Note: Descriptions are shown in the official language in which they were submitted.
1 328 1 44
PHENOLIC CYANATE-PHENOLIC
TRL~ZINE COPOLYMERS
BACKGROUND OF THE INVENTION
1. Field of the Invention
S This invention relates to certain novel phenolic cyanate-phenolic
triazine copolymers, and to a process of preparing same. More
particularly, this invention relates to such copolymers which have improved
properties and to a process for preparing such resins.
2. Prior Art:
Phenolic resins are a class of synthetic materials that have grown
continuously in terms of volume and applications for over several decades.
The building blocks used in greatest volume are phenol and formaldehyde.
Other important phenolic starting materials are the alkyl-substituted
phenols, including cresols, xylenols, p-tert-butyl-phenol,p-phenylphenol, and
nonylphenol. Diphenosl, e.g., resorcinol (1,3-benzenediol) and bisphenol-A
[bis-A or 2,2-bis(4-hydroxylphenyl)propane], are employed in smaller
quantities for applications requiring special properties. In addition to
l formaldehyde, acetaldehyde or furfuraldehyde sometimes are employed but
in much smaller quantities. The greater latitude in molecular structure,
; 20 which is provided by varying the raw materials, chemistry, and
- manufacturing process, has made possible an extremely large number of
applications for these products as a result of the array of physical
~ ~ properties that arise from the synthetic options.
;, The early investigation of the reaction of phenol and formaldehyde
began with the work of von Baeyer and others in the 1870's as an
extension of
'~
.
.
'~ r
.,
-2-
1 3~8 1 44
phenolbased dye che~istry. The initial experiments
result in soluble, a~orphous Products whose properties
elicited little interest. Insoluble, cross-linked
products also were reported in ~he lates 1880's, but
these products also were not ~erceived as useful
materials. In 1988, the first patent for a phenolic-
resin Product intended for use as a hard-rubber substi-
tute was granted. The first commercial product was
introduced as a shellac substitute by the Louis ~luner
Company in the early l900~so Process patents were
issued in 1894 and 1895 for or~ho- and para-methylol-
phenol, respectively.
Key innovations in early phenolic-resin manufacture
included control of the molecular structure and the ue
Of heat and pressure to achieve desirable physical
properties in filled compositions. Studies in the use
of acidic or basic catalysts and of changes in the molar
ratio of formaldehyde to phenol resulted in the defini-
tion of two classes of polymeric ~aterials which are
referred to as ~akelite resins. Caustic-catalyzed
Products, which are prepared with greater than a l:l ~ol
ratio of formaldehyde to phenol, can be used to form
cross-linked, insoluble, and infusible com~ositions in a
controlled fashion. With less than a l:l mol ratio of
for~aldehyde to phenol~ the resultant products remain
soluble; furthermore, acid ca~alysis yields permanently
stable eo~positions, whereas base-catalyzed materials
can be advanced in molecular weight and viscosity.
Possibly of greatest importance to early com~ercializa
tion, howeve, was the reduction to practice of the use
of heat and pressure to produce essentially void-free
molding compositions.
Resole resins are made with an alkaline catalyst
and a molar excess of formaldehyde. Novolak or novolac
resins are prepared with an acid catalyst and less than
one mol of formaldehyde per mol of Phenol. The initial
reaction involved in the preparation of resol~ted
novolacs is carried out with an acid catalyst and less
--~ ~3~ 1 3281 44
than a 1:1 mol ratio of formaldehyde to phenol. After
formation of the novolac, the pH is adjusted so that the
reaction mixture i5 basic and additional fonnaldehyde is
added. Resoles and resolated novolaks are inherently
thermosettincl and require no curing agent for advance-
ment. Novolacs, by comparison, are thernoplastic and
require the addition o~ a curing agent, the most common
being either hexamethylene-~e~ramine or a resole. The
stages of molecular weight advancement are characterized
by liquid or so1id phenolic polymer which is soluble in
cartain organic solvents and is fusible: solid resin
which is insoluble but swelled by organic solvents and,-
although softened by heat, exhibits essentially no flow;
and an insoluble, infusible product which is not swelled
by solvents nor softened by heat, i.e., the system i5 in
a highly cross-linked state.
Phenolic res ins have many use~s. For example, such
materials are used as bonding agents in friction mater-
ials such as braks linings, clutch facings, transmission
bonds and the like. For example, UOS. Patent Nos.
4,268,157; 4,069,108; 4,268,657; 4,218,361: 4,219,452:
and 3,966,670 describe various friction materials in
which a phenolic resin is employed as the honding
agent. Phenolics are also used as molding materials,
and as coat ings and adhes ives. Phenolic res ins
develcped for non-f lammability and long-term temperature
stability to 230C have been studied in carbon-~iber
composites. Potential for such composites lies in
advanced aricraft applicat ion,
While present day phenolics exhibit several benefi-
cial properties, they suf fer from a number of disadvan-
tages which restrict their utility. For examp.e, such
materials exhibit less than desirable thermal oxidative
stability. Other major problems of present day phenolic
35 technology include a need for auxilary chemicals such as
hexamethylenetetraamine to crosslink the phenolic which
often results in the production of volatile by~products
such as ammonia during crosslinking is often extensive
'~ '. ~' ' ',, " '
- : -
1 328 1 44
and is not controllable.
Various modifications to phenolics have been pro-
posed to obviate certain of the disadvantages attendant
to these resins. For example, epichlorohydrin has been
reacted with the hydroxyl groups of novolak forming
epoxy novolak. Moreover, n-chloro-2-propene has been
reacted with the hydroxyl groups of novolac to form the
corresPonding form methylon resin. Similarly, Japanese
Patent Publications Nos. 59-149918, and 58-34R22
describe a method of preparing a phenolic resin
containing cyanate grou~s. In this me~hod, a trialkyl
ammonium salt of a phenol novolak is reacted with excess
cyano halogen in an organic solvent such as methylene
chloride. The am~onium by-product salt is separated
from the reaction mixture by extraction with water.
Several disadvantages are attendant to the process of
~hese references. For example, only low molecular
weight novolacs (MW ~ 325 or less) are partially
soluble in the reaction solvent which reacts in low
reaction yield ~60 to 70%). When higher molecular wight
novolacs are used (MW ~ 500), yields are low (<40%).
U.S. Patent No. 3,448,079 describes aromatic cyanic
acid esters produced by the reaction of phenolic resins
with cyanogen halide in which the hydroxyl groups of the
phenol-formaldehyde resins are replaced with cyanic acid
ester grou~s~ and prooe ss for producing same. U.S.
Patent No. 3,444,137 describes curable phenol-aldehyde
resins characterized by molecules which contain a cyano
group, an amine nitrogen atom, a phenyl group and a
substituted hydroxyl qroup, such molecules having been
made by reacting a phenol, formaldehyde and a cyano
substituted primary or secondary amine~ U.S. Patent No.
4,022,755 describes cyanato-group containin~ phenol
resins, and a prooe ss for preparing same.
Various new polymers have been proposed. For
example, Kunstoffe, Bd, 58, pp. 827 832 (1968) by R.
Kubens, et al. and Dokl, and Akad, Nauk SSR VolO 202,
pp. 347-350 (1972) by V. V. Kovshak, et alO describe the
-
5~ 1 328 1 ~4
"cyclotrimerization" of aryl cyanurate and ~roperties of
crosslinked polymers derived therefromO By the term
"cyclotrimerization" is meant forming a cyanurate ring
system by chain extension polymerization of three
aromatic cyanurate groups to form a crosslinked triazine
ring 9y S tem.
U.S. Patent No. 4,157,360 describes thermoformable
compositions comprising a crosslinked polycyanurate
poly~er a~ a thermoplastic polymer in which the poly
cyanurate is formed by a polycyclotrimerization
reaction.
SUMMARY OF THE INVENTION
The present invention is directed to a phenolic
cyanate/phenolic triazine copolymer comprising three or
more phenolic moieties of the Formula I~
.
Formula I
; 20
~X~
C~ C~ ~hJ~ ~ ~
linked by way of at least one of said open valencies to
one or ~ore triazine moieties of the Formula II:
Formula II
.
~ ~ ~
'
`; ' ' ~. '
- . . : ;:
``` -6- 1 3281 44
and wherein the re~ainder of the oPen valencies of said
phenolic ~oieties are substituted with -OH, -OCN, or
other triazine moieties, provided that at least one o~
said remaining open valencies is substituted with a -OCN
moiety;
wherein:
n is a positive whole number qreater than or equal
to l;
q and r are the same or different at each
occurrence and are whole numbers from 0 to 3, with the
proviso that the sum o~ q and r at each occurrence is
equal to 3;
o and P are the same or different at each occur-
rence and are whole numbers from 0 to 4 with the proviso
that the sum o~ o a~d p at each occurrence is equal to
4;
-X- i5 a divalent orqanic radical; and
R3 is the same or different at each occurrence and
is a substituent other than hydrogen which is unreactive
under conditions necessary to completely cure the
copolymer.
Another aspect of this invention relates to
compositions containing the phenolic cyanate/phenolic
triazine copoly~er o~ this invention, and to partially
cured, completely cured and incompletely cured
ccmposition~ formed by "cyclotrimerization~ of the cyano
groups of said copolymer to varying degrees. As used
herein, "completely cured" phenolic cyanate/phenol
triazine copoly~er are those in which less than about 20
~ol percent o~ the original cyano groups remain
unreacted, i.e. uncyclotrimerized, as determined by the
method of infrared spectrophotometry; "Par~ially cured"
phenolic triazine/phenolic cyanate copolymer are those
in which ~rom about 40 to about 70 mol percent of the
original cyano groups are unreacted, i.e.
uncyclotrimerized, as determined by infrared
spectrophoto~etry; and "incompletely cured" phenolic
triazine/phenolic cyanate copolymer are those in which
`' ' ~ '
; . .,....................... :
: :
:'; '' '~ '
^` ~7~ 1328144
frcm about 40 to about 20 mole Percent of the original
cyano groups are unreacted, i.e. uncyclotrimerized, as
de~ermined by infrared spectrophotometry.
Still, another aspect of this invention relates to
compositions comprising the phenolic cyanate/phenolic
triazine of this invention, or partially cured,
incompletely cured and completely cured embodiments
thereof in admixture with one or more other materials as
for example, thenmoset and thernoplastic polymers such
as kevlar and polyethylene, particulate and fibrous
inorganic fillers, as for example, asbestos, mica,
boron, carbon and the like.
The cured resin derived fram the phenolic
cyanate/phenolic triazine copolymer of this invention
exhibit several advantages over conventional phenolic
resins. For example, these materials ara soluble in one
or more aprotic solvents and are also fusible or
meltable which greatly enhances their processability.
In addition, these materials are self crosslinking, and
thus do not require auxilliary chemicals for
crosslinking and have longer shelf lives as compared to
conventional phenolics and modi~ied phenolics.
Moreover, the crosslinked, i.e. cured, resins of this
invention have greater oxidative, mechanical and thermal
stability as com~ared to conventional phenolic resins,
and non volatile, potentially environmentally hazardous
by-products are produced during crosslinking~
Furthermore, the phenolic cyanate/phenolic triazine
resins of this invention have higher char for~ing
propertie~, better elongation pro~erties and higher
glass transition te~peratures than the conventional
phenolic resins.
DESCRIPTI_N OF_THE PREFERRED EM80DIMENTS
One aspect of this invention relates to phenolic
triazine/phenolic cyanate copolymers having at least
three phenolic moieties of the ~ormula I linked by at
least one of said open valencies to one or more triazine
moieties of the Formula II. The remainder of said open
.. . . .
., .. . - .: . : . .
- . ~
1 328 1 44
valencies being substituted with -OCN, -OH or other
triazine moieties, provided that at least one of said
remaining open valencies is substituted with a -OCN
group, wherein R3, n, q, r, o, and X are as described
above.
In the .structure of Formula I, R3 is an inert
substituent. Illustrative of suitable R3 grous are such
inert substituents as halogen, trihalomethyl, alkyl,
alkoxy, phenyl and the like.
In the structure of Formula I, -X- is a divalent
: organic radical. Illustrative of ~uitable -X groups
are alkylene such as methylene, e~hylmethylene, 2-
ethylpentylmethylene, methylmethylene,
isopropylmethylene, isobutylmethylene, pentylmethylene,
furylmethylene, and the like; arylenes such as 1,3-ben-
: zenedimethylene, phenylmethylene, 1,4-benzenedimethy-
lene, 2,2-bis-(4-phenylene)propane, 4-methoxyphenyl-
methylene, bis-(4-phenylene)methane, 4,4-diphenylene
dimethylethane and the like; and cycloalkylenes such as
cyclohexylene, cyclooctylene, 1,3-cyclohexanedimethy-
lene, and the like~
In the preferred embodiments of the invention;
-X- is substituted or unsubstituted methylene or
1,4-phenyldimethylene wherein permissible substituents
are alky or furyl;
q and r are the same or different at each occur-
~ rence and are positive whole numbers from 0 to 3, with
; the proviso that the sum of 0 and r is 3;
R3 is alkyl;
n is frcm 1 to abou~ 20; and
: o and p are the same or different at each
occurrence and are positive whole nu~bers from 0 to 4,
with the proviso that the sum of o and p is 4;
Wherein up to about 30 mole % of the phenyl
moieties of said copolymer are substituted with saidtriazine moieties, up to about 90 mole % o~ said phenyl
moieties are substituted with -OH groups and up to about
90 mole % of said phenyl moieties are substituted with
~ .
,. ~..
-9- 1 32~ 1 ~4
-OCN groups, said mole % based on the total moles of
phenyl groups in said copolymer.
Amongst the pre~erred embodiments of the invention,
particularly preferred are those embodiments of the
invention in which:
from about 2 to about 25 mole % of said phenyl
groups of the phenolic triazine/phenolic cyanate
copolymer are substi~uted with triazine moieties, from
about 40 to about 90 mole % of said phenyl groups are
1 substituted with -OCN groups and fr~m about 2 to about
50 mole % of said phenyl groups are substituted with -OH
groups, said mole % based on the total moles of phenyl -
group in said copolymer;
-X- is methylene, methylene substi~uted with alkyl
having from about 1 to about 10 carbon atoms, halogen or
furfuryl, or xylene;
R3 is methyl or ethyl;
o is 0 or 1;
n is from about 1 to about 10;
q is 0 or 1:
r is 1 to 3; and
p is 1 to 4.
Amongst these particularly preferred embodiments,
most preferred are those e~bodiments where in:
. 25 n is 3 to about 10;
from about 5 to about 20 mole % of the phenyl
groups of the phenyl triazine/phenyl cyanate copolymer
are substituted with triazine moieties, from about 40 to
about 80 mole ~ of said phenyl groups are substituted
with -OCN groups and from about 5 to about 20 mole % of
said phenyl groups are substi~uted with -0~ groups; said
mole ~ based on the ~otal moles of phenyl groups in said
c opolymer;
q is O;
, 35 o is 0;
X is a moiety of the ~ormula:
', ..
: - - - ,
-lo- 1 328 1 ~4
r ;s 3, and f ~ or -CH? ~ H2
p is 4.
Especially good results are obtained in the
practice of this invention where from about 10 to about
20 mole ~ of the phenyl groups in the phenolic
triazine/phenolic cyanate copolymer are substituted with
triazine moieties, from about 10 to about 20 mole % of
said phenyl groups are substituted with -OH groups and
from about 60 to about 80 mole % of said phenyl groups
are substituted wi~h -OCN groups, said mole % based on
the total moles of phenyl groups in said copolymer.
These especially preferred copolymers are
preferably linear copolymers having recurring units of
the Formula III:
Formula_III
_ Z ~ _
- Z~ Z,
25 (g3)0 (~)p ~ r 1~ P
. wherein R3, o, p,. q, r, -X- and n are as described above
and whereins
Zl i~ OH and -OCN: and
Z2 is a trivalent triazine moiety;
With the proviso that frcm about 10 to about 20
mole % of the phenyl groups of the copolymer are
, substitu~ed wi~h trivalen~ triazine moieties, from about
` 35 70 to about 75 mole ~ of phenyl groups as substituted
with -OCN qroups and from about 10 to about 20 mole % of
. the phenyl groups are substituted with -OH groupsf said
mole % based on the total ~oles of phenyl groups in the
.
~:
:' , .
- ~ :
1 328 1 44
copolymer.
A reinforced a ~/or filled composition comprisinq
~he completely cured, partially cured, and incompletely
cured Phenolic triazine/phenolic cyanate copolymer of
:this invention, as well as the compositions w~ich may be
used in the preparation of such reinforced compositions
are also part of the invention disclosed herein. The
completely cured, precured, partially cured, and
incompletely cured compositions as described, may
contain fillers for use in where the structural strength
and integrity of a structure has to be maintained, and
for other ~urposes known to those of skill in the art.
Any suitable filler known to those of skill in the art
can be used, Such fillers ~ay be selected from a wide
v~ariety of organic and inorganic materials such as
polymers, minerals, ~etals, metal oxides, siliceous
materials and metal salts. Illustrative of useful
fillers are fiber glass, stesl, asbestos ~ibers,
aramide, boron and carbon fibers, as well as vlate like,
fibrous and particulate ~orms of alumina, brass powder,
aluminum hydrates, iron oxide, feldspar, lead oxides,
asbestos, talc, barytes, calcium carbonates, clay,
carbon black, quartz, novaculite and other forms of
silica, koalinite, aluminum silicate bentonite, garnet,
mica, saponite, beidelite, calcium oxide, fused silica,
calcium hydroxide, e~a~ Other useful fillers include
thermoplastic polymer, as for example, polyesters,
polyimides, polya~ides, polysulfones, polyaramids,
polyester carbonates, polyethers, polyethersulfones,
polyethylene, polypropylene, polycarbonates, polyether-
imides, polysulfides, polyacrylatec~ polyvinyls and the
like. The foregoing recited fillers are illustrative
only and are not meant to limit the scope of the fillers
that can be utilized in this invention. Methods for
:~35 producing reinforced and/or filled compositions include
melt blending, extrusion and molding Drocesses, simple
mixing and dispersion of both materials in suitable
medium by methods known in the art.
v
.: . ~
` ~``` -12- 1 328 1 ~4
The phenolic triazine/phenolic cyanate copolymer of
this invention is prepared by controlled "polycyclo-
trimerization" of a modified phenolic resin of the
Formula IV:
Formula IV
10 z~ z~
~0 C~ . C~ (,o
15 to the extent necessary to form the de~irad mole percent
of trivalent triazine moieties, where R3, q, r, o, p, n,
Zl and X are as described above, provided that the
: amount of Zl group which are -OCN is sufficient to
provide the desired mole ~ of triazine moieties and -OCN
moieties in the desired copolymer. By the term
"polycyclotrimeri zat ion" is .neant forming a cyanurate
ring system by the chain extension polymerization of
three aromatic cyanate groups to form the crosslinked
triazine ring system which comprises the following basic
repeat unit of Formula II:
wherein the open valencies are bonded to a phenyl ring
of a phenolic moiety. The methods of cond~cting the
polycyclotrimerization of cyanurate compounds are well
known in the art, and include thermal annealing above
about 200C. For example, such methods are described in
; :
:
` 1 328 1 44
-13-
Kun~t~toffe, Bd, 58, pp. 827-832 (1968) by R. Rubena, et
al. and Polk Ak ad Nauk SSR, Vol. 202, pp. 347-350 (1972)
by V.V. Kor~hak, et al. and U.S. Patant 4,157,360. For
example, an appropriate modified phenolic resin of the
above Formula I can be cro~slinked, preferably neat, with
or without an acceptable cataly~t at elevated
temperatures.
~he polymerization is induced thermally. The
threahold polymerization temperature can Yery widely
depending on a number of factors, a~ for example, the
presence or lack of a cataly~t, the type of aatalyst when
used; the prssence of ~ree hydrogen groups and the like.
In general, tha thre~hold polymerlzation temperature i~
aqual to or greater than about 25 C. In the preferred
embodiments of the invention, the threshold polymerization
t~mperature i8 from about 100 C to about to 350 C, and in
the particularly preferred embodiments i~ from about 100-C
to about 300 C. Amongst these particularly preferred
embodiments, most preferred are tho~e embodimsnt~ in which
the threshold polymerization temperature i~ from about
120-C to about 250-C. Heating can bs accomplished by
conventional msthods known to those oP ~klll in the art.
Illustration of ~uch method are heating with an oil bath,
25 vacuum, hot air annealing, oompression molding and the
like.
~he polymerization i8 preferably carried out in the
pre~ence of a catalytically effective amount of a
catalyst. U~eful cataly~t can vary widely and include
anhydrou~ metal 8alt8 3uch as stannou# chloride dihydrate,
cuprou6 bromide, cuprou~ cyanide, cuprou~ ferricyanide,
zinc chloride, zino bromide, zinc iodide, ~inc cyanide,
zinc ferrocyanide, zinc acetate, ~ilver chloride, ferrous
chloride, n~ckel chloride, ferric chloride, cobaltous
cyanide, nickel aulfate, stannic chloride, nickel
: carbonate, and the like. Alao useful as cataly~t~ are
proton-donating organic reducing agent~
:``
` ~Bi
. .
.... . .. .
~.
.. . . .
, . . j
- :
-14- l 3~81 4~
such as tetrahydropyridine, hydroquinone, 4,4-biphenol
and the like. Amounts of the catalyst when used are not
critical and can vary widely provided that the amount is
sufficient to catalyze the reaction to the desired
extent.
~ eaction pressures are not critical and can vary
widely~ The reaction can be carried out at subatmos-
pheric, atmospheric or super-atmospheric pressure.
However, for convenience, the reaction is carried out at
autogenous pressure or atmospheric pressure.
During the esterification of the phenolic resin, we
have discovered that in addition to formation of -OCN
moieties, carbamate moieties may be formed by reaction
of -OCN functions with active hydrogen containing
materials such as H2O and C2H5OH forming the carbamate
functions -C(O)NH2 or -C(OH) = NH, and -C(OC2H3) = NH
respectively. In addition, when amines are employed as
the base catalyst in the preparation of the phenolic
cyanate of Formula IV as will be described in ~ore
detail below, dicyanamides as for example, (C2H5)2 NCN,
may form in the phenolic cyanate and consequently will
be a contaminant in the desired phenolic cyanate/
phenolic triazine copolymer. We have also discovered
~ that the mole ~ of carbamate functions substituted to
- 25 phenyl grou~s of the phenolic cyanate precursor used in
the preparation of the phenolic triazine/Phenolic
cyana~e copolymer of this invention and/or the amount of
dicyanamide for~ed during the preparation of the
phenolic cyanate precur~or are critical to the shelf
life of the phenolic cyanate precursor and to the
phenolic cyanate/phenolic tria~ine copolymer of this
inven~ion, and to the processibility of the copolymer.
In general, the mole ~ of phenyl groups substitut2d with
carbamate functions is equal to or le~s than about 20
mole % based on the total moles of phenyl groups present
! in the co~olymer, and the weight percent of dicyanamide
, present in the copolymer is equal to or less than about
20 weight peroe n~ based on the total weight of the
~'
.,
.,
S- 1 32~1 44
copolymer. In the preferred embodiments of the
invention, the mole ~ of phenyl groups substituted with
carbamate functions is equal to or less than abou~ 10
mole % based on the total moles o~ phenyl groups, and
the weight percent o~ dicyanamide present in the
copolymer is equal to or less than about 5 weight
percent based on the total weight of the copolymer~ In
the particularly preferred e~bodiments of the invention,
the ~ole % of phenyl groups substituted with carbamate
functions is equal to or less than about 5 mole % based
on the total moles of phenyl groups, and the weight
percent of dicyanamide presen~ in the copolymer is equal-
to or less than about 2 weight percent based on the
total weight of the copolymer. In the mo.~t preferred
embodiments of the invention, the mole ~ of phenyl
groups substituted with carbamate functions is equal to
or less than about 2 mole ~ based on the total moles of
phenyl groups, and the amount of dicyanamide present in
the copolymer is less than about 1 weight peroe nt based
on the total weight of the copolymer; with those
embodiments of the invention in which substantially no
phenyl groups are sub~tituted with carbama~e functions
and in which substantially no dicyanamide is contained
in the copoly~er being the embodiments of choice.
The phenolic cyanate resin used as the precursor in
the preparation of the phenolic triazine/phenolic
cyanate copolymer of this invention is prepared by a
nucleophilic displacement reaction through use of the
~: prooe ss of ~his inven~ion. In this reaction, a cyanoqen
halide, preferably cyanogen chloride or cyanogen
bro~ide, is reacted with a base phenolic salt of Formula
V:
For~ula V
_ ~
~/O~X~X~~ '
' ~:
.
-16- 1 32 81 4 4
wherein R3, -X-, o, p, q, r and n are as defined above,
and V is hydrogen or cation of an organic or inorganic
base which is formed by reaction between said base and
the protons of a phenolic to form the corresponding
basic salt, wherein the mole ratio of cations to
hydrogen are sufficient to form the desired mole ~ of
-OCN groups in the desired phenolic cyanate. The
reaction is preferably under nitrogen in the presence of
an a~rotic solvent in which the salt and cyanogen halide
are soluble in the substantial absence of ~aterials
having active hydrogens.
We have discovered that the reaction temperature
has a significant impact on the mole percent of
carbamate formed during the formation of the phenolic
cyanate. Reaction temperatures can vary widely provided
that they are less than about 0C. It is believed that
use of higher temperatures will result in the formation
of phenolic cyanates having an unacceptable level of
2 carbamate substituents. Preferred reaction temperatures
are equal to or less than about -5C and more preferably
are equal to or less than about -10C~ In the ~ost
preferred embodiments of the invention, reaction
temperatures are equal to or less than about -15C.
It is also preferred that isolation and
purification procedures preferably avoid the use of
temperaturss in excess of about noc. In the more
preferred embodiments of the invention, temperatures in
excess of about -5C are avoided in the isolation and
purification of the product, and in the most preferrad
embodiments ~ mperatures in excess of about -10C are
avoided. Surprisingly, we have also discovered that the
use of tem~eratures in excess of those specified above
during the reaction~ and processing and isolation step
results in the presence of an unacceptably large amount
of carbamate functions.
Useful aprotic solvents can var~ widely, the only
requirements being that the solvent is inert under the
reaction conditions and that the reactants are soluble
.
-17~ 1 32~ 1 ~4
in the solvent. In this respect, the process of this
invention differs significantly from the processes of
Japan Kokai Nos. 59 149918 and 58-34822 in which the
process is carried out in solvents such as methylene
chloride in which relatively high molecular weight
novolac salt is insoluble.
Illustration of aprotic solvents useful in the
conduct of this reaction are amides such as N,N-dimethyl
aceta~ide, N,N-dime~hyl formamide, and N-meth~1 2
pyrrolidone; ketones such as methyl ethyl ketone, ethyl
pro~yl ketone and the like; organic carbonates such as
propyl carbonate; ethers such as digly~e,
tetrahydropyran, 3-methyltetrahydrofuran,
tetrahydrofuran, and glyme; organic sulfur containing
compounds such as dimethyl sulfoxide, sulfones and
; sulphonates; and chlorinated hydrocarbons such as
methylene chloride, carbon tetrachloride, chloroform and
the like. The preferred solvents are ethers, and,
! particularly preferred solvents are cyclic ethers such
as tetrahydrofuran and diethers such as glyme or
digly~e.
Reaction times can vary considerably and will
depend upon such factors as the degree of agitation,
t0mperature, nature and proportion of reactants and the
like. Preferred reaction times are from about 4 hours
to about 6 hours. The reaction product can be recovered
by conventional means with substantially anhydrous
conditions. Usually, the salt by-product is separated
from the dissolved produc~ by filtration. If solid when
neat, the product can be ~reci~itated frcm solution
using standard crystallization techniques, and purified
by recrystallization from one of the above-referenced
aprotic solvents. If liquid when neat, the product can
be conveniently isolated and purified by conventional
distillation techniques.
The base salt of phenolic prepoly~er can be
conveniently prepared by reaction between a base and a
phenolic prepoly~er. As noted above, bases for use in
. :
'
-18- 1 328 1 44
the preparation of the base salt may vary widely and may
include both inorganic and organic bases. Illustrative
of suitable bases are tertiary amines, alkali metal
hydroxides, alkali metal carbonates and the like.
Preferred for use in the product of this invention
are alkali metal hydroxideq such as sodium hydroxide and
potassium hydroxide, and tertiary amines such as
triethyl amine, trimethyl amine and pyridine.
For example, alkali metal phenolic salts can be
obtained by reacting 2 equivalents of sodium hydroxide
with 2 or more equivalents of a phenolic resin such as
phenol for~aldehyde resin, substituted phenol formalde-
hyde resin, cashew nut shell phenol formaldehyde resin,
phenol furfuraldehyde resin, and p-xylene phenolic
resin, in dimethylsulfoxide solvent. Alternatively,
alkali metal phenolic salt~ can be prepared by reacting
phenolic resins and anhydrous potassiu~ carbonate in
dimethylsulfoxide under nitrogen.
The phenolic cyanate/phenolic triazine copolymer of
this invention, completely cured, incompletely cured and
partially-cured compositions of this invention are
useful in forming a wide variety of industrial products,
;~ including shaped articles, as ~roduced by known shaping
processes. The phenolic cyanate/phenolic triazine
copolymer of this invention compositions can be formed
(i.e., shaped) into articles which can then be cured to
form completley cured, incompletely cured and Partially-
cured articles. Shaped articles produced from the
polymer composition include windscreens such as wind
shields, structural ~arts, canopies, door windows, wire
housing and the like. The shaping pro oe ss can be any
`~ process known to one skilled in the art, such as
injection, blow or extrusion molding. Another use of
the crosslinked polymer of the member is a bind agen~ in
the manufacture of friction materials such as brake
linings, clutch facings and transmission bands, as for
example those described in ~.S. Patents 3,966,670;
4,268,657; or 4,281,361. Still other uses of the
-19- 1 3 2 8 1 4 4
copolymers of this invention are molding materials,
composites for use in the manufacture of structural
parts and the like. Yet other copolymers of this
invention are useful as adhesives.
S In order that those skilled in the art will be
better able to practice the invention, the following
examples are given by way of illustration and not by way
of limitation. In the examples, all parts are by
weight.
EXAMPLE 1
A. Preparation of the Phenolic CYanate
A mixture of 1.81 kg Oe novolac (613 number average
molecular weight), and 1.79 kg triethylamine was
dissolved in 7L of tetrahydrofuran at ambient
temperature. Cyanogen bromide (2.04 kg) was dissolved
in 6L of tetrahydrofuran under nitrogen atmosphere. The
solution containing the trialkylammonium salt of novolac
i was added to cyanogen brcmide solution oveer a period of
3-4 hrs. During the addition, the temperature of the
reaction mixture was maintained at -20C to -15C.
After the reaction was completed, the reaction was
i allowed to continue for an additional 16-18 hrs. at rocm
temperature. The product was isolated by filtration to
remove trialkylamine salt, The filtrate was purified by
precipitation in 26L of cold isopropanol/dry ice mixture
(-15C to -20C) (twire), and subsequen~ly dried in a
vacuum oven overnight to produce cff-white phenolic-
; cyanate. The elemental analysis indicated %C=72.25,
~H=3.42, and ~N=10.22. The IR spectrum indicated strongabsorption at -C=N(2250 cm 1) and ~he absence of any
carbamate and dicyanamide functions.
. Preparation of the Phenolic Triazine~Phenolic
Cyanate Co~olymer
A 50g sample of phenolic-cyanate of Step A was
heated in a test tube for about 20 min. at 100C to form
a yellowish white meltable phenolic cyanate-phenolic
:'
,
'' ' " ' '-
, ~, :' ' ' , '
-~ -20- 1 32 ~1 44
triazine copolymer. The IR spectrum indicated the
presence of cyanate functions (2250 cm 1) and triazine
functions (1580 cm 1 and 1380 cm 1), The copolymer was
soluble in tetrahydrofuran, methylene chloride, acetone,
and methyl ethyl ketone. The Elemental analysis was,
~C 72.25, ~H 3.42, ~N 10.22. The IR s~ectrum indicated
about 15 to about 20 ~ole ~ triazine based on the total
moles of phenyl groups in the copolymer.
EXAMPLE 2
A. Formation of the Phenolic-Cyanate
A mixture of 509 of novolac (570 number average
molecular weight) and 51.0g of triethylamine was
dissolved in 1609 of tetrahydrofuran at ambient
15 temperature. A 57.7g sample of cyanogen bromide was
dissolved in 1359 of tetrahydrofuran under nitro~en
atmosphere. The solution of the trialkylammonium salt
o~ the novolac was added to the cyanogen bro~ide
solution over a period of 1 hr. During the addition of
20 the solution, the temperature of the reaction mixture
was maintained at about -10 to -15C. After the
addition was completed, the reaction was allowed to
continue for an additional 1 hour period at room
` temperature. The product was isolated frcm the trialkyl
25 ammonium bromide salt by-product by filtration. The
product was purified by precipitation in isopropanol/dry
ice m~xture (-15C to -20C) and subsequently dried in a
vacuum oven overni~ht to produce off-white phenolic-
~` cyanate.
The structure of the product was confirmed by IR
spectrum which showed the presence of cyanate functions
C=N, 2200-2300) and the absence of carbamate functions
(-NH- and = NH 3330 cm 1).
35 B. Pre~aration of the Phenolic Cyanate/Phenolic
Triazine CoPolymer
.
A 109 samPle of phenolic-cyanate of Step A was
heated in a test tube about 30 min. at 100C to form a
.
-: . - -
' ''
-- -21- l 328 1 ~4
yellowish polymer- The IR sPeCtrUm indicated the
presence of 60 to 65 mole ~ cyanate (2250cm l), 15 to 20
mole ~ triazine (1580cm 1, and 1380cm 1) and about 10
mole % phenolic hydroxyl (3400 cm 1).
The elemental analysis was ~C=72.0, ~H=4.61, and
%N=9.55. The copolymer was soluble in organic solvents
like tetrahydrofuran, methylene chloride and methyl
ethyl ketone.
EXAMPL~ 3
A. Pre~aration of the Phenolic Cyanate
A mixture of 75.89 of cyanogen brcmide was
dissolved in 759 tetrahydrofuran. A 61.2g sample of
high ortho content novolac of number average molecular
weight 620 was dissolved in lOOg of tetrahydrofuran and
15 66.7g of triethylamine was added gradually to form
trialkylam nium salt of novolac. The trialkylammonium
salt of novolac solution was added to the cyanogen
bromide solution gradually during the time of addition
the temperature of the reaction mixture was maintained
20 at about -20 to -10C. After the addition was
completed, the reaction was allowed to continue for 18
hrs. at room temperature. The product was isolated from
trialkylammonium bromide salt by-product by filtration.
The isolated solution was added gradually to
25 isopropanol/dry ice mixture ~-15~C to -20C). A white
precipitate was form~d. The product was redissolved in
tetrahydrofuran and reprecipitate in isopropanol. The
IR spectrum was consistent with the proposed structure
and showed the absence of carbamate functions.
EXAMPLE 4
A. Preparation of the Phenolic CYanate
A sample of 3159 of cyanogen bromide was dissolved
in 5009 of tetrahydrofuran. A 2889 sample of novolac
35 (320 number average molecular weight) was dissolved in
7009 Oe tetrahydrofuran, and 2869 of triethylamine was
added gradually to form the trialkyammonium salt of the
novolac. The solution of the trialkylammonium sal~ of
~' , .
`: :
:. :
-22- 1 328 1 4~
novolac was added to the cyanogen brcmide solution
~radually. During the addition, the temperature of the
reaction mixture was maintained at about -20 to -15C.
After the addition was completed, the reaction was
5 allowed to continue for 20 hrs. at room temperature.
The product was isolated from trialkylammonium bromide
salt by-Product by filtration.
The isolated solution was added gradually to
isopropanol, forminq a white aum. The gum was
10 redissolved in tetrahydrofuran and reprecipitate in
isopropanol. The resulting gum was redissolved in
tetrahydrofuran, and the tetrahydrofuran solution was
concentrated with a rotary evaporator. A light yellow
viscous liquid formed~ The IR spectrum was consistent
15 with the proposed structure and showed the absence of
carbamate functions.
B. Preparation of the Phenolic Triazine/Phenolic
Cyanate Copolymer
Copolymer
A 1009 sample of viscous liquid phenolic-cyanate o~
; Step A was heated ~/2 hrs. under nitrogen to form a solid
product. The IR spectrum indicated the formation of
2sabout 20 mole % linear triazine ring. The product was
soluble in acetone, methyl ethyl ketone and CH2C12.
., '
.~ EXAMPLE 5
Preparation of ~he Phenolic Cyanate/Phenollc Triazine
Copolymer
A 59 sample of the phenolic cyanate from Step A of
Example 1 was heated 5 min. at 125C to form phenolic
cyanate-triazine copolymer. IR spectrum indicate about
;10 mole % triazine formation. The copolymer is soluble
35in organic solvents.
EXAMPLE 6
Preparation of the Phenolic Cyanate
- : .
-23- 132~144
A mixture of 6.5g of novolac (570 number average
molecular weight) and 3.3g of triethylamine was
dissolved in 30 ml of diglyme at ambient temperature. A
3.5g sample of cyanogen bromide solution was dissolved
5in 20 ~1 of diqlyme under nitrogen atmosphere. The
solution containing the trialkylammonium salt of novolac
was added to cyanogen bromide over a period of 20
minutes. During the solution additon, the temperature
of the reaction mixture was maintained at about -10C.
After the addition was completed, the reaction was
allowed to continue for an additional 1 hour period at
room temperature. The product was isolated from
trialkylammonium salt by filtration and the resulting
filtrate was purified by precipitation in
15isopropanol/dry ice mixture at -5C and subsequently
vacuum dried to obtain a white product. The structure
of product was confinmed by IR spectrum.
EXAMPLE 7
' 20Formation of the Phenolic-Cyanate
A mixture of SOg of novolac (570 number average
molecular weight) and 51.09 of triethylamine was
dissolved in 1609 of tetrahydrofuran at ambient
te~perature. A 57-7g sample of cyanogen bra~ide was
25dissolved in 135g of tetrahydrofuran under nitrogen
atmosphere. The solution of the trialkylammonium salt
of the novolac was added to the cyanogen bromide
solution over a period of 1 hr. During the addition of
the solution, the temperature of the reaction mixture
30was main~ained at about -10 to -15C. After the
addition was completed, the reaction was allowed to
continue for an additional 1 hour period at room
temperature. The product was isolated from the trialkyl
ammonium br3~ide salt by-product by filtration. The
3sproduct was purified by precipitation in isopropanol at
room temperature and a white gum formed. The white gum
was difficult to solidify. Analysis by GC indicated
about 2-5~ carbamate, and about 1-2% dicyanamide.
-24-l 3~ 8 1 4 ~
EXAMPLE 8
A. Formation of the Phenolic-Cyanate
A mixture o~ 50g o~ novolac ~570 number average
molecular weiqht) and 51.09 of triethylamine was
dissolved in 160g of tetrahydrofuran at a~bient
tem~erature. A 57.7g sample of cyanogen bromide was
dissolved in 135g of tetrahydrofuran under nitroqen
atmosphere. The solution of the trialkylammonium salt
of the novolac was added to the cyanoqen bromide
solution over a period of 1 hr. During the addition of
the solution, the temperature o~ the reaction mixture
was maintained at about 20C. After the addition was
completed, the reaction was allowed to continue for an
additional 1 hour period at room temperature. The
product was isolated ~rom the trialkyl a~monium bromide
salt by-product by filtration. The product was purified
by precipitation in isopropanol/dry ice mixture (-15C
to -20C) and subsequently dried in a vacuum oven
overnight to produce off-white nhenolic-cyanate.
The structure of the product was confirmed by I~
spectrum which showed the presence of cyanate functions
(-C=N, 2200-2300). The presence of about 2 to 3%
dicyanamide was detenmined by GC.
EXAMPLE 9
A. Preparation of the Phenolic Cyanate
A mixture Oe 1.81 kq of novolac ~613 number average
molecular weight), and 1.91 kg triethylamine was
dissolved in 7L of tetrahydrofuran at ambient
; temperature. Cyanogen bromide (2.16 kg) was dissolved
in 6L of tetrahydrofuran under nitrogen atmosphere. The
solution containing the trialkylammonium salt of novolac
was added to cyanogen brGmide solution over a period of
3-4 hrs. During the addition~ the temperature of the
reaction mixture was maintained at -20C to -lSC.
After the reaction was completed, the reac~ion was
allowed to continue for an additional 16-la hrs. at roo~
--`` 1 328 1 44
temperature. The product was isolated by filtrat ion to
remove trialkylamine salt. The filtrate was purified by
precipitat ion in 26 L of isopropa nol/dry ice mixture (-
20C) (twice), and subsequently dried in a vacuun~ oven
overnight to produce o~f-white phenolic-cyanate. The
elemental analysis indicated %C=72.25, ~H=3.42, and
%N=10.22. Tlle IR spectrum indicated strong absorp~ion
at -C=N(2250 cTn 1) and the absence of any carbamate
~unct ions, and dicyanamide.
a. Preparation of the Phenolic Triazine/Phenolic
Cyanate Copolymer
A 50g sample of phenolic-cyanate of Step A was
heated in a test tube eor about 20 min. at 100C to form
a yello~ish white meltable phenolic cyanate-phenolic
triazine copolymer. The IR spectrum indicated the
presence of cyanate functions (2250 cm l)and triazine
functions (1580 cm 1 and 1380 cm 1). The copolymer was
soluble in tetrahydrofuran, methylene chloride, acetone,
and methyl ethyl ketone. The Elemental analysis was~ %C
72-25, ~H 3,42, %N 10.220 The I~ spectrum indicated
about 15 to about 20 mole ~ triazine based on the total
moles of r~henyl groups in the copolymer.
~Y~8~Y~
(1) Preparation of the Phenolic Cyanate of Japanese
Kokai NoO 149918-1984
To a 2 Liter beaker was added 3849 of novolac t550
numbar average molecular weight), 330.49 of ~riethyl-
amine and 768g of methylene chloride. A highly viscous
solution of the trialkyl ammonium salt of the novolac
resul~ed. A 417~6g sarnple of cyano~en bromide was added
to 976q methylene chloride in a 4 liter beaker, and the
solution was cooled to 0C. The tri alkylammonium salt
solution was added to the cyanogen bromide solution over
a 45 min. period using an addition funnel while
maintaining the temperature of the reaction exotherm at
. . ,
.
_ -26- 1 32~ 1 44
about 0C with a dry ice/isopropanol bath. The
heterogeneous reaction mixture was then allowed to react
for an additional 30 min., after which it was poured
into 300 ml of deionized water with stirring. The
methylene chloride layer was isolated and washed 2 times
with 300 ml of deionized water. U~on concentration in a
rotory evaporator, a semisolid product was obtained
which upon drying under vacuum pump provided a solid
product.
The analysis of the semisolid product by gas
chromatograph indicated the presence of dicyanamide by-
product. IR sPeCtrUm of solid material indicated the
presence of carbamate functions (about 10-15%) at 1740
cm~l and 3300 cm~l.
(2) Preparation of the Phenolic Cyanate/Phenolic
Trlazine Copolymer From the Phenolie Cyana~e.
Using the procedure of Example 1, the phenolic
cyanate of step A was treated to form a phenolic
cyanate/phenolic triazine copolymer.
IR spectrum indicate ~resence of about 15-20 mola
triazine formation. The polymer is soluble in organic
solven~s.
COMPARATIVE EXAMPLE B
No. 4,022,755.
~ ;
To a 2 liter beaker was added 100 9 of novolac (380
number average molecular weight) and 500 ml methylethyl-
ketone. A yellow solution was observed in 10 minutes.
The solution was cooled to 0C, and 113g of cyanogen
bromide was added. A 99.89 sample of triethylamine was
added to the novolac-cyanogen bromide solution. The
rate of addition was controlled to provide a temperature
o~ from 5-10C. After the triethylamine addition, a
heterogeneous reaction mixture was observed. The
triethylammonium bromide salt by-product was filtered
-2 1 3281 4~
from the reaction mixture, and the filtrate was
concentrated on a rotary evaporator under reduced
pres 5U re. The product obtained was insoluble in organic
solvents and a gel was observed. The IR spectrum
i ~ icate formation of carbamate at 1740 cm 1 and 3300
cm 1, The GC analysis of reaction filtrate indicate the
presence of about 5-7~ dicyanamide.
(2) Preparation of the Phenolic Cyanate/Phenolic
Tr~-in~ cco~ly~ ~
The above gel product of Step A was heated at about
125C to for~ phenolicyanate/phenolic ~riazine
copolymer.
This product was moldable at 160C, 300 psi.
COMPARATIVE EXAMPLE C
(1) Preparation of the Phenolic Cyanate of U.SO Patent
No. 4,022,755
To a mixture of 108g (0.999 mole) of m cresol and
659 (0.801 mole as CH2O) of formalin (37% CH2O) were
added 0.29 of (0.0022 mole) oxalic acid and 0.19 (0.0010
mole as HCl) of hydrochloric acid (35%). The mixture
was heated at 99C to 100C to form an emulsion. The
emulsion wa~ refluxed for 4 hours and 30 minutes, and
then dehydrated under reduced pressure to obtain a solid
cresol novolac. The resulting cresol novolac had a
melting point of 92-103C.
In 210 ml of acetone was dissolved 729 (0~6 mole as
-OH) of the m-crecol novolac. The resulting solution
- was cooled to 0C. To the cooled solution was added 70q
(0.661 mole) of cyanogen bromide followed by dropwise
~' addition of 649 (0.632 ~ole~ of triethylamine. After
completion of the reaction, the triethylamine
hydrobromide salt was re~oved. The resulting reaction
mixture was added to vigorously stirred water. A semi-
solid product obtained which was dried 40C in a vacuum
oven to 18 hrs. to obtain a solid powder having a
. ..
'.. ~ : ,,
, ~ .
~~~''' ~
132~144
melting point of 72-78C. IR spec~rum revealed a strong
absorption at 2250 cm 1 which indicated formation of
cyanate (about 80-85%). The spectrum also indicate 5
mole ~ carbamate formation and 10-15 mole ~ of unreacted
hydroxyl groups~
A 50 g sample of the phenolic cyanate was molded in
a 3" x 3" mold at 155C, 300 psi for 10 min. The
materials squeeze out frcm the mold without forming
representative sample for thermal (Tg) and mechanical
measure~ents.
(2) Preparation of Phenolic Cyanate/Phenolic Cyanate
Triazine CoPolymer
A 209 sample o~ m-cresol phenolic-cyanate (M.P 72-
78C) was heated 80C for 20 min. to form a meltable
phenolic cyanate-phenolic triazine copolymer which was
soluble in organic solvents. ~R spectrum analysis
indicated that the copolymer included about 30 mole
linear triazine formation.
The above copolymer was molded in a 3" x 3" ~old at
155C, 300 psi, for 10 min. to obtained a tough
plague. During the time of molding, there was very
little loss of material due to flashout.
COI~ YI~IIV~ e~ L- D
~ Preparation of Phenolic Cyanate of U.S. Patent No.
3 ,448 ,0?9 .
A 1069 sample of novolac (620 number average
molecular weight) and which contains one OH group per
106 molecular weight was dissolved in 250 ml of
acetone. The solution was cooled to 0C after which 128
g of cyanogenbromide was addedO To the solution,was
then slowly added dropwise 145 ml of triethylamineO
35 Cyanogen bramide ~59) was then added to the reaction
mixture during the course of the reaction to replace
evaporation loses. The triethylaminehydrobro~ide salt
produced by the reaction was removed by suction
-29- 1 3 2 ~
filtration, and the filtrate concentrated by evaporation
to provide a solid powder. IR spectrum indicated
cyanate formation and the presence of carba~ate
functions.
(2) PreP~aratlon of the Phenolic Triazine/Phenolic
Cyanate Copoly~er.
A 50g sample of phenolic cyanate o~ SteP A was
heated to 100C for 15 min. to form the phenolic
triazine/phenolic cyanate copolymer having S-10 ~ole %
triazine. This material was molded at 155C for 6 min
to provide a plague. The plague was postcured for about
4 hrs. before any thermal and mechanical properties
measurements were obtained.
COMPAR~TIVE EXAMPLE E
A series of experiments were carried out for the
purpose of evaluating the thermal characteristics of
certain embodiments Oe this invention whose preparation
is described in Examples l(A), l(B), 2(A), and 4(A) and
to compare same to the thernal characteristics of the
materials of Comparative Examples A(l), B(l)~ C(l) and
D(l~ and to the thermal characteristics of a base
phenolic resin~ The ther~al characteristics were chosen
for comDarative purposes because these characteristics
impac~ significantly on the u~e of these materials in
high temperature applications. In these experiments~
thermogravimentric analysis (TGA) was carried out in an
aryon atmosphere to detenmine the wei~ht loss Oe a
sample as a function of temperature -and the % Char at
1000C. These experiments were carried out using a
Dupont-1090 thermogravimeter at a heating rate of
10C/min. The typical size sample was 30-40 m~. The
results of these experiments are set forth in the
following TABLE I.
' ~ - :
:: .
--30--
1 3281 ~4
~81E I
Exp. % Weight Loss a~ C
No. Sa~le 2~0C 300C400C 450C 500C ~00C 70t)C
1. Novolac 0 0 4 25 39 - 5 8
2. EX.
1 (8) 0 0 0 1.2 14 24 30
3. Ex.
1(8) 0 12.5 25 32
4 Ex.
2(E~) 3 3 3 6 13 24 3
5 ~ Ex,
4(B) 0 0 0 2.5 16 25 31
6. Ex.
A( 1) 13 14 15 20 a6 34 40
: 15
7. Ex.
B( 1) 15 16 17 18 24 35 38
8 . Ex .
C(l) 15 15.516 34 38 46 48
9. Ex.
D( 1) 3.5 4.5 10 20 30 39 46
10. Ex.
D( 2) 2.0 3.5 8 17 21 35 44
11. 9(A) 2.4 3 3 15 20 ~ 35
. 1 20 9(B? 0 0 0 1.2 10 22
-
;
- . :. - : :; :.,
: .~ : , ,
. : .
: ~ :
. .
_ -31- 1 328 1 ~4
BIE _I (c~ntinued)
~Char
Exp. % ~iqht La;s at C at
No. Sa~lple 800C 900C 1000C
1. Novolac - 55 45
2. Ex.
l(B) 32 33 66
3, Ex.
l(B) 31 35 65.3
4. Ex
2(B) 34 35 65
5. Ex~
4(B) 33 35 65
6. Ex.
A(l) 42 43 55
15 7. Ex.
8(1) 42 41 56
7. Ex.
C(1) 51 53 46
9. Ex.
D(l) 4~ 47 53
10. Ex.
D(2) 46.5 47 56
11. 9(A) 3~ - 59.64
12. 9(B) 32 - 62.19
2~
COMPARATIVE EXAMPLE F
A series of experiments were carried out for the
purpose of evaluating the glass transition (Tg) of cured
30 compositions of this invention whose preparations are
described in Examples 1(2~), l(B), 3(A) and 3(B) and to
compare same to the glass transition temperature of the
cured compositions forTned from the compositions whose
preparation are described in Comparative Examples B(l),
35 C(1), C(2), D(l) and D(2). In these experiments, the
glass transition temperature was determined on molded
~' articles~ Molding was carried out ~or 6 rninutes at
;, 155-C followed by post curing ~or 4 hours at 22C. The
,
.'':
.:
:.................................... ,, ~ - : .
-32 1 3~8 1 ~4
glass transition te~perature was determined on a 4 cm x
1 cm plaques by dynamic mechanical analysis (DMA) where
the upper limit was 300C. The results of the test are
set forth in the following Table II.
Table II
Exp. No. Sample Tq ~C?
(1) Ex. l(A) >280
(2) Ex. 2(B) >3Q0
(3) Ex. 3(A) >300
(4) ~x. 3(a) >300
(5) Ex. 9(~) >30Q
(6)* Ex~ B(l) 68
(7) Ex. C(l) 250
(8) Ex. C(2) 280
(9) Ex. D(l) 225
(10) Ex. D(2) 250
* The sample did not cure properly, and fo~ned
blisters.
COMPARATIVE EXAMPLE G
-- ,
Usin~ molded plagues fonmed as described in
COMPARATIVE EXAMPLE F, a series of experiments were
carried out for the purpose of evaluating the flexural
modulus and flexural strength of cured COmpositiQnS of
thi~ invention for~ed from the compositions of this
- invention whose preparation are described in Examples
l(A) and 1(8), and to compare same to the flexural
: strength and ten~ile strength of cured compositions
ormed from the compositions whose prepara~ion is
described in Comparative Examples C(l), C(2), D(l) and
D(2). In these experiments, the flexural strength and
the flexural ~odulus were determined using an Instrum
Machine with standard test methods, ASTM D790. The
results of these experimen~s are set ~orth in the
eollowing Table III.
i
. : , - , ., - . . :
.
, ;' '``'~ ' '~ , : . `
. .
~33~ 1 3281 ~4
Table III
Flexural Flexural
Exp. No. S~le Stren~th ~esi) Modulus (psi ) t
1 Ex. l(B) --- ----
2 Ex. 2~B) 9785~687.9kg/cm2) .69xlO6(0.48xlO5kg/cm2)
3 E~. 9 (~) 10 ,937 ( 768 .94 .61x106( 0.4 2xlO5kg/an2)
kg/cm2)
4 Ex. 3(B) --- -~
Ex. C~2) 6275~441.1kg/cm~) .67xlO6~0.47:clO5kg/cm2)
6 Elc. D( 1)
7 Ex. D~2) 8200~576.5kg/cm2) .68xlO6(0~47xlO5kg/cm-2)
CO~AR~IVE E~PMPLE H
A sen~ of ex~erimerts were cart~ed ou~ or the purpose of
evaluating the shel life of each o the composit~ons of this
invertion whose preparatioris are described in Exanples 1, 2 ard 4
and to compare sane to th~ shelf life of each o the campositions
whose preparations are described in Canparative Exa~ples A~l),
- 20 B~l), C(l) and D~l). In these experiments, the shelf ~ the
canposition was dete~nined by s~ring same at roan temperature to
determine the nunber of days nece~;sary for the for~nation of
materials which were insoluble in several organic solverts. The
results o~ these studies are set forth in tl~ fcLlc;wing Table IV.
:
. .
, 35
~,
.
. , ,
:,
.
~: :: . . : .
.
. ~
. ~ :
~ ~ .
-34- 1328144
b le IV
Sample
Exp. No. Solvent Ex 1(A) EX 2tB) EX 2(A) EX 4(A) EX (7)EX (8
(l) Tetrahydro- S(90) S(90) S(>90) S(>90) S(2)S(3)
fura n
(2) Methylene S(90) S(90) S(>90) S(>90)
Ch lo ri de
(3~ Methyl S(90) S(90) S(>90) S(>90) S(2)S(3)
Et hyl
Ketone
Tab le IV ( cont inued )
SanQle
Exp. No. Solvent A(l) B(l) C(1) D(l )
(1) 1~3trahydro~- St3) ItO) S(2) S(l)
furan
(2) Methylere I(Oj I(O) I(O) I(O)
Chlori~3
(3) M2thyl S(3) I(O) I(O) S(1)
Ketone
In the table, the ollowing abbreviations are used:
(a) "S" is soluble and
(b) "I" is insolubleO
The number in the parenthesis is the number of days
on the shelf before becoming insoluble.
` 35
~ -
,. . .
.
; . , ~ ~ : :
