PHENALKAMINE

Multipurpose Epoxy Resin Curing Agents

Zhisheng Dal*, Anton Constantinescu, Adarsh Dalal and Chris Ford
CARDOLITE CORPORATION
500 Doremus Avenue
Newark, New Jersey 07105
Phone: (201) 344-5015
Fax: (201) 344- 1197

henalkamines synthesized from cashew nutshell

liquid (CNSL) combine the properties of the aliphatic
amines (rapid cure, good chemical resistance) with
properties that are characteristic of polyamides (low toxicity, good flexibility, good chemical resistance). Additionally they have outstanding curing properties at low temperatures. Because of these characteristics, phenalkamines are
being widely used in marine, industrial maintenance and
civil engineering applications. The results obtained with
phenalkamine resins demonstrate the following properties:
low temperature cure (as low as 35F), non critical mixing
ratios, excellent water resistance, good flexibility, good
compatibility with different types of epoxy resins, good
adhesion to poorly prepared surfaces and a wide range of
other interesting characteristics deriving from their structure. The great diversity of these curing agents makes them
suitable for almost all epoxy applications.

Introduction:
The most valuable single property of the epoxy resins
is their ability to undergo a quick transformation from the
liquid (or thermoplastic) state to hard thermoset solids at
different temperatures. This conversion occurs without the
formation of by-products and is accomplished by the addition of a chemically active compound known as a curing
agent.
The most common types of epoxy curing agents are:
Amines and amine derivatives: There is a large variety in
the curing rate and hardness of the resulting resins, when
amines are used. Their ratios vary from very low, i.e. 4-10
parts curing agent/100 parts of epoxy compound to very
high i.e. 75-100 parts curing agent/l00 parts epoxy compound.
Acid anhydrides: These curing agents usually have a very
low viscosity. They are used whenever good heat resistance
properties are required. They give the best thermal aging
properties of any of the epoxy curing agents. They require
high temperature and long curing time.
Catalytic curing agents: These compounds promote epoxy
to epoxy or hydroxyl to epoxy reactions and do not serve
as direct crosslinking agents. Tertiary amines. amine salts,
boron tritluoride complexes and amine boraiees belong to
this class. The cured resins thus obtained are very rigid
and hard.
,

Polyamides: The most widely used polyamides are the condensation products of dimerized fatty acids with difunctional amines. Since the polyamides are relatively high
molecular polymers, the ratio between polyamides and
epoxy resins is less critical than in the case of low molecular amines. They can be considered resin modifiers as well
as curing agents. They have a long pot life and an outstanding adhesion, but their viscosity is high, they do not cure
very well when temperature is below 1OC and some
polyamides are incompatible with the usual epoxy resins.
Adducts obtained from aliphatic amines and epoxies
have been tested as substitutes to polyamides and amines.
Curing agents obtained from Mannich bases, in the
reaction between amines (primary and secondary), formaldehyde and phenols have some major advantages, such as:
low temperature cure, even in the range from 0 to YC,
good chemical resistance and moderate color stability. They
also have a good surface appearance, good moisture
tolerance and non blushing properties. But these classical
Mannich bases also have a short pot life, lack of flexibility
(rigidity), and unsatisfactory water and sea water
resistance.
The first phenalkamines were aimed to satisfy the
need to have a longer pot life, better flexibility and an improved water resistance. They were developed by Cardolite
Corporation (formerly part of 3M Company) in the mid
70s, and represent the first generation of phenalkamines,
with high viscosity and dark color curing agents. In the
last few years a new step has been taken, aimed at obtaining lower viscosity, lighter color phenalkamines for high
performance in lower VOC epoxy systems.
Phenalkamines are obtained from cardanol. a major
component of Cashew Nut Shell Liquid (CNSL). The structure of cardanol is presented below:
OH

Phenalkamines contain aliphatic polyaminic substituents

attached to the aromatic ring. Their unique structure can
explain the fact that they have an unusual combination of
desirable properties, which can be identified in the resulting cured resins.

Reprinted from SPI-ERF Conference, September 1994

The aromatic backbone is responsible for the high

chemical resistance that can be seen in these compounds:
the side chain is very hydrophobic, and can make these
resins water resistant; the phenolic OH group makes
phrnalkamines very active even at low temperatures. the
aminic side is responsible for the high crosslinking density
and whenever the molecular weight is not too high. these
curing agents can have a low viscosity (for low VOC purposes). Other properties have allowed us to obtain light
color (6-8 Gardner), combined with a low viscosity and
high chemical activity.

0.5 set

3500

Properties, Results and Discussion:

1. Qpical properties of phenalkamines:
Table 1: Typical Properties of Phenalkamines
I ProDerties

NC541

NC541 LV

NX4641 1
20

90

160

230

300

TEMP C (Heating)

0.5 sac

Flash point F
PHR of epoxy
EEW= 190

145

180

210

55-70

65-80

65-80

Gel time, 509

45

40

30

3500>

2. Compatibility with the epoxy resins:

The compatibilitys were measured by analyzing the
clarity of the cured 8 mil thin film containing epoxy resin
and phenalkamine.

-750

Table 2: The Compatibility of

Phenalkamines with Epoxies
Systems
Liquid Bis A
Solid Bis A
La. Novolac

NC541
clear
clear
clear

NC5411V NX4641 Polyamide Cycloalphatic

clear
clear
clear
hazy
clear
clear
ctear
hw
clear
clear
hazv
clear

We can see that phenalkamines have very good compatibilities with the mentioned epoxy resins, which is very
important for the appearance and properties of the cured
systems.

20

90

160
TEMP C (Heating)

230

300

Figure 1. Qpical DSC Diagram of Liquid Bis A Epoxy

(EEW =190) Cured with NC541LV Cure at
75F and 40F.

3. Temperature Insensitive Cure:

Phenalkamines have phenolic hydroxyl groups that
provide the acid catalyst that facilitates the opening of the
epoxy ring at low temperatures. The long side chain will
reduce the mobility of the curing agent and thus increase
the pot life. In order to measure the degree of cure at different temperatures for phenalkamines mixed with liquid
epoxy resins at theoretical ratios, we have used DSC to
measure the reaction heat that is generated by the epoxidic
ring opening reaction.

From the peak pattern and area of figure 1, we find

that the phenalkamines curing patterns are not affected by
the temperature. The curing reaction is almost completed
after 24 hours without being affected too much by temperature. The second peak of the curing reaction in (a) and (b)
has not been affected by either curing temperature nor curing time. This figure shows that phenalkamine curing
agents give temperature insensitive cure. We can use them
both during the summer time and winter time without
changing the package system. The percentage of cured
resin was calculated according to the area of the corresponding reaction heat. All the other phenalkamines have
similar characteristics and have been analyzed in the
same manner. Figure 2 shows the percentage of cure of
phenalkamines at a given temperature.

sea water resistance. the less chance the resin binder will
have to be broken. The product will have a better adhesion,
a better protection to corrosion and a better capacity to be
linked to the substrate. Figure 3 also shows the water and
sea water resistance of other systems such as polyamides,
cycloaliphatics, and other Mannich bases. All the tested
samples were prepared at room temperature for 1 week and
then immersed at both 25C and 65C for 3 weeks. Finally
the weight changes have been monitored.
0

12

4
5
6
Days of curing

9
% of weight changes
2.25

Theoretical mixing ratios

. NC541

+ NC541LV

2
1.75

NX4641

1.5
1.25
1

Figure 2. Curing Rate of Phenalkamines with Liquid

Bis A epoxy resin at 40F

0.75

Because of the difference in molecular weight and reactivity, these three phenalkamines show some differences in
the degree of cure at the given temperature, but the curing
pattern is the same.
Table 3 shows the through cure time at 5C on 8 mil
thick films of 3 phenalkamines with a liquid epoxy system.

0.5
0.25

I NC541

m NC541 LV

m NX4641

Table 3. Low Temperature Cure Ability

of Phenalkamines
NC541 LV
I Svstems
NC541
NX4641 1

KUI Polyamid

a Cycloaliphatic

0 Mannich base

8 mil clear

film through
cure at 5C

12 hrs

18 hrs

24

hrs

*through cure time is obtained by dry time recorder.

4. Physical properties:
All the phenalkamines have the C,s long linear side
chain that provides flexibility to the whole crosslinked network. The physical properties of phenalkamines are shown
in table 4.
Table 4. Phvsical Prooerties of Phenalkamines
I Svstem

NC541 NC541LV NX4641 1

25 C

65 C
Immersion temperatures

Combined with liquid Bis A epoxy

Rgure 3. Water Resistance of Phenalkamines

The results show that the higher the viscosity of the

phenalkamines, the better the water resistance.

6. Surface tolerance:
Phenalkamines have a very good adhesion on wet or
poorly prepared surfaces, even on water saturated concrete.
Because of the high hydrophobic of the side chain the surface resin bond is not influenced by the presence of water
and thus the obtained adhesion is very good. The results
obtained according to the ASTM 4541-89 method are
shown in table number 5.
Table 5. Adhesion of Phenalkamine Cured Systems
on Water Saturated Concrete

I
All the samples were mixtures of phenalkamines with
liquid Bis A epoxy resin (EEW = 190) at theoretical mixing
ratio and cured at room temperature for one week before
being tested. From the results, we can conclude that the
crosslinking density of the cured resin systems does not
affect the physical properties considerably. It is highly
probable that the C,5 long side chain provides flexibility to
the crosslinked network.

5. Water resistance
The long linear side chain of phenalkamjnes provides
the resins with a high hydrophobicity which reduces the
effect of phenolic hydroxyl on the water sensitivity. The
following table shows the phenalkamines ojater and sea
water resistance. These are key properties for coatings and
adhesives in the sealant industry. The higher the water and

Reference Reference
System NC541
Load
156

NC541LV

NX4641

162

81

1
62

I
I

100

(Psi)

Conclusions
The phenalkamines constitute a new class of low
temperature curing agents. Their unique chemistry creates
a new route of improving a system by chemical modification of its structure. The advantages that result from
these chemical changes have important applications in
many branches of the industrial maintenance and maritime
industries.