New building blocks to expand your formulation options.pda-europe.org/members2/documents/01_HuntsmanPerformanceProducts_G.Dries.pdf · PDA Europe 2011 Annual Conference –The Hague,

PDA Europe 2011 Annual Conference –The Hague, 14-16 November

New building blocks to New building blocks to

expand your formulation expand your formulation

options. options.

Geert Dries

Technical manager urethane chemistries

Huntsman Performance Products

JEFFAMINEJEFFAMINE®® amine amine

JEFFLINKJEFFLINK®® diaminediamine


Content

• What is Polyurea?

• Why develop new molecules?

• JEFFAMINE® amine and JEFFLINK® diamine overview

• Some ideas

• Summary


Urea

Linkage

NR

H

N

O

R'N N

O

HH HnR'

H2N NH2R

OCN NCO +

IsocyanatePrepolymer

Polyamine

POLYUREAPOLYUREA

What is Polyurea ?


Typical formulation

A side: Isocyanate component

Prepolymer, (MDI, HDI, IPDI) 100%

B side: Amine (Resin) component

Polyether amine 40-75%

Amine chain extender 15-50%

Additives 0-10%

System processing: Volume ratio: 1:1. Index 1.05 System processing: Volume ratio: 1:1. Index 1.05 --1.151.15

Application temperature & pressure: 75Application temperature & pressure: 75--8080ººC & 150C & 150--180 bar180 bar


Features and benefits of Polyurea

• Two component, 100% solids system, typically 1:1 volume mix

• Fast reactivity and cure without a catalyst

• Relatively moisture and temperature insensitive during application

• High abrasion resistance

• Excellent physical properties

• Good adhesion to variety of substrates

• Good low and high thermal stability


Typical uses

• Concrete protection

– Secondary containment

– Bridge decking

– Park decks

– Sewage installations

• Flat roofing

• Steel protection


Why develop new molecules?

• We are in the business of making molecules.

• Is there room for improvement?

– Adhesion

– Reactivity

– Wear and tear

– Processing

• Extending and opening new markets


JEFFAMINE® amine

and JEFFLINK® diamine overview


O

O

CH 2

NH2

O NH 2

NH 2

R

x

y

z

n

JEFFAMINE® T-3000 amine (x + y + z) = ~ 50


JEFFAMINE® T-403 amine (x + y + z) = ~ 5-6

PPG based polyether amines(primary)


O

O

CH 2

NH2

O NH 2

NH 2

R

x

y

z

n

JEFFAMINEJEFFAMINE®® TT--3000 amine (x + y + z) = ~ 503000 amine (x + y + z) = ~ 50


JEFFAMINE® T-403 amine (x + y + z) = ~ 5-6



x ~ 3

x ~ 5

x ~ 32

JEFFAMINE D-230 amine



H2NO

ONH2

x

( )



PPG based polyether amines(secondary)

� Proprietary Huntsman catalyst technology allows high secondary amine formation with little primary or tertiary.

� Intrinsic reactivity drops roughly a factor of 20 for secondary compared to primary amines.

� Steric hindrance plays an additional role in slowing the reactivity.

� Cure speed (gel time) of a formulation is dependent on concentrations and inherent reactivity.

� Products are stable, there is no off-gassing of reversible blocking agents.


JEFFAMINE®

SD-231 amine

JEFFAMINE®

SD-401 amine

JEFFAMINE®

SD-2001 amine

Approximate mol weight, g/mol 315 515 2050

Approximate functionality 2 2 2

Kinematic viscosity, 25°C, cSt 7 18 209

Equivalent weight, gram/eq 158 258 1025

NHO

ONH

RR

n

PPG based polyether amines(secondary)

• Designed to be used in conjunction with, or to replace, aromatic or aliphatic

chain extenders, or to partially replace existing primary polyether amines.

– Slow down reactivity

– Produce low viscosity prepolymers


IPDI quasi prepolymers

Comparison of primary vs secondary polyetheramines in IPDI

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

12 13 14 15 16 17 18 19 20NCOv (%)

Vis

co

sity a

t 25°C

(cS

t)

IPDI / Jeffamine® D 2000

IPDI / Jeffamine® SD 2001


H12MDI quasi prepolymer

Comparison of primary vs secondary polyetheramines in H12MDI

0

1000

2000

3000

4000

5000

6000

7000

12 13 14 15 16 17 18

NCOv (%)

Vis

co

sit

y a

t 2

5°C

(c

St)

H12MDI / Jeffamine® D 2000

H12MDI / Jeffamine® SD 2001


Poly(tetramethylene ether)glycol backbone amines -

H2NO

OO

NH2( ))( ( )a n b

PTMEG based polyether amines(primary and secondary)

More hydrophobic, higher performance - “premium soft segment”


PTMEG based polyether amines(primary and secondary)

1245 cst at 40°C916 cSt at 40°C234 cSt at 40°C121 cSt at 40°Cviscosity

35°C33°C16°C8°CMelting

point

1150760710500eq. weight

2300170013501000Mw

22.822Fn

Primary

Primary +

SecondaryPrimaryPrimaryamine

type

XTJ-652 (*)

JEEFAMINE®

THF-170 amine

JEFFAMINE®

THF-140 amine

JEFFAMINE®

THF-100 amine

(*) experimental product


PTMEG based polyether amines(secondary)

1150 cSt at 40°C251 cSt at 40°C261 cSt at 25°Cviscosity

1200715550eq. weight

240014301100Mw

222Fn

SecondarySecondarySecondaryamine type

XTJ-653 (*)XTJ-605 (*)XTJ-604 (*)

(*) experimental product


XTJ-653REFERENCECasting system

70200mg lossTaber abrasion (H-18)

4445shore DHardness

Mechanical properties

240420secondsTack free time

120180secondsGel time

Reactivity

115115Suprasec® 2054

5DETDA

4045BADPM

50XTJ-653

5JEFFAMINE® SD 401 amine

55JEFFAMINE® D 2000 amine

Abrasion is reduced with 70%

Comparing the PPG vs PTMEG based polyether amines


1218secondsTack free time (s)

67secondsGel time (s)

Reactivity

112115MDI prepolymer (16%)

1212BADPM

2020DETDA

68XTJ-652


XTJ-652REFSpray system



100230mg lossTaber abrasion (H-18)

407455%Elongation at break

20.120.3MPaTensile at break

8383N/mmTear strength

4948shore DHardness

XTJ-652REFERENCEMechanical properties


Abrasion is reduced with 55%



2.55.5150 days at RT

1.5230 days at RT

1.51.95 days at RT

XTJ-652REFERENCEwater uptake (%)

Water uptake is reduced with 55%


JEFFLINK® diamine


JEFFLINK® diamine in analiphatic system

texturedsmoothappearance

56/5585/85gloss 20/60

5783N/mmTear strength

444477%Elongation at break

12.318.2MPaTensile at break

3547shore DHardness

Mechanical properties

15570secondsTack free time

614secondsGel time

reactivity

JEFFLINK® 754 diamine JEFFLINK® 136 diamineDiamine used

IPDI + JEFFAMINE® SD 2001 amine to NCOv 16% Prepolymer used


JEFFLINK® diamine features

• Colorless liquids

• Low viscosity

• Prolonged gel time

• Shorter dry time

• Variation in hardness

• Contribute to UV stability

Process

Property

Product


Combining JEFFAMINE® T 3000

amine with PTMEG polyether amines

42

12

114

16

45

24

15

T 3000

/ XTJ-605

20

8

111

20

45

35

T 3000

/ XTJ-605

621216secondsTack Free Time

1368secondsGel time

Reactivity

112111111Suprasec® 2054

10BADPM

162424DETDA

XTJ-605

40XTJ-604

24JEFFAMINE® T 3000 amine

11JEFFAMINE® T 5000 amine


T 3000

/ XTJ-604REF 2REF 1formulation


1.8

1.6

87

337

26.8

42

T 3000

/ XTJ 605

2.1

1.9

82

510

24.1

38

T 3000

/ XTJ 605

100150130mg lossAbrasion (H-18)

Water uptake

1.82.02.1%1 day at RT

1.92.32.3%1 week at RT

%2 weeks at RT

525561541%elongation

27.424.825.5MPaTensile

404445Shore DHardness

T 3000

/ XTJ 604REF 2REF 1

Abrasion is reduced with up to 45%

Combining JEFFAMINE® T 3000

amine with PTMEG polyether amines

Water uptake is reduced with ~20%


Conclusions

• The new building blocks can extend your

market reach

– Improving the abrasion resistance

– Reducing the water absorption

– Widen your formulation latitude

– Increase the processing latitude


What can HUNTSMAN do for you?

• To offer building blocks for making suitable systems towards thespecialist formulators.

– Amine products under the JEFFAMINE® amine and JEFFLINK®

diamine brand name

– MDI products under the SUPRASEC® isocyanate brand name

– Titanium dioxide products under the TIOXIDE® pigment brand name

• Joint projects to develop tailor made products for specific markets eg. Water proofing membranes, metal protection,…

• To assist and offer guidance in the correct and safe use of our products

– EHS, ISOPA, Walk the Talk,…


disclaimer

• Copyright © 2011 Huntsman Corporation. All rights reserved.

• All information contained herein is provided "as is" without any warranties, express or implied, and under no circumstances shall the authors or Huntsman be liable for any damages of any nature whatsoever resulting from the use or reliance upon such information.Nothing contain in this publication should be construed as a license under any intellectual property right of any entity, or as a suggestion, recommendation, or authorization to take any action that would infringe any patent. The term "Huntsman" is used herein for convenience only, and refers to Huntsman Corporation, its direct and indirect affiliates, and their employees, officers, and directors.

• JEFFAMINE® , JEFFLINK®, SUPRASEC® and TIOXIDE® are registered trademarks of Huntsman Corporation or an affiliate thereof in one or more, but not all countries.

• Main Offices US: 500 Huntsman Way / Salt Lake City, Utah 84108 / 801-584-5700

• Technical Service US: 8600 Gosling Road / The Woodlands, Texas 77381 / 281-719-7780

• Main Offices Europe: Huntsman Belgium BVBA / Everslaan 45 / B-3078 Everberg, Belgium / 32-2 -758-9211

• Technical Service Europe: Technical Services Representative / Everberg Office / 32-2-758-9392

• Main Offices Asia Pacific Offices: Huntsman Singapore PTE / 150 Beach Road, #37-00 Gateway West / Singapore 189720 / 65 6297 3363

• Technical Service Asia Pacific: Huntsman Performance Products / 61 Market Road, Brooklyn, Victoria / Australia 3012 / 61 3 9933 6666

• www.huntsman.com

Documents

New building blocks to expand your formulation options.pda-europe.org/members2/documents/01_HuntsmanPerformanceProducts_G.Dries.pdf · PDA Europe 2011 Annual Conference –The Hague,