luropâisches P a t e n t a m t

@ Publication number: 0 0 5 3 4 3 2
9 iuropean Patent Office
)ff ice européen des brevets B1

h E U R O P E A N P A T E N T S P f c U N U A 1 IUIM

Î5) Dateof publication of patent spécification: 27.06.84 © Int. Cl.3: C 08 F 2 9 9 / 0 4 ,

C07C 53/126
y) Application number: 81304794.1
22) Dateof filing: 14.10.81

3) Accelerator Systems for polyester resin compositions.

1 548 @ Proprietor: Nuodex Inc.

^ Priority: 01 .1 2.80 US 21
15)
Turner Place P.O. Box 365
Piscataway New Jersey 08854 (US)
@ Date of publication of application:
09.06.82 Bulletin 82/23 . , Joseph
,
@ Inventor: Buono, Frederick
18 Edgewood Road
@ Publication of the grant of the patent: Robbinsville New Jersey (US)
27.06.84 Bulletin 84/26 Inventor: Hoch, Samuel
1529 - 56th Street
Brooklyn New York (US)
(84) Designated Contracting States:
DEFRGBITNL „ Edward
^ Representative: Oliver, Roy r.J . et„ al,.
(74)
POLLAK MERCER & TENCH High Holborn House
® References cited: 52-54 High Ho Iborn
US - A - 3 281 497 London WC1 V 6RY (GB)
US - A - 3 449 276
US - A - 3 539 479
US - A - 3 920 590
US-A-4175 064
Cl
o

o
o Note: Within nine months from the publication or tne mention OTtne grani orxne european pdiem, any yeioun may
give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall
Q. be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1 ) European patent convention).
Courier Press, Leamington t>pa, tngiana.
 This invention relates to unsaturated polyester resin compositions that are capable of rapid curing
at low temperatures and to a process for the curing of unsaturated polyester resin compositions. More
particularly, it relates to a process for accelerating the curing of peroxide-catalyzed unsaturated poly-
ester resin compositions by the use of an accelerator system that comprises cobalt and potassium salts
of organic acids. It further relates to a metal salt composition that is an effective accelerator for the
peroxide curing of unsaturated polyester resin compositions.
The unsaturated polyester resin compositions to which this invention applies are solutions of
unsaturated polyester resins in a polymerizable monomer which provides cross-linking units to unite
the polymer chains. The polyester and monomer copolymerize upon the introduction of a peroxide
catalyst to form a rigid, insoluble, infusible material. These unsaturated polyester resin compositions
have found widespread use in the production of coatings, laminates, cast articles, molded articles, and
other shaped articles.
Accelerators are usually added to unsaturated polyester resin compositions to accelerate the
decomposition of the peroxide catalyst to free radicals and thereby initiate or speed the curing of the
composition at relatively low temperatures, i.e., at temperatures in the range of 0° to 30°C. Among the
materials that have been reported as being effective accelerators are metal compounds, such as cobalt,
manganese, iron, vanadium, copper, and aluminum salts of organic acids; amines, such as dimethyl-
aniline, diethylaniline, and 2-aminopyridine; Lewis acids, such as boron fluoride dihydrate and ferric
chloride; bases, such as tetraethanol ammonium hydroxide and tetramethyl ammonium hydroxide;
quaternary ammonium salts, such as trimethylbenzyl ammonium chloride and tetrakismethylol phos-
phonium chloride; and sulfur compounds, such as dodecyl mercaptan and 2-mercaptoethanol. Cobalt
salts of organic acids are the most widely-used accelerators for the low temperature decomposition of
peroxide catalysts and the curing of unsaturated polyester resin compositions.
The curing time of unsaturated polyester resin compositions at low temperatures can be further
reduced by the use of a second accelerator in combination with the cobalt compounds. Among the co-
accelerators that have been used in combination with a cobalt salt of an organic acid to promote the
curing of unsaturated polyester resin compositions are amines, such as dimethylaniline, diethanol-
amine, tetramethylbutane diamine, and diethylene triamine, and samarium salts of organic acids. In
U.S. patent No. 4,175,064, Landau et al disclosed accelerator systems for peroxide-catalyzed
unsaturated polyester resin compositions that comprise solutions of cobalt salts and potassium salts of
monocarboxylic acids having 6 to 24 carbon atoms in an organic solvent mixture that contains both
polar and non-polar solvents. The use of these cobalt salt-potassium salt systems results in the rapid
curing of unsaturated polyester resin compositions at low temperatures. Their use also provides shorter
initial gel times and less gel time drift on aging than result when the same amount or a larger amount of
the cobalt salt is used alone or in combination with another co-accelerator. Solutions of the cobalt and
potassium salts of monocarboxylic acids having 6 to 24 carbon atoms that contain 8% or more total
metal, however, are viscous liquids that are often difficult to handle and to incorporate into the
unsaturated polyester compositions. In addition, these salt solutions are relatively costly to manu-
facture and use.
It has now been found that accelerator systems that comprise cobalt salts of monocarboxylic
acids having 6 to 12 carbon atoms and potassium salts of monocarboxylic acids having 1 to 5 carbon
atoms are very effective curing agents for unsaturated polyester resin compositions at low tempera-
tures. Their use provides initial gel times and gel time drift on aging that are equivalent to or better than
those provided by systems that contain cobalt salts and potassium salts or monocarboxylic acids
having 6 to 24 carbon atoms. The novel accelerator systems do not have the aforementioned dis-
advantages of the accelerator systems disclosed by Landau et al. These systems, which may have total
metal contents of up to about 15% by weight, are relatively inexpensive, non-viscous liquids that are
easily handled and incorporated into unsaturated polyester resin compositions.
According to one aspect of this invention, a process is provided for curing a composition
comprising an unsaturated polyester resin and an unsaturated monomer capable of reacting with the
polyester resin to form cross-linkages, by contacting the composition with an organic peroxide catalyst
and an accelerator system comprising cobalt and potassium salts of monocarboxylic acids, charac-
terised in that the accelerator system comprises at least one cobalt salt of a monocarboxylic acid
having 6 to 12 carbon atoms and at least one potassium salt of a monocarboxylic acid having 1 to 5
carbon atoms, in solution in an organic solvent, and that the accelerator system is present in an amount
which provides 0.001% to 0.1% of cobalt (95 as metal) and 0.001% to 0.1% of potassium (as metal),
based on the total weight of the unsaturated polyester resin and the unsaturated monomer. Preferably
the accelerator system is a solution of the cobalt and potassium salts containing by weight about 3% to
6% of cobalt (as metal) and about 5% to 10% of potassium (as metal) and having a total metal content
of 8% to 15% by weight.
According to another aspect of the invention, a polyester resin composition comprises an
unsaturated polyester resin, an unsaturated monomer capable of reacting with the polyester resin to
form cross-linkages as organic peroxide catalyst and an accelerator system as just defined.
 The cobalt salt component of the accelerator systems of this invention is derived from mono-
carboxylic acids that have 6 to 12 carbon atoms. The useful acids include saturated and unsaturated
aliphatic, aromatic, and alicyclic monocarboxylic acids, such as hexanoic acid, heptanoic aicd, n-
octanoic acid, 2-ethylhexanoic (octoic) acid, nonanoic acid, isononanoic acid, n-decanoic acid,
isodecanoic acid, neodecanoic acid, n-dodecanoic acid, neododecanoic acid, decenoic acid, unde-
cylenic acid, benzoic acid, p-tert. butylbenzoic acid, salicylic acid cyclohexanoic acid, cycloheptanoic
acid, methylcyclohexanoic acid and mixtures thereof. Monobutyl maleate and monobutylphthalate, are
also useful and the term "monocarboxylic acids" is used herein to mean not only acids per se, but also
these acid salt forming esters.
The potassium salt component of the accelerator systems is derived from monocarboxylic acids
having 1 to 5 carbon atoms, that is, formic acid, acetic acid, propionic acid, butyric acid, valeric acid and
mixtures thereof.
The accelerator systems preferably comprise cobalt salts of aliphatic monocarboxylic acids having
8 to 12 carbon atoms most preferably cobalt octoate, and potassium acetate.
The cobalt and potassium salts are added to the unsaturated polyester resin compositions as
solutions in organic solvents. Solutions of the cobalt and potassium salts may be added separately, or a
solution which contains both cobalt and potassium salts may be added to the unsaturated polyester
resin composition.
In a preferred embodiment of the invention, the accelerator systems are solutions of cobalt and
potassium salts in a solvent in which both salts are soluble. Suitable solvents include mixtures that
contain from 20% to 80% preferably 40% to 60% by weight of one or more polar solvents and 20% to
80% preferably 40% to 60% by weight of one or more non-polar solvents. The solvent mixtures
preferably contain an alkanol having 3 to 20 carbon atoms, such as propanol, butanol, hexanol, n-
octanol, 2-ethylhexanol, n-decanol, isodecanol, 2-ethyloctanol, dodecanol, tridecanol, or tetradecanol;
a hydrocarbon having 5 to 20 carbon atoms, such as pentane, hexane, octane, decane, and mineral
spirits; and optionally minor amounts of water, monocarboxylic acids, glycols, such as ethylene glycol
and propylene glycol, and/or glycol ethers, such as diethylene glycol, dipropylene glycol, polypropylene
glycol, and monobutyl ether of diethylene glycol.
These accelerator systems can be prepared by mixing together amounts of solutions of the cobalt
and potassium salts in organic solvents that will form a solution that contains from 3% to 6% by weight
of cobalt (as the metal) and from 5% to 10% by weight of potassium (as the metal) and that has a total
metal content of from 8% to 15% by weight. The cobalt salt is usually added as a cobalt salt solution
that contains 4% to 20% by weight of cobalt, and the potassium salt is usually added as a potassium
salt solution that contains 5% to 24% by weight of potassium. The accelerator systems preferably
contain from 3.75% to 4.5% by weight of cobalt and from 6.25% to 8% by weight of potassium and
have a total metal content of from 10% to 12% by weight.
Alternatively, the accelerator systems can be formed by dissolving the metal salts separately in an
appropriate organic solvent or by dissolving a salt of one of the metals in a solution in an organic
solvent of a salt of the other metal in amounts that will form systems that contain from 3% to 6% by
weight of cobalt and 5% to 10% by weight of potassium and have a total metal content of from 8% to
15% by weight.
The amounts of the accelerator systems that are used to accelerate the curing of unsaturated
polyester resin compositions are those that will provide from 0.001% to 0.1% of cobalt (as the metal)
and from 0.001% to 0.1% of potassium (as the metal) and preferably from 0.01% to 0.05% of cobalt
and from 0.01% to 0.05% of potassium, based on the weight of the unsaturated polyester resin
composition. In most cases, from 0.1 % to 3% by weight and preferably 0.25% to 2% by weight of the
accelerator system will provide these amounts of cobalt and potassium.
Analysis of the metal salt solutions of this invention has shown that in solution two moles of the
potassium salt combines with one mole of the cobalt salt to form cobalt complexes whose structure is
not now known. The excellent activity of the accelerator systems of this invention probably arises from
the presence in them of these cobalt salt/potassium salt complexes.
In addition to the cobalt salt/potassium salt complexes, the accelerator systems may contain
cobalt salts and/or potassium salts of the aforementioned monocarboxylic acids.
The polyester resins that are used in the practice of this invention are unsaturated polyester resins
that are formed by condensing a saturated dicarboxylic acid or anhydride and an unsaturated
dicarboxylic acid or anhydride with a dihydric alcohol. Illustrative of these polyester resins are the
products of the reaction of a saturated dicarboxylic acid or anhydride, such as phthalic anhydride, iso-
phthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylene tetrahydro-
phthalic anhydride, tetrachlorophthalic anhydride, hexachloroendomethylene tetrahydrophthalic acid,
succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid, and an
unsaturated dicarboxylic acid or anhydride, such as maleic anhydride, fumaric acid, chloromaleic acid,
itaconic acid, citraconic acid, and mesaconic acid, with a dihydric alcohol, such as ethylene glycol,
propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, and neopentyl glycol. Small
amounts of a polyhydric alcohol, such as glycerol, pentaerythritol, trimethylolpropane, or sorbitol, may
be used in combination with the glycol.
 A three-dimensional structure is produced by reacting the unsaturated polyester through the
unsaturated acid component with an unsaturated monomer that is capable of reacting with the poly-
ester resin to form cross-linkages. Suitable unsaturated monomers include styrene, methylstyrene,
dimethylstyrene, vinyltoluene, divinylbenzene, dichlorostyrene, methyl acrylate, ethyl acrylate, methyl
methacrylate, diallyl phthalate, vinyl acetate, triallyl cyanurate, acrylonitrile, acrylamide, and mixtures
thereof. The relative amounts of the unsaturated polyester resin and the unsaturated monomer in the
composition may be varied over a wide range.
The unsaturated polyester resin compositions generally contain 20% to 80% by weight of the
monomer, with the monomer content preferably in the range of 30% to 70% by weight.
An organic peroxide that decomposes to release free radicals at temperatures in the range of 0°
to 30°C. is used to catalyze the copolymerization reaction between the unsaturated polyester resin and
the unsaturated monomer. Among the peroxide catalysts that can be used are methyl ethyl ketone
peroxide, benzoyl peroxide, cumehe hydroperoxide, cetyl peroxide, lauroyl peroxide, cyclohexanone
peroxide, 2,4-dichlorobenzoyl peroxide, bis(p-bromobenzoyl)peroxide, acetyl peroxide, and di-
tert . butyl diperphthalate. The peroxide catalysts that are most commonly used are methyl ethyl ketone
peroxide, benzoyl peroxide, and cumene hydroperoxide. The amount of peroxide catalyst used is from
0.1% to 1.1% and preferably from 0.6% to 1.0% of the weight of the unsaturated polyester resin
composition.
In addition to the unsaturated polyester resin, crosslinking monomer, peroxide catalyst, and one of
the accelerator systems of this invention, the unsaturated polyester resin compositions may also
contain an inhibitor, such as tert. butylcatechol or hydroquinone, fillers and pigments, dyes, mold
release agents, plasticizers, stabilizers, flame-retardants, and other additives in the amounts ordinarily
used for these purposes.
The unsaturated polyester resin compositions that comprise an unsaturated polyester resin, an
unsaturated monomer, a peroxide catalyst, and an accelerator system of this invention cure rapidly
without application of heat to form rigid, insoluble, and infusible products.
The invention is further illustrated by the following examples. In these examples, all parts are parts
by weight and all percentages are percentages by weight.

Example 1
Accelerator systems were prepared by mixing together a solution of cobalt octoate in mineral
spirits (6% Co) and a solution of potassium acetate in a mixture of isodecanol, water, and butyl cello-
solve (12% K) in amounts that provided two moles of potassium per mole of cobalt and formed
products having total metal contents of either 10% or 12%.
For comparative purposes, accelerator systems were prepared by mixing together a solution of
cobalt octoate in mineral spirits and a solution of potassium octoate in isodecanol in amounts that
provided two moles of potassium per mole of cobalt and formed products having total metal contents
of either 8%, 10%, or 12%. The metal contents and viscosities of the accelerator systems are shown in
Table I.

From the data in Table I, it will be seen that the cobalt octoate-potassium octoate systems of the
comparative examples were substantially more viscous than the cobalt octoate-potassium acetate
systems having the same total metal content and that the cobalt octoate-potassium octoate system
that had a total metal content of 8% was far more viscous than the cobalt octoate-potassium acetate
system that had a total metal content of 12%.
Example 2
Unsaturated polyester resin compositions were prepared by the following procedure:
Portions of a styrenated polyester resin (Stypol 4 0 - 0 8 1 1 , Freeman Chemical Corp.) were mixed
with an amount of an accelerator system that provided 0.02% of metal, based on the weight of the
composition.
Fifty gram portions of the styrenated polyester resin-accelerator system mixtures in four ounce
(approx. 115 gram) jars were placed in a constant temperature bath at 27°C. To each portion was
added 0.45 cc of a 60% solution of methyl ethyl ketone peroxide in dimethyl phthalate. The time
required for the unsaturated polyester resin to gel was measured using a Mol-Rez Gel Time Meter.
The gelation test was repeated after the styrenated polyester resin-accelerator system mixtures
had aged for periods ranging from 1 to 4 weeks.
The accelerator systems used and the results obtained are summarized in Table II.

The results in Table II show that the accelerator system of this invention provided an initial gel
time equivalent to that provided by the comparative system that contained cobalt octoate and
potassium octoate and somewhat less gel time drift on aging. They also show that an accelerator
system having a higher total metal content (12% vs. 8%) can be used to accelerate the curing of an
unsaturated polyester resin composition when the potassium salt component is potassium acetate than
when it is potassium octoate.

Example 3
a. An accelerator system was prepared by mixing together a solution of cobalt octoate in mineral
spirits (6% Co) and a solution of potassium n-propionate in a mixture of isodecanol, water, and butyl
alcohol (12% K) in amounts that formed a solution that contained 3.75% cobalt and 6.25% potassium.
b. An accelerator system was prepared by mixing together a solution of cobalt octoate in mineral
spirits (6% Co) and a solution of potassium n-pentanoate in a mixture of isodecanol, water, and butyl
alcohol (12% K) in amounts that formed a solution that contained 3.75% cobalt and 6.25% potassium.
c. For comparative purposes, an accelerator system was prepared by mixing together a solution of
cobalt octoate in mineral spirits (6% Co) and a solution of potassium octoate in isodecanol in amounts
that provided 3.75% cobalt and 6.25% potassium.
The viscosities of the accelerator systems were as follows:
 From the data in the table, it will be seen that cobalt octoate-potassium salt systems of Ex. No. 3a
and 3b were substantially less viscous than the cobalt octoate-potassium octoate system of the
comparative example having the same metal content.

Examples 4 and 5
Unsaturated polyester resin compositions were prepared by the following procedure:
Portions of a styrenated polyester resin (Stypol 4 0 - 0 8 1 1 , Freeman Chemical Corp.) were mixed
with an amount of an accelerator system that provided 0.02% of metal, based on the weight of the
composition.
Fifty gram portions of the styrenated polyester resin-accelerator system mixtures in four ounce
(approx. 115 gram) jars were placed in a constant temperature bath at 27°C. To each portion was
added 0.45 cc of a 60% solution of methyl ethyl ketone peroxide in dimethyl phthalate. The time
required for the unsaturated polyester resin to gel was measured using a Mol-Rez Gel Time Meter. The
results obtained are shown in Table IV.

The above results indicate that the accelerator systems that contain potassium n-propionate or
potassium n-pentanoate provided gel times equivalent to that provided by the comparative system that
contained cobalt octoate and potassium octoate.
From the results of these experiments, it will be seen that the accelerator systems that comprise
cobalt salts of monocarboxylic acids having 6 to 12 carbon atoms and potassium salts of mono-
carboxylic acids having 1 to 5 carbon atoms are non-viscous liquids that are easily handled and incor-
porated into unsaturated polyester resin compositions and that are very effective curing agents for
unsaturated polyester resin compositions at low temperatures.

1. A process for curing a composition comprising an unsaturated polyester resin and an

unsaturated monomer capable of reacting with the polyester resin to form cross-linkages, by contacting
the composition with an organic peroxide catalyst and an accelerator system comprising cobalt and
potassium salts of monocarboxylic acids, characterized in that the accelerator system comprises at
least one cobalt salt of a monocarboxylic acid having 6 to 12 carbon atoms and at least one potassium
salt of a monocarboxylic acid having 1 to 5 carbon atoms, in solution in an organic solvent, and that the
accelerator system is present in an amount which provides 0.001% to 0.1% of cobalt (as metal) and
0.001% to 0.1% of potassium (as metal) based on the total weight of the unsaturated polyester resin
and the unsaturated monomer.
2. A process according to claim 1, wherein the accelerator system is a solution of the cobalt and
potassium salts containing by weight about 3% to 6% of cobalt (as metal) and about 5% to 10% of
potassium (as metal) and having a total metal content of 8% to 15% by weight.
3. A process according to claim 2, wherein the accelerator system is a solution of the cobalt and
potassium salts containing by weight 3.75% to 4.5% of cobalt (as metal) and 6.25% to 8% of
potassium (as metal) and having a total metal content of 10% to 12% by weight.
4. A process according to any of claims 1 to 3, wherein the accelerator system is a solution of the
cobalt and potassium salts in an organic solvent mixture containing by weight 20% to 80% of at least
one polar solvent and 20% to 80% of at least one non-polar solvent.
5. A polyester resin composition, which comprises:

(a) an unsaturated polyester resin,

(b) an unsaturated monomer capable of reacting with the polyester resin to form cross-linkages,
(c) an organic peroxide catalyst, and
(d) an accelerator system,

characterized in that the accelerator system comprises at least one cobalt salt of a monocarboxylic acid
having 6 to 12 carbon atoms and at least one potassium salt of a monocarboxylic acid having 1 to 5
carbon atoms in solution in an organic solvent, and that the accelerator system is present in an amount
which provides 0.001% to 0.1% of cobalt (as metal) and 0.001% to 0.1% of potassium (as metal),
based on the total weight of the unsaturated polyester resin and the unsaturated monomer.
6. A polyester resin composition as claimed in claim 5, wherein the accelerator system comprises
cobalt octoate and potassium acetate.
7. An accelerator system for peroxide-catalyzed unsaturated polyester resin compositions which
is a solution of one or more metal compounds selected from cobalt salts of monocarboxylic acids
having 6 to 12 carbon atoms, potassium salts of monocarboxylic acids having 1 to 5 carbon atoms,
reaction products of such cobalt and potassium salts and mixtures thereof in an organic solvent,
characterized in that the solution contains by weight 20% to 80% of at least one polar solvent, 20% to
80% of at least one non-polar solvent, 3% to 6% of cobalt (as metal) and 5% to 10% of potassium (as
metal) and has a total metal content of 8% to 15% by weight.
8. An accelerator system as claimed in claim 7, which contains by weight 3.75% to 4.5% of cobalt
(as metal) and 6.25% to 8% of potassium (as metal) and has a total metal content of 10% to 12% by
weight.
9. An accelerator system as claimed in claim 7 or 8, which comprises a solution of cobalt octoate
and potassium acetate in an organic solvent mixture which contains by weight 40% to 60% of at least
one polar solvent and 40% to 60% of at least one non-polar solvent.
10. A cobalt complex comprising the product of reaction of one mole of a cobalt salt of a mono-
carboxylic acid having 6 to 12 carbon atoms with two moles of a potassium salt of a monocarboxylic
acid having 1 to 5 carbon atoms in an organic solvent mixture containing 20% to 80% of polar solvent
and 20% to 80% of non-polar solvent.

1. Verfahren zur Aushärtung einer Zusammensetzung, enthaltend ein ungesättigtes Polyester-

harz und ein ungesättigtes Monomer, das in der Lage ist, mit dem Polyesterharz unter Bildung von
Vernetzungen zu reagieren, durch in Kontaktbringen der Zusammensetzung mit einem organischen
Peroxidkatalysator und einem Beschleunigersystem, das Kobalt und Kaliumsalze von Monocarbon-
säuren enthält, dadurch gekennzeichnet, daß das Beschleunigersystem mindestens ein Kobaltsalz einer
Monocarbonsäure mit 6 bis 12 Kohlenstoffatomen und mindestens ein Kaliumsalz einer Monocarbon-
säure mit 1 bis 5 Kohlenstoffatomen enthält, gelöst in einem organischen Lösungsmittel, und daß das
Beschleunigersystem in einer Menge anwesend ist, die 0,001 bis 0,1% Kobalt (als Metall) und 0,001
bis 0,1% Kalium (als Metall) bezogen auf das Gesamtgewicht des ungesättigten Polyesterharzes und
des ungesättigten Monomers, ergibt.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Beschleunigersystem eine
Lösung der Kobalt- und Kaliumsalze ist und etwa 3 bis 6 Gewichtsprozent Kobalt (als Metall) und etwa
5 bis 10 Gewichtsprozent Kalium (als Metall) enthält, und einen Gesamtmetallgehalt von 8 bis 15
Gewichtsprozent aufweist.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß das Beschleunigersystem eine
Lösung der Kobalt- und Kaliumsalze ist und 3,75 bis 4,5 Gewichtsprozent Kobalt (als Metall) und 6,25
bis 8 Gewichtsprozent Kalium (als Metall) aufweist und einen Gesamtmetallgehalt von 10 bis 12
Gewichtsprozent hat.
4. Verfahren nach jedem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das Beschleuniger-
system eine Lösung der Kobalt- und Kaliumsalze in einem organischen Lösungsmittelgemisch ist, das
20 bis 80 Gewichtsprozent mindestens eines polaren Lösungsmittels und 20 bis 80 Gewichtsprozent
mindestens eines nicht-polaren Lösungsmittels enthält.
5. Polyesterharzzusammensetzung, enthaltend:

(a) ein ungesättigtes Polyesterharz,

(b) ein ungesättigtes Monomer, das befähigt ist, mit dem Polyesterharz unter Bildung von Ver-
netzungen zu reagieren,
(c) einen organischen Peroxidkatalysator, und
(d) ein Beschleunigersystem,

dadurch gekennzeichnet, daß das Beschleunigersystem mindestens ein Kobaltsalz einer Monocarbon-
säure mit 6 bis 12 Kohlenstoffatomen und mindestens ein Kaliumsalz einer Monocarbonsäure mit 1 bis
5 Kohlenstoffatomen, gelöst in einem organischen Lösungsmittel, enthält, und daß das Beschleuniger-
system in einer Menge anwesend ist, die 0,001 bis 0,1% Kobalt (als Metall) und 0,001 bis 0,1% Kalium
(als Metall) ergibt, bezogen auf das Gesamtgewicht von ungesättigtem Polyesterharz und unge-
sättigtem Monomer.
6. Polyesterharzzusammensetzung nach Anspruch 5, dadurch gekennzeichnet, daß das Be-
schleunigersystem Kobaltoctoat und Kaliumacetat enthält.
7. Beschleunigersystem für Peroxid-katalysierte ungesättigte Polyesterharzzusammensetzungen,
das eine Lösung von einem oder mehreren Metallbestandteilen aus der Gruppe Kobaltsalze von Mono-
carbonsäuren mit 6 bis 12 Kohlenstoffatomen, Kaliumsalze von Monocarbonsäuren mit 1 bis 5 Kohlen-
stoffatomen, Reaktionsprodukte dieser Kobaltund Kaliumsalze und deren Gemische in einem
organischen Lösungsmittel darstellt, dadurch gekennzeichnet, daß die Lösung 20 bis 80 Gewichts-
prozent mindestens eines polaren Lösungsmittels, 20 bis 80 Gewichtsprozent mindestens eines nicht-
polaren Lösungsmittels, 3 bis 6 Gewichtsprozent Kobalt (als Metall) und 5 bis 10 Gewichtsprozent
Kalium (als Metall) enthält, und einen Gesamtmetallgehalt von 8 bis 15 Gewichtsprozent aufweist.
8. Beschleunigersystem nach Anspruch 7, dadurch gekennzeichnet, daß es 3,75 bis 4,5
Gewichtsprozent Kobalt (als Metall) und 6,25 bis 8 Gewichtsprozent Kalium (als Metall) enthält und
einen Gesamtmetallgehalt von 10 bis 12 Gewichtsprozent aufweist.
9. Beschleunigersystem nach Anspruch 7 oder 8, dadurch gekennzeichnet, daß es eine Lösung
von Kobaltoctoat und Kaliumacetat in einem organischen Lösungsmittel enthält, das 40 bis 60 Ge-
wichtsprozent mindestens eines polaren Lösungsmittels und 40 bis 60 Gewichtsprozent mindestens
eines nicht-polaren Lösungsmittels enthält.
10. Kobaltkomplex, enthaltend ein Produkt aus der Umsetzung von 1 Mol eines Kobaltsalzes einer
Monocarbonsäure mit 6 bis 12 Kohlenstoffatomen mit 2 Mol eines Kaliumsalzes einer Monocarbon-
säure mit 1 bis 5 Kohlenstoffatomen in einem organischen Lösungsmittelgemisch, das 20 bis 80%
eines polaren Lösungsmittels und 20 bis 80% eines nicht-polaren Lösungsmittels enthält.

1. Procédé de réticulation d'une composition comprenant une résine du type polyester insaturé et
un monomère insaturé capable de réagir avec la résine polyester pour former des réticulations, par mise
en contact de la composition avec un catalyseur formé d'un peroxyde organique et un système
accélérateur comprenant des sels de cobalt et de potassium d'acides monocarboxyliques, caractérisé
en ce que le système accélérateur comprend au moins un sel de cobalt d'un acide monocarboxylique
ayant 6 à 12 atomes de carbone et au moins un sel de potassium d'un acide monocarboxylique ayant 1
à 5 atomes de carbone, en solution dans un solvant organique, et en ce que le système accélérateur est
présent en une quantité apportant 0,001 à 0,1% en poids de cobalt (exprimé en métal) et 0,001 à 0,1%
de potassium (exprimé en métal), sur la base du poids total de la résine du type polyester insaturé et du
monomère insaturé.
2. Procédé suivant la revendication 1, dans lequel le système accélérateur est une solution des
sels de cobalt et de potassium contenant en poids environ 3 à 6% de cobalt (exprimé en métal) et
environ 5 à 10% de potassium (exprimé en métal) et ayant une teneur totale en métaux de 8 à 15% en
poids.
3. Procédé suivant la revendication 2, dans lequel le système accélérateur est une solution des
sels de cobalt et de potassium contenant, en poids, 3,75 à 4,5% de cobalt (exprimé en métal) et 6,25 à
8% de potassium (exprimé en métal) et ayant une teneur totale en métaux de 10 à 12% en poids.
4. Procédé suivant l'une quelconque des revendications 1 à 3, dans lequel le système accéléra-
teur est une solution des sels de cobalt et de potassium dans un mélange de solvants organiques con-
tenant en poids 20 à 80% d'au moins un solvant polaire et 20 à 80% d'au moins un solvent non polaire.
5. Composition de résine polyester, qui comprend:

(a) une résine du type polyester insaturé,

(b) un monomère insaturé capable de réagir avec la résine polyester pour former des réticulations,
(c) un catalyseur formé d'un peroxyde organique, et
(d) un système accélérateur,
caractérisé en ce que le système accélérateur comprend au moins un sel de cobalt d'un acide mono-
carboxylique ayant 6 à 12 atomes de carbone et au moins un sel de potassium d'un acide mono-
carboxylique ayant 1 à 5 atomes de carbone, en solution dans un solvant organique, et en ce que le
système accélérateur est présent en une quantité apportant 0,001 à 0,1% en poids de cobalt (exprimé
en métal) et 0,001 à 0,1% de potassium (exprimé en métal), sur la base du poids total de la résine du
type polyester insaturé et du monomère insaturé.
6. Composition de résine polyester suivant la revendication 5, dans laquelle le système accéléra-
teur comprend de l'octoate de cobalt et de l'acétate de potassium.
7. Système accélérateur pour compositions de résines du type polyester insaturé catalysées par
un peroxyde, qui est une solution d'un ou plusieurs composés métalliques choisis entre des sels de
cobalt d'acides monocarboxyliques ayant 6 à 12 atomes de carbone, des sels de potassium d'acides
monocarboxyliques ayant 1 à 5 atomes de carbone, des produits de réaction de ces sels de cobalt et de
potassium et leurs mélanges dans un solvant organique, caractérisé en ce que la solution contient, en
poids, 20 à 80% d'au moins un solvant polaire, 20 à 80% d'au moins un solvant non polaire, 3 à 6% de
cobalt (exprimé en métal) et 5 à 10% de potassium (exprimé en métal) et a une teneur totale en métaux
de 8 à 15% en poids.
8. Système accélérateur suivant la revendication 7, qui contient en poids 3,75 à 4,5% cobalt
(exprimé en métal) et 6,25 à 8% de potassium (exprimé en métal) et a une teneur totale en métaux de
10 à 12% en poids.
9. Système accélérateur suivant la revendication 7 ou 8, qui comprend une solution d'octoate de
cobalt et d'acétate de potassium dans un mélange de solvants organiques qui contient en poids 40 à
60% d'au moins un solvant polaire et 40 à 60% d'au moins un solvant non polaire.
10. Complexe de cobalt comprenant le produit de réaction d'une mole d'un sel de cobalt d'un
acide monocarboxylique ayant 6 à 12 atomes de carbone avec 2 moles d'un sel de potassium d'un
acide monocarboxylique ayant 1 à 5 atomes de carbone dans un mélange de solvants organiques con-
tenant 20 à 80% de solvant polaire et 20 à 80% de solvant non polaire.