Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
ROOM TEMPERATURE C~OSSL:L~IKING
, _
UNSATURATED POLYESTER RESINS
SIR 2579)
. BACKGROUND OF rye INVENTION
The present- invention pertains to the room
temperature crossl~nking of unsaturated polyester
resin and more particularly, Jo accelerating the
room temperature cross linking of such polyester
resins with an organosulfur compound and metal
salt.
Organo~ulur compounds and metal salts are
known in the prior art for accelerating (also
called promoting the room temperature
cross linking of unsaturated polyester resins in
the presence of a organic peroxide. US. Patent
No. 2~946J770 discloses the use of an organic
sulphoni~m compound in combination with a
quate~nary ammonium compound end a copper or iron
salt Jo accelerate toe polymerization time. US.
Patent No. 3,333,021 teaches thy use of mercap~ans
in combination with vanadium salts as an
accelerator system. British Pun No. 1,170,983
discloses the use of a 2wmercapto-alcohol in
combination with a cobalt or vanadium salt as an
accelerator. None of these patents teaches the
present invert
SUMMARY OF Lowe. INVENTION
The present invention it directed to a
process of cro~slinking an unsaturated polyester
resin comprising admixing to said unsaturated
resin
a) an initiating amount of a peroxyester,
by at least one Merritt compound, and
c) an inorganic metal salt wherein the
metal is elected from the group
consisting of iron and copper
or 2 mixture of the metal salts, and
cross linking the admixture at room temperature.
DETAILED DESCRIPTION OF _ E INVENTION
It has now been found that unsaturated
polyester resins cay be crosslinkled (also called
cured) rapidly and thoroughly at room temperature
using a peroxyes~er initiator and an accelerator
system of a Marquette compound and inorganic metal
salts.
The unstirred polyester resins used in this
invention are reactive resins dissolved in a
polymerizable monomer or mixture of monomers.
These reactive no ins are formed by condensing a
saturated dicar~ox~lic acid or android and an
unworried dicarboxylic acid or android with a
dodder alcohol. Examples of these polyester
resins are the products of the reaction of a
saturated dicarboxylic acid or android ego.
phthalic adored, isophthalic acid,
tet~ahydrophthalic android, hexahydrophthalic
android, endomethylene ~e~rahydrophthalic
android, tetrachloroph~halic android 9
hexachloroendo~ethylene ~etrahydrophthalic acid,
succinic acid, glu~aric acid, adipic acid, pimelic
acid, sub Eric acid azelaic acid or sebacic acid)
and a Imsaturated dicarboxylic acid or android
(e g., malefic android, fumaric acid,
chl.oromaleic acid; laconic acid, citraco~lic acid
or mesa conic acid) with a dihydric alcohol (e.g.,
ethylene glycol, propylene glycol, battalion
glycol, diethylene glycol, triethylene glycol or
neopentyl glycol). Small amounts of a polyhydric
alcohol (e.g., glycerol, pentaery~hritol,
~rimethylopropane or sourball) 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 which is capable of reacting with the
polyester resin Jo form cross-linkages. Suitable
unsaturated monomers include styrenes
methylstyrene, dimethylstyrene, vinyltoluene,
divinylbenzene, dichlorostyrene, methyl acryla~e,
ethyl a relate, methylacrylat~, Delilah phLhalate,
vinyl acetate, triallyl sonority, acryloni~rile,
acrylamide and mixtures thereof. The relative
amounts of the unsaturated polyester resin and the
unwatered monomer in the composition may be
varied over a wide range.
The unsaturated polyester resin compositions
generally contain 2Q% to 80% by weight of the
monomer, the monomer content preferably being in
the range prom 30% to 70% by weight.
:
Also included among useful reactive resins
are those resins which are terminated by
polymerizable unsaturated ester functions but
wherein the polymer repeating unit may or may not
S be of the polyester type, for example, polyethers
terminated with acrylic acid ester groups, blended
with suitable copol~merizable monomers. A typical
series of such resins are commercially available
from Dow Chemical Corp. under the trademark
"Darken" resins and generally comprise
polyethers prepared from an epoxide (e.g.,
glycidol) and a bisphenol ego.,
2,2-di(4-hydroxyphenyl) propane or bisphenol A
which are terminated by acrylic acid ester
functions and blended with Syrian. A more
detailed description of vinyl ester resins may be
found in "Unsaturated Polyester Technology",
Gordon and Breach Science Publishers, New York
1976, p 315 and in Developments in Reinforced
Pluses - 1 edited by G. Pritchard, published by
Applied Science Publishers Ltd., England 1980.
To simplify discussion in the remainder of
this text the term pulse resin will be used to
describe both unsaturated polyester resins and
polyether resins with terminal unsa~uration
(Darken types).
- 6
In the practical utilization of polyester
resins, i c is common to incoxpora'~e fillers and
reinforcements. Fillers are substances added to
poultry resin before curing to enhance various
properties of the final product or to reduce its
cost. Bulk fillers such as carbonates and clays
are used to decrease the cost of the final
precut to give better flow- characteristics to
the resin, and to provide a smoother surface on
the finished Lomb. nether advantage of bulk
fillers is that they absorb some of the exothermic
heat of the curing reaction. This lessens
internal strain and reduces thermal expansion and
shrinkage. Other filler such as hydrated alumina
increase fire Ritz of the final products
Reinforcing fillers include such fibrous
materials as glass, quartz, cotton, nylon,
asbestos and sisal. They are usually incorporated
into the resin to improve strength, particularly
impact and flexural strengths.
A wide variety of fullers and reinforcement
have been found to be compatible with the curing
process of this invention.
To utilize the many advantages of the process
of this invention, an number of a variety of
methods known to Whose skilled in the art may be
-- 7
used to convert the reactive liquid resin into a
useful thermoses solid. The process of this
invention is particularly suited to such known
methods as spray-up t hand lay-up, resin injection,
centrifugal casting filament winding wet
compression molding, continuous laminating,
casting and encapsulation.
The peroxidic compounds of this invention ware
the peroxyesters. Peroxyesters are widely used as
initiators for free radical polymerization and
cross linking a elevated taperers (>150F). A
detailed description of peroxy~sters and their use
in curing unsaturated polyester resins may be
found in the following reference, V. R. Kamath and
R. B. Killer "Initiator Systems for
Unsaturated Puller Resins", Developments in
Reinforced Plastics - I, published by Applied
Science Publishers Ltd., England 1980, pup 121-144.
Peroxyesters have the general structure
I
(R3x(OOC)y(Rl)z
wherein x, y and z are 1 or 2 with the
provisos that
when x, y and z are 1, R is selected from the
group consisting of a substituted or unsubsti.t~l~ed
terti.ary-alkyl of-4 to 8 carbons, tertiary-alkynyl
of 5 Jo 8 carbons, tertiary-cycloa~lkyl of 6 to 10
carbons and tertiary-aralkyl of 9 to 12 carbons,
and Al is selected from the group consisting of
hydrogen, a subs~iLuted or llnsubst:ituted primary,
squanderer ter~iary-alkyl of Jo 20 carbons,
alkenyl of 2 to 20 carbons, alkynyl of Jo 20
carbons, cycloalkyl of 5 to lo cartons, arzLkyL of
7 to 14 carbons, aureole of 6 Jo lo carbons, alkoxy
of 1 to 20 carbons, cycloalkoxy of S to 10 carbons0 or aralkoxy of 7 to 12 carbons
when x and y are 2 and z is 1, R is the-same
as defined above, and R1 is selected from the
group consisting of a substituted or unsubstituted
alkaline diradical of 1 Jo 10 carbons, alkynelene
I diradical of 2 to 10 carbons, alkenylene diradical
of 2 to 10 carbons, cycloalkylene diradical of 5
to 10 carbons, Arlene diradical of 6 Jo 10
carbons, alkylenedioxy di~adical of 2 to 10
carbons, oxyalkylenedioxy ox 4 to 10 carbons, and0 cycloalkylenedioxy of 5 to 10 carbons, and
when y and z are 2 and x is 1, R is selected
from the group consisting of a substituted or
unsubstituted di~tertlary alkaline diradical of 7
Jo 10 carbons, di-tertiary-alkynelene diradical of
8 to 10 carbons, di-te~tiary~cycloalkylene
diradical of 7 to-12 carbons t and
di-ter~iary~aralkylene diradical of 12 to 18
carbons, and Al is the same as when x, y and z are
1, .
the substituents for R and Al being lower
alkyd of l to 4 carbons, Of, F, Bra cyan,
car boxy, lower alkoxycarbonyl, lower acyloxy,
airlocks of 7 to lo carbons, lower alkoxy and
IH3
R200 C-
C~3
wherein R2 is the same a defined above for R when
X 9 y and z are 1.
Specific expels of particularly preferred
peroxyesters of this invention are t-butyl
peroxybenzoate, t-butyl peroxyac~tate, t-butyl
peroxyisobutyrate, t-butyl
porks ethylhexanoa~e J bottle peroxypivalate,
timely peroxypivala~e, t-butyl peroxyneodecanoate,
t-butyl peroxymaleio acid di-t-butyl
I diperoxyphthalate, 00-t bottle 0-isopropyl
peroxycarbonate,
2,5~dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane,,
2-5-dimethyl-2,5~bi~benzoylperoxy)hexane, timely
peroxy-2-ethyl-hexanoate, timely peroxybenzoate,
US 00-t bottle 0-2-ethylhexyl monoperoxycarbonate,
- 10 -
Diablo diperoxya~elate, and OO-t-~nyl
0-2 ethylhexyl monoperoxycarbonate.
In activated cure systems, activity is
independent of half-life temperatures of
peroxides. Therefore, the preferred peroxyester
is one which exhibits good thermal stability and
ease of handling. In this respect, t-butyl
peroxybenzoate is a preferred initiator. In this
invention one can use mixtures of two or more
peroxides wherein at least one of the peroxides is
a peroxyester as defined above. These types of
mixtures are useful for obtaining specific
processing or economic advantages. Thus, a
mixture of t-butyl peroxybenzoate sod cumin
hydroperoxide leads to rapid gel times and fully
cured resin even in thin layer. This mixture
would have the added advantage of being less
expensive. Along similar lives, one can use a
mixture of t-butyl peroxybenzoate and
I l,l-di(~-butylperoxy) cyclohexane might be used to
cure the resin at ambient temperatures. The
undecomposed peroxyKetal could then be thermally
activated by post curing the part a elevated
temperatures. Cured resin with low residual
monomer content could then be obtained more
rapidly than in the absence of the peroxyke~al
In practicing the process of this invention,
an amount of peroxye.ster effective for providing
an optimum cure rate is added Jo the unsaturated
polyester resin. Generally, the peroxyester
compound is added in a proportion to provide from
about 0.1 to ablate 5 . O parts, and preferably about
OHS to 2.0 parts peroxyester per 100 parts by
weight of the polyester no in (phi) includillg
unsaturated monomer The amount of peroxyester
can be varied within this particular range
depending on the no cult desired.
When a mixture of peroxides is used, the
total concentration of initiator would be
preferably about 0.5 to 2.0 parts by weight per
100 parts by weight of the polyester resin
including unsaturated monomer s ) . In this case,
the concentration of pero~yester(s) would be a
least about 0.1 to 1.0 pa by weight per 100
parts by weight of polyester resin.
The Marquette compounds which are used in this
inventiorl are those which contain the markup to
radical or metal salt fumed therefrom and have
the general s true lure
(R )m(S)n~M)~S'
where I and n are 1, 2 or 3 and an is 1 or 2, with
the provisos that
when m, n, and are l, M is hydrogen and R3
is selected from the group consisting of a
substituted or unst~bstitu~ed alkyd of 1 to 18
carbons, aureole of 6 to 14 cartons, cycloalkyl of 5
to 10 carbons, aralkyl of 7 to 14 carbons,
if -R2
(Al) 2N-C---- ,
heterocyclic of 2 Lo 10 carbons and 1 to 3
nitrogen, sulfur or oxygen atoms, wherein Al and
R2 are independently selected from the group
consisting of hydrogen, lower alkyd of 1 to 4
cartons, aureole of 6 to 12 carbons and cycloalkyl of
5 to 10 carbons, and
when m and n are 2 or 3, Crisp 1, M is
selected from the group consisting of copper and
iron, and R3 is the same as mentioned above, and
when n and are 2 and m is 1, M is hydrogen
and R3 is selected from the group consisting of a
substituted or unsubs~ituted alkaline diradical of
2 to 20 carbons, cycloalkylene diradical o f 5 to
lo carbons, Arlene diradical of 6 to 14 carbons,
and a heterocyclic diradical of 2 to 10 carbons
and 1 to 3 nitrogen 9 slur or oxygen atoms, and
wherein substations for R3 being selected from
lower alkyd of 1 to 4 carbons F, C1, Bra cyan,
alkoxycarbonyl of -l to 6 carbons, acyloxy ox 1 to
20 carbons, airlocks of 7 to 10 cartons and a~koxy
of 1 to 6 carbons.
Compounds in which the Marquette grout can
exist in equilibrillm with another chemical structure
are useful. For example, in the case of Thor
or substituted Theresa the Marquette radical can
exist in equilibrium
/ NH2 NH
SAC HS-C
~NH2 NH2
Thor Isothiourea
Examples of the variety of Marquette compounds
which can be used in this invention are as
follows: 2-mercaptobenzothiazole (MET),
n-dodecylmercaptan, n-octadecylmercaptan,
d-limonene dimercaptan, methyl-3-mercaptopropionate,
Marquette ethyl palpitate, dibutyl mercaptosuccinate,
isothiourea, ethylene isothiourea, ferrous
mercaptobenzothiazolate, and cupric mercaptobenzo-
thiazolate.
One of the preferred Marquette compounds is2-mercaptobenzothiazole (MET). This compound is
preferred because it produces significant
acceleration, has essentially no odor, and is
available commercially in large quantities.
14 -
Mixtures of Marquette compounds can also be
used in this invention. Such mixtures allow one
to regulate the rate of cure and, thus, obtain
better processing control. In addition mixtures
5 of markup compounds may also be used to improve
the extent of cure , i . e ., reduce surface tackiness
especially in thin molded samples.
Generally the amount of Marquette compound
required is from about 0.05 Jo 5.0 parts and
I preferably from about O .1 kiwi 2 . 5 parts Marquette
compound per 100 parts by weight of the polyester
rouser (phi) including unsoured monomer. The
amount of markup compound can be varied within
this particular range dependirlg on the result
lo de trod.
Organic salts of transition metals such as
cobalt and vanadium are commonly used as
accelerators (promoters. Off the polyester
resin is prepromoted so thaw the fabricator needs
only to add the required peroxide. Keeping this
in mind, we have found that inorganic salts of
metals such as copper and iron are particularly
preferred as accelerators in our invention. These
inorganic salts include hydrated salts of copper
and iron. Specific examples include cuprous
chloride, cupric chloride, ferris chloride anal
- 15 - .
ferrous chloride. These salts act as good
accelerators and in addition provide long
shelf-life to the prepromo~ed resin, which is very
desirable.
S Salts of cobalt and vanadium have the added
disadvantage of giving a strong color (pink or
green respectively) lo> the cured piece. This is
especially undesirable it clear gel coat
applications. Using halide salts of copper and
iron as accelerators in this invention overcomes
this disadvantage.
Specific examples of useful metal salts
include cuprous chloride, cupric chloride 9. ferris
chloride, ferrous chloride, and their hydrated
salts.
An essential compound of this invention is
cupric chloride, since it is effective at
extremely low concentrations. A particularly
preferred mixture of metal compounds is thaw of
cupric chloride and ferris chloride, since this
mixture offers Improved reactivity as compared to
the use of a single metal compound while providing
increased shelf life of the prepromoted resin.
For example, when the accelerator system consists
of a combination of a mercaptan, such as
mercaptobenzothiazole (MET), and a metal salt,
i
16 -
such as cupric chloride, the shelf-life of the
resin is less than eight hours. However, when
ferris chloride is added in addition to cupric
chloride, the shelf-1ife is greater Han 2 months
S and, ion addition 9 the cure activity is increased.
To facilitate mixing of the metal compound
with the resin, it is preferable to first dissolve
the metal compound. Suitable solvents would
include, Tulane, zillion, dimethylformamide,
lo mineral spirits, dim ethyl sulfoxide, water,
methanol, diethyleneglycol, ethylene chloride,
methyl ethyl kitten, ethyl acetate, hexane,
Delilah phthalate and Sterno.
Generally the optimum amount of metal
compound(s) used is dependent upon the specific
metal compound and is influenced by compound
characteristics such as volubility and
compatibility in the system. Generally 0~00001 to
0.50 part and preferably from about Oily to 0.05
29 part of metal per 100 parts by weight of the
polyester resin (phi) including unsaturated
monomer.
It is well known to those skilled in the art
aye organic peroxides and accelerators
(promoters) should not be mixed together directly.
Such direct contact between peroxides and
I
promoters can result in hazardous decomposition of
the peroxide. To avoid such contact the reactive
ingredients are preferably added to the resin in
the following order: metal solutes Marquette
compounds peroxyester(s). Each ingredient
should be thoroughly mixed into the resin before
adding the next ingredient. The peroxyester may
also be added as- a second component in the
processes (ego spray-up) where the equipment it
designed to dispense a mixture of resin and
promoters as one coupon and peroxide as a
separate component.
- 18 -
EXAMPLES
The following examples are provided Jo
illustrate preferred embodiments of the invention
and are not intended to restrict the scope
thereof. All parts are parts by weight and all
percentages are expressed a weight percentages.
EXAMPLE I
Into a g oz. waxed paper cup was weighed 100
grams of Laminac 4123 resin followed by 0.3 grams
of merc~p~obenzothiazole. After mixing
thoroughly, 0.0003 grams of cupric chloride was
added as a 5% solution in methanol. After mixing
thoroughly, lo gram of t bottle peroxybenzoate was
added Jo the resin. A timer was started and the
peroxide was mixed thoroughly and uniformly into
the resin with a go ass stirring rod. The resin
mixture was poured into a 4 oz. glass jar which
was immersed in a 30C constant temperature water
bath to the level of the resin. A thermocouple
was located at the center of the resin mass to
record exotherm temperature. The time when the
resin golfed was recorded as the gel time. The
- resin was Conrad golfed when inserting a
stirring rod and raising a portion of the rev n
- 19 -
out of the jar resulted in a string of resin that
would snap instead of stretch elastically. The
time a which the peak temperature was reached was
recorded as the cure time. The peak exo~herm
temperature way also recorded. The Berkeley
hardness was measured aver Z4 his. at room
temperature. The range of 10 hardness readings
was recorded, it 40-45.
Parts by weight
1 2 3
Laminac 41~3 (a) 100 100 100
t-Butyl Peroxybenzoate 1.0 1.0 1.0
Mercaptobenzothia~le - 0.3 0.3
Cupric Chloride D - - 0.0003
Gel Time (mint) 200 hrs.240 min. 16. min.
Cure Time (min.) - - 34 min.
Peak Exotherm Ç~ - - 155
Berkeley Hurriedness his.) - 40-45
(a) Orthophthalic type resin, USES. Chemicals
(b) added as a 5% solution ox Quickly in methanol
(c) Measured after 24 his. a room temperature using
Berkeley impresser (yodel 934-1), Barber-Colman Co.
- 20 -
EXAMPLE II
The following experiments (1-:12) illustrate
the variety Go peroxyesters which may be
effectively used in this invention. The procedllre
used was that defined in.Ex~mple I. The resin
formulation is shown below:
Parts by Wt.
Resin (OF Eye) 100.0
Mercap~obenzothiazole 0.40
5% Curl OH O in methanol 0.03
50% Fake OWE in water 0.03
Peroxide (a shown in table)
Peroxyest~rGel Cure Peak Bar-
Expel Perox~esters C got
1 t-Butyl Peroxybenzoate 1.0 . 1 .0
2 t-Butyl Peroxy-2-ethyl-
hexanoate 1.0 6.5 14.5 204 30-35
3 2,5 Dimethyl-2,5-bis(2-
ethylhexa~oylperoxy~-
hexane 0.5 12.5 23.0 188 25-30
4 t-Butyl Peroxyi~obutyrate 1.0 6.0 14.0 208 30-35
S OO-t-Butyl O-Isopropyl
Monoperoxycarbonate 1.0 10.0 21.0 236 30-40
6 t-Butyl Peroxyace~ate 1.0 8.0 .17.0 209 30-40
I 7 Di-~-Butyl Diperoxyaz~la~e 0.5 10.0 21.0 193 25-40
8 2,5-Dimethyl-2,5-bis~b~n-
zoylperoxy)h~xane 0.5 11.0 24.0 184 20-35
hexanoate 1.0 6.0 14.0 205 30-40
10 D -t~But~Jl Diperoxy- 16.0 195 35-40
11 t-butyl perox~maleic acid 1.0 7.5 19.0 199 30-40
Yeroxyest:er Gel Cure Peak Bar-
Jo Peroxyesters Conc.(phr) (mix) (mix) C got
._ .
12 timely peroxybenzoate 1.0 7.5 18.0 205 35-40
13 bottle 0-2 ethylhexyl- 1.0 11.5 22.0 201 30-40
peroxycarbonate
Lo timely 0-2-ethylhexyl- 1.0 12.0 23.0 197 30 40
peroxycarbonate
teakettle peroxyneo- 1.0 14.0 Z2.5 191 30-40
hexanoate
(a) Isophthalic polyester resin containing
approximately 45% by weight styrenes monomer.
Resin solids have an acid value of lo.
available from Owens Corning Fiberglass.
I
22 -
SAMPLE III
The following experiments compare the cure
activity obtained using the process of this
invention to the cure activity obtained with a
S common (standard) cure system.
To facilitate addition of the promoter to the
resin a solution of the mercaptans and metal salts
was prepared as a master batch using dim ethyl
formamide as the solvent.
10 Promoter Solution A
Ingredient Wt.%
Marquette benzothiazole 48.1
Quill 2H2 0.10
Focal 2.75
lo n-dodecylmercaptan 1.72
N,N-dimethyl formamide 47.3
Promoter solution A was added to the
polyester resin (OSSIFY) and after mixing
thoroughly t-butyl peroxybenzoate was added. The
"standard" cure system used for comparison
consists of cobalt neodecanoate (6%) and a
commercial methyl ethyl kitten peroxide containing
9% active oxygen (sold under the trademark
LEPROUSLY DDM-9). Concentrations and cure activity
are shown in the hollowing table. The resin was
cured in a 5.5" diameter plastic mold. Thickness
a
I.,
of the cured resin was approximately 0.23".
Initial resin temperature was 22C.
Experiment # 1 2
OF Resin Eye (g) 100 100
S Promoter Solution A (g) 1.46
t-butyl peroxybenzoate (g) 0.50
6%-Cobalt neodecanoa~e (g) - 0.80
Leprously DDM-9 (go 1.2
Cure Active
10 Gel Time (mint I 5.0
Time to peck . 21.0 22.0
exotherm (mix)
Peak Exotherm (C) 116 43
Surface Tackiness none sticky
15 48 ho Berkeley Hardness:
top 30-40
bottom 35 40 0
This example demonstrates what this invention
gives good cures at much lower peroxide
concentrations than are possible with a standard
cure system.
EXAMPLE IV
EFFECT OF VARIOUS MARQUETTE COMBO W DO
_ _
This example illustrates the variety of
mercap~an compounds which have been found useful
5 in this invention.
Grams
Laminac 4123 100
5% CuC12(C~ 0-007
50% Fake 0.025
10 t-bu~yl peroxybenzoate 1.0
(c) Solvent is methanol (d) Solvent is
dimethylformamide
Results:
EYE 0.2 Phi merca~tan 30C Gel Mooney)
1. Control (no mercaptan) >500
2. n-Octadecyl mercaptan 1.0
3. d-limonene dimercaptan 1.0
4. Methyl-3-mercaptopropionate 0.5
S. erect ethyl palm 35.0
6. Dibutyl mercapto~uccinate I
- 25 -
EXAMPLE V
EFFECT OF VARIOUS COPPER SALTS
ON CURE ACTIVE TRY AT 30C
The following results indicate that both
organic and inorganic salts of copper are useful
in this invention.
Parts by Weight
Item 1_ 2 3
Laminac 4123 100 100 10V
t-Butyl peroxybenzoate1.0 1.0 1.0
-Mercap~ob~nzo~hi~zole0.3 0.3 0.3
8% Copper naphthenate0.24 - -
Copper swept - 0.10
Cupric chloride - - 0.0003
Gel time (mint 16 24 16
Cure time (mix) 28 38 34
Peak Exotherm (C) 163 157 155
Berkeley Hardness (24 hr)40-45 40-45 40-45
- 26 -
SAMPLE VI
effect Of Quick Concentration on Cure Activity]
This example illustrates the effect of the
concentration of cupric chloride on the cure
S characteristics of an orthophthalic type
unsaturated polyester resin at 30C. Gel time,
cure time, and peal exotherm temperature were
determi~cd using thy standard SPY procedure
Cupric chloride was added to the following resin
10 formulation.
Grams
Laminac 4123 100
Mercaptobenzothiazole 0.2
t-Butyl peroxybenzoate 1.0
15 5% Quick (as in table below)
Results:
OWE CuC12~g) Conc.(ppm) Gel (mix) cure (mix) Peacock) (24 ho
0 007 1.6 36 156 40-45
0 013 3.3 8 22 157 40-45
~.025 6.0 3 15 158 40-45
0 Q3~ 8.0 1 12 lS8 40-45
0 047 11.0 1 11 157 ~-45
0.~72 ~7.0 I 12 146 30-40
0.~2 . 28 ~0.5 I 126 0-30
. Results indicate that cure time goes through
a minimum in rheology of 10 15 Pam copper and thaw
high levels of copper, for example 28 Pam, can
cause slower reactivity and result in poor cures.
(a) SPY test procedure reference" Thea Annual
Technical conference 1969 Reinforced
Plastics/Composites Division, The Society of
the Plastics Industry.
by 5% Quickly in methanol.
EXAMPLE YIP
This example illustrates the present
mention (Experiment I and also illustrates the
fact that initiators other Loan peroxyesters do
not function. Experiment Nos. 1 and 2 illustrate
the dramatic effect of Fake on eke shelf
Experiment No. 4, 6 and 9 illustrate thaw
peroxyket~ls, dozily peroxides and dialkyl
peroxides respectively do not function in the
present invention.
Experiment No. 10 illustrates that qua ternary
minim compounds asp a necessary part of the
accelerator system for dozily peroxides such as
bouncily peroxide USA US. 2,946,770).
73
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IT OWE 0 3
En us
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o o to
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N o l X
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I 3 I e o v ox x
r3. 3 3rl a) I 0
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to Do i If) or
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- 29 -
EXAM YE VI I I
This example illustrates the use of metal
salts of Marquette compounds as accelerators for
persisters .
1 2 3_ 4
Laminac 4123 100 100 100 100
Cupric mereaptobenzo-
thia:zolate - 1. 5 0 .1 0 .1
Ferrous mercaptoc~enzo-
thiazolate - - 0 . 4
Mercaptobenzo~hiazole - - - 0 . 4
Tuttle peroa~ybenzoate 1. 0 1. 9 1. 0 1. 0
Room tempt gel time (Mooney 56 21 13
- 30 -
EXPEL IX
This example illustrates the use of peroxide
mixtures.
1 2 3
S Resin OF Eye 100 100 100
Mercaptobenzo-
thiazole 0.70 0.70 0.70
Dodecyl mercaptan 0.02 0.02 0.02
5% Quick in dim ethyl
formamide 0.02 0.02 0.02
50% Fake in water 0.04 0.04 0.04
t-Butyl proxy-
Bassett 1.0 0.5 0.6
t-Butyl proxy 2-
e~hylhexanoate - 0.5
1,1-Bis(t-butylperoxy~
3,3,5-trimethyl cycle-
hexane - - 0.4
Room tempt Mel time Mooney) 10 10 11
experiment No. 2 illustrates the use of a
mixture of two peroxyesters while experiment No. 3
illustrates the use of a mixture consisting of a
peroxyester in combination with a peroxyketal.
