RESISTANT EPOXY COATINGS

ENDUITS RESISTANTS A BASE D'EPOXY

English Abstract

ABSTRACT
The invention relates to polymeric coatings and in
particular coatings formed by reaction of an epoxy resin and
a polyisocyanate where the former disadvantages of slow
curing of the resins has been overcome by introducing into
the epoxy resin molecule, primary hydroxyl groups which
react with the isocyanate groups of the polyisocyanate much
more readily and rapidly compared with the indigenous
secondary hydroxyl groups. Particularly the resin component
comprises the reaction product of a diol of formula:
HO-CH2- (R)a -CH2-OH
wherein R is a straight or branched chain alkylene group
having at most 6, and preferably three, carbon atoms, of the
cyclohexane group where a is 0 or 1. Particularly the epoxy
is selected from a preferred group of low molecular weight
diglycidyl ethers of Bisphenol A and may include other
components. These compositions are particularly weather
resistant.

Claims

The embodiments of the invention in which an exclusive
property or privilege is claimed are defined as follows:
1. A resin product for a two-component coating
composition comprising an epoxide and a polyisocyanate
curing agent, said resin product comprising a resinous
polyol of the following idealized formula B:
<IMG>
wherein R is a straight or branched claim alkylene group
having at most 6 carbon atoms; or the cyclohexane group;
a is 0 or 1; and
R1 is the residue formed upon ring opening, with
a diol of formula HO-CH2-(R)a-CH2-OH wherein R and a are
defined above, of both epoxide groups in a diepoxide resin
selected from the group consisting of:
(a) low molecular weight diglycidyl ethers of
Bisphenol A (DGEBA) epoxy resins
characterized by the following formula A:
<IMG>
wherein n is 0 or an integer from 1 to 2;
(b) diglycidyl ethers of hydrogenated Bisphenol
A;
(c) 3, 4-Epoxy cyclohexylmethyl-3,
4-epoxy-cyclohexane carboxylate; and
(d) vinyl cyclohexene dioxide.
17

2. A resin product for a two-component coating
compsition comprising an epoxide and a polyisocyanate curing
agent, said resin product comprising a resinous polyol of
the following idealized formula C:
<IMG>
wherein R is a cyclohexane group or straight or branched
chain alkylene group having at most 6 carbon atoms; n is 0
or an integer from 1 to 2; and a is 0
3. A resin product according to claim 2 wherein
n = 0.
4. A resin product according to claim 1, 2 or 3
wherein a is 1 and R is a straight or branched chain
alkylene group having at most three carbon atoms.
5. A resin product according to claim 1, 2 or 3
wherein R is the -(CH2)2- or <IMG> group.
6. A resin product according to claim 1, 2 or 3
wherein R is the cyclohexane group.
18

7. A resin product according to claim 1, 2 or 3 in
which said ring opening occurred in the presence of a chain
stopper which is a monofunctional hydroxy or epoxy compound.
8. A resin product according to claim 1, 2 or 3 in
which said ring opening occurred in the presence of a chain
stopper which is a long chain primary monohydric alcohol of
formula
R" - CH2OH
or a long chain monoepoxide of formula
<IMG>
wherein R" is a hydrocarbon moietly containing from 3 to 7
carbon atoms; and
R''' is an ether or ester moietly containing
from 4 to 12 carbon atoms.
9. A resin product for a two-component coating
composition comprising an epoxide and a polyisocyanate
curing agent, said resin comprising a resinous polyol of the
following idealized formula B:
<IMG>
wherein R is the residue formed upon ring opening with a
diol of formula:
HO-CH2- (R)a-CH2-OH
where R is a straight or branched chain alkylene group
having at most 6 carbon atoms; or the cyclohexane group; and
a is 0 or 1;
49

of both epoxide groups in a diepoxide resin which is
diglycidyl ether of hydrogenated Bisphenol A.
10. A resin product according to claim 9 in which
said ring opening occurred in the presence of a chain
stopper which is a monofunctional hydroxy or epoxy compound.
11. A resin product according to claim 9 in which
said ring opening occurred in the presence of a chain
stopper which is a long chain primary monohydric alcohol of
formula
<IMG>
wherein R" is a hydrocarbon moietly containing from 3 to 7
carbon atoms; and
R''' is an ether or esther moietly containing
from 4 to 12 carbon atoms.
12. A resin product according to claim 9, 10 or 11
wherein a is 1 and R is a straight or branched chain
alkylene group having at most three carbon atoms.
13. A resin product according to claim 9, 10 or 11
wherein a is 1 and R is the
-(CH2)2- or <IMG> group
14. A resin product according to claim 9, 10 or 11
wherein a is 1 and R is the cyclohexane group.

15. Process for the production of a resin product
comprising reacting at least 1.5 moles of a diol of formula:
HO-CH2-(R)a-CH2-OH
wherein R is the cyclohexane group or a straight or branched
chain alkylene group having at most 6 carbon atoms, and
a is 0 or 1;
with one mole equivalent of an epoxide resin selected from
the following group:
(a) low molecular weight diglycidyl ethers of
Bisphenol A (DGEBA) epoxy resins
characterized by the following formula A:
<IMG>
wherein n is 0 or an integer from 1 to 2;
(b) diglycidyl ethers of hydrogenated Bisphenal
A;
(c) 3, 4-Epoxy cyclohexylmethyl-3,
4-epoxy-cyclohexane carboxylate; and
(d) vinyl cyclohexene dioxide,
in the presence of a Lewis acid.
16. Process for the production of a resin product
comprising reacting at least 1.5 moles of a diol of formula:
HO-CH2-(R)2a-CH2-OH
wherein R is the cyclohexane group or a straight or branched
chain alkylene group having at most 6 carbon atoms, and
a is 0 or 1,
with a molar equivalent of a diglycidyl ether of Bisphenol A
(DGERA) epoxy resin of formula A:
21

<IMG>
wherein n is 0;
in the presence of a Lewis acid.
17. Process for the production of a resin product
comprising reacting at least 1.5 moles of a diol of formula:
HO-CH2- (R)a-CH2-OH
where R is the cyclohexane group; or a straight or branched
chain alkylene group having at most 6 carbon atoms and a is
0 or 1, with a molar equivalent of a diglycidyl ether of
hydrogenated Bisphenol A in the presence of a Lewis acid.
18. Process according to claim 15, 16 or 17 wherein
the diol of formula HO-CH2-(R)a-CH2-OH a is 1 and R is the
cyclohexane group.
19. Process according to claim 15, 16 or 17 wherein,
in the diol of formula HO-CH2-(R)a-CH2-OH, a is 1 and R is
the -(CH2)2- or <IMG> group
20. Process as according to claim 15, 16 or 17
wherein the Lewis acid is an organic boron trifluoride
complex.
21. Process according to claim 15, 16 or 17 wherein
the Lewis acid is boron trifluoride etherate.
22

22. Process according to claim 15, 16 or 17 wherein
the molar ratio of epoxide: primary hydroxyl is from
1.0:1.5-2Ø
23. Process according to claim 15, 16 or 17 in which
a monofunctional hydroxyl or epoxy chain stopper compound is
present.
24. Process according to claim 15, 16 or 17 in which
a long chain primary monohydric alcohol of formula
<IMG>
or a long chain monoepoxide of formula
<IMG>
wherein R" is a hydrocarbon moietly containing
from 3 to 7 carbon atoms; and
R''' is an ether or ester moietly containing
from 4 to 12 carbon atoms is present as a chain stopper.
25. Process according to claim 15, 16 or 17 in which
a monofunctional hydroxy or epoxy chain stopper is present,
the ratio of basic epoxide:
chain stopper being from 1:0.2 to 1:1.
26. Process according to claim 17 in which the molar
ratio of basic epoxide : primary hydroxyl is from 1.0:1.5-20
and in which a long chain primary monohydric alcohol of
formula:
R"-CH2OH
or a long chain monoepoxide of formulae:
<IMG>
23

wherein R" is a hydrocarbon moietly containing
from 3 to 7 carbon atoms; and
R''' is an ether or ester moietly containing
from 4 to 12 carbon atoms; is present as a chain stopper,
the ratio of basic epoxide:
chain stopper being from 1:0.2 to 1:1.
27. Process according to claim 26 wherein in the
diol of formulae HO-CH2-(R)a-CH2-OH a is 1 and R is the
cyclohexane group or the - (CH2)2- or <IMG> group.
28. Process for the production of an resistant
coating on a substrate comprising mixing a resinous polyol
as defined in claim 1, 2 or 3 with a polyisocyanate,
applying a coating of the resulting mixture to said
substrate and allowing the so-formed coating to set.
29. Process for the production of a resistant
coating on a substrate comprising mixing a resinour polyol
as defined in claim 9, 10 or 11 with a polyisocyanate,
applying a coating of the resulting mixture to said
substrate and allowing the so formed coating to set.
30. Coated substrates whenever produced by a process
as defined in claim 28 or 29.
24

Description

7 ~ 9
BAC~CGROUND OF INVENTION
The present invention relates to polymeric
coatings and in particular such coatings when formed by the
reaction of an epoxy resin and a polyisocyanate.
PRIOR ART
It is well know that diglycidyl ethers of
Bisphenol A (DGEBA) epoxy resins of the following formula: A
CH3 CH~
CH~-CH-CH~ -O ~ C ~ O-CH2-ClH-CH2 -O ~ -C ~ o-CH2-C~-~H2
CH3 OH CH3 0
wherein n ~ 2, react with polyisocyanates to produce, by
cross-linking, chemical coatings which are resistent to a
variety of chemicals. Since the reaction between the epoxy
resin and the polyisocyanate, (the resin is said to have
been "cured" by the isocyanate), commences immediately upon
mixing of those components, the coating "composition" is
supplied as a two component unit or "kit"; one component
comprisins the epoxy resin and auxiliary components such as
pigments, solvents, etc. and a second component comprising
the polysiocyanate.
The reaction "curing" involves the secondary
hydroxyl group of the resin and the isocyanate group of the
polyisocyanate. However, due to the low reactivity between
secondary hydroxyl groups and isocyanate, the ~ ring
reaction proceeds relatively 810wly. Moreover, the
isocyanate group also reacts with water and in some
instances, such as on days of high humidity, that
undesirable competing reaction may occur to such an extent

1 ~37~9
that the cure can be substandard (as evidenced, for example,
by the resultant coating's poor resistance to solvent,
especially where thin coatings or films are involved). It
can be seen that prior coating compositions leave something
~to be desired as regards the coatings or films they are able
to provide.
Statement of Invention
It has now been found, and this finding forms
the basis of the present invention, that the disadvantages
occasioned by the slow curing of the resins in question can
be reduced or even eliminated by introducing into the epoxy
resin molecule, primary hydroxyl groups which react with the
isocyanate groups of the polyisocyanate much more readily
and rapidly compared with the indigenous secondary hydroxyl
groups.
Moreover, and more importantly from a practical
viewpoint, the introduction of such primary hydroxyl groups
into the molecule of weather-stable diepoxides, which by
reason of their sole epoxy or oxirane functionality would
not normally be reactive with isocyanates, has been found to
produce novel resinous polyols which are isocyanate -
curable to produce weather resistant coatin~ compositions.
It is an object of the present invention to
provide a modified DGEBA resin which, upon reaction with
isocyanate is more rapidly cured than conventional DGEBA
resins.
It is a further object of the present invention
to provide selected modified weather resistant diepoxide
resins which are isocyanate c~rable and hence are utilizable
in coating compositions capable of producing weather
resistant coatings.

~ 1~37~
Detailed Statement of Invention
The present invention provides a resin component
for a coatins composition ccmprising a modified epoxy resin
component and an isocyanate curing component, the resin
component comprising the reaction product of a diol of
formula:
HO-CH2- (R)a -CH2-OH
wherein R is a straight or branched chain alkylene group
having at most 6, and preferably three, carbon atoms; or the
cyclohexane group and a is O or l; and an epoxy ~elected
from group
(a) low molecular weight diglycidyl ethers of
Bisphenol A ~DGEBA) epoxy resins
characterized by the following formula A:
CH3 CH3
\ S -0~--C~O--CH2-c~-cH2- -O~C~--O--CH2-CH~-~H2
O CH3 OH CH3 0
_ n
wherein n is O or an integer from 1 to 2;
(b) diglycidyl ethers of hydrogenated Bisphenol
A;
(c) 3, 4-Epoxy cyclohexylmethyl-3,
4-epoxy-cyclohexan carboxylate; and
(d) vinyl cyclohexene dioxide.
The resinous polyol products are believed to
have the following idealized formula B:
HO-CH2-(R) -CH2-O-CH2-CIH-CH2-O-R~-O-CH2-ClH-CH2-O-CH2-(R)a-CH2-OH
OH OH
wherein R and a are defined above; and
Rl is the residue formed upon ring opening of

1 ~374~
both epoxide groups in the diepoxide resins of above groups
(a), (b), (c) or (d), respectively.
For example, it is believed that the resinous
polyols derived from the DGERA resins of (a) have the
following idealized formula C:
CHg
HO-CH-(R)a-CH2-O-cH2-clH-cH2- -O ~ -C ~ O-cH2-~H-cH2- _
CH3 OH CH3 ~ _ n
-O ~ -CH ~ -O-CH2-CH-CH2-O-CH2-(R~ -CH2-OH
CH3 OH
wherein R, a and n are defined above.
The term "idealized formula" is used to denote
that, as a man skilled in the art i6 fully aware, it is not
yenerally possible to characterize resins or the like by
simple formulae and when it is possible to postulate such
formulae to define a resin the formula will usually
represent a "average" since in many instances the resin will
comprise a mixture of resins.
A further consequence of this i9 the relatively
inexact manner in which these types of substances, in
particular those of groups (a) and (b), are defined although
such definitions are well accepted in the art.
In a further aspect, the present invention
provides a process for the production of said novel resinous
polyol products comprising reacting the corresponding
diepoxide of formula as defined above in (a), (b), (c) or
(d) respectively, with at least 1.5 moles of a diol of
formula:
HO-CH2- (R)a-CH2OH

1 1~37~
wherein R and a are defined above; il~ the presellce of a
Lewis acid.
In yet a further aspect, the present invention
provides a method of providing a substrate with ~ resistant
coating comprising adrnixing a resinous polyol of formula B
above with a polyisocyanate; coating said substrate with the
mixture so produced and allowing same to cure so as to form
the desired coating.
With respect to the DGEBA resins of group (a),
such resins where n > 2 contain very undesirable high
molecular weight homologs, branched chain molecules and,
probably, monoglycidyl ethers. On the other hand the lower
molec-ular weight diepoxides wherein n < 2, and especially
wherein n = O which are preferred, give,
(i) reproducible results;
(ii) solutions having low viscosities; and
tiii) give more accurate hydroxy equivalent
weight calculations and, consequently are more convenient to
use.
Turning to resins of group (b), specific
examples thereof are the DRH151 series available from Shell
Chemicals; resins of group (c) include the product available
from Union Carbide Corporation under the trade designation
ERL 4221; and resins of group (d), the product available
from Union Carbide Corporation under the trade designation
ERL 4206.
Products originatiny from the resins of groups
(b), (c) and (d) are preferred on account of their
advantageous resistance to weather and other adverse factors
such as acids, etc.
Suitable diols include the following: straight
chain diols; ethylene, propylene; butylene; pentylene;
,~ .~

I ~fi 374~
hexylene, heptylene, oxtylene, nonylene and decalene diols,
as well as diethylene, dipropylene and other difunctional
polyglycols; branched ehain diols include 2, 2-dimethyl
propanediol; 2-methyl - 2-propane propanediol; 2-ethyl
-2-butyl propanediol; 3-methyl pentanediol and cyclohexane
dimethanol.
Preferred Lewis acid catalysts include organic
boron trifluoride complexes, especially boron trifluoride
etherate, although others which may be used include for
example, boron triamine salts (these compounds requiring
dissociation using heat to become effective).
The polyisocyanates used in the curing of the
resinous polyol may be aliphatic polyisocyanates such as
those sold under the trade names Desmodent N by Bayer and
Isophorone diisocyanate by Veba-Chemie, hydrogenated 4.4
diphenylmethane diisocyanate sold under the trade mark
HYLENE W by Dupont or aromatic polyisocyanates such as
toluene diisocyanate; xylylene diisocyanate; 4,
4-diphenylmethane diisocyanate as well as their NC0
functional adducts.
It has been found that the DGEBA-based resins of
(a) where weather resistance is limited are preferably cured
with aromatic polyisocyanates whereas those based on resins
of groups (b), (c) and (d) preferably cured with aliphatic
polyisocyanates.
The etherification reaction of the epoxy with
the diol obviously results in the regeneration of a hydroxyl
group. As unreacted epoxy may also react with such
hydroxyl, the ratio of epoxy component: diol should be such
so as to ensure there is an excess of primary hydroxyl
groups over epoxy groups present at the start of the
reaction if the production of highly undesirable excessively
-- 7

~ 1~37 ~
higher molecular weight polymers is to be avoided. In
practice, it has been found that 50% or more excess of
primary hydroxyl over the epoxy is highly advantageous, the
preferred epoxy/diol equivalent ratio being from
1.0/1.5-2Ø Alternatively, or in combination, a
monofunctional compound, either a hydroxyl or epoxy, may be
included in the reaction mix and function as a chain stopper
to further suppress molecular weight build up. In general,
any primary monohydric alcohol or monoepoxide will function
as a chain stopper. Long chain alcohols of the general
formula:
R" - CH20H
or long chain epoxides of the general formula
Rl" - CH2 - CH -/ H2
o
wherein R" is a hydrocarbon moietly containing C3 - C7 atoms
and Rl" is an ether or ester moietly containing C4 - C12
atoms are preferred since apart from acting as chain
stoppers, the long chain hydrocarbon portion of the molecule
imparts improved solubility in aromatic hydrocarbon solvents
to the resinous polyols.
The novel products are resinous polyols and a
large series of such products, giving a wide range of
various film properties upon being cured with isocyanates,
can be prepared by utilizing a chain stopper as described
above and/or varying the epoxy/hydroxyl equivalent ratio
and/or the diol used. With respect to the latter, short
chain low molecular weight diols have been found to give the
best hardness in the cured film and excellent solvent

~ 1~3~9
resistance but poorest resin solubility and low tolerance
for aromatic hydrocarbon diluents or solvents, the latter
being economically a disadvantage.
On the other hand the use of a long chain
monepoxide or monofunctional alcohol as a chain stopper
improves resin solubility and aromatic hydrocarbon tolerance
with, apparently, little effect on the speed of curing.
The choice of startiny diepoxide is very
important and interalia determines the type and many of the
characteristics of the film/coating which can be obtained on
polyisocyanate curing: for example, the resinous polyols
from diglycidyl ethers of 8isphenol A are rapidly cured with
polyisocyanates to produce a variety of useful coating
composition~ which give good chemical resistance coatings.
However, their utility as exterior coatings is limited since
DGEBA-based resins in general have relatively poor exterior
durability. On the other hand, the various diepoxides
detailed in paragraphs (b), (c) and (d) on page 3 above, in
general give coatings which are more durable relative to the
DGEBA coatings and hence may be used to advantage in
exterior applications.
The curing of the novel polyols with
polyisocyanates maybe effected by processes well known in
this art and detailed description thereof is deemed
unnecessary. However, reference may be to standard works in
this field, for example, ~he Federation Series on Coating
Technology Unit 15 by David Lasovick, published by the
Federation of Societies for Paint Technology, July, 1970.
The present invention will be further described,
but not limited by, reference to the following specific
examples. For convenience, all the specific examples
relating to the DGEBA based products will precede those

~ 1637~
derived from other diepoxide resins. In the following
E'rocedure, the specific reactants (and ratios thereof) are
contained in the following Tables.
E'rocedure A
. .
All the components, apart from the catalyst,
were added to a 3-necked flask fitted with a condensor,
thermometer and agitator. Agitation was commenced and when
a homogenous reaction mix was attained, 0.1~ Bf3 etherate,
based on total reactants, were added as a 10~ solution of
Bf3 etherate in ethoxyethyl acetate. The reaction is
exothermic and the reaction mixture reached a temperature of
from 90C to 200C the specific value in each instance
depending on the diepoxide, total epoxy content and batch
size. Upon completion of the reaction (when the exotherm
~eased) the resulting resin was allowed to cool and reduced
with a ~olvent comprising a 50/50 volume mixture of xylol
and ethoxyethyl actetate. Where the diol used was a solid
or was incompatable with the e~oxy resin at room
temperature, external heating was applied or a mutually
compatable solvent (ethoxy-ethyl acetate) was added to
facilitate compatability before the catalyst was added.
The specific details as to reactants, epoxide:
diol ratios, etc. used in the production of DGEBA based
resinous polyols according to the presenL invention are
given in Table I.
- ~0

T A B L E
r ~ D
H X ,_1 H H ~ ~ ~Y ~ H ~ ~
tY W O _ O' P- ~ g ~ O' ..
92B *Epon 1:4 None 1:2:0 141 Poor
828 Butanediol
97A Epon 1:4 None 1:1.5:0 161 P-Falr
828 ~utanediol
97A Epon 1:4 None 1:1.5:0 161 P-Falr
828 Butanedlol
100A Epon 1:4 Cardura** 1:2:0.5 195 Good-Excellent
828 Butanediol E 10
100A Epon 1:4 Cardura 1:2:0.5 195 Good-Excellent
B.P. E 10
102A Epon 2.2 Dlmethyl None1:1.5:0 168 F-Good
828 1.3 Propanedlol
102A Epon 2.2 Dlmethyl None1:1.5:0 168 F-Good
828 1.3 Propanediol
104A Epon 1:4 N-Octanol 2:1:1 262 Excellent
828 Butanediol
105A Epon 1:4 N-Octanol 2:1.5: _ Gelled
828 ~utanedlol 0.5
llOA Epon 1:4 Cyclohexane None 1:2:0 160 Fair
828 Dimethanol
114A Epon 1:4 Cyclohexane None 1:1.5:0 198 Falr
828 Dimethanol
116A Epon 1:4 Cyclohexane N-Octanol 2:2:0.5 235 F-Good 828 Dlmethanol
117A tEpon None None 202 Good
* DGEBA Epoxy Resins Manufactured by Shell Chemical-above
formula where n ~ 0
**Glycidyl Ester of Versatic 10 Acld Manufactured by Shell Chemlcal
t DGEBA Epoxy Reslns Manufactured by Shell Chemical-above
formula where n ~ 2
The resinous polyols of Table I we~e converted
to coatings or films on steel panels by curing in a manner
known per se in the art with polyisocyanate. Details of the

~ ~37~9
polyisocyanate and isocyanate (NCO) hydroxyl (OH) ratios
used as well as the properties of the resulting film or
coating on steel panels, is contained in Table II.
T A B L E II
E~ _ ~ ~ ~_
o ~ ~ o W Vl o ~
z o g z ~¢ ~o ~ ~
.
92B *** Mondur CB 75 1:2 24 Hr~ Exc Soft 6 Rubbery, Exc Mar
97A n 1:2 24 Hrs Exc Rubbery & Tough
97A , 1:1 24 ~rs Exc Tough, Hard & Flexible
100A ., 1:2 24 Hr~ Exc Rubbery & Tough
100A - 1:1 24 Hrs Exc Tough, Hard & Flexlble
102A , 1:3 24 Hrs Exc Cheesy, Soft
102A - 1:1 24 Hrs Exc Tough ~ Hsrd
104A .. 1:2 24 Hrs V-Good Tough & Rubbery
110A - 1:2 24 Hrs Exc Tough, Hard & Plexible
114A .l 1:1 24 Hrs Exc Very Tough, Hard &
Flexible Xylol Resistant
within 6 hours
116A ****Mondur MRS. 1:1 24 Hrs Exc Tough & Rubbery
117A Mondur CB 75 1:1 24 Hrs Poor Very Soft
*** Proprietary Tolylene Dilsocyanate Polyol Adduct
Manufactured by Mobay Chemical
****Polymethylene Polyphenyl Isocyanate Manufactured by Mobay Chemlcal
It should be noted that Tables I and II also
detail a control, namely resin code formula 117A. A
comparison of the results achieved with that formulation
with those obtained with formulation 114A which had a
- 12

7 ~
similar hydroxyl equivalent weight and therefore sin;ilar
NCO:OH ratio demonstrates the superiority of the present
i.nvention involving the concept of inserting primary
hydroxyl groups into the resin component. Formulation 114A
novel resinous polyol actually cured within six (6) hours to
a solvent resistant state whereas the control DGEBA resin,
cured with the same polyisocyanate, was still very tacky
after the same six hours air drying time and did not develop
solvent resistance until after forty-eight (48) hours had
elapsed.
Procedure B
This method of producing the resinous polyols
based on the more durable or resistant epoxy resins is
exactly the same Procedure A with the exception that the
temperature during the reaction ranged from 90C to a
maximum of 150C.
Details of the epoxy resin, diol and chain
stopper (if any) as well as the ratio of reactants and the
novel resinous polyol procedure contained in Table III.
- 13

7 ~ ~
TABLE III
~ W ~ e X ~
z ~ z P ~o ~ oP ~
~ x ~ ~ ~ ~: ~ O ~;.
u) O O ~ D O ~ .C p.~ _ ,_1
o~ ~ ~ ~ ~ ~ ~. P~ C ~ ~
I _ ~ a ~ ~ ~ ~ o ~ X o
105B *DRH 151 1:4 ~utanedlol N-Octanol 1:1:0.25 250 Exc~
106A DRH 1511:4 Butanedlol **Cardura E10 1:2:0.5 225 Exc.
106A DRH 1511:4 Butanediol Cardura E10 1:2:0.5 225 Exc.
106A DRH 1511:4 Butanedlol Cardura E10 1:2:0.5 225 Exc.
109A DRH 151Cyclohexane 1.4 _ 1:1.5:0 228 Fair
Dimethanol
10~A DRH 151Cyclohexane 1.4 _ 1:1.5:0 228 Fair
Dlmethanol
111A DRH 151Cyclohexane 1.4 Cardura E10 1:1.5:0.25 270 Good
Dimethanol
113B DRH 151 PCP-0200 _ 1:1.5:0 422 Exc.
Polycaprolactone
A. 115A DRH 151 2.2.4 Trimethyl _ 1:2:0 190 Exc.
Pentanediol 1.3
121A t-ERL-4206 2.2 DimethylCardura E10 1:1.5:0.25 120 Very Good
1.3 Propanediol
122A tERL-4221 22. DimethylCardura E10 1:1.5:0.25 164 Poor
1.3 Propanedlol
126A DRH 151 Cyclohexane 1:4~**Epoxlde 7 1:1.5:0.25 266 Good
Dimethanol
A. Developed Small Gel ParticuLar During Reaction. Probably due to Secondary
Hydroxyl
*Diglycidyl ethers of hydrogenated Bisphenol A ~vailable from Shell
Chemicals
**Glycidyl ester of Versatic 10 Acid suppl1ed by Shell CheGlcal
***Aliphat~c glycidyl ether containing n-octyl and n-decyl
alkyl groups: weight per epoxide 229. (Supplled by Proctor and Gamble.
~vinyl Cyclohexene dioxide
~3, 4-Epoxy cyclohexylmethyl-3, 4-epoxy-cyclohexan carboxylate
Table IV contains details of the curing of the
resinous polyols of Table III and properties of the films
produced.
- 14

3749
TABLE IV
_ ~ .
~ O H ~ 5' E~
O ~ :Z O ~ 1 ~ PC L
1~ ~ ~ O C:~ ~:: 0~ ~ ~
_ _ _
105B *Desmodur N l:l O.l 24 Hrs Exc. Tou~sh & Rubbery
106A Desmodur N 1: 2 0~ 1 24 Hrs Fair Tacky Film
106A Desmodur N l:l O.l 24 Hrs Falr-Good Soft, Slight Tack,
Poor Mar. Hardness
106A ***Isophorone l:l O.l 24 Hrs Falr-Good Soft, Sllght Tack,
Dllsocyanate Poor Mar. Hardness
lO9A Desmodur N l:l 0.1 24 Hrs Exc. Yery Tough ~ Hard,
Exc. Mar. Hardness
& Adheslon
lO9A Desmodur N 1: 2 0.1 24 Hr~ Good-Exc R~ther Cheesy,
Good Mar. Hardness
11lA Desmodur N l:l O.l 24 Hrs Very Good Tough & Hard,
Exc. Mar. Hardness
Rubbery ln Heavy
l13B Desmodur N l:l 0.1 24 Hrs Good Soft, Cheesy,
Slight Surface
Tack
115A Desmodur N l:l 0.1 24 Hr~ Poor-Falr Soft, Cheesy,
Poor Mar. Hardness
121A Desmodur N l:l O.l 24 Hrs Fair-Good Tough, Hard,
Good Mar. aardness
Good Adheslon
122A Desmodur N 1:1 0.1 24 Hrs Good Tough, Hard,
Good Mar. Hardness
Good Adheslon
126A Desmodur N l:l O.l 24 Hrs Good Good reslstance &
Ma_. reslstance
_ . .
* Allphatlc Polyisocyanate Manufactured by Bayer.
***3 Isocyanato methyl 3.5-5 Trimethyl Cyclohexyl
Manufactured by Veba-Chemie
- 15 -

7 4 ~
The present invention, therefore, produces a
novel resinous polyol for use in two component
epoxide/isocyanate chemical setting compositions. The novel
polyols derived for DGEBA enable such compositions to set or
cure to a practical hardness very rapidly compared with
known compositions. Moreover, the polyols derived from the
selected diepoxides of groups (b), (c) and (d) are
isocyanate curable to provides resistant coatinss. Such
compositions are described in detail herein with reference
to their utility in the production of coatings on panels.
However, such compositions have other uses, for example,
they may be used to advantage as adhesives, in reinforced
glass fibre laminated, etc.
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