CA1328144C - Phenolic cyanate-phenolic triazine copolymers - Google Patents

Abstract

PHENOLIC CYANATE-PHENOLIC
TRIAZINE COPOLYMERS
ABSTRACT OF THE INVENTION
The specification discloses a phenolic cyanate/phenolic triazine copolymer comprising three or more phenolic moieties of the Formula I

linked by way of at least one of said open valencies to one or more triazine moieties of the Formula II

and wherein the remainder of the open valencies of said phenolic moieties are substituted with -OH, -OCN, or other triazine moieties, provided that at least one of said remaining open valencies is substituted with a -OCN
moiety. The specification discloses cured resins prepared from these compounds which exhibit several advantages over conventional phenolic resins, including solubility in aprotic solvents or meltability for enhance processability, self-cross linking, great stability, and absence of hazardous by-products during cross-linking, higher char-forming properties, better elongation properties and higher glass transition temperatures.

Description

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 ., 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 '~ '. ~' ' ',, " ' - : -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 .. . . .
., .. . - .: . : . .

- . ~

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 .
~:

:' , .
- ~ :

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 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~~ ' ' ~:
.

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 . :

' 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 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.

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.

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.

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.

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.

' 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 ~

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.

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.

' ~ - :
:: .

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 ~, .

. , , :, .
~: :: . . : .

.
. ~
. ~ :
~ ~ .

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 ~ -,. . .
.
; . , ~ ~ : :

Claims (54)

1. A phenolic triazine/phenolic cyanate copolymer comprising three or more phenolic moieties of the formula:

linked by way of at least one of said open valencies to one or more triazine moieties of the formula:

and wherein the remainder of the open valencies of said phenolic moieties are substituted with -OH, -OCN, or other triazine moieties, provided that at least one of said remaining open valencies is substituted with a -OCN moiety;
wherein:
n is a positive whole number equal to or greater than 1;
q and r are the same or different and are whole numbers from 0 to 3, with the proviso that the sum of q and r at each occurrence is equal to 3;
o and p are the same or different at each occurrence and are positive whole numbers from 0 to 4, with the proviso that the sum of o and p is equal to 4;
-X- is substituted of unsubstituted methylene or 1,4-phenyldimethylene wherein permissible substituents are halo, alkyl or furyl;
R3 is the same or different at each occurrence and is halo, trihalomethyl, alkyl, alkoxy or phenyl.

2. A copolymer according to claim 1 wherein up to about 30 mole % of the phenyl groups in said copolymer are substituted with triazine moieties, saidmole percent based on the total moles of phenyl groups in said copolymer.

3. A copolymer according to claim 2 wherein the mole % of phenyl groups substituted with triazine moieties is from about 2 to about 25 mole %.

4. A copolymer according to claim 3 wherein the mole % of phenyl groups substituted with triazine moieties is from about 5 to about 20 mole %.

5. A copolymer according to claim 4 wherein the mole % of phenyl groups substituted with triazine moieties is from about 10 to about 20 mole %.

6. A copolymer according to claim 1 wherein up to about 90 mole % of the phenyl groups in said copolymer are substituted with -OCN groups, said mole percent based on the total moles of phenyl groups in said copolymer.

7. A copolymer according to claim 6 wherein the mole % of phenyl groups substituted with -OCN groups is from about 40 to about 90 mole %

8. A copolymer according to claim 7 wherein the mole % of phenyl groups substituted with -OCN groups is from about 40 to about 90 mole %.

9. A copolymer according to claim 8 wherein the mole % of phenyl groups substituted with -OCN groups is from about 60 to about 80 mole %.

10. A copolymer according to claim 9 wherein the mole % of phenyl groups substituted with -OCN groups is from about 70 to about 75 mole %.

11. A copolymer according to claim 1 wherein up to about 90 mole % of the phenyl groups of said copolymer are substituted with -OH groups, said mole % based on the total moles of phenyl groups in said copolymer.

12. A copolymer according to claim 11 wherein the mole % of phenyl groups substituted with -OH groups is from about 2 to about 50 mole %.

13. A copolymer according to claim 12 wherein the mole % of phenyl groups substituted with -OH groups is from about 5 to about 20 mole %.

14. A copolymer according to claim 13 wherein the mole % of phenyl groups substituted with -OH groups is from about 10 to about 20 mole %.

15. A copolymer according to claim 1 wherein the mole % of phenyl groups in said copolymer wherein the open valencies are substituted with carbamate functions is equal to or less than about 20 mole %, said mole %
based on the total moles of phenyl groups in said copolymer.

16. A copolymer according to claim 15 wherein the mole % of phenyl groups substituted with carbamate functions is less than about 10 mole %.

17. A copolymer according to claim 16 wherein the mole % of phenyl groups substituted with carbamate functions is less than about 5 mole %.

18. A copolymer according to claim 17 wherein the mole % of phenyl groups substituted with carbamate functions is less than about 2 mole %.

19. A copolymer according to claim 18 wherein none or substantially none of the phenyl groups are substituted with carbamate functions.

20. A copolymer according to claim 1 which comprises less than about 10 weight % dicyanamide based on the total weight of the copolymer.

21. A copolymer according to claim 20 which comprises less than about 5 weight % dicyanamide.

22. A copolymer according to claim 21 which comprises less than about 2 weight % dicyanamide.

23. A copolymer according to claim 21 which comprises less than about 1 weight % dicyanamide.

24. A copolymer according to claim 23 which comprises no dicyanamide or substantially no dicyanamide.

25. A copolymer according to claim 1 wherein X is substituted or unsubstituted methylene wherein permissible substituents are alkyl having from 1 to about 10 carbon atoms and furyl.

26. A copolymer according to claim 7 wherein X is a moiety unsubstituted methylene or methylene substituted with furyl.

27. A copolymer according to claim 1 wherein n is from 1 to about 20.

28. A copolymer according to claim 27 wherein n is from about 1 to about 10.

29. A copolymer according to claim 28 wherein n is from about 3 to about 10.

30. A copolymer according to claim 1 wherein:
o is 0 or 1; and p is 2 or 4.

31. A copolymer according to claim 30 wherein:
o is 0; and p is 4.

32. A copolymer according to claim 1 wherein:
q is 0 or 1; and r is 2 to 3.

33. A copolymer according to claim 32 wherein:
q is 0; and r is 3.

34. A copolymer according to claim 1 wherein R3 is alkyl.

35. A copolymer according to claim 34 wherein R3 is methyl or ethyl.

36. A composition comprising a copolymer phenolic resin according to claim 1 and one or more fibrous or particulate fillers.

37. A composition according to claim 36 wherein said copolymer is free or substantially free of carbamate functions and of dicyanamide.

38. A completely cured composition formed by cyclotrimerization of the copolymer of claim 1.

39. A partially cured composition formed by cyclotrimerization of the copolymer of claim 1.

40. An incompletely cured composition formed by cyclotrimerization of the copolymer of claim 1.

41. A linear phenolic triazine/phenolic cyanate of claim 1 having recurring moieties of the formula:

wherein:
Z1 is -OH and -OCN;
Z2 is a trivalent triazine moiety of the formula:

wherein:
n is a positive number greater than or equal to 1;
q and r are the same or different and are whole numbers from 0 to 3, with the proviso that the sum of q and r at each occurrence is equal to 3;
o and p are the same or different at each occurrence and are positive whole numbers from 0 to 4, with the proviso that the sum of o and p is equal to 4;
-X- is substituted of unsubstituted methylene or 1,4-phenyldimethylene wherein permissible substituents are alkyl or furyl;
R3 is the same or different at each occurrence and is halo, trihalomethyl, alkyl, alkoxy, or phenyl;
with the proviso that from about 10 to about 20 mole % of the phenyl groups of said copolymer are substituted with said trivalent triazine moiety, from about 70 to about 75 mole % of said phenyl groups are substituted with -OCN groups and from about 10 to about 20 mole % of said phenyl groups are substituted with -OH groups, and mole % based on the total moles of phenyl groups in the copolymer.

42. A process for preparing a phenolic cyanate resin of the formula:

which process comprises reacting a cyanogen halide with a base phenolic salt of the formula:

in an aprotic solvent at a temperature equal to or less than about O°C, wherein:
q and r are the same or different and are whole numbers from 0 to 3, with the proviso that the sum of q and r is equal to 3;
Z1 is -OH and -OCN;
o and p are the same or different at each occurrence and are positive whole numbers from 0 to 4, with the proviso that the sum of o and p at each occurrence is equal to 4;
-X- is substituted or unsubstituted methylene or 1,4-phenyldimethylene wherein permissible substituents are halo, alkyl or furyl;
R3 is the same or different at each occurrence and is halo, trihaiomethyl, alkyl, alkoxy or phenyl;
n is a positive whole number equal to or greater than 1; and V is a cation of an inorganic or organic base or hydrogen.

43. The process of claim 42 wherein said temperature is less than about 5°C.

44. The process of claim 43 wherein said temperature is less than about 10°C.

45. The process of claim 44 wherein said temperature is less than about 15°C.

46. The phenolic cyanate prepared in accordance with the process of claim 42.

47. The phenoiic cyanate of claim 46 wherein the mole % of carbamate functions is equai to or less than about 10 mole % based on the total moles of phenyl groups in said cyanate.

48. The phenolic cyanate of claim 47 wherein said mole % of carbamate is less than about 2 mole %.

49. The phenolic cyanate of claim 48 wherein said mole % of carbamate is less than about 1 mole %.

50. The phenolic cyanate of claim 46 wherein the weight % of dicyanamide is equal to or less than about 10 weight percent based on the total weight of the phenolic cyanate.

51. The phenolic cyanate of claim 50 wherein the weight % of dicyanamide is less than about 5 weight %.

52. The phenolic cyanate of claim 51 wherein the weiyht % of dicyanamide is less than about 2 weight %.

53. The phenolic cyanate of claim 52 wherein the weight % of dicyanamide is less than about 1 weight %.

54. The phenolic cyanate of claim 53 which is free or substantially free of dicyanamide.