Fusion product

A process for reacting an acidic compound or anhydride with an epoxy-containing compound is disclosed. In a preferred embodiment this process comprises reacting a polyepoxide having more than one vic-epoxy group with a phenol in the presence of a methylene bis(triphenylphosphonium)halide catalyst.

FIELD OF THE INVENTION 
This invention relates to a process for reacting a phenol, carboxylic acid 
or acid anhydride with an epoxy-containing compound and to the resulting 
products. More particularly, the invention relates to a process for 
effecting a specific reaction between compounds possessing a vic-epoxy 
group and a phenolic hydroxyl group, carboxylic group or anhydride group, 
and to the products obtained thereby. 
BACKGROUND OF THE INVENTION 
Epoxy compounds are well known and include many compounds of varying 
molecular weight and epoxy equivalent weight. To simplify the production 
of a large number of epoxy compounds that vary mainly in molecular weight, 
it is common practice to manufacture a single epoxy compound of relatively 
low molecular weight and react the epoxy compound with a compound 
containing phenolic hydroxyl groups in the presence of catalyst so as to 
obtain epoxy of phenolic hydroxy ether compounds of desired higher 
molecular weight. The conventional catalysts employed are inorganic bases 
or tertiary amines which are also effective catalysts for competing 
reactions of epoxides with alcoholic hydroxyl groups, homopolymerization 
of epoxy groups and the like. As a result, the product obtained is a 
mixture of polymers and resins with varying degrees of molecular weight, 
chain branching and end group functionality. Such a composition detracts 
from the performance and utility of the product. More recent catalysts 
with improved selectivity include phosphonium halides as disclosed in U.S. 
Pat. No. 3,477,990, phosphines as disclosed in U.S. Pat. No. 3,547,881, 
3-(trihydrocarbylphosphoranylidene)-2,5-pyrrolidinediones as disclosed in 
U.S. Pat. No. 3,843,605, alkylammonium halides as disclosed in U.S. Pat. 
No. 3,824,212, and tetrahydrocarbyl phosphonium salts as disclosed in U.S. 
Pat. No. 4,438,254. 
Many of the above catalysts have found commercial utility. However, there 
is a continuing need for process and product improvements. For example, 
when many of these catalysts are admixed with the epoxy resins to produce 
a "pre-catalyzed" epoxy composition, the storage stability at elevated 
temperatures is not acceptable for many applications because of the 
reduced activity of the stored resin. U.S. Pat. No. 4,320,222 discloses an 
improved precatalyzed polyepoxide containing a synergistic catalyst 
composition comprising a phosphonium halide and an alkali metal halide or 
hydroxide. 
In other cases the process steps must be controlled under strict conditions 
so as not to deactivate the catalyst. For example, U.S. Pat. No. 4,438,254 
cited above requires that the fusion process be conducted at a temperature 
under 175.degree. C. and under "essentially anhydrous conditions". 
Patentees define the term "essentially anhydrous" to mean that the 
reaction medium is absolutely free of water or contains a sufficiently 
"small quantity of water" not to deactivate the catalyst. The patentees 
found that deleterious reactions occurred with their catalyst with as 
little as 0.009 weight percent water present in the reaction medium 
(column 6, lines 53-58). 
What is needed is a new catalyst that does not suffer from deleterious 
reactions with small quantities of water, thereby enabling much greater 
freedom of operation. Further, the precatalyzed epoxy resin must be stable 
at elevated temperature and active at the higher fusion temperatures. 
SUMMARY OF THE INVENTION 
The present invention, therefore, relates to the discovering of a specific 
catalyst for use in an epoxy fusion process (i.e., a conversion process 
employing acidic substances and/or anhydrides). In particular, the present 
invention is a process for preparing an advanced epoxy resin by reacting a 
compound containing at least one vic-epoxy group with a compound selected 
from the group consisting of phenols, carboxylic acids and carboxylic acid 
anhydrides in the presence of a catalyst selected from the group 
consisting of salts of the formula 
##STR1## 
where R is hydrocarbyl or inertly substituted hydrocarbyl group and X is a 
compatible anion. 
In a preferred embodiment the catalyst is methylene 
bis(triphenylphosphonium)dibromide (or "MBTPPB") or the structure of 
Formula I. Use of this MBTPPB catalyst in the fusion process has produced 
extraordinary results, as shown in the examples which follow. In 
particular, the above catalyst has markedly superior thermal stability and 
resistance to deactivation by water compared to the catalysts employed in 
the prior art, e.g., the examples used in the '254 patent described above. 
The catalyst of Formula II-e.g., 
triphenylphosphoranemethylenetriphenylphosphonium bromide ("TPPMTPPB") is 
also a very stable and active catalyst. 
As shown in the Examples which follow, the percent conversion to higher 
molecular weight compounds with the catalyst of the present invention is 
not affected by the presence of water. As shown in Example 2, the addition 
of 0.48 percent weight water did not reduce the conversion, contrary to 
the prior art catalysts. Such performance is particularly surprising in 
view of the disclosures in U.S. Pat. No. 4,438,254 where much lower 
amounts of water resulted in dramatic reductions in conversion. 
In a further embodiment the present invention relates to a pre-catalyzed 
epoxy resin composition comprising: 
(a) a polyepoxide; and 
(b) a catalytic amount of a catalyst of the formula I or II above. 
In still further embodiments the catalyst of formula I or II is reacted 
with a polyepoxide and a compound selected from the group consisting of 
phenols, carboxylic acids and carboxylic acid anhydrides. Preferably the 
phenol possesses at least one and more preferably two or more phenolic 
hydroxyl groups. Preferably the carboxylic acid is a polycarboxylic acid 
and the carboxylic acid anhydride is a polycarboxylic acid anhydride. 
DETAILED DESCRIPTION OF THE INVENTION 
In a preferred, specific application the process of the invention involves 
the reaction of an epoxy compound and a phenol in the presence of a 
particular catalyst to form the desired phenolic hydroxy ether of the 
partial formula 
##STR2## 
THE POLYEPOXIDES 
The liquid polyepoxides employed in the present invention include those 
compounds possessing more than one vic-epoxy group per molecule, i.e. more 
than one 
##STR3## 
group per molecule. These polyepoxides are saturated or unsaturated, 
aliphatic, cycloaliphatic, aromatic or heterocyclic, and are substituted, 
if desired, with non-interfering substituents, such as halogen atoms, 
hydroxy groups, ether radicals, and the like. Preferred liquid 
polyepoxides include the so-called liquid glycidyl polyethers of 
polyhydric phenols and polyhydric alcohols. More preferred are the 
glycidyl polyethers of 2,2-bis(4-hydroxyphenyl)propane having an average 
molecular weight between about 340 and about 900 and a epoxide equivalent 
weight of between about 170 and about 500. Especially preferred are the 
glycidyl polyethers of 2,2-bis(4-hydroxyphenyl)propane having an average 
molecular weight of between about 340 and about 900, an epoxide 
equivalent weight of between about 170 and about 500, and containing from 
about 0.01% to about 1.0% weight or higher of saponifiable chlorine. As 
used herein the terms "epoxide equivalent weight" and "weight per epoxide" 
refer to the average molecular weight of the polyepoxide molecule divided 
by the average number of oxirane groups present in the molecule. 
Various examples of polyepoxides that may be used in this invention are 
given in U.S. Pat. No. 3,477,990 (e.g., column 2, line 30 to column 4, 
line 75) and it is to be understood that so much of the disclosure of that 
patent relative to examples of polyepoxides is incorporated by reference 
into this specification. 
THE PHENOLS 
The phenols used in the process of the invention are those compounds 
possessing at least one hydroxyl group attached to an aromatic nucleus. 
The phenols are monohydric or polyhydric and are substituted, if desired, 
with a great variety of different types of substituents. Examples of the 
phenols include among others, phenol, resorcinol, o-cresol, m-cresol, 
p-cresol, chlorophenol, nitrophenol, hydroquinone, 
2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)pentane, and the 
like, and polymeric type polyhydric phenols obtained by condensing 
monohydric or polyhydric phenols with formaldehyde. 
Preferred phenols to be used are the polyhydric phenols containing from 2 
to 6 OH groups and up to 30 carbon atoms. Coming under special 
consideration are the phenols of the formula 
##STR4## 
wherein X is a polyvalent element or radical and R.sup.1 independently is 
a member of the group consisting of hydrogen, halogen and hydrocarbon 
radicals. The preferred elements or radicals represented by X are oxygen, 
sulfur, --SO--, --SO.sub.2 --, divalent hydrocarbon radicals containing up 
to 10 carbon atoms and oxygen, silicon, sulfur or nitrogen containing 
hydrocarbon radicals, such as --OR"O--, --OR"OR"O--, --S--R"--S--, 
--S--R"--S--R"--S, --OSiO--, --OSiOSiO--, 
##STR5## 
--SO.sub.2 --R"--SO.sub.2 -- radicals wherein R" is a divalent hydrocarbon 
radical. 
Various examples of phenols that may be used in this invention are also 
given in U.S. Pat. No. 3,477,990 (e.g., column 5, line 1 to column 6, line 
10) and it is to be understood that so much of the disclosure of that 
patent relative to examples of phenols is incorporated by reference into 
this specification. 
CARBOXYLIC ACIDS AND ANHYDRIDES 
In a further embodiment of the invention the catalyst and polyepoxide may 
be reacted with a carboxylic acid and/or carboxylic acid anhydride in 
place of or in addition to the phenol. 
The carboxylic acids used may be saturated, unsaturated, aliphatic, 
cycloaliphatic, aromatic or heterocyclic. Examples of these acids include, 
among others, succinic acid, glutaric acid, adipic acid, pimelic acid, 
suberic acid, azelaic acid, sebacic acid, oxalic acid, abietic acid, 
maleic acid, aconitic acid, chlorendic acid and phthalic acid. 
The acid anhydrides used may be any anhydride which is derived from a 
carboxylic acid and possesses at least one anhydride group, i.e., a 
##STR6## 
group. The carboxylic acids used in the formation of the anhydrides may be 
saturated, unsaturated, aliphatic, cycloaliphatic, aromatic or 
hetrocyclic. Examples of these anhydrides include, among others, phthalic 
anhydride, isophthalic anhydride, di-, tetra- and hexahydrophthalic 
anhydride. 3,4,5,6,7,7-Hexachloro-3,6-endomethylene 1,2-tetrahydrophthalic 
anhydride (chlorendic anhydide), succinic anhydride, maleic anhydride, 
chlorosuccinic anhydride, monochloromaleic anhydride, 
6-ethyl-4-cyclohexene-1,2-dicarboxylic acid anhydride, 
3,6-dimethyl-4-cyclohexene-1,2-dicarboxylic acid anhydride, 
6-butyl-3,5-cyclohexadiene-1,2-dicarboxylic acid anhydride, 
octadecylsuccinic acid anhydride, dodecylsuccinic acid anhydride, dioctyl 
succinic anhydride, nonadecadienylsuccinic anhydride, adducts of maleic 
anhydride with polyunsaturates, such as methylcyclopentadiene. (Nadic 
methyl anhydride),3-methoxy-1,2,3,6-tetrahydrophthalic acid anhydride, 
3-butoxy-1,2,3,6-tetrahydrophthalic anhydride, trimellitic anhydride, 
pyromellitic anhydride, di-, tetra- and hexahydropyromellitic anhydride, 
polyadipic acid anhydride, polysebacic acid anhydride, and the like and 
mixtures thereof. Derivatives of the anhydrides, such as their partial 
esters, amides, etc., may also be employed. Examples of these include, for 
example, esters of glycols and pyromellitic anhydride and partial esters 
of trimellitic anhydride. 
CATALYST 
The catalysts used in the present invention are selected from the group 
consisting of salts of the formulas 
##STR7## 
where R is a hydrocarbyl or inertly substituted hydrocarbyl group and X is 
a compatible anion. 
The compatible anion, X.sup..crclbar., can be any anion used in the prior 
art for such catalyts. Preferred as anions are halides, i.e. 
Br.sup..crclbar., Cl.sup..crclbar. or I.sup..crclbar. ; carboxylates, such 
as formate, acetate, oxalate or trifluoroacetate; conjugate bases of weak 
inorganic acids, such as bicarbonate, tetrafluoroborate or biphosphate and 
conjugate bases of a phenol, such as phenate or an anion derived from 
bisphenol A. The most preferred anions are halides, with bromide being the 
most preferred halide. 
The R groups borne by the phosphonium cations can be aliphatic or aromatic 
in character. Preferably each phosphonium cation bears at least one R 
group which is aromatic in character, more preferably at least two such 
aromatic groups. These aromatic groups preferably are phenyl or inertly 
substituted phenyl. 
Those R groups which are not aromatic are preferably C.sub.1 -C.sub.20 
alkyl. 
Most preferably, all the R groups are phenyl, and the catalyst of formula I 
is used. Accordingly, the much preferred catalyst is methylene 
bis(triphenylphosphonium)dibromide. 
The methylene bis(triphenylphosphonium)dibromide can be conveniently 
prepared by refluxing under nitrogen for about 2 hours a mixture having a 
mole ratio of methylene bromide to triphenylphosphine of 2. The excess 
methylene bromide is removed by distillation and the crude product 
dissolved in methanol and precipitated by the addition of ethyl actetate. 
In one sample the purified salt had a bromine content (AgNO.sub.3 
titration) of 22.1 %w (theory 22.9 %w). 
Triphenylphosphoranemethylenetriphenylphosphonium bromide can be prepared 
by treating methylene bis(triphenylphosphonium)dibromide (2.5 millimols) 
with Na.sub.2 CO.sub.3 (about 6 millimols) at about 5 %w in water/methanol 
(3/1 by weight) at reflux for about 3 to 4 hours and then removing the 
methanol by distillation. The solids separating from the cooled reaction 
mixture are collected by filtration and recrystallized from methylene 
chloride/ethyl acetate. In one example, the purified salt had 12.95 %w 
bromine (theory 13.0 %w). 
PREATION OF THE PHENOLIC HYDROXY ETHER COMPOUNDS 
The amount of the epoxide and the phenol to be employed in the process 
varies over a wide range depending upon the type of reactants and the type 
of product to be produced. In general, these reactants are used in 
approximately chemical equivalent amounts, i.e., a chemical equivalent 
amount of the phenol will be that sufficient to furnish one phenolic 
hydroxyl for every epoxy group to be reacted. For example, if one is 
reacting a diepoxide with a monohydric phenol and both epoxy groups are to 
be reacted, one mole of diepoxide should be reacted with about two moles 
of the monohydric phenol. On the other hand, if one is reacting a 
diepoxide with a dihydric phenol and a monomer product is desired by 
reacting both phenolic groups, one should react about two moles of the 
diepoxide with one mole of the dihydric phenol. If a polymeric product is 
desired smaller ratios should be utilized as desired, such as, for 
example, 5 moles of the diepoxide and 4 moles of the dihydric phenol. 
Superior results are obtained when the higher molecular weight resins are 
produced and in this case the ratios of reactants are varied depending 
upon the molecular weight desired and upon the type of end groups, i.e., 
whether the product is to be terminated with an epoxide or with a phenol. 
An especially preferred use of the present invention is in the preparation 
of a phenolic hydroxy ether resin having a epoxide equivalent weight of 
between about 400 and about 4000 wherein the resin is prepared by reacting 
2,2-bis(4-hydroxyphenyl)propane with the diglycidyl ether of 
2,2-bis(4-hydroxyphenyl)propane having a saponfiable chlorine content of 
between about 0.01% and about 1.0% weight and an epoxide equivalent weight 
of between about 170 and about 500. 
The amount of the catalyst employed varies widely. In general, the amount 
of catalyst varies from about 0.001% to about 1% by weight, of the total 
reactants, more preferably from about 0.002% to about 0.2% and most 
preferably from about 0.3% to about 0.1% by weight of the reactants. 
The reaction is conducted in the presence or absence of solvents or 
diluents. In most cases, the reactants are liquid and the reaction is 
easily effected without the addition of solvents or diluents. However, in 
some cases, where either or both reactants are solids or viscous liquids 
it is desirable to add diluents to assist in effecting the reaction. 
Examples of such materials include the inert liquids, such as inert 
hydrocarbons as xylene, toluene, cyclohexane and the like. 
If solvents are employed in the reaction and the resulting product is to be 
used for coating purposes, the solvent is typically retained in the 
reaction mixture. Otherwise, the solvent is removed by any suitable method 
such as by distillation or the like. 
Phosphonium salts have been used as catalysts for promoting the reaction 
between epoxides and acidic materials for quite some time. Up to now the 
salts employed have been ones that even at fairly low concentrations of 
water are in the course of the reaction converted into inactive phosphine 
oxides; temperatures higher than about 175.degree. C. are also reported to 
contribute to the loss of catalytic activity (U.S. Pat. No. 4,438,254). In 
contrast the subject salts of this invention are quite tolerant of water 
contents of up to about 0.5 %w and reaction temperature of up to 
195.degree.-200.degree. C. This tolerance for water provides an economic 
advantage since the cost entailed in achieving very low water contents is 
avoided; the tolerance for higher temperature also provides an economic 
advantage since reaction cycle times can be reduced by reacting at higher 
temperatures. 
The products obtained by the above process are the desired phenolic hydroxy 
ether compounds. Their physical characteristics depend upon the desired 
reactants and proportions. In general, the products vary from liquids to 
solids. The polyfunctional reactants also give products terminated in 
phenolic hydroxyl groups and/or epoxy groups, and these are available for 
further reaction. 
A group of products which are particularly outstanding are those resins and 
polymers obtained by the reaction of the polyepoxides and polyhydric 
phenols in controlled proportions. Those which use an excess of the 
polyepoxide are terminated in epoxy groups and can be used as polyepoxides 
in known reactions of polyepoxides and curing agents and the like. These 
high molecular weight polyepoxides are particularly useful in preparing 
surface coatings, adhesives, laminates, filament windings, coatings for 
highways and airfields, structural applications, formation of foams and 
the like. Those prepared from the halogenated polyhydric phenols are 
particularly useful as flame proofing resins for forming laminates, 
coatings and the like. As stated earlier, the present invention is 
particularly useful for preparing epoxy resins to be used as coatings. 
CURING OF THE EPOXY CONTAINING, PHENOLIC HYDROXY ETHER COMPOUNDS 
The epoxy-containing, phenolic hydroxy ether compounds obtained by use of 
the present invention are reacted with various conventional curing agents 
to form hard insoluble, infusible products. Examples of suitable curing 
agents include, among others, the polybasic acids and their anhydrides 
such as the di, tri- and higher carboxylic acids; those acids containing 
sulfur, nitrogen, phosphorus or halogens; amino-containing compounds such 
as, for example, diethylene triamine, aminoethylpiperazine, dicyandiamide 
and triethylenetriamine and pyridine; polyamides containing active amino 
and/or carboxyl groups; and others. 
The amount of curing agent varies considerably depending upon the 
particular agent employed. For the alkalies or phenoxides, 1% to 4% by 
weight is generally suitable. With phosphoric acid and esters thereof with 
appropriate crosslinking resin, good results are obtained with 1 to 10% by 
weight added. The tertiary amine compounds are preferably used in amounts 
of about 1% to 15% by weight. The acids, anhydrides, polyamides, 
polyamines, polymercaptans, anhydrides, etc. are preferably used in at 
least 0.8 equivalent amounts, and preferably 0.8 to 1.5 equivalent 
amounts. An equivalent amount refers to that amount needed to give one 
active hydrogen (or anhydride group) per epoxy group. 
Solvents or diluents are sometimes added to make the composition more fluid 
or sprayable. Preferred solvents or diluents include those which are 
volatile and escape from the polyepoxide composition before or during cure 
such as ketones, ethers, chlorinated hydrocarbons and the like. To 
minimize expense, these active solvents are often used in admixture with 
aromatic hydrocarbons such as benzene, toluene, xylene, etc. and/or 
alcohols such as ethyl, isopropyl or n-butyl alcohol. Solvents which 
remain in the cured compositions are used, such as diethyl phthalate, 
dibutyl phthalate and the like. It is also convenient to employ normally 
liquid glycidyl compounds, glycidyl cyclopentyl ether, diglycidyl ether, 
glycidyl ether of glycerol and the like, and mixtures thereof. 
Other materials are also added to the composition as desired. This includes 
other types of polyepoxides such as described in U.S. Pat. No. 3,477,990. 
This also includes fillers, such as sand, rock, resin particles, graphite, 
asbestos, glass or metal oxide fibers, and the like, plasticizers, 
stabilizers, asphalts, tars, resins, insecticides, fungicides, 
anti-oxidants, pigments, stains and the like. 
The temperature employed in the cure varies depending chiefly on the type 
of curing agent. The amino-containing curing agents generally cure at or 
near temperature and no heat need be applied. The acids, anhydrides, and 
melamine derivatives, on the other hand, generally require heat, such as 
temperatures ranging from about 150.degree. F. to about 400.degree. F. 
Preferred temperatures range from about 200.degree. F. to about 
400.degree. F., and more preferably from about 250.degree. F. to 
380.degree. F. 
The compositions containing the polyepoxides and curing agents are used for 
a variety of important applications. They are used, for example, as 
adhesives for metal, wood, concrete, plaster and the like, and as surface 
coatings for various types of surfaces. The new compositions are also used 
in the preparation of laminates or resinous particles reinforced with 
fibrous textiles. They are also used in the formation of castings and 
molding and for the encapsulation of electrical equipment. 
The invention is further illustrated by means of the following examples. 
Note that the examples are given for the purpose of illustration only and 
that the invention is not to be regarded as limited to any of the specific 
conditions or reactants noted therein. 
As used in the examples which follow, "WPE" refers to weight per epoxide. 
Gardner-Holdt viscosity is measured according to ASTM Method D-1545, and 
the significance of the measurement is discussed in J. J. Mattiello, 
Protective and Decorative Coatings, Volume V, p. 186 (1946).

ILLUSTRATIVE EXAMPLE 1 
In Illustrative Example 1 the storage stability of various diphosphonium 
salts were examined. In all examples, the catalyst concentration was 0.25 
meq/100 g of resin (or 0.125 millimoles/100 g of resin). The starting 
epoxy compound containing the catalyst was a liquid polyepoxide having a 
WPE of about 185. The starting phenolic compound used in the fusion 
reaction was 2,2-bis(4-hydroxyphenyl)propane (BPA). The storage times for 
the precatalyzed resins were as shown in Table 1. 
A small scale reaction was made to assess the retention of activity of the 
stored resin. Thus, about 10 grams of resin was admixed near 
150.degree.-160.degree. C. with sufficient bisphenol-A to give a product 
with a WPE of about 500 at 100% bisphenol-A conversion, the mixture being 
held at 160.degree. C. for about 45 minutes. 
The catalyst employed had the formula 
##STR8## 
where all R are phenyl groups, X is bromide and the Y or Z radical moiety 
is as shown in Table 1. 
As shown in Table 1, the best candidates were MBTPPB and TPPMTPPB. 
TABLE 1 
______________________________________ 
STORAGE STABILITY OF PRECATALYZED RESINS 
BASED ON BIS-TRIPHENYLPHOSPHONIUM BROMIDES 
AT 200.degree. F. (CATALYST CONCENTRATION 
.about.0.25 MEQ/100 G 
WPE of Fusion Resin.sup.1 
After X Days Storage 
Radical For- 0 1 3 6 7 
Moeity mula Day Day Days Days Days 
______________________________________ 
(CH.sub.2).sub.1 
I 493 487 487 -- 502 
(CH.sub.2).sub.2 
I 422 307 -- -- -- 
(CH.sub.2).sub.3 
I 471 436 322 -- -- 
##STR9## I 399 259 -- -- -- 
##STR10## I 333 257 -- -- -- 
(CH) II 495 -- -- 520 -- 
.sym. 
No Catalyst 256 -- -- -- -- 
______________________________________ 
.sup.1 Target WPE = .about.500. 
ILLUSTRATIVE EXAMPLE 2 
Illustrative Example 2 deals with additional storage tests using the 
following catalysts: 
MBTPPB--methylene bis(triphenylphosphonium)bromide 
TPPMTPPB--triphenylphosphoranemethylenetriphenylphosphonium bromide 
ETPPP--ethyl triphenylphosphonium phosphate 
ETPPI--ethyl triphenylphosphonium iodide 
The results are shown in Table 2. The rank order of these systems is 
clearly evident from the active life period, with MBTPPB and TPPMTPPB 
being clearly the best. 
TABLE 2 
______________________________________ 
STORAGE STABILITY OF PRECATALYZED RESINS 
AT 200.degree. C. (CATALYST CONCENTRATION 
.about.0.25 MEQ/100 G) 
Storage 
Time, MBTPPB TPPMTPPB ETPPP ETPPI 
Days As Catalyst 
As Catalyst 
As Catalyst.sup.2 
As Catalyst 
______________________________________ 
A. WPE of Fusion Resin Based On 
0 493 495 484 486 
1 487 -- 489 479 
3 487 -- 483 477 
6 -- 520 -- -- 
7 502 -- 503 298 
14 538 555 454 267 
21 .sup. 556.sup.1 
-- 292 -- 
29 -- 617 -- -- 
B. WPE of Precatalyzed Resin on Storage 
0 189 187 207 189 
14 200 .sup. 197.sup.3 
213 196 
21 204 .sup. 202.sup.3 
214 -- 
54 -- 220 -- -- 
______________________________________ 
.sup.1 Theory WPE = 559 using liquid resin WPE of 204. 
.sup.2 Based on commercial sample, the anion believed to be of the 
phosphate family. 
.sup.3 Estimated. 
It was of great interest to learn how much active catalyst remained in 
these aged systems, so .sup.31 P NMR tests were run on them with the 
following results: the 21-day old ETPPP had no detectable amount of the 
ethyl triphenyl phosphonium cation left but showed the presence of 
ethyldiphenyl phosphine oxide and triphenylphosphine oxide in about a 2/1 
ratio; the 21-day old MBTPPB still had about 90% of the active catalyst 
with about 10% present as probably triphenylphosphine oxide. This 
indicates that the MBTPPB catalyst to be an extremely thermally stable 
catalyst. 
ILLUSTRATIVE EXAMPLE 3 
In illustrative Example 3 the effect of water on catalyst deactivation is 
noted. 
It is quite evident from the data on the percent conversion that water 
increases the rate of inactivation of the ETPP.sup.+, 0.5%w added water 
lowering the percent conversion to the mid nineties for ETPPP and ETPPI. 
Note, however, that the same percent conversion was achieved with 
MBTPP.sup.++ with or without added water. From the .sup.31 P NMR data, 
however, it is clear that for MBTPP.sup.++ water does increase the rate of 
inactivation, there being about 80% active catalyst remaining without 
added water and 60% with added water. However, note below that essentially 
no active ETPP.sup.+ remains in ETPPI even when no water is added. Thus, 
MBTPPB.sup.++ 's inactivation by water is very much slower than that for 
ETPP.sup.+. The results are shown in Table 3. 
TABLE 3 
______________________________________ 
INFLUENCE OF WATER ON FUSION CATALYSTS 
Reaction Conditions: Catalyst at 0.16 meq/100 g, steep temperature 
profile to 380.degree. F., hold at 380.degree. F. for 1 hour. 
Cat. Used 
MBTPPB ETPPP.sup.1 
ETPPI 
______________________________________ 
Added 0.sup.2 0.sup.2 
0.48 0.49 0.49 0.sup.2 
H.sub.2 O, % w 
Theory WPE 
1773 1795 1767 2020 1779 1522 
Fd. WPE 2002 2036 2057 1609 1544 1586 
Conversion 
102.2 102.2 102.7 
95.5 97.1 101 
of epoxide, 
% of Theory 
Active Cat. 
.about.80 
-- .about.60 
0 0 0 
Remaining, %.sup.3 
______________________________________ 
.sup.1 Based on commercial sample, the anion believed to be of the 
phosphate family. 
.sup.2 "As is" water content is between about 0.03% w and 0.07% w. 
.sup.3 Estimated from .sup.31 P NMR. 
ILLUSTRATIVE EXAMPLE 4 
Users of precatalyzed epoxy resins based on ETPPI, who make their own 
fusion resin and esterify the resin with acids to make surface coatings 
must add an esterification catalyst since the phosphonium catalyst is 
"dead" after the initial fusion reaction; with no added catalyst, the 
esterification cook reaches quite high viscosities or even gels before a 
satisfactorily low acid number is reached. Sodium carbonate can be used 
for this purpose at a level of about 0.6 meq of alkalinity/100 g of total 
charge. Since the catalyst of the present invention is not wholly 
inactivated, an ester cook (D-4) with a fusion resin catalyzed with MBTPPB 
was run following the recommendations for typical fusion products but 
omitting the added Na.sub.2 CO.sub.3. As a control a fusion resin 
catalyzed with ETPPI but without carbonate addition was used. The results 
are presented in Table 4 along with typical results for ETPPI-catalyzed 
resins with addition of Na.sub.2 CO.sub.3. Note that ETPPI-catalyzed 
resins without added carbonate ultimately gave a gel at a fairly high acid 
number. 
It is of significant practical interest to note that for the above fusion 
resin made at 350.degree. F. none of the MBTPP.sup.++ was converted into a 
phosphine oxide; in contrast, at 380.degree. F. it was found that about 
20% converted into inactive oxide. 
TABLE 4 
______________________________________ 
RESIN ESTER D-4.sup.1 COOKS WITH 
PRECATALYZED RESINS 
Fusion Catalyst 
MBTPPB ETPPI ETPPI.sup.2 
______________________________________ 
Conc., Meq/100 g 
.about.0.18.sup.3 
0.17 0.17 
Ester. Catalyst Added 
None None Na.sub.2 CO.sub.3 
Ester, Catalyst 
Conc., Meq/100 g 
.about.0.10.sup.4 
0.0 .about.0.6 
Fusion Conditions: 
After exotherm cool to 350.degree. F. 
and hold 1 hour. 
Ester Conditions: 
After adding acid, raise temperature quickly 
to 500.degree. F. removing H.sub.2 O by azeotroping 
with xylene and hold at 500.degree. F. for 4 hours 
after acid addition. 
Theoretical WPE 
865 875 .about.850 
of Fusion Resin 
______________________________________ 
Esterification Data.sup.5 
Fusion Cat. 
MBTPPB ETPPI ETPPI 
Hours After 
Acid .eta. Acid .eta. Acid .eta. 
Acid Add'n. 
No. (G-H) No. (G-H) No. (G-H) 
______________________________________ 
1 18.9 -- 30.7 T+ -- -- 
2 9.2 Q 10.9 U- 4.8 R- 
3 4.8 T+ 6.9 Z-4 2.5 T 
4 2.6 U+ Gel 1.3 T-U 
______________________________________ 
.sup.1 D-4 means that 40% of the total esterificable functionality of the 
resin has been converted by dehydrated castor fatty acid. 
.sup.2 Values in this column are for a typical cook with commercial 
products. 
.sup.3 .sup.31 P NMR showed presence only of MBTPP.sup.++, no oxides for 
this 350.degree. F. fusion reaction. 
.sup.4 This is the concentration of the leftover fusion catalyst after th 
fatty acid had been charged to the reaction. 
.sup.5 Acid number on 100% solids; GardnerHoldt viscosity on 50% w solids 
in xylene, 25.degree. C.