blend viscosity of a
coating system is key for its
application properties
0
200
400
600
800
1000
1200
1400
0 20 40
visc
osi
ty[m
Pa.
s]
X FLO 100/(HDT-LV2 + X FLO 100) [vol. %]
Blend viscosity close to T0 (T.277/T.292)
T.277/T.292 (100/0)
T.277/T.292 (75/25)
Tolonate™ X FLO 100 Can Reduce Initial Blend Viscosity
Tolonate™ X FLO 100
as Reactive Diluent
0%
20%
40%
60%
80%
100%
120%
140%
160%
180%
200%
0% 25% 50%
Rel
ativ
e O
pen
Tim
e
% of X FLO 100 in Isocyanate Blend
Polyurea System with HDT-LV2 / X FLO 100
Open Time: Tolonate™ X-FLO 100
in 100% Polyurea System
Tolonate™ X FLO 100 Can Increase Open Time
Tolonate™ X FLO 100 :
what should be remembered
• Very low viscosity polyisocyanate
• Contains 25 % renewable material
• As a crosslinker, recommendation is to use it combination with
other polyisocyanates (20-30 %)
• Suitable for a large variety of application where main benefits
will be :
─ Low viscosity
─ Flexibility/control of mechanical properties
─ Open time
─ Hydrophobicity
STRICTLY CONFIDENTIAL
Thank you
for your attention!
27
Vencorex is a JV created in 2012 between :
• PTT Global Chemical, Thailand’s largest and Asia’s leading integrated petrochemical and refining
company,
• Perstorp Group, world leader in several sectors of the specialty chemicals market.
10% 90%
A joint venture backed by
two global leaders
A Chemical Flagship of PTTGC Group with Compelling Strengths
• Largest gas-based petrochemical producer in Thailand and the fifth in Asia
• Strong footprint in fast growing regions with 5
operating countries worldwide
• N°22 on the ICIS’ 2014 global TOP 100 leading petrochemicals companies,
• Ranked in Top 10% of Dow Jones Sustainability
indices (DJSI) – World members, and as 6th of
the world’s leading chemicals companies in 2014
• Recognized by the Global Compact for conducting outstanding social responsibility
with business continuity following the UNGC principles. Members of the UNGC advanced
level for 3 years in a row
• Committed to operational excellence targeting best in class/ first quartile business efficiency
10,2 bn$ SALES
$1,4bn EBITDA
754M$ NET PROFIT
6,120 EMPLOYEES
2016 Figures
8.8 MTPA Petrochemical
CAPACITY
•LPG
•Light Naphtha
•Reformate
•Jet A-1
•Diesel
•Fuel Oil
Refinery & shared Facilities
•Benzene
•Toluene
•Paraxylene
•Orthoxylene
•Mixed Xylene
•Cyclohexane
Aromatics
•Ethylene
•Propylene
•Pyrolysis Gasoline
•Mixed C4
Olefins
•HDPE
•LDPE
•LLDPE
•PS
•PVC
Polymers
•Ethylene Oxide/ Ethylene Glycol (EO/EG)
•Ethanolamine
•Ethoxylate
EO-Based Performance
•Methyl Ester
•Fatty Acid
•Fatty Alcohol
•Glycerin
•Specialty Oleochemicals
•Bioplastics
Green Chemicals
•Phenol
•Acetone
•Bisphenol A
•Toluene Diisocyanate (TDI)
•Hexamethylene Diisocyanate & derivatives
High volume Specialties
PTTGC business structure
Perstorp in brief
World leader in various sectors of the specialty chemicals market
• Pioneer in formalin chemistry, plastics and
surface materials
• Perstorp was founded in 1881, over 130 years of
winning formulas
• Controlled by PAI partners,a major
European private equity company
• Sales of over SEK 11,3 billion in 2016
• Around 1,500 employees in 22 countries
• Production plants in Europe, Asia and North
America
• Sales offices in all major markets
2015 Figures
Vencorex global footprint
Freeport
Pont de Claix
Saint Priest
Saint Fons
• Headquarter
• Production sites • R&D Lab • Commercial representations
Shanghai
Sao Paulo
Bangkok
Rayong
Tolonate™ 1989
Easaqua™ 2015
HDI / IPDI 1978
Tolonate™ 1983
Easaqua™ 1997
Tolonate™ 2016
Key business features
• #2 worldwide player with production sites of aliphatic Isocyanates in the 3 main regions
• Well known brand name products
• Tolonate™
• Easaqua™
• Wide range of products that meet the needs of numerous markets including environmentally friendly CASE formulations
• Active member of ALIPA
Specialty Polyurethanes for Coating, Adhesives, Sealants
& Elastomers (CASE)
Polyurethanes foam & Chlor -Alkali
• Aromatic Isocyanate (TDI) key
supplier for flexible and rigid
Foam market
• One of the largest producer of
Chlor-Alkali in Europe
• Excellence in Services
• Active member of Euro Chlor
• 3 different product ranges:
– Monomers: building blocks for resin synthesis
– Tolonate™: crosslinkers of Solvent-Based PU formulations
– Easaqua™: crosslinkers of Waterborne PU formulations
= derivatives
Vencorex’s Portofolio
Tolonate™ Product range
HDI
Biuret
HDI
Trimer
Bio- based
Fast Drying
Low Viscosity
Blocked
Coil & can
coatings
Tolonate™ Plastic &
wood
coatings
Leather
finishing
Adhesives Automotive
(OEM & refinish)
Transportation,
aerospace, ACE
Tolonate™ HDB
Tolonate™ HDB 75 MX
Tolonate™ HDT
Tolonate™ HDT 90
Tolonate™ HDT LV
Tolonate™ HDT LV2
Tolonate™ HDB LV
Tolonate™ X Flo 100
Tolonate™ IDT 70 B
Tolonate™ XFD 90 B
Tolonate™ D2
TOLONATE™ main characteristics
Tolonate
Isocyanate technology Colour
(HAZEN)
Solids content
(%)
NCO%
(on delivery form)
Viscosity at 25°C
HDB HDI biuret ≤ 40 100 22.0 9 000 mPa.s
HDB 75 MX HDI biuret ≤ 40 75 16.5 250 mPa.s
HDB 75 B HDI biuret ≤ 40 75 16.5 150 mPa.s
HDB 75 M HDI biuret ≤ 40 75 16.5 250 mPa.s
HDB-LV HDI biuret, Low viscosity ≤ 40 100 23.5 2 000 mPa.s
HDT HDI trimer ≤ 40 100 22.0 2 400 mPa.s
HDT 90 HDI trimer ≤ 40 90 19.8 500 mPa.s
HDT 90 B HDI trimer ≤ 40 90 20.0 450 mPa.s
HDT-LV HDI trimer, Low viscosity ≤ 40 100 23.0 1 200 mPa.s
HDT-LV2 HDI trimer, Low viscosity ≤ 40 100 23.0 600 mPa.s
X FD 90 B * HDI trimer, Fast Drying ≤ 60 90 17.4 2 000 mPa.s
X FLO 100 Bio-based isocyanate polymer ca. 80 100 12.3 140 mPa.s
D2 Blocked HDI Trimer ≤ 40 75 11.2** 3 250 mPa.s
IDT 70 B IPDI trimer ≤ 60 70 12.3 600 mPa.s
** Blocked NCO
Easaqua™ solutions
for WB Coatings
• Spontaneous emulsification process
• Stable emulsion (physically and chemically) for several
hours
• Formulation, mixing and application operations similar
to 2K solvent-based systems
Easaqua : « self-emulsifiable » polyisocyanates
Hydrophilic isocyanates : two main technologies
Conventional polyisocyanate hydrophilically modified to provide good
dispersion into aqueous phases (used as cross linkers for 2K waterborne
Polyurethane coatings)
POE or ionic grafted groups : Bayer but also BASF and others
Free ionic groups : Easaqua™ technology
Introducing 2K WB
polyurethanes technology
• Specific WAT range for adhesives and leather: WAT 3, WAT 4
• Grades based on old APEO technology no longer promoted: WT 2102, WAT, WAT 1
Easy mixing grades for coatings
Easaqua™ M 501 and M 502 Very good balance between mixing behavior/compatibility
Easaqua™ L 600 Improved adhesion, Good water resistance, Enhanced NCO content/viscosity balance for high gloss systems,
Fast drying grades for coatings
Easaqua™ X D 401 Provides quick drying time and high gloss
Easaqua™ X D 803 Provides quick drying time and high gloss, Ready to use
Easaqua™ X D 870
Provides quick drying time and high gloss, Ready to use, AgBB ‘friendly’
Easaqua™ technology :
product portfolio
Easaqua™ for 2K coatings
main characteristics
Easaqua™ Isocyanate technology
Solids content
(%)
NCO% (on delivery form)
Viscosity at 25°C
M 501 HDI 100 21.6 1 100 mPa.s
M 502 HDI 100 18.3 3 600 mPa.s
X L 600 HDI 100 20.6 1 500 mPa.s
X D 401 HDI & IPDI 85Δ 15.8 1 050 mPa.s
X D 803 HDI & IPDI 69+ 12.2 200 mPa.s
X D 870 HDI & IPDI 69* 12.4 380 mPa.s
Δ in butyl acetate + in butoxl * In PGDA
READY TO
USE !
M 502
L 600
X D 401
M 501
X D 870
X D 803
M 502
X D 803
X D 870
X D 401
L 600
M 501
Ready to use Low hydrophilic
Requires dilution Hydrophilic
Easaqua™ solutions
for WB coatings
• Excellent
durability
• Lower viscosity
Tolonate™ HDT – LV2
• Compatibility
with polyesters
• Low viscosity
Tolonate™ HDB - LV
• Compatibility with polyesters • Lowest visc
• Flexibility
• Increased pot life
Tolonate™ X FLO 100
42
Std Grades for Flooring
Polyaspartics
0
20
40
60
80
100
120
140
100/0 80/20 60/40
König Hardness : T.277/T.292 (25/75) as function of Tolonate blend ratio (HDT-LV2 / X FLO 100)
1d
7d
There is a minor reduction to the final hardness of the coating as a result
of using Tolonate™ X FLO 100
Crosslinker in 2K SB PU coatings
Weathering data : QUV B
White topcoat based on Uracron CY 474 E-70 from DSM
1.5 % Tinuvin 1130
0.5 % Tinuvin 292
0
0,5
1
1,5
2
2,5
500 1000 1500
De
lta
E
QUV B hours
Tolonate™ HDT-Tolonate™ X FLO 100 80/20 Tolonate™ HDT-LV Competitor 1 Competitor 2
Tolonate™ X FLO 100 shows similar durability vs other low
viscosity polyisocyanates after QUV B exposure.
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