EMULSIONS AU PEROXYDE, ET PRODUIT D'ENDUCTION QUI LES RENFERME

PEROXIDE EMULSIONS AND SIZING COMPOSITION CONTAINING SAME

Abrégé anglais

Abstract of the Disclosure
An aqueous emuision of a solid, water insoluble or limited
soluble organic peroxide is provided that has improved stability, dilute
bility and safety but still having an average particle size of 1.5 microns
or less and a good particle size distribution. The emulsion has from about
10 weight percent of the emuision of a solid peroxide selected from the
group of hydroperoxide, ?-oxy and ?-peroxy hydroperoxides, dialkyl
peroxides, aldehyde and ketone peroxides, diacyl peroxides, pernxyesters,
peroxy acids, peroxydicarbonates, monoperoxycarbonates and perketals.
The emulsion also has a hydrocarbon solvent having a high kauri-
but and number if the organic peroxide has a substantial amount of aro-
maticity and a low kauri-butanol number if the organic peroxide has little
or no aromaticity and one or more nonionic emulsifiers and at least about
45 weight percent of water. The method of preparing the emulsion involves
solubilizing the peroxide in the hydrocarbon solvent and adding the emul-
sifiers and emulsifying. The emulsion of organic peroxide can have many
uses including uses in vinyl and diene polymerization, and being used in a
sizing composition for glaes fibers to produce treated glass fiber strands
that can be used in polymer reinforcement such as the reinforcement of
polyolefins, polyemides and polyeater.

Revendications

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An aqueous emulsion with good stability and dilutability and
with an average particle size of around 1.5 microns or less and good par-
ticle size distribution of an organic peroxide that is a solid at about
20°C and that has limited solubility or is insoluble in water, comprises: a) about 1 to about 70 percent by weight of the solid
organic peroxide with limited water solubility or
water insoluble selected from the group consisting
of hydroperoxides, ?-oxy, and ?-peroxy hydro-
peroxides, dialkyl peroxides, aldehyde and ketone
peroxides, diacyl peroxides, peroxyesters, peroxy
acids, peroxy dicarbonates, monoperoxycarbonates
and perketals,
b) about 1 to about 70 weight percent of a hydrocar-
bon solvent having a kauri butanol number from
about 10 to about 60 when the organic peroxide is
substantially aliphatic, or having a kauri butanol
number of about 40 to about 100 when the organic
peroxide has substantial aromaticity,
c) about 1 to about 15 weight percent of one or more nonionic
emulsifiers having an HLB value in the range of about 9
to about 20 and selected form:
i) nonionic emulsifiers having an HLB from
about 12 to about 20,
ii) nonionic emulsifiers having an HLB from
about 6 to about 12, and
iii) nonionic emulsifiers having an HLB from
about 9 to about 15
32

wherein the nonionic emulsifiers are selected from
the group consisting of polyalkylene glycol ethers,
alkylaryl polyether alcohols, polyoxypropylene-
polyoxyethylene condensates, and phenoxypolyethoxy-
ethanols ethoxylated alcohols, ethoxylated fatty
acids, fatty esters and oils; fatty acids, glycol
esters, monoglycerides and derivatives, sorbitan
derivatives and sucrose esters and derivatives
and wherein the emulsifiers selected from each HLB
group are used in an amount to give an HLB for the
system in the range of about 9 to about 20, and
d) at least about 20 weight percent of water.
2. Aqueous emulsion of Claim 1 wherein the organic peroxide has
a half-life exceeding 60 hours at 212°F. (100°C.) and 20 minutes at 300°F.
(149°C.).
3. Aqueous emulsion of Claim 1 wherein the organic peroxide is
alpha, alpha' bis(t-butyl-peroxy)-diisopropyl benzene.
4. Aqueous emulsion of Claim 3 wherein the hydrocarbon solvent
has a kauri-butanol number of around 92 to 93.
5. Aqueous emulsion of Claim 4 wherein the peroxide to solvent
ratio is at least 1/.4.
6. Aqueous emulsion of Claim 1 in an amount sufficient to pro-
vide an amount of active peroxide in an aqueous treating solution in the
range of about 0.1 to about 6 weight percent and combined with about 0.5 to
about 10 weight percent of a coupling agent and about 70 to about 99 weight
percent water to form a sizing composition for glass fibers.
7. Aqueous emulsion of Claim 6 in a sizing composition having
0.1 to 6 weight percent of a lubricant.
33

8. Aqueous emulsion of Claim 6 wherein the coupling agent is
vinyl tris (beta methoxy ethoxy) silane.
9. Aqueous emulsion of Claim 7 wherein the lubricant is a cat
ionic, acid solubilized fatty acid amide.
10. Aqueous emulsion of Claim 7 in a sizing composition having
0.5 to about 12 weight percent of a film-former.
11. Aqueous emulsion of Claim 10 wherein the film-former is a
vinyl acetate copolymer.
12. Aqueous emulsion of Claim 1, wherein the
one or more nonionic emulsifiers is a blend of three nonionic emulsifiers
comprising:
i) one nonionic emulsifier having an HLB from about
12 to about 20,
ii) one nonionic emulsifier having an HLB from about
6 to about 12, and
one nonionic emulsifier having an HLB from about
9 to about 15, and wherein the nonionic emulsifiers
are selected from the group consisting of poly-
alkylene glycol ethers, alkylaryl polyether alcohols,
polyoxy propylene-polyoxyethylene condensates, and
phenoxypolyethoxyethanols, ethoxylated alcohols,
ethoxylated fatty acids, fatty esters and oils;
fatty acids, glycol esters, monoglycerides and deri-
vatives, sorbitan derivatives and sucrose esters
and derivatives and wherein the emulsifiers selected
from each HLB group are used in an amount to give
an HLB for the system in the range of about 9
to about 20.
34

13. Aqueous emulsion of claim 12, wherein the water present is at least
about 45 weight percent.
14. Aqueous emulsion of Claim 12 wherein the three emulsifiers
are present in equal amounts.
15. Glass fibers with dried residue of sizing composition of
Claim 6.
16. Glass fibers with dried residue of sizing composition of
Claim 7.
17. Glass fibers with dried residue of sizing composition of
Claim 10.
18. Polymer matrix reinforced with glass fibers of Claim 15.
19. Polymer matrix reinforced with glass fibers of Claim 16.
20. Polymer matrix reinforced with glass fibers of Claim 17.
21. Reinforced polymer matrix of Claims 16 or 17 wherein the
polymer is polypropylene.
22. Method of preparing an aqueous emulsion of alpha, alpha'
bis(t-butyl peroxy)-diisopropyl benzene comprising:
a) solubilizing the alpha, alpha' bis(t-butyl peroxy)-
diisopropyl benzene in a hydrocarbon solvent having
a kauri-butanol number in the range of about 70 to
about 100 in a ratio of peroxide to solvent of at
least about 1 to about 0.4,
b) adding about 1 to about 15 weight percent of the
emulsion one or more emulsifiers selected from

1) one or more polyalkylene glycol ethers, or
2) one or more alkylaryl polyether alcohols, or
3) one or more polyoxypropylene-polyoxyethlylene
condensates, or
4) one or more phenoxypolyethoxyethanols or in any
mixture thereof in ratios to give an HLB for
the one or more emulsifiers in the range of
about 9 to about 20, and
c) adding water in an amount of at least about 20
weight percent of the emulsion to emulsify the
peroxide, solvent and one or more emulsifiers into
an oil-in-water emulsion.
23. Method of Claim 22 wherein the one or more emulsifiers is a
three emulsifier blend comprising:
0.1 to about 5 weight percent of the emulsion of
trimethyl nonyl polyethylene glycol ether with an
HLB of 11.7,
0.1 to about 5 weight percent of the emulsion of
nonylphenoxypoly(ethyleneoxy)ethanol with an HLB of
13, and
0.1 to about 5 weight percent of the emulsion of
condensates of ethylene oxide with hydrophobic
bases formed by condensing propylene oxide with
propylene glycol having an HLB of 17Ø
24. Method of Claim 23 wherein the trimethyl nonylpolyethylene
glycol ether and nonylphenoxypoly(ethyleneoxy)ethanol and first portion of
the total amount of ethylene oxide condensate emulsifiers are added sepa-
rately or together to the peroxide-solvent mixture and the remaining
portion of the ethylene oxide condensate emulsifier is mixed in around a
50/50 mixture with water and added to the mixture.
36

25. Method of Claim 23 wherein the hydrocarbon solvent has a
kauri-butanol number of around 92 to 93.
26. Aqueous emulsion prepared by method of Claims 22 or 23.
27. Aqueous emulsion prepared by the method of Claims 24.
28. An aqueous emulsion with an average particle size of around
1.5 microns or less and with good stability of an organic peroxide that is
a solid at about 20°C. and that has limited solubility or is insoluble in
water and that has a half-life exceeding 60 hours at 212°F. (100°C.) and
20 minutes at 300°F. (149°C.), comprising:
a. about 1 to about 70 percent by weight of an organic
peroxide having the formula:
(R-O-O-)XR'
where R is a tertiary alkyl, aryloyl or alkyloyl
radical with or without a phenyl group attached to
the tertiary carbon atom,
where x is a number 1, 2 or 3,
where R' or the same as R or is an organic moiety having the
formula:
<IMG>
-37-

where RIV is selected from phenyl, alkylphenyl,
alkyne, or alkyl radicals having the formula
(CH2-CH2)n where n is 1, 2 or 3;
where R" and R"' are selected from hydrogens,
(R-O-O-), alkyl, cycloalkyl, aralkyl, or aryl
hydrocarbon radicals, where when RIV is a phenyl
group either R" or R"' hydrocarbon radicals are
radicals selected from phenyl, aryl or alkyl with
more than seven carbon atoms;
b. about 10 to about 55 weight percent of a hydro-
carbon solvent having a kauri-butanol number from
about 10 to about 60 when the organic peroxide has
R, R', R", R"' and RIV radicals having aliphatic
radicals or a minor amount of aromaticity, or hav-
ing a kuari butanol number of about 40 to about
100 when the R, R', R", R"' and RIV have a sub-
stantial amount of aromaticity
c. about 1 to about 15 weight percent of one or
more emulsifiers selected from
i) one or more polyalkylene glycol ethers, or
ii) one or more alkylaryl polyether alcohols, or
iii) one or more polyoxypropylene-polyoxyethylene
condensates, or
iv) one or more phenoxypolyethoxyethanols giving
an HLB for the one or more emulsifiers in the
range of about 9 to about 20; and
d. at least about 20 weight percent of water.
-38-

Description

7~3
PEROXIDE E~ULSIONS AND SIZING
COMPOSITION CO~TAINING SA~E
Background of the Invention
The present invention is dirPcted to an aqueous emulsion prepared
from a solid organic peroxide, an aqueous size containing the emulsion, and
sized glass fibers. More particularly, the present invention is directed
to an aqueous peroxide emulsion made from a solid organic peroxide, aqueous
treating solution containing same, and sized glass fibers prepared for
bonding to polymers in the reinforcement of polymeric materials.
Organic peroxides that decompose by initial cleavage of the
oxygen-oxygen bond to produce free radicals act as initiators for vinyl
monomers and other vinyl containing materials. There are over fif~y -
different organic peroxides classified into nine major types that are used
commercially in the polymer and resin industries. The half-life (Tl/2)
which is given as a function of te~perature can range for the various
peroxides from a short half-life at 0.01 hours at an elevated temperature to a
longer half-life of 1,000 hours at lower temperatures. The
half-liEe is a measure of the thermal stability of organic peroxides by
measuring the time for decomposition of 50 percent of the original amount
of peroxide which is a half~life for a first-order reaction. These organic
peroxides have been used in the polymerization of vinyl monomers to produce
bulk polymers, polymer films and other polymer compositions.
Depending on the thermal stability and other physical charac-
teristics of the particular peroxides, ~arious organic peroxides can be
used in different forms when acting as an initiator or curing agent for
vinyl polymerization. Some of the organic peroxides such as the highly
~f q~ .

'7ti~3
reactive percarbonates are so unstable that they must be shipped as a
frozen solid or an undiluted liquid under refrigeration. Some less reac
tive organic peroxides, such as lauroyl peroxide and dibanzoyl peroxide are
more stable ae room temperature and can be activated with greater facility
and with less stringent precautions. For example, the relatively more
stable benzoyl peroxide, which is a solid at room temperature having a
melting point of 106 to 107C. can be used as granules or crystals or in a
thick paste compounded with a phlegmatiser such as tricresyl phosphate.
Also, benzoyl peroxide can be used in an aqueous solution as is shown in
U.S. Patent 2,343,084 (Smith) wherein the small amount o benzoyl peroxide
is dissolved in one or more polyrnerizable conjugated compounds and may also
contain a resin in solution. This solution can be combined with a water
solution of a partially saponified polyvinyl acetate. ~lso, it has been
suggested in U.S. 3,795,630 (Jaspers et al) to have a chemically stable
non-separating organic peroxide composition of an organic peroxide which is
a solid at room temperature. The composition is obtained by mixing the
solid peroxide, like benzoyl peroxide, with a liquid phlegmatiser like
phthalate plasticizers, epoxidized soya bean oil and glycols, and a hydro-
phobic alkyl group containing silica. In addition, it is sho~n in U.S.
Patent 4,039,475 (Jannes) to have a stable, pumpable aqueous suspension of
organic peroxides containing one nonionic emulsifier having a maximum HLB
value of 12.5 and a second nonionic emulsifier having a minimum HLb value
of 12.5 or a second emulsifler that is anionic.
Organic peroxides such as aryl alkyl peroxide like dicumyl
peroxide; ester peroxides and aromatic and aliphatic acyl peroxides have
been used in compositions for sizing fibrous materials for use in polymer
application as shown in U.S. Patent 3,013,915 (Morgan). These peroxides

:~i76~73
which have low volatilities and low decomposition temperatures, usually
below about 180F. (8~C.), are deposited from an organic solution. In the
composition along with the organic peroxide, there is present a suitable
coupling agent.
It is also known as is sllo~n in U,S. Patent 3,837,898 (McCombs et
al) to form a polybutadiene emulsion that contains heat activated curing
agents to operate as a catalyst in the size coating on the fibers. The
~uring agents are the well-known free radical catalysts such as organic
peroxides, e.g., benzoyl peroxide, lauroyl peroxide, tert-butyldiethyl
peracetate, diacetyl peroxide, as well as inorganic peroxides, such as
potassium persulfate. The polybutadiene emulsion is prepared by mixing the
polybutadiene with an emulsifying agent and with benzoyl peroxide. To this
mixture there is added suf~icient water to form an emulsion of the liquid
polymer in aqueous medium. The emulsion is then mixed with a mixture of
water, glass Eiber anchoring agents and a gel agent and the resulting com-
position is homogenized to form a sizing composition having a solids con-
tent of about 2.80 and a p~ of about 10.0 to 10.5. The emulsiEying agents
that can be used are any conventional emulsifying agents, but preferably
are the nonionic emulsifying agents such as the polyoxyethylene derivatives
of fatty acid, partial esters of sorbitol anhydrides, or the polyoxyethyl-
ene derivatives of fatty alcohols, or of the alkyl substituted phenols.
It was recently suggested in IJ.S. Patent 3,849,148 (Temple) to
prepare an aqueous size for glass fibers to be used in reinforcing poly-
olefin materials wherein the size contained a coupling agent, a heat stable
organic peroxide, a nonionic surfactant and usually a lubricant or softener,
and optionally a film-former. The heat stable organic peroxide includes
organic peroxides having peak decomposition temperatures above about 200F.

- ~L'7~;~73
(93C.), for example, alpha alpha' bis(t-butyl peroxy)-diisopropyl benzene,
tris(t-butyl peroxy)-diisopropyl benzene, 2,5(t-butyl peroxy)hexane, and
2,5(t-butyl peroxy) hexyne. These heat stable peroxides are used in emul-
sions with nonionic surfactants such as polyethoxy phenols being prepared
and dispersed in ~ater containing a coupling agent. Emulsions prepared at
temperatures in the range of 120F. (49C.) to 210F. (99C.) including
isooctyl phenyl polyethyo~y ethanol are particularly useful. Other useful
nonionic surfactants belonging to the class of polyethyoxy phenols are
nonyl polyethoxy ethanol and alkyl etherpolyethoxyethanol. Other nonionic
surfactants which are useful are polyalkylene glycol ethers, alkyl poly- -
ether alcohol and alkyl aryl polyether alcohol. The emulsion is prepared
by thoroughly mixing the peroxide initiator with the nonionic surfactant
maintaining the temperature of the mixture above the melting point of the
free radical initiator. Suitflble temperature control i~ possible by
immersing the mixing vessel in a bath of boiling waterO ~fter thoroughly
mixing the free radical peroxide initiator with nonionic surfactant, water
is slowly added to the mixture at a temperature above the melting point of
the free radical initiator, preferably in the range of about 140~F. (60C.
to 150F. (66C.) until ~he emulsion inverts. The emulsion is slowly
cooled to ambient conditions by continued water addition. This emulsion is
then 910wly added to the aqueous mixture containing the coupling agent and
the remaining water is added to the mixture to form an aqueous sizing
composition for treating glass fibers.
In forming an emulsion for use in a si~ing composition for glass
fibers, it is necessary to obtain an emulsion with a small particle size
and that has shear, shelf and process stability, that is, the particles of
the internal ph4se do not coalesce when the emulsion is stirred or is
.'f ~ :

73
stored for a period of time or is applied to the glass fibers. It is
necessary to have an emulsion rather than a dispersion because of the par-
ticle size limitation. An emulsion is a two-phase system consisting of two
incompletely miscible liquids, the one being dispersed as fine droplets in
the other, whereas a suspension is a two phase system where the dispersed
phase is a solid. The particle size and particle size distribution of an
emulsion are controlled by such factors as the quaneity or the efficiency
of the emulsifier, the order of mixing and the type of agitation employed.
The stability of an emulsion depends upon such factors as (1) particle
size, (2) difference between the densities of the material in the internal
phase, which is the liquid broken-up into droplets and of the material of
the external phase, which is the surrounding water, (3) the viscosity of
the emulsion concentrate, (4) the charges on the particles~ (5) choice of
emulsifier type and amount of emulsifier used, and (6~ the conditions of
storage and use, including the temperatures of storage and use, agitation,
dilution, and evaporation.
The average particle size and particle size distribution of the
emulsion are controlled by such factors as the quantity or the efficiency
of the emulsifier, the order of mixing and the agitation employed. The
average particle size and particle size distribution of the emulsion are
important factors, since large liquid particles or droplets in the emulsion
or, for that matter, particles of solid material as in a suspension ~ould
not provide an adequate unifonn coating to the glass fibers. Also solid
particles would abraid the glass fibers, and large liquid particles would
cover the surface of the glass fiber in a spotty fashion leaving hiatuses
in the coating along the fibers that as a result would not adequately
contact the matrix resin to be reinforced.

~71~67~3
The emulsion in a si~ing composition for glass fibers must be
diluted to the extent of approaching a water thin liquld in order to facili-
tate application to the gla8s Eibers during formation of the fibers.
~ilution of an emulsion, especially dilution to the extent of a water thin
liquid, can lead to an unstable emulsion. Also, the emulsion in a sizing
composition must be shear stable to withstand the mixing of the sizing
composition before being applied to the glass fibers. In addition, the
emulsion must be shelf stable for periods of three days to more than a week
so that the material may be stored before application to the glass fibers.
lD Also, the emulsion must be process stable so it can be applied to the
glass fibers.
~ problem that has recently surfaced with the use o~ heat stable,
solid organic peroxides i9 that when they are used in an emulsion which i9
formed at tempera~ures above the melting point oE the peroxide the result-
ant emulsion tha~ is used at temperatures below the melting point of the
peroxide tends to have particle sedimentation or particle creaming.
An additional problem with the use of solid organic peroxides
in aqueous treating solutions in general is the chance of a violent decom-
position reaction during the emulsification process. Since the solid
2~ peroxides must ~e heated to be melted, the use of the elevated temperatures
would bring the peroxide closer to its decomposition temperature and a
possible violent reaction could occur if the decomposition temperature is
reached.
It is an object of the present invention to provide a safer
method of preparing an emulsion of a solid organic peroxide that has a
melting point and decomposition temperature at elevated temperatures.

~7~7~3
It is another object of the present invention to provide an emul-
sion of a solid peroxide that can be diluted to have a viscosity approching
the viscosity oE water and tha~ has improved shear stability and improved
shelf stability, and improved process stability.
It is an additional object of the present invention to provide an
emulsion of a heat-stable organlc peroxide that can be used in a sizing
composition for glass fibers~ where the emulsion is shear stable and shelf
stable and process stable within the sizing composition.
It is a further additional object of the present in~ention to
provide processes for preparing an emulsion of a heat-stable organic per- -
oxide and a sizing composition containing same where tlle peroxide emulsion
has improved dilutability, shear stability, and shelf stability, and
process stability and fine particle size with a minimum particle size
distribution.
It is another furt~er object of the present invention to provide
sized glass fiber strands having fibers in the strand with a coating of an
aqueous sizing composition containing a coupling agent, an emulsion of heat
stable organic peroxide that has improved dilutability, improved shear,
shelf and process stability, and a minimum particle size distribution and
fine average particle size; and usually a lubricant or softener; and
optionally a film-former.
The average particle size and particle size distribution of the
emulsion i9 an important factor, since large liquid particles in the emul-
sion, or for that matter particles of solid material as in a suspension
would not efficiently coat the surface of the glass fibers and would be
prone to separate from the sizing composition. In addition, solid hard
particles in the sizing composition could abrade the glass fibers.

7~ 73
SummAry of the_ nvention
The aforementioned ob~ects and other ob~ects of the present inven-
t~on that can be eclectlcally gleaned from the following descrlption are
accompl~shed by having an oil-in-water emulslon of an organic peroxide that
is a solid at 20C. and that forms active free radicals at elevated tempera-
~ures and that is water insoluble or that has limited water solubility, one
or more hydrocarbon solvents, one or more emulslflers wlth an HLB value ln
the range of about 9 to about 20 and water.
Thus~ the present inventlon provides an aqueous emulsion with good
stabllity and dilutability and with an average particle siae of around 1.5
microns or less and good particle slze distribution of an organic peroxide
that ~s a solid at about 20 C. and that has l$mited solubillty or i9 insoluble
~n ~ater, co~prise~:
a) about 1 to ~bout 7U p~rc~nt by ~ei8ht of the ~olid
organic peroxide with l~ited ~ater ~olubility or
w~t~r insoluble selected rom the group con~isting
of hydroperoxides,C~C--Dxy, and ~ -pero~y hydro-
peroxides, d;alkyl perox~de~, aldehyde ant ketone
peroxidea, tiacyl peroxide~, ~eroxyesters, peroxy
acids, peroxy dicarbonate~, monoperoxycarbonates
snd perketsl~,
b) about 1 to about 70 we;ght percent of a hydrocsr-
bon solvcnt having 8 kauri butanol number from
about lO~ to about 60 when the organic peroxide i8
substsntially aliphatic, or having a kauri butanol
number of about 40 to about lO0 when the organic
peroxide has subatantial aro~aticity,
c~ about 1 to about 15 weight percent of one or more nonionic
emulsifiers ~aving an HLB value in the range of about 9 to about
20 and selected from
. ~ .

~'76~73
i) one nonlonic emulsifier having an HLB from about
12 to about 20,
ii) one nonionic emulsifier having an HLB from abou~
6 to about 12, and
iii) one nonionic emulsifier having an HLB from about
9 to about l5
wherein the nonionic emulsifiers are selected from the
group consisting of polyalkylene glycol e;thers, alkylaryl
polyether alcohols, polyoxypropylene- polyoxyethylene con-
densates, and phenoxypolyethoxyethanols ethoxylated alcohols,
ethoxylated fatty acids, fatty esters and oils; fatty acids,
glycol esters, monoglycerides and darivatives, sorbitan
derivatives and sucrose esters and derivatives and wherein
the emulsifiers selected from each HLB group are used in an
amount to give an HLB for the system in the range of about 9
to about 20, and
d) at least about 20 wei~ht percent of water.
In another aspect, the invention provides method of preparing an
aqueous emulsion of alpha, alpha' bis(t-butyl peroxy)-diisopropyl benzene
0 comprising:
a) solubilizing the alpha, alpha' bis(t-butyl peroxy)-diisopropyl
benzene in a hydrocarbon solvent having a kauri-butanol number
in the range of about 70 to about 100 in a ratio of peroxide to
solvent of at least about l to about 0.4,
b) adding about l to about 15 weight percent of the emulsion one
or more emulsifiers selected from
1) one or more polyalkylene glycol ethers, or
2) one or more alkylaryl polyether alcohols~ or
- 8a -

~L~'7~7~3
3) one or more polyoxypropylene-polyoxyethylene
condensates, or
4~ one or more phenoxypolyethoxyethanols or in any
mixture thereof in ra~ios to give an HLB for the one
or more emulsifiers in the range of about 9 to about
20, and
c) adding water in an amount of at least about 20 weight percent
of the emulsion to emulsify the peroxide, solvent and one or
more smulsifiers into an oil-in-water emulsion.
The solid peroxides that are water insoluble or that are of
limited water solubility include hydroperoxides, ~ -o~y and ~ ~peroxy
hydroperoxides, dialkyl peroxides, aldehyde or ketone pero~ides, diacyl
peroxides, peroxyesters, peroxyacids, peroxydicarbonates, peroxy~onocar-
bonates and perketals.
The hydrocarbon solvent for use in the inventive emulsion can be
any of the low polar, strongly hydrophobic solvents includlng pine oils,
white spirits, special boiling point spirits and aromatic solvents. The
one or more hydrocarbon solvents ha~e a kauri-butanol nu~ber from about
50 to about 100 when the solid peroxide is of aromatic character or have
a kauri-butanol number of around 10 to about 50 when the solid peroxide is
of an aliphatic character. Character in this sense means the main portion
of the peroxide molecule is aromatic with aromatic or aliphatic side groups,
or the main portion is aliphatic with alipha~ic or aromatic side groups.
In addition, it is most beneficial if the hydrocarbon solvent is a fugitive
solvent that can be removed from the aqueous emulsion when ~he emulsion is
dried on a substrate.
The emulsion also has one or more nonionic emulsifiers with an
HLB (hydrophilic-lipophilic balance) value in the range of about 9 to
about 20.
3~
- 8b -
g

:~'7~7~73
Non-exclusive examples include emulsifier types such as polyethoxy phenols,
polyalkylene glycol ethers, alkyl polyether alcohol, al~ylaryl polyether
alcohol, ethylene, o~ide, ethoxylated alcohols; ethoxylated alkyl phenols,
etho~ylated fatty acids, fatty esters and oils, fatty acids, glycerol
esters, glycol esters, monoglycerides and derivatives, sorbitan derivatives,
and sucrose esters and derivatives, alkylated phenol condensation products
and condensation products of ethylene oxide and propylene glycol in suf~i-
cient amounts to emulsify the organic peroxide. The emulsifiers are most
useful in a three emulsifier blend with emulsifiers from the aforementioned
emulsifier types selected in proper weight ratios to give an overall HLB in
the range of about 9 to about 20.
The emulsion also contains water in sufficient amounts to make
the emulsion an oil-in-water emulsion. If the emulsion is to be sh;pped
any considerable distance, the amount of wflter added is just that amount
needed to invert most of the water insoluble or limited soluble material to
an oil-in-water emulsion thereby making the emulsion a concentrated oil-in-
water emulsion. The concentrated oil-in-water emulsion can be further
diluted at the location of use.
The aforedescribed emulsion of the organic pero-~cide has many
uses in the polymerization of vinyl and diene polymers. The emulsion is
particularly useful in a sizing composition for glass fibers to be used in
polymer applications. The sizing composiSion is an aqueous composition
containing a coupling agent, tlle organic pero~ide-containing emulsion, and
usually a lubricant or softener, and optionally a Eilm-former.
The process for preparing the emulsion containing the organic
peroxide involves first solubilizing the solid organic peroxide in the
hydrocarbon solvent and tllen adding one or more sur~actants and adding

73
water and emulsifying using equipment and techniques known to those skilled
in the art.
~ he aqueous size containing the organic peroxide emulsion i9
used to treat glass fibers during the forma~ion of the glass fibers. The
glass fibers so treated are then heated to drive off a predominant amount
of the water in the aqueous sizing composition and the dried treated glass
fihers are used Eor bonding or reinforcing polymers such as homo and
copolymers of polyolefins, polyamides, polyesters and the like.
The most useful solid, water-insoluble, or limited water soluble,
organic peroxides in the aqueous sizing co~position are those having the
formula:
(R-0-0-)x - R'
where R is a tertiary alkyl or aralkyl or aryloyl or alkyloyl radical and x
is a number 1, 2, or 3, and
R' is the same as R or of the structure:
R" R"
C-R IV _f
R"' R"'
where RIV i9 a phenyl, alkylphenyl, alkyne or alkyl group having the
structure:
(CH2-CH2)n
where n i9 1, 2 or 3; and
where R" and R"' are either hydrogens, or individual hydrocarbon radicals
or are alkylene radicals connected to form a cycloalkylene radical. Either
hydrocarbon radical R" and R"' may be alkyl, cycloalkyl, aralkyl, or aryl
hydrocarbon radicals, when RIV is a phenyl group, and either R" or R"'
hydrocarbon radicals are phenyl, aryl or larger than C7Hls radical when RIV
-- 10 --
.

~7~'773
is the ~CH2-CH2)n radical. The (R-O-O) can be attached at any position on
the ~' group, for example in bis or tris arrangement ~hen R' is di or tri-
alkyl benzene where the alkyl groups are located on any position such as
ortho, meta and/or para or in 8,11 arrangement when R' is (CH2-CH2).
Detailed_Description of the Invention
For preparation of a more stable, dilutable and safe emulsion,
non-exclusive examples of the solid, water-insoluble, organic peroxides
include:
2,5 dihydroperoxy; 2,5-dimethylhexane; 1,4 dihydroperoxy-1,4-
dimethylbutane; 1,4 dihydroperoxy-1,4-dimethyl-2-butyne; 1,3- and 1,4-
bis( ~-hydropero~yisopropyl)-benzene; bis(l-hydroxycyclohexyl)peroxide,
l-hydroperoxy~ hydrodicyclohexyl peroxide, dicumyl peroxide, 2,5-di-
(hydroperoxy)-2,5-dimethylhexyne, 2,5-di~llydroperoxy)-2,5~dimethyl hexane
and hydroperoxides having structural formulas as follows: tert butyl
C~eEt O OH; HO ~CMe2 (CH2)4 CMe2-o-oH; ~o-o-cMeEt-c=c-csc-cMeEt-o-oH;
; . . . ~ .. .
HO-O-CIC(cH2)51-c-c ~ CH2)S~l-O-OH; ~10-0-CCC(CCH2)5~-C-C-C-C-C{C(CH2)~;
1,3-and 1,4(di-tert butylperoxyisopropyl)benzene, 8,11 bis-
(tertiary butylperoxy)-8,11 dimethyl octadecane, and mixtures thereof, tri-
benzyl; tertiary butyl bis peroxide; di-tetradecone peroxide; di-hexadecane-
zO peroxide; di-tribenzyl methyl peroxide; dilauroyl peroxide; didecanoyl
peroxide; dipelargonyl peroxide; dicaprylyl peroxide; diisononanoyl peroxide;
dibenzoyl peroxides and nuclear substituted derivatives thereof; 2,5-dimethyl-
2,5-di(benzoylperoxy)hexane; dimyristyl peroxydicarbonate; dicetyl peroxidi-
carbonate bis(4-tert butyl cyclohexyl peroxydicarbonate; and 2,2 bis 4,4
ditert butyl peroxycyclohexyl propane l,l-ditert butylperoxy-4-tert butyl- -
clohexane; 2,5-bis-(tertiary amylperoxy)-2,5 dimethylhexane; I,l'ethylene

~7~ 73
bis[l-(tertiary-amylperoxy)cyclohexane]; 2,5-bis (tertiary-butyl peroxy)-
2,5-diphenylhexane; 2,6-bis(tertiary-butyl peroxy)-3,6-dimethyloctane;c~ ,
~, c~c', c~'-tetramethyl isophthalyl di-t-butyl bis peroxide; and ~ ,~ ,
C~ C~' tetramethyl isophthalyl dicumyl bis peroxide; and tris-(t-butyl
peroxy)diisopropyl benzene.
An aqueous emulsion can be made with any oE the a~oredescribed
solid, water-insoluble, or limited water soluble, organic peroxides that
are more dilutable~ stable and safer and that has a fine particle size and
minimum particle size distribution by using ehe hydrocarbon solvent and one
or more emulsifiers and then emulsifying with water.
The particular hydrocarbon solvents, emulsifiers, and method of
making the emulsion would be the same for any of the aforementioned solid,
water insoluble or limited water soluble organic pero~ides. The solid,
water-insoluble or limited water soluble organic peroxides for which the
aqueous emulsion and method of making same is most useful are the peroxides
having a melting point closer to the decomposition temperature of the
peroxide than to ambient temperature. For these peroxides the temperature
required for melting would cause a safety risk in to closely approaching
the decomposition temperature. As a result, especially in production
facilities with less than perfectly controlled and monitored equipment,
violent decomposition reactions may occur.
The emulsion and method of making the emulsion is most useful for
even the more heat stable organic peroxides, since even these peroxides may
have melting points that approach the decomposition temperatures of the
peroxide and could be used in a safer operation.
The more heat stable organic peroxides can be used as fre radi-
cal initiators in the polymerization of vinyl and diene containing monomers

~.~.t;i>~6t;;~
or polymers. By more heat stable organic peroxide it is intended that
those peroxides having a half-life exceeding 60 hours at 212F. (100C.)
and 20 minutes at 300F. (149~.) be encompassed. The term halE~life is a
rneasure of reactivity of tlle organic peroxide and is defined as the time it
takes for one hal~ of a given quantity of peroxide to decompose at a par-
ticular temperature. Particularly useful more heat stable organic perox-
ides are like those with the formula as shown above, i.e.,
R" ~.,
(R ~x~Rl and where R' is -C - RIV _
~"' R~
Non-exclusive examples of these organic peroxides include solid dialkyl
peroxides and diaralkyl peroxides such as the bis(tertiaryallcyl peroxy)
alkanes in which R is a tertiary alkyl radical having 4 to 8 carbon ato~s
and either R" and R"' are primary alkyl radicals havin~ 1 to 8 carbon
atoms, while the other has ~reater than 3 carbon atoms. Additional non-
exclusive examples include: 2,5-bis-(tertiary amylperoxy)-2,5 dimethyl-
hexane, 1,1' ethylene bis[l (tertiaryamylperoxy)cyclohexane]; 2,5-bis(ter- -
tiary-butyl peroxy)-~,5-diphenylhexane; 3,6-bis(tertiary-butyl peroxy)-3,6
dimethyloctane. A non exclusive example of the diaralkyl peroxide that can
be used is 1,3 and/or 1,4(ditertiary butyl peroxy) diisopropylbenzene; or
alpha, alpha, alpha', alpha'~tetramethyl-isophthalyl-di-t-butyl bis perox-
ide; and alpha, alpha, alpha', alpha' tetramethyl-isophthalyl-di--cumyl-bis-
peroxide; and tris(t butyl peroxy)diisopropyl benzene. Other dialkyl per-
oxides that can be used include 2,5(t-butyl peroxy)hexane and 2,5(t-butyl
peroxy)hexyne and 8,11-bis(tertiary butylperoxy)-8,11-dimethyl octadecane.
In adùition, the tert-alkyl peroxy esters, also known as peresters, that
are more stable can also be used. Sevesal o~ these peroxy esters include
tert-butyl peroxy acetate; tert-butyl peroxy benzoate; di-tert-butyl
- 13 -

\
i7~3
dipero~yphthalate; mono-tert-butyl permaleate; di-tert-butyl peroxy hexa-
hydro terephthalate; di-tert-butyl peroxy adipate; di-tert-butyl peroxy
terephthalate; di-tert-butyl peroxy phthalate; and mono-tert-butyl pero~y
phthalate. The amount of the solid peroxide used in the emulsion is that
amount needed to incorporate into the si~ing composition an amount of
active peroxide in the range of about 0.1 to about 6.0 percent by weight.
Generally the amount can range from about 1 to about 70 weight percent of
the emulsion, and preferably has a lower limit of at least 10 weight
percent for use in a si~ing composition.
Acceptable fugitive hydrocarbon solvents for use in liquiEying or
solubilizing the solid organic peroxide, which, if predominantly aliphatic,
will have a low kauri-butanol value such as from about 10 to about 50 and
have boiling ranges which ~ie within the range of ambient temperature to
about 200C. If the organic peroxide compound has more than about 60 per-
cent aromaticity the acceptable hydrocarbon solvent will have a kauri-butanol
value of from about 50 to about 100 ~Jith a boiling range which lies within
the range of about 100 to about 250~C. The kauri-butanol number is a mea-
sure of solvent power of petroleum thinners where the value is the nu~ber
of milliliters of solvent required to cause cloudiness when added to ~0 grams
of a solution of kauri gum in buSyl alcohol. The solution is prepared in
the proporation of 100 grams of kauri gum and 500 grams o butyl alcohol.
Solvents of low aromatic content are strong precipitants for the resin and,
therefore, give low values. Conversely, the solvents having a high aroma-
ticity give high values. The kauri-butanol numbers are preferably deter-
mined against one of two standards where the one standard is a one degree
toluene with a value of 105 used when the hydrocarbon solvent gives a kauri-
butanol value of over 60 and the other standard is a mixture of 75 percent
- 14 -

:~t~7~3
of n~heptane and 25 percent toluene when the hydrocarbon solvent has a kauri-
butanol number of 40. This is discussed in ASTM Standard D .~133-5~ T.
~ xamples of hydrocarbon solvents ~ith lo~ kauri-butanol numbers
useful, when the organic peroxide has a substantial amount of aliphatic com-
ponents, or only a minor amount, if any, of aromatic components, are the iso-
paraffinic hydrocarbon solvents. Suitable examples are those of the 3eries
of commercially available isoparaffinic hydrocarbon solvents sold by ~xxon
Company, U.S.A. under the trademark "ISOPAR" or Phillips Petroleum, under
the trademark "SOLTROL", which have boiling ranges within the above ranges.
Examples of hydrocarbon solvents with high kauri-butanol values
include the solvent commercially available under the trade ~ark HI-SOL 10 or
HI-SO~ 15 available from Ashland Chemical Co., Ohio, where the ~II-SOL-10
has a boiling point of 308F. (153C.) and a flash point of 105F. (40.6C.)
and an evaporation rate of 25.0 using ether base of 1. Also, the hydrocar-
bon solvent sold by Exxon Co. USA division of Exxon Corp. Company under the
trade mark "SOLVESSO 150" or "SOLVESSO lOO" can be used.
The ratio of organic peroxide to hydrocarbon solvent is at least
a ratio of 1 to 0.75 when the hydrocarbon solvent has a kauri-butanol nu~-
ber of 70. If the solvent is a better solvent for the peroxide, like Bi-
Sol-lO solvent that has a kauri-butanol number like 92-93 when the organic
peroxide is alpha, alpha' bis(t-butyl peroxy)-diisopropyl benzene, the
minimum amount of solvent that could be used would be less than that in the
ratio above, such as 1 peroxide to around 0.4 and even as low as 0.19 sol-
vent. If the solvent is a poorer solvent than the onc having the kauri-
butanol value of 70 when the organic peroxide is alpha, alpha' bis(t-butyl
peroxy)diisopropyl ben7ene, then the minimum amount of solvent would be
higher than the above ratio. The amount of the hydrocarbon solvent used in
D~
`''',

'77~ -
making Ip the emulsion of the solid organic peroxide will generally vary
within the range of about l to about 70 and preferably about 10 to about
55 percent by weight of the emulsion. ~ore solvent can always be added,
but there is no benefit to such a practice, since the solvent is usually
removed at some later time.
The non-ionic emulsifiers that are preferably selected from
polyethoxy phenols, polyalkylene glycol ethers, alkyl polyether alcohol,
alkylaryl polyether alcohol, ethylene oxide alkylated phenol condensation
products, and condensation products of ethylene oxide and propylene glycol
having an HLB value in the range of about 9 to about 20 can be used singly
or in a combination in the emulsion to give the desired HLB value. An
example of an e~ulsifier used singly is the octyphenoxy polyethoxy ethanol
available from Rohm & Haas Company, under the trade mark
"Triton X-lO0", which i5 nonionic and has a HLB of 13.5. The HLB as
used herein refers to the hydrophilic/lipophilic balance. The types of
emulsifiers such as the "Triton X-100" can be prepared from alkyl substi-
tuted phenols, where the alkyl group has 6 to 12 carbon atoms. The number
of moles of ethylene oxide per mole of hydrophobe (alkyl phenol) can vary
between 1.5 and about 30~ The weight percent of combined ethylene oxide is
usually from about 40 to about 95 percent to achieve good water ~olubility,
more typically, about 6~ to about 95 percent. Another exa~ple of such a~
emulsifier is nonylphenoxy poly(ethyleneoxy) ethanol. It is not necessary
that a single emulsifier be used to give the proper HLB. Any two or more
surfactants having known HLBs can be combined using the proper proportions,
and if the IILB is not known for a particular emulsiEier it can be calcu- -
lated from one of several known formulas. See the article by W. C. Griffin,
entitled: "Calculation of HLB Nonionic Surfactant" in the December 1954
- 16 -
,~
~, '.

~ ~ t~7~3
issue of the Jourllal of the Society of C03metic Chemistry. TypicalLy, the
emulsiEier represents between about 1 and about 15 weight percent, more
usually between about 3 and about 12 weight percent, of the emulsion. The
exact amount of the emulsifier required can be ascertained easily by simple
trial and error technique using the aforementioned ranges as a guideline. -
Once a stable emulsion is obtained, use of more emulsifiers is not neces-
sary and would not give any further beneEits and could prove detrimental in
leading to increased migration of an aqueous treating solution containing
the emulsion from a treated substrate like a package of fibrous material.
It is particularly useful to use a three emulsifier blend in
the emulsion of the present invention. The three emulsifiers are selected
with proper weight ratios to give an overall HLB value in the range of about
9 to about 20 and preferably 9 to 15. One emulsifier is selected that has
a high ~ILB value in the range of about 12 to about 20. A second emulsifier
has a lower ULB value in the range of about 6 to about 12, and a third
emulsifier has a HLB value in a middle range of about 9 to about 15. The
threa emulsifiers are used in amounts that give a total HLB in the range of
about 9 to about 20. It is particularly useful to use the emulsifiers in
equal proportions, although any proportion of the various emulsifiers can
be used to give the desired H~B range.
In preparing the emulsion of the present invention, one or more
of the desired perDxides is dissolved in the fugitive hydrocarbon solvent
suitable for the particular organic peroxides involved. This mixture may
be subjected to moderately elevated temperatures to facilitate solubiliza-
tion of the organic peroxide. The mixture of peroxide dissolved in the
hydrocarbon solvent has added to it the one or more emulsiEiers, and this
mixture is emulsiEied using standard techniques, conditions and apparatu~.

773
~ nen the emulsifier is the three component emulsifier blend the
individual emulsifiers can be added separately to the mixture of peroxide
and hydrocarbon solvent, or they can be added in a combination oE all
three, or any two can be added as a combination and then the third emulsi-
fier added individually. After the emulsifiers are added, the resulting
mixture is sub;ected to standard techniques, conditions and equipMent oE
emulsification ~nown to those skilled in the art. Such techniques include
subjecting the ;nixture to high shear and diluting slowly with water, where
the water can be at ambient temperature or at some elevated temperature.
The water is added until the emulsion inverts to an oil-in-water emulsion
and then the emulsion is slowly cooled to ambient conditions by continued
water addition. The amount of water added to the emulsion is at least
a~out 35 percent of the emulsion composition. If the emulsion is to be
shipped any considerable distance, the least amoun~ of water is used so
that there is inversion of most of the water insoluble or limited water
soluble m~terials to an oil-in-water emulsion.
The emulsion composition is then formed into an aqueous sizing
composition having a coupling agent, and usually a lubricant or softener,
and optionally a film-former. This for.nation can involve slo~ly adding the
emulsion to an aqueous mixture containing the coupling agent and any lubri-
cant or softening agent and film-former and the remaining water to make the
aqueous sizing composition. Also, any lubricant or softening agent or film-
former to be used in the sizing composition can be added after the emulsion
is addecl to the aqueous mixture containing the coupling agent. The amount
of the emulsion composition incorporated into the sizing composition
depends on the amount of peroxide in the e,nulsion composition. Depending
on this amount of peroxide, the amount of emulsion used in the sizing
-- 1~ --

73
composition is that amount to give an amount of active organic peroxide in
the sizing cornposition in the range of about 0.1 to about 6 percent by
weight of the si7-ing composition. Once the emulsion of the present inven-
tion is prepared the aqueous sizing composition can be made in a manner
similar to that as described in U.S. Patent 3,849,148 (Temple).
Generally, the amount of organ~c-silane
coupling agent that is usually a vinyl-containing silane in the sizing
composition is in the range of about 0.5 to about lO percent by weight of
the aqueous sizing composition. The amount of lubricant in the sizing
composition, which i9 a cationic active acid solubilizable fatty acid amide,
is generally in the range of about 0.001 to about l percent by weight of
the aqueous sizing composition. If a film-former is used, it is usually a
polyvinyl acetate polymer or copolymer in an amount in the range of about
0.05 to about l2 weight percent of the size.
rne aqueous sizing composition is applied to individual glass
fibers during their formation by any conventional ~ethod of applying sizing
to glass fibers. Such methods ~re shown in U.S. Patent 3,849,148 (Temple)~
m e sized glas~ fibers are dried to remove moisture and the
fugitive hydrocarbon solvent, although some residual moisture and solvent
may remain on the glass fibers. The dried sized glass fibers can be used
in any form such as fibers, strands, wet or dry chopped strands, mats
and the like for reinforcing polymers, like polyamides, polyesters, and
particularly polyolefins. Glass fiber mats for reinforcing polyolefins are
shown in U.S. Patent 3,849,148 which shows the production of glass fiber
reinforced polyolefin laminatesg
~,

P7'73
Preferred Embodiment
The emulsion of the present invention is preferably an emulsion
of alpha, alpha' bis(t-butyl peroxy)-diisopropyl benzene including meta and
para isomers which is commercially available from Hercules, Inc., under the
-trade mark "Vu1-Cup R" vulcanizing agent and polymerization catalyst.
The solid peroxide is used in a ratio oE peroxide to hydrocarbon solvent in
amounts to facilitate solubilization of the peroxide, but preferably in a
ratio of peroxide to solvent in the range of about 50/50 to about 70/30,
and most preferably a ratio of around 60/40 peroxide to solvent. The hydro-
carbon solvent is preferably the solvent commercially available under the
trade mark "HI-SOL 10", available from Ashland Chemical Company.
The organic peroxide is dissolved in the HI-SOL-lO where the amount oE
HI-SOL-10 is in the range of about 10 to about 30 weight percent oE the
aqueous emulsion composition.
It is preferred to use the three emulsifier blend, in the prepa- -
ration o~ the emulsion of the present invention. The first emulsifier i9 a
trimethyl nonyl polyethylene glycol ether, such as, that commercially
available from Union Carbide Corpora~ion by the trade mark "Tergito1
T~N-6" having an HLB of 11.7. This ether is used in an amount of about 0.1
to about 5 weight percent of the emulsion. The ether emulsiEier is com-
bined with the second emulsifier which is nonyl phenoxy polyethyleneoxy
ethanol, commercially available from GAF Corporation Chemical Products,
under the trade mark "Igepal C0-630" having an HLB of 13 and used in
an amount of about 0.1 to about 5 weight percent of the aqueous emulsion.
These two cmlllsifying agents are combined and stirred until clear. The
third emulsifying agent is a condensate of propylene oxide with hydrophilic
bases formed by condensing ethylene oxide with ethylene glycol and is
- 20 -

i7~3
col~nerci~lly available from BASF Wyandotte Industrial Chemical Group, under
the trade mark "Pluronic-P-65" which has a HLB of 17 and is ùsed in
an amount in the range of about 0.l to about 5 weight percent of the aque-
ous emulsioll col~position. The total amount oE the three emulsifier blend
in the aqueous emulsion composition is in the range of about 1 to about
15 weight percent (preferably about 3 to about l2 weiOht percent) of the
sizing composition. An amount in excess of 15 weight percent could be
used but it would lead to migration of the size from the sized glass fibers.
It is preferred to add the emulsifier blend in the following
manner The glycol-o~ide product emulsifier has the total amount to be
added split into two portions. The Eirst portion, preferably around
one-half of the total amount, is added to the peroxide in the solvent along
with the mixture of the ether emulsifying agent and the ethanol emulsi~ying
agent that is added to the hydrocarbon pero:~ide solution. The remaining
portion of the glycol-oxide product emulsifier is dissolved in water with
agitation in around a 50 to 50 blend and is added to the other materials
during the emulsification operation. This emulsification operation includes
agitating the materials and adding an amount of warm water of about 25 to
about 30C. in the range of about 15 to 30 weight percent of the aqueous
emulsion composition. An amount oE cold water is added to give an amount
of active peroxide in the range of about 35 to 65 weight percent and pref-
erably around 50 weiJht percent oE the aqueous emulsion.
The aqueous emulsion is preferably added to an aqueous compo-
sition containing a coupling agent, that is preferably vinyl tris(beta
methoxy ethoxy) silane, present in an amount of about 0.5 to about lO weight
pPrcent of the aqueous sizin~ compo:;ition. ~n an alterllative embodi~.nent, a
lubricant such as r'Emerylube" 6717 (Trade Mark) commercially
available from Emery Industries,

:~7~7~3
is present in the sizing CompoSitiOn in an amount in the range of about
.001 to about 3 weight percent of the aqueous sizing composition. In
another alternative embodiment a film-former like a polyvinyl acetate
copolymer is used in an amount of around 0.5 to about 12 weight percent of
tlle aqueous sizing compoæition. The amount of water in the aqueous sizing
composition usually ranges from about 70 to about 99 weight percent of the
sizing composition.
l~e aqueous sizing composition is applied to individual glass
fibers during their formation according to the manner illustrated in ~.S.
Patent 3,849,148 (Templej. The aqueous
emulsion of the organic peroxide can be used in any of the sizing composi-
tions described in ll.S. Patent 3,849,148.
The aqueous emulsion of the present invention will be Çurther
elucidated by ma~ing reference to the follo~ing examples.
Table I presents exampleæ showing components of the aqueous emul-
sion in their gram weight amounts and weight percent amount.
~^~ 3

as ~ P'~n ~ ~ C ~ ~ 03 ~l7~3
~ ~ ' o't- I oO p~ ~
~ 3 ~ ~ S ~ o~D O D~ ~1
~ rD ~ n ~ ~ rt ~ o P~ ~
?C ~ r
O ~ I O tD rl ::~ ~ ~J ~ O ~ 0 5~ '<; ~
-- r1 r~ X O G~ OtD ~ D O ~ _ ~ S
~, 3 0 ~~ X~ ~o~ u~ tn '
`--O ~ XO O O
t~ I O ~Dr~ ~ u~ C C O N
:~ rt O ~ G~ O tD
:~ ~- 5 1 (D ,~ t ~C n rr ~ rD r~
o n ~c~ ~rt ~ 0~0 (~
X I ~~ ~o ~ ~ r
~ 5 ~ ~ rt
S Vl:~ ~ ~ rt . ~--
p) _ O t~ Z tD _l
3 ;~O I P a~
ID O O
l_ X
o~ I
_ _ _ _ _ _l ~ _
n ~
rt
O
~Jl rr
O O
G~
1~ c~ o ~ ~
O ~D O O O ~ W Iw 3
~J ~I
Vl ~) ~D
~ ~ o~
o l ~3
G ~i
1 00 w P~ ~
w w w --~ w j ~ E3 H
Co0~ ~ _ rt
rt
a~
_
c~
w ~ O
~, g O ,~, O W
w O~
~D-- --
O O o Co w
1 ~ o
O~ ~~ _ ~ ~\O ~ I
-
Co W W W
r _l
~D ~n ~ ~ ~ O I ~O w
o o o
~_ _ _ _ O
-
00 0 _
W ~
- ~ w ~ ~ I r~o
w ~ ' O
_, _ r,t~
-
-- 23 --

~773
:1: tD O ~ O ~--~ Z --~ (D ~ ~ ~ sa ~ D~ ~ 0~ ~ P~
~ o n X ~~ ~ 0 ~3 rt ~1 0 0 D~ O
rr 5 r~ o~ ~ ~5 Y. ~ ~ El
D. ~(9 ~C ~ r~ tt N O ~ 'U
O 1 00 0 X g X ~ P
u~ n ~ ~ r :~ 5 ~- r o I p~ 5
_ o ~ ~ J ~ :~
~ ~; ~ o C~ x ::1oq ~ ~ o ~ ¢ 1'~ rt
o p~ r~ X ~ oI ~: o ~3 r~ a a
-- rt Y~ ~ ~ X~ X ~ O ~ r1 0 ~ 1-- W
a rt ~ u~ n 1 ~ o ~ w o
O o ~ QO rr I O ~ u) ~ O ~J C~ ~ V
~o ~ ~ a e O W
I n --nO ~rr o ~ O ~ ~-: n
~ S ~ 5~ 1
O O
~: O ~ ~ `C
_ ~ _ _ _ I_~ ~
o
O ~
O` O O ~ O ~-- I O O I~D
'~ ~ ~ ~ O,_ ~
~ ~-- ~ _
~ o 1 3 1 ~i OD a` lo ~
U~ . ~ ~ ~-
P
c
~
~ ~ ~ o`
~ I I t
o~ o~ ~
.
o ~, _ .
~._
r~ ~ O ~D ,_
~o , ~ ~ ~ ,_ , ~ *
^ O ~n ~ ~ OI
t--~
o I ~ ~ ~ w 1'-
~ ~ ~ o
W W ~ ~I
-- 24 --
'~

:~'7~i~7~3
In Table I, the emulsion preparation, number 5, was made by
initially melting the organic peroxide using a hot water bath at a tempera-
ture of 140 to 150F. (60 to 66C.). Afterwards, the hydrocarbon solvent
was added with mixing. The ether and ethanol type emulsifiers were added
next with continued mixing. This blend was subjected to a high speed
Eppenbach mixer without heat in order to uniformly distribute the emulsi-
fiers. One half of the total amount of the propylene oxide ethylene oxide
condensate emulsifier was added and the blend was agitated for around 10
minutes. The other half of the propylene oxide ethylene oxide condensate
emulsifier was combined wi~h water and added to the blend with continuous
agitation. This split addition avoids any possibility of any salting out
oE the emulsiEier. ~ilute cold water was added to the Eppenbach to bring
down the temperature to 110F. (43C.) or less. The blend was emulsi~ied
by adding cold water with high speed mixing. After around 10 to 30 minutes
the speed o~ the high speed mixer was reduced and the emulsion was diluted
to the desired concentration.
In the other emulsions and si~ing compositions the organic per-
oxide was dissolved in the hydrocarbon solvent with a slight heating
usually not above 100F. (378 C.) A standard mixer was used for approxi-
mately 45 minutes and the final solution was usually clear. The ether type
and ethanol type emulsifiers were added to this mixture and then the con-
densate type emulsi~ier was dissolved in hot water, and stirred about
30 minutes until cool. The hydrocarbon mixture of emulsifiers and organic
peroxide was subjected to an Eppenbach mixer then the aqueous solution of
the propylene oxide-ethylene oxide condensate type emulsifier was added to
the mixture slowly until the inversion phase occurred. The inverted mix-
ture was then diluted with cold water to the desired peroxide concentration.

~.~ 7~'7~3
Table II shows sizing compositions made with several oE the emul-
sions of Table I.
Th~ s;zing compositions were prepared by plac;ng approximately
2 1/2 gallons (9.5 lii~ers) of cold water in a mix tank, and adding acetic
acid with stirring. Slowly the silane was added to the main mix tanlc and
stirred for around 30 minutes unt;l near complete hydrolysis of the silane
ocurred. The lubricant, partially amidated, polyalkylene amine was dis-
solved in hot water and diluted with cold water until reaching a tempera-
ture of 100F. (37.8C.) and then added to the main mix tank. The emulsion
which was previously prepared was then added to the main mix tank. The
polyvinyl acetate film-former was added to cold water with agitation and
added to the main mix tanlc. The volume of the sizing composition was then
brought to 10 gallons.
- 26 -

~,7~7t73
O ;~ a o
D rr ~ D (D L 3
It ~ O ~ ~ C)
O ~ ~
It O tD
tD O' ~ . ~n
o a~ ~') 3 3
3 P~
5 P~3
rt(9 r q f~
0 ~0
1 1 X
rS O
_l
._ I
w
~ ~n O ~I
O O~ O ct~ ~ ot) 1
_~ . . .
Vl . ~ .
_ O 1-`' '~
~q
U~ ~1
~ --I
O O ~ GO O rr
GO O
Ul ~ 00
W _ _ _
`_
~ ~a
t-- ~ 00 w
~- w `- ~ ~ ~ ~ ~ s 1~ u7
,.~ ~ . . ~ e~ ~ ,
_l ~ ~I W ~ 00 . . N
a~ . o
_ O ~h
~_ ~ ~ ~S
_~ O
w ~ 3
ao 3 3 a
~D W ~ r~ ~. ~ t~
.,_ o a~ ~_ o~
_ ~n 1~-
w ~ ~' ~ ~
_, w ~ ~ ~ ~
w o ~ ~'
~ ,_ ~ ,_ 3
w w ~ ~ I o
~ ~ Y
_ ~n
~_ o~ W
~ CO _,
_, ~ ~ ~q
co co ~ ~ o cr
w i~ co w v~ ~n r-
. ~ . ~ .
~" - o - ~
-
~ `~ w o ~ oq
a
O O ua ~ ~ ~ l ~~
a` ~ ^ o o ~ ~ o~ ~
w ~ ~ _
W ~
_~ o -- `'
w
_,
w
oq
7 o ~ v~ 3 1
oo ~ . . I w
I ~ 1-- ~ W W ~ ~
~!
-- W
`_ _ o `-- ~
~ ~ ~D
- 27 -

7~73
Table III sho~s physical characteristics for several emulsions of
Table I and of the sizing cornpositions of Table II. These physical charac-
teristics include the particle si~e of ~he emulsion and sizing compos;~ion
along with the stability of the emulsion in sizing COrnpOSitiOn at various
periods of kime.
- 2~ -
.

-~'7~i773
r~ t ~ rr p~
U~ cr~ a. ca crl ~ Ct~ C~ ca C~ ca crl U~ ca C~
. 3 P~ ~, rl p~ 5 r~ 3 5 ~ 3 ~ C7' ~. 3 rr
N r ~: N C 'C N c: ~ N C. r N C. rt ~D rr ~_ N
O ~~n ~o ~n . cn . Cn . ~ . ~ . in 1--
0 0 0 ~ o cn O cn ~--~ O
P ~ ~) ~ P 5 p 5 :~ c~a
1~ 3 N
r~ ~ rn ~n rn
~: (D Ca ~ W Cn ,_
rt rr rr rr ~ 3
C~
~D O1'. ~J Cl' CT' ~ r)
.. cn ~ 0
~ ~ ~ 1'- P
t~ ~ rr rt rr U~
rr r~ ID ~ `~ ~ ~'
Co ~ ~
rr rr ~.
O O ;'D ~ ~q 0~ 0~ Y ~--
oo II II oo ~ 1
rr I O O I I I I O O ~ Vl
~ L~ ~ ~ W `D
Or'
& 5 ~D
, . rr c: rt C
cn ~n oQ tD ~ ~D
ID ~ cn g ~ ~Q O ~ rJ~
Pi I rt r;~ c~ i ¦ O O W i~
r1 ~n p~ 0 ~ oq c~ v
- rt C 1~
rr r' rt _ ^
O ~ ~. Y
,~ O
,~
Il O O or; oq ~ o
c-~ Oæ ~~ ¦ g O ~ rr
.. r............... __
0~~D 0~
rrPr~ rt
Cl~ (D r~
tD ~D El
O O ~_
3 ~ I I I) I I I I ~ ~o I
~r ~ ) I II I I I Ir ~ ~ ~
rrrr rr cn t~
rr
~t ~..
P ca
OCl OQ Oq ~q OQ OQ t--
O O O O O O I I O N
O O O O O O I I cn
~i
~ O o O O O ca
o `d ;~ t I
P~ O O O O~ O : O I I I
H
rt
r~
r,~ O
P~ CC ~ ~ t ¦ ¦ i
rr ~ r~
~D
cn
Oq oq OqOq OQ ~Q
O O O O O O
O o O O O O
O o o o o O
_-- :-- : C
~_
_,
- 2~ -

73
The foregoing has described an emulsion of a solid, water insolu-
ble or limiced water soluble organic peroxide in a hydrocarbon solvent
along with one or more emulsifiers to produce a stable emulsion which can
have a shelf stability of as long as three months and that is dilutable and
safe and that requir~s fewer precautions when prepared. The organic pero~ide
can be selected rom various organic peroxides as discussed above and
the hydrocarbon solvent varies somewhat with the type of organic peroxide.
For example, when the organic peroxide has a low amount of aromaticity, the
hydrocarbon solvent will have a kauri-butanol number in the range of about
10 to about 60. If the organic peroxide has a s~lbstantial amount of
aromaeicity, the hydrocarbon solvene w;ll have a kauri-butanol number in
the range of about 40 to about 100. One or more emulsifiers can be used
for emulsification, but it i9 preferred to use the three component em~llsi-
fier blend wherein one emulsifier has a H~B in the range of about 12 to
about 2~ while the second emulsifier has a U~B in the range of about 6
to about 12, and the third emulsifier has a ~l~B in ~he middle range, a
range of about 9 to about 15.
The sizing composition contains the above-described emulsion
along with any of the conventional sizing composition components, such as
2~ coupling agenes, film-formers, lubricants, and the like.
The process of producing the emulsion involves solubilizing
the organic peroxide in the hydrocarbon solvent and then producing the
emulsion.
Sized glass fibers in any form such as chopped fibers, strands,
chopped strands, roving, and woven glass fiber strands made from any type
of glass but usually made from "E-glassl' or "621-glass" or low boron and/or
low fluorine modifications thereof can be used for polymer reinforcement.
- 30 -

~L7~i7'73
Such a polymeric reinforced product is a polyolefin type product, namely
polypropylenel reinforced with glass fiber strands sized with a si~ing
composition containing the aforedescribed emulsion. Other polymeric
reinForced products include other polyolefins, polyamides, e.g., nylon,
themosetting polyesters and the like.
- 31 -
. ,, ",, ~ ,