tech

paper
VeoVa 9 Acrylic Modified Powders for Automotive Clear-Coat Applications*

SC:3006-01

By

Annie Fonz Christian De Cock Hlne Petit Resolution Performance Products LLC Coordination Centre Louvain-la-Neuve, Belgium

*Presented at the International Coatings Expo 2000, Chicago, IL, October 18-20, 2000.

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Abstract

Today, powder coating is one of the high growth areas in the paint and coatings market. This growth has been sustained by the constant development of new applications and the higher demand for VOC compliant systems. In automotive applications, powders based on GMA, styrene and other acrylic monomers have been developed for clear-coat applications. They generally show good coating properties but the powders may either lack stability, or may not provide good flow and appearance. Resolution Performance Products LLC (RPPLLC) has developed new acrylic resins based on VeoVa 9,the vinyl ester of Versatic acid. VeoVa 9 allows the powder resins to be prepared with a relatively high Tg (and therefore good storage stability), and at the same time a relatively low melt viscosity which contributes to good flow. VeoVa 9 is also a good chain transfer agent, which allows the preparation of low viscosity resins in mass. As a consequence, the good balance of powder and film properties of VeoVa 9 modified acrylic powders, as well as the economical mass process, make these new resins very good candidates for the demanding automotive industry.

Introduction

Powder Coatings in the World The powder coating industry is today the fastest growing technology in the United States. A growth rate of 10 percent/year in pound was quoted at the end of 1999 by the Freedonia Group1 (Cleveland, OH). In other areas of the world, powder coatings are also very strong especially in Western Europe, which represents 47% of the world demand (see Figure 1). This growing demand for powders can be explained by the increasing pressure on VOC emissions. It is also related to the development of new technologies that better match the coating properties of the solvent based systems.

Figure 1/World Powder Coating Demand by Region (1998)

Rest of the world 9% Western Europe 47% U.S. 27%

Other Asia /Pacific 10%

Japan 7%

Source: Freedonia Group

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Introduction (cont.)

Powder Coatings for Automotive Original Equipment Manufacture (OEM) Applications Powder coatings are also a very attractive technology when it comes to choosing paint systems that will reduce the total emissions from an automotive assembly plant paint shop. This is why powder coatings are also growing in this segment. There are approximately 17 vehicle production facilities worldwide either currently painting with powder, or in the launching phase. In terms of achievements, powder coatings for automotive exterior body applications overall are already used on 5.5% of world light vehicle builds. The penetration of powder coatings in automotive applications has been driven by chip resistant primers in North America and exterior clear-coats in Europe. For OEM primers, different powder types are used, with a clear preference for hybrid systems2 (see Figure 2).

Figure 2/Automotive OEM Powder Primer Market by Chemistry (1998)

Hybrid (71%)

Polyurethane (5%)

Acrylic (18%)

Polyester (6%)

However, for automotive clear-coat applications, GMA-acrylic powders are preferred. Today, they represent a growing part of the acrylic market segment.3 These GMA-acrylic resins are epoxy functionalized polymers which react, according to Figure 3, with any acid to form a cross-linked network that resists chemical attack and mechanical stress. Dodecanoc di-acid is usually used as cross-linker for the GMA powders because of the flexibility and the stability it imparts to the system. These powders also show an increased brilliance compared to the traditional OEM clear-coats, and they are getting more and more popular among car manufacturers. However, the automotive industry has very high standards. GMA-acrylic powder clear-coats need to match the coating performance of standard solvent based clear-coat formulations. Achieving a very good flow with a powder coating that matches the automotive industry standards often means that the physical stability of the powder is low. This paper shows that because of its bulky structure, its chain transfer activity and its high Tg, VeoVa 9 allows the preparation of GMA-acrylic resins that combine a high Tg with a relatively low molecular weight.

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Introduction (cont.)

Figure 3/Cross-linking of GMA-Acrylic Resins with DDA

O HO O OH

H 2C

CH

Dodecanoc diacid

GMA acrylic resin

OH O O

O O OH

Crosslinked coating

Modified Acrylic Powders for Automotive Clear-Coat

VeoVa 9 Monomer VeoVa 9 is the vinyl ester of the Versatic 9 acid. This monomer has a unique branched structure (see Figure 4) that leads to a homopolymer Tg of 70 C. The bulky nature of VeoVa 9 provides the polymer with a more compact structure, which means a relatively short chain length for a given molecular weight and Tg. In addition, VeoVa 9 has the natural tendency towards chain transfer. This reduces the molecular weight of the polymer without the use of expensive initiators, while keeping a high Tg. As a consequence, polymers with a high Tg and a low molecular weight can be prepared by using VeoVa 9.

Figure 4/General Chemical Formula of the VeoVa Monomers and their Homopolymer Tg (R1 + R2 = 6 Carbon Atoms for VeoVa 9)

Homopolymer

Tg + 70 C

O O
2

CH3
1 R R

VeoVa 9

VeoVa 10 VeoVa 11

- 3 C - 40 C

Vinyl Ester of Versatic Acid 9, 10, 11

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Modified Acrylic Powders for Automotive Clear-Coat (cont.)

VeoVa 9 Monomer (cont.) Solid VeoVa 9 based polymers can be made by radical polymerization of the monomers in solution, with subsequent solvent removal by distillation or wipe film evaporator, or in bulk (mass polymerization). As shown in Table 1, VeoVa, styrene and acrylic monomers have large differences in reactivity ratios. VeoVa 10 and VeoVa 9 have similar reactivity ratios towards other monomers. In solution polymerization of styrene/acrylates and VeoVa, this difference in reactivity leads to an uncompleted conversion of the VeoVa monomers. A multi-stage feed is then needed to avoid the formation of block copolymers and a low conversion. In bulk polymerization, this difference in reactivity can be exploited to prepare a homogeneous polymer without the use of a multi-stage feed of monomers. If VeoVa 9 is used as an initial reactor charge (IRC), it is gradually built up in the resin, acting as a reactive solvent that absorbs the heat of the reaction. It limits the polymerization rate, and hence the heat generation, because of its reactivity difference with the other acrylic and styrenic monomers. Since VeoVa 9 allows the preparation of resins in bulk without the use of a multi-stage monomer feed, the solvent removal at the end of the polymerization can be avoided. This results in a more cost effective production of the resin.

Table 1/Reactivity Ratio of the VeoVa Monomers with Acrylates and Styrene at Various Temperatures
Monomer 1 Styrene Monomer 2 VeoVa 10 VeoVa 10 2-Ethylhexylmethacrylate VeoVa 10 VeoVa 10 Methyl methacrylate Ethyl acrylate Butyl acrylate Vinyl acetate Vinyl acetate VeoVa 9 Ethylene VeoVa 10 VeoVa 9 Ethylene Temp., C 140 170 140 170 60 60 60 60 130 r1 25 23 10.5 3.6 20 6 13.94 0.99 0.93 1.02 r2 0.04 0.06 0.08 0.06 0.015 0.10 0.01 0.92 0.90 0.97 Source* 2 2 2 2 1 2 1 1 1 1

*1 = Young, Polymer handbook, Chapter II, J. Brandrub, E.H. Immergut and W. McDowell, Eds., Wiley-Interscience, New-York, 1975. 2 = Resolution Performance Products LLC Laboratory measurements.

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Modified Acrylic Powders for Automotive Clear-Coat (cont.)

Polymer Design and Consequent Properties Several polymers were prepared in bulk, using VeoVa 9 and dimethyl maleate (DMM) as the initial reactor charge. The IRC was heated up to 155 C under a nitrogen blanket and the monomers were fed during 5 hours. The polymerization was then completed by 2 hours of post-cooking at 170 C. Reduced pressure was applied to remove volatiles and initiator residues. On a lab-scale (5L stainless steel reactor), wall cooling of the reactor was applied during the process. However, this is not considered sufficient to control the process on a commercial scale, as a very high cooling capacity would be required. The same reaction was therefore carried out in the same set-up using reduced pressure (250-500 mbar). The resins showed equivalent properties. When designing these modified acrylic resins, a Tg of around 50 C, and a Mw below 10000 were targeted. The GMA content was varied between 25% and 40% to provide an increasing cross-linking density (see formulation in Table 2). These VeoVa based polymers were then compared to standard GMA-acrylic systems4,5 with the same target Tg and molecular weight. As these benchmark resins do not contain any VeoVa, solvent was needed to control the exotherm of the reaction. Xylene and butyl acetate were used during the polymerization and were then removed by distillation under vacuum (see Table 3 for the resin formulation). The resins characteristics were then determined, and are shown in Table 4.

Table 2/Formulation of the VeoVa Based Resins

Polymer formulation Initial reactor charge VeoVa 9 Dimethyl maleate Monomer-initiator feed Styrene Glycidyl methacrylate Methyl methacrylate Di-ter butyl peroxide Resin 1 22.0 6.5 30.0 25.0 16.5 2.0 Resin 2 22.0 6.5 30.0 30.0 11.5 2.0 Resin 3 22.0 6.5 30.0 40.0 1.5 2.0

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Modified Acrylic Powders for Automotive Clear-Coat (cont.)

Table 3/Formulation of the Standard GMA-Acrylic Resins

Polymer formulation Solvent Xylene Butyl acetate Monomer-Initiator feed Styrene Glycidyl methacrylate Methyl methacrylate Butyl acrylate Butyl methacrylate Initiator Sty/Ac 1 33.3 10.0 30.0 49.0 11.0 2.0 Sty/Ac 2 41.1 10.0 40.0 40.0 10.0 5.0 Sty/Ac 3 32.7 5.0 50.0 35.0 10.0 8.0

Table 4/Properties of Standard and VeoVa Based Acrylic Resins

Polymer formulation Resin 1 Resin 2 Resin 3 Sty/Ac 1 Sty/Ac 2 Sty/Ac 3 7700 2.8 2055 50 Stable Stable 8500 2.8 2728 46 Stable Stable 15200 3.48 2030 47 Stable Stable 4500 1.99 2679 40 Stable Caking 3100 1.56 3345 30 Caking Caking

Average molecular weight, Mw 9000 Polydispersity, Mw/Mn 2.7 Epoxy group content, meq/kg 1713 Tg measured, C 53 Physical stability, At 23 C, > 6 weeks Stable At 40 C, 24 hours Stable

Table 4 shows that a Tg well above room temperature is needed to have a good resin stability. Styr/Ac 2 and 3 which have a Tg below 45 C show blocking after 24 hours at 40 C, and even at 23 C, Sty/Ac 3 is caking.

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Modified Acrylic Powders for Automotive Clear-Coat (cont.)

Polymer Design and Consequent Properties (cont.) Besides, Sty/Ac 1 has a molecular weight of 15200, which is about twice the molecular weight of any VeoVa 9 based resin. This shows the good chain transfer activity of VeoVa 9 for the same initiator concentration, lower molecular weights are achieved in the presence of VeoVa 9. Moreover, because of the bulky structure of VeoVa 9, these low molecular weights do not result in low Tg values. As highlighted in the next section, VeoVa 9 resins having low molecular weights lead to coatings with a high flow, and having a high Tg to powders with a good storage stability. Cross-linking As mentioned earlier, the GMA-acrylic resins are usually cross-linked with a linear, flexible acid such as dodecanoc diacid (DDA), which imparts good properties to the powder and to the final coating. However, DDA is an expensive material, so we looked at an alternative cross-linker for GMA-acrylic powders. A model compound based on di-trimetylolpropane (DTMP) and hexahydrophtalic anhydride (HHPA) was synthesized, as shown in Figure 5.

Figure 5/Synthesis of the Polyester Cross-linker

O HO OH O OH 150 C , N2 OH 4 O O

HO

O O O O O OH O O O

OH

O O OH

This polyester cross-linker imparts hardness to the coating and excellent chemical resistance because of its high cross-linking density. DDA this model polyester, as well as a blend of the DDA and model polyester, were evaluated as cross-linkers for the different resins (see their characteristics in Table 5).

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Modified Acrylic Powders for Automotive Clear-Coat (cont.)

Table 5/Cross-linker Composition and Properties

Blend, parts weight 1000 407 6013 Waxy solid

Cross-linker type Composition Acid functional polyester 1,10 Decanedicarboxylic acid Properties Acid value (meq/kg) Appearance

Polyester 1000 4878 Clear solid

DDA 1000 8684 Waxy solid

Cross-linking (cont.) The polymer and the cross-linker were separately coarse ground before extrusion. The polymer and cross-linker were blended with a degassing agent (1% benzoin) and flow control agent (1.5% MODAFLOW Powder III) for about 30 minutes on a roller bank. The mix was then extruded using a Buss PLK46 single screw extruder. The extruder was operated in a temperature range of 70-90 C with a screw speed of 80 rpm. The resulting extrudate was flattened using cooled rolls, stabilized for 24 hours, and fine milled in an Alpine AFG jet grinding mill at 1790 rpm to obtain an average powder particle size below 100 micron. The powder was sieved using a 300 mesh sieve to avoid granules. The powder was then electrostatically sprayed by Gema gun onto an uncoated Q-panel and cured for 30 minutes at 140 C. The results obtained with Resin 2 are presented in Table 6.

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Modified Acrylic Powders for Automotive Clear-Coat (cont.)

Table 6/Powder and Clear-Coat Properties of VeoVa 9 Based Resin 2

Powder formulation Cross-linker type Coating properties Coating thickness, microns Knig hardness, sec Direct impact strength, in-lb MEK resistance, double rubs Gasoline resistance Acid resistance, max. 30 Flow, max. 10 Powder stability Physical stability, At 23 C At 40 C Chemical stability, At 10 C At 23 C At 40 C PC1 Polyester 54-60 201 12 > 100 OK 30 4 PC2 Blend 54-60 207 14 > 100 OK 30 6 PC3 DDA 45-52 194 24 > 100 OK 30 7

N.D. > 24 hours N.D. N.D. N.D.

> 4 weeks > 24 hours > 5 weeks 4 weeks < 1 week

> 5 weeks > 24 hours > 5 weeks > 5 weeks < 1 week

Cross-linking (cont.) These results show that the main difference between the cross-linkers is the flow and flexibility of the coating, as well as the stability of the powder DDA gives the best balance of flow, hardness and stability. The model polyester does not lead to a good coating flow, but the DDA/polyester blend performs very similarly to DDA. As a consequence, this blend was used for the curing of all other benchmark and VeoVa resins (see Tables 7 and 8). Table 7 shows that coating and powder properties are not strongly affected within the range of GMA we studied they all show excellent acid and gasoline resistance and good hardness. The coating gains in flexibility with a lower cross-linking density, but at a GMA level of 25% it shows a somewhat matte appearance after contact with MEK, indicating a borderline performance. A minimum level of 30% GMA should be used from this perspective.

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Modified Acrylic Powders for Automotive Clear-Coat (cont.)

Table 7/Powder and Clear-Coat Properties as a Function of the GMA Content

Powder formulation Polymer GMA content Cross-linker type Coating properties Coating thickness, microns Knig hardness, sec Direct impact strength, in-lb MEK resistance, double rubs Gasoline resistance Acid resistance, max. 30 Flow, max. 10 Powder stability Physical stability, At 23 C At 40 C PC4 Resin 1 25% Blend 64-66 212 18 > 100 matte OK 30 6 PC2 Resin 2 30% Blend 54-60 207 14 > 100 OK 30 6 PC5 Resin 3 40% Blend 52-58 204 14 > 100 OK 30 6

N.D. > 24 hours

> 4 weeks > 24 hours

N.D. > 24 hours

Table 8/Powder and Clear-Coat Properties of Standard Styrene/Acrylic Resins

Powder formulation Polymer Tg measured, C Weight average molecular weight Cross-linker type Coating properties Coating thickness, microns Knig hardness, sec Direct impact strength, in-lb MEK resistance, double rubs Gasoline resistance Acid resistance, max. 30 Flow, max. 10 Powder stability Physical stability after 24 hours, At 23 C At 40 C PC6 STY/AC1 47 15200 Blend 51-58 168 16 > 100 OK 30 3 PC7 STY/AC2 40 4500 Blend 52-58 192 20 > 100 OK 30 4 PC8 STY/AC3 30 3100 Blend 50-54 202 14 > 100 OK 30 8 PC2 Resin 2 50 7700 Blend 54-60 207 14 > 100 OK 30 6

Lumps Blocked

OK Blocked

Blocked Blocked

OK OK

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Modified Acrylic Powders for Automotive Clear-Coat (cont.)

Cross-linking (cont.) The evaluation of the standard styrene/acrylic systems with the DDA/polyester blend showed that all systems have good chemical resistance as well as high hardness. However: The standard styrene/acrylic systems need to be formulated at a considerably lower average molecular weight than the VeoVa 9 based polymers in order to achieve good flow PC7 showed a borderline stability, but leads to a poor flow PC8 has a good flow, but shows blocking tendency As a consequence, the VeoVa based system is the only one which combines good resin and powder stability together with a good flow.

Conclusion

The results presented in this paper demonstrate that the unique fundamental properties of VeoVa 9 make a valuable contribution to both the performance of styrene/acrylic polymer systems and (optionally) to their manufacture, by allowing mass polymerization. The bulky structure of VeoVa 9 and its chain transfer activity lead to a polymer with low molecular weight, providing the powder clear-coat coating with a good flow. In addition to this, VeoVa 9 maintains a high Tg of the polymer, which leads to a good stability of the powder. As a consequence, this delicate balance between flow and stability of the powder can be achieved by using VeoVa 9. The formulation given in this paper is considered as a good starting point, and even better results could be obtained by further optimizing the resin formulation, the type of additives and the extrusion conditions.
1

References

Coatings World, J. Hess: Powder, powder everywhere, September 1999, p. 36. Proceedings of the 1st International Conference on Car-body Powder Coatings, Berlin: Automotive Powder Coatings Achievements & Challenges, R. Domitrz, June 1998. Modern Paint and Coatings, R. Amey, R. Farabaugh, DuPont Nylon intermediates and Specialities: Automotive Applications Drive Growth of GMA Acrylics, June 1997, p. 28. WO 99/33889 patent, C.de Cock, C.Gerets, Resolution Performance Products LLC International Research. U.S. patent 5,625,028 Eastman.

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EPI-CURE

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H E LOX Y

C A R D U R A

V E O VA