US 2016.

0075805A1
(19) United States
(12) Patent Application Publication (10) Pub. No.: US 2016/0075805 A1
Pinto et al. (43) Pub. Date: Mar. 17, 2016

(54) CNSL-BASED HYDROCARBON RESINS, (52) U.S. Cl.

PREPARATION AND USES THEREOF CPC .................................... C08F 216/10 (2013.01)
(71) Applicant: Cardolite Corporation, Newark, NJ
(US) (57) ABSTRACT
(72) Inventors: Mauricio Pinto, North Brunswick, NJ
(US); Hong Xu, Montgomery, NJ (US); -
Anbazhagan Natesh, North Wales, PA The present invention is directed to resins made from cashew
(US); Junhong Wei, Zhuhai (CN) nutshell liquid and vinyl hydrocarbons and processes for
manufacturing the resins. These resins exhibit lower viscosity
(21) Appl. No.: 14/951,597 than the phenol-based homologs. They also exhibit good
compatibility with a wide range of solvents, mineral and
(22) Filed: Nov. 25, 2015 natural oils, epoxy curing agents, liquid epoxy resins, and
O O polymers, which make them suitable additives as non-reac
Related U.S. Application Data tive diluents for solvent-free coating formulations; tackifiers
(63) Continuation of application No. 14/509,473, filed on for structural adhesive, pressure sensitive and hot-melt adhe
Oct. 8, 2014, now Pat. No. 9,228,040. sives; stabilizers for lubricants, fuel and polymer formula
(60) Provisional application No. 61/888.209, filed on Oct. tioins; plasticizers for thermoplastic polymers and processing
8, 2013. aid for rubber compounding and stabilizers for respective
s rubber artifacts. These resins are also valuable precursors for
Publication Classification the manufacture of epoxy resins and polyols for coating,
adhesive and composite omulations exhibiting ameliorated
(51) Int. Cl. performance in water repellency, anti-corrosion, and fast
CSF26/It (2006.01) hardness development during cure.

OH H2CS
p-toluenesulfonic acid
-bes

100-20°C, 3 hours

cardanol Hydrocarbon
OOC

CNSL-Hydrocarbon
resin Hydrocahon vinyl
dimers

n = 1, 2 or 3
R = H, Styrene
or R = -CH, alpha-methylstyrene
Patent Application Publication Mar. 17, 2016 Sheet 1 of 4 US 2016/0075805 A1

F.G. 1

C1534-2,
Patent Application Publication Mar. 17, 2016 Sheet 2 of 4 US 2016/0075805 A1

F.G. 2

OH H2Os-R
-- in p-toluenesulfonic acid
---------------------------------------------

1. Cishiz7 100-120°C, 3 hours

cardanol Hydrocarbon
OOC

O
-- CH
} NS --
:
-2
R C15H27

CNSL-Hydrocarbon
resin Hydrocabon vinyl
dimers

n = 1, 2 or 3
R = H, Styrene
or R = -CH3, alpha-methylstyrene
Patent Application Publication Mar. 17, 2016 Sheet 3 of 4 US 2016/0075805 A1

x 8. Phenol-hydrocarbon
x CNS. Hydrocarbon
Resin (Example 3)

O 5 1O 15 20 25 30
Diluent as Percent of Epon 828
Patent Application Publication Mar. 17, 2016 Sheet 4 of 4 US 2016/0075805 A1

FIG. 4

F.G. S
US 2016/0075805 A1 Mar. 17, 2016

CNSL-BASED HYDROCARBON RESINS, be more difficult to stabilize the process and minimize the
PREPARATION AND USES THEREOF variability between batches as the number of steps and raw
materials are increased.
RELATED APPLICATIONS 0005 Cashew nutshell liquid (CNSL) contains a large
0001. This application claims priority under 35 U.S.C. concentration of cardanol and cardols, a natural source of
S120 to U.S. application Ser. No. 14/509,473 filed on Oct. 8, meta-substituted alkylated phenols and resorcinols. CNSL is
2014, which claims priority to U.S. Provisional Patent Appli relatively low cost, and it is a globally available bio-renew
cation No. 61/888,209 filed on Oct. 8, 2013, the contents of able commodity, which makes it an ideal building block for
each of which are incorporated herein by reference in their the manufacturing of phenol-modified hydrocarbons resins.
entirety. Due to the structure of the components of CNSL, the hydro
carbon resins can be manufactured with fewer steps and/or
FIELD OF THE INVENTION raw materials.
0006 Among the advantages of cardanol-based hydrocar
0002 The invention generally relates to resins made from bon resins are low viscosity, improved solubility with organic
cashew nutshell liquid and vinyl hydrocarbons, and processes Solvents, very low cloud points, and compatibility with a
for manufacturing the resins. great number of resins and polymer formulations.
BACKGROUND OF THE INVENTION SUMMARY OF THE INVENTION
0003 Phenol-modified hydrocarbon resins are widely 0007. The present disclosure relates to resin compositions
used in coatings and adhesive formulations, and also widely comprising cardanols obtained from Cashew Nut Shell Liq
used in the manufacturing of rubber products. These resins uid (CNSL) and processes for making the resins. In one
improve the compatibility of the ingredients in Such formu embodiment, the resins may be comprised of vinylated car
lations. In addition, the resins provide improved chemical and danols and vinylated cardols, wherein the cardanols and car
weathering resistance to finished products designed to per dols are obtained from CNSL, as well as hydrocarbon cyclic
form under harsh environmental conditions, such as wide dimers. The resin may include one or more additional poly
variation oftemperature, oxidation by air, and light exposure. CS.
Other advantages include the substantial improvement of the 0008. The resin may be manufactured by combining in a
adhesive properties in coating and adhesive formulations. reactor vessel a quantity of CNSL, an acid catalyst, and a
0004 Phenol-modified hydrocarbon resins encompass a vinyl monomer, and maintaining the reactor vessel at a pre
wide range of products produced by the reaction between determined temperature for a predetermined period of time to
phenols and vinyl aliphatic and aromatic monomers. In gen achieve the desired degree of polymerization. As one skilled
eral, the composition of these resins is quite complex, which in the art will recognize, the proportions of the components to
can be simply characterized by a mixture of monomeric and be used, the temperature and the time may be adjusted as
polymeric components bearing distinct chemical functional desired to achieve a desired degree of polymerization of the
ities. For instance, the reaction of unsubstituted phenol with components.
vinyl hydrocarbon monomers, such as styrene, alpha-meth 0009. The resins may be used in coatings, as tackifiers, and
ylstyrene, vinyltoluene, indene, coumarone, or any other for numerous other products that may use or include hydro
similar vinyl monomers, or a mixture thereof, catalyzed by carbon resins.
strong acids, produces liquid to wax-like resins containing DESCRIPTION OF THE FIGURES
variable amounts of short polymers of vinyl monomers, in
addition to the alkylated phenol components. The polymer 0010 For a better understanding of the present invention,
fraction is mostly composed of cyclic dimers and trimers of reference is made to the following detailed description of an
the vinyl monomers, with Small amounts of respective linear exemplary embodiment considered in conjunction with the
oligomers. The alkylated phenol fraction is also multicompo accompanying drawings.
nent, as it contains variable amounts of monosubstituted, 0011 FIG. 1 shows an exemplary cardanol molecule.
disubstituted, and trisubstituted phenolic compounds. The 0012 FIG. 2 illustrates generally the reaction mechanism
compositions of these resins can be controlled by careful for one embodiment of the disclosure.
adjustments of the reaction conditions. However, the most 0013 FIG. 3 shows the effect of different concentrations
significant factor to control the desired physico-chemical of a commercial phenol-hydrocarbon resin and CNSL hydro
properties is the judicial selection of structural variations on carbon resin on the Viscosity of a liquid epoxy.
the phenol and on the vinyl hydrocarbon monomer building 0014 FIG. 4 shows the results of a cross-hatch adhesion
blocks. Mixtures of phenols and/or vinyl monomers are very test on rusted S-36 panels treated with a pigmented white
often employed to achieve the right balance of polarity, Solu epoxy base formulation comprising CNSL hydrocarbon
bility, and fluidity, which is intimately related to the hydroxyl resin.
functionality, the content of aromatic, hydrophobic moieties, (0015 FIG. 5 shows a tested panel image of CNSL hydro
and polymer fractions, in addition to the molecular weight carbon system after 668 hours salt spray exposure.
distribution. For this purpose, it is a common practice to
incorporate Small portions of an alkyl-substituted phenol to DETAILED DESCRIPTION OF THE INVENTION
the reaction mixture. The most commonly used alkyl-substi
tuted phenols are ortho- and para-tert-butylphenol, octylphe 0016. In one embodiment, the present disclosure is
nol, and nonylphenol. These phenols can be produced in-situ, directed to resins produced by the reaction between Cashew
prior to or after the reaction with the intended vinyl mono Nut Shell Liquid (CNSL) and respective derivatives with
mers. These variations in the process can add cost and com vinyl hydrocarbons. The reaction may be promoted by acid
plexity to the manufacturing of such resins. In addition, it can catalysts. These resins are generally comprised of about
US 2016/0075805 A1 Mar. 17, 2016

20-95% by weight of “vinylated cardanols and cardols, CNSL can contain relatively high amounts of polymer,
about 1-40% by weight of hydrocarbon cyclic dimers, and between about 5-35% by weight of the total resin. In certain
about 0-50% by weight of polymers, which may be a mixture embodiments, the resins derived from non-purified CNSL
of short chains composed of vinyl hydrocarbon monomers contain about 5%, 10%, 15%, 20%, 25%, 30% or 35% poly
and cardanol units, with degree of polymerization of no less merby weight of the total resin. Any of these values may be
than 2 and no more than 10 repeating monomer units. used to define a range for the percentage of polymer in the
0017. In certain embodiments, the CNLS hydrocarbon resin. For example the percentage of polymer in the resin may
resins comprise about 20%, 25%, 30%, 35%, 40%, 45%, range from about 10% to about 30%, about 15% to about
50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95% by 30%, or about 20% to about 25% of the total resin. The main
weight of vinylated cardanols and vinylated cardols. Any of advantages of hydrocarbon resins made with non-purified
these values may be used to define a range for the percent by CNSL are related to their low migration, high hydrophobicity,
weight of the vinylated cardanols and vinylated cardols and tackifier features. The most appropriate applications are
depending on the application. For example, the amount of additives for Sealants, building materials, structural adhe
vinylated cardanols and vinylated cardols in the CNSL hydro sives, and in manufacture of compounded rubber products.
carbon resin may range from about 25% to about 90% by 0021. In another embodiment, purified CNSL is reacted
weight, from about 30% to about 85% by weight, or from with vinyl hydrocarbon monomers to make CNSL-based
about 40% to about 80% by weight. hydrocarbon resins. Depending upon the purification proce
0018. In certain embodiments, the CNLS hydrocarbon dure, the purified CNSL will contain reduced amounts of
resins comprise about 1%,2%,3%, 4%, 5%, 10%, 15%, 20%, cardols, preferably below about 5%, and very low content of
25%, 30%, 35%, or 40% by weight of hydrocarbon cyclic polymer species, preferably no more than about 2%. Also,
dimers. Any of these values may be used to define a range for anacardic acid is Substantially completely removed from the
the percent by weight of the hydrocarbon cyclic dimers. For CNSL. The major components of purified CNSL are the
example, the amount of hydrocarbon cyclic dimers in the cardanol isomers, which are differentiated by the number of
CNSL hydrocarbon resin may range from about 5% to about carbon double bonds on the side chain, as shown in FIG.1 and
35% by weight, from about 10% to about 30% by weight, or described in U.S. Pat. No. 6,229,054, the contents of which
from about 15% to about 25% by weight. are hereby incorporated by reference in their entirety. The
0019. In certain embodiments, the CNLS hydrocarbon total cardanol content is typically about 80 to 99% by weight,
resin comprises vinylated cardanols, vinylated cardols, and and is preferably about 85-99%, about 90-99% or about
hydrocarbon cyclic dimers, and does not comprise any addi 95-99% by weight. The hydrocarbon resins made with puri
tional polymers. In other embodiments, the CNLS hydrocar fied CNSL are light colored, and exhibit low viscosity. The
bon resin comprises about 1%, 2%, 3%, 4%, 5%, 10%, 15%, content of vinylated cardanols in the resins is typically about
20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or 20-99% by weight, and preferably about 50-95%, about
70% by weight of one or more additional polymers. Any of 60-95%, about 70-95%, or about 80-95% by weight. Among
these values may be used to define a range for the percent by the advantages of hydrocarbon resins made with purified
weight of additional polymers. For example, the percent by CNSL are their light color, and anti-oxidant properties. These
weight of one or more additional polymers in the CNLS resins are particularly useful for coatings applications.
hydrocarbon resin may range from about 1% to about 70%, 0022. In yet another embodiment, highly purified CNSL is
from about 5% to about 45%, or from about 10% to about used. Depending upon the purification procedure, highly
40%. In certain embodiments, the one or more additional purified CNSL may contain only trace amounts of cardols,
polymers are linear oligomers of vinyl hydrocarbon mono and essentially no polymer components and anacardic acids.
mers and cardanols, with a degree of polymerization of 2, 3, They are essentially very pure cardanol mixtures, composed
4, 5, 6, 78, 9, or 10 repeating monomer units. Any of these of only cardanol isomers which are differentiated by the
values may be used to define a range for the degree of poly number of carbon double bonds on the side chains. The total
merization of the additional polymers. For example the cardanol content is typically about 96% to 100% by weight,
degree of polymerization of the additional polymers may and preferably about 97% to 99.9%, about 98% to 99.9%,
range from 2 to 10, 3 to 9, or 4 to 8 repeating monomer units. about 99% to 99.9%, or about 99.5% to 99.9% by weight.
0020. In another embodiment, non-purified CNSL is Depending upon the purification procedure the composi
reacted with vinyl hydrocarbon monomers to make CNSL tional distribution of the four cardanol isomers may vary
based hydrocarbon resins. Non-purified CNSL is the raw greatly. In most cases, the content of cardanols with triene,
product originated from the extraction process of the cashew diene, monoene, and saturated side chains are about 30-45%
shells. Depending upon the extraction procedure, the non by weight, about 15-25% by weight, about 30-45% by
purified CNSL may contain relatively large amounts of car weight, and about 0-10% by weight, respectively. In special
dols compared to purified CNSL. Also, depending upon the cases, the content of isomers bearing multiple carbon double
source, the total amount of cardols in non-purified CNSL can bonds on the side chains are intentionally depleted by means
be as high as 25% by weight. Non-purified CNSL may con of physical separation or chemical reactions, to produce
tain large amounts of cardol and cardanol oligimers. The CNSL with better oxidation, color stability, and higher ther
polymerization of cardols and cardanols can occur slowly mal transitions. For Such purpose, the compositional distri
under normal environmental conditions, although it can be bution of cardanol triene, diene, monoene, and Saturated iso
accelerated by high temperature treatment, or it may be mers are preferably about 0-5% by weight, about 0-10% by
caused by oxidation processes during the CNSL extraction weight, about 70-95% by weight and about 0-15% by weight,
procedure. Also, depending upon the process of extraction, respectively.
anacardic acid can be present in relatively high concentra 0023. In another embodiment, the distillation residue from
tions. The advantage of using non-purified CNSL is the lower the manufacturing process of the purified CNSL or the highly
cost of the raw material. The resins derived from non-purified purified CNSL, characterized as a side stream, is also reacted
US 2016/0075805 A1 Mar. 17, 2016

with vinyl hydrocarbon monomers to make hydrocarbon res mentioned CNSL-based hydrocarbon resins can be epoxi
ins. Depending upon the purification procedure, these side dized with hydrogen peroxide, or organic peroxides, or a
streams contain very high amounts of polymer components, combination of hydrogen peroxide and organic carboxylic
high contents of cardols, and very low content of cardanols, acids. The degree of epoxidation can be selectively controlled
and are Substantially free of anacardic acids. The polymer by the reaction conditions, and by adjusting the Substrate to
content is characterized as a complex mixture of polymerized peroxide feed ratios. These epoxidized CNSL-based hydro
cardol and cardanols, normally caused by side chain poly carbon resins are suitable for lubricant compositions. The
merization, mostly through isomerization and cycloaddition side double bonds can also be fully brominated with molecu
reactions. The polymer can also originate from oxidative lar bromine or other Suitable organic and inorganic brominat
reactions. The molecular weight of the polymer fraction ing agents, to produce resins with flame retardant character
ranges from about 500 to 10,000 g/mol. The polymer level in istics.
this CNSL is about 20-95% by weight, and preferably about 0028. Other common phenols can also be incorporated in
30-80%, 40-70% or 40-60% by weight. The hydrocarbon hydrocarbon resins along with the CNSL to make resins
resins produced using these side streams exhibit very high comprised of variable amounts of CNSL building block in the
Viscosity and enhanced hydrophobic properties. The resin final resin. These modifications may be useful for enhance
may be used as a rheology modifier, an impact modifier, a ment of specific desirable features. For instance, addition of
tackifier, a plasticizer, a weathering stabilizer, and/or an anti bisphenol-A to the reaction mixture produces resins with high
oxidant. They may also reduce cracking and brittleness of glass transition temperature. Lighter color, anti-oxidant prop
thermoplastic and thermoset polymer formulations, and the erties, and light stability are other common enhanced features
products made from these polymers. Due to the high polymer that can be achieved by the addition of about 2-70% by
content of these resins, they may also be used in applications weight, and preferably 5-50%, 5-40%, 5-30% or 5-20% by
where control of leachates, migration, VOC, and other restric weight of other simple synthetic phenols prior to or during the
tive regulatory controls are required. reaction of CNSL with the hydrocarbon vinyl monomers to
0024. In another aspect, for the purpose of this disclosure, make the respective blend of the desired CNSL and phenol
chemically modified CNSL streams are reacted with vinyl based hydrocarbon resins. Examples of suitable phenols
hydrocarbon monomers to make CNSL-modified hydrocar include, but are not limited to: phenol, nonylphenol, ortho
bon resins. Suitable chemical modifications can be carried out tert-butylphenol, para-tert-butylphenol, ortho-cresol, para
on the aromatic ring reactive sites, or on the double bonds of cresol, meta-cresol, technical grade mixture of cresols,
the side chains of the cardol, cardanols and anacardic acids bisphenol-A, bisphenol-F, hydroquinone, resorcinol, cat
components. echol, butylhydroxytoluene, methoxyphenol, tert-butylcat
0025. Any of the aforementioned purified or non-purified echol.
CNSL may react with aldehydes and ketones promoted by 0029 Suitable vinyl hydrocarbon monomers used in the
acid catalysts to form polymers of the novolac resin type. The manufacture of CNSL-based hydrocarbon resins are prefer
same catalyst that converts CNSL substrates to CNSL hydro ably the aromatic vinyl monomers, in which one or multiple
carbon resins, can also promote the polycondensation reac alkenegroups are linked directly to an aromatic hydrocarbon
tion of cardol, cardanols oranacardic acids with aldehydes or group, or to multiple aromatic groups that can be fused
ketones. Therefore, the CNSL-novolac-hydrocarbon resins together or linked by single carbon-carbon bonds. Examples
can be made in one single batch process. The process can start include, but are not limited to, styrene, alpha-methylstyrene,
with the production in-situ of the hydrocarbon resin, and then vinyltoluene (mixture of ortho, meta, and para isomers),
the polycondensation reaction is carried out with aldehyde or indene, indene-coumarone streams from coal tar distillation,
ketones in a Subsequent step. Alternatively, under the same alpha-Vinylnaphthalene, diisopropenylbenzene (and respec
principle, the order of above steps can be reversed, in which tive mixture of ortho- meta- and para-disubstituted isomers),
case the CNSL-novolac resin is made first as an intermediate, the C9 fraction from a petroleum cracking process, divinyl
followed by the reaction with the vinyl hydrocarbon mono benzene, and mixtures of divinylbenzene and ethylvinylben
mers in a Subsequent step. From the manufacturing perspec Zenes. Aliphatic and cycloaliphatic vinyl monomers can also
tive, the former manufacturing process is the simplest one, be used alone or in a mixture with aromatic vinyl monomers.
and therefore the preferred one. Examples of Suitable aliphatic and cycloaliphatic hydrocar
0026. Any of the aforementioned types of CNSL may be bon vinyl monomers include, but are not limited to, isobuty
catalytically reduced with hydrogen under pressure and pro lene, butadiene, isoprene, pentadiene, cyclopendadiene, dicy
moted by active metal catalysts to produce a partially or clopentadiene, pinenes (alpha and beta isomers), limonene,
completely saturated product. This hydrogenated CNSL is cyclohexane, vinylcylohexane, and mixtures of unsaturated
allowed to react with vinyl hydrocarbon monomers promoted olefins from the so called “C5 fraction' originated from oil
by acid catalysts to produce CNSL-based hydrocarbon resins refineries.
featuring very low color, high chemical resistance and Stabil 0030) Suitable catalysts for the preparation of CNSL
ity in weathering conditions. These hydrocarbon resins may based hydrocarbon resins may be strong inorganic protic
be used in coating formulations, or in polymer product com acids, including, but not limited to, Sulfuric acid, hydrofluoric
positions that are intended to resist intense exposure to natural acid, hexaflyorophosphoric acid, tetrafluoroboric acid, per
light. Alternatively, the hydrogenation process can also be chloric acid, or a mixture thereof. Lewis acids are also another
done after the reaction between any type of CNSL stream and good alternative to the inorganic protic acids, as they are very
hydrocarbon vinyl monomers under similar conditions. effective promoting Friedel–Crafts reactions, and similar
0027. Anyaforementioned CNSL-based hydrocarbon res alkylation reactions of phenols. Examples of Suitable cata
ins can be chemically modified afterwards, to attain special lysts include, but are not limited to: boron trifluoride, boron
desirable features. As part of this disclosure, the carbon trichoride, and respective complexes with phenol, alcohols,
double bonds on the side chains of the cardanol in the afore or tetrahydrofuran; Zinc chloride, aluminum chloride, tita
US 2016/0075805 A1 Mar. 17, 2016

nium (III) chloride, titanium (IV) chloride, zirconium (III) finished products. Very low levels of acid catalyst are not
chloride, zirconium(IV) chloride, aluminum trichloride, alu satisfactory, because the conversion rate becomes very slow.
minum phenoxide, reaction product of activated aluminum In addition, the reactivity of the batch can be seriously com
powder and CNSL. Boron trifluoride and respective com promised by the possibility of reaction inhibition (quenching)
plexes are the most preferred among the Suitable Lewis acid caused by Small unpredictable and unwanted impurities. For
catalysts because of their volatility, which simplify the pro strong inorganic and Lewis acid catalysts, which exhibit the
cedure of catalyst removal from the finished product. A highly higher catalytic activity, the optimal catalyst level is about
preferred catalyst class is the organic sulfonic acids, due to 0.01 to 1.00% of the total weight of the reactants, and pref
their moderate strength and activity to promote the reaction erably about 0.05 to 0.2% of the total weight. In certain
between CNSL-streams and vinyl hydrocarbon monomers. embodiments, the level of strong inorganic acid catalyst or
In addition, organic Sulfonic acids are widely commercially Lewis acid catalyst is about 0.01%, 0.05%, 0.10%, 0.20%,
available in high purity, they are relatively low cost, and pose 0.30%, 0.40%, 0.50%, 0.60%, 0.70%, 0.80%, 0.90% or
less hazardous conditions on handling. More specifically, in 1.00% of the total weight of the reactants. Any of these values
respect to the manufacturing processes involving CNSL may be used to define a range for the percentage of the strong
streams, organic Sulfonic acids offer the best reaction control, inorganic acid catalyst or Lewis acid catalyst. For example
with minimal side reactions, and better product composition the percentage of the strong inorganic acid catalyst or Lewis
uniformity. Examples of Suitable organic Sulfonic acids are, acid catalyst may range from about 0.05% to about 0.5%, or
but not limited to, benzensulfonic acid; ortho-isomer, or para from about 0.1% to about 0.5% of the total weight of the
isomers of toluenesulfonic acid, or mixture thereof alpha reactants. In the case of sulfonic acids, which exhibit moder
isomer, or beta-isomer of naphthalenesulfonic acid, and mix ate catalytic activity, the optimal catalyst level is about 0.05 to
tures thereof 1.5-isomer, or 2,6-isomer of 5.0% of the total weight of the reactants, and preferably about
naphthalenedisulfonic acid, and mixtures thereof, nonylphe 0.3 to 1.0% of the total weight.
nolsulfonic acid, and mixture of respective isomers; dinonyl 0033 FIG. 2 illustrates generally the reaction mechanism
naphthylsulfonic acid, and mixture of respective isomers; for one embodiment of the disclosure. As shown in FIG. 2,
dodecylbenzenesulfonic acid, methanesulfonic acid; trifluo cardanol may be combined in a reactor vessel with a hydro
romethanesulfonic acid, laurylsulfonic acid; phenolsulfonic carbon monomer in the presence of p-toluenesulfonic acid.
acid and respective isomers; cresylsulfonic acid, and respec The reactor vessel is maintained at a temperature of between
tive isomers. Preferably, all of the aforementioned sulfonic 100-120° C. for a period of about 3 hours. The cardanol and
acids should have about 50-100% purity, and more preferably hydrocarbon monomers react to form a CNSL hydrocarbon
about 95.00-99.99% purity. The crystallized hydrate state of CS1.
all of the aforementioned sulfonic acids are also suitable 0034 Prior to or after the production of CNSL-based
catalysts for the manufacture of CNSL-based hydrocarbon hydrocarbon resins, certain additives can be added to attain
CS1S.
certain desirable properties, or for better control of the manu
0031 Solid state or supported acid catalysts are also suit facturing process, or to control the intended specifications of
able to promote the reaction between the aforementioned the final product.
purified and non-purified CNSL and vinyl hydrocarbon 0035. The molar ratio between the CNSL and the vinyl
monomers. These solid catalysts are insoluble in the reaction hydrocarbon resin plays a significant role on the physico
media, and generally they are in the form of microbeads, or chemical properties of the resulting resin. More importantly,
coarse particulates, which are designed to have high Surface it can deeply influence the performance of the resin for the
area, improving the conversion rate. The major advantage of intended application. Low vinyl hydrocarbon monomer/
these catalysts relates to the simplification of the process for CNSL molar ratio ranges, such as about 0.8 to 1.8, produce
extraction of the acid catalyst from the final product by a resins with the lowest viscosity, with good compatibility with
simple filtration procedure. Conversely, Soluble organic cata a variety of resins and polymer formulations, but reduced
lysts, in general, require neutralization, and Subsequent wash color and weathering stability. Medium vinyl hydrocarbon
and filtration steps, which can increase the time and cost of the monomer/CNSL molar ratio ranges, such as about 1.8 to
manufacturing process. These catalysts are very well Suited 3.0, produce resins with intermediate to high viscosity, but
for semi-batch or continuous manufacturing processes for the they exhibit enhance compatibility, color and weathering sta
production of CNLS-based hydrocarbon resins. Examples of bility. High vinyl hydrocarbon monomer/CNSL molar
Suitable solid state or Supported acid catalysts include, but are ratio ranges, such as above about 3.0, produce resins with
not limited to, nafion resins, Sulfonated poly(styrene-co-divi high to very high viscosity, and they may exhibit reduced
nylbenzene) resins, Sulfuric acid doped silica powder, acid compatibility or phase stability with other resins and polymer
activated montmorillonite, activated acid fullers earth, Zeolite formulations, but they have excellent color and weathering
Y hydrogen form, Zeolite ZSM-5 hydrogen form, Zeolite beta stability, and enhanced anti-oxidant properties.
hydrogen form, Zeolite mordenite hydrogen form, and acid 0036. In certain embodiments, the molar ratio of the vinyl
activated bentonite clays. hydrocarbon monomer to the CNSL in the reaction mixture is
0032. The type and the amount of catalyst to be used in the about 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0,
manufacturing of CNSL-based hydrocarbon resins should be 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.5, 4.0, 4.5, 5.0,
carefully selected based on the reactivity of the substrates, 6.0. 7.0, 8.0, 9.0 or 10.0. Any of these values may be used to
and the desired specification of the finished product. CNSL define a range for the molar ratio of the vinyl hydrocarbon
has the propensity to self-polymerize under the influence of monomer to the CNSL wherein the properties of the different
strong acid catalysts at high temperatures. Therefore, under embodiments may have more than one property associated
these conditions, the resulting CNSL hydrocarbon resin may with more than one molar ratio range. For example, the molar
exhibit high polymer fraction content as a consequence of ratio of the vinyl hydrocarbon monomer to the CNSL may
these side reactions, which will result in high viscosity of range from about 0.8 to 10.0 or about 0.8 to 3.0.
US 2016/0075805 A1 Mar. 17, 2016

0037. The reaction between CNSL and vinyl hydrocar 0043. In each of the embodiments described above, the
bons is carried out in sealed reactors in batch, semi-batch or temperature is maintained in the ranges discussed above
continuous modes, protected from exposure to air, and pref depending upon the type of vinyl monomer and the type of
erably blanketed with an inert or reducing atmosphere. The catalyst used.
temperature of reaction is a function of the reactivity of the 0044. In another embodiment, CNSL hydrocarbon epoxy
CNSL, the vinyl hydrocarbon monomer, and the activity of resins, specifically glycidyl ethers of the aforementioned
the acid catalyst. For example, when the vinyl monomer is an CNSL hydrocarbon resins, can be made from the reaction
aliphatic type and a Lewis acid catalyst is used, the tempera between epichlorohydrin and the desired CNSL hydrocarbon
ture range for the process may range from about -10°C. to resin promoted by Strong bases, such as sodium hydroxide or
about 90°C., and is preferably between about 40°C. to about potassium hydroxide. CNSL hydrocarbon epoxy resins
60° C. When the vinyl monomer is an aromatic type and a enhances the flexibility, and toughening characteristics of
Lewis acid catalyst is used, the temperature range for the epoxy curing compositions, such as protective coatings,
process may range from about -10°C. to about 90°C., and is adhesives, and composites, without compromising the
preferably between about 20° C. to about 60° C. When the mechanical properties, compatibility, weather and chemical
vinyl monomer is an aromatic type and an inorganic acid or resistance. This feature makes them very advantageous over
Sulfonic acid catalyst is used, the temperature range for the the traditional long aliphaticg glycidyl ethers, which also
process may range from about 50° C. to about 150°C., and is promotes good flexibility, and toughening characteristics but
preferably between about 100° C. to about 120° C. at expense of reduced overall performance.
0038 Even for the combination of substrates with the 0045. As noted in previous inventions Process for manu
lowest reactivity, an exothermic reaction is observed at early facture of glycidyl ethers of polyhydric phenols, U.S. Pat. No.
stages of conversion. As the reactivity of the Substrates 2.801.227 A; and Preparation of liquid epoxy resins from
increase, the temperature of the reaction must be adjusted to bisphenols, U.S. Pat. No. 4,132,718 A, the use of a large
avoid side reactions due to temperature spikes, and the pos Stoichiometric excess of epichlorohydrin, and controlling the
sibility of runaway reaction at early stages of conversion. The amount of water and the pH in the reaction medium also play
CNSL streams with relatively higher content of cardol exhibit a crucial role in minimizing side reactions that lead to signifi
higher reactivity. The less sterically hindered aromatic vinyl cant amounts of undesirable inactive side products, high vis
hydrocarbon monomers are the most reactive ones. cosity, low epoxy equivalent weight values, and high concen
Cycloaliphatic and aliphatic vinyl hydrocarbon monomers tration of compounds with hydrolysable chlorine fragments.
exhibit very low reactivity toward CNSL, and for such com 0046 Alternatively, CNSL hydrocarbon epoxy resins can
bination, high catalytic activity is required to achieve be made from the epoxidation reaction of the allyl ethers of
adequate conversions. For instance, for the reaction between the desired CNSL hydrocarbon resin with inorganic or
any aforementioned CNSL streams and styrene or vinyltolu organic peroxides, or mixtures of hydrogen peroxide and
ene, the ideal temperature range for high active catalysts. Such carboxylic acids, such as acetic or formic acids. In turn, the
as boron trifluoride-phenol complex, the ideal reaction tem referred allyl ethers of CNSL hydrocarbon resins can be made
perature is in the range of about -10° to 90° C., and preferably by the reaction between any aforementioned CNSL hydro
from about 40° to 60° C. For this same combination, but using carbon resin and allyl chloride promoted by inorganic bases,
para-toluenesulfonic acid monohydrate, the ideal reaction Such as Sodium hydroxide or potassium hydroxide. Allyl bro
temperature is in the range of about 50° to 150° C., and mide and allyl iodide are also suitable and more reactive
preferably from about 100° to 120° C. alternatives to allyl chloride. The epoxidation of CNSL
0039. In certain embodiments the temperature for the hydrocarbon resin allyl ethers may occur not only on the
reaction between CNSL and vinyl hydrocarbons is about intended allyl group, but the unsaturations of the side chain
-10° C., 0°C., 10°C., 20° C., 30° C., 40° C., 50° C., 60° C., can also be epoxidized all together. The allyl ether groups are
70°C., 80°C.,90° C., 100° C. 110°C., 120°C., 130° C., 1400 more reactive, and hence more prone to epoxidation by
C., or 150° C. Any of these values may be used to define a organic and inorganic peroxides than the side chain double
range for the temperature for the reaction between CNSL and bonds of the CNSL building blocks. Therefore the degree of
vinyl hydrocarbons. For example, the temperature may range epoxidation can be controlled by the reaction conditions and
from about -10° C. to about 150° C., about 50° C. to about the stoichiometric ratio of the reactants.
150° C., or about 100° C. to about 150° C. 0047. In another embodiment, alkoxylated CNSL hydro
0040. One embodiment of the process for carrying out the carbon epoxy resins can be made from the reaction between
reaction between CNSL and the vinyl hydrocarbon monomer any aforementioned CNSL hydrocarbon resin and an alke
comprises dispersing the catalyst into the CNSL, followed by lene or cycloalkelene oxide promoted by acid or base cata
slow and controlled addition of the vinyl monomer into the lysts under high temperature and pressure. The resulting alco
CNSL/catalyst mixture. hol or polyol are suitable for the 1-part or 2-part polyurethane
systems used in semi-flexible and rigid foams, building mate
0041. A second embodiment of the process comprises rials, and adhesives. These polyurethane-polyols systems are
adding at the same time the catalyst and the vinyl monomer very hydrophobic, and exhibit good mechanical behavior that
through two different inlet ports (to avoid premature mixing is comparable to a great number of conventional aromatic
of the catalyst with the vinyl monomer). polyether polyesters, in addition to improved impact resis
0042. A third embodiment comprises dispersing the vinyl tance and flexibility. Examples of alkelene oxide include, but
monomer into the CNSL, and then slowly adding the catalyst, not limited to, ethylene oxide, propylene oxide, cyclohehane
or a Suitable catalyst dispersion, with mixing. In this specific oxide, dicyclopentadiene diepoxide, and styrene oxide. The
case, at early stages of conversion, the temperature should be process for alkoxylation of CNSL hydrocarbon epoxy resins
significantly lower than the optimal level to avoid any poten involves slow addition of alkelenes oxides to a mixture of
tial temperature spikes or runaway reaction. CNSL hydrocarbon resin and catalyst at temperature in
US 2016/0075805 A1 Mar. 17, 2016

between 80 and 220° C., more preferably between 150 and #3)=358 cls; Gardner color=10; free alpha-methylstyrene
180° C., and under pressure of 10-150 psi, more preferably (by GC)=0.04%; free cardanol (by HPLC)=4.7%
between 30-75 psi, and catalyzed by inorganic base, such as
Sodium hydroxide, or potassium hydroxide. The Stoichiomet Example 2
ric ratio between CNSL hydrocarbon resin and the alkelene
oxide is judiciously chosen based on the desirable amount of
alkelene oxide monomeric units appended to the hydroxyl Hydrogenated CNSL. Vinyltoluene Resin
groups of CNSL hydrocarbon resin. Large alkelene oxide to
CNSL hydrocarbon resin equivalent ratios produce resins 0.052 A1 L round bottom multi-neck glass flask, equipped
with long chains of polyalkene oxide appended to the CNSL with a thermometer, a condenser, a mechanical stirrer, and an
hydrocarbon resins, which may render Surfactant properties inlet port controlled by a peristaltic pump, was charged with
to the final product. Hence, Surfactant is suitable for pigment 304 g or 1.0 mol of hydrogenated and distilled CNSL (NC
dispersion aid, and rheology modifier in paint formulations. 510, Cardolite Co.). The whole set up was continually purged
0048 Alternatively, ethoxylated or propoxylated CNSL with a gentle flow of pure dry nitrogen. The temperature of the
hydrocarbon polyol resins can be made by reacting any afore flask contents was raised to 80° C., and then 3.0 g of pure
mentioned CNSL hydrocarbon resin with ethylene carbonate para-toluenesulfonic acid were added to the flask. Upon dis
or propylene carbonate respectively, using the similar estab persion of the acid catalyst, 312 g or 3.0 mol of vinyltoluene
lished manufacturing procedure for ethoxylated of plain car (Acros Chemicals Co, 98%, mixture of isomers) were added
danol Cardanol derivative and method of making the car to the reaction mixture via the peristaltic pump, while the
danol derivative EP 1137620 A1. This reaction is catalyzed content of the flask was vigorously stirred. As soon as the
by an organic or inorganic base. This procedure offers an addition started, the temperature was allowed to rise up to
advantage over traditional alkoxylation with organic oxides 120° C. The addition rate of the vinyltoluene was adjusted to
because it can be run at normal pressure, which simplifies the take about 15 minutes to completion. Then, the reaction mix
basic manufacturing equipment requirements. The most com ture was allowed to react for an additional 60 minutes. The
monly catalysts employed for this specific mechanism of non-reacted vinyltoluene was vacuum distilled using an oil
alkoxylation reactions are volatile organic amines, because pump, at 0.05 mmHg. The resin was dispensed as is without
they are very effective, and they can be easily removed from any further purification step.
the reaction product by simple vacuum distillation. The reac 0053. The yield was 605 g of resin having the following
tion between CNSL hydrocarbon resin and ethylene or pro characteristics: Brookfield Viscosity (300 rpm, 25° C.,
pylene carbonate is conducted at 100-220° C., more prefer spindle #3)=2640 cps; Gardner color=<1; free styrene (by
ably between 150-180° C., and the amount of catalyst is GC)=0.04%; freehydrogenated cardanol (by HPLC)=0.25%
generally between 0.1 to 10% of the total charge of reactants,
but more preferably between 1-3%. Example 3
0049. The following examples provide exemplary
embodiments of the present invention, and the examples are
not intended to limit the scope of the invention in any way. Ultra-High Pure CNSL Styrene Resin
EXAMPLES 0054. A 500 mL round bottom multi-neck glass flask,
equipped with a thermometer, a condenser, a mechanical
Example 1 stirrer, and an inlet port controlled by a peristaltic pump, was
charged with 150 g or 0.5 mol of highly purified CNSL with
Pure CNSL Alphamethylstyrene Resin cardol content lower than 0.1% (GX-2512, Cardolite Co.).
The whole set up was continually purged with agentle flow of
0050 A1 L round bottom multi-neck glass flask, equipped pure dry nitrogen. The temperature of the flask contents was
with a thermometer, a condenser, a mechanical stirrer, and an raised to 80°C., and then 1.5g of pure para-toluenesulfonic
inlet port controlled by a peristaltic pump, was charged with acid were added to the flask. Upon dispersion of the acid
300 g or 1.0 mol of distilled CNSL (NX-4708M, Cardolite catalyst, 104 g or 1.0 mol of Styrene (Acros Chemicals Co.
Co.). The whole set up was continually purged with a gentle 99.9% pure, stabilized with 0.1% TBC) were added to the
flow of pure dry nitrogen. The temperature of the flask con reaction mixture via the peristaltic pump, while the content of
tents was raised to 80° C., and then 3.0 g of pure para the flask was vigorously stirred. As soon as the addition
toluenesulfonic acid were added to the flask. Upon dispersion started, the temperature was allowed to rise up to 100°C. The
of the acid catalyst, 300 g or 2.54 mol of alpha-methylstyrene addition rate of the styrene was adjusted to take about 45
(Acros Chemicals Co, 98% pure) were added to the reaction minutes to completion. Then, the reaction mixture was
mixture via the peristaltic pump, while the content of the flask allowed to react for an additional 90 minutes. The non-reacted
was vigorously stirred. As soon as the addition started, the styrene was vacuum distilled using an oil pump, at 0.05
temperature was allowed to slowly rise up to 120° C. The mmHg. Then, a solution of 2.0 g of Sodium bicarbonate
addition rate of the styrene was adjusted to take about 15 (Acros Chemicals Co) in 50 mL of distilled water were added
minutes to completion. Then, the reaction mixture was to neutralize the catalyst. The waste was vacuum distilled, and
allowed to react for an additional 120 minutes. The non the resulting hazy oil was treated with filtration aid ceramic
reacted alpha-methylstyrene was vacuum distilled using an and filtered through a fritted funnel under vacuum.
oil pump, at 0.05 mmHg. The resin was dispensed as is 0055. The yield was 232 g of resin having the following
without any further purification step. properties: Brookfield Viscosity (300 rpm, 25°C., spindle
0051. The yield was 552 g of resin having the following #3)=455 cBs; Gardner color=3; free styrene (by GC)=0.07%;
properties: Brookfield Viscosity (300 rpm, 25°C., spindle free cardanol (by HPLC)=1.9%
US 2016/0075805 A1 Mar. 17, 2016

Example 4 stirrer, was charged with 336 g (1 equivalent-weight.based on

Pure CNSL Divinylbenzene Resin hydroxyl group content) of styrenated ultra-high pure CNSL
resin described in example 3, and 4.9 g (0.08 equivalent
005.6 A1 L round bottom multi-neck glass flask, equipped weight) of triethylamine as a catalyst, and the resulting mix
with thermometer, a condenser, a mechanical stirrer, and an ture was stirred under nitrogen and heated up to 155°C. Then,
inlet port controlled by a peristaltic pump, was charged with 58.1 g (1.1 equivalent weight) of molten ethylene carbonate
300g or 1.0 mol of distilled CNSL (NX-4708, Cardolite Co.). were added to the flask over 3 hours period. Once completed
The whole set up was continually purged with a gentle flow of the addition, the batch was stirred for another hour at 155°C.,
pure dry nitrogen. The temperature of the flask contents was followed by vacuum distillation at 80-85°C. and 100 mmHg
raised to 100° C., and then 2.5g of pure para-toluenesulfonic to remove any unreacted ethylene carbonate and triethy
acid were added to the flask. Upon dispersion of the acid lamine.
catalyst, 195g or 1.5 mol of Divinylbenzene (TCI America 0061 The yield was 362 g having the following charac
Co, mixture of meta-, and para-isomers, also containing 40% teristics: Brookfield Viscosity (100 rpm, 25° C., spindle
ethylvinylbenzene) were added to the reaction mixture via the #3)=655 cFs: Gardner color=7: Hydroxyl value=109
peristaltic pump, while the content of the flask was vigorously mgkOH/g.
stirred. As soon as the addition started, the temperature was
allowed to rise up to 140°C. The addition rate of the divinyl Example 7
benzene was adjusted to take about 30 minutes to completion.
Then, the reaction mixture was allowed to react for an addi Application
tional 30 minutes. The non-reacted vinyl monomers were
vacuum distilled using an oil pump, at 0.05 mmHg. The resin 0062. The ability of CNSL hydrocarbon resin (from
was dispensed as is without any further purification step. Example 3) to reduce the viscosity of liquid epoxy at different
0057 The yield was 485 g having the following charac concentrations was investigated (e.g., viscosity reduction
teristics: Brookfield Viscosity (100 rpm, 25° C., spindle property). Six Systems were tested in which the percentage of
#3)=6035 cFs; HPLC/GPC results: Mn=1,384 g/mol, Mw =2, CNSL hydrocarbon resin in Epon 828 was 5%, 10%, 15%,
241 g/mol, polymer dispersity=1.62; free cardanol=0.8%. 20%, 25% or 30%. The viscosities of the six systems were
Example 5 measured by using a CAP 2000+ VISCOMETER (BYK).
Similar systems using a commercial phenol-hydrocarbon
Glycidyl Ethers of CNSL Hydrocarbon Resin resin were tested for comparison.
0058. A 1000 mL round bottom multi-neck glass flask, 0063. As shown in Table 1 below and FIG.3, use of CNSL
equipped with a thermometer, a condenser, a mechanical hydrocarbon resin as a diluent resulted in a greater reduction
stirrer, and an inlet port with a addition funnel with pressure in Viscosity of the liquid epoxy in comparison to the commer
equalizer feature, was charged with 336 g (1 equivalent cial phenol-hydrocarbon resin.
weight.based on hydroxyl group content) of styrenated ultra
high pure CNSL resin described in example 3, and 222 g (4 TABLE 1
equivalent-weight) of epichlorohydrin, and the resulting mix Viscosities of Liquid Epoxy and Hydrocarbon Resin Blends
ture was stirred for stirred and warmed up to 65° C. in 30
minutes. Then, 52.8 g (1 equivalent weight) of a 50% by Percentage of Viscosities of liquid epoxy and hydrocarbon
weight solution of sodium hydroxide in water were added via hydrocarbon resin blends (225 C./cps
the addition funnel over 3 hours period. Meanwhile the water resin in With commercial phenol- With CNSL hydrocarbon
epichlorohydrin azeotrope from the reaction mixture was liquid epoxy modified hydrocarbon resin resin (from Example 3)
distilled under vacuum at 150-170 mmHg out to a Dean-Stark O% 1428O 1428O
trap, in which the condensed epichlorohydrin-water heterog 59 106SO 916S
enous mixture was decanted, and the epichlorohydrin layer 10% 10O31 7512
was allowed to return to the reaction flask. Upon completion 15% 9638 6313
the addition of epichlorohydrin, the reaction mixture was 20%
25%
91SO
8588
5575
4853
stirred at 68-72 hours for one additional hour. Then, the 30% 8156 4313
excess of epichlorohydrin was removed from the reaction
mixture by vacuum distillation at 70-90° C. and 100 mmHg.
The resulting thick slurry was then extracted with a mixture of 0064. Investigation of Persoz, hardness development was
100 g of xylenes and 100 g of water. The aqueous phase was performed on a clear coating system (no pigment, additive
decanted out, and the organic phase was filtered and evapo and solvent added). A liquid epoxy Epon 828 and curing
rated under vacuum to remove Xylenes. The resulting light agent Versamid 115x70 system was used at stoichiometric
color oil was then filtered through a shrt plug of Celite filtra ratio. 30% CNSL hydrocarbon resin or phenol-hydrocarbon
tion aid. resin (based on the weight of liquid epoxy) was evaluated.
0059. The yield was 365 g having the following charac 0065 For the Persoz, hardness measurement, the testing
teristics: Brookfield Viscosity (100 rpm, 25° C., spindle panels were prepared by a BYK 15 Mirs wet application bar
#3)=609 cls; Gardner color=6: Epoxy equivalent over QD-36 cold rolled steel panels (Q-panel, 3"x6"x0.020").
weight=618, hydrolizable chlorine content=0.18%. Persozhardness numbers were obtained by using a Pendulum
Example 6 hardness tester (BYK Gardner) based on ASTM D 4366.
0066. As shown in Table 2 below, the Persoz hardness
Ethoxylated CNSL Hydrocarbon Resin results indicated that the system with 30% CNSL hydrocar
0060 A 1000 mL round bottom multi-neck glass flask, bon resin gave faster cure property in comparison to the one
equipped with a thermometer, a condenser, and a mechanical with commercial hydrocarbon resin.
US 2016/0075805 A1 Mar. 17, 2016

TABLE 2 exhibited no rust underneath the coating film except for a few
small blisters near the scribed lines.
Persozhardness development of different 1. A Cashew Nut Shell Liquid based hydrocarbon resin
SYStems at 25 C. Cure condition comprising:
Persozhardness.sec. a) between about 40% by weight to 90% by weight viny
lated cardanols;
Cure time (a) With commercial phenol- With CNSL hydrocarbon b) between about 5% by weight to about 25% by weight
25° C./day modified hydrocarbon resin resin (from Example 3) vinylated cardol; and
2 30 40 c) between about 5% by weight to about 30% by weight of
5 125 149 one or more additional polymers.
9 168 187 2. The hydrocarbon resin of claim 1, wherein the vinylated
cardanols comprise vinyl hydrocarbon monomers selected
from the group consisting of Styrene, alpha-methylstyrene,
0067. The adhesion tape test (ASTM D 3359-97) was vinyltoluene, indene, alpha-Vinylnaphthalene, diisoprope
performed on rusted S-36 panels (Q-panel. 3"x6"x0.020") nylbenzene, the C9 fraction from a petroleum cracking pro
(adhesion over rust metal substrate). To obtain a uniform cess, divinylbenzene, and mixtures of divinylbenzene and
rusted surface, the clean S-36 panels were immersed in a 60° ethylvinylbenzenes.
C. water bath (Precision circulating water bath, Model 260) 3. The hydrocarbon resin of claim 1, wherein the vinylated
for 24 hours followed by a warm tap water rinsing to remove cardanols comprise vinyl hydrocarbon monomers selected
the loosened rust. The panels were roughly dried with a paper from the group consisting of isobutylene, butadiene, iso
towel and stored at room temperature for seven days before prene, pentadiene, cyclopendadiene, dicyclopentadiene,
SC. pinenes, limonene, cyclohexane, and vinylcylohexane.
4. A Cashew Nut Shell Liquid based hydrocarbon resin
TABLE 3 comprising:
a) between about 80% by weight to 99% by weight viny
Pigmented white epoxy base formulation lated cardanols;
Gray epoxy base b) less than about 5% by weight vinylated cardol; and
Composition (grams) c) less than about 2% by weight of one or more additional
Liquid epoxy 30
polymers.
CNSL hydrocarbon resin 6 5. The hydrocarbon resin of claim 4, wherein the vinylated
(from Example 3) cardanols comprise vinyl hydrocarbon monomers selected
Dispersant 3 from the group consisting of Styrene, alpha-methylstyrene,
Extender
pigment
65
13
vinyltoluene, indene, alpha-Vinylnaphthalene, diisoprope
Solvent 7.5 nylbenzene, the C9 fraction from a petroleum cracking pro
Flow control O6 cess, divinylbenzene, and mixtures of divinylbenzene and
ethylvinylbenzenes.
Total of white epoxy base 125.1 6. The hydrocarbon resin of claim 4, wherein the vinylated
Curing agent 44.7
cardanols comprise vinyl hydrocarbon monomers selected
from the group consisting of isobutylene, butadiene, iso
0068 Pigmented systems were applied over the rusted prene, pentadiene, cyclopendadiene, dicyclopentadiene,
panels via a 10 Mirs wet application bar. After a seven-day pinenes, limonene, cyclohexane, and vinylcylohexane.
room temperature cure, the cross hatch adhesion test was 7. A Cashew Nut Shell Liquid based hydrocarbon resin
performed. As shown in FIG. 4, there was 100% adhesion comprising between about 20% by weight to about 95% by
with no failure. The addition of CNSL hydrocarbon resin to weight vinylated polymerized cardanols and vinylated poly
coating system gave good adhesion property to rust metal merized cardol.
substrate. 8. The hydrocarbon resin of claim 7, wherein the resin
0069 Salt spray exposure (ASTM B117) was evaluated comprises between about 40% by weight to about 60% by
based on the same formulation shown in Table 3 (anti-corro weight vinylated polymerized cardanols and vinylated poly
merized cardol.
sion property). As shown if FIG. 5, after 668 hours salt spray
exposure, the test panel with 20% CNSL hydrocarbon resin