130226 composites expo 2013

NEW DOW EPOXY PRODUCTS =

NEW OPPORTUNITIES FOR COMPOSITE INDUSTRY

THE DOW CHEMICAL COMPANY IS A GLOBALLY LEADING SUPPLIER OF INDUSTRIAL RAW

MATERIALS FOR MANY APPLICATIONS. OVER THE LAST DECADES DOW HAS ESTABLISHED

ITSELF AS A MAJOR GLOBAL PRODUCER OF EPOXY PRODUCTS. BEING FULLY COMMITTED

TO THE EPOXY INDUSTRY AS DEMONSTRATED BY RECENT INVESTMENTS AND ALSO BY

INVESTMENT IN INNOVATION, CONTINUOUS DEVELOPMENT OF NEW PRODUCTS HAS AND

IS BEING ENSURED. SOME RECENT NEW ADDITIONS TO THE EPOXY PORTFOLIO ARE

BEING DESCRIBED AIMED AT ADDRESSING COMPOSITE CUSTOMER NEEDS

Composite-Expo - 2013

6th International Specialized Exhibition

on composite materials and technologies

Moscow, Russia Toine Dinnissen, February 26th 2013

Toine Dinnissen, February 26th 2013

Outline

The Dow Chemical Company

Dow Epoxy business

• History & Commitment,

• Product Organisation

Recent Innovation

• Lower Viscosity

• Faster Cure

• More Flexibility

• Higher Temperature Performance

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• Founded in 1897 by Herbert H. Dow in Midland, Michigan

• Supplies broad range of products / services in about 160 countries

• More than 5,000 products manufactured at 188 sites in 35 countries

• Employs 52,000 employees worldwide

• Annual sales of $60 billion (2011)

• $1.7B in R&D investment in 2010

Our Mission

To passionately innovate what is essential to human progress by providing sustainable solutions to our customers

Connecting chemistry, innovation and sustainability to help

address world’s challenging problems:

• Need for clean water

• Need for renewable energy

• Need for energy conservation solutions

• Need for increased agricultural productivity

2010 – Dow becomes a Worldwide Partner and the “Official Chemistry Company” of the Olympic Games


D.E.R.™ Epoxy Resin in Composites

Features:

• Excellent adhesion to many (difficult) substrates

• Low shrinkage upon cure

• Excellent Chemical Resistance

• Excellent Mechanical Properties

• Good Heat Resistance

• …

Often used to produce light weight composite parts that can replace metal articles.

e.g. FRP pipes, automotive parts, storage tanks, wind-mill blades, ….

™ Trademark of The Dow Chemical Company


Dow Epoxy

•The world’s largest producer of epoxy resins & intermediates.

• Broad product mix & strong global presence.

• Eight manufacturing facilities in:

• Asia Pacific – China, Korea

• Europe – Germany, Italy

• Latin America – Brazil

• North America – USA

• Backward integration into feed-stocks that allows consistent,

reliable product supply.

• Over 50 years of industry service

• Strong commitment to product technology & solution innovation

• Strong re-investment in the business


Global Manufacturing, R&D, TS

Gumi

Shanghai

Pisticci

Epoxy Manufacturing Site

R&D Center

Technical Service Center

Guaruja

Freeport

Zhangjiagang

Rheinmuenster

Horgen

Stade

Sao Paulo

Baltringen

Roberta


Integrated Business Model

Allyl

Chloride EPI Liquid

Epoxy

Specialty

Epoxies

Blends

Hardeners

Solid/Solid

Solutions

Brominated

Epoxies

Cumene

Acetone Benzene

Phenol BPA

Caustic

Propylene

Chlorine

Water

Treatment

Polymers

Civil Engineering

Adhesives

Coatings.

Composites

Electronics

Poly-

carbonate

Dow upstream and downstream of epoxies

Core Dow epoxy products

External downstream

Dis

trib

uto

rs

Fo

rmu

lato

rs

Amines


Innovation

1st Epoxy NovolacDER438 – later usedin Apollo heat shield

1960 1970 1980 1990 2000 2010

Brominated FRE

Jeffamine Hardeners

Derakane

Waterborne BeverageCan Coatings

Quatrex, Tactix, CyanateEsters, and Trisphenol Epoxies- High performance resinsfor electronics and aerospace composites

Glycidyl Methacrylatefor automotive clear coats

1st large scale continuousLER process

Oxazolidone Epoxies

DOPBN HalogenFree Hardener

Next Gen. LER

Peroxide Epi

E12

GTE

Increased Tgvia Boric Acid

Airstone wind energy systems

A1 catalystfor SER

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Investment in Epoxy

We will Invest;

• To maintain Dow leadership in Epoxy products and technology

• To meet emerging needs with technology, product and process innovations

• To establish and maintain a close and collaborative relationship with you.

Investments;

• Dow Epoxy to buy 3 medium sized curing agent companies (UPPC, GNS, PolyCarb)

• Dow Liquid Epoxy Resin Expansion – Stade, Germany (30 kT)

• To come online Q4 2012

• Increase Dow global capacity by 10%

• Reliably support growth with strategic customers

• Dow Propylene & Ethylene Expansion in the US

• Capitalize on shale gas in US

• Feedstock flexibility for cracking Ethane and Propane

• Key to fuel growth of downstream Dow businesses (i.e. Epoxy)

• Dow and Aksa Sign Memorandum of Understanding to Form Integrated Carbon Fiber and Derivatives Joint Venture


DOW Epoxy Products

Name Product Type

D.E.R.™ 31x / 31xx Liquid epoxy resin with non-reactive diluents / additives

D.E.R. 32x / 32xx Liquid epoxy resin with reactive diluent(s)

D.E.R. 33x / 33xx Unmodified bisphenol-A Epoxy Resin

D.E.R. 34x / 34xx Accelerated liquid epoxy resin

D.E.R. 35x / 35xx Bisphenol-F epoxy resin containing liquid epoxy resin, might contain reactive diluent (3rd digit can indicate the main reactive diluent type)

D.E.R. 36x / 37x Few “exotic” grades

D.E.R. 38x Only D.E.R. 383 = US version of D.E.R. 330

D.E.R. 39xx Specialty epoxy resin

D.E.R. 5xx Brominated epoxy resin

D.E.R. 6xxx Solid epoxy resins

D.E.R. 9xx Emulsions, Dispersions or water-emulsifiable epoxy resins


DOW Curing Agents

Name Product Type

D.E.H.™ 1xx / 1xxx Polyamide and Amidoamine curing agents

D.E.H. 2x Polyamine building blocks

D.E.H. 2xx / 2xxx Modified polyamine(s) / blends

D.E.H. 3x AEP and Accelerators

D.E.H. 4xx / 4xxx Formulated Epoxy – Amine adducts

D.E.H. 5x Simple adduct / blend (her. Dow)

D.E.H. 5xx Formulated Epoxy – Amine adducts; US only (her. GNS)

D.E.H. 6xx Fast & Low temperature curing agents

D.E.H. 7x Anhydride

D.E.H. 8x Phenolic hardeners (powder coatings)

D.E.H. 8xx Curing agents for aqueous systems.


Recent Innovation - Low Viscosity

Designation Type

D.E.R.™ 72x mono-functional reactive diluents

D.E.R. 73x di-functional reactive diluents

D.E.R. 74x Multi-functional reactive diluents


Recent Innovation – Faster Cure

Product / Formulation 1 2 3 4 5

D.E.R.™ 330 epoxy resin

EEW = 185 gr/eq

100 100 100 100 100

Isophorone diamine

AHEW = 43 gr/eq

22 23 24 25 26

Liquid properties

Reactivity at 25°C

Gel time [min] 161 158 156 152 151

Time to peak [min] 315 303 321 321 332

Exotherm [°C] 42 57 46 43 50

Reactivity at 50°C

Gel time [min] - 48 47 - -

Time to peak [min] - 51 50 - -

Exotherm [°C] - ca. 250 ca. 250 - -

Physical properties 2)

Tg (by DMA) after 1 h [°C] 161.5 167.2 170.5 167.4 166.1

Tg (by DMA) after 2 h [°C] 161.4 167.6 170.6 167.6 167.5

Tg (by DMA) after 3 h [°C] 164.4 170.4 172 170.5 167.6

Tensile test @ 1 h at 150 °C cure

Stress [MPa] 76.9 73.4 80.2 74.5 73.3

Modulus [GPa] 2.8 2.79 2.62 2.69 2.54

Strain [%] 4.19 4.14 5.7 4.51 5.27

160

162

164

166

168

170

172

174

21 22 23 24 25 26 27

1 hour

2 hours

3 hours

Theoretical mixing Ratio : 23.0 phr D.E.R. 330 epoxy resin Empirical mixing ratio : 24.0 phr D.E.R. 330 epoxy resin



0

10

20

30

40

50

60

70

80

90

100

0 50 100 150 200 250 300

% F

.S.

Gel-time [min]

100% D.E.R.™ 330 epoxy resin

95% D.E.R. 330 + 5% D.E.R. 3414

90% D.E.R. 330 + 10% D.E.R. 3414

80% D.E.R. 330 + 20% D.E.R. 3414

22

Gel-times; resp. 262, 69, 39 and 22 minutes

at Room Temperature



Formulations [pbw] A B C

D.E.R.™ 330 epoxy resin 85 70 55

D.E.R. 3415 epoxy resin 15 30 45

IPDA (not optimized level) 27 27 27

Tg, °C (4.5 min @ 90 °C) 38 47 49

Tg, °C (5.5 min @ 90 °C) 45 51 53

Tg, °C (6.5 min @ 90 °C) 55 62 63

Tg, °C (7.5 min @ 90 °C) 58 63 67

• D.E.R. 3415 is a bisphenol-A based epoxy resin modified with a catalyst which can be activated at temperature above 50 C while maintaining very good pot life at ambient temperature

• It can be blended with any other epoxy resins (either aromatic and aliphatic)

• It is compatible with most of the amine curing agents (aromatic and aliphatic amines)

• It can be used to adjust the reactivity of different amine curing systems by adding different levels into the curing systems


Recent Innovation – More Flexibility

Color 30 APHA

Amine number 472 mg KOH/g

Viscosity 15 mPa.s @ 25 °C

Density 0.96 g/cm3

Mol. Weight 230

20

30

40

50

60

70

80

90

100

20 24 28 32 36 40 44

Glass Transition Temperature [°C]

Heat Deflection Temperature [°C]

Theoretical mixing Ratio : 31.1 phr D.E.R. 330 epoxy resin Empirical mixing ratio : 32.0 phr D.E.R. 330 epoxy resin

D.E.R.™ 330 epoxy resin 100 100

D.E.H.™ 23 amine hardener 32 25

IPDA - 5

Mix-viscosity [mPa.s @ 23°C] 320 620

Tg [°C]; DSC 90 98

Flexural Strength [MPa] 102 131

Flexural Modulus [GPa] 3.14 3.38

Tensile Strength [MPa] 66.9 73.8

Izod impact Strength [cm-kg/cm] 7.08 8.17

Elongation at Break [%] 10.0 8.0

D.E.H. 23


Recent Innovation – High Temperature

4,4'-Methylenedianiline (MDA) is a suspected

carcinogen. It is included in the "substances of very

high concern" list of the European Chemicals Agency

(ECHA).

Pure methylenedianiline is a highly toxic, colorless solid.

May be fatal if swallowed, inhaled or absorbed

through skin. Causes irritation to the skin, eyes and

respiratory tract. Combustible solid or liquid when heated.

May cause methemoglobinemia. Affects blood,

cardiovascular system, central nervous system, liver and

kidneys and may cause cancer.

Ancamine DL-50 (MDA-blend)

Highly viscous / solid = light to dark brown @ 50,000 - 55,000 mPa.s (AHEW = 51 gr/eq)

DETDA

Low viscosity liquid = clear amber liquid @ 100 - 200 mPa.s (AHEW = 46 gr/eq)

Need 10% less per 100 kilo epoxy

Much lower viscosity = allows blending and use at much lowers

temperatures (room temperature)

DiethyleneTolueneDiamine


Recent Innovation – High Temperature

D.E.H.™ 650 Curing Agent


Recent Innovation – Higher Temperature

ASTM D-790 3 point Flex

MDA Ref. D.E.H.™ 650

Tg (DSC, °C) 167 178

Flexural Strength [MPa]

110 116

Modulus [MPa] 2707 3137

Strain [%] 8.3 6.3

Stress @ Break [MPa]

106 116

K1c Fracture Toughness

0.76 0.61

Labeling according to EC Directives: Hazard Symbol: Xn - Harmful N - Dangerous to the Environment Risk Phrases: R 21/22 - Harmful in contact with skin and if swallowed. R 48/22 - Harmful: danger of serious damage to health by prolonged exposure if swallowed R 36 - Irritating to eyes. R 50/5 - very toxic to aquatic organisms, may cause long-term adverse effect in aquatic environment

Pot-life 150 grams

MDA-reference @ 57 °C

D.E.H.™ 650 hardener @ 37 °C


Summary


Dow Epoxy business

• History & Commitment,

• Product Organisation

Recent Innovation

• Lower Viscosity

• diluents

• Faster Cure

• Room temperature or Latent master-batch accelerated resins

• More Flexibility

• Amines, diluents (flexible epoxy resins)

• Higher Temperature Performance

• Alternative to MDA


Контакты

ЗАО "НЕО Кемикал"

Юлия Ташкинова

[email protected]

(8313) 32-06-74, 33-68-68, 32-59-63

Дау Юроп, Московское Представительство

Дмитрий Белобородов

[email protected]

Dow Europe GmbH

Toine Dinnissen

[email protected]

mailto:[email protected]




what is essential to human progress

HEALTH & NUTRITION

Agriculture

Functional Foods

Healthcare

CONSUMERISM

Electronics & Communications

Home & Personal Care

Appliances

ENERGY

Alternative Energy & Feedstocks

Energy Production & Efficiency

Energy Storage

TRANSPORTATION & INFRASTRUCTURE

Construction

Water

Automotive


Mechanical Properties Comparison

Black Steel Stainless Steel

316

Hastelloy® C GRP

(Mat & Roving)

Density [gr/cm3] 7.8 7.9 8.9 1.5

Tensile Modulus [GPa] 207 193 180 10-15

Tensile Strength [MPa] 450 590 550 120-250

Heat Conductivity [W/mºC] 46 15 12 0.2

Thermal Expansion

Coefficient

[mm/mm ºC]x10-6

12 16 12 23

PE PP PVC PVDF GRP

Density [gr/cm3] 0.95 0.90 1.4 1.75 1.5

Tensile Modulus [MPa] 80 80-130 300-350 1200 10,000-15,000

Tensile Strength [MPa] 30 30 60 50 120-250

Heat Distortion

Temperature [ºC]

40 45 75-100 90 100-200

All data are typical data and not to be construed as specifications


Fibre Reinforced Composites

Property Epoxy Unsaturated Polyester (UPR) and

Epoxy Vinyl Ester Resin (EVER)

Phenolic

Cure mechanism Polymerization of resin

plus hardener

Catalytic

copolymerization

Condensation

Polymerization

(produces water)

Wet impregnation, typical

system

Liquid resins plus amine

or other hardeners

Styrene-modified resins plus peroxide

catalysts

Liquid phenolics plus acid

catalysts

Cure temperature (°C) 25-150 25-100 25-170

Typical cure time (min) 60-180 10-60 60-180

Stability of resin (alone) Excellent Fair Poor

Cure-shrinkage of system Low (2-3%) High (6-8%) High

Adhesion to metal Excellent Fair Fair

Physical properties of

cured laminate

Excellent Excellent Excellent/Bad (best heat

resistance, most brittle)

All data are typical data

and not to be construed

as specifications


MTHPA versus DETDA

D.E.H.™ 70 DiEthyleneTolueneDiAmine [DETDA]

Resin D.E.R.™ 330 D.E.N.™ 438™ D.E.R.™ 330 D.E.N.™ 438™

EEW [gr/eq] 176 – 185 176 - 181 176 – 185 176 - 181

Mix-ratio [phr] D.E.H. 70 / MI

85 / 1

D.E.H. 70 / MI

85 / 1

26.0 26.3

Cure Schedule; Hours @ °C 2 hrs @ 85 °C

3 hrs @ 150 °C

2 hrs @ 85 °C

2 hrs @ 150°C

2 hrs @ 200 °C

2 hrs @ 120 °C

2 hrs @ 177 °C

2 hrs @ 120 °C

2 hrs @ 177°C

2 hrs @ 225 °C

Glass Transition Temperature [°C] 148 149 182 220

Coefficient of Linear Expansion [ppm/°C] 70 66 74 69

Water Absorption, 2 weeks boil [%] 1.45 1.49 2.35 2.47

Flexural Strength [MPa] 128 138 108 110

Flexural Modulus [GPa] 3.27 3.51 2.64 3.06

Strain @ Yield [%] 6.7 6.7 6.9 6.1

Cured density [gr/cm3] 1.190 1.224 1.140 1.210

130226 composites expo 2013

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