Polyisocyanathärter für umweltfreundliche Beschichtungen für … · 2020. 3. 16. · • Partially bio-based, Tolonate™ X FLO 100 is an aliphatic isocyanate polymer • 25% of

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







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™ L 600

• Easaqua™ M 501

• Easaqua™ M 502


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


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


Reduction of drying times thanks to IPDI derivatives


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


Formulation based on Setaqua™ 6522/6516

Anfeuerung : Easaqua™ X D 870 closer to the “wet look”


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


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


Formulation based on Setaqua™ 6522/6516, 200µm wet film on glass panels According to EN 12720, 0 = bad, 5 = good


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


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:


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







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


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


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.

Documents

Polyisocyanathärter für umweltfreundliche Beschichtungen für … · 2020. 3. 16. · • Partially bio-based, Tolonate™ X FLO 100 is an aliphatic isocyanate polymer • 25% of