Challenges for Methacrylate Monomers for Low VOC Coatings

John Wey / Gerold Schmitt

1) High Solid Monomers for Reduction of Resin Viscosity 2) Methacrylic LACE (Long Alkyl Chain Ester) Monomers for the Formulation of Solvent Based Coating Resins 3) Oxidative Crosslinking VISIOMER MUMA (Multiple Unsaturated Methacrylates) 4) Adhesion Promotion Using Wet Adhesion Monomer VISIOMER MEEU

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Bulky Side Chain Methacrylic Monomers

O O

O O

O O

Specification purity acid content water content colour min. max. max. max. % % %

IBOMA 98,00 0,50 0,20 50

IBOA 98,5 0,50 0,20 50

cHMA 98,00 0,01 0,10

stabilization HQME

ppm

150 30

250 25

50 5
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Influence of High Solid Methacrylates on Resin Viscosity

109000
100000

109000 98000

101000

80000

87000

resin viscosity [mPas]

68000 60000 53000

60000

40000

20000

bulky side chain monomers are used for the synthesis of high solids resins because they significantly reduce the resin viscosity
cHMA

0
high so

20 lids mon o me r

IBOMA 25 [wt %] 30

Solution polymerization in BuAc @ 140C Mn ~ 2000-3000 g/mol 75% solid content Brookfield viscosity @ 23C, Sp II
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Increase of Solid Content by Incorporation of High Solid Methacrylates

29 15 21 41 4

MIBK 4

increase of solvent polarity

BuAc Xylol cHMA IBOMA

The solvent polarity influences the increase of the solid content with the individual high solid monomers

increase of solid content [%]

high solids monomer

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Low Tg Resin compositions using LACE Monomers

[wt % of monomer in solid resin] without LACE monomer BA EHMA HEA TMCHMA GMAA LACE MMA 27 10 40 10 3 10 with LACE monomer 7 10 40 10 3 30

10% MMA and 20% BA in the comparative sample were replaced by 30% LACE monomers

Polymerization was performed in Solvesso 100 / BuAc = 2:1 at 144C with 75% solid content

OH content acid content Mn PD

~ ~ ~ ~

142 [mg KOH / g] 16.5 [mg KOH / g] 2200 g / mol 2.5

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Properties of Crosslinked Films versus Resin Tg

IPDI crosslinking HDI crosslinking Tg (resin polymer)

171 197

non

16

148 198

C13-MA

137 202

C17,4-MA

-6

210

200

190

180

170

160

150

140

130

120

110

-25

-20

-15

-10

-5

10

15

20

pendulum hardness [sec]

Temp. [C]

linear LACE monomers render a film hardness depending on the resin glass transition temperature
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Solvent Resistance of Resins Containing LACE-Monomers

break fluid 2-propanol original hardness value diesel oil methyl ethyl ketone

200 180 pendulum hardness 160 140 120 100 80 60 non C13-MA C17,4-MA

linear LACE monomers with longer side chains resist better against automotive fluids and organic solvents

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Oxidative Crosslinking VISIOMER MUMA

Oxidative crosslinking VISIOMER MUMA
O O
X-linkable

VOC reduction
film formation at low temperature improved film properties through post-crosslinking Need for improvement

Oxidative crosslinking

Emulsion X-linkable
O

O2 Crosslinking

Copolymerization

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VISIOMER MUMA Incorporated into Emulsion Polymers

Pure Acrylic System chemical & mechanical properties improvement via crosslinking improvement of open time
VISIOMER MUMA
X-linkable

O O

Improvement of Alkyds compatibility improvement in alkyd-acrylic blends and hybrids enhanced weathering resistance improvement of open time
Emulsion polymers (exemplary, amounts in wt%)
MUMA MMA BuA GMAA 1 5 44 50 1 10 42 47 1 15 39 45 5 20 32 43
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Benefits of VISIOMER MUMA

Superior chemical resistance
VISIOMER MUMA-ctg. dispersion

Nivea HOAc EtOH NH3

commercial PUmodified alkyd dispersion

Furniture Test (DIN 68861-1)

0 1 2 3 4 5

poor

good

Improved resistance compared to PU-modified alkyd dispersion

Formulation without the use of solvents Improved film properties through oxidative crosslinking Crosslinking is accelerated by drying agents
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Benefits of VISIOMER MUMA

Increased block temperature improved dirt pick-up resistance Good (wet) adhesion Excellent adhesion to old alkyd paints Good compatibility with alkyds Excellent weathering resistance
Adhesion on aluminium Cross hatch with and without adhesive tape good
w ith ta p e

Adhesion of VISIOMER MUMA on alkyd paints Cross hatch with and without adhesive tape excellent

Cross hatch (DIN EN ISO 2409)

w /o ta p e

5
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Wet Adhesion Monomer VISIOMER MEEU

O N O O
Specification VISIOMER MEEU 25 M VISIOMER MEEU 50 W

NH

N-(2-Methacryloyl oxyethyl)ethylene urea content Methyl methacrylate content water content

25 3 %

reactive ester content

50 2,5 %

73 5 %

Methyl methacrylate content water content

max. 5 %

max. 1,0 %

50 2,5 %

colour

max. 250

colour

max. 500

stabilization

500 100 ppm HQME max. 100 ppm Phenothiazine

stabilization

800 100 ppm HQME max. 200 ppm Phenothiazine

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VISIOMER MEEU
O N O O NH

VISIOMER MEEU

penetrating moisture new paint layer

hydrophilic interlayer

aged paint layer

How does it work: adhesion of emulsion coatings to the substrate is deteriorated under moisture contact consequence: blisters and cracks VISIOMER MEEU provides excellent adhesion Advantages: excellent wet adhesion and increased wet scrub resistance low concentrations required (0,5 3 % by weight of the binder) easy incorporation into the binder Typical Application: emulsion coatings for exterior applications and humidic conditions

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Further Information Available.

please visit us at booth 1244

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