Patented Apr.

22, 1952 - 2,593,787

UNITED STATES PATENT OFFICE 2,593,787

STABILIZATION OF POLYMERIZABLE UN
SATURATED DICARBOXYLEC ACID POLY
ESTERS AND MIXTURES THEREOF WITH
VINYLIC MONOMERs
Earl E. Parker, Milwaukee, Wisassignor to Pitts
burgh Plate Glass Company, Allegheny County,
Pa., a corporation of Pennsylvania
No Drawing. Application March:30, 1951,
Serial No. 218,534
- 265 Claims. (C.260-45:4)
1. 2 s
The present invention relates to stabilization which the carboxylic groups are linked to loe
of polymerizable unsaturated alkyd resins, es or both of the ethylenic carbonatoms, were ca
pecially materials which are polymerizable by pable of polymerization by addition reac
addition reaction of double bonds in a structure
of the partial formula,
tween the ethylenic groups of a
----0
involving carbon-oxygen conjugation...and it has
particular relation: to such materials when:they
include:a: compound involving a chain like poly
ester structure Such as is obtained by condensing
an a Siethylenica B dicarboxylic acid with a di closed in the foregoing.patents, with ethyleni
hydric alcohol, cally unsaturated monomiers and copolymerize
One object of the invention is: to provides'a. the two by heating the mixture in the presence
polymerizable material of the foregoing type 5 of asperoxide catalyst. This reaction has bee
which is stabilized against- premature gelation extensively elaborated upon in patents an
during relatively prolonged periods of storage. lications. Typical examples of publ
...A Second object, is to provides amaterial which to be foundin Industrial and Enginee
is stable during extended periods of storage but istry, December 1939, page 1512.
which can readily be cured to...a resinous state 20 1940, page 64.
The foregoing polymerizable compositions
under appropriate conditions.
A third object is to provide a stabilized com undergo addition reaction, that is reaction at
position of the foregoing, type which is highly the points of carbon-carbon unsaturation, even
resistant to gelation in the absence of peroxide 25 in the absence of polymerization catalyst
catalysts of polymerization but which resinifies room temperature or thereabouts.
quickly at relatively low temperattres. Whenia, pecially true in the case of copolymerizal
catalystis added. tures of the polyesters and the ethylenical
A fourth object is to provide a copolymerizable vinylically unsaturated monomers. Ölyester
mixture of an ethylenically unsaturated mon
Omer and a polyester of a dihydric alcohol and propylene glycolor diethylene glycol,in the pres--
30
a dicarboxylic acid at least a part of which is ence of a vinylic monomer such as styrene, unless
a B ethylenic, a g dicarboxylic, which mixture is inhibited, will begin to gelalmost at once. This
stable against gelation under conditions of stor is true-leven in the absence of polymerization
age and readily curable to a resinous state under catalysts and at room temperatur
appropriate conditions. 35 may be desirable to obtain.co.
A fifth object is to provide-a-copolymerizable mixture-inia reasonable time.
mixture of the foregoing type which cures rapidly polymerization will quickly pr
and smoothly without excessive rise of tempera uncatalyzed mixtures, as to prevent orgat.
tre. i interfere with normal casting or la
A sixth object is to provide such copolymer 40 operations.
This, strong tendency, of the copolymerizable
izable mixtures which will cure readily to pro
vide 'relatively large castings which are sound mixtures to set prematurely, was early-recognize
and of good color. m (see Ellis. Patent 2,255,313). In the pate
These and other objects will be apparent from proposed to improve this property by incorpora 48

consideration of the following specification and 45 tion a cellulose as a filler. This, of course, greatly.
the appended claims. restricts the field-of-application of the mixtures.
It has heretofore been recognized that linear It has further been proposed to improve the
polyesters of dihydric-alcohols and dicarboxylic storage characteristics. of the copolymerizable
acids, at least a portion of which were a B mixtures by adding small, amounts of stabilizers
ethylenically unsaturated, dicarboxylic acids in 50 such as phenolic compounds, e.g. hydroquinone
 2,593,787
4.
U. S. Patent 2,409,633 contains such suggestion. Table B
However, for many applications, the phenolic Ethylene glycol
compounds were poor inhibitors of gelation. . Diethylene glycol
They often continued to inhibit the polymeriza Triethylene glycol
tion even when the catalyst was added and the . . Polyethylene glycol
mixture was heated. Therefore, they unduly . 1,3 dipropanediol
slowed up the reaction and necessitated unduly 12 propylene glycol
high curing temperatures. This was objection . Dipropideneglycol or di-1,3 propanediol
able in making castings. The inhibitors also : Butylene glycol. va- -- -
tended to discolor the resins, a feature highly
objectionable in the casting art. Castings of Sub
O
Halogen substituted glycols, e.g., mono-chlor de
stantial size also tended strongly to crack or rivatives are contemplated.
breakin the curing operations. THE SATURATED DICARBOXYLIC ACIDs
The present invention is designed to provide a
resinifiable composition that comprises an unsat It is to be understood that the invention con
templates the presence of a non-ethylenic di
urated alkyd polyester, a component of which is . carboxylic acid component along with the ethylen
an a 3 ethylenically unsaturated dicarboxylic ically unsaturated dicarboxylic acid in the poly
acid (or a mixture of such polyester and a vinylic ester composition. Indeed, in most instances the
monomer), which is highly stable in storage, but mixed polyesters are preferred.
which will cure readily without substantial dis Examples of appropriate Saturated dicarboxylic
coloration or cracking. acids are tabulated as follows:
The invention is based upon the discovery that
salts of quaternary ammonium hydroxides are Table C
outstandingly successful as gelation inhibitors . Phthalic acid
during storage of the foregoing polyesters or Tetrachlorophthalic acid
mixtures of such polyesters. . Succinic acid
THE POLYMERIZABLE MIXTURES Adipic acid
. Suberic acid
: The polymerizable mixtures to be stabilized un . Azelaic acid
der... the provisions of the present invention are. 30 Sebacic acid
now conventional in the art. The foregoing pat , Dimethyl succinic acid
ents and articles in Industrial and Engineering . Chlorinated derivatives of the above acids
Chemistry are illustrative of the fact. These prior For purposes of the present invention, the aro
art references are herewith incorporated as a part matic nuclei of Such acids as phthalic are re
of this disclosure. The mixtures should contain garded as saturated since the double bonds do
but little or no water. not react by addition as do ethylenic groups. The:
THE"ETEIYLENICALLY UNSATURATED DICARBOXYLIC term "acid' also contemplates the anhydrides of
is . . . .. . . . . ACID the acids. Mixtures of any two of the acids 1 to 9
It is apparent that an appropriate a Bethylenic 4) areNaturally
contemplated.
some of the members of Tables A, B
dibasic acid for use in the preparation of an and C are preferable to others. For example,
ethylenically unsaturated polyester may comprise Some of them may presently be unduly expensive,
a large class. Some of them in which the carboxyl but since this condition is often
groups thereof are linked to one or both of the they are properly to be included.Subject to change,
carbon atoms of the ethylenic group designated.
as component A are tabulated as follows: DRYING OIL ACID CoMPONENT
... : . . . . . . . . . Table A It may also be desirable to include a small
1. Maleic acid .. amount of a drying oil acid in the polyester.
2. Funnaric acid . Such acids impart air drying characteristics to
3. Aconitic acid 50 the polyester, or the mixture of the polyester and
4.-Miesaconic acid - the vinylic monomer. Appropriate drying oil
5. Citraconic acid : acids termed acid D include those of the following
6.Ethyl maleic acid table: .
7. Pyrocinchoninic acid : Table D
8.Xeronic acid 55. Linolenic acid
9:Itaconic acid . Linoleic acid
Carbic acid (endomethylene A 4 tetrahydro . ElaeoStearic acid
phthalic acid of my prior application Serial No. . Clupanodonic
Octadecatrienoic
acidacid
598,639, filed June 9, 1945, now abandoned, of
which this application is a continuation-in-part), 9. Mixtures of these acids are contemplated.
although not strictly a Bethylenic is also contem
plated. The chlorine substituted derivatives of PREPARATION OF THE POLYESTER
themplated."
acids, e.g., chloromaleic acid, are also con In the preparation of the polyesters, the dihy
dric alcohols of Table B which preferably con
The anhydrides of these acids, where the an tain no. more than 10 carbon atoms are usually
hydrides exist, are, of course, embraced under the employed in approximate molar-equivalency or
term "acid; since the reaction products or poly slightly in excess of such equivalency of the sum
esters are the same. Often it is preferable to of the acids of Tables A, C and D. Usually, this
operate with the anhydride rather than the free excess Will not much exceed 10 or 20% and it may
acid. . . . . . . . . . . be lower. The excess glycol facilitates reduction,
THE DIHYDRIC ALCOHOLS - of the acid number of the polyester.
The dihydric alcohols termed component (B) of The a Bethylenically unsaturated dicarboxylic
acid may constitute the whole of the acid com.
the polyester. embrace such compounds as are in ponent of the polyester, but usually it is pre
cluded in the following table: ..., s.
 2,593,787.
6
ferred to include at least some of One or more
of the non-ethylenic acids from Table C. The
THE QUATERNARY AMMONIUM SATs.
amount of acid or acids from the latter table is The quaternary ammonium salts have been
extensively developed as a chemical class. There
capable of variation over a broad range. The are many such compounds available. However,
minimum is, of course, none at all, and the maxi 5 all herein contemplated will comprise the foll
mum may be 0 or 2 mols per mole of the acid lowing basic structure:
from Table A. Naturally, as the percentage of
the acid from Table C is reduced, the polyester .R.R
assumes more and more closely the character of
the polyester containing only acid or acids from 10
N-X
ri?k,
Table A. It is impossible to state an absolute where Ri, R2, R3, and R4 are organic radicals
minimum to the effective amount of acid from
Table C. Amounts at least as low as % mol and X is an acid radical. The salts may be con
per mol of the first mentioned acids are sug sidered as the reaction products of a quaternary
gested. ammonium hydroxide of the formula:
A component from Table D is also optional, R. R.
dependent upon whether an air drying poly
ester is desired. A range of one:mole of acid R?k,
D to 2 to 12 mols of acids A or A and C is sug
gested. and an acid of the formula H-X, where X is
Appropriate ranges of the several components the negative radical of the acid.
of the polyester may be tabulated as follows: In the formulae the organic groups R1,R2.
R3, R4 may be of a single kind or they may be
Component (A)--a 6 ethylenic a 3 dicarboxylic mixed. All of then may be hydrocarbon such
acid-2 to 12 mols as alkyl, alkenyl or alkynyl, e. g. ethyl, methyl,
Component (C).--Non-ethylenically unsaturated propyl, isopropyl, n-butyl, Secondary butyl, tertie
dicarboxylic optional, but if present-26 to 144 arylbutyl, vinyl, methallyl, or they may be oleyl.
miols or Stearyl. All or a part may be aryl, e.g. phenyl,
Component (D)-Drying oil acid, optional but if benzyl. It is further to be recognized that in
present-1 mol per 2 to 12 mols A-C 30 Some instances, a group Such as R4 may bean
Component (B). Dihydric alcohol-Equivalent organic acid residue, Such as one of the formula
to or in slight excess of A-C-D w-C-R
CoNDITIONS OF REACTION IN PREPARING POTYESTER y
In conducting the esterification of the dihydric 35 Where R is hydrocarbon of 1 to 18 carbon atoms
alcohol and the acid or acids, conventional prin and may be alkyl, aralkyl or aryl, e. g., lauryl,
ciples are adhered to. Acid catalysts may be oleyl, phenyl, benzyl or the like.
added. The reaction may be conducted under Some of the possibilities for the Severals groupS
an atmosphere of carbon dioxide or nitrogen gas. R1, R2, R3, R4 are tabulated as follows:
Xylene or other non-reactive solvent may be in 40 Table E.
cluded and the reaction may be conducted by
heating the mixture to reaction temperature, R1 R Rs R.
e.g., to that at which water is expelled from the
system. It is continued until water ceases to 1. Methyl- Methyl.
evolve and the acid value of a sample is reason 2.
3.
Ethyl-
Propyl---
Ethyl.
Propyl. . .
ably low, e.g., 5 to 50. It should not be continued 4. Isopropy - Isopropyl Isopropyl.
so long as to result in infusibility of the poly 5. n-butyl------- n-butyl-------n-butyl.
ester. Usually a temperature of 150 to 190 or 6. Sec. butyl----. See, butyl---- Sec.-buty.
7. Tert, butyl Tert, butyl Tert...butyl,
200° C. and a reaction time of 2 to 20 hours is 8. Amyl----- Amyl-...-- Anyl.
sufficient to effect the esterification. 9. Octy--- Octy.
50 10, Phenyl- - Phenyl.
If desired, monohydric alcohol and/or mono 1.
12.
Tolyl-.
Benzyl-.
- Toly).
Benzyl.
basic may be added to the reaction product of 13. Cetyl- Cetyl.
dibasic acid and dihydric alcohol after such reac 14. - Octadecyl----- Octadecyl----- Octadecyl.
15. Alkyl or aryl-...--Alkyl or aryl-...--Alkyl or aryl-Lauroyl.
tion is substantially complete. Thereafter the 16. Alkylor aryl-...--Alkyl or aryll. Alkylor aryl-Palmitoyl.
mixture may beheated to cause further reaction 55 7. Alkylor aryl-....Alkyl or aryl. Alkyl orary. Benzyl.
and unreacted components finally distilled off.
Usually, the unsaturated polyester is very It is to be understood that the various possible
viscous or even solid, but is soluble in the vinyli combinations of the groups 1 through 16 in the
cally unsaturated monomer, at least where several positions R1, R2, R3, R4 are contemplated:
Warned. 60 That is, the compounds may be homogeneous or
STABILIZING THE POLYESTER COMPOSITION so mixed as to include any combination of the
abOWe groupS desired.
It is usually desirable to add the salt of a In some instances, it will be apparent that two
quaternary ammonium to the polyester in the of the groups R are joined or interconnected in a
absences of monomer regardless of whether it is 65 ring structure. This is represented by the pyrid
the polyester to be stabilized or the mixture there inium salts. Salts of the formula:
of with a vinylic monomer. To this end, the
quaternary ammonium salt is conveniently added R
to the polyester while it is warm. It will then Chs /
dissolve immediately and will arrest any tendency 70. (th), N.
of the batch to gel as it cools down. An appro
priate temperature at which to make the addi Hé '" YR
tion of the salt is about 150° C. though, of course, where n is a whole number, e.g., 2 or 3 and R1,
it could be lower. It could also be higher so R2 and X are as above defined, and also belong.
long as the Salt is not decomposed. . - 75: in this class, . .. . .
 3,393,787.
7
it is further to be appreciated that a plurality
of quaternary ammonium groups may share a
common hydrocarbon radical. Such compounds
is represented by ethylene bis(pyridinium chlo
ride) and ethylene bis(trimethyl ammonium
bromide).
Ethylene, propylene, butylene and higher
alkylene or ethylenically unsaturated hydrocar
bOn groups are also contemplated in One or
more of positions R2, R1, R3, R4.
f The presence of non-functioning substituents
such as one or more chlorine or bromine atoms in
the hydrocarbon radicals is not precluded.
In the acid component of the salt, whose nega
tive radical is represented by the group X, the
latter group should be at least as Strongly nega
tive as acetic acid and should not involve heavy
radicals or groups that would reduce its negative
character or unduly impair its mobility in the
mixture. The use of excessively heavy Organic
acids to form the salts may also unduly increase
the amount of salt required to attain Stability.
Organic acids employed preferably are of , a
weight not much above 200. Salts of Weak acids,
of course, are of basic character, Owing to the
strong basicity of the quaternary ammonium hy
droxide from which the salts are derived. Bases,
usually, promote gelation rather than inhibiting
it. The salts of the strong non-oxidizing mineral
acids usually are the most satisfactory. The acid
organic substitution products such as the acid
sulfates, sulfonates and phosphonates of these
acids are also contemplated. The following are
some of the acids that may be employed to supply
the radical X:
Table F
1. Acetic
2. Succinic
Sulfuric
Phosphoric
Hydrochloric
Hydrobromic
Chloroacetic
Malonic
Hydriodic
10, Oxalic
Hydroxy acids such as:
ll. Malic acid
12, Tartaric acid
13. Tactic acid
It is desirable that the quaternary ammonium
salt-be. soluble in, or compatible with, the poly
ester or mixtures of polyester and monomer at
least in amount to attain desired Stability.
The invention contemplates the use of the
various quaternary ammonium compounds which
are presently enjoying use as germicides and sur
face tension reducing agents.
Quaternary ammonium salts of more strongly
oxidizing acids, such as nitric acid, chromic acid
and the like, are less desirable inasmuch as they
may strongly influence the gelling characteristics
of the mixture by their oxidizing effects. Sula.
furic acid or phosphoric acid are not of this type.
Hence salts of acids which have an oxidizing
power no greater than that of phosphoric or sul
furic are. Within the contemplation of this inven
tion.
The following constitute specific examples of 70
quaternary ammonium salts which are contem
plated as stabilizers or gelation inhibitors for
polymerizable polyesters or mixtures of such
polyesters and ethylenically unsaturated mono
es;
Table G
. Trimethyl benzyl ammonium acetate
Trimethyl benzyl ammonium chloride
Trimethyl benzyl ammonium bromide
Triethyl benzyl ammonium chloride
Tripropyl benzyl ammonium chloride
. Tributyl benzyl ammonium chloride
Cetyl trimethyl ammonium chloride
0. Octadecyl trimethyl ammonium chloride
Trimethyl benzyl ammonium sulfate
. Lauroyl pyridinium chloride
. Phenyl trimethyl ammonium chloride
. Tolyl trimethyl ammonium chloride
5 . Benzyl trimethyl ammonium phosphate
. Benzyl trimethyl ammonium iodide
. . Ethyl pyridinium chloride
. Phenyl trimethyl ammonium chloride
. Octyl trimethyl ammonium bromide
20 . Ethylene bis (pyridinium chloride)
. Ethylene bis (trimethyl ammonium bromide)
. Trimethyl benzyl ammonium oxalate
. Trimethyl benzyl ammonium malate
. Trimethyl benzyl ammonium tartrate
25 . Trimethyl benzyl ammonium lactate
One important group of quaternary salts
comprises those with a benzyl group and three
alkyl groups, (methyl, ethyl, propyl, butyl, amyl
or the like) directly attached to ammonium
30 nitrogen. These compounds may be represented
by the formula:
alkyl alkyl
benzy-NN
35 alkyl X
X being an acid radical of an acid as strong as
acetic acid (dissocation constant 1.75x10-5 or
Stronger.
Another important class comprises quaternary
40 annonium Salts where one hydrocarbon group
is higher alkyl and contains at least 8 and up to
18 carbon atoms; three hydrocarbon groups are
lower alkyl containing up to 6 carbon atoms
(methyl, ethyl, propyl, butyl, hexyl). The struc
ture of Such compound may be represented by
the formula:
lower alkyl lower alkyl
higher alkyl-NN
50 lower alky X
X again being an acid or negative group of an
acid at least as strong as acetic acid.
Salts of quaternary ammonium hydroxide can
be dissolved in polyesters of a B ethylenic a B di
carboxylic acids and dihydric alcohols (or their
derivatives as modified by dicarboxylic acids
and/or drying oil acids) to provide products that
can be stored for very long periods without fear
of gelation. The stabilizers are preferably added
60 to the polyester while the latter is hot.
A curing catalyst, e. g., benzoyl peroxide,
tertiary butyl hydroperoxide, cyclohexyl hydro
peroxide, acetyl peroxide, lauroyl peroxide, or
the like can be added to the stabilized mixture.
65 in appropriate amount (.01 to 5% by weight)
at any time. The mixture when heated will
cure rapidly and completely with but little in
terference from the inhibitor. -
CoPOLYMERIZABLE MIXTUREs oF PolyESTERS AND
WINYLIC MoNOMERS
The copolymerizable mixtures of the poly
esters and vinylic monomers are, of course, much.
more reactive than the polyesters per se, and
75 the stabilization of these mixtures is usually
 9. O. W
more urgent, than that of the polyester. Such they should be sufficiently warm to mix with
copolymerizable mixture may comprise any of and dissolve in the monomeric or vinylically un
the polyesters which have already been described saturated compound. The quaternary ammo
and these may be incorporated with a suitable nium salts as herein disclosed, stabilize the co
vinylically unsaturated monomer such as those polymerizable mixtures while the ethylenically
referred to in the foregoing patents. unsaturated or vinylically unsaturated compound
THE WINY LIC. AIONOMERS is incorporated therein. When the mixture is
cooled down to room temperature, it will remain
The monomers comprise any of the common stable for a considerable period. To cure the
vinylic compounds capable of cross linking un O mixture, catalyst is added and the mixture is
Saturated polyester molecules at their points of raised to curing temperature. The salts do not
unsaturation. Usually they contain the reactive substantially interfere with the desired cure.
group H2C=C3. The ethylenically unsaturated The mixtures usually are free of water or nearly
polyesters and the vinylically unsaturated com SO
pounds are mutually soluble. The monomeric 15 The resultant mixtures are stable in storage
compound is also normally a liquid, polymeriz for long periods of time, in some cases for a
able compound. Some of the monomers are period of at least three years, which is often
tabulated as follows: better stability even than is required.
Table H However, when the mixtures are to be cured,
1. Styrene 20 they can easily be incorporated with a peroxide
2. a methyl styrene catalyst such as benzoyl peroxide or tertiary
3. p-methyl styrene butyl hydroperoxide or others in conventional
4. Divinyl benzene amounts, e.g., .1 to 5%, and cured. The ten
5. Indiene perature of cure can be moderate, e.g., below
. Unsaturated esters such as: 25 100° C., but may be much lower, e.g., room tens
6. Winyl acetate perature (22° C.) or thereabouts. The resins
7. Methyl methacrylate may be further hardened by baking them at
8 Methyl acrylate 125 to 150° C. or thereabouts. Higher tempera
9 Allyl acetate tures of initial curing and baking are permissible.
10. Diallyl phthalate 30 However, they should not be so high as to volatil
1. Diallyl succinate ize the monomer (in initial cure) or to char or
2. Dialyl adipate discolor the final product. The time of curing
13. Dially Sebacate and baking, of course, will vary greatly depending
14. EDiethylene glycol bis (ally carbonate) upon such factors as the size and thickness of
15. Triallyl phosphate 35 the body to be formed and the temperature of
6. Winyl chloride reaction. Usually 5 minutes to 2 hours are sufs
Any one of these vinylic monomers may be
ficient. However, it is easy to determine by
hardness tests when the articles are cured to
combined with any of the polyesters prepared hard, clear State.
from components A and B, A, B and C, A, B and 40 It is an important feature of the use of the
D or A, B, C and D as previously described. quaternary ammonium salts as inhibitors of
Mixtures of any two or more of the foregoing gelation that although they are very effective in
vinylic compounds and the polyesters are con periods of storage of the uncatalyzed mixture,
templated. the catalyzed mixtures cure very readily and
The vinylic monomer usually will comprise completely at low temperatures. Where the mix
from 10 to 60% upon a weight basis of the cos ture is employed to embed delicate objects such
polymerizable mixture, and mixtures containing as insects, biological specimens or the like, cure
20 to 40 or 50% by weight of monomer are to be can be effected without damaging them. Also, in
preferred. -
To formulate stabilized or non-gelling mixtures
making castings in molds of latex or the like,
the low curing temperature is desirable to avoid
of (I) an unsaturated polyester of a dihydric 50 damage to the molds. . . .
alcohol and an acid comprising an a 3 dicar It is also a feature of the use of the quater
boxylic, a B ethylenically unsaturated acid and nary ammonium salts that they do not discolor
(II) a vinylic monomer, it is preferred to diss the product in which they are employed. Fur
solve a quaternary ammonium salt (for example 55 thermore, castings formed from copolymeriz
one of those listed in Table G) as an inhibitor able mixtures are Souad and free of cracks. Prod
in the polyester component. This is best accom ucts in which conventional inhibitors are en
plished by adding the salt to the polyester while ployed during storage often are cracked or
the latter is hot, e. g., about 150° C. or to such broken. This is especially true in the case of
other temperature as will effect rapid and com 60 realitively massive castings. . . . . .
plete solution. This can be determined by ob It is to be understood that While the quaternary
servation, as it is easy to see when all of the ammonium salts, taken by themselves, are ex
quaternary salt has disappeared into the poly cellent gelation inhibitors for copolymerizable
ester. The quaternary ammonium salt may be mixtures of unsaturated polyesters and vinylic
added in an amount of about .01 to 2% by weight 65 monomers, other inhibitors, such as those of
of the ultimate mixture of components I and II. conventional type, such as hydroquinone, can
Ehis is essentially the same procedure as is emi also be included along with the salts. These may
ployed to stabilize the polyester without mon be employed, for example, in a proportion of
omer. approximately 1% by weight based upon the
The monomer such as one of those from Table 70 weight of the quaternary salt or such other pro
H is added in appropriate amount at 120° C. or portion as is expedient. Such additional inhibi
lower temperatures (e.g., 10 to 60% by weight of tors sometimes are helpful where the time and
the monomer-stabilized polyester mixture). . . temperature of the cure is relatively unimportant
Since the unsaturated polyesters are usually and where it is desirable to increase the so
quite viscous or even solid at room temperature, called "tanklife' of the mixture, that is to in
 2,593,787
11
crease, the period in which catalyzed mixtures
can be stored without gelation.
It is understood that such vinylic monomers
as styrene, as sold commercially, normally con
tain Small amounts of inhibitors to admit of 5
Storage and shipment thereof without gelation or
polymerization. Commercial monomers contain
ing such inhibitors, e. g., quinone or hydro
quinone, in Small amounts can be employed in
the present process. Obviously, the inhibitor in
the monomer is greatly diluted when the latter
is incorporated with a polyester under the pro
visions of the present invention. Also, in many
instances, the effectiveness of the added inhibitor
carried in the monomer has been greatly reduced
by the period of storage which the monomer
has undergone before it is admixed with the
polyester. Normally the inhibiting effect of the
stabilizer in the monomer will not be objec
tionably great. However, if so desired, the in
hibitor of commercial styrene or other monomer
can be eliminated by distillation before the mon
omer is incorporated with a polyester contain
ing a quaternary ammonium salt as an inhib
itor.
Applications of the principles of the inven
tion are illustrated by the following examples:
EXAMPLE
Trimethyl benzyl ammonium chloride, in a
proportion of .003 part by weight was incorpo
rated into 2 parts by weight of propylene mal
eate phthalate which was a polyester of approxi
mately 1 mol of maleic acid and 1 mol of phthalic
acid with 2 mols, or a slight excess thereof of
propylene glycol. The addition of the salt was
effected by adding it to the polyester while the
latter was at a temperature of about 150° C.
This mixture was quite stable over long pe
riods of time. When it is desired to effect a
cure of the mixture, a catalyst, e.g., benzoyl
peroxide, or any of the others herein enumerated,
e.g.,.1 to 5%. The mixture can be readily poly
merized by heating it in the usual manner.
Products resulting from such mixture are hard,
clear and sound.
- To the stabilized mixture a monomer such as
styrene or any of those from Table H can be
added to provide a stabilized copolymerizable
mixture. The mixture cures rapidly when a
catalyst such as tertiary butyl hydroperoxide is
added. The amount of monomer may be within
a range of 10 to 50% by weight of the total mix
ture.
EXAMPLE II
To a mixture of 2 parts by weight of propylene
maleate phthalate and a quaternary ammonium
salt, e.g., .003 part trimethylbenzyl, as above de
scribed in Table G, was added 1 part by weight
of diethylene glycol bis(allyl carbonate). This
mixture was stable for more than 18 days at
150°F. (an accelerated aging test) and for 6
months at 70° F.
EXAMPLE II
In this example, 2 parts by weight of propylene 65 equal amount by weight of diethylene glycol bis
maleate phthalate were stabilized with trimethyl
benzyl ammonium chloride as described in con
nection with Example I. This mixture consti days. It was stable at a storage temperature of
tuted a stabilized unsaturated polyester which
could be stored for long periods of time without 70
objectionable polymerization. To this mixture
could be added 1 part by weight of methyl meth
acrylate as a monomer. Such mixture is stable
for more than 40 days at 150 F. and more than 75 dinium
180 days at 70° F. Corresponding mixtures of
12
propylene maleate phthalate and methyl meth
acrylate in the absence of the gelation inhibitor
gelled in less than 1 day at 150 F. and within
30 days at 70° F.
EXAMPLE IW
In this example, 2 parts by weight of propylene
maleate phthalate containing 0.003 part by
Weight of trimethyl benzyl ammonium chloride
Were incorporated with 1 part by weight of vinyl
0. acetate. The mixture did not gel in 40 days at
150 F. or within 180 days at 70° F. The unsta
bilized mixtures gelled in 1 day at 150 F. and
within 30 days at 70° F.
EXAMPLE W
5
In this example, 2 parts by weight of diethylene
fumarate were stabilized with .003 part by weight
of trimethyl benzyl ammonium bromide in the
manner already described. This mixture was
stable and could be preserved for long periods of
20
time without gelation. It could be cured in
conventional manner. Two parts by weight of
this mixture were added to 1 part by weight of di
ethylene glycol bis (allyl carbonate). The mix
ture was stable for more than 50 days at 150° F.
25
and for more than 180 days at 70°F. A like mix
ture free of quaternary ammonium salt gelled in
1 day at 150 F. and in 30 days at 70° F.
EXAMPLE WI
30 In this example, 1 part by weight of a polyester
which was propylene maleate was stabilized with
0.002 part by Weight of triethylbenzyl ammonium
chloride. The polyester could be preserved satis
factorily and would cure in the conventional
35 manner in the presence of suitable peroxide cata
lysts. To the polyester mixture was added an
equal amount by weight of diethylene glycol
bis (allyl carbonate). This mixture Was stable
for more than 50 days at 150 F. and for more
40 than 180 days at 70 F. A. like mixture free
of added inhibitor gelled in a single day at 150. F.
and in 30 days at 70° F. r
EXAMPLE WI
In this example, 2 parts by weight of propylene
aZelate maleate could be stabilized with .001 to .01,
e.g., .003 part by weight triethyl benzyl ann
monium chloride to provide a stabilized polyester.
The stable polyester was then further incorpo
50
rated with 1 part by weight of diethylene glycol
bis (allyl carbonate) to provide a copolymerizable
mixture. This mixture was stable for more than
20 days at 150° F. and 180 days at 70° F. The
corresponding mixture without the inhibitor
55 gelled in 1 day at 150° F. and in 30 days at 70° F.
EXAMPLE WII
To 1 part by weight of propylene maleate
phthalate was added .001 to .01 part of phenyl
trimethyl ammonium chloride thereby providing
60 a stabilized propylene maleate phthalate poly
ester. This mixture was, Suitable for use as a
polymerizing type of alkyd resin. When a per
oxide catalyst was added, it would cure by addi
tion reaction. To the mixture Was added an
(allyl carbonate). The mixture successfully with
stood an accelerated gelling test at 150 F. for 20
77 F. for 120 days.
EXAMPLE IX
To 2 parts by weight of diethylene fumarate
adipate was added .0015 to .015 part lauroyl pyri
chloride to provide a stabilized polyester
mixture and to the mixture was then added 1
 2,593,78?
13
part by weight of diethylene glycol his callyl
carbonate) to form a mixture that was stable for
20 days at 150° E. and for 120 days at 77 F.
EXAMPLE X
To a mixture of .003 part by Weight of any one
of the quaternary ammonium salts from Table G,
e. g., trimethyl benzyl ammonium bromide in
2. parts by weight of diethylene fumarate Was
added 1 part by weight of diallylphthalate. Such
mixture was stable for more than 50 days at 150
F, and 180 days at 70° F.
EXAMPLE X
To a mixture of 1 part propylene maleate add
.002 part by weight of any one of the quaternary
ammonium salts from Table G, e. g., triethyl
benzyl ammonium chloride, and to the resultant
mixture add 1 part by weight diallyl phthalate.
The resultant mixture will withstand an accel
erated gelling test at 150° F. for 50 days and will
withstand storage at 70° F. for 180 days.
EXAAPLE X
In this example, 2 parts by weight of diethylene
fumarate phthalate may be stabilized by means
of .015 part trimethyl benzyl ammonium acetate
and to the stabilized polyester may be added 1
part by weight of diallyl phthalate to provide a
copolymerizable mixture stable for 10 days at
159° E. or 20 days at 70° F. When it is desired
to cure the mixture, a peroxide type catalyst may
be added in appropriate amount, e. g., .1 to 5%,
and the mixture cured in conventional manner.
EXAMPLE XI
In this example, propylene azelate maleate in
a proportion of 2 parts by weight may be en
ployed. Octadecyltrimethyl ammonium chloride
in an amount of .001 to .1, e. g., 0.01 part, parts
by weight may be incorporated as a stabilizer.
One part by weight of diallyl phthalate may be
added as a vinylic monomer. This mixture is
stable for 40 days at 150 F. and will withstand
storage for 180 days at 77 F.
EXAMPLE XIW
Propylene adipate fumarate in a proportion of
2 parts by weight was stabilized with .001 to .01,
e.g., 0.003, part by weight octyltrimethylam
monium bromide and 1 part by weight diallyl
phthalate was added as a monomer. The result
ant mixture was stable for 30 days at 150 F. and
180 days at 70°F.
EXAMPLE XV
Propylene maleate phthalate in a proportion of
part by weight was stabilized with .001 to .01,
e.g., 0.003, part by weight of benzyl trimethyl
ammonium sulfate and to the Stabilized polyester
was added 1 part by weight of diallyl phthalate
to. form a copolymerizable mixture which Would
withstand an accelerated gelling test of 150 F.
for 15 days and storage at 70 F. for 150 days.
EXAMPLE XWI
Add to 2 parts by weight of diethylene fumarate
0.003 part by weight of any one of the other
quaternary ammonium salts from Table G, e. g.,
trimethyl benzyl ammonium bromide. Then add
1 part by weight of vinyl acetate to the mixture.
This copolymerizable mixture will withstand the
accelerated gelling test at 150°F, for 50 days and
will withstand storage at 70° F. for 180 days.
The mixture can readily be incorporated with
catalyst of the peroxide type and successfully
cured to a hard durable resin in the usual man
e.
4.
EXAMPLE XVI
Diethylene maleate phthalate in a proportion
of 2 parts by weight was stabilized with 0.003
part by weight of triethylbenzyl ammonium chlo
5
ride and to the stabilized polyester Was added 1
part by weight of vinyl acetate to form a mixture
that will withstand the accelerated gelling test
at 150°F, for 50 days and which can be stored at
O 70 F. for 180 days.
EXAMPLE XVII
In this test, a stabilized mixture of 2 parts by
weight propylene azelate maleate, 1 part vinyl
acetate and .001 to 0.1, e.g., 0.02, part by Weight
of trimethylbenzyl ammonium acetate Was pre
pared. The mixture withstood the accelerated
gelation test at 150°F. for 10 days and withstood
storage without gelation for 120 days at 70° F.
20 The corresponding mixture without stabilizer
gelled in 1 day at 150 F. and in 25 days at 70°F.
EXAMPLE XIX
Propylene adipate fumarate in a proportion of
25 2 parts by weight was stabilized with triethyl
benzyl ammonium chloride in a proportion of .00
to .01, e. g., .006, part by weight and then Was
admixed with 1 part by weight of vinyl acetate
to provide a mixture stable for 30 days or more
at 150 F. and which could withstand storage for
more than 180 days at 70° F. The corresponding
mixture in the absence of stabilizer gelled at
150°F, within a day and within 27 days at 70° F.
EXAMPLE XX
A mixture of 2 parts by weight of diethylene
maleate phthalate and 1 part by weight of methyl
methacrylate stabilized with 0.003 part by weight
triethylbenzyl ammonium chloride was stable for
40 11 days at 150 F. and for over 90 days at 70 F.
EXAMPLE XXI
Propylene adipate fumarate in a proportion of
1 part by weight and methyl methacrylate in a
proportion of 1 part by weight was stabilized with
.001 to 0.1 part by weight of trimethylbenzyl am
nonium bromide. This mixture could be stored
under atmospheric conditions and when incor
porated with benzoyl peroxide or tertiary butyl
50 : hydroperoxide or other catalyst of polymerization
could be cured to a satisfactory resin.
EXAMPLE XXI
In this example, a similar mixture was prepared
from 2 parts by weight of diethylene maleate
phthalate, 1 part by weight of methyl methacry
late and .001 to 0,1 part trimethyl ammonium
phosphate.
60
EXAMPLE XXIII
In this example, 2 parts by Weight of propylene
maleate phthalate (equal mols of maleic acid and
phthalic acid) were stabilized. With trimethyl
benzyl ammonium paratoluene sulfonate. To this
mixture was added 1 part by weight of styrene.
With a total mixture containing .1% by weight
of the salt, a stability of 4 days at 150°F, was
obtained.
EXAMPLE XXIV
70 35 parts propylene maleate phthalate
i8 parts styrene
0.1 to 5% inhibitor
.001% quinone
75 In the polyester, maleic acid and phthalic acid
 2,598,787
15 16
were equimolar. The inhibitors and the storage pages 704-711, Carleton Ellis, copyrighted 1935,
tests are tabulated below: Reinhold Publishing Corporation. Mixtures of
the two types of catalyst, e. g., 1% of benzoyl
Per
,
Storage Life peroxide or tertiary butyl hydroperoxide, with
Inhibitor ent butyraldehyde-aniline may be employed.
Used 1500 F. 770 F. In order to promote the polymerization of a
mixture such as is disclosed in Examples I to XXV
CEce.trimethyl ammonium bro- 0.5 21 days---- inclusive, a catalyst, e. g., benzoyl peroxide, or
any of the others mentioned, in an amount of
Octadecyltrimethyl ammonium 0.5 30 days---- 10 .1 to 5% by weight is added and the mixture is
chloride.
Biltrimethyl ammonium chlo- 0.1 - 20-40 days lyr. heated up to an appropriate temperature, for
Ole.
Benzyltrimethyl ammonium bro- 0. 8 days----- 6 months. example, to about 93° C. Lower temperatures,
Incle, say 75 C., may also be employed. By heating
Benzyltrimethyl ammonium sul- 0.1 3 days.---- 3 months. the mixtures at this latter temperature for a
fate.
Binyltrimethyl annonium ace- 0.13 days..... 45 days. period of about an hour, it can be polymerized
tate.
Lauroyl pyridinium chloride---- 0.133 days.--. to the setting stage. Subsequently, it can be
Phenyl trimethyl ammonium 0.1 20 days rendered harder and more durable by baking at
chloride. a temperature of about 125 to 150° C. Of course,
Benzyl trimethyl animonium. 0.1 20 days higher temperatures of baking can be employed
chloride.
Ethylene
Ce).
bis (pyrodinium chlo- 0, 1 - 14 days 20 provided they are not so high as to chair or dis
Ethylene bis (trimethyl ammo- 0. 10 days---- Color the product. The products normally will
nium bromide).
Control----------------------------------- 1 hour----- i day. be clear and strong. The polymerizable mixtures
may be cast and cured in suitable molds with or
In Examples I through IV, VII, VIII and IX, without pressure.
XII, XIII, XIV, XV and XVII through XXIII, Fillers such as cellulose fibers, asbestos and
the ethylenically unsaturated and the saturated glass fibers can be added to the stabilized poly
dicarboxylic acids are in approximately equal merizable mixtures in amounts, for example, up
molar ratios. This ratio can be varied in the to 300% or more based upon the polymerizable
lmanner heretofore described.
liquids. Fabrics of glass fibers can also be im
pregnated or coated With the polymerizable mix
A trace of quinone, e. g., about 1% based on tures. Mixtures of fibrous material and resin
the tertiary amine or quaternary ammonium constituents can be heated under pressure to
salt content of the mixture can be added, further form hard, strong bodies of appropriate form.
to stabilize the mixtures in the preceding exam Plasticizers Such as dimethyl phthalate can
ples but in most cases stability is adequate with also be added to the polymerizable mixtures in
Out it. amounts, for example, of 5 to 40% based upon
From the foregoing examples it will be apparent polymerizable constituents. .
that polymerizable dihydric alcohol esters of The polymerizable mixtures can be applied as
alpha-beta, unsaturated, alpha-beta, dicarboxylic coatings to. metal, Wood, paper, cotton or other
acids, or copolymerizable mixtures thereof with 4) cloth and cured in situ to form protective films.
monomeric olefinic compounds capable of effect EXAMPLE XXV
ing cross-linkage of the polyester nuclei can
readily be stabilized with salts of quaternary This example is for purposes of comparing.
ammonium compounds to provide mixtures that quaternary ammonium salts as inhibitors of gela
can be stored without gelling for long periods of tion in polyesters of alpha-beta ethylenic alpha
time. 45 beta dicarboxylic acids and glycols or mixtures
It is to be appreciated that in order to effect Of Such polyesters and monomers with other
a rapid cure of the mixtures of polyester and common types of inhibitors. In the tests, a poly
the olefinically unsaturated monomer, a catalyst ester which was the condensation product of
of the addition reaction involved in copolymeriza 2.2 mols of 1,2 propylene glycol, 1 mol of maleic
tion is usually desirable. However, in Some in 50 anhydride and 1 mol of phthalic anhydride was
stances, e. g., where high curing temperatures prepared, and was then divided into 4 equal
or long curing times are permissible, or ultra Samples of 200 grams each. To sample I was
violet irradiation is available, catalysts may be added .1 part by weight of trimethylbenzyl am
Omitted. . monium chloride.
Appropriate catalysts include peroxides such 55 Samples II was stabilized with .1% by weight
aS Of parabenzyl amino phenol.
Benzoyl peroxide Sample III was stabilized with .1% by weight
Tertiary butyl hydroperoxide of di-beta naphthyl paraphenyl di-amine.
Cyclohexyl hydroperoxide Sample IV was stabilized with .0168% by weight
60 of hydroquinone.
Acetyl peroxide To each of the four samples was added 100
Lauroyl peroxide grams Of Styrene.
- These are merely typical, others are available. To the foregoing samples was added 5% by
The catalysts will usually be employed within Weight of tertiary butyl hydroperoxide which is
a range of .01 to 5%, e. g., 1% of the mixture. 65 the catalyst most commonly used in casting mix
Preferably the catalyst is added shortly before tures of the foregoing type. The samples were
the mixture is to be polymerized. then placed in pint jars of common Mason type
Other types of catalysts such as thioglycollic So that the depth of the copolymerizable mixture
acid or catalysts such as are employed as accel in all jars was about equal and greater than 1
erators of rubber vulcanization or as rubber pre 70 inch. The jars were then placed in a water bath
Servatives, obtained by condensation of amines at 100°F. for 1 hour.
and aldehydes, e. g., formaldehyde or acetalde At the end of this period, sample I containing
hyde or butyraldehyde and andline or toluidine trimethyl benzyl ammonium chloride as a sta
may be employed. Many of these are described bilizer had gelled, indicating that the stabilizer
in The Chemistry of Synthetic Resins, vol. I, 75 had but little retarding effect upon the rate of
 2,593,787
- - 17. 18
cure of the catalyzed mixture at moderate tem weight of styrene. This mixture was divided into
peratures. This stabilizer would be very desir the requisite number of Samples for the several
able in mixtures employed in forming castings tests.
where low temperatures of cure were required. The accelerated aging test hereinafter desig
None of the other samples had gelled. This was 5 nated as "Test A' was conducted by incorporat
an indication that the inhibitors in these sam ing the gelation inhibitor to the uncatalyzed co
ples had materially retarded the rate of cure of polymerizable mixture and subjecting the sta
the mixture at 100°F. bilized mixture to a temperature of 150°F. until
The water bath was then gradually warmed gelation occurred. . -
over a period of 1 hour to a temperature of 190° F. 10 The low temperature test, “Test 3' Was con
at which value it was held for a further period of ducted at slightly above normal room temperature
15 minutes. At the conclusion of this period, it with benzoyl peroxide as a catalyst. The latter
was found that all Samples had resinified and was added to the stabilized mixtures and the mix
the products were of the following character tures were stored at 77 F.
istics: 15 Further to determine the retarding effect of the
Saraple I which was stabilized with trimethyl inhibitors upon the copolymerizable mixtures af
benzyl ammonium chloride was a hard, sound ter the addition of catalyst, tertiary butyl hydro
casting which was clear, colorless and free of peroxide was added to samples stabilized with .1%
Cracks. by weight of the several inhibitors in a propor
Sample II which had been stabilized with .1% 20 tion of .1% by weight and the stabilized mixture
by weight of parabenzyl amino phenol resulted was then stored at 77 F. until gelation occurred.
in a product which was brown in color and severe This test is hereinafter designated as “C.'
ly fractured. s - A similar test was conducted upon certain of
Sample III which was from the mixture sta the stabilized mixtures including the various
bilized with di-beta, naphthy paraphenyl di- 2 gelation inhibitors with .5% of tertiary, butyl
amine Was black in color and was severely frac hydroperoxide as a catalyst. This test, is herein
tured. after designated as “D.'
Sample IV which had been stabilized with Finally, to determine the retarding effect of
hydroquinone formed a resin which was of a the gelation inhibitors upon the catalyzed mix
yellow color and was severely fractured. This 30 tures at normal curing temperatures, a series of
test demonstrated the fact that the quaternary samples was prepared containing 1.5% by weight
ammonium compound was of Outstanding merit of benzoyl peroxide as catalyst and, of course,
in the protection of mixtures employed as casting containing gelation inhibitors. Test tubes, 16
resins, especially those to be cast at low or mod millimeters in diameter containing the mixture
erate temperatures and in the absence of sub to a depth of 3 inches were placed in a water
stantial pressures because the stabilized mixtures bath at a temperature of 180° F. The tempera
could be cured so readily to provide. Such satis tures of the mixtures during the curing opera
factory products. tion were determined by means of conventional
EXAMPLE XXVI 40
thermocouples and the time in minutes required
in this example, a series of tests were conducted for the temperatures of the samples to rise from
to determine the stabilizing effect of a number of 150 F. to the maximum, which was termed the
different quaternary ammonium salts in the ab peak exotherm, was observed and is hereinafter
sence of catalysts at an elevated temperature and recorded in the test designated as 'E.' This
further to test the curing rate of these samples test constitutes a good indication of the rate at
after the catalyst had been added. For purposes which the catalyzed mixtures will cure when
of comparison, similar tests Were conducted upon heated.
samples stabilized with certain conventional-in The results of these several tests are recorded
hibitors of gelation. In the example, a polyester as follows:

Test B-. Test, C., Test.D. - Test E

No. The Inhibitor Compound
SEE.
O'Cata' Beniy E.E.E.E.
lyst 150°F. pered oxide, oxide,
E.
r- nydroper-' peroxide
bath,
Tine
days
in is
770 F.
17 F.
Time in
77°F.
Time in
180° F.
Tineia
. hours hours minutes

-------- .1%Lauroyl pyridiniuin chloride. 8 1-5 4% 2 3:2

2.------- .1% Styltrimethyl
C8
annonium bro- 8 4-8 4. 2 -
3.
8-------- .1% Phenyltrinethyl ammonium. 8 17 4. 2 2.9
chloride.
4--------
w
1%,Egethyl
chloride.
benzyl ammonium . .
8 11-15 4. 1.5 3.5
5--------.1% Trimethylbenzyl ammonium. 9 ------------ 7 2 ------------
chloride - quinone (0.0012).
6-------- 5%. Trimethyl benzyl ammonium .
hydroxide. -
1.5 ------------------------
7.------- .1% Hydroquinoneill-------------.. - 8 92 216
8--. .1%. 4-tertiary butyl catechol- 8 92 216
9. ..1% Catechol.--- 8 192 216
10 -.1% Ascorbic acid.
11------- .1%. Alpha naphthol-----------------
12------- .1%. Tertiary butyl catechol -- n
butylamine. ----
8.------ .1%Dig-naphthyl p-phenylene di.
annine. v. v

which was prepared from 2.2 moles of 1,2 propyl In the tests, the inhibitors 1 to 5 were quater
ene glycol, 1 mole of maleic anhydride-and-1 mole nary ammonium salts of the type contemplated
phthalic anhydride was employed. To 2-parts. herein. The remaining compounds represented
by weight of this polyester was added 1-part by 75 inhibitors, or presumed inhibitors selected from

19
the prior art. Compounds 1 to 5 gave mixtures
which were well stabilized for storage, and would
withstand an accelerated gelation test at 150 F.
for 8 or 9 days. They would gel quickly, even
at low temperatures, when the catalysts were
added. When the catalysts of polymerization
were added and the mixtures were heated to the
normal curing range, the cure proceeded very
rapidly and the peak of the exotherm was at
tained in 3 or 4 minutes.
. In contradistinction with compounds 6 to 13,
some did not substantially retard gelation of the
mixtures even before the catalyst was added.
Some, Such as the phenolic compounds, did sta
bilize the uncatalyzed mixtures, but they also 15 phthalic anhydride and maleic anhydride in the
greatly interfered with subsequent cure of the proportion of 2.2 moles of glycol, one mole of
Catalyzed mixtures. In most cases several days
were required to attain gelation at normal room
temperature and the catalyzed mixtures even
when heated did not reach the peak of their exo-.
thermal rise even in many minutes.
EXAMPLE XXVII
In this example, a resin-like polyester or alkyd
body resulting from conventional esterification
of 1.2 propylene glycol in a ratio 2.2 moles, maleic 25
anhydride mole, and 1 mole of phthalic an
hydride was prepared. The polyester was cooked
until it was solid or nearly solid but was still
fusible. Any of the other unsaturated polyesters 30 iDi-(trimethyl
or alkyds herein disclosed could be employed in
this example. To this mixture was added .01
to 2%, e. g., .1%, by Weight of trialkyl benzyl
ammonium oxalate, e.g., triethyl or preferably
trimethyl benzyl oxalate. The mixture. Was
warmed until the oxalate salt dissolved. Solu-. . Distartarate.
tion took place below 150° C.
A liquid soluble monomer, namely styrene, was Trimethyllate.
added to the stabilized polyester in a proportion
of 2 parts by weight of. polyester per 1 part by
weight of monomer. The temperature was se 40 be From
lected to attain reasonable fluidity of the poly
ester, thus facilitating addition of the monomer. ammonium
Usually Such addition can be effected at about
120° C. However, if the polyester is inherently
soft or fluid, this temperature may beit reduced.
If a harder polyester is employed, may be
desirable to increase the temperature.
The polyester and the quaternary ammonium
oxalate readily dissolved in each other. Like
wise, the polyester and the vinylic compound,
namely styrene, could readily be admixed in the
presence of the salt without danger of premature
gelling.
The stabilized mixture could be stored for long
periods at room temperature without gelling.
The stabilized mixture withstood an accelerated
gelation test in the absence of catalyst and at
150 F. for 4 days before gelation occurred.
An outstanding characteristic of mixtures sta
bilized With quaternary ammonium oxalate is
unusual "tank life' (resistance to gelation after
the catalyst is added) coupled with remarkable
ease of curing at the normal curing temperature
of the catalyzed mixture. This combination of
characteristics is demonstrated by the following
tests:
EXAMPLE XXVIII
To a set of samples of the copolymerizable mix
ture of the polyester and styrene of Example
XXVII stabilized with .1% by weight of trimethyl
benzyl ammonium oxalate was added 1.5% by
weight of benzoyl peroxide. These samples with
stood gelation at a temperature of 71 F. for a
period of 54 to 58 hours,
Samples of the same mixture similarly stabi
2,593,787
20
lized and catalyzed when subjected to an “LPE"
test in the manner already described to determine
rate of cure, reached "peak exotherm' in 2.6
minutes. This is a very rapid rate of cure. .
The samples, when gelled, can be baked at 100
or 150° C. for a period, e.g., 5 minutes to.2 hours,
in order fully to harden them. The time required
for gelling and curing, naturally, will vary, de
pendent upon the thickness or mass of the body
O formed, the hardness desired, the catalyst em
ployed, etc.
EXAMPLE XXIX
S. .. '
400 grams of propylene maleate phthalate
(prepared by heating together propylene glycol,
phthalic anhydride and one mole of maleic an
hydride, to an acid number of about 45) was
mixed with 200 grams of styrene and the amounts
20 of 0.1 percent by weight inhibitor set forth in the
table below. These mixtures were tested for
storage stability at 150° F. and for tank life at
77 F. in the presence of 1.5% benzoyl peroxide.
The results were as follows:
Inhibitor Stability
656. Tank Life
Trimethyl (benzyl ammonium) acid 25 Over 100 hours.
oxalate.
benzyl ammonium) 28 T)0,
oxalate.
Mono. (trimethyl benzyl annonium) 8 Do.
maleate.
Di (trimethyl benzyl ammonium) 5 I)0.
maleate.
Mono (trimethyl benzyl amnonium) 18 Do.
tartarate.
(trimethyl benzyl annonium) 17 T)0.
Trimethylbenzyl ammonium lactate- 8 DO
benzyl ammonium glyco- 18 ibó.
the above disclosure and examples, it will
apparent that a wide variety of quaternary
salts stabilize the contemplated poly
merizable compositions without adversely affect
ing the rate of cure. Since the Salts of weaker
45. acids are less effective than salts of strong acids,
it is found desirable to use salts of acids which
are at least as strong as acetic acid.
AS a general proposition, the Soluble Salts of
non-oxidizing acids which have dissociation con
50 stants for the first acid hydrogen of at least
1x108 are superior. Thus the halides have been
found to be especially valuable.
As shown above, the oxalate salts have been
found to be unusually effective in promoting long
55 "tank life.' That is, polymerizable compositions
containing a quaternary ammonium oxalate and
a peroxide, catalyst are stable at room tempera
ture for unusually long periods of time and in
this respect at least. are superior even to the
60 halide. Unlike many of the phenolic compounds
such as hydroquinone, the oxalic acid salts of
quaternary ammonium bases do not interfere
appreciably with the rate of cure of the catalyzed
copolymerizable mixtures when the latter are
65 heated to normal curing temperatures, e. g.,
150 F. or thereabouts.
The quaternary ammonium oxalates such as
trimethylbenzyl ammonium oxalate may be emi
ployed in polymerizable mixtures of any of the
70 liquid or fusible ethylenically unsaturated poly
esters and any of the Soluble vinylically unsatu
rated polymerizable compounds herein disclosed.
The Oxalate Salts can be substituted for all or a
. .... part, e.g., 10 to 90% of any of the other quater
75 nary ammonium salts, e.g., trimethyl or triethyl
 2,593,787
21 22
benzyl chloride, etc., in Examples Ithrough XXVI. This application is a continuation-in-part of
By thus admixing the quaternary ammonitin application Serial No. 166,068, filed June 3, 1950,
oxalates with other quaternary ammonium salts which is a continuation-in-part of my copending
Such as the halides, e.g., trimethyl benzoyl chloa application Serial No. 807, filed January 6, 1948,
ride, in the resinifiable mixtures, mixtures of which further is a continuation of my prior ap
outstanding storage stability and exceptional plication Serial No. 630,551, filed November 23,
"tank life' combined with an exceptionally good 1945, now abandoned. It is further a continua
rate of cure may be obtained. tion-in-part of my prior application Serial No.
Good “tank life' is a desirable property in 598,639, filed June 9, 1945.
certain instances where it is desired to store the O The Several embodiments of the invention here
copolymerizable mixture for several hours or a in disclosed are representative. It will be ap
day or two after the peroxide catalyst has been parent that numerous modifications may be made
added. - therein without departure from the spirit of the
Among the oxalate salts which may be used invention or the scope of the following claims.
according to this invention are those salts in I claim:
which the hydrocarbon groups are any of the 1. As a new composition of matter, a mixture
groups listed in Table E. s of (A) a liquid, polymerizable, ethylenically un
In lieu of oxalate salts, salts of other carboxylic Saturated compound, (B) a polyester of a dihy
acids in forming the quaternary ammonium salts, dric alcohol and an alpha-beta dicarboxylic, eth
particularly those having a dissociation constant 20 ylenically unsaturated acid, said ethylenically un
of at least 1x10-3 may be used. Examples of Saturated compound and said polyester being co
these are the hydroxy acids such as malic, tartaric polymerizable and (C) a small stabilizing amount
or lactic orbychloracetic
prepared reacting anacid, etc. These
appropriate salts are
quaternary of a dissolved added salt of a quaternary am
nonium hydroxide and oxalic acid.
ammonium hydroxide, e.g., trimethyl, triethyl, 2. As a new composition of matter, a copoly
tripropyl or tributylbenzyl ammonium hydroxide, merizable mixture of (A) a liquid, polymerizable,
with an acid such as maleic, tartaric or lactic (or ethylenically unsaturated compound, (B) a poly
their anhydrides). ester of a dihydric alcohol and a dicarboxylic,
Naturally the resultant salt will be of the ethylenically unsaturated acid, and (C) a small
formula: 30 stabilizing amount of a dissolved added salt of a
R. R. quaternary ammonium hydroxide and a hydroxy
NRs k s Substituted carboxylic acid which is at least as
Strong as acetic acid.
3. An unsaturated alkyd resin which is a fusi
X is acid radical as herein disclosed and N is ble, Soluble polyester of a dihydric alcohol and an
the number of carboxyls of the acid which are ethylenically unsaturated dicarboxylic acid and
neutralized. Groups R1, R2, R3, and R4 may be being stabilized with a small stabilizing amount
various radicals including those listed in Table E. of a dissolved quaternary ammonium oxalate.
Webs or sheets of fibrous materials such as 4. A fusible, soluble unsaturated alkyd resin
asbestos, cotton fibers, glass fibers, or the like can 40 which is a polyester of a dihydric alcohol and an
be dipped or otherwise treated with catalyzed ethylenically unsaturated dicarboxylic acid, said
mixtures of unsaturated polyester and vinylic resin being stabilized with a small stabilizing
monomer stabilized with the oxalate salts of amount of a dissolved quaternary ammonium salt
quaternary ammonium hydroxide. These webs of a carboxylic acid which has a dissociation con
can be stored in uncured state for a substantial Stant not less than 1x10-3.
period and still the webs can readily be cured 5. A new composition of matter comprising a
when they are subjected to infra-red radiation polyester of a dihydric alcohol and an alpha-beta
or are passed over heated surfaces such as a ethylenic, alpha-beta dicarboxylic acid, said poly
hot drum. ester being stabilized by an effective amount of a
Naturally, a salt of a quaternary ammonium dissolved added quaternary ammonium salt of a
base to be fully effective must be soluble at least non-Oxidizing acid at least as strong as acetic
to a reasonable degree in the mixture to be sta acid.
bilized. Solubility of the salts will vary, some 6. As a new composition of matter a copoly
being more soluble than others. A salt which if merizable mixture of: (A) a polyester of a dihy
sufficiently soluble, may be an excellent stabilizer, 55 dric alcohol and an alpha-beta dicarboxylic,
may fail to produce optimum results in a given alpha-beta ethylenically unsaturated acid and
polyester mixture simply because it does not dis (B) an ethylenically unsaturated compound co
Solve to a sufficient degree. In Some mixtures a polymerizable with the polyester, said mixture
given salt is often more soluble than in other being stabilized against gelation in the absence
mixtures. It is probable that the nature of both 60 of peroxide catalysts by a Simall effective amount
the polyester and of the liquid polymerizable com of a dissolved added salt of a quaternary ann
pound affect the Stability. Mixtures containing monium hydroxide and a non-Oxidizing acid at
homogeneous esters of maleic or fumaric acid least as strong as acetic acid.
gel more rapidly than those of mixed polyesters 7. A new composition of matter comprising a
containing large amounts of dicarboxylic acids 65 polymerizable unsaturated polyester of an eth
free of unsaturation and therefore are more dif ylenically unsaturated dicarboxylic acid and a
ficult to stabilize. The mixtures containing dihydric alcohol, said polyester containing in So
styrene as the vinylic compound gel more quickly lution a small stabilizing amount of a dissolved
than those containing alpha methyl styrene or a quaternary ammonium salt of a non-oxidizing
vinylic ester. 70 acid at least as strong as acetic acid.
Accordingly, it Will be apparent that a salt of 8. As a resinifiable material a polyester of a
a quaternary ammonium base that may not be dihydric alcohol and an alpha-beta ethylenic,
of optimum value in some copolymerizable mix alpha-beta dicarboxylic acid, Said polyester being
tures will perform substantially better in another stabilized against premature gelation by a dis
and will be completely satisfactory. 75 solved quaternary annonium halide.
 2,593,787.
23 24
9. As a new composition of matter, a mixture ration therein, said mixture being stabilized
of a polyester of a dihydric alcohol and an against premature gelation during Storage by a
alpha-beta dicarboxylic, alpha-beta ethylenically Small stabilizing amount of trimethylbenzyl am
unsaturated acid and an ethylenic compound co monium halide, the methyl groups in Said Salt
polymerizable with said polyester, Said mixture 5 being attached to the ammonium nitrogen, said
containing in solution a small stabilizing amount mixture being stable against gelation for periods
of a quaternary ammonium halide. of over 90 days at 70 °F.
10. A composition as defined in claim 9 in 19. As a new composition of matter, a copoly
which the halide is of trialkyl benzyl annonium merizable mixture of an alpha-beta ethylenically
hydroxide. 0 unsaturated, alpha-beta dicarboxylic acid poly
11. A composition as defined in claim 9 in ester of a dihydric alcohol and an ethylenically
which the halide is of a quaternary ammonium unsaturated. Inonomer capable of cross-linking
hydroxide containing 4 hydrocarbon groups di the polyester molecules at the points of unsatu
rectly attached to ammonium nitrogen. ration therein, said mixture being stabilized
12. A composition as defined in claim 9 in against premature gelation during storage by a
which the quaternary ammonium halide is cetyl Small stabilizing annount of triethyl benzyl am
trimethyl ammonium chloride. monium halide, the ethyl groups in said Salt be
13. A composition as defined in claim 9 in ing attached to the ammonium nitrogen, Said
which the quaternary annonium halide contains mixture being Stable against gelation for periods
four groups directly attached to the ammonium of over 90 days at 70°F.
nitrogen, 3 of the groups being hydrocarbon of 20. As a new composition of matter, a copoly
1 to 6 carbon atoms, the fourth group being of merizable mixture of (A) a dihydric alcohol poly
a class consisting of benzyl, phenyl, alkyl of 8 ester of a mixture of an alpha-beta ethylenically
to 18 carbon atons and unsaturated, alpha-beta dicarboxylic acid and a
-C-R Saturated dicarboxylic acid of a class consisting
I Of phthalic acid, adipic acid and azelaic acid
() and (B) an ethylenically unsaturated monomer
where R is a hydrocarbon radical containing up capable of cross-linking the polyester molecules
to 18 carbon atoms. at points of unsaturation therein, said mixture
14. As a new composition of matter a mixture being Stabilized against premature gelation dur
comprising (A) a polyester of a dihydric alcohol ing storage by a Small stabilizing amount of
and an alpha-beta ethylenic, alpha-beta dicar a trialkyl benzyl ammonium halide.
boxylic acid and (B) an ethylenically unsatu 21. The composition of claim 22 wherein the
rated compound copolymerizable With the poly unSaturated dicarboxylic acid is endomethylene
ester, and (C) a salt of a 'quaternary ammonium A4 tetrahydrophthalic acid.
hydroxide and a non-oxidizing acid at least as 22. A composition of matter comprising a co
strong as acetic acid which has a molecular polymerizable mixture of (A) a polymerizable
weight not exceeding 200. unsaturated polyester of an ethylenically un
15. A new composition of matter cornprising Saturated dicarboxylic acid and a dihydric alco
(A) a polyester of a dihydric alcohol and an 40 hol and (B) an ethylenically unsaturated com
alpha-beta ethylenic, alpha-beta dicarboxylic pound copolymerizable with the polyester, the
acid and (B) styrene, said mixture being stabi mixture being Stabilized with a small stabilizing
lized against premature gelation by a Small, effec amount of a dissolved quaternary ammonium salt
tive amount of a dissolved added quatel'nary of a non-Oxidizing acid which is at least as strong
ammonium salt of a non-Oxidizing acid at least aS acetic acid. -
as Strong aS acetic acid. - 23. The composition of claim 22 wherein the
16. As a new composition of matter, a copoly Salt is a halide.
merizable mixture of (A) a polyester of an alpha 24. The composition of claim 22 wherein the
beta dicarboxylic, alpha-beta ethylenic acid and Salt is a halide and the ethylenically unsaturated
a dihydric alcohol and (B) styrene, said mixture Compound is styrene.
being stabilized against premature gelation in 25. The composition of claim 22 wherein the
storage by a small, effective amount of a dissolved unsaturated dicarboxylic acid is maleic acid.
halide salt of a quaternary ammonium hydroxide 26. A composition of matter comprising a co
containing 4 groups directly attached to the am polymerizable mixture of (A) a polymerizable
monium nitrogen, three groups being hydrocar polyester of maleic acid and a dihydric alcohol
bon of 1 to 6 carbon atoms, the fourth being 55 and (B) Styrene, the mixture being stabilized
of the class consisting of benzyl, phenyl, alkyl With a Small Stabilizing amount of a dissolved
of 8 to 18 carbon atoms and quaternary ammonium halide.
-C-R
EARL E. PARKER,
() 60
where R is a hydrocarbon radical containing up REFERENCES CITED
to 18 carbon atoms. The following references are of record in the
17. A stabilized composition as defined in claim file of this patent:
16 in which the polyester is an ester of an alpha
beta, dicarboxylic, alpha-beta ethylenic acid and UNITED STATES PATENTS
another dicarboxylic acid which is free of un Number Name Date
saturated groups capable of polymerizing by ad 2,255,313 Ellis -------------- Sept. 9, 1941
dition, the latter acid being present in an amount 2,351,658 Berne-Allen ------ June 20, 1944
of .25 to 6 mols per mol of the former acid. 2,351,664 Cockerille ---------- June 20, 1944
18. As a new composition of matter, a copoly 70 2,361,538 Franz ------------- Oct. 31, 1944
merizable inixture of an alpha-beta, ethylenically 2,453,666 Kropa ------------- Nov. 9, 1948
unsaturated, alpha-beta, dicarboxylic acid poly
ester of a dihydric alcohol and an ethylenically FOREIGN PATENTS
unsaturated monomer capable of croSS-linking Number Country Date
the polyester molecules at the points of unsatu 75 540,167 Great Britain ----- Oct. 8, 1941