Progress in Organic Coatings 53 (2005) 246255

New green surfactants for emulsion polymerization

Ana Maria Fernandez a , Uwe Held b , Andreas Willing b , Wolfgang H. Breuer b,
b a Cognis Corporation Ambler, PA, USA Cognis Deutschland GmbH & Co. KG, Duesseldorf, Germany

Received 19 July 2004; received in revised form 23 September 2004; accepted 20 December 2004

Abstract Nonylphenol ethoxylates (NPEOs) are widely used as surfactants for emulsion polymerization and for post adding stabilization for latex applications in formulations with high ller content. However, the current exposure situation of NPEOs in Europe gives rise to environmental concern, despite of the fact that some industry associations have already pro-actively taken measures to phase out these chemistry of their products, e.g. the European detergent industry (AISE) by a voluntary commitment. As a consequence, the EU Commission has recommended to implement a risk reduction strategy, which foresees the ban of all applications leading to direct emissions to waste water and strict emission controls for all other technical processes using NPEOs as surfactant. The effectiveness of the risk reduction measures will be monitored by the authorities. In case that the environmental concentrations of NPEOs and their metabolites do not decrease by at least 70 percent, additional risk reduction measures for technical applications are planned. In one of the major elds of application, alkyl phenol-free emulsiers with a more favorable ecological prole are becoming key ingredients for eco-friendly emulsion polymers and polymer dispersions: the Disponil AFX-Series (Cognis) is a NPEO-free surfactant system for emulsion polymerization and polymer dispersant also as a supposition for getting the European eco-label for indoor paints and varnishes. These new non-ionic surfactant system exhibits an effective performance during polymerization and as post reaction stabilizers. These products are environmentally compatible, mostly derived from natural renewable resources and readily biodegradable. The underlying chemistry is in compliance with relevant indirect food contact applications [BfR recommendations, respectively, FDA CFR 21 (federal drug administration)], and a dossier to register the surfactants in the positive list of the EU Directive 2002/72/EC for application in plastic has recently been submitted. Clear, high solid liquids at room temperature, these surfactants are easy to handle and very effective with regard to controlling particle size, lm properties and overall latex stability. This paper summarizes their chemical and surface properties, as well as their performance in model emulsion polymerization formulations for architectural coatings. 2005 Elsevier B.V. All rights reserved.
Keywords: NPEO; Surfactants; Alkyl phenol-free; Emulsion polymerization

1. Background/market data Specialty surfactants play a critical role in many technical applications. Manufacturers have also dealt with globalization and the complexities of providing uniform products on a global basis. The world surfactant market is somewhat about 8.600 kt volume with a value of about D 10.500 million, each about D 3.300 million for Western Europe, North America, and Asia-Pacic.

Corresponding author. Tel.: +49 211 7940 3111; fax: +49 211 798 2641. E-mail address: wolfgang.h.breuer@cognis.com (W.H. Breuer).

The plastics and rubber industries consume surfactants primarily as polymerization emulsiers. Almost 93.000 metric tons of surfactants, valued at about D 187 million, were consumed as surfactants for emulsion polymerization for 2000 in North America [1]. About 52% are anionic surfactants, 47% non-ionics and for the rest mainly amido betaines and quarts. The main part of non-ionics today is still covered by alkylphenol ethoxylates (APEOs), the other being (fatty-) alcohol ethoxylates. These products with well-improved ecotoxicity data as so-called green surfactants will further change the picture on both sides of the Atlantic Ocean in the near future [2], even if it is well accepted that the substitution

0300-9440/$ see front matter 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.porgcoat.2004.12.011

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in the polymerization and application process is difcult and will take time [3]. In spite of all this, nonylphenol ethoxylates are by far the most important products within the APEOs, with an European consumption of about 75.000 to in 1995 [4]. It is estimated that the emulsion polymerization industry makes use of about 11.000 to APEOs [5]. They have been popular for their effectiveness, economy and easiness of handling and formulation for over 40 years. Because of their chemical characteristics, APEOs and NPEOs are high-production volume (HPV) chemicals with potential environmental relevance which have been in a controversial discussion for many years. The search for environmentally friendly alternatives is one of the major topics within Western Europe.

aquatic organisms will die due to the general toxicity of the substance before the endocrine disrupting properties become apparent. 2.2. Biodegradability of NPEOs The biodegradability of nonylphenol ethoxylates has been studied comprehensively. Almost all degradation studies indicate that the overall degradation kinetic of NPEOs is slower than that of comparable linear fatty alcohol ethoxylates (FAEOs). The slower degradation kinetic is most likely related to an adverse steric effect of the aromatic ring, making it increasingly more difcult for the degradation enzymes to attain a proper reaction position. This has the consequence that the closer the cleavage site gets to the aromatic ring, the slower the degradation kinetic becomes. Therefore, the lower ethoxylated degradation intermediates are slower (more difcult) degradable than the parent compounds, which could depending on the actual exposure situation result in an increased environmental concentration. Studies in the socalled Henkel metabolite test (a modied Coupled units test [7]) indicate that the degradation kinetic of NPEO (NP 10 was used a test product) is indeed signicantly lower than of other commonly used detergent surfactants [e.g. FAEO, FAS (fatty alcohol ether sulfates)]. Whereas the oleochemical based surfactants are completely mineralised under these experimental conditions, biodegradation of NP 10 leads to recalcitrant metabolites, which enrich over time in the test system. Similar results have been published for linear alkyl benzenesulfonate (LAS), another technical surfactant containing an aromatic ring system [8]. For that reason the European Surfactant Producers Association (CESIO) recently recommended to classify NPEOs as not readily biodegradable (see 2.5), whereas other commonly used detergent surfactants (e.g. FAEO, FAS) are classied as readily biodegradable. The biodegradation of fatty alcohol polyglycol ethers was studied in comparison to alkyl phenol ethoxylates. The results are summarized in Fig. 1, indicating that there is a degradation on both sides of the fatty alcohol ethoxylates and that the degradation of the alkyl chain is faster than the polyethylene glycol moiety [9]. 2.3. Environmental risk assessment for NPEOs In 1993, the EU Commission issued Council Regulation 793/93/EEC on the evaluation and control of the risks of existing chemicals, requiring that the chemical industry has to provide all available information on the physicochemical, toxicological and ecological properties of HPV substances that have been on the EU market before September 1982. Based on the high production volume and the ecological and toxicological prole nonylphenol (NP, CASno. 25154-52-3) has been classied as a priority substance with the consequence that the corresponding IUCLID dataset (International Uniform Chemical Information

2. Ecological properties of NPEOs 2.1. Ecotoxicity of NPEOs Studies show that the aquatic toxicity of NPEOs is dependent on the degree of ethoxylation. The lower the number of EOs (ethylene oxides) in the molecule, the higher the aquatic toxicity observed. This structure/activity relationship is explained by the specic mode of action, which in case of surfactants is a general narcotic one. Narcosis is linked to the hydrophobicity of the molecules. Shorter EO-chains, respectively, longer alkyl (side) chains, increase the hydrophobicity of the molecules and therefore increase their aquatic toxicity. The specic problem of NPEOs is that biodegradation leads to more hydrophobic metabolites (i.e. NP 13EO), which are very toxic for aquatic organisms and itself difcult to degrade. Therefore, these very toxic metabolites tend to enrich in the environment. A recent publication indicates that recalcitrant metabolites from technical surfactants are of environmental relevance, e.g. they may be linked to the declining sh population in Swiss rivers [6]. Another concern is that NPEOs have endocrine disrupting properties. Endocrine disruptors are substances that interfere with the hormone system, disrupting its natural balance. Therefore, endocrine disruptors can adversely inuence the reproductive success of a species, e.g. by changing the natural sex ratio (turning male sh into female). Based on structural similarities between NPEOs and steroid hormones (ring system), NPEOs are often suspected to be endocrine disruptors. It has indeed been shown in vitro that NPEOs can interfere with the hormone system. However, compared to hormones (estrogen) the effect is rather weak, i.e. much higher (several orders of magnitude) concentrations of NPEOs are required to observe hormone-like effects. The only weak endocrine effect of NPEOs is reected by the fact that the predicted no effect concentration (PNECendocrine ) of 1020 g/l is at least an order of magnitude higher that the PNEC for aquatic toxicity (PNECaquatic toxicity = 0.33 g/l). In other words, the

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Fig. 1. Comparison of degradation between NPEOs and FAEOs.

Database) had to be submitted to the authorities by June 1994. Based on these data the authorities established priority lists for substances for which in-depth risk assessments should be conducted. NP (nonylphenol and phenol, 4-nonyl-, branched) is on the second priority list (Commission Regulation no. 2268/95). Subsequently, an environmental risk assessment according to the EU Technical Guidance Document has been conducted. As the nonylphenol ethoxylates are a major source of environmental NP (NP is formed as a breakdown product during biodegradation) NPEOs have been included in the ofcial EU risk assessment on NP [10]. The basic principle of the environmental risk assessment comes down to the derivation and comparison of two concentrations: the Predicted Environmental Concentration (PEC) and the Predicted No Effect Concentration (PNEC) for a given environmental compartment (water, soil, sewer sludge) (see Annex 1). If the PEC is below the PNEC, the substance is of no concern. If, however, PEC > PNEC it cannot be excluded that the organisms in the environment are adversely affected by the chemical. In this case, the authorities shall dene appropriate risk reduction measures. The PEC is generally derived from production volume, environmental release factor, biodegradability and waste water treatment situation. Based on the environmental exposure situation, taking into account all applications (also of derivatives like NPEO) an EU-wide regional environmental concentration of 0.8 g/l is predicted for NP (PECregional = 0.8 g/l). The PNEC is derived from data on the aquatic toxicity of the substance applying appropriate safety factors to extrapolate to the situation of real environment. Based on the long-term toxicity studies a No Observed Effect Concentration of 0.33 g/l is predicted for NP (PNEC = 0.33 g/l). Based on these gures the EU risk assessment for NP (including NPEO) comes to the conclusion that there is concern for the aquatic environment (PEC/PNEC > 1).

2.4. Risk reduction strategy To reduce the environmental risk to an acceptable level the EU authorities have recommended a risk reduction strategy (2001/838/EEC). This strategy is based on a stepwise approach. In the rst step marketing and use restrictions for applications that result in direct emissions of NPEOs into waste water (detergents and cleaning products, cosmetics, textile and leather processing products, paper and pulp production, etc.) are established. In addition to the above, and recognizing development of new Community procedures,1 additional pollution control measures for NP and NPEOs should be considered for the following sectors: - production of NP and NPEOs, - use of NPEO in the synthesis of other chemicals (e.g. NPEO phosphates), - use of NPEOs in emulsion polymerization in particular use in acrylic esters for specialist coatings, adhesives and bre bonding, - production of phenol/formaldehyde resins using NP and - production of plastic stabilizers using NP. The results achieved through marketing and use restrictions and pollution control measures should be monitored and if necessary additional measures should be considered. If the above measures should turn out to be not sufcient to reduce the environmental risk to an acceptable level, marketing and use restrictions for additional applications will be

1 Directive 200/60/EEC introduces provisions for pollution reduction measures at Community level. Based on the list of priority substances in Annex X of the Directive, the Commission will propose quality standards and emission controls, including emission limit values 2 years after adoption of the list. For certain priority hazardous substances the emission controls shall aim at the cessation or phase-out of discharges, emissions and losses within 20 years. Nonylphenols are classied as priority hazardous substances. The rst list of priority substances including NP was adopted on 11 June 2001.

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considered in a second step, e.g. for use of NPEOs in emulsion polymerization. Producers of consumer products like washing powders or dispersion adhesives had already voluntarily agreed not use this kind of chemistry for their products [11]. This natural trend is ongoing for surfactants beside the use in detergents and personal care products also for use in industrial applications [12]. 2.5. Supplementary remarks Environmental classication according to the EU Directive for labelling of chemicals as dangerous for the environment (92/69/EEC) [13]. On the basis of an evaluation of all available data on ecotoxicity and biodegradability CESIO recommends to classify NPEO as follows: - Alkylphenol ethoxylates branched, C8-9, 3-10 EO: N, R51/53. - Alkylphenol ethoxylates branched, C8-9, >10 EO: R52/53. German water pollution class: according to the VwVwS of May 1999 NPEO are classied as water polluting (WGK 2) [14].

sides the ecotoxicological arguments, the performances during the polymerization process and in the following coating and/or adhesive application tests are the main reasons why success is still limited at the moment. The surfactant properties of products based on methyl esters for example have been described and their performance attributes in emulsion polymerization and in paint applications [21]. Different nonionic products based on sugar surfactants were used in acrylate formulations with some good results but showing less water resistance [22]. For anionic systems, products based on sulfosuccinates are also playing an important role as alternatives to anionic APEOs. A summary for the use of these chemical products in the emulsion polymerization process is given [23]. Other surfactants based on tridecyl alcohol ethoxylates or synthetic secondary alcohol ethoxylates are also announced to be used for emulsion polymerization processes in the annual listing of commercial surfactants [24], but show fewer properties in the application (see below in this paper). Few years back, positive results were presented where modied fatty alcohol ethoxylates of the Disponil A Series showed promising results concerning emulsion polymerization and application tests [25]. Based on this important chemistry Cognis develops the second generation of surfactants showing better performance in the application and in their ecotoxicological behavior. 3.1. Surfactant composition and properties All these new products with an ethoxylation degree between 7 and 40 are clear, high solid liquids at room temperature exhibiting excellent water miscibility and performance in emulsion polymerization. Table 1 lists the products, composition and properties. The hydrophobe in the surfactants is mostly made from natural renewable resources. This portion of the molecule is based on C1214 fatty alcohols consisting of primary and secondary alcohol isomers. Non-ionic surfactants based on fatty alcohol with high ethoxylation degrees are known to be solid under ambient temperatures. By dilution with water high viscous liquid crystalline phases are formed in the medium concentration range. Formulations of the surfactants were optimized to reduce these viscous phases to a minimum. An example for the 30 EO based product is given in Fig. 2. As can be seen, the jelly phase is somewhat between 35 and 65%, to avoid handling problems by dilution with water the temperature should be higher than 35 C. 3.2. Structure/property relationships of the new surfactants Adsorption of these surfactants at the airwater interface was investigated through surface tension measurements at 25 C using the Wilhelmy plate method and a Kr ss surface u tensiometer. Dynamic interfacial tensions were measured us-

3. Alternatives to NPEOs for emulsion polymerizationdevelopment of new chemistry The history and progress about development of surfactants in the last 50 years is a story of innovations, both in product and technology [15]. About 1960, one of the milestones was the substitution of tetrapropylenebenzene sulfonate (TPS) in washing powders with the readily biodegradable linear alkylbenzene sulfonates due to the heavy foaming of the high environmental resistance of TPS. Parallel to the rst regulations set by authorities, which also became the basis for the general environmental legislation in Germany, better biodegradable surfactants and their analysis were developed. To name some: in 1980, the rst esterquat was commercialized as a fabric softener [16], in 1990, the sugar-derived alkyl polyglucosides as fully renewable, no-EO non-ionics were successfully introduced [17], followed by fatty acid N-methyl glucamides in 1994, and in 2000 the rst Gemini surfactant started into commercial application [18]. Driven by the personal care and cleaning applications, new and better performed surfactants were also introduced for technical purposes, even if alkylphenol ethoxylates are widely used as secondary surfactants in the emulsion polymerization process, as they are reasonably economic and have good stabilizing properties for a variety of monomers. Because of the concerns about the discussed alkylphenol residues, which are formed when these surfactants are released into the environment, many recipes have been reformulated to fatty alcohol ethoxylates [19,20]. Although great success has been achieved, there is still a long way to go. Be-

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Table 1 Physico-chemical properties of the Disponil AFX series Product name Disponil AFX 780 Disponil AFX 1080 Disponil AFX 1580 Disponil AFX 2075 Disponil AFX 3070 Disponil AFX 4060
a b

Alkyl chain C1214 C1214 C1214 C1214 C1214 C1214

EO degree 7 10 15 20 30 40

Solids (%) 80 80 80 75 70 60

Pour point ( C) <10 <10 <20 <15 <15 <15

Cloud point ( C)a 6973b 6670 7680 7882 7680 7478

Tested at 1% in 10% aqueous NaCl solution. Tested at 1% in dest. water.

Fig. 2. Phase diagram of Disponil AFX 3070.

ing the pending drop method and the Tracker drop tensiometer from Kr ss as well. The results are summarized in Table 2 u and in Figs. 3 and 4. The surface excess concentration max denes the effectiveness of adsorption of the surfactants at either air/water or water/monomer interfaces. max was calculated from the Gibbs equation according to: = 1 RT (ln C)

Table 2 Characteristic data of Disponil AFX Series Product name Disponil AFX 780 Disponil AFX 1080 Disponil AFX 2075 Disponil AFX 3070 Disponil AFX 4060 HLB 12.5 14.5 17.0 17.5 18.0 CMC (mg/l) n.m. 27 100 270 500 (mN/m) n.m. 31.2 39.5 43.2 44.5

Fig. 3. CMC measurement of Disponil AFX 1080.

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Fig. 4. Dynamic surface tension of Disponil AFX 3070. Given concentration (c) in active matter.

where (mol/cm2 ) refers to the surface excess concentration, the interfacial tension for either air/water or water/monomer systems. The surface excess is obtained from the slope of versus ln C plot. The area (as ) occupied by the molecule at the interface is inversely proportional to as (m2 /molecule) is calculated as follows: as = 1016 NA

NA being the Avogadro number. as is a good indicator of the orientation of the molecules at the interface. A very low value of as indicates a closely packed interface, where the molecule is oriented perpendicular to the surface. On the other hand, a large value of as reveals a loosely packed interface with the molecules lying at on the surface. The area occupied by the surfactant molecules increases as EO content increases and reaches a plateau at 30 EO. The 10 EO based product at airwater interface shows a closer packing than the 40 EO equivalent, which is highly hydrated.

As expected the physico-chemical values for the hydrophilic lipophilic balance (HLB) and critical micelle concentration (CMC) calculations and measurements are increasing with the degree of ethoxylation. The HLB values are relatively similar to those determined for the products with the same ethoxylation degree based on nonylphenol. In Fig. 3 an example of the measurement of the CMC is given. The test was run according to Lecomte de No y at 25 C with u a plate system. The surface tension at CMC is also given in this test. As mentioned earlier, dynamic interfacial tensions were measured using the pending drop method and the tracker drop tensiometer from Kr ss. Typical results are shown in u Figs. 4 and 5 comparing 30 mol ethylene oxide based products (fatty alcohols and nonylphenols). Both surfactants compared in general show the same reduction of the surface tension with increasing concentration. There are no big differences in the speed of the surfactants, with increasing bubble frequency the dynamic surface tension is slightly increasing as well.

Fig. 5. Dynamic surface tension of a NP 30. Given concentration (c) in active matter.

252 Table 3 All-acrylic formulation Ingredients

A.M. Fernandez et al. / Progress in Organic Coatings 53 (2005) 246255 Table 5 Styrene/butyl acrylate formulation Parts of weight (g) 140.0 140.0 52.5 17.5 2.0 2.0 10.0 636.0 1000.0 Ingrediences Styrene Butyl acylate Acrylic acid Acryl amide Potassium peroxodisulfate Anionic surfactant, 100% active substance Non-ionic surfactant, 100% active substance Water, demineralized Ammonia aqueous for neutralization Polymer dispersion Parts of weight (g) 241.5 241.5 11.5 5.5 3.7 8.2 1.5 466.6 Approximately 20.0 1000.0

Ethyl acrylate Methyl methacrylate Butyl acrylate Acrylic acid Texapon K 12 Ndl. Potassium peroxodisulfate Non-ionic emulsier, 100% active substance Water, demineralized Polymer dispersion

4. New chemistry used in emulsion polymerization processes The mechanism of emulsion polymerization as well as the role of the surfactants have been described elsewhere [26]. To show the behavior and performance of the discussed surfactants different monomer systems have been chosen for different application systems. Tests are showing that in many cases replacements in existing formulations are possible without losing application performances. Some examples are mentioned. 4.1. All-acrylic screening system In Table 3 the behavior of the discussed products with different degrees of ethoxylation is shown in a standard acrylate formulation in comparison to well known used non-ionic surfactants. Trying to eliminate any differences in particle size distribution, the polymerization was started with small amounts of pure C12 -SLS (sodium lauryl sulfate, Texapon K 12 Ndl) until a seed latex was formed. Further on, the non-ionic surfactant was added and the polymerization process was continued. The amount of wet coagulate indicates the stabilizing properties of the discussed non-ionic surfactants, collected by ltration through 80 m lter. As shown in Table 4, linear fatty alcohol ethoxylates like lauryl alcohol 30 EO are showing a poor stabilizing behavior in this simple screening formulation. The reference emulsier based on NP 30 with an amount of about 3% coagulum has relatively unsatised stabilization properties, even when these kinds of surfactants are very well known under industrial conditions. This indicates that a sensitive screening formulation is in our hands. The higher ethoxylated products are relatively better performed for this kind of latex stabiTable 4 Comparison of different ethoxylates in all-acrylic formulations Non-ionic surfactant Lauryl alcohol 30 EO Nonylphenol 30 EO Octyl phenol 40 EO C1215 s alcohol 40 EO i-C13 alcohol 40 EO Coagulum (%) >10 approximately 3 0.51 0.51 0.51

lization with a low amount of coagulates between 0.5 and 1%. The stabilization performance of the newly developed products is not so sensitive concerning the hydrophilic surfactant part, in fact, with all new products very low precipitations are achieved. Under laboratory conditions with the aim of getting low amounts of coagulum, a ne tuning of the product range was not done due to the reason that no further application tests were run, either. From the standpoint of the emulsion polymerization process it is possible to develop green surfactants and products under industrial conditions which in comparison with the earlier developed Disponil A series are alkylphenol-free, readily biodegradable, have improved ecotoxicological properties and cause lattices with a very low amount of coagulum [25] in laboratory screeing tests. 4.2. Styrene/butyl acrylate system Styrene acrylate dispersions are very unique dispersion that are well known for different applications, like standard binders for indoor paints, concrete applications like primer and trowelling compounds, and as modier for silicate paints. Typical minimum lm-forming temperature is about 20 C. Standard formulations are based on NP 30 in combination with some anionic surfactants typically also based on NPether sulfates as shown in Table 5 with the results in the corresponding diagram. The replacement of both alkyl phenol based surfactants was successfully done in two steps: - substitution of the non-ionic surfactant by the new development and - substitution of the anionic surfactant with fatty alcohol ether sulfate

Non-ionic surfactant Disponil AFX 1080 (10 EO) Disponil AFX 2075 (20 EO) Disponil AFX 3070 (30 EO) Disponil AFX 4060 (40 EO) Disponil AFX 5060 (50 EO)

Coagulum (%) <0.5 <0.5 <0.5 <0.5 <0.5

A.M. Fernandez et al. / Progress in Organic Coatings 53 (2005) 246255 Table 6 Latex properties in styrene/butyl acrylate formulation Coagulum (%) Disponil NP 30 Disponil AES 72 Disponil A 3065 Disponil AES 72 Disponil A 3065 Disponil FES 77 Disponil AFX 3070 Disponil FES 77 1 1 1 1 Particle size (nm) 135 147 124 133 Storage stability (50 C, 4 weeks) Stable Stable Not stable Stable Freeze-thaw stability (25 C) Stable Stable Not stable Stable

253

Water resistance Good Good Good Good

As shown earlier, NP 30 and the 30 mol ethoxylated product could be replaced by Disponil A 3065. Particle size distribution, storage and freeze-thaw stability and water adsorption are very close to each other. To replace the NP 30 ether sulfate it was necessary to optimize the surfactant system by increasing the efciency of the non-ionic surfactant. In fact, this formulation was the main reason to start the optimization program and to realize the second generation of the NP replacement. With development of these new high ethoxylates the technical application deciencies were overcome, nding good matches between the NP-containing and NP-free lattices as shown in Table 6. The improvements were done in a way that the storage and the freeze-thaw stabilities are now on the same level in comparison to the NP-based surfactants. In all cases the test results showed a sufcient water resistance between 4 and 5%. 4.3. Vinyl acetate/butyl acrylate systems The vinyl acetate/butyl acrylate system is well known as low-VOC binder for typical paint applications. The performance of different non-ionic surfactants as primary emulsiers in this system is discussed in the comparison between the new generation of green surfactants and traditionally used APEOs and sec-alcohol ethoxylates. The result from the formulation in Table 7 is summaried in Table 8 and compares the new 40 EO non-ionic surfactants to the well known octyl phenol 40 EO. The data also compares a synthetic sec-alcohol bearing the same ethoxylation level (40 EO). The results show that OP-40 produces somewhat slightly smaller particle size latexes than the new chemistry; however, the particle size can be effectively controlled by varying the surfactant concentration. The new surfactants gave cleaner latexes with acceptable mechanical, electrostatic
Table 8 Latex properties in vinyl acetate/butyl acrylate formulation Surfactant Disponil AFX 3070 Disponil AFX 4060 Octyl phenol 40 EO Sec-alcohol + 40 EOa
a b c

Table 7 Vinyl acetate/butyl acrylate formulation Ingredients Vinyl acetate Butyl arcylate Methacrylic acid Ammonium peroxodisulfate Non-ionic surfactant, 100% active substance Water, demineralized Polymer dispersion Parts of weight (g) 400.0 95.0 5.0 2.5 5.0 492.5 1000.0

and freeze/thaw stabilities. These data also suggest that the new emulsiers are excellent candidates to replace APEOs and synthetic sec-alcohol ethoxylates in vinyl acetate/butyl acrylate systems. In this latex system, combination of anionic and non-ionic surfactants can also be used as emulsier system and for stabilisation. The combination with a long chain alkyl ether sodium sulfate as co-stabilizer demonstrates the effect of surfactant combinations to control particle size, overall stabilization and low coagulum content. These surfactants produced clean latexes with controlable particle sizes and acceptable overall stability. Table 9 demonstrates the positive results of the surfactant combination for vinyl acetate/butyl acrylate system, comparible to the formulation in Table 7. The amount of the used fatty alcohol ether-30 EO sulfate was in the same concentration as the used new chemistry. On basis of these lattices semi-gloss paints were formulated. Results shown in Table 10 summarize the wet scrub cycles determined for these paints formulated with the vinyl acetate/butyl acrylate as discussed earlier. Different paints are identied by the name of the non-ionic surfactant used in the acrylic latex preparation.

EO degree 30 40 40 40

Coagulum (%) 0.34 0.26 0.52 0.47

Particle size (nm) 373 370 327 362

Freeze-thaw stabilityb Stable Stable Stable Stable

Mechanical stabilityc Pass Pass Pass Pass

C1215 s alcohol + 40 EO. Freeze/thaw stability: stable for 5 cycles between 15 and 25 C. All passed thermal stability 30 days at 60 C.

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Table 9 Application properties in vinyl acetate/butyl acrylate formulation Surfactant Disponil AFX 2075 Disponil AFX 3070 Disponil AFX 4060 Octyl phenol 40 EO Sec-alcohol + 20 EOa
a b c

EO degree 20 30 40 40 20

Coagulum (%) 0.11 0.09 0.10 0.08 0.10

Particle size (nm) 236 240 267 233 213

Freeze-thaw stabilityb Stable Stable Stable Stable Stable

Mechanical stabilityc Pass Pass Pass Pass Pass

C1215 s alcohol + 20 EO. Freeze/thaw stability: stable for 5 cycles between 15 and 25 C. All passed thermal stability 30 days at 60 C.

Table 10 Properties of vinyl acetate/butyl acrylate semi gloss paints Number of cycles to failure Wet Scrub Test Anionic surfactant (same) Fatty alcohol ether sulfate Non-ionic surfactant (different) Disponil AFX 2075 Disponil AFX 3070 Disponil AFX 4060 Octyl phenol 40 EO Sec-alcohol 20 EO Pigment concentration Volume solids Wt solids 620 844 627 728 469 23.2% 33.0% 47.2%

ulum formed in samples of equal weights of stabilized latex and 5% calcium chloride solution. Both surfactants restored the electrostatic stability of the latex at 0.4% post addition. However, the amount of coagulum formed by post adding the synthetic sec-alcohol was higher than the amount of coagulum formed by post adding of the new developed chemistry with 40 EO. The post reaction stabilization is important for latex applications in formulations with high ller content. In summary, Disponil AFX non-ionic surfactants offer improved environmental compatibility, effective performance, compatibility with a broad range of additives for adhesives and coatings, biodegradability, broad formulation capabilities easy handling, compliance with relevant BfR and FDA requirements for indirect food contact applications. Disponil and Texapon are registered trademarks of Cognis.

It is interesting to observe the high numbers of cycles at least for the 30 EO surfactant, which is outstanding for paints made without wet adhesion monomers or other paint improving additives. These high scrub cycles are indications of excellent adhesion and water resistance as known from the classical octyl phenol based surfactants like OP 40. It is important to note that the 30 EO based product is the most stabilizing surfactant in these systems, although it shows signicantly better results in comparison to the classical systems. The signicantly cleaner latexes and high number of cycles to failure in the vinyl acetate/butyl acrylate paints, further demonstrate the suitability of the new emulsiers to replace APEOs and synthetic oxo-secondary alcohol ethoxylates in commercial formulations. 5. New surfactants used for post reaction stabilization The high ethoxylation bearing these surfactants have shown excellent post stabilization performance. The 40 EO based product was evaluated as a post addition emulsier and compared to a C1215 synthetic secondary alcohol ethoxylate with 40 EO units. The test consisted in measuring the coagulum formed in a model acrylic latex after the post addition of surfactant, followed by the addition of a 5% solution of calcium chloride. The acrylic latex was made with sodium lauryl sulfate (SLS) surfactant as the primary emulsier. The stabilization effectiveness was evaluated by measuring the coag-

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