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Hydrogen peroxide initiated acrylic polyols for 1K and 2K

solvent borne topcoats.


Denis Heymans, Momentive Specialty Chemicals and Griet Uytterhoeven.
1 Avenue Jean Monnet, 1340 Ottignies Louvain-la-Neuve, Belgium.
denis.heymans@momentive.com

Abstract
Conventional acrylic polyols used for 1K and 2K topcoats are usually initiated by organic
peroxides and contain some hydroxylated (meth)acrylate monomers. Both ingredients contribute
significantly to the total raw material cost of the polyols. In this paper, a new route is presented,
replacing the organic peroxide and part of the hydroxylated monomers by hydrogen peroxide,
H2O2, This replacement faces two main challenges; a phase separation, organic-aqueous, during
polymerization and the need to keep the pH around 4.5 to maximize free radical formation. Both
issues are solved by a two step cooking process. First, a high acid value acrylic copolymer is
prepared, using H2O2 as initiator. The acid groups of this polymer are then reacted with the
glycidyl ester of Versatic acid, yielding a high performance acrylic polyol at significantly lower raw
material cost. Isocyanate and melamine cured automotive topcoats based on these polymers
exhibit excellent solution and film properties.

1. Introduction
High quality topcoats are most often composed of an acrylic polyol (APO) and a curing agent;
isocyanate or melamine based. For both pigmented and clear coats applications such as
automotive, airplanes, industrial and marine coatings, topcoats require a wide variety of
properties including; durability, solvent and scratch resistance, hardness, flexibility, appearance,
and drying speed. The composition and the preparation route of the APO’s have a significant
effect on both cost and performance of the derived coatings.

1.1. Conventional acrylic polyols


APO’s are synthesized by radical co-polymerization of monomers including one or more hydroxyl-
functional monomers such as hydroxyethyl methacrylate. The hydroxyls are then distributed
randomly along the acrylic polymer chains. Typical hydroxyl levels vary from 2 to 6 wt%
corresponding to 70 to 200 mg KOH/g solid resin. They are needed for the cross linking of the
coatings but add significantly to the total resin cost. Higher levels of cross-links correlate with
improved coatings performance and higher cost.

Depending on the targeted paint viscosity and VOC level, the acrylic polyols have a molecular
weight (Mw) between 2 000 and 25 000 Dalton. The appropriate Mw can be achieved by varying
one of the following five factors; the polymerization temperature, the use of chain transfer agent
and the concentrations of initiator1, monomers and solvents. At higher polymerization
temperatures, chain transfer and termination reactions are favored over propagation reactions
and, therefore, the average Mw of the polymer is reduced at relatively low cost. The other options
are less cost efficient and have some negative impact on the final performance of the derived
coatings. Therefore, increasing the polymerization temperature is the preferred parameter to
reduce the polyol’s Mw. However, it is limited by the boiling point of the reaction mixture during
polymerization, which is usually close to the boiling temperature of the solvent used.

The Mw of commercial APO’s was continuously reduced in recent years to meet the lower VOC
levels required by legislation. However, at constant polymer composition, shorter polymer chains
have, on average, less hydroxyl per chains. The probability that some chains have no or only one
hydroxyl then increases significantly. This consequence of the random distribution of the
hydroxyls would have had a dramatic effect on the coatings performance without an increased
level of hydroxylated monomer. However, this has a significant effect on the total coatings cost
because of the higher levels of curing agents required.

A technically elegant solution to minimize this cost increase is to control the distribution of the OH
groups along the polymer chains. Ideally, all polymer chain ends should have a hydroxyl group
and the polymers should contain a few additional hydroxyls distributed evenly along their chains.
Various approaches have been investigated to this end. For example, it was found that Hydroxy-
functional allylic monomers, which behave as chain transfer agents, increase the amount of
terminal OH functionality in the polymer2,3.

1.2. Glycidyl neodecanoate based acrylic polyols


Glycidyl neodecanoate (Figure 1) containing APO’s are widely used for automotive coatings for
several reasons including an easy polymerization process at high temperature and an improved
topcoat appearance, durability and low VOC.

Cardura E10PTM

Figure 1: Glycidyl neodecanoate

The process to make glycidyl neodecanoate based APO’s differs somewhat from the
conventional process where the reactor is initially charged with solvents. Instead, these solvents
are partly or totally replaced by the glycidyl neodecanoate in the initial reactor charge which is
then heated to the desired reaction temperature before feeding the acrylic monomers. The
presence of solvents in this initial reactor charge is thus optional and the very high boiling
temperature of glycidyl neodecanoate (>250°C) permits a very high polymerization temperature
without pressure build-up (Figure 2). When the initial reactor charge has reached the
polymerization temperature, the acrylic monomers can be dosed at the desired rate. This process
allows the preparation of low Mw resins with a solids content of up to 100% which is, for example,
ideal for the preparation of solvent-free waterbased APO dispersions.

Two chemical reactions happen simultaneously during polymerization; a conventional radical


polymerization and the reaction of the glycidyl ester with some acrylic or methacrylic acid added
to the monomer mixture. In this way the glycidyl ester serves as reactive solvent and is gradually
incorporated in the polymer (Figure 3).
Cooler

Initial reactor charge:


Glycidyl neodecanoate
(Optionally, solvents)

Pump

Monomers
+ (meth)acrylic acid
+ initiator

Figure 2: APO copolymerization process using


glycidyl neodecanoate as reactive solvent.

STY

R1 O
HEMA
R2 (Meth)
O + Acrylic acid +
CH3 O
MMA
.
O
Initiators
HO

Simultaneous reactions!

STY (M)AA HEMA MMA


. O

OH
OH for curing reactions
CH3
R2
O
R1
O
Figure 3: Preparation of glycidyl ester based APO’s; simultaneous radical copolymerization and
condensation reactions

1.3. Hydrogen peroxide initiated radical polymerization


H2O2 is relatively cheap and safer than organic peroxides; additionally it offers the possibility to
functionalize polymer chain ends with hydroxyl groups. High performance, Low Mw APO’s should
therefore be possible to prepare with H2O2 at low cost. However, there are two significant hurdles
to overcome before using it for solvent borne polymerization; miscibility and the need for an acid
catalyzed decomposition.

Firstly, hydrogen peroxide is usually sold in aqueous solutions and forms additional water during
reaction. Therefore, H2O2 blends with acrylic monomers and polymers form two phases water/oil
systems. In these conditions, the radicals formed by the thermal dissociation of H2O2 in the water
phase can hardly react with the monomers. Furthermore, traces of water in the final APO would
also be detrimental for the final coating properties. This water needs thus to be removed during
and/or after polymerization. Second, H2O2 requires acidic conditions to dissociate in two hydroxyl
radicals. Acidic catalysts can be used to this end but if they are not removed from the APO’s, they
will affect negatively the performance of the derived coatings. Nevertheless, the literature
describes several methods to prepare hydrogen peroxide based acrylic copolymers.

Burke, Kizer and Davis6 filed a patent application in 1970 claiming the use of select amphiphilic
solvents to improve the miscibility between the water phase and the organic phase during
polymerization. In 1994, Toba et al. disclosed a batch process whereby amphiphilic solvents are
combined with an acidic catalyst7. The yield of this process however seems very low and
monomer conversion is far from the required level. In 1985, Das and Dowbenko 8, filed another
patent describing a process whereby water and low boiling organic solvents are continuously
removed from the reaction mixture by azeotropic distillation.

2. Experimental part
The glycidyl neodecanoate based process developed in our work9, combines these three
approaches in various ways and eliminates the need for an acid catalyst by using high amounts
of acrylic acid in the monomer mix. Two subsequent steps are followed; the radical
polymerization of a hydrophilic monomer blend followed by condensation reaction with glycidyl
neodecanoate, (Figure 4). An acrylic acid rich polymer backbone is prepared using hydrogen
peroxide as initiator and the water is continuously removed from the reactor by azeotropic
distillation with the appropriate solvent. Such hydrophilic, acid-rich polyol has an improved
compatibility with water and hydrogen peroxide compared to a conventional resin which ensures
homogenization of the reactor content and therefore, a smooth polymerization. The hydrophilic
character of this APO is essential to enable polymerization with H2O2 but makes it totally
unsuitable for coatings applications. Therefore, after polymerization the acid groups are reacted
with glycidyl neodecanoate to convert them in hydrophobic esters. The synthesis and
performance of these polyols is described hereunder. Our work has, however, not yet included a
minimization of the cost associated with the treatment of the contaminated water obtained via the
Dean Stark.

2.1. Material
All ingredients used were laboratory grade except the products hereunder:
Glycidyl neodecanoate; Cardura E10PTM, Momentive Specialty Chemicals.
Butylated melamine resin: Cymel 1158, Cytec Surface Specialties
Di-tertiary amyl peroxide Trigonox 201, AkzoNobel
Di-tertiary butyl peroxide Trigonox B, AkzoNobel.
Hexamethylene di-isocyanate trimer Desmodur N3390, Bayer MaterialScience
Styrene acrylate
+

(M)AA H2O2

Step 1: polymerization of an acid rich, Temperature & azeotropic distillation of


hydrophilic, styrene/acrylic backbone. water during polymerization.

HO Polymer Styrene (M)AA acrylate OH


. O

OH

R1 O
Step 2: Reaction with + R2
O
glycidyl neodecanoate. CH3 O

HO Polymer STY (M)AA acrylate OH


. O

CH3 OH
R2
O
R1
O

Figure 4: Preparation of hydrogen peroxide based acrlylic polyols. Radical


polymerization (possible simplified mechanism) followed by condensation reaction
between (meth)acrylic acid (M)AA and glycidyl neodecanoate
2.2. Test methods
The important test methods used in this work are described in reference 9.

2.3. Resins preparation


The reactor setup presented in Figure 2 was slightly modified by the addition of a Dean Stark trap
to the cooler to remove water during and after polymerization. Selected solvents were charged in
the reactor and heated to the desired reaction temperature before addition of a (meth)acrylic acid
containing monomer mixture and hydrogen peroxide. Water was continuously removed during
polymerization via the condenser Dean Stark setup. After completion of the radical
polymerization, the resin was reacted with glycidyl neodecanoate.

2.4. Resins composition and properties


The composition and properties of two hydrogen peroxide based polyols designed for automotive
OEM and refinish clearcoats are detailed in Table 1. The H2O2 resins were designed to be
comparable to organic peroxide-based resins in terms of Mw, glass transition temperature,
hydrophobicity and hydroxyl value.

For both hydrogen peroxide initiated resins a very significant amount of hydroxyl originating from
hydrogen peroxide, about 2.1wt % was found by titration. This value, converted in number of
hydroxyl per chains give the surprising value of about 9 hydroxyls per polymer chain derived from
H2O2. Far more than suggested by the simplified mechanism, presented in Figure 4, where only
two OH radicals are incorporated at the chain ends. Furthermore, a separate quantification of the
hydroxyls by titration has shown that a significant fraction of these hydroxyls are actually
secondary hydroxyls. The ratio between primary and secondary hydroxyls was found to vary as a
function of reaction conditions such as the type of solvent used, the reaction temperature and the
polymer composition. It has to be concluded form the above discussion that, as usual for radical
polymerization mechanisms, many side reactions such as chain transfer and grafting occur,
leading to a variety of chemical structures.

3. Automotive clearcoats evaluation


3.1 OEM clearcoats
Automotive OEM clearcoats are often cured with melamine resins instead of isocyanates to
minimize cost. Theses systems usually have a poor balance between resistance to acid attacks
(environmental etching) and scratch resistance. To ease the acid resistance issue, the Tg can be
increased however this worsens the scratch resistance of the coatings. Formulators of OEM
clearcoats have therefore made significant effort to solve this issue at reasonable cost10 - 14.
Amongst others, Uytterhoeven et al.15 have demonstrated that glycidyl neodecanoate based
coatings show an improved balance between these properties.

To assess the influence of the H2O2 technology on this critical property balance, the OEM resins
described above were formulated in clearcoats and compared with a well-known commercial
resin. The level of butylated melamine was adjusted for each resin to obtain the best balance
between hardness and flexibility. Table 2 demonstrates the excellent properties of both glycidyl
ester based coatings (H2O2 and reference), in particular a superior acid resistance and a high
gloss recovery after scratch.
Table 1: Composition and properties of APO’s
Application: Automotive OEM Automotive Refinish
Intake (parts by weight) Reference H2O2 based Reference H2O2 based
Glycidyl neodecanoate 20.0 20.0 20.0 24.8
Methacrylic acid 9.4 8.5 8.9
Acrylic acid 7.9
Hydroxyethyl methacrylate 11.5 0.0 20.4 0.0
Hydroxpropyl methacrylate 4.9
Styrene 20.0 20.0 30.0 20.0
Isobutyl methacrylate 14.8 2.5 46.3
Methyl methacrylate 20
Butyl acrylate 30.0 30.0
2-Ethylhexyl acrylate 5.7 5.7
Total monomers 100 99.9 101.4 100
Di-tertiary amyl peroxide 3.5
Di-tertiary butyl peroxide 5.0
Hydrogen peroxide
8.9 8.9
(50% aqueous)
Xylene 35 11.0
Butyl acetate 8.0
Isobutyl isobutyrate 24.8 23.4

Resins properties
Calculated Tg [°C] (Fox) 2 8 67 52
Mw [g/mol] 7978 7864 4132 6665
Polydispersity 2.1 2.9 1.9 2.5
Acid value [mg KOH/g] 11.0 18.5 13.9 19.4
Color Apha [Pt/Co] 18 41 nd 38

Total OH value [% wt] 3.7 3.7 4.1 3.9


OH from glycidyl ester [% wt] 1.4 1.5 1.4 1.8
OH from H2O2 [% wt] 2.2 2.1

Table 2: Properties of automotive OEM clearcoats


Commercia
Reference H2O2
l
Butylated melamine/acrylic ratio 25/75 30/70 35/65
VOC [g/l] 558 524 528
Coatings Tg [°C] 53 40 36
Koenig Hardness [s] 196 133 124
Solvent resistance (MEK double rubs) >100 >100 >100
Initial gloss @ 20° 96 87 86
Acid resistance (best score is 30) 4 12 19
Scratch resistance; gloss retention [%] 49 69 62
Gloss recovery after scratch [%] 1 6 7
Outdoor durability (gloss retention after nd 86 87
1000 hours QUVA) [% of initial gloss]
3.2 Refinish clearcoats
The Automotive refinish clearcoats were formulated using an isocyanate/hydroxyl ratio of 1. The
catalyst content (dibutyl tin dilaurate, DBTDL) was adjusted to obtain a potlife of more than one
hour. The viscosity of the formulation was adjusted to the spray viscosity (30 mPas) with solvents
and the clearcoats were barcoated directly on Q panels. The clearcoats were dried either in
continuously ambient temperature or cured for 30 minutes at 60°C then at ambient temperature
for one week which are usual conditions of automotive repair bodyshops.

Table 3 shows that, after adjusting the catalyst level, the H2O2 based APO has similar drying
speed and clearcoat properties to the reference resin. In particular, the very high acid and MEK
resistances demonstrates that the coatings are well cross-linked. However, a much higher level of
DBTDL was needed for the H2O2 resin to achieve the potlife and curing speed target. This is
probably a consequence of the higher level of secondary hydroxyls present in this resin
discussed above.

Table 3: Properties of the refinish clearcoats.


Reference H2O2
VOC [g/l] 472 526
DBTDL [% wt] 0.03 0.5
Spray viscosity [mPas] 30 30
Potlife [min] 151 79
Ambient cure coatings (@ 23°C)
Dust-free time [min] 13 8
Koenig Hardness [s]
After 4 hours 11 20
After 1 day 70 58
After 7 days 144 103
MEK resistance (double rubs) >100 >100
Acid resistance (best score is 30) 24 26
Coatings cured 30’ @ 60°C
Koenig Hardness
Out of oven 54 64
After 4 hours 67 76
After 1 day 121 122
After 7 days 176 154
MEK resistance (double rubs) >100 >100
Acid resistance (best score is 30) 24 26
4. Conclusions and way forward
The preparation of acrylic polyols via different processes combining radical polymerization and a
condensation reaction with glycidyl neodecanoate offers various possibilities to adjust the polyol
composition and properties for high quality topcoats. Glycidyl neodecanoate can be used to
replace partly or completely the solvents during the polymerization for the preparation of low VOC
coatings. Glycidyl neodecanoate can also be reacted after radical polymerization with H2O2
initiated, acid rich, copolymers.

This H2O2 technology offers cost savings possibilities replacing both the hydroxy acrylate
monomers and the organic peroxide. It could also reduce the need for curing agents in the
topcoat formulations.

Future work will be needed to optimize these acrylic polyol formulations and to minimize the cost
associated with the treatment of the contaminated water generated by this process.

5. References
1. Callais, P.A., Moskal, M.G., Higher solids, higher quality acrylic coatings resins produced with organic
peroxide initiators, Arkema Inc., King of Prussia, PA.
2. Shao-Hua Guo et al, ARCO Chemical Company, in Solvent-Free Polymerizations and Processes,
Chapter 7, pp 113–126.
3. US Patent 6,455,657, filed February 14, 2001, Lyondell Chemical Company.
4. Denis Heymans, Griet Uytterhoeven, Nathalie Henry and Annie Fonze, Pitture e vernici
2006, vol. 82, no17, pp. 33-42.
5. Griet Uytterhoeven, Annie Fonze, Nathalie Henry and Denis Heymans, proceedings of the ICE-
futurecoat congress, 2006.
6. US patent 3,673,168 filed January 22, 1970.
7. US patent 5,470,930 filed February 16, 1994, Nippon Shokubai.
8. US patent 4,600,755 filed April 3, 1985, PPG Industries.
9. Patent WO 2005040235 filed October 24, 2003, Heymans, Uytterhoeven and De Cock, Resolution
Research Belgium.
10. Marvin L. Green, Journal of Coatings Technology, July 2001, Volume 73, Number 918, 55-62.
11. US Patent 5,886,125, filed February 25, 1997, Dupont de Neumours.
12. US Patent 7,342,071, filed September 15, 2005, BASF corporation.
13. US Patent 6,607,833, filed August 8, 2001, Dupont de Neumours.
14. US Patent 6,387,519, filed July 31, 2000, PPG Industries.
15. Griet Uytterhoeven, Annie Fonzé, Hélène Petit, Macromolecular Symposia, Volume 187, Issue 1, pages
515–530, September 2002.