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Control of The Reaction Between Polyaspartic Esters and Aliphatic Polyisocyanates

Polyaspartic esters are a new type of amine functional coreactant for polyaliphatic polyisocianates

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Franco Carli
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542 views

Control of The Reaction Between Polyaspartic Esters and Aliphatic Polyisocyanates

Polyaspartic esters are a new type of amine functional coreactant for polyaliphatic polyisocianates

Uploaded by

Franco Carli
Copyright
© © All Rights Reserved
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Control of the Reactions Between Polyaspartic Esters and Aliphatic Polyisocyanates Bayer Polymers CONTROL OF THE REACTION BETWEEN POLYASPARTIC ESTERS AND ALIPHATIC POLYISOCYANATES Dr. Douglas A. Wicks and Dr Philip E, Yeske. ‘Coatings and Colorants Division, Bayer Corporation 100 Bayer Road, Pittsburgh, PA 15205-9741 Presented at the Water-Borne & Higher Solids and Powder Coatings Symposium February 24-26, 1993 New Orleans, LA, USA ‘Symposium Sponsored by ‘The University of Southern Mississippi Deparment of Polymer Science Southern Society for Coatings Technology ABSTRACT Polyaspartic esters are a new type of amine functional coreactant for aliphatic polyisocyanates. Currendy, a number of polyaspartic ester products are coming to marker te in very high solids two component automotive coatings. In addition to providing tough, high gloss finishes, the polyurea coatings produced fy this chemise show superior weathering and environmental etch performance. ‘The polyaspartic esters themselves are characterized by their low viscosity, moderate equivalent weight and good storage stability. These polyaspantc esters are noteworthy for possessing reactivities with aliphatic polyisocyanates which are much closer to compounds than they are to other amine functional resins. However, in terms of catalysis, they are markedly different from conventional coreactants. This paper details a method for controlling the reactvicy of these resins toward isocyanates and how they can'be successfully employed in producing very high solids coatings. ‘As the 1990's unveil a new era of more stringent environmental regulations, raw material suppliers to the paint industry are being asked to supply resins which meet and exceed these new requirements without sactificing performance. The push to reduce emissions of volatile organic compounds (VOCS) has shifted 2 great deal of resin development toward finding and exploiting new reactive diluents. Polyfunctional amine compounds have been used as coreaccants for polyisocyanares in many applications. Their use in coatings however has been limited due to their very high reactivity. Typical primary and secondary amine based systems are characterized by very shore gel times, resulting in litde or no potlife and films which, due to restricted flow and Ieveling, do not possess cass A Gnishes. Polyaspartic esters (PAEs), a specific class of secondary amine-fancrional isocyanate coreactants, are characterized by their moderate reactivity.! This moderate reactivity allows their use in coatings formulations which are characeriaed by: + acceptable potife!2 + high hardness and gloss + excellent weathering and environmental etch resistance. Background Earlier work by Zwiener et al125 showed the applicbiliry of polyaspartic esters as coreactants for polyisocyanates. They reported that PAEs were easily prepared from a wide variety of polyainiucs through icaction of the amine funcdonality with dialkyl maleates.$ Ir ‘was reported that the structural variations in the amines leads to significant differences in viscosity and reactivity (Table 1). In this cxample the reported gel times correlate to differences in reactivity. Specifically, higher reactivity corresponds to a shorter gel time and infers a shoreer podife in a coatings formulation. For many coatings applications, the intrinsic reactivities of polyaspartic esters A, C wand D would appear to aor eC eal the polyasparti ester derived from bist amino,3-medhyloydohen methane and diethyl ey reacts i ate Iyisocyanates more slowly. As a consequence, acceptable pot lifes are achieved bur, as we Fhovr later on, atthe expense of excessively long dry dines. Introduction Ie thus became our goal ro understand how to contrel the reactivity of polyaspartic cescer resins in such a way so as to maximize pot life while minimizing dry time. To bewer define the concept of pot life, we developed a parameter to measure viscosity build of a model formulation based on the ratio of viscosities taken at time 65 minutes vs. 5 minutes (s/s), The larger this value becomes, the faster the viscosity build is, chus implying a shorter pot life in an actual formulation. Our intention was to minimize this value while maintaining short dry times. ‘The model formulation by which to test this method is described in Figure 1 and unless otherwise specified the solvent is methyl ethyl ketone (MEK), Table 1. Properties of Polyaspartic Esters ea E20,C- -R- E0,€ PAE R EW —o -. © Ore = c CH 229 i OL ini + 100% Solids, mPars at 23°C ‘+ HDI Polyisocyanurate)PAE, NCO/NH: 1.0, 65% solids in 1:1 MEK/Aromatic 100 CO;Et 1,500 150 Gel Time** 2-3br 24hr 24hrs). A larger Nigs/Ms value (shorter pot life) for A than for B is in agreement with Zwiener’s gel time data! Ie is not suprising chat the ks sttielly hindered bis(t- aminocyclohexyl)methane adduct reacs and oures faster with a polyisocyanate crosslinker than does the bis(4-amino,3-methylcylohexyl)methane adduct. As can be seen in Figure 3 the ring methyl group in B is in close proximity to the site of reaction. Figure 3. Pe tc Enters Based on Bis(-aminocyelohery!)methane (A) and Bis(4amino, 3- Be ahayDachane ee A Me YD a Shin B Our goal was to develop a method by which to further reduce the reactivity of polyaspartic eser coreaccants toward aliphatic polyisocyanates. Our two measures of success ‘were por life and dry time. The short dry time for A is favorable while the shore pot life is not. For maximum efficiency, spray applications (e.g. automotive refinish) require extended pot life buc fist dry times. The remainder of this paper describes a general method for reducing the reactivity of PAEs using tin (IV) compounds, the desired result being longer potlife and shore dry times. The results of varying the tin ligand seructure and level along ‘with polyaspartic ester and polyisocyanate structure are additionally reported. Results and Discussion Effect of Diburylrin Dilauarate Our initial scudies of this area centered on the effect of including a tin additive ina ‘wo component clearcoat polyurea formulation (model system as above). We found that charging 0.1% by weight of a diburyltin dilaurate solution (10% in MEK) into a solution of A and MEK (component 1), prior to charging the aliphatic polyisocyanate (component II), resulted in a viscosity buildup over one hour subscantially smaller than that observed withour tin present (Table 2). In fac, the viscosity after 65 minutes was 100 mPars as opposed to 660 mPars when no tin was present. Over the course of an hour, the pot life of the slower reacting B was slighty improved while the dry time was cut in halE. Table 2. Effece of 0.19 by Weight of Diburléin Dilurateon the Model Sysiem ca ‘tg (mPars) Desms Mar-Free No Additive 30 22.0 39min 0.1% Tin Additive 20 50 45min B . No Additive 20 18 >24 hours 0.1% Tin Additive 20 15 11 hours Subsequeat trials with the same formulation charged with lower or higher amounts of dibunyltin dilaurate indicate an additive effec of the tin on pot life (Table 3). Also of note is Seda day times remained ls han one hear forall ches formulations Even of tin additive above 196 by weight would seem to be advantageous for podlife purposes, greater amounts were not practical because of diminished quality of films made from such formulations. ‘Table 3. Effect of Variable Diburyitin Dilaurate Levels on the Model System Using A Additive Level (%) ‘Ts (mPass) nems Mar-Free 0 30 22.0 39min 0.01 20 10.5 48 min 0.1 20 5.0 45min 10 30 33 39min Effect. of Tin Ligand Struceure To investigate the scope of this finding on potlife and dry time, we next focused our research efforts on varying the ligands of the tin additive. The data in Table 4 summarizes the results of induding various tin additives at 0.1% by weight in the reaction of A with an aliphatic polyisocyanate. ‘Table 4. Effect of Various Tin Additives on the Model System Using A Additive 0.1%) ng(mPas) ngs Mar-Free None 30 2.0 + 39min Dibutyltin Diacetate 25 42 > 60min Dibutyltin Disulfide 30 50 ‘55min Dibutyltin Dilawrate 30 50 45 min Dibutyltin Mercaptide 30 30 0 min Dibutyltin Bis(mereaptide) 30 57 > 60min ‘Nearly all the tin additives we investigated were successful at inhibiting the amine- isocyanate reaction and maintaining relatively shore dry tines. The ligand structure on tin was seemingly of litde consequence, as both acid and sulfur-substicuted tin additives were effective. Interestingly, further testing on other urethane catalysts showed that tin (IV) ompounds appear to be the only ones that inhibit the reaction, Diburla diaure displayed the best cure profile and was chosen as the standard additive for evaluating other parameters. Solvent Effects Solvent effects were noted, as clearly solvent choice plays a role in both the magnitude and breadth of viscosity build (Table 5). For eample, formulations examined in xylene or bury acetate had higher absolute viscosities than those done in MEK, but the same a effect on pot life (ie. extension) was observed when tin was added to the mulation. ‘Table 5. Solvent Effects on the Mode System Using A Solvent ng (mPas) —ngsms Mar-Eree n-Butyl Acetate NoAdditve 50 65.0 46 min 0.1% Tin Additive 50 60 46 min ‘Methyl Ethyl Ketone No Additive 30 220 39 min _ 0.1% Tin Additive 20 50 45 min Xylene No Additive 50 72.0 45min 0.1%Tin Additive 50 34 45 min MEK had the slowest viscosity build when no additive was present. This may result from an amine-enamine equilibrium berween the polyaspartic ester and the ketonic solvent. This possibilty does for burl accate snd Syne, however the tin modifiation appeats wm overwbelm dis efter and males all hres solve choices pail MEIC was as the standard working solvent because of its combination of solvating ability and poulife/dry time properties. : Effict of Pobyisocyanate Structure ‘Up until this point, the importance of the tin additive in consrolling reactivity of polyaspartic esters has been stressed. We further wanted to investigate the impact of changing polyisocyanate or polyaspartic ester seruczure on this effect. Several different types of polyisocyanates (experimental, isocyanurate, uretdione) based on hexamethylene di-isocyanate (HDI) were investigated as crosslinkers with A. ‘Without fail, the reaction of each with A was retarded in the presence of 0.1% by weight of iburyltin dilaurate as is indicated in Table 6. The isocyanusate polyisocyanate derived from the trimerization of isophorone diisocyanate (IPDI) was also less reactive in the presence of tin, The ability of both linear and cycloaliphatic-based polyisocyanates ro successfully participate in the tin modification means that the coatings fermulator can tailor this method to the specific application at hand. For example, a more rigid coating would be © result from the IPDI isocyanurate than from the HDI isocyanurate, yer both could be spray- applied and dried within an hour iftin is induded in the formulation. Table 6. Effect of Polyisocyanate Structure on the Model System Using A Polyisocyanate ‘ng (mPa's) ~ ngsms Mar-Free E ital HDI lyisocyanate No Additive 30 22.0 39 min 0.1% Tin Additive 20 5.0 45 min BDI Isocyanurate No Additive 40 69.0 >60 min 0.1% Tin Additive 30 10 ‘45 min HDI ‘ ce Uretdione/Isocyanurate No Additive 20 31,0 >60 min 0.1% Tin Additive 20 43 >60:min IPDI ite No Additive 230 21.0 57min 0.1% Tin Additive 220 52 50min Effect of Pobyaspartic Ester Srrucrure Even though our research to date has focused on cydoaliphatic PAEs A and B, the ease with which polyaspartic ester resins may be prepared has led us to evaluate a series of polyamines as reactive diluents. The results are tabulated in Table 7 and clearly show the versatility of the tin modification in controlling amine-isocyanate reactions. ‘The polyaspartic ester based on hexamethylene diamine (C) is not included in the table but does deserve mention. Wichout any tin additive, the gel time of this PAE with an aliphatic polyisocyanate is less than five minutes. When 0.1% of diburyitin dilaurate is added to the formulation the gel time increases to one hour. Though not a practical alternative, this linear aliphatic PAE is illustrative of the power ofthe tin modification. Table 7. Effect of Polyaspartic Ester Struccure on the Model Sytem. RolyasparticEster = ng (mPars) ggg nespms Mar-Eree A No Addi 30 22.0 - 39 min B 0.1% Tin Additive 20 5.0 ca 45min No Additi 20 18 125 >wh * 7 0.1% Tin Additive 20 1s 3.0 Uh No Addit 235 24.0 - . 60min 7 0.1% Tin Additive 25 5.0 - >60 min No Additive 35 14 os. >24h 0.1% Tin Additive 35 14 9.0 >4h ‘Two of the polyaspartic esters (B and E) display a large difference in reactivity when tin is induded, over a much longer timespan than the other amines. For B, this effect most likely resules from its inherent lack of reactivity due to stetic inhibition. However steric ‘encumbrance can not be used to explain the apparant lack of reactivity of E, a polyaspartic ester based on an amine-functional polypropylene oxide with a molecular weight of 2,000 gizel (effamine D-2000) and ‘dechyh maleate. Further research is underway in our iboratories to better understand why a linear polyether such as E should exhibit this kind of reactivity. : Conclusion This paper details a method for controlling the reaction profile berween polyaspanic esters and polyisocyanates using tin (IV) additives. The fdvanage denved from this method is increased potlife in a two component clearcoat coatings formulation while maintaining shore dry times. The method is robust to variance of additive, polyisocyanate, and polyaspartic eseer serucrure and thus can be tailored to the specific high solids coatings need. Experimental Coatings formulations were prepared by 1g 1.0 equivalents of the polyaspare eset, MEK, the additive GF preset, ux sare cette Produes) and 1-1 equivalents of the polyisocyanate to a 2.0 oz. jar and stiing for one minute. MEK was used in an amount sufficient to reduce the solids content of the formulation to 75%. A3 mil drawdown on glass was immediately prepared and the resulting film placed in a 23 °C/50 % relative humidity room with a 1 hour Gardner Drytime meter on the film. The cong was deermined robe mar fice when che sas no longer marred che sufce of the film, The remainder of the mixzure was monitored for viscosity build using 2 Brookfield Viscomerer, spindle LV-3, 60 rpm. Measurements were recorded every 15 minutes after 5 minutes of reaction time. Materials polyaspantic esters (A-E) were to the method of Zwiener et als ei a the otras wy maleate (practical grade, Easeman-Kodal). References 1, Zwiener, Ch., Schmalsticg, L, Sonntag, M., Nachtkamp, K, Pedain, J New Concepts for Tue Pack Plprethone Coatings Fabs und Lack (199%), Nr. 12, 8.1052; Zwienen Ch, Schmalsieg,L~ Sonntag, Ms European Coatings Touma 1992 (10), 588. 2. Zwiener, Ch, Sonntag, M., Kahl, L; Aspartic Acid Eners - A New Line of Reactive Diluents for Hig) Two-Pack Polyurethane Coatings, Proceedings of the Twentieth EATIPEC Congress, 1990. 267. 3. Jorissen, S.A., Rumer, RW., Wicks, DA; Higher Soli as ra § i ‘Symposium, February 26-28, 1992, 182. A, Jotissen, S.A; Polyurethane Coatings for Automotive Plastics, Finishing Ausomative Plastics, April 28-29, 1992, EM92-157. 5. United States Patent # 5,126,170. Polyurethane Coatings, a ‘The mannorin which you uso andthe purpoze to which you put and utlize our products, technical assistance and information (whether verbal, weton oF by way of production evaluations), iuding any suggested formulations and recommendations are beyond our contra. 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