BASF SPECIALTY MONOMERS FUNCTIONAL SOLUTIONS FOR...

BASF SPECIALTY MONOMERS – FUNCTIONAL SOLUTIONS FOR THE COATINGS MARKET

Ritesh Nair BASF Corporation

CONFIDENTIAL

Overview

2

Part of BASF

1

Facts and figures 2

Product areas 3

Innovations

4

Specialty Monomers Overview

5

CONFIDENTIAL

3

Part of BASF

1

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BASF – The Chemical Company We create chemistry for a sustainable future

4

Sales 2012

€72,129* million

EBIT 2012

€6,742* million

Employees

(as of Dec 31, 2012)

110,782*

New patents

1,170 in 2012 worldwide

6 Verbund sites

380 production sites

worldwide

We are the world’s leading chemical company

* new financial reporting standards (IFRS 10 and 11, IAS 19)

Our chemicals are used in almost all industries

We combine economic success, social

responsibility and environmental protection

CONFIDENTIAL

Structure of BASF’s segments

5

Performance

Products

Dispersions &

Pigments

Care Chemicals

Nutrition &

Health

Paper Chemicals

Performance

Chemicals

Functional

Materials &

Solutions

Catalysts

Construction

Chemicals

Coatings

Performance

Materials

Agricultural

Solutions

Crop Protection

Oil & Gas

Oil & Gas

Chemicals

Monomers

Petrochemicals

Intermediates

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BASF’s Verbund network

Advantages for economic performance and environment

Extremely efficient use of raw materials and energy

Conservation of natural resources

Reduction of emissions and waste

Innovations for BASF and our partners

6

Verbund network

Production plants

Research units

BASF team

Customers

Site community

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7

Facts and figures

2

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BASF Petrochemicals Our key capabilities

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Acting as profitable cornerstone of BASF´s value chains

Supplying highly competitive solutions for raw material

requirements of internal and external customers

Positioned globally with growth opportunities in emerging

and established markets

Leading in process technology and efficient production

processes

Convincing with a strong market position and application

know-how

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BASF Petrochemicals Our philosophy

We act according to “Safety first” in all that we do

We are “The Heart of the Verbund”

9

Our mission

“Excellence in Petrochemicals“

Reliable and competitive supplier

to BASF‘s value chains

Reliable partner and supplier of

customer-oriented solutions for

our external customers

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BASF Petrochemicals Part of BASF´s balanced portfolio

10

Oil & Gas 21%

2012 sales

to 3rd parties:

€72.1 billion*

Functional Solutions 15%

Other** 6%

Performance Products 21%

Chemicals 18%

Plastics 14%

Agricultural Solutions 6%

* new financial reporting standards (IFRS 10 and 11, IAS 19)

** activities not assigned to a particular division are reported in „Other“

thereof

Petrochemicals 12%

€8.260 billion*

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11

Product areas

3

CONFIDENTIAL

Product areas

12

Plasticizers Alkylene oxides

& Glycols

Cracker

products

Alcohols

& Solvents

Basic Petrochemicals Industrial Petrochemicals

Industrial

gases Acrylics

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13

Innovations

4

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Product innovations: HPCA Highly functionalized specialty monomer

14

Product

Hydroxypropylcarbamate acrylate; carbamate function

that can be crosslinked with melamine resins resulting

in new polyurethane applications

Benefits

HPCA shows superior results in clear coating systems

(e.g. automotive) and is expected to offer further

application potential in adhesives and industrial coatings

Status

New plant on stream

Market launch

Product launched in 2010

Partner

BASF Coatings

We innovate to make our

customers more successful

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15

Initial situation

Increasing criticism of traditional phthalate plasticizers

in certain applications

Targets

Sensitive applications with human contact such as

medical devices, toys, food packaging

Idea

Develop an innovative plasticizer with an excellent

toxicological profile and good technical performance

Product

Hexamoll® DINCH® – more than 5 mio. € have been

invested in toxicological tests make Hexamoll® DINCH®

best researched non-phthalate plasticizer on the market

We innovate to make our

customers more successful

Product innovations: Hexamoll® DINCH® The safe plasticizer for applications with close human contact

CONFIDENTIAL

16

Specialty Monomers Overview 5

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BASF Specialty Monomers Attractive portfolio for your needs

Acrylate

Monomers

Methacrylate

Monomers

Amine

Methacrylate

Monomers

Multi Functional

Methacrylate

Crosslinkers

PEG

Methacrylate

Monomers

Automotive Coatings

Architectural Coatings

Industrial Coatings

Construction

Plastics

Paper

Personal Care

Adhesives UV Curables

Mining & Oilfield

Inks

CONFIDENTIAL

Market driven development of New Products

Coatings Industry Trends

Improved efficacy of polymers to lower the total cost of formulation

Low VOC formulations with equal or better performance

Improved performance at low bake or ambient crosslinking

High pigment (TiO2) efficiency

New Specialty Monomers

Adhesion

Rheology

Hardness/Flexibility

Hydrophilic/Hydrophobic

Polarity/Solubility

Ionic/Nonionic

Ambient Crosslinking

CONFIDENTIAL 18

BASF Specialty Monomer Technology

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BASF Alcohols Alkyl-OH Amino-alcohols Ether-alcohols Heterocycle-OH

(Trans)- esterification

• Synthetic and Biocatalytic • High purity of monomers • High selectivity • Tolerance to functional groups • Mild processing conditions • Solvent free direct esterification providing cost efficiency

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• 1,3-Butanediol Dimethacrylate

• Ethylene Glycol Dimethacrylate

• Diethylene Glycol Dimethacrylate

• Polyethylene Glycol 200 Dimethacrylate

• Triethylene Glycol Dimethacrylate

• Trimethylolpropane Trimethacrylate

Acrylates

• Behenyl Acrylate 1822

• Behenyl Acrylate 1822 F

• iso-Butyl Acrylate

• tert-Butyl Acrylate

• n-Hexyl Acrylate

• iso-Decyl Acrylate

• Stearyl Acrylate 1618

• Stearyl Acrylate 18

• Lauryl Acrylate 12

• Lauryl Acrylate 1214

• 2-Propylheptyl Acrylate techn.

• 2-Propylheptyl Acrylate high grade

• Ethyldiglycol Acrylate

• Dicyclopentadienyl Acrylate

• Hydroxypropylcarbamat Acrylate

Methacrylates

• Allyl Methacrylate

• Behenyl Methacrylate 1822

• tert-Butyl Methacrylate

• tert-Butyl Methacrylate low acid

• Cyclohexyl Methacrylate

• iso-Decyl Methacrylate

• Lauryl Methacrylate 1214

• Stearyl Methacrylate 1618

• Stearyl Methacrylate 1618 F

• Stearyl Methacrylate 1618 F HS

• iso-Tridecyl Methacrylate

• Ureido Methacrylate

• 2-Hydroxyethyl Acrylate

• Hydroxyethylcaprolactone Acrylate

• 2-Hydroxypropyl Acrylate

• 4-Hydroxybutyl Acrylate

Hydroxy Acrylates

• N,N-Dimethylaminoethyl Methacrylate

• N,N-Diethylaminoethyl Methacrylate

• tert-Butylaminoethyl Methacrylate

Amine Methacrylates

Multifunctional Methacrylates

Specialty Monomers

BASF Specialty Monomers

Product Portfolio

CONFIDENTIAL

tert-Butylaminoethyl Methacrylate (TBAEMA)

21

O

O

NH

• Secondary amine monomer for crosslinking reaction with Isocyanate groups and/or

• hydrogen bonding that provides Adhesion to various substrates

• tert-butyl group provides hydrophobic and barrier properties

• High humidity and temperature resistance • Amine functionality acts as a synergist/catalyst in

crosslinking reactions • Can be used in combination with other acrylates for

Low VOC systems that can cure rapidly • Low odor and lower toxicity to corresponding

acrylates/acrylamides • Typical loading is 1% - 5% on weight of total polymer

solids

Key Technical Properties

Tg 22 °C

Purity ≥97.5%

Color APHA 50 max

Listing REACH, TSCA, DSL, CHEMINV, IECSC, AICS, ENCS, ISHL, ECL, NZIOC, PICCS

CONFIDENTIAL

N,N-Dimethylaminoethyl Methacrylate (DMAEMA)

22

• Tertiary amine monomer that can be quaternized to provide high cationic charge

• Amine functionality provides adhesion to glass/metal and act as synergist during UV curing

• Methacrylate version has lower toxicity than the acrylate version

• Typical loading is about 5% to 15% on total polymer solids for formulating polymers for cationic clear coats


Tg 10 °C

Purity ≥99.0%

Color APHA 30 max


O

O

N

CONFIDENTIAL

Synthesis of AA & DMAEMA Co-polymer Dispersant

Ingredients Wt%

50% NaOH Solution 7.6%

Add drop wise to the following

Acrylic Acid 6.8%

Ice 8.5%

DMAEMA quat 20%

Water 57%

Mix at 700C, under Nitrogen purge, for 3 hrs

Add Initiator 1 over 3.5 hrs 0.04%

Add Initiator 2 over 2 hrs 0.01%

Adjust pH to 6.5

Total 100%

CONFIDENTIAL 23

Source: Acrylic Resins; U.Poth, R. Schwalm, M. Schwartz

Ureido Methacrylate (UMA)

24

• Excellent wet adhesion monomer for wood surfaces

• Hydrogen bonding to build-up adhesion – interaction with amido groups such as peptides and polypeptides

• Better hydrolytic stability, freeze/thaw and aged heat stability

• Typical loading is about 0.5% to 3% on total polymer solids for formulating emulsion polymers for architectural coatings


Tg -

Purity 25±2% in MMA

Color APHA 200 max


O

O

NNH

O

CONFIDENTIAL

Lauryl/Stearyl/Behenyl (Meth)Acrylate

25

• Monomer partially derived from natural source with very low toxic profile

• Excellent reactive diluent that provides low viscosity enabling higher solids formulation

• Low odor • Low Tg enables to formulate soft polymers • Provides Hydrophobicity and improves the

appearance of the coating film • Loading can go upto 15% on total polymer

solids for formulating solventborne polymers


Tg (Lauryl Acrylate) -3 °C

Purity ≥98.0%

Color APHA 100 max


O

On-1

n = 12

n=12/18/18-22

CONFIDENTIAL

Influence of growing side chain length on the properties of poly(meth)acrylates

Influence on properties

Growing side chain length Hardness decreases

Flexibility and extensibility increases

UV stability rises

Gloss retention improves

Tackiness increases

Alkali resistance increases

Water sensitivity decreases

Alcohol resistance increases

Hydrocarbon solubility increases

CONFIDENTIAL 26

Source: Acrylic Resins; U.Poth, R. Schwalm, M. Schwartz

Cyclohexyl Methacrylate (CHMA)

27

• Cycloaliphatic moiety provides excellent weathering & UV stability and chemical resistance

• Due to high UV stability of the monomer, loading of UV stabilizers can be reduced to lower the cost of formulation

• Typical loading is about 15% to 30% on total polymer solids for formulating solution polymers for automotive coatings


Tg 83 °C

Purity ≥98.0%

Color APHA 10 max


O

O

CONFIDENTIAL

Tert-butyl Methacrylate (TBMA)

28

• Tert-butyl group provides hydrophobicity

• High Tg provides hardness and scratch resistance

• Enables high solids formulation – low viscosity

• Considered as an alternative to IBOMA


Tg 107 °C

Purity ≥98.0%

Color APHA 100 max


O

O

CONFIDENTIAL

Tert-butyl Acrylate (TBA)

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• Tert-butyl group provides hydrophobicity

• High Tg provides hardness and scratch resistance

• Enables high solids formulation – low viscosity

• Can be hydrolyzed to release the acid group to provide future crosslinking, Hydrophilicity, adhesion promotion, etc


Tg 55 °C

Purity ≥98.0%

Color APHA 100 max


O

O

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4-Hydroxybutyl Acrylate (4HBA)

30

• Much faster crosslinker than conventional hydroxy/hydrophilic monomers (HEA, HPA, HEMA, HPMA)

• Co-monomer in making cloud-point resistance adhesives

• Provides efficient hydrogen bonding as the OH group is father away from the polymer backbone

• Low Tg also helps in formulating soft polymers • Typical loading is about 15% to 30% on total

polymer solids for formulating solventborne/waterborne polymers


Tg -65 °C

Purity ≥97.0%

Color APHA 50 max


O

O

OH

CONFIDENTIAL

Composition of hydroxy-functional acrylic resin

Ingredients Wt%

Aromatic solvent (b.p.: 158 to 170 0C) 55.7%

Charge, heat to 1400C, hold temperature

Styrene 10.0

N-Butyl Methacrylate 62.3

4-Hydroxybutyl acrylate 25.6

Acrylic Acid 2.1

Total Monomers 100.0

Mix, add over 4h

tert.-Butylperethyl hexanoate 4.3

Aromatic solvent (bp: 158 to 1700C) 4.3

Mix, add in parallel over 4.75h, hold for 2.0h, then cool down

Total 146.3

CONFIDENTIAL 31 Source: Acrylic Resins; U.Poth, R. Schwalm, M. Schwartz

Hydroxyethylcaprolactone Acrylate (HECLA)

32

• Hydrophilic monomer • Reactive diluent that provides excellent

solvancy/dilution power • Provides low viscosity • Low odor, low toxicity, low skin irritation • Low Tg provides flexibility • Hydrogen bonding available for adhesion

to various substrates • Low shrinkage


Tg NA

Purity ≥98.0%

Color APHA 100 max


O

O

OO

H

O

n

CONFIDENTIAL

Hydroxypropylcarbamate Acrylate (HPCA)

33


Tg 32 °C

Purity ≥ 80.5%

Hydroxypropyl carbamate

9.5 ± 2.7%

Physical Form Solid

Melting Point 43°C

Listing REACH, TSCA

O

O

O NH2

O

OO

O

NH2

O

+

OO

O

O

NH

N

N

N

N

NR1R

2

NR1R

2

R2

Carbamate Crosslinking Mechanism

Improved: Scratch Resistance Wetherability Chemical durability

N

N N

N

N

N

OMe

OMe

OMeOMe

MeO

MeO

OO

O

NH2

O

Reaction with -NCO OH

Interaction with surface

No processing of polymers with methlycarbamate

Flexible choice of co-monomers

Acrylate reacts faster than methacrylates

CONFIDENTIAL

Rankings for the Application and Film Properties

Property OH-Acrylic Resins OH-Polyesters OH-Alkyd Resins

Wetting 3 2 1

Adhesion 3 2 1

Physical Drying 1 2 3

Flow and Leveling 3 2 1

Hold Out 3 2 1

Gloss 1 3 2

Crosslinking Efficiency

3 1 2

Hardness 1 2 3

Flexibility 3 1 2

Chemical Resistance 1 2 3

Solvent Resistance 1 2 3

Weatherability 1 2 3 CONFIDENTIAL 34 Source: Acrylic Resins; U.Poth, R. Schwalm, M. Schwartz

Ethyldiglycol Acrylate (EDGA)

35

• Reactive diluent that provides excellent solvancy/dilution power

• High solids formulation • Provides low viscosity • Low odor and low toxicity • Low Tg provides enables to make

very soft polymers • Low shrinkage • Hydrophilic


Tg -58 °C

Purity ≥95.0%

Color APHA 100 max


O

O

OO

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1/24/2012 36

Functional Methacrylate Monomers

Monomer Structure Key Features

1,3-Butanediol Dimethacrylate

(1,3-BDDMA)

Crosslinkers for ambient,

UV and thermally cured

resins

Hydrophilic

Reactive Diluents for

radiation curing

Improve resistance

properties and flexibility

Can be used for dense

networks (TMPTMA)

High temperature

resistance (TMPTMA)

Low toxicity

Diethylene Glycol

Dimethacrylate (DEGDMA)

Ethylene Glycol Dimethacrylate

(EGDMA)

Polyethylene Glycol 200

Dimethacrylate (PEG200DMA)

Triethylene Glycol

Dimethacrylate (T3EGDMA)

Trimethylolpropane

Trimethacrylate (TMPTMA)

O

O

O

O

O

O

OO

O

O

O

O

O

O

O

O

O

nn = 4

O

O

O

O

nn = 3

O O

O O

O

O

CONFIDENTIAL

Heptadecyl (Meth)Acrylate (C17A/C17MA)

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• Highly branched long chain monomer which is liquid at room temperature

• Very low freezing point (<-100 ºC) and extremely low Tg provides unique properties for low temperature applications

• Excellent reactive diluent providing low viscosity

• Provides hydrophobicity & extreme softness to polymers

• High branching provides elastomeric properties


Tg -72 °C (C17A)

Purity ≥98.0%

Color APHA 100 max

Listing Pending

Highly branched!

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BASF SPECIALTY MONOMERS FUNCTIONAL SOLUTIONS FOR...

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