12 Rubber & Plastics News • December 2, 2002 www.rubbernews.

com

Technical
Effect of extreme conditions on polyurea coatings
By Jay A. Johnston and Primeaux first reported the effects of
Samantha Smith 2,4’-isomer MDI on spray polyurea coat-
Huntsman Polyurethanes Executive summary ings. Increasing the level of the 2,4’-iso-
The use of spray polyurea coatings in Spray polyurea elastomer systems are rapid curing coatings that can be ap- mer MDI extended the gel times of aro-
large commercial projects has continued plied over broad temperature and humidity ranges where other coating types matic polyurea systems and provided
to increase in volume and scale over the immediately fail. Due to the productivity gains of a rapid curing coating, improvements in the performance of the
past five years. The coatings’ fast cure polyurea coatings now are being used in more aggressive environments. These cured polyurea elastomers.1 Broekaert
rate, excellent physical properties and environments include higher temperatures and contact with reactive and non- and Pille-Wolf reported similar observa-
ability to be applied under adverse con- reactive liquids. Coating failures are possible if an inappropriate polyurea coat- tions upon investigation of the influence
ditions have led to the increased use of ing is selected for an application. Unfortunately, very little reference informa- of isocyanate isomer composition. An-
spray polyurea coatings in industrial ap- tion is available on the ability of polyurea coatings to resist temperature and other aspect of their paper reported the
plications. Large commercial and gov- solvents. This paper reports on the fuel resistance, chemical resistance, water influence of isocyanate functionality on
ernmental projects such as the San Ma- resistance and temperature resistance of polyurea coatings prepared with dif- gel time and performance of polyurea
teo Bridge, the Boston Tunnel, the ferent levels of urea groups in the backbone of the polymer. Prepolymers with spray systems.2 Their work examined
NCO contents from 9 to 20 percent were evaluated. The effects of hard block the performance of polyurea elastomers
TECHNICAL NOTEBOOK content on the standard physical properties and the resistance properties were after typical laboratory cure schedules.
Edited by Harold Herzlichh determined. Long-term cure schedules of systems
utilizing both high and low 2,4’-isomer
Dallas-Fort Worth Airport and the Pen- MDI products previously were examined
tagon have specified polyurea spray which gelled quickly, typically within 2 proved physical properties vs. the previ- by Perez and Johnston.3
elastomers as the preferred coating. The to 3 seconds. The fast gelation caused ous generation of polyurea technology. The use of hindered amines to slow the
unique performance and processing coating defects, lowered the coatings’ ad- The new commercial products contain reactivity of polyurea coatings also has
characteristics of spray polyurea coat- hesion to the substrate and caused pro- several levels of 2,4’-isomer MDI. The been reported. Secondary amines, such
ings have made it a technology that can cessing difficulties. Progress has been 2,4’-isomer MDI introduces sterically as Unilink 4200 amine and Clearlink
compete and win in applications once made on both the isocyanate chemistry hindered reaction sites into the prepoly- 1000 amine, have been shown to slow
exclusively held by more mature coating and the amine chemistry to slow the re- mer. The sterically hindered 2,4’-isomer the reactivity of polyurea coatings and
systems. activity of polyurea coatings. Huntsman MDI reduces the reactivity of the iso- caulks. Several groups have demonstrat-
Several recent accomplishments in Polyurethanes has introduced a series of cyanate with the amine. Varying the ed the use of secondary amines to slow
polyurea technology have increased the isocyanate terminated prepolymers that 2,4’-isomer MDI content of a prepolymer the reactivity of polyurea systems.4, 5, 6
versatility and simplified the application decrease the reactivity of polyurea sys- allows the systems reactivity to be opti- Spray polyurea coatings increasingly
of polyurea coatings. The first spray tems. The prepolymers also were devel- mized for each application. See Polyurea, page 14
polyurea systems produced coatings oped to provide elastomers with im-
Table II. Huntsman Polyurethanes isocyanate terminated prepolymers.
Table I. List of chemicals and suppliers.

Table III. Experimental polyurea spray formulations.

Table IV. Physical properties of polyurea coatings.

Fig. 1. Acetone resistance of polyurea coatings.

14 Rubber & Plastics News • December 2, 2002 www.rubbernews.com

Polyurea attached to the spray unit were set at

71°C with the system pressure set to
2,500 pounds per square inch (psi).
Primeaux and Anglin published back-
used in this study.
Polyurea coatings typically are de-
signed to be applied with 1:1 volume ra-
tio equipment. Equal volume spray
tent from 9 to 20 percent were sprayed
in Phase III of this study.

Phase I. Effects of Unilink 4200

Continued from page 12 ground information on the equipment equipment eases the application process amine on solvent resistance of
are being used in high technology appli- and spray parameters required for and helps ensure proper index. Due to polyurea coatings
cations under aggressive conditions. In- spraying polyurea coatings.11 the limitations imposed by the 1:1 ratio Many different B-side formulations
formation has been published sporadi- Elastomer samples were obtained by equipment, a limited NCO range of pre- can be sprayed with each prepolymer in
cally on the chemical resistance, solvent application of the polyurea spray coat- polymers gives consistently good results Table II. To limit the possible number
resistance and temperature resistance ings onto metal panels that were first when sprayed. Typical prepolymers for of B-side formulations, the effect of
of typical polyurea coatings. Baseline coated with a silicone release agent. Af- polyurea coatings have an NCO content Unilink 4200 amine on solvent resis-
solvent resistance information was pub- ter de-molding, tensile and tear speci- between 9 and 20 percent. Coatings pre- tance will be determined first. Deter-
lished on the original polyurea systems.7 mens were die cut from the elastomers. pared from an isocyanate with a 15 to 16 mining if Unilink 4200 amine has a pos-
Information on solvent permeability of The specimens were tested for their percent NCO content typically have a itive or negative effect on solvent
polyurea coatings was published later.8 physical properties after 30 days storage good combination of physical properties. resistance will influence what level of
Limited information on solvent resis- at normal laboratory conditions. Unilink 4200 amine will be required in
tance and temperature stability of new- Physical property determination of Results and discussion the subsequent experimentation. This
er polyurea coating systems was pre- the cured elastomer samples was per- will reduce the total number of experi-
sented recently.9 Data on the low formed using an Instron model number The objective of this study is to pre-
pare polyurea coatings and determine ments required for the remaining study.
temperature flexibility of polyurea coat- 4202, electro-mechanical test machine, B-side formulations
ings were published.10 with a crosshead speed of 20 inches per the physical property performance of the
The objective of this paper is to pre- minute. The standard test methods per- coatings after exposure to adverse condi- Rubinate 9009 MDI was sprayed with
pare a range of polyurea coatings and formed were as follows: tions. The physical property perfor- four B-side formulations. The B-side for-
determine the chemical resistance and mance of the coatings at high tempera- mulations are given in Table III. The
Tensile Strength ASTM D412-92 tures and the resistance of the coatings B-side formulations contained either
high temperature resistance of the coat- Tensile Strength* ASTM D638-94
ings. The standard physical properties three or four amine monomers. The Jef-
Percent Elongation ASTM D412-92
of coatings also will be determined. Tear Strength
Hardness
ASTM D624-91
ASTM D2240-95
Technical famine amines are amine terminated
polyether oligomers. Jeffamine D-2000
Experimental Taber Abrasion FIA #2, 302, 800 to select chemicals were determined.
amine is a difunctional amine with a
molecular weight of 2,000. Jeffamine T-
Materials and methods Flexural Modulus ASTM D790-92 The project was conducted in three 5000 amine is a trifunctional amine
All the equipment and chemicals uti- Impact Resistance ASTM D3763-93 phases. Phase I of the project studied with a molecular weight of 5,000.
lized in this study are commercially *Used where noted the effect of Unilink 4200 amine on sol- Ethacure 100 is a tradename for diethyl-
available. The reagents and the source Prepolymer formulations vent resistance. From the data collected, toluene diamine (DETDA). The DETDA
for the reagents are listed in Table I. All of the prepolymers used in this an optimized B-side formulation was se- is used to increase the hard block con-
Solvents, acids and bases were pur- study are described in Table II. The pre- lected. This B-side formulation will be tent of the final coating. Unilink 4200
chased from Fisher Scientific Interna- polymers have several similarities and a used in subsequent experiments. Phase amine is a difunctional secondary
tional Inc. and diluted with water to the few differences. Several of the differ- II of the project examined the spraying amine. Unilink 4200 amine is used
appropriate strength. ASTM oil (IRM ences are known to impact the process- of typical 15 to 16 percent NCO prepoly- widely in polyurea coatings formula-
903) and methyl tert-butyl ether ing, cure rate and physical properties of mers. The temperature and solvent re- tions to slow the cure rate of polyurea
(MTBE) were purchased from Penreco spray polyurea coatings. The largest im- sistances of these coatings were evaluat- coatings.
and Huntsman Performance Chemicals, pact on the cure rate and processing of ed fully. Phase III examined the effect of Two additives are used in each B-side
respectively. polyurea is the 2,4’-isomer MDI content hard block content on solvent resis- formulation. Titanium dioxide is added
Many experimental aromatic polyurea of the prepolymer. The effects of 2,4’-iso- tance. Prepolymers with an NCO con- See Polyurea, page 16
systems were prepared in this study. mer MDI on cure rate and processing of
The polyurea coatings were produced polyurea coatings were described in a pa-
with a Gusmer H-2035 proportioning per by Johnston and Perez.3 Prepolymers Table VI. Physical properties of polyurea coatings.
unit and a Gusmer GX-7 Series 400 with both a low 2,4’-isomer MDI content
spray gun. The block and hose heaters and a high 2,4’-isomer MDI content were

Fig. 2. ASTM oil resistance of polyurea coatings.

Fig. 4. Tensile strength of polyurea coatings vs. temperature.

Fig. 3. Ethylene glycol resistance of polyurea coatings.

Fig. 5. Maximum elongation of polyurea coatings vs. temperature.

Table V. Experimental polyurea spray formulations.

Fig. 6. Tensile strength of 150°C post cured polyurea coatings.

16 Rubber & Plastics News • December 2, 2002 www.rubbernews.com

Polyurea ing levels of Unilink 4200 amine. The

maximum elongation increases with in-
creasing amounts of Unilink 4200
amine.
cent NCO content prepolymers. Phase II
of this paper describes the chemical re-
sistance of six polyurea coatings. The
coatings were prepared from standard
dramatically different morphologies.
Coatings produced from the fastest re-
acting prepolymers had an “orange peel”
surface morphology. The coating pre-
Continued from page 14 Chemical resistance of polyurea coat- 15 to 16 percent NCO prepolymers. pared from Rubinate 9009 MDI, coating
to pigment the coating white. Silquest ings containing Unilink 4200 amine B-side formulations E, had the roughest “orange peel.” The
A-187 silane is added to the formulation The four coatings were immersed in An optimized B-side formulation, cho- Rubinate 9495 MDI-based coating had
as an adhesion promoter. Silquest A-187 three chemicals—acetone, ASTM oil and sen in Phase I for its solvent resistance, less of an “orange peel” surface than the
silane is a difunctional molecule with ethylene glycol—to test their chemical was used in this phase of the project. Rubinate 9009 MDI-based coating. The
two different reactive end groups. One resistance. The coatings were first cut Phase I of this project clearly demon- slower reacting prepolymers, like Rubi-
moiety on the molecule is an epoxy into “tensile bars” for ASTM D412 ten- strates that a B-side composed of DET- nate 9484 MDI and Rubinate 9520 MDI,
group and the other moiety is a trimeth- sile strength testing. The specimens DA and Jeffamine amines gives a sol- produced coatings with no visible areas
oxysilane group. then were immersed in the chemicals for vent-resistant polyurea coating. The of “orange peel.” The slowest reacting
Processing performance of the poly- one, three, seven and 21 days. After the formulations of the coatings are shown prepolymer, Rubinate 9483 MDI, pro-
urea coatings required immersion time, the coatings in Table V. duced the smoothest coating with the
The Rubinate 9009 MDI prepolymer were removed from the liquid. The ten- Processing performance highest gloss.
was sprayed with four B-side formula- sile strengths and maximum elonga- Six commercial prepolymers were Standard physical properties of the
tions to prepare four polyurea coatings. tions of the coatings were determined. sprayed with the B-side formulations to coatings
The gel and tack free times of the four The tensile strengths of the coatings prepare six polyurea coatings. The gel The standard physical properties of
coatings are entered into Table IV. No- immersed in acetone, ASTM oil and eth- and tack free times of the coatings are the six coatings were determined and
table differences were found in the gel ylene glycol are shown in Figs. 1, 2 and entered into Table VI. Notable differ- entered into Table VI. The coating pre-
and tack free times of the four coatings. 3, respectively. The coatings immersed ences were found in the gel and tack free pared from Rubinate 9484 MDI, coating
The fastest reacting coating, coating A, in acetone had a large reduction in ten- times of the six coatings. The fastest re- H, had the best overall physical proper-
was made from the B-side containing no acting coating, coating E, was made ties. This coating had the highest tensile
Unilink 4200 amine. The gel and tack
free times of the coating increased as Technical from Rubinate 9009 MDI. The second
fastest gel time was recorded when Ru-
strength, tear resistance and modulus
value measured in this study. Coatings
prepared from Rubinate 9480 MDI had
the level of Unilink 4200 amine in- binate 9495 MDI was used as the pre-
creased in the B-side formulation. sile strength after one day. Acetone low- polymer. The Rubinate 9483 MDI-based the second best overall physical proper-
The level of Unilink 4200 amine in the ered the physical properties of the coat- coating, coating I, had the longest gel ties.
formulations impacted the surface mor- ing more than the other chemicals and tack free times. The remaining coat- The maximum elongation of a coating
phology of the coatings. Coating A, con- tested. Acetone had the greatest effect ings had similar gel and tack free times. was dependent on the functionality of
taining no Unilink 4200 amine, had an on the all Unilink 4200 amine coating, Gel times of 4 seconds were recorded for the prepolymer. As expected, coatings
“orange peel” surface morphology. Addi- coating D. ASTM oil had the smallest ef- the Rubinate 9480 MDI-, the Rubinate prepared from difunctional isocyanates
tion of a small amount of Unilink 4200 fect on coating properties. Tensile 9484 MDI-, and the Suprasec 9520 MDI- had the greatest maximum elongations.
amine, coating B, improved the surface strengths of the elastomers changed lit- based coatings. The gel times of the The coatings prepared from the higher
morphology. The coatings with the tle on exposure to ASTM oil. Ethylene coatings roughly can be correlated to the functionality prepolymers, Rubinate
largest amounts of Unilink 4200 amine, glycol had a negative effect on the physi- 2,4’-isomer MDI content of the prepoly- 9009 MDI and the Rubinate 9495 MDI,
coatings C and D, had a smooth surface. cal properties of some of the formula- mer. The fastest gelling coating had the had lower elongations.
Physical properties of the polyurea tions. The coatings containing Unilink lowest 2,4’-isomer MDI content. The The abrasion resistances of the six
coatings 4200 amine, coatings B, C and D, were slowest gelling coating had the highest coatings were measured and entered
The standard physical properties of affected negatively by ethylene glycol. 2,4’-isomer MDI content. into Table VI. All six coatings were
the four coatings were determined and The coating without Unilink 4200 The morphologies of the six coatings found to have excellent abrasion resis-
entered into Table IV. The data indi- amine, coating A, did not lose tensile were dependent on the gel rate of the tance. The abrasion resistance was mea-
cate that tensile strength and tear resis- strength when exposed to ethylene gly- coatings. While the difference in gel sured using a very abrasive H-18 wheel.
tance decrease with increasing levels of col. Coating A, without Unilink 4200 time between the fastest and slowest The weight lost after 1,000 cycles is re-
Unilink 4200 amine. The maximum amine, performed the best in all three coatings is only a few seconds, the differ- ported in the table.
elongations of the four coatings were chemicals. ence in gel times produce coatings with See Polyurea, page 18
similar.
The four coatings were then subjected Phase II. Typical polyurea coat- Fig. 10. Maximum elongation of polyurea coatings aged in 49°C water.
to a 90°C heating cycle for eight hours. ings prepared from 15 to 16 percent
The physical properties of the samples NCO prepolymers
were determined and entered into The primary objective of this paper is
Table IV. As previously determined in to examine the solvent resistance of
the unheated samples, tensile strength polyurea coatings. Typical polyurea
and tear resistance decline with increas- coatings are prepared from 15 to 16 per-
Fig. 7. Maximum elongation of 150°C aged polyurea coatings.

Fig. 11. ASTM oil resistance of polyurea coatings.

Fig. 8. Tensile strength of 125°C aged polyurea coatings.

Fig. 12. Fuel #3 resistance of polyurea coatings.

Fig. 9. Tensile strength of polyurea coatings aged in 49°C water.

18 Rubber & Plastics News • December 2, 2002 www.rubbernews.com

Polyurea sults are entered into Fig. 5.

Maximum use temperature studies of
polyurea coatings
Polyurea coatings not only are ex-
binate 9480 MDI-based coating lost 23
percent of its original tensile strength.
The Rubinate 9480 MDI- and the Ru-
binate 9009 MDI-based coatings heat
ings was determined by immersing the
coatings in ASTM fuel number 3. The
results are plotted in Fig. 12. The coat-
ings absorbed between 60 and 70 per-
Continued from page 16 posed to elevated temperature for a aged at 125°C maintained their maxi- cent of their weight in fuel. The fuel re-
Properties of polyurea coatings vs. short duration, but they also are ex- mum elongation properties over eight sistance of the coatings was identical.
temperature posed to continuous elevated operating weeks. While weight gain data are valuable
Polyurea coatings sometimes are used temperatures. A study was conducted to Water resistance of polyurea coatings tools for evaluating chemical resistance,
in applications at elevated tempera- determine the effects of long-term, high- Polyurea coatings often are used as the real goal is to understand how phys-
tures. The coatings must maintain their temperature exposure on polyurea coat- primary containment for process water ical properties of the coating are impact-
physical properties and protect the sub- ings. Four sets of coatings were placed at chemical plants. The coatings should ed when chemicals contact a contain-
strate at these elevated temperatures. in ovens at four different temperatures. not lose physical properties on immer- ment coating. To determine how coating
Several experiments were conducted to The ovens were set at 200, 175, 150 and sion in water. The water resistances of properties are affected by chemicals, the
determine the tensile strengths and 125°C. The samples placed in the 175 the Rubinate 9480 MDI- and Rubinate Rubinate 9480 MDI-based coating was
maximum elongations of polyurea coat- and 200°C ovens became brittle and 9495 MDI-based coatings were deter- cut into “tensile bars.” The tensile bars
ings at elevated temperatures. The shrank in size. The samples cured for mined by immersing the coatings in wa- were immersed in several different
physical properties of two coatings were one week at 175 and 200°C were too ter for eight weeks. The physical proper- chemicals. The chemicals were ASTM
determined. The two coatings were the brittle for further testing. ties of the coatings were periodically oil, MTBE, ethylene glycol, acetone, sul-
Rubinate 9009 MDI-based coating and The tensile strengths of the coatings tested. The results are entered into furic acid, hydrochloric acid, nitric acid
the Rubinate 9480 MDI-based coating, placed in the 150°C oven were tested pe- Figs. 9 and 10. Tensile strength and and a sodium hydroxide solution. The
coatings E and G, respectively. The riodically over four weeks. The results maximum elongation improved over the tensile strengths of the coatings were
specimens were allowed to equilibrate at are entered into Fig. 6. The Rubinate eight-week test period. measured after one, three, seven, and 21
the test temperature before they were 9009 MDI-based coating outperformed Chemical resistance of polyurea coat- days immersion. The tensile strength
pulled. the Rubinate 9480 MDI-based coating. ings results are entered into Fig. 13. All of
The tensile strengths of coatings E After four weeks at 150°C, the Rubinate One of the primary uses of polyurea the chemicals had an effect on the coat-
and G were determined at a series of el- 9009-based MDI coating had lost 30 per- coatings is in secondary containment ings after one day. The ASTM oil had
cent of its tensile strength. The Rubi- coatings in chemical storage facilities. the smallest initial effect on the tensile

Technical nate 9480 MDI-based coating lost 61

percent of its tensile strength.
The maximum elongations of the coat-
The ability to apply a fast-curing coating
with good solvent resistance is of prima-
ry importance. Polyurea coatings most
strength of the coating. Acetone had the
greatest effect on the tensile strength of
the coatings. After one day, the coating
evated temperatures. The data were ings heat aged at 150°C over four weeks often are used for secondary contain- properties leveled off or increased
plotted in Fig. 4. Both coatings main- are entered into Fig. 7. The maximum ment of chemicals as opposed to primary slightly. It appears that the coating ab-
tained good tensile strength up to 65°C. elongations of both coatings gradually containment. Secondary containment sorbs an equilibrium level of solvent or
At higher temperatures, the Rubinate decreased over the four-week period. applications require that the coating chemical. Once equilibrium is estab-
9009 MDI-based coating had higher ten- The tensile strengths of the Rubinate “contain” a chemical for a defined period lished the tensile strength of a coating is
sile strength than the Rubinate 9480 9009 MDI- and Rubinate 9480 MDI- of time. relatively constant.
MDI-based coating. based coatings aged at 125°C were de- In the previously reported testing, oils The physical property results of poly-
The maximum elongation of the Rubi- termined periodically over eight weeks. had little effect on polyurea coatings.7 To urea coatings in the acid and base solu-
nate 9009 MDI-based coating and the The losses in tensile strength of the determine the effects of oil on polyurea tions are recorded in Fig. 14. Weak
Rubinate 9480 MDI-based coating vs. coatings were reduced vs. the coatings coating, five different polyurea coatings acids and bases did not have a large ef-
temperature also were measured. Up to held at 150°C. Once again the Rubinate were immersed in an ASTM reference fect on the strength of the coatings.
121°C, the Rubinate 9480 MDI-based 9009 MDI-based coating had better tem- oil. The percent weight gain of each Strong acids and acids at a high concen-
coating has higher elongation properties perature stability. Both coatings showed coating over time was measured. The tration negatively impacted the tensile
than the Rubinate 9009 MDI-based no loss in tensile strength until the percent weight gain data are entered strength of the polyurea coatings. Nitric
coating. The Rubinate 9009 MDI-based eighth week of the test. The Rubinate into Fig. 11. The Rubinate 9009 MDI-, acid completely decomposed the elas-
coating maintained its maximum elon- 9009 MDI-based coating lost 8 percent Rubinate 9483 MDI- and Rubinate 9495 tomers in two days.
gation properties up to 177°C. The re- of its original tensile strength. The Ru- MDI-based coatings had the best oil re-
sistance. These coatings absorbed less Phase III. Effect of hard block
Fig. 13. Solvent resistance of polyurea coatings made with Rubinate 9480 MDI. than 10 percent oil over a 3,000-hour content on solvent resistance of
time period. polyurea coatings
The fuel resistance of polyurea coat- See Polyurea, page 19

Table VIII. Physical properties of polyurea coatings.

Fig. 14. Acid and base resistance of polyurea coatings made with Rubinate 9480
MDI.

Fig. 15. Acetone resistance of polyurea coatings.

Table VII. Experimental polyurea spray formulations.

Fig. 16. Sulfuric acid resistance of polyurea coatings.

www.rubbernews.com Rubber & Plastics News • December 2, 2002 19

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Polyurea prepolymers gave coatings with the fast application time, fast return to ser- 2,4’-MDI,” presented at Polyurethanes Conference
greatest amount of “orange peel.” vice time, insensitivity to moisture and 2000, Oct. 8-11, 2000.
4. Perez, A., Hillman, K.M., House, D.W., Scott Jr.,
Standard physical properties barrier properties are the major reasons R.V., Ilijevski, D., “Secondary Aliphatic Diamine
The standard physical properties of for the application of polyurea coatings Chain Extenders in Aliphatic Polyurea Spray Appli-
Continued from page 18 the coatings were determined and en- on concrete. This research clearly cations,” UTECH 2000 conference paper, The
The effects of hard block content on tered into Table VIII. demonstrates that some solvents and Hague, Netherlands.
5. House, D.W., Scott Jr., R.V., Wetherall, J., “The
solvent resistance were examined in a Chemical resistance some chemicals negatively affect the Versatility of UOP Unilink and Clearlink Diamines
series of polyurea coatings. The hard The chemical resistances of the five physical properties of polyurea coatings. in Polyurethane and Polyurea Systems,” UOP
block contents of the coatings were ad- coatings were determined in three Care must be taken in selecting a suit- L.L.C. technical publication.
justed by spraying prepolymers with chemicals. These chemicals were select- able polyurea coating for a particular 6. Primeaux II, D.J., “Spray Polyurea Elastomers
Offer Performance Advantages,” Modern Paint and
NCO contents from 9 to 20 percent. ed because of their aggressive tendency application. These results were not un- Coatings, June 1991.
B-side formulations to attack polyurea coatings. The chemi- expected. Polyurea coatings are used 7. Texaco bulletin on Polyurea Solvent Resistance.
Each prepolymer in Phase III re- cals were acetone, sulfuric acid and ni- most often in secondary containment ap- 8. Darden, W., Loomis, R., Roehm, F.T., “Spray
quired a different B-side formulation. tric acid. The results are entered into plications, not primary containment ap- Polyurea Coatings for Primary and Secondary Con-
tainment,” presented at the Geosynthetics ’97 Con-
The B-side formulations were adjusted Figs. 15, 16 and 17. plications. Secondary containment ap- ference, March 11, 1997.
to compensate for each prepolymer’s The polyurea coatings were attacked plications require that a coating resist a 9. Smith, S., Johnston, J.A. “Chemical and Tempera-
NCO content. The B-side formulations rapidly by acetone. The softer coatings chemical for a predetermined period of ture Resistance of Standard Aromatic Polyurea Elas-
are described in Table VII. Due to the had low tensile strength before and after time. tomer Coatings,” presented at Fourth Pan-American
Coatings Expo, Mexico City, July 17-19, 2002.
fast gel time of the highest NCO content exposure to acetone. The coatings pre- Only a small percentage of all the 10. Primeaux II, D.J., “Study of Polyurea Spray
prepolymer, Unilink 4200 amine was pared from Rubinate 9480 MDI had the commercial polyurea coatings are used Elastomer Systems,” High Solids Coatings, Volume
added to the formulation. in above ambient temperature applica- 15, 1994.
Prepolymers
Prepolymers with a wide range of
NCO contents were sprayed in this
Technical tions. Specification of polyurea coatings
in higher temperature applications is
difficult without background informa-
11. Primeaux II, D.J., Anglin, K.C., “The Processing
of Spray Polyurea Elastomer Systems,” Polyure-
thanes 92, proceedings of the SPI 34th Annual
Technical/Marketing Conference, 1992.
phase of the paper. The lowest NCO con- best initial resistance to acetone. In- tion on the heat resistance of polyurea
tent prepolymer had a high viscosity. creasing the hard block content of the coatings. This research demonstrates Rubinate and Suprasec are registered
High viscosity resins are difficult to coating further did not improve the ace- that polyurea coatings maintain their trademarks of Huntsman International
spray. Rubinate 9524 MDI, was diluted tone resistance of the coating. physical properties at 150°C for several L.L.C. in one or more, but not all coun-
with Jeffsol PC to reduce the viscosity of The acid resistance of the coating was weeks. The coatings maintained their tries.
the prepolymer. tested in 25-percent sulfuric acid and physical properties at higher tempera- Jeffamine, Jeffsol and Tioxide are reg-
Processing performance 25-percent nitric acid. The softer coat- tures for only a short period of time. istered trademarks of Huntsman Corp.
The five prepolymers were sprayed ings had poor acid resistance in both With this information now available, or an affiliate thereof in one or more, but
with the five B-side formulations in sulfuric and nitric acid. The 16-percent polyurea coatings now can be specified not all countries.
Table VII. The gel and tack free times NCO prepolymers gave coatings with into higher temperature applications. Clearlink is a registered trademark of
decreased as the NCO content of the the best sulfuric acid resistance. The UOP L.L.C.
prepolymer increased. The data are pre- coatings made from Rubinate 9009 MDI References Ethacure is a registered trademark of
sented in Table VIII. The highest NCO and Suprasec 9549 MDI displayed the 1. Primeaux II, D.J, “Polyurea Spray Technology in
Albemarle Corp.
content prepolymers produced rapid best nitric acid resistances. Commercial Applications,” presented at 60 Years of Silquest is a registered trademark of
curing coatings. Low NCO content pre- Polyurethanes: International Symposium and Exhi- Crompton OSI Specialties.
bition, 1998. Unilink is a registered trademark of
polymers produced slow curing coatings. Conclusions 2. Broekaert, M., Pille-Wolf, W., “The Influence of
UOP.
The morphologies of the coatings also Isomer Composition and Functionality on the Final
were dependent on the NCO contents of Commercial projects utilizing poly- Properties of Aromatic Polyurea Spray Coatings,”
the prepolymers. The low NCO prepoly- urea coatings’ unique application speed UTECH 2000 conference paper, The Hague, Nether- Presented at a meeting of the Alliance
lands.
mers gave very smooth surfaces. No “or- and physical properties continue to in- 3. Perez Jr., A., Reddinger, J., Johnston, J.A., “Per-
for the Polyurethanes Industry, held Oct.
ange peel” was detected on the surface crease in terms of scale and complexity. formance and Processing Enhancements of Aromat- 13-16 in Salt Lake City, where it was
of the coatings. As the NCO content in- Protective coatings on concrete continue ic Polyurea Elastomer Systems Prepared form High honored with a best paper award.
creased, the surface morphologies be- to be the major application area for
came worse. The highest NCO content polyurea coatings. Polyurea coatings’
The authors
Fig. 17. Nitric acid resistance of polyurea coatings. Jay A. Johnston graduated with a doctorate in polymer chemistry from the Univer-
sity of Akron in 1991. He is a technical associate in the Adhesives, Coatings and Elas-
tomers Group at Huntsman Polyurethanes in Auburn Hills, Mich.
Johnston joined ICI Polyurethanes (now Huntsman Polyurethanes) in 1994. Previ-
ously, he completed postdoctoral fellowships at General Electric Co.’s corporate re-
search and development center and at the University of Akron’s Institute of Polymer
Science. Johnston currently is responsible for development of isocyanates and pre-
polymers for the ACE markets in North and South America.
Samantha A. Smith received her bachelor’s degree in chemical engineering from
Wayne State University in Detroit in 1999. She began working for Huntsman
Polyurethanes in November 1999 in the Automotive Group. In June 2000, Smith
transferred to the ACE group where she works on the development of isocyanates and
prepolymers.