US 20210054134A1

IN
( 19) United States
( 12 ) Patel
Patent Application Publication ( 10 ) Pub. No .: US 2021/0054134 A1
et al . (43) Pub. Date : Feb. 25 , 2021
( 54 ) CYCLOALIPHATIC AMINES FOR EPOXY C08J 5/24 ( 2006.01 )
FORMULATIONS : A NOVEL CURING C08J 5/04 (2006.01 )
AGENT FOR EPOXY SYSTEMS (52 ) U.S. CI .
CPC ... C08G 59/5026 ( 2013.01 ) ; C08G 59/5033
( 71 ) Applicant: Evonik Operations GmbH , Essen (2013.01 ) ; C08G 59/56 (2013.01 ) ; C08J
( DE ) 2363/00 ( 2013.01 ) ; C08J 5/24 ( 2013.01 ) ;
( 72 ) Inventors : Pritesh G. Patel , Breinigsville, PA C08J 5/04 (2013.01 ) ; C08G 59/22 (2013.01 )
(US ) ; Gamini Ananda Vedage, ( 57 ) ABSTRACT
Bethlehem , PA (US ) ; Peter Lucas ,
Allentown, PA (US ) ; Joseph DiBiase , The present invention related to an epoxy curing agent
Nazareth , PA (US ) comprising a first amine component and a second amine
component. The present invention also relates to an epoxy
(21 ) Appl. No .: 16 /976,660 resin system containing the reaction product of an epoxy
resin component and an amine -based curing agent compo
( 22 ) PCT Filed : Mar. 4 , 2019 nent comprising a first amine component and a second
amine component. The present invention also relates to a
( 86 ) PCT No .: PCT/EP2019/ 055237 method for producing the epoxy resin system comprising
§ 371 (c ) ( 1 ) , combining an epoxy resin component with an amine - based
( 2 ) Date : Aug. 28 , 2020 curing agent component, the amine - based curing agent com
ponent comprising a first amine component and a second
Related U.S. Application Data amine component; and reacting the amine - based curing
( 60 ) Provisional application No. 62 / 638,413 , filed on Mar.
agent component and the epoxy resin component to form a
5 , 2018 . cured epoxy resin composition. The first amine component
is N-( 3 -aminopropyl) cyclohexylamine. The second amine
Publication Classification component is the hydrogenated product of oligomeric struc
ture from the 4,4 '-Methylenedianiline process . N-(3 -amino
( 51 ) Int . CI . propyl) cyclohexylamine enhances desirable properties of
C08G 59/50 ( 2006.01 ) epoxy resin compositions without the negative impact on
C08G 59/56 ( 2006.01 ) mechanical properties in the cured product normally seen
C08G 59/22 ( 2006.01 ) with cycloaliphatic amine -based curing agents.
Viscosity Profile @ 40° C
2,500

2,000

iscosity 1,500
V(
)
CP

1,000

****
!!

500

minutes
******** 100 % APCHA --50 % APCHA / 50 % MPCA ... : * 100 % Anchor IPD

-50 % MPCA / 50 % IPD w 100 % PACM * 100 % Ancamine 2264

****** 70 % APCHA / 30 % MPCA w 70 % MPCA / 30 % APCHA

Patent Application Publication Feb. 25 , 2021 US 2021/0054134 A1

Viscosity Profile @ 40°C

2,500

2,000

iscosity 1,500
V(
)
CP

1,000 .

..
***************

500

0
minutes
100% APCHA 50% APCHA / 50% MPCA 100 % Anchor IPD

50 % MPCA / 50 % IPD W100 % PACM * 100% Ancamine 2264

****** 70 % APCHA / 30% MPCA 70 % MPCA / 30% APCHA

Fig . 1
US 2021/0054134 A1 Feb. 25 , 2021
1

CYCLOALIPHATIC AMINES FOR EPOXY volatile components , and (2 ) an excessive exothermic tem
FORMULATIONS : A NOVEL CURING perature ( >200 ° C. ) during the cure process which may
AGENT FOR EPOXY SYSTEMS create a hot ( burn ) spot in the parts and could melt the
thermoplastic liner ( e.g. HDPE liner use for Filament wound
BACKGROUND OF THE INVENTION Pressure Vessels ).
[ 0001 ] Cycloaliphatic amines are commonly used as [ 0006 ] For an advanced composite to achieve higher per
epoxy curing agents for heat cured structural composite formance, multifunctional resins and curing agents are often
applications. The class of amine used as a curing agent is used . The multifunctional materials usually have a very high
vital to achieve the final performance of the cured product. starting viscosity. To reduce the formulation viscosity, heat
Each of the amine classes , primary or secondary, is cured at is commonly used . This approach increases the reactivity,
a specific temperature in order to achieve full cure . The cure thus causing some handling issues . As the composite parts
temperature dictates the final service temperature, which is get bigger and thicker the formulation viscosity needs to be
indicated by its T. In general, epoxy resins are predomi lower to have an optimum wetting of a reinforcement (e.g.
nately cured with primary and secondary amines. Tertiary glass , carbon , Kevlar, natural fiber etc ).
amines are generally used as co - curing agents or catalysts in [ 0007] Systems for composite processing require an initial
combination with primary and secondary amines . mixed viscosity low enough and rate of viscosity increase at
[ 0002 ] Epoxy resin systems are used in the manufacturing the impregnation temperature low enough to enable the
of various structural parts, including composites. Examples reinforcing fiber preform to be completely wet with resin
of articles that are being evaluated for manufacturing from before the resin system becomes too viscous for satisfactory
epoxy resin systems include composite pipes , pressure ves flow through the fibers and fabric of the substrate. The
sels , automotive parts and windmill blades . Fabricating such requirement for low initial viscosity and long pot life
parts includes a number of requirements for effective manu becomes more stringent as the size of the composite part
facturing especially when complex manufacturing processes increases.
are used . These processes include but are not limited to resin [ 0008 ] WO2016208618A1 discloses a fiber - reinforced
infusion , resin transfer molding , filament winding and large composite material obtained using an epoxy resin compo
casting. One need in the art is for reduced exothermic heat sition where the epoxy resin composition comprises an
release during the epoxy resin system cure of the article in epoxy resin including an aromatic ring and having a func
thicker sections of the article, since in such sections , the tionality of 2 or higher and an amine -based hardener or an
exothermic heat released during cure cannot be easily con acid - anhydride based hardener.
ducted away from the article . If excessive temperatures are [ 0009] In light of the above, there is a need in the art for
reached during the cure process , thermal degradation of the improved curing agents for producing epoxy resin systems
cured resin in the " hot spots” can occur with resultant which have reduced exothermic heat release combined with
mechanical property loss in the fabricated parts. desired cured mechanical properties when compared to the
[ 0003 ] Additionally, during cure, the composite parts may prior art resin compositions. Such curing agents must be free
undergo thermal shrinkage. Thermal shrinkage of a cured of undesirable features such as volatile emissions .
epoxy resin causes stresses to build up in a composite during BRIEF SUMMARY OF THE INVENTION
cool down from the maximum temperature reached at or
after gelation. The stresses sometimes lead to interlaminar [ 0010 ] It has been discovered that cycloaliphatic amines,
cracking in the article, with resultant loss of mechanical preferably N-( 3 -aminopropyl) cyclohexylamine ( APCHA )
properties. The higher the temperature reached during cure and the hydrogenated product of oligomeric structure from
after the gel point, the greater the amount of stress that will the 4,4 '-Methylenedianiline process, can be used as the main
accumulate in the article during cooling. curing agent for epoxy resin compositions without inducing
[ 0004 ] Standard epoxy systems for fabricating structural the negative impact on mechanical, thermal and chemical
parts are cured with stoichiometric quantities of aliphatic properties of the cured product normally seen with cycloa
amines , usually primary amines . The systems generally have liphatic amine - based curing agents. The major drawback
high cure exothermic temperatures, with the center of a with cycloaliphatic amines is that they require a higher
100 - gram mass of resin / curing agent mixture contained curing or processing temperature to achieve full cure . Using
within a three inch diameter cylinder often reaching a peak APCHA and the hydrogenated product of oligomeric struc
temperature of 250 ° C. or higher when cured in a 70 ° C. ture from the 4,4 '-Methylenedianiline process as the main
oven . Alternatively, epoxy systems cured with anhydride curing agent achieves full cure at a significantly lower
based curing agents may often have lower cure exothermic temperature than current cycloaliphatic amine curing agents .
heat release than those cured with primary amines. However, Test results show that using APCHA and the hydrogenated
anhydride -cured systems typically require higher mold tem product of oligomeric structure from the 4,4 -Methylenedi
peratures than systems cured with primary aliphatic amines aniline process as the main curing agent maintains good
to reach an acceptable degree of cure and level of cured mechanical, thermal and chemical performance in the cured
properties. epoxy composition and exceeds the mechanical properties of
[ 0005 ] Cycloaliphatic amines currently used in epoxy for other cycloaliphatic amines. In addition , formulations con
mulations are known to require a higher temperature (> 130 taining APCHA and the hydrogenated product of oligomeric
C for 2 hrs ) to achieve full cure in a short time . Some structure from the 4,4 '-Methylenedianiline process give
limitations to achieving full cure at such a high temperature lower viscosity, longer pot life, low temperature T , devel
include ( 1 ) increased fuming/volatility of an amine before it opment and lower exotherm during cure compared to cured
crosslinks with the epoxy group which creates an environ epoxy compositions using current cycloaliphatic amine cur
mental concern and unsafe working conditions for the ing agents . APCHA and the hydrogenated product of oligo
worker in the manufacturing site who may inhale the highly meric structure from the 4,4 '-Methylenedianiline process
US 2021/0054134 A1 Feb. 25 , 2021
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can also be used in combination with primary and secondary

amines as co -curing agents to further enhance the desirable H
properties. The lower viscosity of APCHA helps in fiber NH2
wetting. Preliminary results using APCHA and the hydro
genated product of oligomeric structure from the 4,4 '-Meth
ylenedianiline process in composite applications (filament
wound pipes & fittings, wind blades , high pressure vessels ,
structural laminates , automotive body parts, aerospace, etc. )
are quite encouraging. The second amine component is represented by the formula :
[ 0011 ] An aspect of the invention is an epoxy curing agent
comprising a first amine component, a second amine com
ponent, and optionally, a third amine component. The first
amine component is N-( 3 -aminopropyl) cyclohexylamine
( APCHA ) , represented by the formula : H2N R,

H
where R is NH2 . The second amine component is formed as
NH2 a hydrogenated product of oligomeric structure in the 4,4'
Methylenedianiline process. The second amine component
is formaldehyde, polymer with benzenamine, hydrogenated
(MPCA , CAS # 135108-88-2 ) . The third amine component
consists of at least one primary amine, at least one secondary
The second amine component is represented by the formula : amine , and / or at least one tertiary amine . The third amine
component preferably comprises one or more amine com
pounds selected from the group consisting of a polyether
amine , polyether diamine , a saturated aliphatic ring diamine,
a linear aliphatic amine , a cycloaliphatic amine, a polycy
cloaliphatic amine , an aromatic amine , and combinations
R H2N R, thereof.
[ 0014 ] In one embodiment, the first amine component
comprises at least 1 % by weight of the amine -based curing
where R is NH2 . The second amine component is formed as agent. In another embodiment, the first amine component
a hydrogenated product of oligomeric structure in the 4,4' comprises at least 10 % by weight of the amine- based curing
Methylenedianiline process . The second amine component
is formaldehyde, polymer with benzenamine , hydrogenated agent. In another embodiment, the first amine component
( MPCA , CAS # 135108-88-2 ) . The third amine component comprises at least 30 % by weight of the amine - based curing
consists of at least one primary amine, at least one secondary agent. In another embodiment, the first amine component
amine , and / or at least one tertiary amine . The third amine comprises at least 50 % by weight of the amine - based curing
component preferably comprises one or more amine com agent. In another embodiment, the first amine component
pounds selected from the group consisting of a polyether comprises at least 70 % by weight of the amine -based curing
amine , polyether diamine , a saturated aliphatic ring diamine, agent. In another embodiment, the first amine component
a linear aliphatic amine, a cycloaliphatic amine, a polycy comprises at least 90 % by weight of the amine - based curing
cloaliphatic amine , an aromatic amine, and combinations agent .
thereof.
[ 0012 ] In one embodiment, the first amine component [ 0015 ] Another aspect of the invention is a method for
comprises at least 1 % by weight of the epoxy curing agent. producing a cured epoxy resin composition , comprising ( a )
In another embodiment, the first amine component com combining an epoxy resin component with an amine - based
prises at least 10 % by weight of the epoxy curing agent. In curing agent component, the amine- based curing agent com
another embodiment, the first amine component comprises ponent comprising a first amine component and a second
at least 30 % by weight of the epoxy curing agent. In another amine component; and (b ) reacting the amine -based curing
embodiment, the first amine component comprises at least agent component and the epoxy resin component to form a
50 % by weight of the epoxy curing agent. In another cured epoxy resin composition . The first amine component
embodiment, the first amine component comprises at least is N- ( 3 - aminopropyl ) cyclohexylamine ( APCHA ), repre
70 % by weight of the epoxy curing agent. In another sented by the formula :
embodiment, the first amine component comprises at least
90 % by weight of the epoxy curing agent.
[ 0013 ] Another aspect of the invention is a composition
containing the reaction product of an epoxy resin component
and an amine -based curing agent component. The amine
based curing agent component has a first amine component,
a second amine component, and optionally, a third amine
component. The first amine component is N-(3 -aminopro
pyl ) cyclohexylamine ( APCHA ) , represented by the for
mula :
oh NH2 ,
US 2021/0054134 A1 Feb. 25 , 2021
3

and the second amine component is represented the formula : DETAILED DESCRIPTION OF THE
INVENTION
[ 0022 ] The epoxy resin system of the invention includes
the reaction product of at least one epoxy resin component
and an amine -based curing agent component comprising a
R H2N R, first amine component and a second amine component. The
first amine component is N-( 3 -aminopropyl) cyclohexylam
where R is NH2 . The second amine component is formed as
ine ( APCHA ) and the second amine component is the
a hydrogenated product of oligomeric structure in the 4,4' hydrogenated product of oligomeric structure from the 4,4'
Methylenedianiline process . The invention comprises the
Methylenedianiline process . The second amine component use of APCHA in combination with the hydrogenated prod
is formaldehyde, polymer with benzenamine, hydrogenated uct of oligomeric structure from the 4,4 '-Methylenedianiline
( MPCA , CAS # 135108-88-2 ) . In one embodiment, the first process as a curing agent for epoxy resins , especially in
amine component comprises at least 1 % by weight of the composite applications or ambient and heat cured coating
amine -based curing agent. In another embodiment, the first applications .
amine component comprises at least 10 % by weight of the [ 0023 ] The amine - based curing agent component can fur
amine -based curing agent. In another embodiment, the first ther comprise a third amine component consisting of at least
amine component comprises at least 30 % by weight of the one primary amine, at least one secondary amine, and / or at
amine -based curing agent. In another embodiment, the first least one tertiary amine .
amine component comprises at least 50 % by weight of the [ 0024 ] In prior art epoxy resin systems , the amine curing
amine -based curing agent. In another embodiment, the first agent is usually added to the epoxy in such an amount that
amine component comprises at least 70 % by weight of the for each epoxy group in the system there is one reactive
amine -based curing agent. In another embodiment, the first hydrogen atom in the curing agent. These are known as
amine component comprises at least 90 % by weight of the stoichiometric quantities . However, one aspect of the pres
amine -based curing agent. ent invention is that when primary and secondary amines are
[ 0016 ] The weight ratio of the epoxy resin to N-( 3 used as co -curing agents with the N-( 3 - aminopropyl) cyclo
aminopropyl( cyclohexylamine) and second amine is 1 : 0.05 : hexylamine ( APCHA ), the NH bonds of the primary
0.95-1 : 0.95 : 0.05 . In another embodiment, the weight ratio is and / or secondary amines may be provided with stoichio
1 : 0.95 : 0.05 . In a further embodiment, the weight ratio is metric ratios to epoxy groupssl.
1 : 0.29 : 0.4 .
[ 0017] The amine - based curing agent component can fur [ 0025 ] In comparison with prior art systems based on
ther comprise a third amine component. The third amine mixtures of epoxy resins with stoichiometric quantities of
component consists of at least one primary amine, at least primary and / or secondary amines, the epoxy resin systems
one secondary amine and / or at least one tertiary amine . The described herein have unexpectedly and surprisingly pro
third amine component preferably comprises one or more vided the advantages of lowered cure exothermic tempera
amine compounds selected from the group consisting of a tures and heat generation with improved control on cure
polyether amine, polyether diamine, a saturated aliphatic shrinkage, and in some cases , a more rapid cure rate under
ring diamine, a linear aliphatic amine , a cycloaliphatic lower temperature ( enabling reduced cycle times ) .
amine , a polycycloaliphatic amine , an aromatic amine , and [ 0026 ] As used herein , the term “ amine -based curing
combinations thereof. agent” means a curing agent for which amines comprise at
[ 0018 ] The polyether amine may have the formula: least 80 % (by weight) of the overall weight of the curing
agent.
HUNCH (CH )CH [OCH_CH (CH3) NH2, and x is from 2 [ 0027] As used herein , the term “ amine ” or “ amine com
to 70. The third amine may comprise a mixture of 4,4' pound” means any derivative of ammonia in which alkyl or
methylene bis cyclohexylamine, isophorone diamine, 1,2
diamino cyclohexane, 4,4 '-methylenebis ( 2-methylcyclo aryl groups replace one or more hydrogen atoms bonded to
hexyl amine ) , 1,3 - bis aminomethyl cyclohexane and the nitrogen. The term “ primary amine” or “ primary amine
polyether amine : H NCH ( CH3) CH [OCH CH (CH )]2. compound ” means an amine where one of the three hydro
SNH gen atoms in ammonia is replaced by an alkyl or aromatic
[ 0019 ] A modified amine compound such as a Mannich group (a C - N bond ). The term “ secondary amine” or
base , a polyamide compound, an amine- epoxy adduct, and “ secondary amine compound ” means an amine having two
combinations thereof may be used as a co -curing agent for alkyl or aryl groups in place of two hydrogens. The term
use with the N-( 3 - aminopropyl (cyclohexylamine) com “ tertiary amine ” or “ tertiary amine compound ” means an
pound as described herein . amine having three alkyl or aryl groups in place of three
[ 0020 ] The epoxy resin component may comprise a hydrogens. Any amine having more than one class of amine
polyglycidyl ether of a compound selected from the group functional group may be categorized according to more than
consisting of an aliphatic glycol , a cycloaliphatic glycol , a one class of amine ( primary , secondary, or tertiary ).
triol, a polyol , a polyglycol , and combinations thereof. The [ 0028 ] Referring to FIG . 1 , the viscosity profile at 40 ° C.
epoxy resin system may further comprise a polyacrylate or for epoxy resin compositions comprising 100% APCHA is
polymethacrylate ester of a polyol . compared to the viscosity profile for epoxy resin composi
tions comprising a combination of APCHA and the hydro
BRIEF DESCRIPTION OF THE DRAWINGS genated product of oligomeric structure from the 4,4'-Meth
ylenedianiline process . The time (min ) of reactivity of the
[ 0021 ] FIG . 1 shows the viscosity profile at 40 ° C. for compositions is significantly increased in the presence of
epoxy resin compositions comprising APCHA . APCHA .
US 2021/0054134 A1 Feb. 25 , 2021
4

[ 0029 ] Epoxy Resin Composition bis- ( 4 -hydroxyphenyl ) -propane ( commercially known as

[ 0030 ] One aspect of the invention comprises an epoxy bisphenol A ) , bis- ( 4 -hydroxyphenyl)-methane ( commer
resin composition including a reaction product of an epoxy cially known as bisphenol - F, and which may contain varying
resin component and a curing agent component comprising amounts of 2 -hydroxyphenyl isomers ), and the like , or any
N- ( 3 - aminopropyl) cyclohexylamine ( APCHA ), and the combination thereof. Additionally, advanced dihydric phe
hydrogenated product of oligomeric structure from the 4,4' nols of the structure of formula ( 1 ) also are useful in the
Methylenedianiline process. Hereinafter, the portion of the present disclosure:
curing agent consisting of N- ( 3 - amino propyl(cyclohex
ylamine ) is referred to as the first amine component and the
portion of the curing agent consisting of the hydrogenated (1 )
product of oligomeric structure from the 4,4 '-Methylenedi OH
aniline process is referred to as the second amine compo
nent. The curing agent component can further comprise a
third amine component consisting of one or more primary 17

amines , one or more secondary amines, and / or one or more

tertiary amines. where m is 0 to 25 , and R is a divalent hydrocarbon radical
[ 0031 ] In the epoxy resin composition, the weight ratio of of a dihydric phenol, such as those dihydric phenols listed
the epoxy resin component to the first amine component in above .
the curing agent ranges from 1 : 0.05 to 1 : 0.95 . In one [ 0037] Materials according to formula ( 1 ) can be prepared
embodiment, the range is 1 : 0.29 . The equivalent ratio of by polymerizing mixtures of a dihydric phenol and epichlo
resin to an amine is 1 : 0.1 to 1 : 0.5 . The weight ratio of the rohydrin , or by advancing a mixture of a diglycidyl ether of
epoxy resin component to the second amine component the dihydric phenol and the dihydric phenol. While in any
ranges from 1 : 0.05 to 1 : 0.95 . given molecule the value of m is an integer, the materials are
[ 0032 ] In one embodiment, the first amine component invariably mixtures which can be characterized by an aver
comprises at least 1 % by weight of the overall weight of the age value of m which is not necessarily a whole number.
curing agent. In another embodiment, the first amine com Polymeric materials with an average value of m between 0
ponent comprises at least 10 % by weight of the overall and about 7 can be used in one aspect of the present
weight of the curing agent. In another embodiment, the first disclosure . In other embodiments, the epoxy component
amine component comprises at least 30 % by of the overall may be a polyglycidyl amine from one or more of 2,2'
weight of the curing agent. In another embodiment, the first methylene dianiline, 4,4 ' -methylene dianiline, m -xylene
amine component comprises at least 50 % by weight of the dianiline, hydantoin , and isocyanate.
overall weight of the curing agent. In another embodiment, [ 0038 ] The epoxy resin component may be a cycloali
the first amine component comprises at least 70 % by weight phatic ( alicyclic ) epoxide. Examples of suitable cycloali
of the overall weight of the curing agent. In another embodi phatic epoxides include diepoxides of cycloaliphatic esters
ment, the first amine component comprises at least 90 % by of dicarboxylic acids such as bis ( 3,4 -epoxycyclohexylm
weight of the overall weight of the curing agent. ethyl )oxalate, bis ( 3,4 -epoxycyclohexylmethyl ) adipate , bis
[ 0033 ] In one embodiment, the epoxy component com ( 3,4 - epoxy - 6 -methylcyclohexylmethyl )adipate, vinylcyclo
prises 30 % to 99 % (by weight) of the overall weight of the hexene diepoxides; limonene diepoxide ; bis( 3,4
epoxy resin system . In another embodiment, the epoxy epoxycyclohexylmethyl )pimelate; dicyclopentadiene
component comprises 40 % to 92 % (by weight) of the overall diepoxide ; and other suitable cycloaliphatic epoxides . Other
weight of the epoxy resin system . In another embodiment, suitable diepoxides of cycloaliphatic esters of dicarboxylic
the epoxy component comprises 50 % to 85 % (by weight), of acids are described , for example, in Patent Application
the overall weight of the epoxy resin system . Publication No. WO 2009/089145 Al , which is hereby
[ 0034 ] Epoxy Resin Component incorporated by reference in its entirety.
[ 0035 ] The epoxy resin component can consist of a single [ 0039 ] Other cycloaliphatic epoxides include 3,3 -epoxy
resin , or it can be a mixture of mutually compatible epoxy cyclohexylmethyl- 3,4 -epoxycyclohexane carboxylate such
resins . The epoxy resin may include, but is not limited to , as 3,4 - epoxycyclohexylmethyl -3,4 -epoxycyclohexane car
bi - functional epoxies , such as , bisphenol- A and bisphenol- F boxylate ; 3,3 - epoxy - 1-methylcyclohexyl-methyl-3,4 -ep
resins . Multifunctional epoxy resin , as utilized herein , oxy - 1 -methylcyclohexane carboxylate; 6 -methyl-3,4 -ep
describes compounds containing two or more 1,2 - epoxy oxycyclohexylmethylmethyl-6 -methyl-3,4
groups per molecule . Epoxide compounds of this type are epoxycyclohexane carboxylate; 3,4 -epoxy - 2
well known to those of skill in the art and are described in methylcyclohexyl -methyl- 3,4 - epoxy - 3 -methylcyclohexane
Y. Tanaka, “ Synthesis and Characteristics of Epoxides ” , in carboxylate. Other suitable 3,4 -epoxycyclohexylmentyl- 3,
C. A. May , ed . , Epoxy Resins Chemistry and Technology 4 -epoxycyclohexane carboxylates are described, for
(Marcel Dekker, 1988 ) , which is incorporated herein by example, in U.S. Pat. No. 2,890,194 , which is hereby
reference in its entirety. incorporated by reference in its entirety. In other embodi
[ 0036 ] One class of epoxy resins suitable for use in the ments, the epoxy component may include polyol polygly
epoxy resin component comprises the glycidyl ethers of cidyl ether from polyethylene glycol , polypropylene glycol
polyhydric phenols, including the glycidyl ethers of dihydric or polytetrahydrofuran or combinations thereof.
phenols. Illustrative examples include, but are not limited to , [ 0040 ] In another aspect , epoxy novolac resins , which are
the glycidyl ethers of: resorcinol, hydroquinone, bis- (4 the glycidyl ethers of novolac resins , can be used as multi
hydroxy -3,5 -difluorophenyl )-methane, 1,1-bis-(4 -hydroxy functional epoxy resins in accordance with the present
phenyl )-ethane, 2,2 -bis- (4 -hydroxy -3 -methylphenyl)-pro disclosure. In yet another aspect , the at least one multifunc
pane, 2,2 -bis- ( 4 -hydroxy - 3,5 -dichlorophenyl) propane , 2,2 tional epoxy resin is a diglycidyl ether of bisphenol - A
US 2021/0054134 A1 Feb. 25 , 2021
5

( DGEBA) , an advanced or higher molecular weight version [ 0047] Second Amine Component
of DGEBA , a diglycidyl ether of bisphenol - F, an epoxy [ 0048 ] The second amine component is the hydrogenated
novolac resin , or any combination thereof. Higher molecular product of oligomeric structure from the 4,4 -Methylenea
weight versions or derivatives of DGEBA are prepared by niline process , represented by the formula :
the advancement process , where excess DGEBA is reacted
with bisphenol- A to yield epoxy terminated products. The
epoxy equivalent weights (EEW) for such products range
from about 450 to 3000 or more . Because these products are
solid at room temperature, they are often referred to as solid
epoxy resins. R H?N R,
[ 0041 ] DGEBA or advanced DGEBA resins are often used
for structural formulations due to a combination of their low where R is NH2
cost and generally high performance properties. Commercial [ 0049 ] Third Amine Component
grades of DGEBA having an EEW ranging from about 174 [ 0050 ] The third amine component can consist of a single
to about 250 , and more commonly from about 185 to about amine or a mixture of amines . The amines in the third amine
195 , are readily available . At these low molecular weights, component are primary, secondary , and / or tertiary amines .
the epoxy resins are liquids and are often referred to as liquid [ 0051 ] In some applications, the following are suitable as
epoxy resins . It is understood by those skilled in the art that the third amine component: a polyether diamine , a saturated
most grades of liquid epoxy resin are slightly polymeric , aliphatic ring diamine , a linear aliphatic amine , a cycloali
since pure DGEBA has an EEW of 174. Resins with EEWs phatic amine, a polycycloaliphatic amine, an aromatic
between 250 and 450 , also generally prepared by the amine , and combinations thereof. The weight ratio of the
advancement process , are referred to as semi - solid epoxy epoxy resin to N- ( 3 - aminopropyl (cyclohexylamine ) and
resins because they are a mixture of solid and liquid at room second amine is 1 : 0.05 : 0.95-1 : 0.95 : 0.05 . In another embodi
temperature. Generally, multifunctional resins with EEWs ment, the weight ratio is 1 : 0.4 : 0.6 . In another embodiment,
based on solids of about 160 to about 750 are useful in the
present disclosure. In another aspect , the multifunctional the weight ratio is 1 : 0.29 : 0.4 . Polyamines selected from one
epoxy resin has an EEW in a range from about 170 to about or more of an aliphatic polyamine such as diethylenetri
250 . amine (DETA ), triethylenetetramine ( TETA ), tetraethylene
( 0042 ] Depending upon the end -use application , it can be pentamine ( TEPA ), pentaethylenehexamine (PEHA ), hex
beneficial to reduce the viscosity of the compositions of the amethylenediamine (HMDA ), N - 2 -aminoethyl) -1,3
present disclosure by modifying the epoxy resin component. propanediamine ( N - Amine ), N , N '- 1,2-ethanediylbis- 1,3
The epoxy resin component, which comprises at least one propanediamine (N4 - amine ), or dipropylenetriamine; an
arylaliphatic polyamine such as m -xylylenediamine
multifunctional epoxy resin , further comprises a monofunc (mXDA ), or p -xylylenediamine; a cycloaliphatic polyamine
tional epoxide . Examples of monospoxides include , but are such as 1,3 -bis aminomethyl cyclohexane ( 1,3 - BAC ) , iso
not limited to , styrene oxide , cyclohexene oxide and the phorone diamine ( IPDA ), 4,4 ' -methylene bis cyclohexylam
glycidyl ethers of phenol, cresols, tert -butylphenol, other ine ( PACM ), 1,2 - diamino cyclohexane, or 4,4 '-methylen
alkyl phenols, butanol, 2 -ethylhexanol, C4 to C4 alcohols, ebis-( 2 -methyl -cyclohexyl -amine ); an aromatic polyamine
and the like , or combinations thereof. The multifunctional such as m - phenylenediamine, diaminodiphenylmethane
epoxy resin can also be present in a solution or emulsion, ( DDM ) , or diaminodiphenylsulfone ( DDS ) ; a heterocyclic
with the diluent being water, an organic solvent, or a mixture polyamine such as N -aminoethylpiperazine (NAEP ), or 3,9
thereof. bis (3 -aminopropyl) 2,4,8,10 - tetraoxaspiro (5,5 )undecane; a
[ 0043 ] Curing Agent Component polyalkoxypolyamine where the alkoxy group can be an
[ 0044 ] As noted above , the curing agent component is an oxyethylene, oxypropylene , oxy - 1,2 -butylene, oxy - 1,4
amine -based curing agent having a first amine component butylene or co - polymers thereof such as 4,7 -dioxadecane
and a second amine component. The first amine component 1,10 - diamine , 1 -propanamine, 3,3 '-(oxybis (2,1 -ethanediy
consists of N- ( 3 - aminopropyl) cyclohexylamine (APCHA ). loxy ) ) bis (diaminopropylated diethylene glycol
The second amine component consists of the hydrogenated ANCAMINE? 1922A ) , poly (oxy (methyl - 1,2 -ethanediyl)),
product of oligomeric structure from the 4,4 '-Methylenedi alpha- ( 2 - aminomethylethyl) omega- ( 2 -aminomethylethoxy )
aniline process. The curing agent component can further ( JEFFAMINE® D 230 , D - 400 ) , triethyleneglycoldiamine
comprise a third amine component consisting of at least one and oligomers ( JEFFAMINE® XTJ - 504 , JEFFAMINE?
primary amine , at least one secondary amine , and / or at least XTJ-512 ), poly ( oxy (methyl - 1,2 -ethanediyl) ), alpha ,alpha'
one tertiary amine . (oxydi - 2,1- ethanediyl) bis (omega - aminomethylethoxy ))
[ 0045 ] First Amine Component ( JEFFAMINE® XTJ - 511 ) , bis (3 -aminopropyl)polytetrahy
[ 0046 ] The first amine component is N-( 3 -aminopropyl) drofuran 350 , bis ( 3 - aminopropyl)polytetrahydrofuran 750 ,
cyclohexylamine (APCHA) , represented by the formula: poly (oxy (methyl- 1,2 -ethanediyl), a -hydro - w - 2 -aminom
ethylethoxy ) ether with 2 - ethyl- 2-(hydroxymethyl )-1,3 -pro
panediol ( 3 : 1 ) ( JEFFAMINER T -403 ), and diaminopropyl

???
H
dipropylene glycol . JEFFAMINE® is a registered trademark
NH2 . of Huntsman Petrochemical LLC .
[ 0052 ] Particularly suitable polyamines include iso
phoronediamine ( IPDA ) , 4,4 '-methylene bis cyclohexylam
ine (PACM ), 3,3 -dimethyl PACM (ANCAMINE? 2049 ) ,
N -aminoethylpiperazine (NAEP ), 4,7 -dioxadecane- 1,10 -di
amine,l-propanamine,3,3'-(oxybis(2,1 -ethanediyloxy ))bis
US 2021/0054134 A1 Feb. 25 , 2021
6

( ANCAMINE? 1922A ) , poly (oxy (methyl - 1,2 -ethanediyl)), tinuous fiber such as fiber glass , carbon fiber, carbon nano
alpha- ( 2 - aminomethylethyl )omega- ( 2 -aminomethylethoxy ) tubes, nano composite fibers, polyaramide fibers such as
( JEFFAMINER D 230 , D -400 ), poly (propylene glycol ) bis those sold under the trade name KEVLAR® , Poly (p -phe
( 2 - aminopropyl ether ), triethylene glycol diamine (JEF nylene benzobisoxazole ) fiber such as those sold under the
FAMINER XTJ - 504 ) , and poly (oxy (methyl- 1,2 -eth trade name ZYLON® , ultrahigh molecular weight polyeth
anediyl))alpha, alpha'-(oxy (di- 2,1-ethanediyl))bis(omega ylene fibers such as those sold under the trade name SPEC
( aminomethylethoxy )) ( JEFFAMINE® XTJ - 511 ) ormixture TRAR , high and low density polyethylene fibers, polypro
thereof. ANCAMINE® is a registered trademark of Evonik pylene fibers , nylon fibers , cellulose fibers, natural fibers,
Degussa GmbH . biodegradable fibers and combinations thereof.
[ 0053 ] Suitable tertiary amines include N -hydroxyethylpi
peridine, N -hydroxypropylpiperidine, 2 -methyl-N -hydroxy [ 0060 ] These fibers (woven or non- woven) can be coated
ethylpiperidine, N -hydroxymethylpiperidine, N -hydroxy with the solvent or solvent free epoxy resin mixture by the
ethylmorpholine, 1,4 -bis ( 2 -hydroxyethyl )piperazine, 1,4 standard impregnating methods, in particular for filament
dimethylpiperazine, N -cyclohexyl- N , N - dimethylamine, winding ( FW ) , pultrusion , sheet molding compound, bulk
N -cyclohexyl- N , N -diethylamine, N -cyclohexyl-N -ethyl- N molding compound autoclave molding, resin infusion ,
methylamine, N , N -dimethyl -N- ( 2 -methylcyclohexyl )amine, vacuum assisted resin transfer molding (VARTM ), resin
N , N -dicyclohexyl - N -methylamine, N -hydroxyethyl-N -cy transfer molding (RTM ), wet/hand lay -up, vacuum bagging ,
clohexyl -N -methylamine , N -cyclohexyl-N ,N -dipropylam resin impregnation, prepreg , fiber impregnation, compres
ine , N -cyclohexyl- N , N -dioctylamine, benzyldimethylamine sion molding (CM ), brushing, spraying, or dipping , casting,
(BDMA ), tris (dimethylaminomethyl)phenol (DMP - 30 , injection molding or combination thereof.
K54 ) , TEDA , N , N -dimethylpiperazine, 2-(dimethylami
nomethyl )phenol, and combinations thereof. [ 0061 ] Forming a Cured Epoxy Composition
[ 0054 ] Additional amines suitable for forming the third [ 0062 ] Mixing of the curing agent component and the
amine component are polyamines comprising at least one or epoxy component to form the epoxy resin composition can
more multifunctional amine of structure (3 ) . be in any order and by any appropriate means known in the
art for two component epoxy compositions. The mixing may
(3 ) be accomplished according to any known method for mix
RU R2 ing , including, but not limited to , mixing by magnetic
stirrers , high shear mixing , hand mixing , mechanical mixing
R4 R3 or other suitable mixing method . The mixing of the curing
component is preferably carried out at a temperature in the
range of 0 to 150 ° C. , preferably 30 to 60 ° C.
where R? is CH2CH2CH2NH2 ; R2 , R and R4 independently
are H or CH2CH2CH2NH2 ; and X is CH CH , or [ 0063 ] The curable epoxy resin compositions and cured
CH2CH2CH2 . In one embodiment R2 and Rz are not H products described herein may be useful as structural and
simultaneously. electrical laminates , coating, casting, structural components
[ 0055] Optional Additives for aerospace industries, and as circuit boards and the like
[ 0056 ] The epoxy system formulation for the composite for the electronics industry , among other applications. The
may optionally include additives , such as , but not limited to , curable epoxy resin compositions disclosed herein may also
non - reactive plasticizer ( s ), filler (s ), processing aid ( s ) , stabi be used in electrical varnishes , encapsulants, semiconduc
lizer, air release agent, viscosity modifier ( s ), UV absorbent tors , general molding powders , filament wound pipes and
agent, a flame retardant, and / or an impact modifier . fittings , filament wound pressure vessels , low and high
[ 0057] The optional acrylate or methacrylate esters of the pressure pipes and fittings, low and high pressure vessels ,
polyols are blended with the epoxy resin component in a storage tanks, wind turbine blades, automotive structural
weight ratio of from 0 to up to about 100 parts of ester for parts, aerospace structural parts , oil and gas buoyance mod
each 100 parts of epoxy resin component. In another ules , rigs , well plugs , cured -in - place -pipe (CIPP ), structural
embodiment, the acrylate or methacrylate esters of the bonding adhesives and laminates, a composite liner, liners
polyols are blended with the epoxy resin component in a for pumps, corrosion resistant coatings, and other suitable
weight ratio of about 5 to about 100 parts of ester for each epoxy containing products.
100 parts of epoxy resin component. [ 0064 ] The curable epoxy resin composition may be used
[ 0058 ] Nano materials/ fillers may be included . The term to form composite materials on a reinforced fiber substrate .
“ nanomaterials , " includes , but is not limited to , multi - wall The reinforced fiber substrate may be one or more layers of
carbon or boron nitride nanotubes, single -wall carbon , car fiberglass material . Contacting the reinforcing fiber substrate
bon or boron nitride nanoparticles, carbon or boron nitride with the epoxy resin system may comprise an application
nanofibers, carbon or boron nitride nanoropes , carbon or process selected from the group consisting of including hand
boron nitride nano ribbons, nanoclays; nanoclays compris lamination , an infusion process , filament winding , pultru
ing tubules; layered inorganic clay material; talc ; carbon sion , resin transfer molding , fiber pre -impregnation pro
black ; cellulose fibers; silica ; and alumina. cesses , and combinations thereof.
[ 0059 ] Reinforcing fibers may also be included in the
epoxy resin system . Suitable fibers include organic or inor [ 0065 ] In an embodiment, a method for producing the
ganic fibers, natural fibers or synthetic fibers, and may be cured epoxy resin composition comprises ( a) combining an
present in the form of wovens or non -crimp fabrics, non epoxy resin component with an amine - based curing agent
wovens webs or mats , and also in the form of fiber stands component, the amine - based curing agent component com
( rovings ), or staple fiber formed of continuous or discon prising a first amine component represented by the structure :
US 2021/0054134 A1 Feb. 25 , 2021
7

70 MPa with a strain of 2 % or greater and transverse tensile

H modulus of greater than 40 GPa , an in -plane inter- laminar
NH2, shear strength of greater than 40 MPa .
[ 0068 ] The following invention is directed to the follow
ing aspects :
< b > A method for producing a cured epoxy resin composi
tion , comprising :
(a ) combining an epoxy resin component with an amine
and a second amine component represented by the structure : based curing agent component , the amine - based curing
agent component comprising a first amine component rep
resented by the structure :

ch
H
R H?N R,
NH2 ,
where R is NH2 ;
and ( b ) reacting the at least one amine compound and the
epoxy resin to form a cured epoxy resin composition. The
method steps (a ) and ( b ) may be performed in an oven at a and a second amine component represented by the structure :
first ambient temperature and a maximum internal tempera
ture during steps (a ) and (b ) maintained that is no more than
175 ° C. above the first ambient temperature. The first
ambient temperature is 25 ° C. The maximum internal tem
perature is no more than 200 ° C. The amine- based curing
agent component can further comprise a third amine com R H2N R,
ponent consisting of primary, secondary, and / or tertiary
amines . In one embodiment, the first amine component
comprises at least 1 % by weight of the amine -based curing wherein R is NH2 ; and
agent. In another embodiment, the first amine component ( b ) reacting the amine -based curing agent component and
comprises at least 10 % by weight of the amine - based curing the epoxy resin component to form a cured epoxy resin
agent. In another embodiment, the first amine component composition.
comprises at least 30 % by weight of the amine- based curing <2 > A preferred method of aspect < b > wherein the first
agent. In another embodiment, the first amine component amine component comprises at least 1 % by weight of the
comprises at least 50 % by weight of the amine - based curing amine -based curing agent.
agent. In another embodiment, the first amine component <3 > A preferred method of aspect < b > further comprising a
comprises at least 70 % by weight of the amine - based curing third amine component having at least one amine compound
agent. In another embodiment, the first amine component selected from the group of a primary amine, a secondary
comprises at least 90 % by weight of the amine - based curing amine , and a tertiary amine .
agent. <4 > A preferred method of aspect <3 > wherein the third
[ 0066 ] When cured , the reaction product of the epoxy amine component comprises at least one polyether amine ,
resin component and the curing agent component may polyether diamine , a saturated aliphatic ring diamine, a
exhibit a Ty of 70 ° C. or greater at a cure time of less than linear aliphatic amine , a cycloaliphatic amine , a polycycloa
2 hours as measured by Differential Scanning Calorimetry liphatic amine , an aromatic amine, and combinations
thereof.
(DSC ). The glass transition temperature ( To) was measured
using DSC of the epoxide -based composition cured at 100 ° < 5 > A preferred method of aspect < b > further comprising:
C. for 2 hours according to the present invention . 20 mg of performing steps ( a) and (b ) at a first ambient temperature ;
the cured composition was carefully measured in an alumi and maintaining a maximum internal temperature during
num pan and sealed with the lid . A sample of this cured steps ( a ) and (b ) that is no more than 175 ° C. above the first
composition was analyzed by DSC ( TA Instruments QA20 ) ambient temperature .
using a program that starts at 25 ° C. and heats at 10 ° < b > A preferred method of aspect < b > further comprising:
C./minute up to 250 ° C. , cools and scans a second time to applying the epoxy resin composition to a reinforcing fiber
250 ° C. The first scan provides residual peak exotherm if prior to step (b ) .
any and heat of reaction , while the second scan confirms the <7 > A preferred method of aspect < 6 > wherein the reinforc
glass transition temperature . When curing, the reaction ing fiber is selected from the group consisting of woven or
product of the epoxy resin component and the curing agent non - crimp fabrics, nonwoven webs or mats, fiber stands,
may exhibit a maximum exothermic temperature of below staple fiber formed of continuous or discontinuous fiber, and
50 ° C. or lower for a 100 gram mass in an oven at 70 ° C. combinations thereof.
[ 0067] The product formed from the epoxy resin compo < 8 > A preferred method of aspect < b > wherein the reinforc
nent and the curing agent may exhibit a maximum exother ing fiber is selected from the group consisting of fiberglass,
mic temperature of 50 ° C. or lower during formation. The carbon fiber, carbon nanotubes, nano composite fibers, pol
product may further include a reinforcing fiber substrate . yaramide fibers, poly (p -phenylene benzobisoxazole) fiber,
The product may be in the form of various structural parts. Aramid Kevlar fiber, ultrahigh molecular weight polyethyl
The product may exhibit a flexural strength of greater than ene fiber, high and low density polyethylene fibers , poly
US 2021/0054134 A1 Feb. 25 , 2021
8

propylene fibers, nylon fibers, cellulose fibers, natural fibers , < 15 > A preferred composition of aspect < 14 > wherein the
biodegradable fibers, and combinations thereof. first amine component comprises at least 1 % by weight of
< 9 > A preferred method of aspect < 8 > wherein the epoxy the amine -based curing agent.
resin composition is made from a process selected from the < 16 > A preferred composition of aspect < 14 further com
group consisting of resin infusion, vacuum misted resin prising a third amine component having at least one amine
transfer molding ( VARTM ), resin transfer molding (RTM ), compound selected from the group of a primary amine , a
filament winding (FW ) , compression molding ( CM) , wet/ secondary amine , and a tertiary amine.
hand lay - up , vacuum bagging , injection molding , prepreg , < 17 > A preferred composition of aspect < 16 > wherein the
fiber impregnation, casting , and combinations thereof. third amine component comprises at least one polyether
< 10 > An epoxy curing agent comprising a first amine amine , polyether diamine , a saturated aliphatic ring diamine,
component represented by the structure : a linear aliphatic amine, a cycloaliphatic amine, a polycy
cloaliphatic amine , an aromatic amine , and combinations
H thereof.
< 18 > A preferred composition of aspect < 14 > wherein the
NH2, epoxy resin component comprises about 1 % to about 99 %
by weight of the composition .
< 19 > A preferred composition of aspect < 14 > wherein the
epoxy resin component comprises a glycidyl ether of poly
hydric phenol.
and a second amine component represented by the structure : <20> A preferred composition of aspect < 14 wherein the
epoxy resin composition comprises at least one glycidyl
ether selected from the group of glycidyl ethers of resorci
nol , hydroquinone, bis-(4 -hydroxy - 3,5 - difluorophenyl)
methane, 1,1 -bis- ( 4 -hydroxyphenyl ) -ethane, 2,2 -bis-(4 -hy
R H2N R,
droxy - 3 -methylphenyl ) -propane, 2,2 -bis- (4 - hydroxy- 3,5
dichlorophenyl) propane, 2,2 -bis-(4 - hydroxyphenyl)
propane, bis- ( 4 -hydroxyphenyl )-methane, novolac resins,
wherein R is NH2 . and combinations thereof.
< 11 > A preferred epoxy curing agent of aspect < 10 > <21 > A preferred composition of aspect < 14 > wherein the
wherein the first amine component comprises at least 1 % by epoxy resin component comprises at least one dihydric
weight of the epoxy curing agent . phenol of the following structure :
< 12 > A preferred epoxy curing agent of aspect < 10 > further
comprising a third amine component having at least one
amine compound selected from the group of a primary
Varen
OH
amine , a secondary amine, and a tertiary amine.
< 13 > A preferred epoxy curing agent of aspect < 12 > R
wherein the third amine component comprises at least one 171

polyether amine , polyether diamine, a saturated aliphatic

ring diamine , a linear aliphatic amine , a cycloaliphatic wherein m is 0 to 25 and R is a divalent hydrocarbon radical.
amine , a polycycloaliphatic amine , an aromatic amine , and 22 > A preferred composition of aspect < 14 wherein the
combinations thereof.
< 14 > A composition comprising the reaction product of an epoxy resin component comprises at least one member
epoxy resin component; and an amine -based curing agent selected from the group of bis (3,4 -epoxycyclohexylmethyl)
component, wherein the amine -based curing agent compo oxalate , bis(3,4 - epoxycyclohexylmethyl)adipate, bis (3,4
nent comprises a first amine component represented by the epoxy - 6 -methylcyclohexylmethyl ) adipate, vinylcyclohex
structure : ene diepoxides; limonene diepoxide; bis (3,4
epoxycyclohexylmethyl)pimelate; dicyclopentadiene
H diepoxide, 3,3 - epoxycyclohexylmethyl- 3,4 -epoxycyclo
| hexane carboxylate such as 3,4 -epoxycyclohexylmethyl- 3 ,
NH ,
4 -epoxycyclohexane carboxylate ; 3,3 -epoxy -1 -methylcy
clohexyl -methyl -3,4 -epoxy - 1 -methylcyclohexane
carboxylate; 6 -methyl-3,4 -epoxycyclohexylmethylmethyl
6 -methyl -3,4 - epoxycyclohexane carboxylate ; 3,4 -epoxy - 2
methylcyclohexyl -methyl- 3,4 - epoxy - 3 -methylcyclohexane
and a second amine component represented by the structure : carboxylate, and combinations thereof.
<23 > Use of the composition of aspect < 14 , optionally in
combination with reinforcing fiber, for the production of
filament wound pipes and fittings, filament wound pressure
vessels , low and high pressure pipes and fittings, low and
R H2N R, high pressure vessels , storage tanks, wind turbine blades ,
automotive structural parts, aerospace structural parts, oil
and gas buoyance modules, rigs , well plugs , cure- in - place
wherein R is NH2. pipe (CIPP ) , structural bonding adhesives and laminates ,
US 2021/0054134 A1 Feb. 25 , 2021
9

encapsulants, semiconductors, corrosion resistance coatings, Example 2

a composite liner and other suitable epoxy containing appli [ 0073 ] This example describes the preparation of epoxy
cations.
curing agent blends and testing of cured epoxy resin for
EXAMPLES mulations.
[ 0069 ] These Examples are provided to demonstrate cer TABLE 2
tain aspects of the invention and shall not limit the scope of Hydrogenated Mixed Viscosity
the claims appended hereto . product of oligomeric with Epoxy
Example 1 Epoxy structure from the N -cyclohexyl ( EEW190 ) @
curing 4,4 '-Methylenedianiline 1,3 - propane 40 ° C.
agent process diamine ( CPs )
[ 0070 ] This example describes the preparation and testing
of curing agent blends . 1 100 % 0% > 100,000
[ 0071 ] The N - cyclohexyl- 1,3 -propane diamine ( APCHA ) 2 0%
70 %
100 % 183
1,000
is mixed with the hydrogenated product of oligomeric 3
4 50 %
30 %
50 % 333
structure from the 4,4 '-Methylenedianiline process (MPCA , 5 30 % 70% 267
CAS # 135108-88-2 ) to make the liquid curing component.
TABLE 1 [ 0074 ] Several curing agent formulations were prepared .
The hydrogenated product of oligomeric structure from the
Hydrogenated 4,4 '-Methylenedianiline process ( MPCA) was mixed with
product of oligomeric N Amine Amine N - cyclohexyl - 1,3 -propane diamine ( APCHA ) at different
structure from the cyclohexyl- Blend Blend
ratios to make curing agents for epoxy resin . Both products
4,4 '-Methylene 1,3 -propane Viscosity @ Viscosity @ were mixed in the amounts shown in Table 2. To facilitate
dianiline process diamine 25 ° C. 40 ° C.
Blend ( MPCA) ( APCHA ) ( cPs ) ( cPs ) mixing, both the hydrogenated product of oligomeric struc
1 100 % 0 Semi - Solid > 100,000 ture from the 4,4 '-Methylenedianiline process (MPCA) and
2 90 % 10 % 13,679 1,600 the N -cyclohexyl - 1,3 -propane diamine ( APCHA ) were pre
3 80 % 20 % 2,135 409 heated separately at 50 ° C. for 1 hour. Curing agents 3-5
4 70 % 30 % 459 128
62
were mixed with magnetic stirrer at 1000 rpm at 50 ° C. for
5
6
60 %
50 %
40 %
50 %
184
81 31 1 hour. Resulting curing agents were used to cure epoxy
7 40 % 60 % 40 20 resin ( epoxy equivalent weight ( EEW) 180) at varied stoi
30 % 70 % 24 12 chiometric ratios shown in Table 3. The liquid epoxy resin
9
10
20 %
10 %
80 %
90 %
15
10
10
6
(LER) (EEW180) EPON®828 . EPON® is a registered
11 0% 100 % 7 trademark of Hexion Specialty Chemicals, Inc.
[ 0075 ] The viscosity of all formulations shown in Tables
2 and 3 were measured at 40 ° C. using Brookfield viscom
[ 0072 ] In Table 1 , the hydrogenated product of oligomeric eter RV with spindle number 27. 12 grams of epoxy resin
structure from the 4,4 '-methylenedianiline process ( MPCA) composition were used to measure the viscosity.
was mixed with N -cyclohexyl- 1,3 -propane diamine (AP [ 0076 ] The reactivity of all formulations shown in FIG . 1
CHA) at different ratios to determine their efficiency to were measured at 40 ° C. using Brookfield viscometer RV
lower the viscosity. It is desirable to use formulated curing with spindle number 27. 12 grams of epoxy resin compo
agents in a liquid form for composite applications. The sition were used to measure the reactivity.
hydrogenated product of oligomeric structure from the 4,4' [ 0077] FIG . 1 shows formulations 2-5 listed in Tables 2
methylenedianiline process ( MPCA) are either semi - solid at and 3. The formulation 1 reactivity study was not performed
25 ° C. or high viscosity at 40 ° C. The N -cyclohexyl- 1,3 due to its higher viscosity and difficulty getting a homoge
propane diamine (APCHA ) was found to be a very effective neous mixture. Based on the reactivity study shown in FIG .
reactive solvent at very low loading ( 10 % ) that significantly 1 , it is possible to use up to 70 % of the hydrogenated product
reduced the viscosity of the hydrogenated product of oligo of oligomeric structure from the 4,4 '-methylenedianiline
meric structure from the 4,4 ' -methylenedianiline process process (MPCA) , when used with N -cyclohexyl-1,3 -pro
( MPCA) . The reactivity of N -cyclohexyl - 1,3 -propane with pane diamine (APCHA) and Epon 826. Typically for com
epoxy resin maintained the physical, thermal and chemical posite applications, lower than 1,500 cPs viscosity is accept
properties desired for composite applications. able to adequately process the composite parts.
TABLE 3
Formulation 1* 2 3 4 5

Hydrogenated product 100 70 50 30

of oligomeric structure
from the 4,4'
Methylenedianiline process
N -cyclohexyl- 1,3 100 30 50 70
propane diamine
LER EEW - 180 100 100 100 100
Phr used 29 29 29 29
Mix Viscosity @ 40 ° C. 183 1,000 333 267
with EEW180
US 2021/0054134 A1 Feb. 25 , 2021
10

TABLE 3 - continued
Formulation 1* 2 3 4 5

Tg C ( ISO ) 2 hrs @ 100 ° C. 94/95 109/125 110/114 93/96

1st scan / 2nd scan up to 250 ° C.
Time to 10,000 cps @ 40 ° C. 107 79 79 102
Mix vis @40 ° C. with EEW180 183 1,000 333 267
Mechanical Properties
Tensile Strength (psi) 9,725 8,233 9,736 9,235
Tensile Modulus (psi) 298,000 327,000 318,000 310,000
% Elongation at Break 8.1 5.5 5.2 6.3
Flexural Strength (psi ) 16,892 15,758 17,950 15,926
Flexural Modulus (psi ) 382,000 414,000 401,000 415,000
Comp Strength (psi ) 11,693 16,808 19,183 17,246
Comp Modulus (psi ) 270,000 262,093 256,000 250,453
* Not performed due to the solid form of Hydrogenated product of oligomeric structure from the
4,4 '-Methylenedianiline process it was difficult to get homogeneous mixing with epoxy resin .

[ 0078 ] The epoxy component and amine curatives shown TABLE 4

in Table 3 were hand mixed at 40 ° C. for 3-5 minutes.
Entrapped air was removed by placing the mixture in a Formulation 1* 2 3 4 5
centrifuge for 5 minutes or until the mixture was clear. The Hydrogenated 100 70 50 30
mixture was then poured into a 1/8 " aluminum mold . The product of
oligomeric
system in the mold was cured at 80 ° C. for 2 hours plus 150 ° structure from the
C. for 3 hours . Molds were allowed to cool to room 4,4 '-Methylene
temperature before removing the cured sample. Specimens dianiline process
were prepared from the cast samples according to ASTM N -cyclohexyl 100 30 50 70
1,3 -propane
methods to perform the mechanical testing ; tensile test diamine
(ASTM D638 ) , flexural test ( ASTM D790 ) , and compres LER EEW - 180 100 100 100 100
sive test ( ASTM D695 ) . Additional 1" X3" x1/8" samples were Phr used 29 29 29 29
prepared to perform chemical resistance testing in different Flexural Modulus retention after Chemical immersion
reagents. Flexural Modulus (psi)
[ 0079 ] The reactivity of all formulations shown in Table 3 No exposure 383,000 415,000 402,000 416,000
were measured at 40 ° C. using Brookfield viscometer RV After 30 days in Fractured 344,000 350,000 346,000
with spindle number 27. 12 grams of epoxy resin compo Acetone @
sition were used to measure the reactivity. 25 C. (psi)
After 30 days in Fractured 376,000 323,000 367,000
[ 0080 ] A TECHNE® gel timer was used to measure the Methanol @
25 C. (psi)
gel time of all the formulations shown in Table 3. The one
end of the metal rod was connected to the TECHNE® gel *Not performed due to the solid form of Hydrogenated product of oligomeric structure
timer and another end with the 1" diameter dish . The epoxy from the 4,4 ' -Methylenedianiline process it was difficult to get homogeneous mixing with
epoxy resin
component and curing agents were preheated separately at
25 ° C. A total of 150 grams of mixture (epoxy component [ 0083 ] The neat cast panels for formulations 2-5 were
and curing components ) was mixed for 3-5 minutes. The 1 " prepared using the process described in Example 2. The
diameter dish was immersed into the beaker content mixture flexural specimens ( 1/2 " X3 " x1/8 " ) were machined according
and Gel time was turned ON immediately to obtain an to ASTM D790 . The specimens were immersed into differ
accurate reading . ent reagents for 30 days @ 25 ° C. to understand the flexural
[ 0081 ] The results for formulations 2-5 are reported in modulus retention before and after immersion. The reagents
Table 3. Formulations 2 , 4 and 5 , according to the present used were ; water, acetone , toluene, methanol, ethanol, 25 %
disclosure, give similar initial viscosity < 350 cPs . However, acetic acid , 10 % nitric acid , and 10 % ammonium hydroxide.
formulations 2 and 5 have a pot life ~ 100 mins (time to The flexural modulus of formulation 2 was retained in most
10,000 cPs ) and formulations 3 and 4 have a pot life ~ 80 of the reagents except specimens that were fractured in
mins . Formulations 3 & 4 provide a Tg in the range of 110 either acetone or methanol. These reagents are considered as
C - 125 C and formulations 2 & 5 provides a Tg in the range very aggressive for attaching an epoxy crosslinked network .
of 90 C - 95 C. The presence of N - cyclohexyl - 1,3 -propane In formulations 3-5 the incorporation of hydrogenated prod
diamine in the formulation gives very high elongation and uct of oligomeric structure from the 4,4 ' -Methylenedianiline
the addition of hydrogenated product of oligomeric structure into N -cyclohexyl- 1,3 - propane diamine improves the flex
from the 4,4 '-Methylenedianiline process improves the ural modulus in these formulations. The flexural modulus in
modulus of the cured formulations . these formulations were regained by having unique amines
combinations.
Example 3 1. A method for producing a cured epoxy resin compo
sition, comprising:
[ 0082 ] This example describes the testing of cured epoxy ( a) combining an epoxy resin component with an amine
resin formulations after chemical immersion . based curing agent component, the amine -based curing
US 2021/0054134 A1 Feb. 25 , 2021
11

agent component comprising a first amine component 10. An epoxy curing agent comprising a first amine
represented by the structure : component represented by the structure :
H

NH2, NH2,

and a second amine component represented by the structure : and a second amine component represented by the struc
ture :

wherein R is NHz ; and

( b ) reacting the amine -based curing agent component and wherein R is NH2 .
the epoxy resin component to form a cured epoxy resin 11. The epoxy curing agent of claim 10 wherein the first
composition. amine component comprises at least 1 % by weight of the
2. The method of claim 1 , wherein the first amine com epoxy curing agent.
ponent comprises at least 1 % by weight of the amine -based 12. The epoxy curing agent of claim 10 further compris
curing agent. ing a third amine component having at least one amine
3. The method of claim 1 , further comprising a third compound selected from the group of a primary amine , a
amine component having at least one amine compound secondary amine , and a tertiary amine .
selected from the group of a primary amine , a secondary 13. The epoxy curing agent of claim 12 wherein the third
amine , and a tertiary amine . amine component comprises at least one polyether amine ,
4. The method of claim 3 , wherein the third amine polyether diamine , a saturated aliphatic ring diamine, a
component comprises at least one polyether amine , linear aliphatic amine, a cycloaliphatic amine , a polycycloa
polyether diamine, a saturated aliphatic ring diamine , a liphatic amine , an aromatic amine, and combinations
linear aliphatic amine , a cycloaliphatic amine , a polycycloa thereof.
liphatic amine, an aromatic amine, and combinations 14. A composition comprising the reaction product of:
thereof. an epoxy resin component; and
5. The method of claim 1 , further comprising performing an amine -based curing agent component, wherein the
steps ( a) and ( b ) at a first ambient temperature; and amine - based curing agent component comprises a first
maintaining a maximum internal temperature during steps amine component represented by the structure:
(a ) and (b ) that is no more than 175 ° C. above the first
ambient temperature .
6. The method of claim 1 , further comprising: H

applying the epoxy resin composition to a reinforcing NH2,

fiber prior to step (b ) .
7. The method of claim 6 , wherein the reinforcing fiber is
selected from the group consisting of woven or non - crimp
fabrics , nonwoven webs or mats , fiber stands, staple fiber
formed of continuous or discontinuous fiber, and combina
tions thereof. and a second amine component represented by the structure :
8. The method of claim 6 , wherein the reinforcing fiber is
selected from the group consisting of fiberglass, carbon
fiber, carbon nanotubes, nano composite fibers, polyaramide
fibers, poly ( p -phenylene benzobisoxazole ) fiber, Aramid
Kevlar fiber, ultrahigh molecular weight polyethylene fiber,
high and low density polyethylene fibers, polypropylene
fibers, nylon fibers, cellulose fibers, natural fibers, biode
gradable fibers, and combinations thereof. wherein R is NH2
9. The method of claim 6 , wherein the epoxy resin 15. The composition of claim 14 , wherein the first amine
composition is made from a process selected from the group component comprises at least 1 % by weight of the amine
consisting of resin infusion, vacuum assisted resin transfer based curing agent.
molding ( VARTM ), resin transfer molding (RTM ), filament 16. The composition of claim 14 , further comprising a
winding (FW ), compression molding ( CM ), wet/hand lay third amine component having at least one amine compound
up , vacuum bagging , injection molding, prepreg , fiber selected from the group of a primary amine, a secondary
impregnation, casting , and combinations thereof. amine , and a tertiary amine .
US 2021/0054134 A1 Feb. 25 , 2021
12

17. The composition of claim 16 , wherein the third amine wherein m is 0 to 25 and R is a divalent hydrocarbon
component comprises at least one polyether amine , radical.
polyether diamine, a saturated aliphatic ring diamine , a 22. The composition of claim 14 , wherein the epoxy resin
linear aliphatic amine , a cycloaliphatic amine , a polycycloa component comprises at least one member selected from the
liphatic amine, an aromatic amine, and combinations group of: bis ( 3,4 -epoxycyclohexylmethyl )oxalate , bis(3,4
thereof. epoxycyclohexylmethyl )adipate, bis ( 3,4 - epoxy -6 -methyl
18. The composition of claim 14 , wherein the epoxy resin cyclohexylmethyl) adipate , vinylcyclohexene diepoxides ;
component comprises about 1 % to about 99 % by weight of limonene diepoxide; bis ( 3,4 - epoxycyclohexylmethyl)pime
the composition . late ; dicyclopentadiene diepoxide , 3,3 -epoxycyclohexylm
19. The composition of claim 14 , wherein the epoxy resin ethyl -3,4 -epoxycyclohexane carboxylate such as 3,4 -epoxy
component comprises a glycidyl ether of polyhydric phenol.
20. The composition of claim 14 , wherein the epoxy resin cyclohexylmethyl-3,4 - epoxycyclohexane carboxylate; 3,3
composition comprises at least one glycidyl ether selected epoxy - 1-methylcyclohexyl-methyl-3,4 -epoxy -1
from the group of glycidyl ethers of: resorcinol , hydroqui methylcyclohexane carboxylate ; 6 -methyl- 3,4
none , bis- (4 -hydroxy - 3,5 -difluorophenyl)-methane, 1,1-bis epoxycyclohexylmethylmethyl-6 -methyl- 3,4
( 4 -hydroxyphenyl)-ethane, 2,2 -bis-(4 -hydroxy -3 -meth epoxycyclohexane carboxylate ; 3,4 - epoxy- 2
ylphenyl) -propane, 2,2 -bis- ( 4 -hydroxy - 3,5 -dichlorophenyl) methylcyclohexyl-methyl-3,4 -epoxy - 3 -methylcyclohexane
propane , 2,2 -bis- ( 4 -hydroxyphenyl) -propane, bis-(4 -hy carboxylate, and combinations thereof.
droxyphenyl )-methane, novolac resins , and combinations 23. An article ofmanufacture comprising the composition
thereof. as set forth in claim 14 , wherein the article is selected from
21. The composition of claim 14 , wherein the epoxy resin the group consisting of filament wound pipes and fittings,
component comprises at least one dihydric phenol of the filament wound pressure vessels , low and high pressure
following structure : pipes and fittings, low and high pressure vessels , storage
tanks, wind turbine blades , automotive structural parts,
aerospace structural parts, oil and gas buoyance modules ,
OH rigs, well plugs , cured - in - place -pipe (CIPP ) , structural
bonding adhesives and laminates, encapsulants, semicon
ductors, corrosion resistance coatings, a composite liner and
177
other suitable epoxy containing applications .