Note: Descriptions are shown in the official language in which they were submitted.
533 ; ~
Backqround of the Invention
The present invention relates to isocyanurates, and ~ :
to compositions useful in the preparation of polymeric iso-
cyanurates, More particularly, the present invent:ion relates
to isocyanurates which when cured have excellent physical pro~
perties at high temperatures,
The expression "vinylidene group" when used in this
application means the group characterized by the ormula:
CH2 = C
wherein the two free valence bonds are not both connPcted to
the same carbon atom,
The expression "aromatic polyisocyanate" when used :~
in this application means a compound contalning at least ~ iso- :
cyanate group~ attached directly to the carbon atom o an
aromatic ring.
The expression "isocyanurate" means a compound
containing the structure~
,~, O
/C\ ~`:
:~: 20 ~~ ~~
I
O=C C=O
\ / ~ ::
N
:~ The products o this invention may be generally clas-
: sified as ther~oset resins, The prior art thermoset resins lack
one or more important physical properties which would be de
sirable in their use~ It is an ohject of this invention to ~
prepare curable thermosetting compositons which combine e~cel- ~ :
lent viscosity control at low as well as high dissolved solids
concentrations; which are easily handled or laminate prepa-
ration, which may be blended with copper salts to yield a low
,, 1 ~k
: . .
;' ~ .
,::
'- : . .,
6~;33
exotherm on cure to prevent bubbling and warpage, which
have a broad range of solubility in vinylidene monomers
with which it is copolymerizable; which when cured form
thermoset resins which exhibit good corrosion resistance in
a variety of media, including water, acid and alkali; and
which yield cured resins with superior stiffness and rigidity
and excellent retention of physical proper-ties at elevated
temperatures,
It has been discovered that all of -these properties
are now achievable with the products of this invention and
that it is also possible to combine these desirable properties
with fire retardance and low smo}ce, The versatility of these
resin systems maXes possible the preparation of a wide xange
of pr,oducts with properties superior to general purpo~e poly-
ester resins and isophthalic resins, as well as other specialty
vinyl ester resins.
The resins of this invention are further character-
;l ized by a very high level of aromatic and cyclic character which
are derived both from the aromatic polyisocyanate and from the
isocyanurate ring, This high degree of aromatic and cyclic
character is believed to con-tribute substantially to the im-
proved thermal stability and to the stiffness and rigidity of
the products prepared therefrom. The combination of these
highly aromatic and cyclic compositions with acrylate and
methacrylate unsaturation makes possible a rapid curing system
with excellent retention of physical properties not readily
achievable from prior art products, It also allows for a ver-
satile solubility in a variety of comonomers with which the
products of this invention will copolymerize, The products
of this invention have a molecular weight range that allows
33 --
the proper solution viscosity (about 100 to about 1000 cps)
for good handling and lay-up when making ~aminates. Products
of this invention having a viscosity above lOOO cps may also
be pxepared for use in applications requiring high viscosity.
The products of this invention can be prepared at low solids
concen-tration and still exhibit the proper viscosity for good
handling.
. The isocyanurates of this invention are isocyanurates
of urethanes of an aromatic polyisocyanate and at least one
vinylidene carbonyl oxy alkanol characterized by one of the
following formulae: '- `
Rl
(1) (OEI2 - C - C - O - CH2)3C - CHzOH
. O
Rl Rz R3 ;~
(2) CH2 = C - C - O - C - C - O - H
. , : ~
O H H n
Rl R4
(3) (CH2 = C - C - O - CH2t2 C - CEI20H
0
H O R
..
~4) H ~ C - O - C - C = CH2
H - C - O - C - C = CHz
Il
O R
H - C - OEI
H and
H O Rl
(5) H - C - O - C - C = CH2
H - C - OH
30 H - C - O - C - C - CH2
- .
~ H O Rl
llS?~i33
,
wherein Rl is hydrogen or an alkyl group containing from 1
to 4 carbon atoms, R2 is hydrogen, alkyl containing from 1 to
12 carbon atoms, or a chlorina-ted, brominated, or fluorinated
alkyl group containlng from 1 to 12 carbon atoms, R3 is hydrogan,
alkyl containing from 1 to 12 carbon atoms, or a chlorinated,
brominated, or fluorinated alkyl group containing rom 1 to
12 carbon atoms, R4 is hydrogen, methyl or ethyl, and n is
from one to four, with the proviso that R2 and R3 on adjacent
carbon atoms are not both alkyl or chlorinated, brominated,
or fluorinated alkyl, that is at least one of R2 and R3 must . !
be hydrogen. In order to obtain resins having the excellent
combina-tion of high temperature physical properties provided
by the present invention, it is essential that the resin be
prepared from an unsaturated isocyanurate composition wherein
at least a major amount of the isocyanurate moiet;es are based
on one or more vinylidene caxbonyl oxy alkanols defined abo~e.
Illustrative examples of such alkanols include; hydroxypropyl
methacrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate,
hydroxyethyl acrylate, pentaerythritol triacrylate, pentaeryth
ritol trimethacrylate, and diacrylates and dimethacrylates of
trimethylol propane, trimethylol ethane, trimethylol methane,
and glycerol. A preferred group of vinylidene carbonyl oxy
alkanols include hydroxypropyl methacrylate, hydroxyethyl
methacrylate, hydroxypropyl acrylate, hydroxyethyl acrylate, `~
and blends thereof, Another pre~erred group of such alkanols
~- are blends of polyfunctional acrylates or methacrylates such as
pentaerythritol triacrylate, pen-taerythritol trimethacrylate,
and mixtures thereof, with one or more monofunctional acrylates
or methacrylates such as hydroxypropyl acrylate, hydroxypropyl
methacrylate, hydroxyethyl acrylate, and hydroxyethyl methacrylate~
33
While the isocyanurates of -this inv~ntion m~st contain ~ :
moieties derived from one o~ the vinylidene carbonyl oxy al-
kanols defined above, the moieties derived from an aromatic
polyisocyanate may be based on any trimerlzable aromatic poly~
isocyanate~ In fact, any trimerizable aromatic polyisocyanate
which is conventionally used in the art for the preparation of
isocyanurates may be used to prepare the isocyanurate composi- ;~
tions of the present invention For exar~le, the aromatic poly-
isocyanate may or may not contain ethylenic unsaturation and
it may be monomeric or polymeric The only requirements are
that the aromatic polyisocyanate contain at least tWQ aromatic
isocyanate groups, be trimerizable, and be free of any groups
which inter~ere with the trimerization o~ isocyanate groups
or which inter~ere in the reaction of an isocyanate group with
a hydroxyl group. Illustrative examples of aro~atic polyiso-
cyanates which are particularly useful in the preparation o~
isocyanurate compositions of this invéntion include: 2,4-
tolylene diisocyanate; 2,6-tolylene diisocyanate; m-phenylene
diisocyanate, p-phenylene diisocyanate; 1,5-naphthalene di-
isocyanate; 4,4'-dipehyl ether diisocyanate; 4,4',4"-tri-
phenylmethane triisocyanate; 2,4,4'-triisocyanatodiphenyl- .. -
methane; 2,2',4-tri.isocyanato diphenyl; 4,4'-diphenylmethane
diisocyanate; 4,4'-ben~ophenone diisocyanate; 2,2-bis(4-iso-
cyanatophenyl)propane, 1,4-naphthalene~diisocyanate; 4-methoxy-
1,3-phenylene diisocyanate; 4-chloro-1,3-phenylenediisocyanate;
4-bromo-1,3-phenylene diisocyanate; 4-ethoxy-1,3-phenylene
diisocyanate; 2,4'-diisocyanatodiphenyl ether, 4,4'-diiso-
; .
; cyanatodiphenyl; 9,10-anthracene diisocyanate; 4,6-dimethyl-
1,3-phenylene diisocyanate; 4,4'-diisocyanatodibenzyl; 3,3'-
dimethyl-4~4'-diisocyanatodiphenylmethane; 3t3'-dimethyl-
4,4l-diisocyanatodiphenyl; 3,3'-dimethoxy-4,4'-diisocyanato-
diphenyl; 1,8-naphthalene diisocyanate, 2,4,6-tolylene
; .
-- 5
33
~` ~'` ;
triisocyanate; 2,4,4'-triisocyanatodiphenyl ether, diphenyl-
methane diisocyanate, polymethylene polyp'henylene polyiso-
cyanate available under the txademarks Mondur and Papi, having
a functionality of 2.1 to 207; 1,3-xylene 4,6-diisocyanate;
aromatic isocyanate terminated polyurethanes; and aromatic
isocyanate terminated pre-polymars of polyesters. Although'
it is preferred to use all aromatic polyisocyanate, small
amounts of an aliphatic po-yisocyanate, for example, 1,6-
hexamethylene diisocyanate, isophorone diisocyanate, or alpha,
alpha'-diisocyanato-p xylene, may be used in combination with
the aromatie polyisocyanate.
Small amounts of monoisocyanates may be present to
modify the structure of the isoeyanurate formed. The use of
small amounts of monoisoeyanates improves elongat~on and gives
better control of the reaetion to prevent gelation, partieular-
ly when triisoeyanates ara used. The amount of monoisocyanate
used is usually selected to furnich a ratio of isocyanate groups
f` originating with monoisoeyanates to isoeyanate groups originatin~
~ .
with polyisocyanate of not more than about 0.5, and preferably
a ratio of not more than about 0.3. Typieal examples of mono~
isoeyanates whieh may be used include p-tolylisoeyanate, phenyl-
isoeyanate, and n-butylisocyanate. Pre~erred polyisocyanates
are 2,4-tolylene diisoeyanate, 2,6-tolylene diisocyanate,
4,4'-diphenylmethane diisocyanate, polymethylene polyphenylene
polyisocyanates ha~ing an average functionality of 2 1 to 2 7,
and mixtures khereof~
The unsaturated isocyanurate eompositions of this
invention are a mixture of urethane containing unsaturated
isoeyanurates of an aromatic polyisocyanate and at least one
vinylidene carbonyl oxy alkanol charaeterized by one of the
above formulae. The exact structure of each componen-t of these
:` '.
-- 6
:, , ~ , -
compositions and the precise amount of each component present
în the compositions are not known. However, it is known that
the essential components of the isocyanurate compositions of
this invention contain vinyl groups, ester groups, urethane
groups and isoc~anurate ~roups It is ali-io be~ieved that
these ~roups are linked together in the following sequence:
vinyl-ester-urethane-isocyanurate ring Although applicants
do not wish to be bound to a particular structural formula, . ~ - ;
it is believed that preferred unsaturated isocyanurate compo-
sitions of this invention are a mixture of isocyanuratescharacterized by the following formulae:
R''(R')X ~ 1
wherein R" is an aromatic radical free of a group which is .
reactive with an isocyanate group and is obtained by xemoving
the isocyanate groups from an aromatic polyisocyanate,
wherein x is an integer which is one less than the number of
isocyanate groups present in the polyisocyanate,
wherein each R' is independently
. O
-Nl ~ - R''(R')X
O = C - O '
~/
R"(R')x
or
o
-N - C - OR"'
R""
:~:
~ - 6a --
; ~ , .
~ :
33
,
with the proviso that at least one R' is
o
~C\
-M N - R (~ )x
o = ~ ~ = O
R (R )x
and ~ith the proviso that each terminal R' is
-N - C - OR'''
' , ,
wherein R''' is a monovalent organic radical having the ~ :;
formula ~btained by removing a hydroxyl yroup from a vinyl-
idene carbonyl oxy alkanol characterized by formulae (1)
thru (5) recited above and where each R'''' iB independently
-H or O R''''
~: - C - N - R''(R')X and
w~erein the total number of isocyanurate xings in each
molecule is less than about 400
It is apparent from the foxegoing f~rmula that the
isocyanurates of this invention may also be descr.ibed as
esters of carboxy amino phenyl isocyanurates and vinylidene
: carbonyl oxy alkanols. ~hese esters contain one or more iso-
cyanurate ring per molecule or, as is usually the case,
comprise a mixture of ester containing one isocyanurate ring :~
per molecule with ester containing more than one isocyanurate
ring per molecule These esters may or may not contain allo-
phanate groups. Prior to curing, the solid isocyanurates of
`~ this invention are ~usible, that is, they exhibit a so~tening
point by the Ring and Ball method described in the A S~T M
Designation E28-58T~
533
Preferred isocyanurate compositions of this invention
exhibit cha.racterist.ic infra-red (IR) peaks at 5.75 - 6 microns
(carbonyl), 6.1 - 6.35 microns (amidic hydxogen), 6.9 ~ 7 2
microns (isocyanurate), and 10.15 - 10.85 microns (vinyl).
A preferred class of isocyanurates have I:R peaks at 5 8 - 5.95
microns, 6.2 - 6.3 microns, 7 00 - 7,15 microns, and 10 2 -
10 75 microns Preferred isocyanurates of this invention which
are prepared with toluene diisocyanate and hydroxylpropyl
methacrylate exhibit IR peaks in styrene at about 5 85 microns,
about 6.23 microns~ about 7.1 microns, and about 10.6 :microns,
The isoc~anurate compositions of this invention which
. are styrene solutions of isocyanurates based on toluene di-
isocyanate and hydroxylpropyl methacrylate may be further
chaxacterized within experimental error by the following nuclear
magnetic resonance (NMR) signals at: 9.6 -~ 0 2, 8 8 -~ 0.2, 7.50,
7u4~, 7.~4, 7.41, 7.36, 7.33, 7 29, 7,26, 6.79, 6.71, 6.57, 5.93,
5.91, 5.70, 5.69, 5.33, 5.31, and 5.19 The isocyanurate com-
positions of this invention which contain allophanate groups
will give an additional NMR signal at 10.6 ~ O,2 All NMR
measurements recited in this application were determined by
proton magnetic resonance spectral measurements on a Varian
CFT-20 spectrometer operating at 79.54 MEIz (nominal 80 MEIz) at
30C. Dimethyl sulfoxide was used as solvent, The results
are quoted as chemical shifts in parts per million ~ppm) rela-
tive to tetramethyl silane as internal standard
The unsaturated isocyanurate compositions of this
inventions are all soluble in at least one of the following
free-radical polymerizable ethylenically unsaturated monomers:
divinylbenzene, styrene, methyl acrylate, methyl methacrylate,
30 ethyl acrylate, ethyl methacrylate, ~-ethylhexyl acrylate,
. - 8
'~
33
2-ethylhexyl methacrylate, butyl acrylate, butyl methacrylate,
tetramethylene gIycol diacrylate, trimethylol propane tri-
acrylate, pentaerythritol triacrylate, neopentyl glycol di-
acrylate, l,3-butylene glycol diacrylate, 2,3-dibromopropyl
acrylate, 2,3-dibromopropyl methacrylate, cyclohexyl acrylate,
cyclohexyl methacrylate, acrylic acid, methacrylic acid,
hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxy-
; propyl acryla~e, hydroxypropyl methacrylate, chlorostyrene,
acrylonitrile, vinylidene chloride, vinyl acetate, vinyl ~ ;
stearate, vinyltolylene, hexanediol diacrylate, hexanediol di-
metha~rylate, and mixtures thereof. The term "soluble" means
that at least two grams of the isocyanurate composition can
be dissolved in 100 grams of at least one of the above-listed
ethylenically unsaturated monomers at 25C.
The ethylenically unsaturated isocyanurate compositions
of this invention may be prepared by reacting an aromatic poly-
isocyanate with one of the above-described vinylidene carbonyl ~-~
oxy alkanols to form an isocyanate containing urethane and then
trimerizing the isocyanate-containing urethane until essentially
~0 all isocyanate groups have reacted to form the ethylenically
unsaturated isocyanurate composition of this invention. It will
be understood, of course, that the resulting isocyanate compo-
sition may contain some residual isocyanate groups. Other
- methods of preparing the isocyanurates will be apparent to those
~ skilled in this art.
; - 8a
:' ~
.
"
*~
33
More particularly, the isocyanurate compositions of this
inven-tion may be prepared by the method described in Canadian
Patent No. l,0~4,497 ~ranted to ICI Americas Inc on August
26, 1980. Briefly, this process is a two-step process which
comprises a firs-t step of reacting an aromatic polyisocyanate
with a vinylidene carbonyl oxy alkanol i.n the presense of a.
copper salt, such as cupric acetate, to form an isocyanate-
containing urethane and a second step of trimerizing the iso-
10 cyanate-containing urethane in the presence of an isocyanate
trimerization catalyst to form the ethylenically unsaturated
isocyanurate composition of this invention
The solution viscosity of the unsaturated isocyanurates
of this invention can be varied over a wide range by adjusting
15 the stoichiometric of the aromatic polyisocyanates and vinyl-
idene carbonyl oxy alcohols employed in their synthesis and/or
the temperature of the trimerization. Thus by varying the degree
of the excess isocyanate groups compared to hydxoxyl groups it
is possible -to ad~ust the formation of high molecular weight
20 species and solution viscosities at a fixed concentration
Increasing the excess of isocyanate groups compared to hydroxyl
groups favors higher molecular weight species and therefore
higher viscosities, conversely lowering the excess isocyanate
groups compared to hydroxyl groups favors lower moleculare
25 weight species and therefore lower viscosities. By appropriate
adjustment of this excess a curable resin soluti~n of the desired
viscosity can be obtained. This may be done by experiment,
realizing that higher solids concentration, and higher reaction
temperatures also lead to resins of increased moleculax weight
30 and solution viscosity ~he converse oE this is also true
: The excess of moles of NCO groups compared to moles of -OH per
mole of polyisocyanate should be kept in the range rom about
0 75 to about 1 6, and preferably from about 0.8
:;
., .
'` ~
to about 1.4. In a solution comprising equal parts of solvent
and a mixture of hydroxypropylmethacrylate and toluene diiso-
cyanate, the excess of moles of NCO groups fox laminate ap- :
plications is preferably from about 0 ~ to about 1 05.
The expression "excess of rnoles of NCO gxoups com- ::
pared to moles of -OH per mole of polyisocyanate" means the
excess of moles of ~Co groups is equal to the moles of ~CO ~ ::
used minus the moles of -OH used divided by the moles of poly-
isocyanate used.
The solution viscosity is also increased as the .
temperature used in the trimerization reaction increases~
but this is not as important a variable as the excess of iso-
cyanate groups compared to hydrox~l groups However, the txi-
merization temperature is most often maintained from about 0C
to about 95C, since the trimerization reaction i5 slow at
lower temperature and higher temperature may cause the vinyli-
dene group to polymerize prematurely. ~A preferred trimeriza-
tion temperature is from about 50C to about 90C. ~ :
The particular trimerization tamperature chosen will
20 control the amount of allophanate remaining in the isocyanate
composition. In general, the higher the temperature the lower
the allophanate content Allophanate-free isocyanurate may be
prepared by conducting the trimerization at a temperature of
above about 85C. Allophanate-free isocyanurates may be pre- ;~
pared also by heating an allophanate-containing isocyanurate ~
product o~ this invention to a temperature of, preferably, from ; :
abou-t 85C to about 95C in the presence of a trimerization ~ .
: catalyst. Higher temperatures may be employed subject to the
stability of the resin system The isocyanurate products of
this invention usually have an allophanate content sufficient
-- 10 -- ~:
,,
~ir~s~3
to give an allophanate to urethane stoich:iometric ratio of from
about 0 to 0.7, and preferably from about 0 to 0 2, as determined
by ~MR measurements.
The characteristic of an allophanate free resin are
(1) less evolut~on of gases when a peroxide and resin is heated
and (2) longer shelf life of the uncured resin in the presence
of unpromoted peroxides ~llophanate free resins may be pre-
pared for the preparation of thick laminates in order to
minimiæe gas evolution at elevated temperatures ;~
It will be readily apparent to one skilled in the
art that some isocyanurate compositions of this invention may
contain as a by-product urethanes which do not contain an iso-
cyanurate ring. These urethanes may be formed by the reaction
o~ all the isocyanate groups of the polyisocyanake used with
hydxoxyl groups from the vinylidene carbonyl oxy alkanol used.
For example, isocyanurate composition of this invention made
with tolylene txiisocyanate and hydroxypropyl methacrylate may
1- contain as a by-product the diurethane o~ one mole of tolylene
; diisocyanate and two moles oL hydroxypropyl methacrylate.
20 These urethanes may be characterized by the ~ormula
(Ra) (~b)k
; where Ra is an aromatic radical free o~ a group which îs re-
active with an isocyanate group and is obtained by removing
the isocyanate groups from an aromatic polyisocyanate, k is
an integer which is equal-to the number of isocyanate groups ~:
present in tha polyisocyanatet and Rb is
-N - C - OR
:~ '
,
where Rc is a monovalent organic radical having the formula
obtained by removing a hydroxyl group from a vinylidene carbonyl
- 11 -
~3
i533
oxy alkanol characterized by formula (1) thru (5) recited above
The amount of such urethanes present in the compositions of
this invention will depend mainly on the trimerization tem-
pera-ture and on the hydroxyl to isocyanate ratio used to pre-
pare the isocyanurate composition In general, the higher the
trimerization temperature and~or higher the ratio of hydroxyl
groups to isocyanate groups, the higher will be the amount of
such-urethanes in the final product. In some cases the amount
of such urethanes may amount to up to 65% by weight but more
usually in the range of 10% to 50% by weigh-t of the total :
composition.
Generally, as the solid content of the resin system
decreases so does the solution viscos:ity, and to compensate
for this xeduction in viscosity which may make preparation of
laminates a difficult task, the amount of high molecular weight
polyisocyanurate structure is increased by increasing the
: excess of isocyanate groups to hydroxyl groups The amount of
j these species may also be controlled by adjusting the trimeri-
zation temperature
,,
- 12 ~
ii33
The following Table I illustrates ways to obtain
vinylidene carbonyl oxy alkanol containing urethane iso~
cyanurate solu-tions over a broad viscosity range, Although
the table refers to the reaction products from hydroxypropyl-
methacrylate (HPMA) and toluene diisocyanate (TDI) d.issolved
in styrene, those skilled in the art will understand that
similar relationships hold true for other solvent systems :
using other polyisocyanates or vinylidene alcohols, The
examples in Table I illustrate the effect of the three im-
portant reaction parameters on the viscosity of the final
product, Examples F and G as well as H and I show the effect
of trimerization temperature on the viscosity of the final
product, Examples D and F and J and L illustrate the effect
of c~ncentration on the visco~ity, whereas, examples B and C,
E, F, and I and also J and K demonstrate the effect of the molar
excess of NC0 groups compared to hydroxyl groups per mole of
polyisocyanate, on the viscosity of the final product, All
reactions listed in the table were carried to completion~
i,e,, the residual isocyanate content was essentially zero,
Additional viscosity control may be achieved also by stopping
` the react.ion short of completion as can be done in the usual
manner by addiny active hydrogen compounds compatible with
the system and/or destru~tion o~ the trimerization catalyst,
All reaction runs are in styrene using HPMA and TDI, Reaction
runs B through L were made using the procedure outlinea in
example 1 whereas reaction run A was made according to the
procedure outlined in example 8, The procedure used fox
run A involves a somewhat different mode of addition of poly-
isocyanate than used in runs B through L and is used primarily
for the synthesis of low concentration products,
- 13
i33
TABLE I
~oles(NCO)-Mol~s~~) % Trimerization Final Visc.(l)
Moles Styrene Temperature (CP~
Polyisocyanate
A 1.26 75 30 998(22.4C)
1~16 70 45 395
C 1.20 70 45 10,000
: ~ 1.10 60 55 37
E 1.22 50 55 17,000
F 1 10 50 55 2,200
G 1.10 50 25 1,050
H 1.00 50 75 790 :
I 1.00 50 55 450
0 95 40 55 1,400
K 0.91 40 55 . 800
L 0.97 30 55 66,000
(1) Determined on a Brookfield Viscometer, Model ~VT,
No 2 spindle, at 30 rpm at 25C. ~
While it is essential that the isocyanurate compo- ~ :
sitions of this invention be based on one of the vinylidene
carbonyl oxy alkanols defined above in order to obtain pro~ ;~
ducks having excellent high temperature properties, it is con-
templated by the present invention that a minor amount of
moieties derived from the vinyl.idene carbonyl oxy alkanols
may be replaced with moieties derived from other monohydric
alcohols, dihydric alcohols, monohydric pheno1s, or dihydric ;;
phenols~ The saturated monohydric alcohols are especially useful
with polyisocyanates of functionality greater than two Although ~:
it has been found that the high temperature propert:ies decrease
as the amount of vinylidene carbonyl oxy alkanol decreases, one
' ~
:" .
~ .
33
may be willing to sacxifice some-~hat on the hiyh temperature
properties in order to introduce other desirable properties.
For example, in some applications, one may be willing to
sacrifice some high temperature properties ~or the inclusion
of flame-retardancy or low smoke properties. The flame-re-
tardance properties may be introduced by substituting a minor
amount of the vinylidene carbonyl oxy alkanol with a phospho-
rus or florine, chlorir.e or bromine containing alcohol or
phenol. Similarly, low smoke properties may be introduced by
substituting a minor amount of the vinylidene carbonyl oxy
alkanol with sulphur containing alcohols or phenols While
minor amount of any hydroxyl or phenolic material may be in-
cluded in the isocyanurate compositions of this invention, it
should be remembered khat the isocyanurate compos.itions of
this in~ention must be fu~ible and must meet the ~olubility
test described a~ove and must contain at least a ma~or amount
o~ isocyanurate moiet.ies derived ~rom a vinylidene carbonyl
oxy alkanol described above
Illustrative examples of monohydric alcohols and
monohydric phenols which may be used to replace up to 49 mol
percent of the vinylidene carbonyl oxy alkanols described above
include: methanol, ethanol, propanul, butanol, isobutanol,
octyl alcohol, cyclohaxanol, benzyl alcohol, allyl alcohol,
glycerol diallyl ether, trimethylolpropane diallyl ether,
saturated halogenated alcohols, halogenated alcohols containing
ethylenic unsaturation, of example, dibromoneopentyl glycol
monoacrylate and monomethacrylate, halogenated allyl alcohols,
;~ monohydric alcohols such as 2-bromo ethanol, 3-bromo-1-propanol,
4-chloro-1-butanol, 2-chlorethanol, 4-chloro-1-hexanol, 3-
chloro-l-propanol, 2,3-dibromo-1-propanol, 2,3-dichloro-1-
- 15
. ~ .
;33
propanol, 2,2,2--trichloroethanol, 1-bromo-2-propanol, 1-
chloro-2-propanol, 1,3-dibromo-2-propanol, and 1,3-dichloro-
2-propanol, mono acrylate and mono me-thacrylate estexs of
alkoxylated bisphenol A and alkoxy lated tetra bromobisphenol
A, and polyoxyethylene and polyoxypropylene ethers of mono-
hydric phenols
Illustrative examples of dihydric alcohols which may
be used to replace up to 33 mol percent, and preferably up to
10 mol percent, of the vinylidene carbonyl oxy alkanols
described above include: ethylene glycol, propylene glycol,
polyethylene glycol, polypropylene glycol, compounds character~
ized by the formula:
O
(Rlo)2pcH2N(OEI2cH2oH)2
wherein Rl is an alk~l group containing from 1 to 4 carbon atoms,
1,4-butane diol, pentamethylene glycol, hexamethylene glycol,
glycerol methyl ether, polyoxyethylene and polyoxypropylene ~ ~`
i ethers of dihydric phenols such as bisphenol A, glycerol mono-
chlorohydrin, glyceryl monostearate, dihydroxy acetone, and
monoesters of the above polyols and acrylic acid or methacrylic
acid.
In general, phenols in small amounts (up to 20 mole
pexcent) that are reactive with aromatic isocyanates may be used
in the practice of this invention When reactive phenols are
used, it is particularly important that essentially all of the
~- phenolic hydroxyl groups are reacted with isocyanate groups so
that unreacted hydroxyl groups will not be available to inter
fere with subse~uent free radical curing reactions. Phenols
such as 4-hydroxyphenyl 4'-chlorophenyl sulfone are especially
useful because they characteristically improve the fire retar-
dant and smo~e properties of the product while still retaining
- 16
. ~ - .
33
elevated temperature retention of physical properties Phenol
may also be used to block a minor portion of the isocyana-te
functionality which may later be regenerated at elevated tem-
peratures to produce products with improved bonding to a
substrate, especially glass fibres Nitrophenols do not react
readily with isocyanates and are not w.ithin the scope of this
invention,,
The unsaturated isocyanurate compositions o~ this
invention may be homopolymerized or copolymerized with one or
more other ethylenically unsaturated copolymerizable compounds.
Where the unsaturated isocyanate composition of this invention : :~
is to be copolymerized with a copolymerizable monomer, the i~o-
cyanurate composition may be dissolved in the copolymeriable
monomer or it may be desirable to utilize the copolymerizable
compound as a solvent for the xeaction system in which the
ethylenically unsaturated isocyanurate compositions o~ this
invention are formed If the ethylenically unsaturated co- ~: :
; pol~mexizable monomer is to be used as a solvent for the pre-
paration of the unsaturated isocyanurate products, the solvent
should not contain any groups which would react with isocyanate
gxoups or in any way inter~ere with the urethane formation
reactions or trimerization reac-tions which occur in the ~orma-
tion of the isocyanurate products of this invention. Thus, the
solvent should not contain any hydroxyl, carboxyl, or amine
groups which might interfere with these reactions This limits
. the suitable solvents to esters, ethers, hydrocarbons and similar
: solvents containing non-reactive groups~ Illustrative examples ~.
o solvents which may be employed in the preparation of the iso-
cyanurate products of this invention include: divinyl benzene,
styrene, methyl acrylate, methyl methacrylate, ethyl acrylate, : .
. - 17
,
,
ethyl me-thacrylate, 2-ethylhexyl acrylate, 2-ethylhèxyl
methacrylate, butyl acrylate, butyl methacrylate, cyclohexyl
acrylate, cyclohexyl methacrylate, chlorostyrene, acrylonitrile,
vinylidene chloride, vinyl acetate, vinyl stearate, vinyltoly- -:
lene, hexanedio~ diacrylate, hexanediol dimethacxylate, tetra~
hydrourfuryl methacrylate, diethylene glycol diacrylate, tri~ ~
ethylene glycol diacrylate, allyl methacrylate, ~iallyl fumarate, ~:
tetramethylene glycol diacrylate, trimethylolpropane triacrylate, ;~
neopentyl glycol diacrylate, l,3-butylene glycol diacrylate,
l,3-butylene glycol dimethacrylate, polyethylene glycol di-
acrylate, dimethylstyrene, ethylstyrene, propylstyrene, para-
chloromethyl styrene, meta-dibromoethyl styrene, bromo styrene, .-
~dichloro styrene, t-butyl styxene, vinyl propionate, and vinyl
butyrate. Nonpolymerizable solvents may also be used,for
axample, ben~ene, toluene, xylen~, and ethylbenæene. ~he solvent ~ ;
; may be removed from the reaction mixture after the ormation of
the isocyanurate to give a solid product. The solid product
.: ,:~ :
may be dissolved in the same or a different polymeriæable solvent .
prior to curing. Mixtures of solvents may also be used Prefer~
red solvents are styrene, a mixture o~ styrene and methyl meth-
acrylate~ and a mixture o~ styxene and divinylbenzene~
When the isocyanurates of this invention are prepared
in the absence of solvent, the product formed is a solid and
requires special processing which permits the easy removal of
: the heat generated by the reaction and which prevents the re- ..
action mixture from reaching high temperatures which may induc~
insolubility and gelation of the products. Among these special
processing techniques may be the trimerization of the monoureth-
; ane in thin layers on moving temperature-controllad belts or in
temperature-controlled trays
.
.
- 18
The amount of solvent employed to dissolve the iso-
cyanurate compositions of this invention may vary over a very
wide range. The particular amount of solvent used will de-
pend somewhat on tha nature of the solvent and on the solubi-
lity of the particular isocyanurate used. The polymeric
charac-ter of the isocyanurate product allows main-tenance
of adequate working viscosity at relatively low concentra-tions
of dissolved solids Products of this invention may be made
which permit adequate laminate working viscosity, which is
defined as 100 to 1,000 centipoises Brookfield as determined
on a Brookfield Viscometer, Model LVT, No. 2 spindle, at 30 :
rpm, at 25C. The amount of solvent will also depend on the
nature of the properties des.ired in the final cured product~
Thus, if one is interested in preparing a copolymer of styrene
and an isocyanurate of a monourethane of tolylene diisocyanate
and hydroxypropyl methacrylate, for example, the high tempera- ~ :
ture properties o~ the final product will increase as the con-
centration of -t~e styrene decreases In general, however, the
. amount of solvent used will be from 5 to 95 weight percant of .
; 20 the total composition and preferably from 30% to 80% by weight
of the total compositions. A particularly preferred concentra~
tion i8 about 50% by weight.
The unsaturated isocyanurate compositions prepared
by the process of this invention and solutions thereof in co-
polymerizable solvent may be polymerized or cured in accordance
with polymerization condltions conventional in the art for the
;: polymerization of ethylenically unsaturated materials, Iso-
cyanurates of this invention, particularly styrene solutions
of isocyanurates made with tolylene diisocyanates or poly-
- 30 methylene polyphenylene polyisocyanate and hydroxyl propyl
.
- 19
' ~
33
methacrylate, hydroxyl ethyl methacrylate, or hydroxyl propyl
acrylate, are less sensitive to oxygen than conventional ~inyl
systems in yielding tack-free surfaces In ~eneral, the poly~
mariza-tion may be carried out by reacting the unsaturated iso-
cyanurate in the presence of a polymerization catalyst Suit~
able polymerization initiators include the various peroxide
initiators such as benzoyl peroxide, methyl ether ~etone per- `
oxide, di(2-ethylhexyl) peroxydicarbonate, t-butyl perbenzoate,
dicumyl peroxide, and t~butyl hydroperoxide. Other polymerisa-
tion catalysts which may be used include azo type initiators
such a azobisisobutyronitrile. The amount Qf initiator employed
is usually very small For example, from about 1 part of initi~
ator per 1000 parts of the polymerizable mixture to about 5
parts per 100 parts of said mixture.
In many applications, it is desirable to start the
polymerization without the application of external heat In
such cases it is customary to add an accelerator to the system
, Suitable accelerators include cobalt, manganese, lead, and iron
compounds, such as cobalt naphthenate and manganese naphthenate,
and tertiary amines such as dimethyl aniline.
The following are three illustrative examples of per-
oxide-promoter formulations which may be used to cure the un-
saturated iso~yanurates of this invention:
Formulation I
1% Benzoyl peroxide
0.2% Dimethyl aniline
Formulation II
0.02% Dimetnyl aniline
0 06% Cobalt naphthenate
2 0% Methyl ethyl ketone peroxide
. ~ .
- 20
'~
'' ' ,
Formulation III
0~03% Cobalt naphthena-te
0 5% Ace-tylacetone peroxide (4% active oxygen)
1 5% t-butyl perbenzoate
In order to avoid premature polymerization of the iso-
- cyanurate composition of this invention, a small amount of a
cupric salt such as cupric acetate, or a conventional polymeri-
zation inhibitor, such as hydroquinone, methyl ether of hydro-
quinone, phenothiazine, and tertiary butyl catechol, may be in-
corporatad either into the reaction mixture prior to prepara- :
tion of the isocyanurate product or into the final product or
both
The resulting isocyanurate product, particularly w~en
prepared as a soluti.on in a copolyrnerizable monomer, may contain
any of the additives which are conventionally employed in poly-
merization systems, for example, antioxidants, U ~. absorbers,
dyes and pigments
The unsaturated isocyanurate products of this inven~
:
tion have been found to be particularly useful in applications
such as castings, coatings, and laminates where it is desirable ~.
:~ to have excellent flexural and tensile properties and good cor-
rosion resistance at elevated temperatures. Laminates prepaxed
with wettable ibres preferably contain at least 20% by weight
of isocyanurate composition and up to 80% by weight o~wettable
~ibre. Cured products obtained from polymerizing concentrated
isocyanurate solutions of this invention exhibit thermal stabi-
lity at temperatures above 325Fo
The products of this invention may be used alo~e or
in combination with other ethylenically unsaturated monomer ~ :
compositions In addition, these products may be used in com-
bination with inorganic ~illers, such as calcium carbonate,
magnesium oxide, alumina trihydrate; organic polymers such as
- 20a
~3~ 3
. ,,~ .
polyethylene, polymethylmethacrylate and o-ther additive3 to
reduce shrinkage; and fire retardant additives or other poly- :~
merizable resins, such as general purpose polyester resins.
The products of this invention are especially useful when used
in combination w.ith glass fibres, cellulosic fibres, aramide .
fibres, or other fibres to produce reinforced structuras, such
as laminates and pipe The products of this invention exhibit ; :~
excellent wettability when used with these fibres. ~:
The invention will be better understood from a conside- .
ration of the following examples which axe presented for illustra-
~tive purposes and are not to be considered as defining or li~
miting the scope o~ this invention All parts and percentages
are by weight unless otherwise specified :
In the following e~ample~, the castings and laminates
are prepared as follows: :
Castings are prepared by pouring the isocyanurate
solution containing the curing reagents between two sheets of
:~, plate glass separated by a 1/8" polytetrafluoroethylene covered :
; wire spacer The curing reagents are added to the solution of
isocyanurate in copolymerizable solvent by first adding the
indicated promoter and accelerator to the isocyanurate solution
and then adding the indicated peroxide, The casting is main-
tained at room temperature for 18-24 hours and then the resin
is hea-ted one hour at 100C. in an oven to undergo postcuring;
Laminates are prepared by rolling the indicatad iso- : :
cyanurate solution containing the curing reagents evenly onto
glass fibre mats with a paint-type roller then rolling thoroughly
with a grooved laminating roller~ The curing reagents are
added to the solution of isocyanurate in copolymeriæable solven~
by first adding the indicated promoter and accelerator to the
''
- 21
., .
.
,
: .
i33
isocyanurate solution and -then adding the indicated paroxide.
1/8" thick laminates are prepared with two layers of split s-trand
1 1/2 ounce glass mats sandwiched between two 10 mil surfacing
"C" glass mats The weight of the glass is 25% of the total
resin glass weight. 1/4 inch thlck lami.nates are made by the
following combination of glass mats impregnated with resin:
10 mil surfaciny "C" glass mat, two layers of 1 1/2 ounce
chopped strand mat, 1 layer woven roving, one layer of 1 1/2 : ;
ounce chopped strand mat, 1 layer of woven roving and a final
layer of 1 1/2 ounce chopped strand glass mat The amOunt of :.
resin used to make this 1/4" laminate is adjusted to give a
resin ratio of 70%. Laminates are covered with a thin poly-
ester film to ex~lude air from the sur~ace during cure. After
18-24 hours at room temperature the cured lami.nates are heated . .
for 1 hour at 100C in an oven ~or postcure
~ Physical properties of the castings and laminated
; prepared in the following examples are measured by the indicated ::
ASTM test methods:
Physical Property ASTM Test Method
.
Flexural strength D 790
Flexural modulus D 790
Tensile strength D 638
Tensile modulus D 638
% Elongation D 638
~; Izod Impact strength D 256 .
-. Barcol Hardness D 2583
; Heat Deflection Temperature t264 psi) D 648
EX~MPLE 1
A three-neck, round-bottom, 5-liter glass ~lask, ~:
e~uipped with thermometer, air inlet, dropping funnel, and
- 22
.
condenser is charged with 865 ml of hydroxypropyl methacrylate, -.
2144 ml of s-tyrene, 1,8 g of cupric aceta-te, and 800 mg of
hydroquinone, The solu-tion is heated to 85C, and 852 ml of
toluene diisocyanate are, slowly added over a 150 min, period, ~ :~
The temperature of the reaction medium during the addition of
the toluene diisocyanate is maintained between 88C and 90C,
After the addition of the toluene diisocyanate is complete,
the temperature of the reaction mixture is maintained at. about
90C for an additional 90 min, The resulting dark green li~uid
is cooled to 55C, and 5 ml of a 40% solution of benzyltri-
methylammonium hydroxide dissolved in methanol is added over
a 13 min, period, Eeating is then continued at 55C for 2 hrs, ,: .
to form an ethylenically unsaturated isocyanurate,
EX~MPLE 2
611,0 g of styrene, 33,1 g of hydroxyp~opyl meth-
acrylate, 225 mg of cupric acetate, 100 mg of hydroquinone,
are added to the reaction vessel described in Example 1~ The
resulting solution is heated to ~0C while stirring vigorouslyD
At this point, 34,8 g of toluenediisocyanate are added dropwise ~:
. :
at a rate of approximately 6 to 10 ml/min, to the reaction
flask, The temperature of the reaction medium is maintained
:.~ at 90C until the addition of the toluenediisocyanate is com-
plete and then fox an additional 40 min, The resulting clear,
emerald green solution is cooled to 55C, and 1,5 ml of a 40%
solution of benzyltrimethylammonium hydroxide in methanol
is added~ The solut~on remains unchanged for several minutes ;~
then begins to turn brown, The temperature of the solution
is maintained at 55C until the isocyanate content falls to
about 0, The resulting product is a styrene solution of the
ethylenically unsaturated isocyanurate of toluene diisocyanate
and hydroxypropyl methacrylate~
. - 23
Examples 3-5 are prepared according to the process
recited in Example 2 except that the amounts of styrene, hydro-
xypropyl methacrylate (HPMA), hydroxyethyl methacrylate (~EM~),
and toluene diisocyanate (TDI) used are those indicated in the
following Table II.
TABLE II
. . , . . . .. _ .
Example Styrene HPMA ~EMA TDI
umber (grams) (grams) (grams) (grams)
3 282 0 70.8 87 ~-;
4 214 0 99.5 115.8
~ 109.9 _ 130.5
: :
EXAMPLE 6
According to the process of Example 1, 1314 gram~ of
styrene, 232 grams o~ hydroxypropyl methacrylate, 4 ml o a
10% solution of tertiary butyl catechol in styrene, and 920
millgrams of cupric acetate monohydrate are heated to 90C under
an air sparge and nitrogen blanket and 325 grams of toluene di-
isocyanate (25% excess) are then added slowly over 60 minutes~
; The temperature is maintained at 90C during the addition and
for 60 minutes a~terward. The product is cooled to 41C and
5 ml of 4/~ benzyltrimethylammonium hydroxide (Triton B - Reg.
TM) in methanol are added. The temperature is maintained at
45C for 4 hours. 5 ml of tertiary butyl catechol (10% solu-
tion in styrene) and 1 05 ml of methanesulfonic acid are added
and the product is cooled The resulting polymeric, ethylenic~
ally unsaturated polyisocyanurate contains a high proportion
of product of molecular weight about 200,000 as determined by
gel permeation chromatography. The viscosity after sitting
"
overnight at room temperature is about 10,000 centipoise
EXAMPLE 7
A 3-liter, 4-neck flask e~uipped with temperature
' :
- 2~ -
~ .
5i3~3 :
control, air sparge, ~2 blanket, condenser, addition funnel,
and stirrer is charged with 1254 grams of styrene, 227 grams
of hydroxypropyl methacrylate (hydroxyl number 364), 460 milli- :
gra~s of cupric ace-tate monohydrate, and 4 0 ml of 10% terti-
ary butyl catechol (TBC1 in styrene The flask was then heated ::
to 90C and 313 grams o~ toluene d.iisocyanate (TDI) is dripped . .
in over a 55 minute period while the temperature is maintained
at 90 - 98C. At the end of the TDI addition the temperature
is maintained at 90C for an hour and a half, after which the :~
solution is cooled to 45C S cc of a 40% solution of benzyl-
trimethylammonium hydroxide in methanol is added The resin
turns very dark and an exotherm occurs which is controlled by :
means of a water bath so that the temperature does not exceed
50C, and is restored to 45C and is maintained there. A~ter
3,1 hours 1.20 cc of methanesulfonic acid is added and a cooling
water bath is applied, At 30C 5 ml of 10%~t-butyl catechol
: solution in styrene is added. At 25C the resin is poured into . ::~
cans. The Brookfield viscosity is 395 cps at 25C Physical
properties are measured on a 1/8" casting that is postcured at
100C for 1 hour. The cure system comprises 100 grams resin,
0.4 gram dimethyl aniline, 0.5 gram cobalt naphthenate, 0.5 gram
Lupersol 224 (acetylacetone peroxide solution), and 1.5 grams
tertiary butyl perbenzoate The casting (30% solids in styrene)
has the following physical properties: `
Tensile modulus (pSl) O, 49 ~ 03 x 106
Tensile str~ngth tpsi) 10,900
% Elongation 2 58
~lexural strength
(25OC, psi) 17,300
Flexural modulus (psi) 0O53 x 106
Heat distortion temperature lll~C
Unnotched izod impact 2 91
- 25 - .
.
i33
~.
.
E~A~IPLE 8
A 3~1iter, 4-neck :Elask is equipped with mechanical
stirrer, thermometer, air sparge, reflux condenser, and N2
inlet is charged with 17:1: 9 grams hydroxypropyl methacrylate .`:
(1 14 equiv ), 1315 8 grams styrene (12 64 equiv.), 0.4535 gram
Cu (OAc)2 H20, and 3.75 ml 10% tertiary butyl catechol (TBC)
in styrene solu tion and the mixture is heated while stirring
to 9~C. 206 9 grams toluene diisocyanate (TDI) (lvl9 equiv )
is added dropwise over a 1 hour period, while maintaining the
10 tamperature at 90 ~ 5C The reaction mixture is kept at
90 _ 5C for an additional hour, then cooled over a 1 hour
period to 35C, After adding 62.1 grams TDI (0.36 equiv,),
is cooled further to 30C. 4.8 ml benzyltrimethylammonium
hydroxide (40% is MeOH) is then added, causing an exotherm which
is controlled by use of a water bath. The trimeriza-tion re-
action is terminated after 2,6 hours by addition o:F 14.9 grams
- dibutylamine; after 15 minutes, 1.49 ml methanesulfonic acid
(MSi~) is added. The resulting product has a viscosity of 998
cps at 22 4 C A 1/8" cast.ing i9 made and cured according to
the method described in Example 7 The casting t25% solids ~ : :
in styrene) has the following properties:
rrensile modulu.s (psi) 0.55 x 10
Tensile strength (psi) g,a~oo
% Elongation 2 28 . ;~
Flexural strength (psi) 16,700
Unnotched izod (ft lbs) 2 97
Heat distortion temperature 221F
Flexural modulus (psi) 0 85 x 106
EX~PLE 9
Into a 3-liter, 4-neck flask equipped wi-th mec'nanical
-- 26
~1
6~33
stirrer, thermometer, air sparge, reflux condenser, and nitrogen
inlet is charged methyl methacrylate (892 grams, 8.91 m~les),
hydroxypropyl methacrylate (414 grams, 2 78 moles)! copper
acetate monohydrate (0.403 gram), and 10/~ tertiary butyl
catechol/styrene solution (4.0 cc) 1'he mixture is stirred
and heated to 90C, and toluene diisocyanate (TDI) (468 grams,
2 69 moles) added slowly over two hours wnile maintaining the
temperature at 90C After all the TDI is added, the tempera-
ture is maintained at 90C ~or an hour while stirring and the
reaction mixture is then cooled to 50C. Triton B (40% benzyl-
trimethylammonium hydroxide in methanol~ (5.0 ml) is added.
An exothermic reaction occurs and the temperature of the re-
- action mixkure is maintained at 55C b~ external cooling
After keeping the mixture at 55C for two hours, it is then
cooled to room temperature and 1.2 ml methanesul~onic acid
added. The resin has a viscosity of 1050 cps at 23C~ A 1/8"
casting is made and cured according to the method of Example 7. -~
A 1/8" laminate is prepared using two plies of 1 1/2 ounce
chopped fiberglass strand mat between two 10 mil surfacing
"C" glass mats and cured at 100C for one hour. The casting
and laminate have the following properties:
1/8l' 25% glass
Casting laminate
1/8" thick
Tensile modulus ~psi) 0.60 x 106 1~41 x 10
. . .
Tensile strength (psi) 8.500 14,800
% Elongation 1 65 1.47
Flexural modulus (psi) 0 60 x 106 0 80 x 106
~otched izod (ft-lbs) - 5.51
Heat deflection temperature266 9 F
Flexural strength (300F, psi) - 14,000
_ 27
;~
i33
,.
Flexural modulus (300F. psi) - 0.51 x 106
Barcol (300F) -- 21-24
Barcol ~room temperatura) 55-62
Flexural strength (psi) 15,130 16,500
EXAMPLE 10
A 3-liter, 4-necked flask equipped with a mechanical
stirrer, thermometer, air spaxye, reflux condenser, dropping
funnel and nitrogen inlet is charged with hydroxypropyl meth-
acrylate (414 grams, 2 8 moles), styrene (772 grams, 7 4 moles),
divinylbenzene (124 grams of a 72% active solution~ 0 68 moles),
cupric acetate monohydrate (0.45 gram), and 20% solution of
tertiary butyl catechol in styrene (2 ml). The mixture is
heated to 40C and toluene diisocyanate (TDI) (80/20 mixtur~
of 2,4- and 2,6-isomers, 486 gram9, 2 8 moles) added over one
hour. The reaction temperature is gradually increased to 90C :~
by a combination o~ external heat and the exothermic nature o* ~
the reaction. The reaction mixture is kept at 90~C for an ad- ~ :
ditional hour and then cooled over ninety minutes to 45 ~ 5C. ~
; Triton B ~40% solutio~ of benzyltrimethylammonium hydroxide ~ ~:
in methanol, 5 ml~ is then added and the exotherm controlled
by use of a water bath The reaction mixture is kept at
55 ~ 5C for 2.5 hours and the trimerization reaction terminated
by addition of methanesulfonic acid (1.2 ml). The product has
a viscosity of 1060 cps at 21C A laminate is prepared and
cured according to the method used in Exampla 9~ The cured
. laminate has a flexural strength of 18,800 psi at room tempera-
ture and 11,100 psi at 350F
EXAMPLES 11-17
The procedure and apparatus o~ Example 1 are used in
Examples 11-17 The indicated amount of toluene diisocyanate
- 28
~rl
is added dropwise under a nitrogen blanket and air sparge to
~ the copper catalyst, t-butyl catechol, ànd unsaturared alcohol
in styrene at about 90C. When the ~Co content has dropped
to about half the original content, the solution is cooled to
about 55C, Triton B added, and stirring is continued until
: the reaction is complete The methanesul~onic acid and/or TBC i
is then added to stabilize the product resin solution The ;
specific reactants, solvent, and catalysts used and the amounts
thereo~ are shown in Table III. :
.: .....
' :
: - 28a
. I
, . . .
.;~
:'
.
.
.`~
:, .
;33
.
TABLE I.II
Example Grams Grams Unsatd, Gxams Solvent Grams
Number TDI Alco- Alco- Solvent Cupr.ic
hol hol Acetate
__ Monohydra-te
11 129 1 82.2 ~MA 358 Styrene O,23
1 2~,8 PETA
12 519, 8 ! 260 HPM~ 1000 Styrene O,92
¦ 218 DBP
10 . 13 519.8 ! 288 HPMA 1134,8 S-tyrene 1,09
324,84 TBNA : :
14 150.8 163.97 HPM~ 402,9 Styrene O,387
173,2 72 HPM~ 616 Styrene O.597 i:
400 ~2) . ~ .:
16 173,2 117 6 HPMA 345,4 Styrene 0.36
17 520 220,5 HPMA 954,9 Styrene O,92
. 220.5 HEMA . . .. _ .
20 EIPMA = hydroxypropyl methacrylate
PETA = pentaerythritol triacrylate
DBP = 2,3-dibromopropanol :
TBNA = tribromoneopentyl alcohol ~ :
HEMA = hydroxyethyl methacrylate
TBC = t-butylcatechol (10% in styrene) ::
Triton B = benzyltrimethylammonium hydroxide (40% in methanol)
TDI = toluen~ diisocyanate
(1) monomethacrylate of 2,2-polyoxypropylenebisphenol A
(2) monomethacrylate of 2,2-polyoxypropylene tetrabromobis-
30 (3) 4-hydroxy~4'-chlorodiphenyl sulfone phenol ;~
(4) diluted with 26,25 g HPM~ and 17~4 g styrene to 37% solids,
viscosity 1150 cps
(5) diluted with 7.2 t EIPMA, viscosity 2600 cps
- 2g
'X
.
i33 ; .
TABLE III (continued~ :
.
~Example cc. 10% cc. cc, Meth- _ % Un- Product :
- ¦ t-butyl Triton ane~ul- Solids reacted Visco-
Number I catechol- B fonic . -NC0 sity in
I styrene I acid Group Cp5 at :~
I room Tem-
l l perature
! '
. 11 1 1 0~3 40 3.g 20,000
12 4 5~2~2 1.5 5~ 8,7 _
13 5 5 1'5 S 50 6 720 ~
14 2 3 (3 TBS) 5~ 7 _ .,
3 3 _ 50 5 , 4,400 :~
. (3 TBS) (5)
16 3 2 4~TBS 50 2 1~500
17 ~ 5 _ 50 0 360
. (5 TBS) .
HPMA = hydroxypropyl methacrylate
PETA = pentaerythritol triacetate
DBP = 2,3-dibromopropanol
TBNA = tribromoneopentyl alcohol :~
: HEMA = hydroxyethyl methacrylate
TBC = t-butylcatechol (10% in styrene)
Triton B = benzyltrimethylammonium hydroxide (40% in methanol)
~: TDI = toluene diisocyanate
(1) monomethacrylate oE 2,2-polyoxypropylenebisphenol A
(2) monomethacrylate oE 2,2-polyoxypropylene tetrabromobis-
(3) 4-hydroxy-4'-chlorodiphenyl sul:Eone phenol A
~4) diluted with 26,25 g ~MA and 17,4 g styxene to 37% solids,
vi~cosity 1150 cps
~(5) diluted with 7.2 t HPMA, viscosity 2600 cps
- - 30
;
,
~X'
_X~MPLES 18-20
Examples 18-20 are prepared according to the proce~s
of Example 17 except that the indicated amoun-ts of toluene di-
isocyanate, unsaturated alcohol, solven-t and catalyst used are
those indicated in Table~IV.
TABLE IV
.
Example Grams Grams Unsatd. Grams Grams - ;~
TDI alco- alco- solvent Solvent Cupric
~umber
hol hol Acetate
Monohydrate
18 228.8 169,B HPA 398,6 Styrene O,4
19 519,7 441 HPMA 700 Styrene 0,92
262 MMA
494 441 HPM~ 307 MMA
Example cc, 10% cc. cc, % % ~n- Product
Num~er S~BrCene Triton MeS03H Solids reacted Visco~ity
Y B -NC0 in cps at
l Group Room Temp.
18 ~1) 3 _ 50 0 10,600
19 4 5 (5 TBC) 50 0 350
4 5 51,5BC 75 U (bigh)~2)
TDI = toluene diisocyanate
TBC = t-butylcatechol (10% in styrene)
Triton B = benzyltrimethylammonium hydroxide (40% in methanol)
MeS03H = methanesul~onic acid
HPA = hydroxypropyl acrylate
~MA - hydroxypropyl methacrylate
MMA = methyl methacrylate
(1) 200 my hydroquinone
(2) diluted with 252 g MMA, viscosity 725 cps
- 31
:'
, .
.
" :
EX~MPLES 21-26
The procedures o~ Example 17 is used in Examples 21-26.
The indicated reactants, catalysts and solvent and the amounts
used are shown in Table V,
TABLE V
Example Grams Isocyanate Grams Grams Ratio Grams ¦
Nu~er Iso- HPMA Sty- Alc"/ Cupric
. cyanate rene -NCO Aceta-
te Mono ~-
. __ . hydrate .
_ I'
21 176 Mondur* MR 125 122 1:1,6 0,268
:~ 22 184,2 Isonate* 125M 115,8 298 1:1,9 0,23
23 190,9 Isonate* 143L 109,1 2~8 1:1,8 0,23 ::
. 24 216,6 Takenate* 500 147,4 238 1:2,3 0,23
238 Mondur* MR 372,5 813 1,1,7 0.92
, 213,2 TDI . ~
26 52~3 PAPI 400 928 1:1,6 0,84
. .
HPM~ = hydroxypropyl methacrylate
TBC = t-butylcatechol (10% in styrene~
Triton B = ben~yltrimethylammonium hydroxide ~40% in methanol)
MeSO~H = methanesulfonic acid
Mondur MR -- diphenylmethane contg, 2,6 isocyanate groups avg,
Isonate 125M = diphenylmethane contg, 2,0 NC0 groups avg.
Isonate 143L = diphenylmethane contg, 2,1 NC0 groups avg,
Takenate 500 = 1,3-xylene-4,6-diisocyanate
TDI = toluene diisocyanate
PAPI = polyphenylenepolymethylene polyisocyanate contg,
2,2 NC0 groups avg,
* ~eg, TM
,:
,:
.
:
~ ~3fi~33
TA~LE V (Continued) :: -
Example cc, 10% cc. cc. I % % Un- Product
Number TBC in Triton MeS03H I Solids reacted Viscosity
Styrene B I l -NC0 in cps at
l l room temp. ::
. _ . I _ ~:
21 1 1 1 TBC 50 5. 6 495
. 22 1 0. 5 1 TBC 50 3 .1 473
2 3 . 1 1 1 ' T+C 50 1. 5 182 5
24 1 2 1 TBC 60 6, 5 305
4 5 ___ 50 3,~ 1275 :
(6 TBC)
. 26 3, 6 5 ___ 50 5, 2 135
i . (4 TBC) _ . , .
. _
HPMA = hydroxypropyl methacrylate
TBC = t-butylcatechol (10~/o in styrene)
Triton B = benzyltrimethylammonium hydroxide (40~0 in methanol)
MeS03H = methanesulfonic acid ~ :
Mondur MR = diphenylmethane contg, 2,6 isocyanate groups avg,
Isonate 126M = diphenylmethane contg. 2.0 NC0 groups avg,
Isonate 143L - diphenylmethane contg, 2 ,1 NC0 groups avg,
Takenate 500 = 1,3-xylene-4,6-dilsocyanate
TDI = toluene diisocyanate :~
PAPI = polyphenylenepolymethylene polyisocyanate contg,
2,2 NC0 groups avg,
.
' ~ ,
33
,
EXAMPLES 27-34
The isocyanurate pxoduc-ts of Examples 27-34 are
prepared according to the procedure of Example 1, excep-t for
the variations in reactants, solvent and catalysts indicated
in Table VI.
TABLE VI :
. Example Grams Grams Grams Grams Copper ¦ cc. 10%
Number TDI HPMA Styrene Copper salt ¦ TBC in
Salt Styrene
, ,, ,, __ _ - _ ,., _~
27 170,5 1~7 318,3 0,307 chloride 1
28 520,2 441 962 1.0 naphthena ta 4 .
. 29 161.1 138~9 298 0.72 nitrate 1
520.2 441 954,9 0,~ acetate 4
31 130 110 23~.7 0.92 acetate 1
32 130 110 238.7 0.92 ace-tate 1
33 520.2 440 961.6 0.92 acetate __
: (0.4 HQ)
: 34 ---- 520.2 441 954.9 0.92 acetate._ _ _
-I
TDI = toluene diisocyanate
: E~MA = hydroxypropyl methacrylate
MeSO3H = methanesulfonic acid
Triton B = benzyltrimethylammonium hydroxide t40% in methanol)
Polycat 41 = a poly~unctional aliphatic tertiary amine (Abbott)
Me4N.OH = tetr~methylammonium hydxoxide (40% in methanol)
Et~.02CH = tetraethylammonium formate
K0Ac = potassium acetate
. Et4N,OAc = tetraethylammonium acetate
TBC = t-butylcatechol (10% in styrene)
~Q = hydroquinone
. - 34
,
i3~
. TABLE VI (Continued)
Example Trimer- Trimeriza- cc % ¦% Un- ¦Product
ization tion MeSO~H Solids reacted¦Viscosi-
No, Catalys-t Catalys-t -NCO ty in cps
Group at Room
, Temperature
, ... ... _. . .. _ .
27 1 cc Triton B* 0,3 50 4,6 222,5
28 5 cc Triton B* (5 TBC) 50 Z,3 1600
29 5 cc Triton B* 1.5 50 0,33 395 .
2,5 cc Polycat 41* ~ 5 TBC 50 6,2 800
31 1,25 cc Me4N,OH 0,375+ 50 2,6 410
1,25 TBC
32 0.5 g Et4N,02CH 0 375+ 50 3,1 280
33 5 cc KOAc _ 50 O _ .
~0.5 HQ)
34 2,0 g. Et4N,OAc 1 5 1 50 2,3 350
TDI - toluene diisocyanate
HPMA - hydroxypropyl methacrylate
25 MeSO3H = methanesulfonic acid :
~ Triton B = benzyltrimethylammonium hydroxide (40% in methanol~
: Polycate 41 = a polyfunctionsl aliphatic tertiary amine (~bbott) .
Me4N,OH = tetramethylammonium hydroxide (40% in methanol)
Et4N,02CH = tetraethylammonium formate
KOAc = potassium acetate
Et~N,OAc = tetraethylammonium acetate
TBC = t-butylcatechol. (10% in styrene)
HQ = hydro~uinone
* Reg, TM
' '~ :,.
".~
'~ "/"' , .
j3~
EX~MPLE 35
A preferred method of preparing an isocyanurate
composition of this invention containing allophanate groups
is as follows. A chemical reac-tor equipped with agitator,
condenser, gas pipe connections, vents and port holes is fixst
flushed with subsurface nitrogen Subsequently an air sparge
and nitrogen stream having relative flow rates of 1 to 3 are
introduced into the reactor. 2 7 parts of hydroxypropylmeth-
acrylate (HPMA) are then charged to the reactor. The air sp~rge
and nitrogen streams are temporarily turned off and 0.0029
~ parts of copper acetate monohydrate and 0.012 part of 20~ solu-
: tion of tertiary butyl catechol tTBC) in styrene are charged to
the reactor under continuous agitation. The a.ir sparge and
nitrogen blanlcet streams are tuxned on again and 5.7 parts of
styréne are charged to the reactor. The reaction mixture is
~; then heated to about 40C. When the temperature of the re-
action mixture reaches 40C. the incremental addition of an
80/20 mixture of 2,4- and 2,6-toluene diisocyanates ~TDI) ;~
.~ starts, An overall amount of 3.1 parts of TDI are char~ed
over about one hour period During -this period the exotherm
of the reaction of TDI with the alcohol raises the temperature
o the reaction mixture to about 90C. If at the end of the
TDI addition the temperature i9 lower or higher than 90 external
: heating or cooling is applied respectively to bring the tempera-
ture to about 90C. The reaction mixture remains at about
90C for at least one hour after the total amount of TDI has
been added and until the NCO content of the reaction mixture
drops to below 4,5% by weight After both conditions are met
tha reaction mixture is cooled to about 50C. 0 018 part of
40% solution of benzy~-trimethylammonium hydroxide in methanol
: - 36
:
~9,.
... ,. _ .. .. .,. _ .. . .. .. , . ....... ~ . . ......... .... ,.. . .. , . ,__ . ... .. _ _ . , ,_,__ .... _ ~.. ,._ _ _ .
. ........ _
~Triton B~ (a trimerization catalyst), are then added to the
reaction mixture. Soon after the addition of Triton B an
exothermic reaction star-ts durin the duration of which the
temperature of the reaction mixture i5 m intained between
50-600C, From the time the exotherm appears the viscosity
and NC0 conten-t of the reaction mixture are monitored very
closely~ When the viscosity of the reaction mixture reached ?
400-500 cps and the NCO level drops to below 0,2%, 0.007 part
of methanesulfonic acid are added to the reactîon mixture and
10the mixture is then cooled, When the temperature reaches
about 35C,, 0,014 part of TBC are added and the reaction is then
cooled to room temperature, The resulting vinyl isocyanura-te '
is clear, has a light yellow brown color, a viscosity of about
400-500 cps and a shelf life longer than 3 months. ~aminates
axe ~repared ~rom this isocyanura-te solution usiny a curing
system of 0.2% dimethylaniline, 0.2% tertiary butyl catechol,
and 2,0% benzoyl peroxide solution (50% active). 1/8" 2-ply
laminates prepared from this resin retain more than 80% of
their room temperature flexural and tensile strength at 300F,
The reaction product has a number average molecular
weight of about 1160, a weight average molecular weight of ~
about 2000, and a polydispersity of about 1.9. Ahout 95% of ~ ;
the isocyanurates present have a molecular weight of below
about 5200 and contain some isocyanurates having a molecular
weight about 5200 and below about 26,000, This product corres-
ponds to a product of formula II above where the number of iso-
cyanurate rings in most of the isocyanurate molecules is less
than 10, This product has a ball and ring mel-ting point of
about 95C. and a viscosity of about 400-600 cps at 25C, and ~-
a refractive index of about 1,557 ND The infra-red spectrum
- 37
~ .
i3~
of this product shows absorption bands characteristic of
isocyanurates and the essential absence o~ isocyanate funct-
ionality, The hydroxyl number of the product is essentially
zero,
1/8" 2-ply laminates prepared from this resin retain
more than 80% of their room temperature flexural and tensile
strength a-t 300F, The curing reagents used to cure the resin
are ,0.2% dimethyl aniline, 0,2% of a 10% solution of tertiary
butyl catechol in styrene, and 200% benzoyl peroxide ~50% active),
EXAMP~E 36
To a solution of 307 grams of a mixture of 1- and 2-
hydroxydecyl methacrylate in 481 grams methyl methacrylate is
added 0.3 grams of cùpric acetate monohydrate and 1,3 ml of 10%
solution of t-butyl catechol in methyl methacrylate, The solution
i9 heated to 90C and 174 grams of t~luene diisocyanate added
during 30 minutes, The temperature is maintained at 90C for
an additional one hour, The solution is cooled to 55C and ~
1,7 ml of a 40% methanolic solution of benzyltrimethylammonium ~ -
hydro~ide is added, The reaction is completed by heating for an
additional 3 hours at 60C, The reaction is terminated by the
addition of 1,7 ml, 10% solution of t-butyl catechol in methyl
methacrylate and 0.5 ml methar.esulfonic acid.
EX~MPLE 37
To a solution of 165 grams of 2-hydroxybutyl methacrylate
in 71 grams of styrene is added 313 mg of cupric acetate mono-
hydrate and 0,75 ml of a 10% solution in styrene of a 50/50 mix-
ture of t-butyl catechol and mono-methyl ether of hydroquinone,
The solution is heated to 90C and 174 grams of toluene diiso-
cyanate is added over one hour. Heating at 90C is continued
for one hour, Then 268,3 grams of additional styrene i5 added,
38
. ~;3~
the solutlon cooled to 55C, and 2 5 ml of a 40% methanolic
solution of benzyltrimethylammonium hydroxide added. The solu-
tion is maintained at 55C for one hour. The reaction is ter-
minated by the addition of 1.3 ml of a 10% soluti~n in styrene
of a 50/50 mixture of t-butyl catechol and mono-methyl ether
of hydxoquinone. The product has a viscosity of 200 cps at 25C
Two-ply glass laminates (25% glass, 0 125 inch thick) of the
resulting 50% resin solution in styrene and which are cured with
0 1% dimethylaniline, 0.5% acetylacetone peroxide solution (4/~
acti~e oxygen), 1.5% tertiary butyl perbenzoate~ and 0.1% of a
10% solution oftertiary butyl catechol in styrene, have the ~::
following physical properties measured at 300F: ~lexural strength
17,600 psi; flexural modulus 0.48 x 10 psi; ten.sile strength
11,90~ psi; tensile modulus 0.66 x 106 psi; Barcol haxdness
25-28; elongation 2,2%; notched ~zod 4.05. :
EX~MPLE 38
Into a 2-liter 3-neck flask equipped with mechanical
stirrer, thermometer, and air sparge is charged toluena diiso-
cyanate (rrDI) (80/20 mixture of 2,4- and 2,6-isomers, 342 ml, ~.
2 44 mole) and the contents of the flask are heated to S5C.
solution consisting of copper acetate monohydrate t0.4 gram~
and 3.0 ml of a 10% ter-tiary butyl catechol in toluene solution,
w/w, in hydroxypropyl ntethacrylate (360 ml, 2.44 mole), having
an acid number of 18, is added dropwise from an addition funnel
over a period of 31 minutes into the TDI 49.4% of the original
: isocyanate concentration remains unreacted ~analysis by infra-
red spectrophotometer). while the resulting green mix-ture has a
viscosity of 550 cps. 2 5 ml of a 20% tertiary butyl catechol
in toluene solution, w/w, and Triton B (40% benzyltrimethylam-
monium hydroxide in methanol) (0.8 ml) are added to 150 yrams of
- 39
the above mixture at 40C, The mixture is stirred vigorously and
placed in a pan submerged in a constant temperature bath at 45C.
After 12 minutes bubbles begin forming on the surface of this
green mixture and after 35 minutes the color begins changing to
brown, Concurren-tly, the temperature rises to 84~C in 16 minutes
and the product solidifies, The product is allowed to cool to
40~C and then removed from the pan to be ground into a fine
powder, The product is then dissolved in an equal weight of
~: s-tyrener 1.5% tertiary butyl perbenzoate, 0,5% of a 6% solu-
tion of cobalt naphthenate, and 0,4% dimethylaniline are added
: and then 0.5% of acetylacetone peroxide solution (4% active
oxygen) is added to the solution, The solution containing the
curing reagents is used for the preparation of a 1/8" laminate ;
containing about 25% glass, The physica1 properties of the la-
minate are as follows:
Temperature
.: Property 73F - 300F
~ Tensile strength (psi) 14,300 -
:1
Tensile modulus (psi) 1.43 x 106 _
% Elongation 1,26
Flexural strength (psi) 16,600 17,200
Flexural modulus (psi) 0.84 x 106 0,45 x 10
Notched Izod (ft-lbs) 4,5
A 1/8" casting prepared from the same 50% solution of
the solid VIC resin in styrene exhibits a heat deflection tem- ~ -~
perature of 255F,
EX~MPLE 39
This example illustrates the preparation of an allo- : -
phanate-free resin from a resin containing a large amount of
allophanate.
- 40
.. .. . .
~ .
A small reaction vessel is charged with 100 g o~ a :
resin pr~pared according to Example 35, which by NMR analysis
had an allophanate to urethane ratio of 0.45. 0.4 ml of Triton
B ~40% solution of benzyltrimethylammoni.um hydroxide in meth-
anol) is added and 0.5 ml of a 10% solution of equal amounts of
t-butylcatechol and the monomethyl e-ther of hydroquinone. The ~.
resulting mixture is heated for 1 1/2 hours at g5C. The final
product is free of all detectable allophanate linkages upon
~MR analysis
EXAMPLE 40
A 500 ml, 3-necked flask equipped with mechanical .~ .
stirrer, thermometer, air sparge, reflux condenser and dropping ~ `~
funnel is charged with 28.1 g toluene diisocyanate ~TDI) (80/20
mixture of 2,4- and 2,6-isomers) and 300 ml dxy benzene. The : :
~ mixture is heated to 55C and 21 3 grams of hydroxypropyl meth-
acrylate is added over a 6-minute period The reaction mixture
is kept at 55C for an additional 16 minutes and then charged
with 0~37 g hydroquinone, 8 9 g (0.07 moles) phenylisocyanate ~:~
:~ and 0 75 ml Triton B (40% solution of benzyltrimethylammonium ~:~
hydroxide in methanol) Heating at 50~C is continued for 45
minutes. A white precipitate is formed and is removed by ~iltra-
tion The precipitate is identified as an isocyanate containing
both pehnyl and tolyl groups by IR analysis.
EXAMPLE 41 ~ .
A preferred method of preparing an allophanate-free ~:
. isocyanurate composition of this invention is as follows: a 4- ~ :
neck, round-bottom, 3-liter glass flask equipped with a thermo-
meter, air and nitrogen inlet, dropping funnel and condenser is
. ~
charged with 430 g of hydroxypropyl methacrylate, 856 g of sty-
rene, 0 43 g of cupric acetate monohydrate and 3~6 ml of a solu-
,, ~
:~ - 41
, .
: ~ :
tion of t butyl-ca-techol in styrene The solu-tion .is heated to
40C and 426 g o:E toluene diisocyanate aclded over ~5 minutes
The -temperature of the reaction medium during the addition of
the toluene diisocyanate is allowed to gradually rise. By a
combination of the exothermic nature of the reaction and external
heating the final temperature is 90C. After the addition of
the toluene diisocyanate, the temperature of the reaction mix-
ture is kept at 90C for a further 15 minutes The resulting
dark green liquid is cooled to 70C and 2 8 ml of a 40% solu~ion.
of benzyltrimethylammonium hydroxide dissolved in methanol is
: added in one lot After the reaction mixture exotherms to 90C, ~.
the temperature is held at 90C for 1 hour~ Methanesulfonic
acid (1 33 ml) is then added, the reaction mixture cooled and
4 4 ml of a 10% solution of t-hutylcatechol in styxene added.
The NMR spectrum of the product does not contain allophanate
proton signals at about 10.6 ppm. This resin has a ~tability
to 1% benzoyl peroxide of at least 7 hour.s at room temperature
EXAMPLE 42 .:
'. A 4-neck, round-bottom, 5-liter glass flask equipped :
with a thermometer, air and nitrogen inlet, dropping funnel and
condenser is charged with 860 g hydroxypropyl methacrylate,
1735 g of styrene, 0.86 g of cupric acetate monohydrate and 7 2 ~:
ml of a 10% solution of t-butylcatechol in styrene The solution
is heated to 41C and 876 g of toluene diisocyanate adaed over
45 minutes. By a combination of the exothermic nature of the
reaction and external heatlng, the temperature of the mixture is
allowed to rise to 90C gradually during the 45 minutes. After
the addition of the toluene diisocyanate, the temperature of the
; reaction mixture is kept at 90C for a further 15 minutes. The
resulting dark green liquid is.cooled to 67C (over 37 minutes)
- 42
. ~
~r~
and lO mls of a 40% solution of benæyltrimethylammonium hydro- --
xide dissolved in methanol added in one lot. The mixture is
heated over 5 minu-tes to 70C After a further 5 mi.nutes an
exotherm to 94C is observed. The exotherm is controlled by
external cooling to 90C and the mixture then held at 90C for
a further 131 minutes 8~8 mls of a 10% solution of t-butyl-
catechol in styrene is added and the mixture cooled to 60C. :~
lO00 mls of the reaction mixture is retained and 1 9 mls of
methanesulfonic acid added to the bulk of the reaction mix-
ture rrhe ~MR spectrum of this product does not contain any
allophanate proton signal at 10.6 pprn This product has a
stability at room temperature to 1% benzoyl peroxide of at ~ ~ :
least 8 hours. ~ . :
EXAMPLE 43
A 4-neck, round-bottom, 5-liter glass Elask equipped
with a thermometer, air and nitrogen inlet, dxoppin~ ~unnel
and condenser is char~ed with 876 g toluene diisocyanate, 1736 ~
g of styrene, 0.86 g of cupric acetate monohydrate and 7.2 mls ~;:
of a 10% solution of t-butylcatechol in styrene The solution :
is heated to 40C and 860 g of hydroxypropyl methacrylate added
o~er 45 minutes By a combination of the exothermic nature
of the reaction and external heating, the temparature of the
mixture is allowed to rise to 90C gradually during the 45
minutes. Aft~r the addition of the toluene diisocyanate,
the temperature of the reaction mixture is kept at 90C for a
further 15 minutes. The resulting dark green liquid is cooled
to 72C over 30 minutes and 10 mls of a 40/O solution of benzyI-
trimethylammonium hydroxide dissolved in methanol added in one
lot. After 18 minutes at 71C, an exotherm to 90.5C over 5
minutes is observed. The reaction mixture is held at 90C for
.
- 43
~'
l~P~
.
59 minutes and 2~66 mls of methanesulfonic acid added followed :
by 8 8 mls of a 10% solution of t-butylcatechol in styrene
The reaction mix-ture is then cooled to room temperature and
~ stored. The NMR spectrum of this product does not contain an
allophanate pro-ton signal at 10.6 ppm A 1/8 inch two-ply
laminate of this resin containing 25% glass and cured with 1% ~ :
benzoyl peroxide and 0 2% dimethylaniline at room temperature
overnight followed by a l-hour postcure at 100C has the fol-
lowing properties: .
Flexural Strength Flexural Modulus
Temperature psi psi x 106
Room temperature 14,100 0 79 : .
300F 13,600 0.32 .
EXAMPLE 44
:. A 4-neck, round-bottom, 5-liter glass flask, equipped
with a thermometer, air and nitrogen i~llet, 2 dropping funnels
and condenser is charged with 1736 g of styrene, 0.86 g of
cupric acetate monohydrate and 7.2 mls of a 10% solution of t- :
, butylcatechol in styrene. The solution is heated to 41C and .
860 g of hdyroxypropyl methacrylate and 876 g of toluene diiso-
cyanate added simultaneously over 44 minutes By a combination
of the exothermic nature of the reaction and external heating,
the temperature of the mixture is raised gradually to 90C
during the 45 minutes~ After the addition, thetemperature of
the reaction mixture is kept at 90C for 15 minutes. The result-
- ing liquid is cooled to 70C over 25 minutes and 10 mls of a.
~- 40% solution of benzyltrimethylammonium hydroxide dissolved in
methanol added in one lot After 15 minutes at 71C an exotherm
to 90.5C over 4 minutes is observed~ The reaction mixture is
held at 90C for 59 minutes and 2 66 mls of methane sulfonic
acid added followed by 8 8 mls of a 10% solution of t-butyl-
_ 44
,: '
, ~ ~. . .'
1~ i33
catechol in styrene. The reac-tion mix-ture i5 coQled to room
temperature. The NMR spectrum of the product does not contain
an allophanate proton signal at 10.6 ppm~ A 1/8 inch two-ply
laminate of this resin containing 25% glass and cured with 1%
benzoyl peroxide and 0.2% dimethylaniline at room temperature
overnight followed by a l-hour postcure at 100C has the fol-
lowing properties:
Flexural Strength Flexural Modulus
Temperature psi psi x 106
-
~oom temperature13,900 0~8
300F 14,200 0 4
Although the process of this invention has been
described with re~erence to specific xeactions, conditions and
reactants, it will be apparent that still other difEerent and
equivalent reactants and process conditions may be substituted
for those specifically described, all within the sphere and
scope of this invention
EX~MPLE 45
A 3-liter, 4-necked flask equipped with a mechanical
stirrer, thermometer, air sparge, reflux condenser and dr~pping
funnel is charged wlth hydroxypropyl methacrylate (441 g, 2 94
moles), styrene (954.9 g, 915 moles) cupric acetate monohydrate
(0.92 g) and 4 ml of a 10% solution of equal amounts of t-butyl
catechol and the monomethyl ether of hydroquinone. The mixture
is heated to 90C and toluene diisocyanate (TDI) (80/20 mixture
of 2,4- and 2,6-isomers, 496.2 g, 2.85 moles) added over 30 ~-
minutes The reaction mixture is held at 90C for 15 minutes
and then cooled within 10 minutes to 65C. Triton B (40% solu-
tion of benzyltrimethylammonium hydroxide in methanol, 5 ml) is
then added and heat applied to raise the reaction temperature to
- 45
. ~
;33
85~C (10 minutes) and then raised to 95C for 35 minutes The
reaction mixture is stabili~ed wi-th 2.5 ml of a 10% solution of
equal amounts of t-butylcatechol and the monomethyl ether of
hydroquinone The trimerization reaction is terminated by the
addition of methanesulfonic acid (1.5 ml)~ NMR analysis showed
no detectable a~lophanate grouping~
EXAMPLE 46
A 3-liter, 4-neck flask equipped with a mechanical
stirrer, thermometer, air sparge, reflux condenser and dropping
:~ 10 funnel is charged with hydroxypxopyl methacrylate (441 g, 2.~4
moles), styrene t954.9 g, 915 moles), cupric ace-tate monohydrata ;
(0.92 g) and 4 ml of a 10% solution of equal amounts of t-butyl~
catechol and the monomethyl ether of hydroquinone The mixture
: is heated to 90C and toluene diisocyanate (TDI) (80/20 mixture
of 2,4 and 2,6-isomers, 522 3 g, 3.00 moles) added over a one
. houx period. The reaction mixture is kept at 90C for an addi-
tional hour and then cooled within 20 minutes to 55C Triton B
(40% solution of benzyltrimethylammonium hydroxide in methanol,
5 ml) i5 then added and the exothem controlled by use of a water
bath. The reaction is permitted to exotherm to 65C~ As the
reaction proceeds it will cool slowly and heat it only applied to
keep it at 55C. After two hours holdin~ the isocyanate peak
has completely disappeared in the IR The trimerization reaction
is terminated by the addition of methanesulfonic acid (15 ml)
and stabilized by the addition of 5 ml of a 10% solution of
equal amounts of t-butylcatechol and the monomethyl ether of
hydroquinone The product by ~MR analysis shows an allophanate .
to urethane ratio of 0.1.
EXAMPLE 47
A chemical reactor equipped with agitatsr, condenser,
gas pirpe connections, vents, and port holes is first flushed :~
~' ~
- ~6 - :
,
6~33
with subsurface ni-trogen. Subsequently an air sparge and
nitrogen stx~am having relative flow rates of 1 to 3 are
intxoduced into the reactor. 2,7 parts o:E hydroxypropyl
methacxylate (~M~) are then charged to the reactor. The air
~j sparge and nitrogen streams are temporarily turned o~f and
- 0,0029 parts of copper acetate monohydrate and 0.012 parts
of 20% solution of t-butylcatechol (TBC) in styrene are
charged to the reactor continuous agitation, The air sparge
; and nitrogen blanket streams are turned on again and 5,7 parts
of styrene are charged to the reactor. The reaction mixture
is then heated to about 40C. When the temperature of the
reaction mixture reaches 40C the incremental addition of an
80/20 mixture of 2,4- and 2,6-toluene diisocyanates (TDI)
starts. An overall amount of 3.1 parts of TDI are charged
over about one hour period the exotherm of the reaction of
, TDI with the alcohol raises the temperature of the reaction
mixture to about 90C. If at the end of the TDI addition ~ L
the temperature is lower or higher than 90 external heating ~ ;
or cooling is applied respectively to bring the temperature to
about 90C, The reaction mixture remains at about 90C for at
least one hour after the total amount of TDI has been added
and until the NC0 content of the reaction mixture drops to
below 4.5% by weight. After both conditions are met the re-
action mixture is cooled to about 50C. 0.018 part of 40% so-
lution of benzyltrimethylammonium hydroxide in methanol (Triton
; B)(a trimerization catalys-t), are then added to the reaction
mixture, Soon after the addition of Triton B an exothermic
reaction starts during the duration of which the temperature
.~
o* the reaction mixture is maintained at 5GC, From the time
the exotherm appears the viscosity and ~CO content of the re-
action mixture were monitored very closely, When the viscosity
.
', '
.
.. ...
33
.~
of the reac-tion mixture reaches 400-500 cps and the NC0
level drops to below 0 2%, 0.007 part of methanesulfonic
acid are added to the reaction mixture and the mixture is
then cooled. When the temperature reaches about 35C,
0 014 part of TBS are added and the reaction is then cooled
to room temperature. The resulting vinyl isocyanurate is
clear, has a light yellow brown color, a viscosity of about
400-500 cps and a shel-f life longer than 3 months. NMR .
analysis of the product shows an allophanate to urethane .:
ratio of 0 46 Laminates are prepared rom this isocyan- .
urate using a curing system o-f 0 2% dimethylaniline, 0.2%
t-butylcatechol, and 2 0% benzoyl peroxide solution (50%
active) 1/8" two-ply laminates prepared from this resin
retain more than 80% of their room temperature flexural and
tensïle strength at 300F.
- 48
