Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~:S~7~47
THERMALLY STABLE THERMOPLASTIC RESIN
The present invention concerns thermoplastic
resins and coatings prepared therefrom.
Thermoplastic (non-thermoset) epoxy resins
have been employed in the formulation of highway,
pavement, marking paints as disclosed by J. M. Dale in
DEVELOPMENT OF LANE DELINEATION WITH IMPROVED DURABII.ITY,
Report No. FHWA-RD-75-70, July 1975. The paint formula-
tions are maintained at eleva-ted temperatures, about
450F (232C), during application. While they provide
an excellent highway marking paint in -terms of abrasive
resistance, they are deficient in terms of applicabi.li-tv
since they exhibit a substantial increase in viscosity
while being mainta.ined at the application temperature.
The present invention provides a thermo
plastic resin which exhibits a much reduced viscosity
increase at elevated -temperatures, i.e. more stable.
The present invention pertains to a thermally
stable, thermoplastic resin prepared by reacting
(A) at least one epoxy resin having an
average of more than one vicinal epoxy
33,127A-F -1-
~%'57 2~
group per molecule;
(B) optionally, one or more polyhydric
phenols; and
(C) at least one material selected from
. monohydric phenols and alcohols, mono~
carboxylic acids and anhydrides thereof,
aliphatic and aromatic mono-second~ry
amines, mono-thiols, mono-isocyanates,
water and combinations thereof;
lG in the presence of an effective quantity of a suitable
catalyst and wherein components (A), (B) and (C) are
reacted in quantities which provide an equlvalent ratio
of componen-t (B) to component (A) of from 0:1 to 0.95:1,
preferably from 0.3:1 to 0.9:1, most preferably from
0.45:1 to 0.85:1 and an equivalent ratio of component
(C) to component (A) of from 0.87:1 to 1.1:1, prefer-
ably from 0.93:1 to 1.05:1, most preferably from 0.95:1
to 1:1, and wherein the equivalent ratio of components
(B-~C) to component (A) is from 0.87:1 -to 1.96:1, prefer-
ably from 0.93:1 -to 1.95:1, most preferably from 0.95:1
to 1.85:1.
The thermoplastic resin of the present inven-
tion is suitable for incorporation in a pain-t formula-
tion comprising
(A) the aforementioned thermally stable
thermoplastic resin; and
(B) at least one of
(1) one or more pigments or dyes; and
(2) one or more fillers.
Suitable epoxy resins which can be employed
in the process of the present invention include, for
example, those represented by the formulas
33,127A-F -2-
~.
o (~) ~ o
H2C-C-cH2-o{~ o-CH2-C-CH2
33 ,127A-F -3-
~,S7~
o
o
~C ~C - V -
~r O
X.~ ~X
X ~
~0
o ~ ~
o~ ~X
$ $
O ~ (~ i O
~3 0 ~ 0 C~
o , ,_
~ X
. , . o
H H
I
33 ,127A-F -4-
--5--
wherein each A is independently a divalent hydrocarbyl
group having from 1 to 10, preferably from 1 to
O O o
6 carbon atoms, -S-, -S-S-, -S-, -S-, -C-, -O-C-O-
o
or -O ; each A' is independently a divalent hydrocarbyl
group having from 1 to 10, preferably from 1 to 6
carbon atoms; each R is independently hydrogen or a
hydrocarbyl group having from 1 to 4 carbon atoms; R'
i5 hydrogen or a hydrocarbyl ~roup having from l to 10,
preferably from 1 to 6 carbon atoms; each X is inde-
penden-tly hydrogen, a halogen, preferably chlorine or
bromine, o. a hydrocarbyl group having from l to i2
carbon atomsi n has a value of zero or 1; n' has an
average value of from zero to 15, preferably from zero
to 11.5; m has an average value of from 0.001 to 6,
preferably from 0.1 to 3; and m' has an average val.ue
of from zero to 4, preferably from 0.1 to 2.
Particularly suitable epoxy resins include,
for example, the glycidyl ethers of p~lyhydric phenols
such as resorcinol, catechol, hydroquinone, bisphenol
A, bisphenol E', bisphenol K, tris-hydroxyphenyl methane,
and mixtures thereof.
Suitable polyhydric phenolic compounds ~hich
can be employed herein include, for example, those
represented by the formulas
~.~X)~
V. HO. ~ ~ OH
33,127A-F -5-
~2~ 4~
--6--
(X)4 (2~)4
VI . HO~(A)n~ OH
OH ~ OH OH
[~ n
(X)4 (X)3
VIII. OH OH
10 (X)~ C _~--(X)4
~OH
( X ) 4
wherein A, A', R', X, n and m are as hereinbefore
defined.
Particularly suitable polyhydric phenol.ic
materi.als include, for example, resorcinol, catechol,
hydroquinone, bisphenol A, bisphenol F, bisphenol K,
tris-hydroxyphenyl methane, and mixtures thereof.
Suitable monohydric phenol.ic compounds include,
20 for example, -those represented by the formula
IX. OH
(X)5~
and each X ls as hereinbefore defined.
33,127A-F -6-
. ~
~ Z ~7~ 7
Particulariy suitable monohydric phenolic
materials include, for example, phenol, alkylphenols,
such as nonylphenol and t-butylphenol, cresol, and mix-
tures thereof.
Suitable monohydric alcohols which can be
employed herein include, for example, methanol,
ethanol, propanol, isopropanol, butanol, pentanol,
hexanol, ethylene glycol monomethyl e-ther, propylene
glycol monomethyl ether, ethylene glycol monoethyl
ether, propylene glycol monoethyl ether, and com-
binations thereof.
Sul-table monocarboxylic acids whi.ch can be
employed herein include, for example, acetic acid,
propionic acid, butyric acid, valeric acid, caproic
acid, caprylic acid, capric acid, lauric acid, myristic
acid, palmitic acid, stearic acid, oleic acid, phenyl-
acetic acid, toluic acid, and combinations thereof.
Suitable anhydrides of monocarboxylic acids
which can be employed herein include, for example,
acetic anhydride, propionic anhydride, buty:ric anhy-
dride, valeric anhydride, and combinations thereof.
Suitable mono-secondary amines which can be
employed herein include, for example, dimethyl amine,
diethyl amine, methyl ethyl amine, dibutyl amine,
methyl butyl amine, ethyl butyl amine, and combinations
thereof.
Suitable mono-thiols which can be employed
herein include, for example, propanthiol, butanethiol,
pentanethiol, hexanethiol, dodecanethiol, thiocresol,
and combinations thereof.
33,127A-F -7-
. , .
~ZS7~
--8--
Sui-table mono-isocyanates which can be employed
herein include, for example, ethyl isocyanate, propyl
isocyanate, butyl isocyanate, phenyl isocyanate, tolyl
isocyanate, and combinations thereoE
Suitable catalysts for effectiny the reaction
between the epoxy resin and -the phenolic hydroxyl-
containing materials include, for example, those disclosed
in U.S. Pa-t. Nos. 3,306,872; 3,341,580; 3,379,684;
3,477,990; 3,547,881; 3,637,590; 3,843,605; 3,948,855;
3,956,237; 4,048,141; 4,093,650; 4,131,633; 4,132,7~6;
4,171,420; 4,177,216 and 4,366,295.
Particularly suitable catalysts are those
quaternary phosphoni.um and ammonium compounds such as,
for example, ethyltriphenylphosphonium chloride, ethyl-
triphenylphosphonium bromide, ethyltriphenylphosphonium
iodide, ethyltriphenylphosphonium ace-tate, ethyl-triphenyl-
phosphonium diacetate (ethyltriphenylphosphonium
acetate-acetic acid complex), tetrabutylphosphonium
chloride, tetrabutylphosphonium bromide, tetrabutylphos-
phonium iodide, tetrabutylphosphonium acetate, tetra-
butylphosphonium diacetate (tetrabu'ylphosphonium
acetate-acetic acid complex), butyltriphenylphosphonium
tetrabromobisphenate, butyltriphenylphosphonium bisphenate,
butyltriphenylphosphonium bicarbonate, benzyltrimethyl-
ammonium chloride and tetramethylammonium hydroxide.
Qther suitable catalysts include tertiaryamines such as, for example, triethylamine, tripropylamine,
tributylamine, 2-methylimidazole, benzyldimethylamine,
N-methyl morpholine, and mixtures thereof.
33,127A-F -8-
.:
. :
7~
_9_
Suitable pigments which can be employed
herein include any which ~ill provide the coating with
the desired color such as, for example, titanium dioxide,
lead chromate, zinc chromate, chome green, pthalocyamine
green and blue, iron oxide, and combinations thereof.
Suitable fillers which can be employed herein
include, for example, calcium carbonate, talc, glass
beads, powdered or flaked zinc or alumina, powdered or
flaked glass, colloidal silica, and combinations thereof.
The following examples are illustrative of
the presen-t invention, but are not to be construed as
to limiting the scope thereof in any manner.
I
EXAMPLE 1
A. Preparation of Cap~ed Epoxy Resin
To a reaction vessel equipped with a means
for stirring and temperature control was added 37.1 lbs
(16.8 kg, 10.2 gram epoxy equiv.) of a diglycidyl e-ther
of biaphenol A having an average epoxide equivalen-t
weight (EEW) of 1646, 18 lbs (8.2 kg, 43.8 gram epoxy
equivalents) of a diglycid~l ether of bisphenol A
having an average EEW of 187, 23 lbs (10.4 kg, 47.3
gram hydroxyl equiv.) of nonyl phenol and 0.077 lbs
(0.169 kg) of a 70 percent solution of ethyltriphenyl
phosphonium acetate-acetic acid complex in methanol.
The mixture was heated to 160C at a rate of 1.5C/min.
(0.025C/s) and main-tained -thereat for 2 hours (7200 s).
The resultant product was a colorless to pale yellow
resin, solid at room temperature.
33,127A-E' -9-
.,
,................ :- ::
- ~ .
~s7a~7
--10--
B. Prepara-tion of Traffic r~arking Paint
A mixture was prepared at 200C o~ the follow-
ing components:
1. 100 parts by weight of the resin from (A) above
2. 20 parts by weight of Tio2
3. 20 parts by weight of CaCO3
4. 28 parts by weight of 200 mesh (0.074 mm sieve
- opening) glass beads
Componen-ts 1, 2 and 3 were mixed under high
shear conditions. Component 4 was mixed at low speeds.
The properties of the traffic paint formula-
tion are given in the following Table.
For comparative purposes, a similar paint
formulation was prepared from an epoxy resin mixture
without nonyl phenol capping. The formula-tion was as
follows:
1. 40 parts by weight of a diglycidyl ether of bisphenol
A (DGEBA) having an epoxy equivalent weight (EEW)
between 186 and 192
2. 60 parts by weigh-t of a DGEBA having an EEW
between 1600 and 2000
3. 20 parts by weight of Tio2
4. 20 parts by weight of CaCO3
5. 28 parts by weight of 200 mesh (0.074 mm sieve
opening) glass beads
The properties are given in the following Table.
.
33,127A-F ~10-
;.: :
- : ~. - : . :
:
~2~7447
--11--
TABLE
Formulation Formulation
1-B l-C
Present
Invention Comparative
Mettler Softening Point, C 89 77
Cold flow at 25C No ~es
Initial Viscosity @ 450F
(232C), cps/pa s 505/0.505 480/0.480
Viscosity after 8 hours
(28800 s) at 450F
(232C), cps/pa s 510/0.51 1500/1.5
Condition after 24 hours
(86400 s) at 450~ (232C) slight gelled,
yellowiny brown
EXAMPLE 2
A. Preparation of Non-Capped Epoxy Resin Blend (Epoxy
Resin Blend)
To a reaction vessel equi.pped with a means
for stirring, nitrogen purge and temperature control
was added 725.2 g (3.9 epoxy equiv.) of a diglycidyl
ether of bisphenol A having an average epoxide equiva-
lent weight (EEW) of 186 and 374.8 g (3.29 equiv.) of
bisphenol A. The mixture was then heated to 90C at
which time 1.69 g (0.003 mole) of a 70 percent solution
of ethyltriphenyl phosphonium acetate-acetic acid complex
in methanol was added. The temperature was increased
to 150C and then the reaction mass exothermed to
206C. The temperature was maintained at 190C for 1
hour (3600 s). The percent epoxide was 2.48. To this
material was added 528.4 g (2.84 epoxy equiv.) of a
diglycidyl ether of bisphenol A having an average EEW
of 186. The temperature of the mixture was decreased
to 150C. This product had a percent epoxide of 9.1
(473 EEW)-
33,127A-F -11-
,
~` ~
~ , :
~a2~;74~
-12-
B. Prepara-t1on of Capped EpoxY Resin
To a reaction vessel equipped with a means
for stirring and -temperature control was added 180 g
(0.38 epoxy equiv.) of epoxy resin blend prepared in A
above and 76.2 g (0.38 mole) of lauric acid. The
mixture was hea-ted to 90C whereupon 0.21 g (0.0004
mole) of a 70 percent solution of ethyltriphenyl phos-
phonium ace-tate acetic acid complex in methanol was
added. The temperature was increased to 156C and
maintained at about 155C for 1.5 hours (5400 s). The
product was dried in a vacuum oven at 160C for 2 hours
(7200 s). The product had a viscosity of 74.5 cps
(0.0745 pa s) at 450F (232C) and a softening point of
60.1C.
EXAMPLE 3
To a reaction vessel equipped with a means
for stirring and temperature control was added 150 g
(0.32 epoxy equiv.) of epoxy resin blend prepared in
Example 2A and 100 g (1.35 mole) of n-butanol. The
mixture was heated to 50C whereupon 0.3 g (0.002 mole)
of boron trifl~oride etherate was added. The temper-
ature was increased to 60C and maintained between 60
and 63C for 3.17 hours (11412 s), heated to 200C and
vacuum stripped for 2.08 hours (7488 s). The product
was dried in a vacuum oven at 160C for 2 hours (7200 s).
The product had a viscosity of 189.5 cps (0.1895 pa s)
at 450F (232C) and a softening point of 78C.
EXAMPLE 4
To a high pressure reaction vessel equipped
with a means for stirring, nitrogen purge and tempera-
ture control was added 200 g (0.42 epoxy equiv.) of
epoxy resin blend prepared in Example 2A, 200 g (2.77
moles) of ~ethyl ethyl ketone, 43 g (2.39 moles) of
33,127A-F -12-
~ . .
. :.
... . ' ~,
., ' .~.' , ~ '
~25~ 7
water, 1.7 g (0.003 mole) of a 70 percen-t solution of
e-thyltriphenyl phosponium acetate acetic acid complex
in methanol and 2.09 g (0.016 mole~ of oxalic acid 2H2O.
Reactor was purged with ni-trogen and then pressure
increased to 80 psig (552 kPa gage). The reactor
temperature was increased to 135C and maintained for
about 4.5 hours (16200 s) then the temperature was
increased to 145C and maintained for 5 hours (18,000 s).
The excess volatiles were removed in the reaction
vessel at a tempera-ture of about 200C for about 0.25
hour (900 s). The product was dried in a vacuum oven
at 160C for 2 hours (7200 s). The product had a
viscosity of 362 cps (0.362 pa-s) at 450F (232C) and
a softening point of 106.6C.
EXAMPLE 5
To a reaction vessel equipped with a means
for sti.rring and temperature control was added 50 g of
propylene glycol monomethyl ether acetate and 13.6 g
(0.105 mole) of dibutylamlne. Over a perlod of 1 hour
20 (3600 s) added 100 g (0.106 epoxy equiv.) of a 50
percent solutiorl of epoxy resin blend prepared in
Example 2A. The temperature was increased to 140C and
maintained for 2 hours (7200 s). The temperature was
increased to abou-t 200C for about 0.25 hour (900 s) to
remove the solvent. The product was dried in a vacuum
oven at 160C for 2 hours (7200 s). The product had a
viscosity of 100.5 cps (0.1005 pa-s) at ~50F (232C)
and a softening point of 72.4C.
EXAMPLF 6
To a reaction vessel equipped with a means
for stirring and temperature control was added 97 g of
propylene glycol monomethyl ether acetate, 8 g (0.078
33,127A-F -13-
,,
-14-
mole) of acetic anhydride, 70 g (0.074 epoxy equiv.) of
a 50 percent solution of epoxy resin blend prepared in
Example 2A in propylene glycol monomethyl ether acetate
and 0.25 g (0.0009 mole) of a 70 percent solution of
ethyltriphenyl phosphonium acetate acetic acid complex
in methanol. The temperature was increased to 120C and
maintained for 5.2 hours (18,720 s). A portion of the
solvent was removed by heating at 145C for about 0.5
hour (1800 s). The resultant material was then placed
on a hot plate for 1 hour (3600 s) at 206C. The
product was dried in a vacuum o~en at 160C for 2 hours
(7200 g). The product had a viscosity of 154 cps
(0.154 pa-s) at 450F (232C) and a softening point of
79.5C.
EXAMPLE 7
To a reaction vessel equipped with a means for
stirring and temperature control was added 84 g of
Dowanol~ PM acetate, 8.5 g (0.082 mole) of 1-pentane-
thiol, 70 g (0.074 epoxy equiv.) of a 50 percentsolution of epo~y resin blend prepared in Example 2A in
propylene glycol monomethyl ether acetate and 0.25 g
(0.0009 mole) of a 70 percent solution of ethyltri-
phenyl phosphonium acetate-acetic acid complex in
methanol. The temperature was increased to 100C and
maintained for 3.55 hours (12,780 s). An additional
2 g (0.019 mole) of 1-pentanethiol and 0.25 g (0.0009
mole) of ethyltriphenyl phosphonium acetate-acetic
acid complex solution was added. After 2.5 hours
3 (9000 s) an additional 0.25 g (0.0009 mole) of
ethyltriphenyl phosphonium acetate-acetic acid
complex solution was added. After l hour (3600 s) an
additional 2 g (0.019 mole) of 1-pentanethiol and
0.25 g (0.0009 mole) of ethyltriphenyl phosphonium
acetate-acetic acid complex
33,127A-F -14-
~:2~;744L'7
was added. The temperature was maintained for 1 hour
(3600 s) at 100C and then increased to a~ou-t 150C for
about 1 hour (3600 s) to remove solvent. The product
was dried in a vacuum oven at 160C for 2 hours (7200 s).
S The product had a viscosity of 119 cps (0.119 pa-s) at
450F (232C) and a softening point of 72.4C.
_XAMPLE 8
To a reaction vessel e~uipped with a means
for stirring, nitrogen purge and temperature control
was added 200 g (0.423 epoxy equivalent) of epoxy resin
blend prepared in Example 2A, 49.5 g (0.416 mole) of
phenyl isocyanate. The temperature was maintained
between 130 and 145C. The phenyl isocyanate addition
took 0.73 hour (2628 s). After 0.77 hour (2772 s), ,
0.75 g (0.0022 mole) tetrabutylphosphonium bromide in
2.5 g of methanol was added. The temperature was
increased to 155C and maintained between 155 and
160C for 6.75 hours (24,300 s). The product was dried
in a vacuum oven at 160C for 2 hours (7200 s). The
product had a viscosity of 670 cps (0.67 pa s) at 450F
(232C) and a softening point of 123.5C.
EXAMPLE 9
To a reaction vessel e~uipped with a means
for stirring, condensing and temperature control was
added 50 g (0.106 epoxy equivalent) of epoxy resin
blend prepared in Example 2A and 150 g (1.531 mole) of
cyclohexanone. The temperature was increased to 90C
to dissolve the epoxy resin blend then cooled -to 45C,
whereupon 12 g (0.375 mole) of methanol was added. The
temperature was decreased to 33C in 0.75 hour (2700 s)
then 12.2 g (0.103 mole) of phenyl isocyanate was
added. The temperature was increased to 45C, -then
33,127A-F -15-
~.2~
-16-
0.12 g (0.0004 mole) of tetrabutylphosphonium brom1de
in l g (0~031 mole) of methanol was added. The tem-
perature was increased to 145C and maintained for 2.17
hours (7812 s). Then solvent was removed at 150C for
0.75 hour (2700 s). The resultant material was placed
on a hot plate for 1.5 hours (5400 s) at 208C. The
product was dried in a vacuum oven at 160C for 2 hours
(7200 s). The product had a viscosity of 2520 cps
(2.52 pa-s) at 450F (232C) and a softening point of
128.3C.
The uncapped epoxy resin blend of Example 2A
and the capped epoxy resins prepared in ~xamples 5, 6
and 8 were subjected to a thermal stabllity test. The
results are given in the following Table.
THERMAL STABILITY TEST
Test Temperature 450F (232C)
VISCOSITY
EPOXY RESIN TIME AT 450F ~32C) cps/pa-s
Epoxy Resin Blend Initial 211/0.211
8 hours (28,800 s) 4~5/0.495
Example 5 Initial 100.5/0.1005
7.5 hours (27,000 s) 133.5/0.1335
Example 6 Initial 154/0.154
7 hours (25,200 s) 173/0.173
Example 8 Initial 670/0.670
8 hours (28,800 s) 684/0.684
33,127A-F -16-
.~ ~ .
