Note: Descriptions are shown in the official language in which they were submitted.
1 1 6~993
ANTIOXIDANTS AND REINFORCED POLYMERS AND
OIL-IN-WATER EMULSIONS OF A~TIOXIDANTS
Background of the Invention
The present invention is directed to approaches to increase the
performance of fiber reinforced polymers under aging conditions including
the use of oil-in-water emulsions of antioxidants that are water insoluble
or immiscible or have limited water solubility, wherein the emulsions have
a small particle size and good stability.
More particularly, the present invention is directed to methods
and compositions for increasing the performance of glass fiber reinforced
polymers under thermal aging conditions. The compositions include the
use of oil-in-water emulsions of antioxidants that are water insoluble or
immiscible or have limited water solubility and that are of low volatility
and good thermal stability and non-discoloring for use in treating glass
fib~rs. The oil-in-waeer emulsion provides a method to reduce chemical
degradation of polymers reinforced with glass fibers containing sizing
compositiong.
In order to stabilize polymers from degradation due to oxygen
and ozone~ various antioxidants of the hindered phenol and diaryl amines
types have been incorporated into polymer formulations. Another type of
degradation that polymers may encounter is degradation due to various
chemicals other than oxygen and ozone with which the polymers may come in
contact. Such chemical degradation may occur when the polymers are rein-
forced with material that has been treated with various chemicals to pro-
vide efficient processing of the materials and to provide compatibility
of the materials with the polymers. Care must be ta~en in producing
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9 9 3
reinforcement materials containing treatment chemicals, such as sizing
compositions for glass fibers, to avoid any problem of interaction between
the chemistry on the reinforcing material and the polymers. Any possible
interaction between the various chemical agents in the system or reaction
or decomposition products of these chemical agents with the polymer may
degrade the polymer to some degree. This degradation would reduce the
mechanical properties of the reinforced polymer over time and especially
under thermal aging conditions. ~hen the reinforced polymer is subjected
to elevated temperatures for a period of time, i.e., thermal aging, degrada-
tion of the polymer may be accelerated due to thermal autooxidation and
increased reaction rates for chemical interaction. This degradation short-
ens the useful properties of the reinforced polymer which usually have
extended properties due to the presence of the reinforcement.
Antioxidants that have been added to polymer compositions that
are to be used in preparing reinforced polymers have also been added in the
form of the antioxidant alone as a solid or liquid. Also, antioxidants
have been added to latex formulations such as rubber latices in the form of
emulsion and dispersions. For example, the antioxidant "Age Rite Resin D"
available from R. T. Vanderbilt Company, Inc. which is the antioxidant
polymerized 1,2-dihydro-2,2,4-trimethyl quinoline can be prepared in a 30~ -
emulsion by melting the "~ge Rite Resin D" antioxidant in light process oil
and oleic acid at 104C. and removing the mixture from the heating source
and adding xylol. Then the emulsifier nonylphenoxy poly(ethyleneoxy)ethanol
available from GAF Corporation Chemical Products under the trade designa-
tion "Igepal C0-630" is diluted. Dissolved potassium hydroxide pellets are
mixed with the emulsifier and the mixture is heated to about 88C. Ihe
emulsifier mix is then added to the antioxidant mix with vigorous agitation
* This symbol designates a Trade Mark throughout the disclosure.
:,~
I 1 6~993
to produce an emulsion having about 32.1 percent oil to 31.~ percent water.
Other similar emulsions and dispersions are available in the publication
"Vanderbilt News" volume 34, number 2, 1972, pp 13-24.
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. As stated above both emulsions and dispersions of antioxidants have
been used in formulations for rubber latices. The stability of antioxidant
emulsions depends upon the factors for emulsions in general: (1) particle
size, (2) difference betwe~n the densities of the material in the internal
phase, which is the liquid broken into droplets and of the material in the
external phase, which i9 the surrounding material, (3) the viscosity of the
emulsion concentrate, (4~ the charges on the particles, (5) choice of emul-
sifier type and amount of emulsifier used, and (6) the conditions of stor-
age such as agitation, temperature, dilution, and evaporation.
Additional applications of antioxidant emulsions may be devel-
oped if the emulsions have a small average particle size of around 1.5
m;crons and a sufficiently narrow particle size distribution. Such addi-
tional application can be found in the coating industry where coating or
treating solutions for various materials would benefit from a small average
particle size, fairly narrow particle size distribution antioxidant emul-
sion. Antioxidants that would be particularly useful in a small average
particle size, fairly narrow particle size distribution emulsion would
be those that are of low volatility, and/or heat resistant and/or non-
discoloring.
It is an object of the present invention to provide an oil-in-
water emulsion of an antioxidant and especially antioxidants of low volatility,
5 9 9 3
and/or heat resistant, and/or non-discoloring that has an average particle
size of less than 1.5 microns9 a fairly narrow particle size distribution,
good stability and good dilutability to a low concentration.
It is an additional object of the present invention to provide
a treating composition for glass fibers that are to be used for reinforce-
ment of various polymeric materials and that reduce degradation of the
reinforced polymer due to an interaction between the chemicals in the
treating composition or their reaction or decomposition products and the
polymeric material.
It is a further additional object of the present invention to
provide a method for reducing degradation of a glass fiber reinforced poly-
mer due to any interaction between the materials present in the sized glass
fiber strand and/or reaction or thermal clecomposition products thereof
under thermal aging conditions, thereby reducing any decrease in mechanical
properties of the reinforced polymer due to such degradation.
Summary of the Invention
In accordance with the present invention, the aforementioned
objects and other objects which are inherent from the following discussion
are achieved by having a method for reducing chemical degradation of poly-
mers due to chemical interaction between chemicals in the sizing composi-
tion of the reinforcement and/or chemical reaction or thermal decomposition
products of said chemicals and the polymer by adding an antioxidant either
to the treating composition for the reinforcement or adding an additional
amount of one or more antioxidants with low volatility and good heat
resistance to the polymeric material.
Thus, the present invention provides an oil-in-water emulsion of an
anti-oxidant having low volatility and good thermal resistance, where the
i.~
` J~6'j~93
aqueous emulsion has an average particle size of less than 1.5 microns and improved
stability, comprising:
a. about 5 to about 60 weight percent of the antioxidant selected from
hindered phenolic antioxidants or diarylamine antioxidants having low volatility
and good thermal resistance, that has limited solubility or miscibillty in water
as a liquid or solid,
b. about 0.5 to about 50 weight percent of an organic solvent or mixture
of organic solvents having a kauri butanol value of from about 10 to about 50, if
the antioxidant is substantially aliphatic, or a kauri butanol value of about 50 to
about 100 if the antioxidant is substantially aromatic;
c. about 3 to about 15 weight percent of one emulsifier or a blend of
emulsifiers selected from the group consisting of nonionic and anionic emulsifiers
or mi~tures thereof wherein the one emulsifier or the emulsifler blend has a total
hydrophilic lipophilic balance in the range of about 12 to about 27.
~0
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The treating composition for the reinforcement such as sizing
compositions used with glass fibers, has the antioxidant present in the
form of an oil-in-water emulsion that has a small average particle size and
a fairly fine particle size distribution in order that the treating compo-
sieiOn adequately coats the surface of the reinforcement. The treating
composition can contain other components that are conventionally used in
treating compositions for glass fibers. Non-exclusive examples of these
include coupling agents, film-formers, lubricants, surfactants, and the
like.
~0 The oil-in-water emulsion of the antioxidant allows for high con-
centrations, up to about 60 weight percent of the aqueous emulsion, of the
water immiscible or water insoluble or lim ted water soluble and miscible
hindered phenol or diaryl amine antioxidant with low volatility and good
thermal resistance and good polymer compatibility. The emulsion also has
an organic solvent that is fugitive at just above ambient temperatures to
temperatures greater than those just above the temperature used to treat
and process the reinforcement treated with the emulsion. The emulsion also
has one or more emulsifiers or emulsifier blend wher~in the hydrophilic/
lipophilic balance (HLB) for the blend is in the range of about 12 to about
27.
Low volatility refers to the antioxidant having a percent weight
loss measured by thermal gravimetric analysis (TGA) of less than about 20
percent when about 6 mg of antioxidant is heated to 250C. and held for 30
minutes. This assures the presence of a sufficient amount of anti-oxidants
in the reinforced polymer.
The good heat or thermal resistance or stability of the anti-
oxidant refers to the antioxidant not decomposing in any way to lose its
effectiveness at temperatures of less than around 200F. (93C.).
~ ~ ~59~
The compatibility between the antioxidant and the polymer to be
reinforced refers to the antioxidant having the capability of forming second-
ary bonds such as hydrogen bonding, Van der Waals bonding, and dipole inter-
actions and ionic bonding with the polymers. If the antioxidant is very com-
patible with the polymer and has a high degree of at least secondary bonds,
the volatility of the antioxidant can approach the upper limit of weight loss.
In general, the process of this invention comprises the following.
The oil-in-water antioxidant emulsion is prepared. The aqueous treating
solution containing the emulsion is prepared with at least a film-former
and coupling agent and optionally a lubricant and other conventional sizing
additives used to treat glass fibers. The glass is formed into glass fiber
strands, and during the formation the aqueous treating solution is applied
to the glass fibers. The treating solution, also known as a sizing compo-
sition, in contact with the glass is dried to remove moisture and the fugi-
tive organic solvent. The dried, treated glass fibers are used in any form
as reinforcement for polymeric materials.
In addition to incorporating the antioxidant into the reinforced
polymer by use of the oil-in-water emulsion, the low volatile, heat resis-
tant antioxidant may be incorporated into the polymer during polymerization
andlor dry compounding to prepare the fiber reinforced polymer. This addi-
tion is in excess of the usual amount of antioxidant added to the polymer
formulations. Usually less than 1 part per hundred parts of polymer up to
around 3 parts per hundred of polymer are added to polymer formulations.
This addition protects the polymer during processing and in use from degra-
dation due to oxygen, ozone and water. The additional amount in excess of
that added for such protection protects a fiber reinforced polymer from
chemical degradation. The chemical degradation is that associated with
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~ ~ 65~3
interactions of chemicals in treating solutions and/or reaction and/or
thermal degradation products thereof used to treat the reinforcement
material.
Detailed Description of _ e Invention
Althou~h the theory of the degradation of the reinforced polymer
is not completely understood, it is believed that there is a chemical
interaction between the chemical compounds of the sizing composition on the
glass fibers or reaction products and/or thermal decomposition products of
these chemicals and the polymer. This interaction leads to chemical degra-
dation of the polymer over and above any degradation due to oxygen, oæone
and/or water. This chemical degradation is especially prevalent when the
reinforced polymer is subjected to elevated temperatures and thermal aging.
It is believed that the degradation i9 more than thermal autooxidation,
since the molding of the fiber reinforced polymers taltes place in closed
molds that would reduce the amount of oxygen present, and since the rein- -
forcement such as glass fiber contains little, if any, moisture because
the glass fibers have been dried to reduce their moisture content before
the molding operation is performed. It is further believed that certain
types of compounds present in the treating solution and on the dried
treated glass fibers may be subject to thermal degradation at conditions
that are milder than those conditions that cause polymer degradation. It
is believed that an example of these compounds are the polyoxyalkylene type
compounds that are used as nonionic emulsifiers in the treating solutions.
It has been discovered that the addition or incorporation of
hindered phenolic or diaryl amine antioxidants having low volatility, good
thermal stability and good polymer compatibility into the polymer or into
1 ~ ~5~9~
an aqueous sizing composition for treating glass fibers during their forma-
tion reduces the amount of chemical degradation of the fiber reinforced
polymer. The reduction in chemical degradation extends the mechanical
properties and service life of the fiber reinforced polymers and this is
especially so under conditions of thermal aging.
The types of hindered phenolic andtor diaryl amine antioxidants
that can be used include the non-exclusive examples of high molecular
weight hindered phenolic compounds, high molecular weight hindered bis-
phenolic compounds, high molecular weight hindered phenolic amines, high
molecular weight hindered mono-phenolic compounds; 3,5-di tert butyl-4
hydroxy hydrocinnamic acid triester with 1,3,5-tris(2-hydroxy ethyl)-bis
triazine-2,4,6(1 ~, 3 H, 5 H)-trione; alkylated phenols and bis-phenols a~d
phenol condensation products such as a 3:1 condensate of 3 methyl, 6 ter-
tiary buLyl phenol with cro~on-aldehyde; tetra-functional hindered phenols
such as tetrakis(methylene 3-) 3', 5'-di--t-butyl-4' hydroxy phenyl (pro-
pionate) methane; oc~adecyl(di-t-butyl hydroxy phenyl propionate) and other
such phenolic compounds havin~ the following structure:
(lower alkyl) 0
H0- -(CAH2A)-C-0-(CBH2B)-R
(lower alkyl)
wherein A has a value of from 0 to 6 inclusively and B has a value from
2 to 30 inclusively and ~ is a membe~ consisting of hydrogen, hydroxy,
such as the following compounds 1,2-propylene glycol bis-[3,5-di-t-butyl-
4-hydroxyphenyl)-propionate; ethylene glycol bis[3-(3,5-di-t-butyl-4-
hydroxyphenyl)propionate; neopentyl bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)
propionate]; ethylene bis (3,5-di-t-butyl-4-hydroxyphenyl acetate; glycerine-
[n-octadecanoate-2,3-bis-(3,5-di-t-butyl-4-hydroxyphenyl acetate); sorbitol
~ 3 ~ 393
hexa-[3(3,5-di-t-butyl-4-hydroxyphenyl)propionate]; 2-hydroxyethyl 7-(3-
methyl-5-t-butyl-4-hydroxyphenyl)heptanoate; N,N'-hexamethylene bis (3,5-
di-tert-butyl-4-hydroxy)-hydrocinnamamide and the like; polybutyl bis-
phenol; esters of ethoxylated aryl phenols and bis aryl phenols such as the
acetate ester of the condensation of 5 moles of ethylene oxide with 1 mole
of benzylphenol; the lauric ester of the condensation product of 24 moles
of ethylene oxide and 1 mole of bis benzylphenol; the stearate ester of the
condensation product of 10 moles of ethylene oxide and l mole of alpha
methyl benzylphenol; neutral adipate esters of the condensation product of
2 moles of ethylene oxide with l mole of alpha, alpha' dimethyl benzylphenol;
the dipelargonate ester of the condensation product of 17 moles of ethylene
oxide and l mole of bis methyl benzylphenol; the neutral malonate ester of
the condensation product o 8 moles of ethylene oxide with l mole of alpha-
ph'enyl-benzyl-phenol; the palmitate ester of the condensation product of
3 moles of ethylene oxide with 1 mole of a]pha methyl benzylphenol and the
like; condensation products of oxalyl dihydrazide and 3-tertiary butyl-4-
hydroxy aryl carbonyl compounds such as 3,5-ditertiary butyl-4-hydroxy-
benzaldehyde. Especially useful are the antioxidants like tetrakis(methyl-
ene 3-3', 5'-di-t-butyl-4' hydroxy phenol)propionate methane, substituted
diphenyl amine like 4,4'-[2-(2-phenyl)propyl~diphenylamine; a 3:1 condensate
of 3 methyl,6 tertiary butyl phenol with croton aldehyde and octadecyl 3-
(3', 5'-di-tert-butyl-4-hydroxy phenyl) propionate and the like; condensa-
tion product of oxalyl dihydrazide and 3,5-di-tertiary-butyl-4-hydroxy aryl
carbonyl compounds; esters of ethoxylated aryl phenols and 1,3,5-trimethyl-
2,4,6-tris[3,5-di-tert butyl-4-hydroxybenzyl]benzene. The aforementioned
antioxidants that benefit most from the present invention are those that
are water immiscible or water insoluble.
9 ~ 3
When any of the aforementioned antioxidant stabilizers have a
high degree of compatibility with monomers polymerized to produce polymers
to be reinforced with fibrous materials, the antioxidant stabili~er can be
added directly to the polymer to overcome the chemical degradation due to
chemical compounds present on the fibrous reinforcement material or their
chemical and/or thermal degradation products.
Synthetic organic polymeric substances which are to be reinforced
with fibrous materials, useful with the present invention, include the non-
exclusive examples of vinyl polymers such as poly-alpha-olefins such as
polyethylene, polypropylene, polybutylene, polyisoprene and the like includ-
ing copolymers of poly-alpha-olefins; polyurethanes such as are prepared
from polyols and organic polyisocyanates; polyamides such as polyhexa-
methylene adipamide; polyesters such as polymethylene terephthalates and
polybutylene terephthalates and polyethylene and polypropylene terephtha-
lates; polycarbonates, poly-acetals, polystyrene, and copolymers such as
those of a high impact polystyrene containing copolymers or butadiene and
styrene and those formed by the copolymerization of acrylonitrile, butadiene
and/or styrene.
In general, small amounts of the antioxidant stabilizers are
added to the polymers during polymerization, although larger amounts are
added to polymers during formulations, compounding and fabrication and
final manufacture of the reinforced polymeric material. In general, the
antioxidants are employed in an amount of from about 0.00~ percent to about
3 percent by weight based upon the stabilized composition. In polypropyl-
ene, amounts of from about 0.01 percent to about 3 percent by weight are
advantagous with from about 0.01 to about 1 percent by weight being espe-
cially preferred. Therefore, the amount of antioxidant stabilizer needed
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~ 1 6~9'33
to overcome the chemical degradation of any compounds on the reinforcement
material to be used for reinforcing the polymer or the reaction and/or
decomposition products of the compounds must be an extra amount in the
range of about 0.25 to about 1.0 part per hundred parts of polymer and
reinforcement that is added to the Polymer that may already have up to
3 percent of some type of antioxidant. This additional amount of anti-
oxidant can be added to the polymer to be reinforced at any time before the
final production of the reinforced polymeric material. It is most advan-
tageous to add the additional amount of antioxidant to the polymerized
polymer that is ready to be compounded with the reinforcement, preferably
glass fibers are used to produce the reinforced polymeric material. The
antioxidant can be added in any form such as the solid form, liquid or as
an emulsion or dispersion in aqueous or non-aqueous solvents.
When the additional amount of the antioxidant is incorporated
into the aqueous treating solution or sizing compound placed on the rein- -
forcing material such as glass fibers, the antioxidant is added to the
treating solution for the glass fibers as an oil-in-water emulsion. The
aqueous emulsion is necessary in order to provide near uniform coating of
the glass fibers as they are formed. In order to reduce the amount of
degradation of polymeric materials that are reinforced with fibrous rein-
forcement having chemical agents present that upon thermal aging cause
chemical degradation in the polymer, the amount of antioxidant present in
the emulsion should be in the range cf about 5 to about 60 weight percent
of the emulsion.
The oil-in-water emulsion of the aforementioned antioxidants
that are water immiscible or water insoluble comprises in addition to the
antioxidant one or more organic solvents and one or more emulsifiers.
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~ ~ 65993
The organic solvent will vary with the different antioxidants
used in such a way that if the antioxidant is predominantly aliphatic the
organic solvent will have a low kauri-butanol value such as from about 10
to about 50 and have a boiling range within the range of from ambient tem-
peratures to about 250C. where the boiling point is above the temperature
of use for the emulsion that is the treating of glass fibers with aqueous
sizing compositions. If the antioxidant has more than about 60 percent
aromaticity the acceptable organic solvent will have a kauri-butanol value
of from about 50 to about 100 with a boiling range which lies within the
range of about ambient temperature to about 250C. and which is above the
temperature of use for the emulsion. The use of organic solvents with a
boiling point above 250~C. is not advantageous since the solvent is to be
removed after the reinforcement is treated. When the organic solvent has a
boiling point below around 100C. to arouncl 150C., the use of suction
equipment to control the escaping vapor is necessary.
The kauri-butanol number is a measure of solvent power of petro-
leum thinners where the value is the number of milliliters of solvent
required to cause cloudiness when added to 20 grams of 8 solution of kauri
gum in butyl alcohol. The solution is prepared in the proportion of 100
~o grams of kauri gum and 500 grams of butyl alcohol. Solvents of low aro-
matic content are strong precipitants for the resin, and therefore, give
low values. Conversely the sclvents having a high aromaticity give high
values. The kauri-butanol numbers are preferably determined aguinst one of
two standards where the one standard is a one degree toluene with a value
o~ 105 used when the organic solvent is a kauri-butanol value over 60, and
the other standard is a mixture of 75 percent of N-heptane and 25 percent
toluene when the organic solvent has a kauri-butanol number of 40. This is
discussed in ASTM Standard D.1133-54T.
~ 1 6~93
Organic solvents from which the low and high kauri-butanol sol-
vents are selected are solvents such as aliphatic hydrocarbons, aromatic
hydrocarbons, esters, ethers, alcohols~ ketones, petroleum distillates
and coal tar distillates and mixtures thereof. Examples of organic sol-
vents with low kauri-butanol numbers use~ul when the antioxidant has a
substantial amount of aliphatic components are the isoparaffinic hydrocar-
bon solvents. Suitable examples are those of the series of commercially
available isoparaffinic hydrocarbon solvents sold by EXXON Company USA
under the trademark "ISOPAR" or Philips Petroleum under the trademark
"SOLTROL" which have boiling ranges within the above ranges. Examples of
or~anic solvents with a high kauri-butanol value include the solvent
* *
commercially available under the trade name "HI-SOL-10" or "HI-SOL-15"
available from Ashland Chemical Company, Ohio. The "HI-SOL-10" solvent has
a boiling point of 308F. (150C.) and a flash point of 105F. (40.6C.)
and an evaporation rate of 25.0 using an ether base of 1. Also, the
organic solvént sold by EXXON Company USA, ~ivision of EXXON Corp. Co.
under the name "SOLVESSO 150" or "S0LVESS0 100" can be used. Additional
examples of organic solvents that can be used in forming the antioxidant
oil-in-water emulsion of the present invention are the following non-exclu-
~U sive examples xylene, methyl ethyl ketone, cyclohexanone, cyclopentanone,methyl isobutyl ketone, toluol, ethyl cellosolve, toluene, butyl carbitol-
acetate, butyl cellosolve acetate, trichlorethylene, methylene chloride,
amylacetate, ethyl acetate, and the like.
The ratio of the antioxidant to the organic solvent will vary
depending on the particular antioxidant and solvent employed, but generally
ehe ratio will be in the range of at least about SO to about 40 of anti-
oxidant to solvent and preferably up to about 40:60 and most preferably
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1 ~6~93
about 50 to about 60. Less solvent will be needed if the organic solvent
has a higher kauri-butanol number when the antioxidant has substantial aro-
maticity and when the kauri-butanol number approaches 50, when the anti-
oxidant has a substantial amount of aliphatic character. The amount of the
organic solvent used in making up the emulsion of the antioxidant will gen-
erally vary within the range of about 1 to about 50 percent by weight of
the emulsion. More solvent can always be added, but there is no benefit to
such practice since the solvent is usually removed at some later time.
The one or more emulsifiers of the present invention is selected
from nonionic emulsifiers or a mixture of one or more nonionic emulsifiers
with an anionic emulsifier. When more than one emuslifier is used, the
emulsifiers constitute an emulsion blend of at least two emulsifiers. The
emulsifiers are selected to give a hydrophilic-lipophilic balance (HLB
value) for the emulsifier or emulsifier blend in the range of about 12 to
about 27. Non-exclusive examples of chemical types of emulsifiers for use
in the blend of emulsifiers are nonionic emulsifiers such as ethoxylated
alcohols, ethoxylated alkyl phenols, ethoxylated fatty acids, ethoxylated
fatty esters and oils, fatty esters, glycerol esters, glycol esters, mono-
glycerides and derivatives, sorbitan derivatives, sucrose esters and deriv-
atives, alkylene glycol ethers, alkyl polyether alcohol, alkyl aryl poly-
ether alcohol, and polyoxide alkyl condensates. Non-exclusive examples of
the anionic emulsifiers include alkyl sulfonates, phosphate esters, poly-
aminocarboxylic acids and related sequestering agents, succinates sulfo
derivatives, alcohol sulfates, ethoxylated alcohol sulfates, sulfates and
sulfonates of ethoxylated alkyl phenols, oils and fatty esters and the like.
The amount of the emulsifier or emulsifier blend added to the emulsion is
in the range of about 3 to about 15 weight percent of the emulsion.
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,
In addition to the antioxidant, organic solvent and one or more
emulsifiers, the emulsion contains an amount of water that is necessary to
make the emulsion an oil-in-water emulsicn which is generally in the range
of about 2B to about 70 weight percent. If the emulsion is to be shipped for
any considerable distance, it is most p~actical to add just the amount of
water needed to make the emulsion an oil-in-water emulsion that is actually
a concentrated emulsion that can be further diluted at the location of use.
In preparing the emulsion of the present invention, one or more
of the aforementioned antioxidants is dissolved in one or more of the fugi-
tive organic solvents suitable for the particular antioxidants involved.Also, the antioxidant or antioxidants may be meltsd and then added to the
fugitive organic solvent. The mixture of the one or more antioxidants with
one or more organic solvents may be subjected to moderately elevaeed tem-
peratures to facilitate solubili7ation of the antioxidants. The mixture of
the antioxidant dissolved in the organic solvent has added to it the one or
more emulsifiers, and this mixture is emulsified using standard techniques,
conditions and spparatus. Such standard techniques include the direct method
of preparing an emul~ion or the indirect ~ethod of preparing an emulsion
wherein water is added until the oil inverts into an oil-in-water emulsion.
ao The amount of w~ter added to the orsanic solution of the ~ntioxidant and
emulsifier blend is that to give an emulsion containing from about 28 to
about 70 percent by weight water. The homogenizing action can be carried
out in a variety of equipment which can subject the aqueous organic mixture
to high shear forces. ~n example of such equipment i~ an Eppenbac~ colloid
mill with a gap setting at 20. A ~anton-Gaulin homogenizer can be used
~lso at pre~sure of 3000 ~o 6000 p.s.i. (210 ~o 420 kg/cm2). The emul-
sifier or emulsifier blend can be added to the mixture of one or more
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1 1 6~993
antioxidants and one or more organic solvents by adding the emulsifer
separately to the mixture or by adding any combination of the emulsifiers.
~fter the emulsifiers are added, the resulting mixture is dilluted slowly
with water according to the invert emulsion technique, where the water can
be at ambient temperature or at some elevated temperature. The water is
added slowly until the emulsion inverts to an oil-in-water emulsion and
then the emulsion is cooled to ambient conditions. During the cooling
operation or afterwards additional water is added to bring the emulsion eO
the desired concentration. The amount of water added to the emulsion is at
least about 28 weight percent of the emulsion composition.
One usage for the antioxidant emulsion which is particularly
beneficial is the use in a treating solution for glass fibers. The emul-
sion has a fine droplet or particle size sufficient to allow for near uni-
form coating of the treating solution on the glass fiber surface. The
oil-in-water antioxidant emulsion can be formed into an aqueous treating
solution or as termed in the art a sizing composition, for glass fibers by
combining the emulsion with sizing composition ingredients such as film
formers, coupling agents, lubricants and perhaps additional components such
as softeners, wetting agents, anti-foaming agents and additional surfac-
tants. This formation can involve slowly adding the emulsion to an aqueousmixture containing one or more coupling agents and any lubricants or soft-
ening agents and film formers and the remaining water to ma~e the aqueous
sizing composition. It is also possible to add the one or more coupling
agents, lubricants, softening agents, film formers, or other sizing agents
to a mixture containing the emulsion alone or the emulsion and any one or
more of the afore-mentioned sizing composition ingredients. Once the emul-
sion of the present invention is prepared, the aqueous sizing composition
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can be made in any manner known to those skilled in the art. For example,
the amounts of coupLing agents, lubricants, film-formers and other sizing
ingredients can generally be in the following ranges.
in weight percent of the aqueous size:
coupling agent about 0.5 to about 10
lubricant about 0.001 to about 1
~ilm-former about 0.5 to about 15
The aqueous sizing composition is applied to individual glass
fibers during their formation by any conventional method of applying sizing
compositions to glass fibers. The glass fibers are attenuated from molten
streams of glass which can be an E glass or 621 glass composition or any
low polluting derivative thereof. Such methods are shown in U.S. Patent
4,027,071 (Motsinger).
Sized glass fibers are dried to remove moisture and the fugi-
tive organic solvent. The drying can be accomplished by air drying or
drying in a heated oven. 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 such as polyamides, like Nylon 6; polyesters, like
polybutyleneterephthalate, polyolefins like polyethylene, polypropylene and
copolymers thereof and the like.
Preferred Embodiment
In the preferred embodiment of the present invention, the
antioxidant used to overcome chemical degradation of a reinforced polymeric
material due to chemical interaction between chemical compounds present on
the fibrous reinforcement or the compounds reaction or thermal degradation
psoducts and the polymer is added to the aqueous treating solution for the
L_ ~ ~
~ 5 ~ ~ 3
fibrous material which is preferably glass fibers. It is preferred to
incorporate the antioxidant into the aqueous treating solution by a
combination of the oil-in-water antioxidant emulsion with other components
to prepare the aqueous treating solution.
In the preferred oil-in-water emulsion the antioxidants used have
fairly low volatility, good thermal stabiliey, and good polymer compati-
bility. The preferred emulsion uses about 5 to 60 and most preferably
about 5 to about 25 weight percent of octadecyl 3-~3', 5'-di-tert-butyl-4-
hydroxyphenyl, propionate) available from Ciba Geigy Corporation under the
*
trade designation "IRGANOX 1076". This antioxidant which is a white,
crystalline, free-flowing powder with a melting range between 50 and 55C.
and a molecular weight of around 531 is dic;solved preferably in about a 1
to 1 ratio with xylene. To this mixture there is added about 3 to about 15
preferably 3 to about 12 weight percent of an emulsifier blend. It is
preferred that the emulsifier blend be a combination of three emulsifiers
that when used ;n certain weight ratios to each other give a total HLb for
the emulsion blend in the range of about 12 to about 27. It is preferred
that one emulsifier have a high HLB value in the range of about 12 to about
27. ~nother emulsifier has a lower HLB value in the range of about 6 to
about 12 and another emulsifier has an HLB value in the middle range of
about 9 to about lS. 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 HLB range.
It is most preferred to have a first emulsifier which is a tri-
methyl nonyl polyethyleneglycol ether such as that commercially available
from Union Carbide Corporation under the trade designation "T~RGITOL TMN-6!'
having an HLB of 1l.7. This ether is used in an amount of about 1 to about
18 -
,'.
.. :
3 659~3
5 weight percent of the emulsion. The ether emulsifiers combined with
another emulsifier which is nonyl phenoxy polyethyleneoxy ethanol, commer-
cially available from GAF Corporation Chemical Products under the trade
designation "IGEPAL C0-630" having an HLB of 13 and used in an amount of
about l to about 5 weight percent of the aqueous emulsion. These two emul-
sifying agents are combined and stirred until clear. Then another emulsi-
fying agent whicll is a condensate of ethylene oxide with hydrophilic bases
formed by condensing propylene oxide with propylene glycol and is commer-
cially available from BASF Wyandotte Industrial Chemical Corporation under
the trade designation "Pluronic-P-65" which has an HLB of 17 and is used in
an amount in the range of about l to about 5 weight percent of the aqueous
emu 1 9 ion composition.
It is preferred to add the emulsi~ier blend in the following
manner. A mixture of the ether emulsifying agent and ethanol emulsifying
agent are combined with the mixture of the antioxidant and organic solvent.
The polyoxyalkylene oxide block copolymer emulsifier is split into two por-
tions, preferably around a 50/50 split wherein the first portion is added
to the mixture of the emulsifiers, antioxidant and solvent, and the second
portion is added to water preferably in around a 50/50 blend and then this
portion of the oxide block copolymer emulsifier in water is combined with
the emulsifier, antioxidant, solvent mixture. The final mixture is then
agitated with the addition of an amount of warm water of about 25 to about
30C. in the range of about 15 to about 30 weight percent of the aqueous
emulsion. Then an amount of cold water is added to give an amount of
active antioxidant in the range of about 5 to about 25 weight percent to
produce the aqueous emulsion.
- 19 -
~;`
5 ~ 9 3
In an alternative embodiment, the antioxidant tetrakis(methylene-
3-3',5'-di-t-butyl-4'-hydroxy phenyl)propionate methane available from Ciba
Geigy Corporation under the trade designation "IRGANOX 1010" antioxidant is
dissolved in an amount of about 5 to about 20 weight percent of the emul-
sion in the organic solvent methyl ethyl ketone. The amount of methyl
ethyl ketone used is in the range of around a 1 to 1 ratio with the anti-
oxidant. The emulsifier blend is combined with this mixture by any of the
aforementioned manners of addition. The emulsifier blend comprises the
~mulsifier polyoxyethylene (~) sorbitan monolaurate (Tween 21 available
fror~l ICI Americas, Inc.) wherein the amount of the monolaurate emulsifier
is in the range of about 1 to about 5 weight percent. Another emulsifier
that is used is a condensate of ethylene oxide with hydrophilic bases
formed by condensing propylene oxide and propylene glycol which is availa-
ble from BASF Wyandotte under the trade designation "Pluronic F-85" having
an ULB of 24 and used in an amount of about 1 to about 5 weight percent.
Another emulsiEier that is used is the polyethoxylated vegetable oil avail-
able from GAF Corporation under the trade designation "EMULPHOR EL-719"
having an HLB of 13.6 and used in an amount of about 1 to about 5 weight
percent. In addition to the antioxidant, the methyl ethyl ketoneJ and the
2~ emuls;fiers, an amount of polyalkylene polyol lubricant available under the
trade designation "Pluracol V-10" available from BASF ~yandotte Corporation
is added to the emulsion in an amount of about l to about 5 weight percent.
This lubricant is added to give the emulsion additional stability. This
lubricant can also be added to the si~ing composition rather than to the
emulsion. The polyalkylene glycol "Pluracol V-10" is a viscous, high
mGlecular weight, liquid with a specific gravity at ~5/25 C. by BWC Test of
1.089 with a flash point by ASTM D92-52 of 510F. To the mixture of the
- 20 ~
9 ~ ~
antioxidant, methyl ethyl ketone, monolaurate, oxide glycol condensate and
vegetable oil emulsifiers and polyol lubricant there is added the requisite
water to produce an oil-in-water emulsion as for the preferred antioxidant
discussed above.
Another alternative embodiment is to use 3 substituted diphenyl-
amine antioxidant ~,4'-[2-(2-phenyl)propyl]diphenylamine available from
Uniroyal Chemical Corporation under the trade designation "NAUGARD 445" in
an amount preferably in the range of about 5 to about 25 weight percent
dissolved in acetone used in an amount of around a 1 to 1 ratio with the
antioxidant. To this mixture of antioxidant and solvent the emulsifier
blend is added by any of the methods discussed in the preferred antioxidant
emulsion. The emulsifiers include the condensate of ethylene oxide with
hydrophobic bases formed by condensing propylene oxide and propylene glycol
which is available from BASF Wyandotte Corporation under the trade designa-
tion "Pluronic F-87" having an HLB of 24 and used in an amount of about 0.5
to about 5 weight percent along with another ethylene oxide-propylene oxide
glycol condensate available under the trade designation "Pluronic P-65"
that has an HLB of 17 and is available in a paste form. ~nother emulsifier
that is used is the polyethoxylated vegetable oil available from GAF under
the trade designation "EMULPHOR EL-719" having an HLB of 13.6c To this
mixture there is added a requisite amount of water by any of the methods
discussed above for the preferred embodiment.
~nother alternative embodiMent is to use an antioxidant that is a
3:1 condensate of 3 methyl-6-tertiary butyl phenol with crotonaldehyde,
available from ICI US, Inc. under the trade designation "TOPANOL CA" in an
amount in the range of about 5 to about 25 weight percent of the emulsion.
This antioxidant which is a fine white crystalline powder with a melting
- 21 -
5993
point of 182.5C. to 188~0. is dissolved in cyclopentanone which is used in
an amount of around a 1 to l ratio with the antioxidant. To this mixture
there is added an emulsifier blend by any of the methods used in the pre-
ferred embodiment where the emulsifier blend comprises an octyl phenoxy
polyethoxyethanol emulsifier available from Rohm & Haas Company under the
trade designation "TRITON X-lOO" which is used in an amount of about 1 to
about 5 weight percent of the emulsion. Another octyl phenoxy polyethoxy-
ethanol emulsifier that is used is available from Rohm & Haas Company under
the trade designation "TRITON X-45", and it i9 used in the same amounts as
the Triton X-100 emulsifer. The X-lOO has an HLB of 13.5 and the X-45 has
an Hl.B of 10.4. In addition to the antioxidant, solvent, emulsifier blend
mixture an amount of epoxy resin such as Epon 828 epoxy resin available
from Shell Chemical Company can be added to the emulsion in an amount of up
to about 40 weight percent of the emulsion. This mixture is then emulsi-
fied by the indirect method by adding water to invert the oil to an oil-in-
water emulsion. The amount of water that is added and the method it is
added is similar to that discussed for the preferred embodiment. This
emulsion of the antioxidant with the solvent and emulsifiers and epoxy
resins allows for the simultaneous emulsification of the antioxidant and
the epoxy resin.
Any of these aforementioned oil-in-water emulsions and preferably
the emulsion having the octadecyl 3-(3',5'-di-tert-butyl-4-hydroxyphenyl)
propionate antioxidant can be formulated into a sizing composition for
treating glass fibers. This formulation preferably occurs by adding to an
aqueous composition containing a coupling agent that is preferably a mix- -
ture of coupling agents such as an organo diamino silane coupling agent
and an epoxy containing organo silane coupling agent wherein both are
- 22 -
t~
c, . ..
._. ...
~` ~
1 1 65~93
present in an amount of about 0.5 to about 10 weight percent of the aqueous
siæing composition. To this mixture there is also added film-formers
like epoxy-containing resin in an amount of about 0.5 to about 12 weight
percent of the aqueous sizing composition. In an alternative embodiment
other sizing ingredients may be added like lubricants, such as the Pluracol
V-10 lubricant, wetting agents, and additional surfactants and cationic
agents. The amount of water in the aqueous sizing composition usually
ranges from about 70 to about 99 weight percent of the sizing composition.
The aqueous sizing composition is applied to individual glass
fibers during their formation according to the manner illustrated in U.S.
Patent 4,027,071 and the sized glass
fibers are subsequently dried to remove the moisture and organic solvent.
The antioxidant oil-in-water emulsion used with the aforementioned si~ing
composition having a mixture of silanes and a film-former reduces the
chemical degradation of polymers that are reinforced with these glass
fibers, especially at exposures to sever, end use, elevated temperatures.
This is particularly beneficial when these si~ed glass ibers are used to
reinforce polyesters such as polybutylene terephthalate.
The aqueous emulsions of the present invention will be further
elucidated by making reference to the follo~ing examples.
Example I
An emulsion was prepared by the following method. First, 180
grams (8.7 weight percent of the emulsion) of a 3:1 condensate of 3 methyl-
6-tertiary butylphenol with crotonaldehyde antioxidant available from ICI
U.S. Inc. as Topanol CA antioxidant was dissolved in an epoxy resin solu-
tion at 120F. (49C.). The solution contained 540 grams (26.2 wt.%) of
- ~3 -
~ir~, .. i .
1 1 ~5~393
epoxy resin available from Ciba Products Corporation under the trade desig-
nation "Araldite 540 X90" and 100 grams (4.9 wt.%) of methyl ethyl ketone
and 140 (6.8 wt.%) grams of trichloroethylene.
Second, two emulsifiers that are condensates of ethylene oxide
with hydrophobic bases Eormed by condensing propylene oxide with propylene
glycol were blended into the antioxidant emulsion. The one emulsifier was
Pluronic L-35 having an HLB of 18.5 used in an amount of 66 grams (3.2 wt.%)
and the other emulsifier was Pluronic F-127 emulsifier that has an HLB of
22 and used in an amount of 33 grams (1.6 wt.%). Both of these emulsifiers
are available from BASF Wyandotte Industrial Chemical Group. The emulsi-
fier blend had a combined HLB of 19.6. The two were blended into the anti-
oxidant mixture until the F-127 emulsifier was completely melted.
The blended mixture was cooled before being homogenized in an
Eppenbach homogenizer with the slow addition of 1000 grams of water at room
temperature. This emulsion could be used in fl sizing composition for glass
fibers.
EXAMPL~ 2
Using the same preparation procedure another emulsion was
prepared that had the following formulation:
wt~ grams
A. Epoxy resin (Araldite 540 X90) 25.4 540
Antioxidant tNaugard 445) 8.5 180
trichloroethylene 6.6 140
methyl isobutyl ketone 4.7 100
Blended with A was
Pluronic Condensate emulsifier
L-35 5.2110 grams
F-127 2.452 grams
water 47.11000 grams
~'
9 9 3
EXAMPLE 3
Using the same preparation procedure as in Example 1 an emulsion
was prepared that had the following formulation:
wt% gm.
A. Epoxy resin (Araldete 540X90) 29.6 685
Antioxidant (Naugard 445)7.8 180
~lethyl ethyl ketone 4.3 100
Butyl Gellosolve acetate 4.3 100
l,l,l-tri-chloroethane 6.0 140
*
B. Nonionic emulsifier (Pluronic L-35) 3.0 70
Nonionic emulsifier (Pluronic F-108) 1.6 36
Water 43.3 1000
This three solvent blend, dual emulsifier blend yielded an
emulsion with good stability.
EXAMPLE 4
Employing the identical preparation procedure as in Example 1
an emulsion was prepared that had the following formulation:
wt% gm.
*
A. Epoxy resin (Araldete 540X90) 25.4 540
*
Antioxidant (Naugard 445) 8.5 180
2~ Methyl carbitol acetate9.4 200
methyl ethyl ketone 4.7 100
Nonionic emulsifier Pluronic L-353.3 70
Nonionic emulsifier Pluronic F-127 1.6 35
Cold Water 47.1 1000
- 2S -
"
~ v 1 1 65~93
The inversion occurred with the addition of 700 grams of water
and the entire complement of water was added to produce a stable emulsion.
EX~MPLE 5
An amount of 720 grams 25.8 weight percent of the aqueous emul-
sion of antioxidant tetrakis[methylene 3-(3',5'-di-t-butyl-4'-hydroxyphenyl)
propionate]methane Irganox 1010 was dissolved in a mixture of 720 grams
(25.8 wt%) of cyclohexane. This dissolution occurred at a temperature in
the range of 80-90 F. (26-33 C.). To this mixture there was blended 45 grams
(1.6 wt%) of the nonionic emulsifier Tergitol TMN-6 and 45 grams (1.6 wt%)
of the nonionic emulsifier Igepal C0-630 and 65 grams (2.3 wt%) of nonionic
emulsifier Triton N-401. The emulsifier blend had an overall HLB of 19.7.
To emulsify to an oil-in-water emulsion 1200 grams t42.9 wt%) of water was
added with shear mixing. A stable emulsion was produced having a fine to
medium particle size distribution with hardly any coarse particles.
EXAMPLE 6
The emulsion of Example 5 was used in preparing a sizing composi-
tion that was used to treat glass ~ibers. The sizing composition contained:
wt% gms.
Epoxy resin (Genepoxy 370 H55 55% solids)8.3 2730
~0 Emulsion (30.6% solids) 6.7 2210
Film-for*mer (polyurethane resin Wyandotte24.2 7980
X-1042 50% available from BASF
Wyandotte)
diamino organosilane 9.1 3000
water 18.2 6000
epoxy-containing silane 0.5 150
water 32.8 10,800
acetic acid .18 60
.01 5
- 26 -
~ 165993
The sizing composition was prepared by hydrolyzing the silanes
in the indicated amounts of water and combined. The antioxidant emulsion
was combined with the silane mixture and to this mixture there was added
the polyurethane resin. The epoxy resin available from General Mills
Company was added co the mixture. This sizing composition is hereinafter
referred to as Size 1.
The siæing was used to treat K-37 1/0 glass fibers in a wet chop
process to produce 1/8" (inch) chopped glass fibers.
EXAMPLE 7~
1~ An amount of 313 grams (7.9 weight percent of the emulsion) of
antioxidant Naugard 445 was dissolved in acetone. The amount of acetone
was 500 grams (12.7 wt%) which gave a 0.6 to 1 antioxidant solvent ratio.
This mixture was added to 1250 grams (31.6 wt~) of warm epoxy resin (Epon
828 resin~. To this mix there was added 48 grams (1.2 wt~) of the nonionic
emulsifier Pluronic F-87 and 82 grams (2.1 wt~) of nonionic emulsifier
Pluronic P-65 and 32 grams (0.8 wt%) of nonionic emulsifier Emulphor EL-719.
The latter emulsifier is a polyoxyethylated vegetable oil available from
GAF Corporation. This gives a total HLB for the emulsion blend of 18.4.
The mi~ was heated to remove the acetone although the acetone
could even be evaporated off before the addition of the emulsifier blend.
Once about 90-95~ of the acetone was removed, emulsification was
commenced using Eppenbach equipment. The water was added gradually until all
of the water was added. The emulsion mix was cooled back to room temperature.
EXAMPLES 8, 9 and 10
The emulsion of Example 7 was used in preparing three sizing com-
positions for glass fibers. These compositions are depicted in Table I
below.
- 27 -
~`
~ 1 65~3
TABLE I
Size Formulation Size 2 Size 3 Size 4
gm/wt% gm/wt% gm/wt%
Emulsion concentrate *
50% Epoxy Resin/Naugard 445
An~ioxidant 305/8.1310/8.5305/8.3
Film-former:
Urea Melamine Resin
(Resimene*resin Monsanto Chem. Co.) 36/1.0 --- ~~~
Urethane latex *
Witcoband W-210
(Witco Chemical Corp.) 200/5.3 --- ---
Urethane latex
Nopcothane UOI
(Diamond Shamrock Chemical Co.) --- 100/2.7 - -
Urethane latex *
Wyandotte X-1042H
(BASF Wyandotte Corp.) --- -- lOQ/2.7
Water 957/25.51000/27.3 1000/27.3
Water 2176/582176/59,42176/59.5
amlnosilane*
(A-llOO Union Carbide Corp.) 60/1.660/1.6 60/1.6
Urea 18/0.518/0.518/0.5
Total Solids 7.1~ 7.0% 6.84%
No problems were encountered in using the emulsions in Si~ings 2,
3 or 4. These sizing compositions were used to treat glass Eibers made
from a glass batch marble melter used to make wet chop glass fibers.
EXAMPLE 11
An oil-in-water emulsion of Irganox 1010 antioxidant was prepared
by dissolving 160 grams ~7.4 wt%) of the antioxidant in 160 grams (7.4 wt%)
methyl ethyl ketone at a temperature up to 130F. ~54C.). To this mix-
ture there was blended 50 grams of POE (4) sorbitan monolaurate (Tween 21
- - 28 -
~,
5 9 9 3
emulsifier from ICI Americas Inc.) and 50 grams of Emulphor ~L-719 material,
and 50 grams of Pluronic P-65 emulsifier and 50 grams of Pluronic F-87
emulsifier. The emulsifier blend nad a combined HL~ of 17.
Also blended into the mixture was 640 grams (29.3 wt~) of Epon
*
828 epoxy resin. The total mixture was emulsified using an Eppenbach
mixer with the addition of 1000 grams (46.5 wt%) of water.
The stability of the emulsion is good on storage of 4 hours and 5
days. Although after 5 days of storage some surface film formed which might
be due to solvent evaporation since container was open to the atmosphere.
EXAMPLE 12
An oil-in-water emulsion of Irganox 1076 antioxidant was prepared
by dissolving 160 grams (7.4 wt%) octadecyl 3-(3',5'-di-tert-butyl-4-
hydroxyphenyl)propionate in 160 grams (7.4 wt~) of toluene solvent at a
temperature of 80 to 90 F. t26C. to 33 C.). To this mixture there was
added 50 grams of POE (4) sorbitan monolaurate (Tween 21), 50 gram~s of
Emulphor EL-719 material, 50 grams of Pluronic P-65 emulsifier and 50 grams
of Pluronic F-87 emulsiEier. The emulsifier blend had a combined HLB of
17. An epoxy resin, Epon 828 resin, was stirred into the mixture, and the
resultant mixture was emulsified at a temperature of 110F. (43Co) with
the addition of 1000 grams of water.
Storability and dilutability o the emulsion was good.
EXA~PLE 13
An oil-in-water emulsion of tetraki~s(methylene 3-3'5'-di-t-butyl-
4'-hydroxyphenyl)propionate methane was prepared with the following Eormula-
tion and in the following manner. An amount of 480 grams of the antioxidant
29 -
5 ~3 ~ 3
was dissolved at 120F. (49C.) in 480 grams methyl ethyl ketone. Blended
with mixture was 150 grams of POE (4) sorbitan monolaurate (Tween 21),
150 grams of Emulphor EL-719 material and lSO grams of Pluronic P-65 emul-
sifier and 50 grams of Pluracol V-10, a lubricant. The emulsifier blend
had a combined HLB of 17 and the lubricant was added to improve the sta- -
bility of the emulsion. After these materials were blended 1960 grams of
Epon 828 epoxy resin were stirred into the blend. At a temperature of
105 F. (41 C.) the resultant mixture was emulsified with the addition of
6000 grams of water.
The dispersibility and stability of the emulsion was good. The
stability was good after two days of storage.
EXAMPLE_14
An oil-in-water emulsion of octadecyl 3-(3',5'-di-tert-butyl-4-
hydroxyphenyl)propionate was prepared in the same manner as Example 13.
The emulsion had a higher amount of solids, 34 percent. The only exception
to the manner of preparation was the dissolving of the antioxidant in the
toluene at room temperature. The formulation was:
gms.¦wt~
Octadecyl 3-(3',5'-di-tert-butyl-
4-hydroxyphenyl) propionate 480/14.4
toluene 480/14.4
POE (4) sorbitan monolaurate 105/3~1
polyethoxylated vegetable oil
~Emulphor EL-719)* 105/3.1
Condensates of ethylene oxide and
propylene oxide with propylene glycol
Pluronic P-65 100/2.9
Pluronic F-87* 100/2.9
polyalkylene polyol
(Pluracol V-10) 50/11.5
Wa~er 1920/57.5
30 ~
~ ~ ~5~3
The emulsion blend h~d a total HLB of 16.8. The emulsion had
good stability and dilutability. On storage for 4 hours and two days the
emulsion was good.
EX~MPL~ 15
An oil-in-water emulsion of an antioxidant of 3:1 condensate
of 3 methyl 6 tertiary butylphenol with crotonaldehyde antioxidant was
prepared. An amount of 160 grams (6.9 wt%) of the antioxidant was dissolved
in 160 grams (6.8 wt%) of cyclopentanone. To this mixture there was
blended 100 grams of POE (4) sorbitan monolaurate (Tween 21), and 100 grams
of polyethoxylated vegetable oil (Emulphor EL-719). The emulsifier blend
had a total HLB of 13.4.
To this blended mixture there was added 655 grams ~27.9 wt%) of
Epon 828*epoxy resin. The resultant mixture was emulsified with the
addition of 1175 grams (50 wt~) of water.
The emulsion had good dispersibiLity and good storageability for
4 hours and one day.
EXAMPL~ 16
An oil-in-water emulsion of octadecyl-3-(3',5'-di-tert-butyl-4-
hydroxyphenyl3propionate was prepared. An amount of 288 grams (17.7 wt%)
2~ of the antioxidant was dissolved in 288 grams (17.7 wt%) of xylene at
around 110F. (43C.). To this mixture there was added an e~ulsifier
blend of 18 grams (1.1 wt%) of trimethyl nonyl polyethylene glycol ethers
(Tergitol TMN-6 emulsifier available from Union Carbide Corp.), and 18
grams (1.1 wt%) of nonyl phenoxypolyethyleneoxyethanol (Igepal C0630
from GAF Corp.). Also, 18 grams (1.1 wt~) of condensate of ethylene oxide
with hydrophilic bases formed by condensing propylene oxide with propylene
31 -
~ L~
5 9 9 3
glycol (Pluronic ~-65 emulsifier available from BASF Wyandotte) was combined
with 200 grams of warm water at 80 F. (27 C.) and added to the antioxidant
mixture. The emulsifier blend had a total HLB of 13.7.
The resulting mixture was emulsified with the addition of 800
grams (49.1 wt%~ of water. m e emulsion had good dispersibility and
storageability.
EXAMPLE 17
The antioxidant tetrakis(methylene-3-3',5'-di-t-butyl 4'-hydroxy-
phenyl3propionate methane was emulsified in the following manner. An
amount oÇ 720 grams (22.7 wt%) was dissolved in a solvent mixture of petro-
leum solvent ~i-Sol-10 available from Ashland Chemical Co. in an amount of
720 grams (22.7 wt%) and 80 grams (2.5 wt%~ of methyl ethyl ketone. The
temperature was 150F. (66C.) for dissolut:ion in Hi-Sol-10 and the tem-
perature was cooled to 90 F. before the adclition of methyl ethyl ketone.
To this mixture there was added 45 grams (1.4 wt%) of trimethyl
*
nonyl polyethylene glycol ethers (Tergitol TMN-6), and 45 grams (1.4 wt%)
of nonylphenoxypolyethyleneoxyethanol (Igepal C0-630) and 65 grams (2.0 wt%)
*
of nonylphenoxypolyethoxyethanol (Triton N-401 702) available from Rohm and
~laas Co. The emulsifier blend had a combined HLB of 15.3.
The resultant mixture was emulsified with the addition of 1500
grams (47.2 wt%) of water.
EXAMPLE 18
The anti-oxidant which is a three-to-one condensate of 3-methyl,6-
tertiarybutylphenol with crotonaldehyde was emulsified by combining 315 grams
or 16.8 weight percent of the antioxidant with 500 grams or 26.6 weight
- 32 -
I 1 ~5993
percent of cyclohe~anone at a temperature of around 104 F. (40C.). To
this mixture there was added an emulsifier blend comprising 32 grams or 1.7
weight percent of polyethoxylated vegetable oil (emulphor EL 719), and 82
grams or 4.4 weight percent of a condensate of ethylene oxide with hydro-
philic basis formed by condensing propylene oxide with propylene glycol
(Pluronic P-65) and 48 grams or 2~6 weight percent of another condensate of
ethylene oxide with hydrophilic basis formed by condensation of propylene
oxide with propylene glycol (Pluronic F-~37). The emulsion blend has a
total HLB of 18.4. The mixture was cooled back to 80F. and emulsified
while adding 900 grams or 47.9 weight percent water.
Example 19
Another formulation of the 3:1 condensate of 3-methyl;6-tertiary-
butylphenol with crotonaldehyde anti-oxidant prepared in a similar manner
to that of Example 18 is as follows:
Antioxidant 315 Grams 20 Weight Percent
Cyclohexanone Solvent 350 Grams 22.2 Weight Percent
Polyethoxylated Vegetable Oil 22 Grams 1.4 Weight Percent
Condensate of ethylene 54 Grams 3.4 Weight Percent
Oxide with Hydrophilic basis
~ Eormed by condensing propyl- -
ene oxide with propylene
glycol ~Pluronic P-65)*
Another Condensate of 16 Grams l Weight Percent
ethylene Oxide with
Hydrophilic basis formed
by condensing propylene
oxide with propylene glycol
(Plurcnic F-77)*
Pluronic F-77 Emulsion 15 Grams in 500 Grams l Weight Percent in
in Water 31.8 Weight Percent
Water to Complete 300 Grams 19.1 Weight Percent
Emulsion
- 33 -
~"~
1 1 65~3
The emulsifier that is a condensate of ethylene oxide with hydro-
philic basis formed by condensing propylene oxide with propylene glycol and
available as Pluronic F-77 was added to the anti-oxidant mixture by adding
a first portion of the emulsifier directly to the antioxidant mixture con-
taining the antioxidant, solvent and other emulsifiers which is preferably
a fifty-fifty split and then adding the second portion of the emulsifier to
water and adding the diiuted emulsifier to the antioxidant mixture.
The emulsion had a thin viscosity and blue white coloration.
Example 20
An emulsion of octadecyl 3-(3'5'-di-tert-butyl-4-hydroxyphenyl)
proprionate was prepared by dissolving 160 grams or 20.8 weight percent of
the antioxidant in 160 grams or 20.8 weight percent of a petroleum solvent
*
(Hi Sol 10) at room temperature but with the use of heat to assist sol-
vency. To this mixture there was added an emulsifier blend of 25 grams or
3.2 weight percent of POE (4) sorbitan monalaurate Tween 21 emulsifier,
and 12.5 grams or 1.6 weight percent of condensate of ethylene oxide with
hydrophilic basis formed by condensing propylene oxide with propylene
*
glycol (Pluronic P-65) and an amount of 12.5 grams or 1.6 weight percent of
another condensate of ethylene oxide with hydrophilic basis formed by coo-
densing propylene oxide with propylene glycol (Pluronic F-87) dilluted with
100 grams or 13 weight perceot of water. This mixture was emulsified with
the addition of 300 grams or 39 weight percent of water. The emulsion had
a thio viscosity aod blue white coloration.
Example 21
The emulsioo of Example 13 was prepared into a si~ing composition
for treatiog glass fibers by taking 4,080 grams of a 32 percent concentrate
5 ~ g 3
of the emulsion and combining it with 1,060 grams of a polyurethane latex
film fornler available for BASF Wyandotte Corp. under the trade designation
*
WYANDOTTE X-1042H and with 4000 grams of warm water at 110 F. (43 C.). To
this first mixture there was also added 5000 grams of water and 189 grams
of gamMa-aminopropyltriethoxysilane. The amount of the anti-oxidant emul- -
sion in the sizing composition was about 9.1 weight percent based on the
32 percent concentration of the antioxidant emulsion. The amount of the
film former was 3.7 weight per~ent based on the 50 percent concentrated
polyurethane film former and the amount of the silane in the sizing compos-
ition was 1.3 weight percent.
The sizing composition had a total solids of 32.3 percent.
The sizing composition was used to treat glass fibers that were
formed by attenuation from molten streams of glass from small orifices in
a bushing which were prepared by a conventional method. An example of
such a conventional method can be found in U.S. Patent No.43027,071.
The sized glass fibers were dried and chopped
into one-eighth inch and three-sixteenth inch lengths.
Example 22
The antioxidant emulsion of Example 14 was used to prepare a
sizing composition for treating glass fibers. The sizing composition was
formulated as follows:
A)
Anti-oxidant emulsion 34.3 3,794 Grams 25.6 Wet Weight Percent
percent concentrate
Polyurethane latex film * 1,059 Grams 7.1 Wet Weight Percent
former (Wyandotte ~-1042H)
(50% solids~
Water, warm, around 110 F. 4,800 GraMs 32.3 Wet Weight Percent
- 35 -
~,~
~.`i,~
9 9 3
B)
Water 5,000 Grams 33.7 Wet Weight Percent
Gamma-aminopropyltri- 189 Grams 1.3 Wet Weight Percent
ethyoxysilane
Acetic acid adjustment
of ph to be in the
range of about 6.S
to about 7.0
The sizing composition had 13 percent solids. This sizing compo-
sition, hereinafter rPferred to as Size #5, was used to treat glass fibers
that were formed by attenuation of molten streams of glass from small ori-
fices in a bushing. An example of a conventional method for producing
glass fibers is found in ~.S. Patent 4,027,071. The gathered sized glass
fiber strands were dried and chopped into 1/8 inch and 3/16 inch lengths.
The chopped strands were tested for loss on ignition and gave a 1.29 per- -
cent LOI.
Example 23
An oil-in-water emulsion was prepared in a manner similar to that
of Example 5 having the following formula:
Grams Wt. %
octadecyl 3 - (3', 5' - ditert butyl-
4' - hychoxyphenyl propionate
antioxidant 720 25.8
Amyl acetate 720 25.8
Trimethyl nonyl polyethylene*
glycol ether (Tergetol TMNG) 45 1.6
Nonylphenoxy polyethoxy ethanal
(Triton N-401)* 65 2.3
Nonylphenoxy poly (ethylene
oxy) ethanal (Igepal C0-630)` 45 1.6
Cold Water 1,200 42.9
- 36 -
;,~
1 1 ~5993
This emulsion was prepared ineo a sizing composition in a similar
manner to that of Example 6. The si~ing composition had the following for-
mulation:
Grams Wt.
Epoxy resin (Genepoxy 370
H-55 available from
General Mills Co. 55~ solids) 2,730 9.0
Antioxidant emulsion
27.6% 30lids 2,210 7.3
polyurethane resin *
(Wyondotte X-1042~ 7,980 26.4
Water 6,000 18.2
gamma-aminopropyltri
ethoxysilane
Water lO,800 35.8
Acetic Acit 5 .02
epoxy eontaining silane 150 .5
This si~ing composition was used to treat glass fibers in a
manner simil&r to that of Example 21. The s~zed glass fibers were dried
ao snd chopped into one-eighth inch and three-sixteenth inch lengths.
Dried, sized glass fibers treated with sizing compositions #1,
#2, #3, #4 and #5 were used to reinforce polybutylene terephthla~e. The
reinforced polymer was prepared by using 30 parts of the various si~ed
glass fibers in the chopped form and 70 part~ of polymer. This mixture was
injection molded in a New~ury*injection machine in a one ounce shot.
The reinforced polymeric materials were tested in the accelerated
aging test known as thermal aging. This test is conducted by placing ten-
sile bars of the specimen in a high velocity air circulating oven at a tem-
perature of 185 + l-C. for tests of Table II. Specimens are removed at
various time intervals and tested for the mechanical property of tensile
strength measured in pounds per square inch (psi) on an Instro~ machine.
;~ '
37 -
~ 1 65993
Polymeric material reinforced with dried sized glass fibers with
si~ing composition 1, 2, 3, 4, and 5 were tested in this manner. These
reinforced polymeric materials were compared to reinforced materials having
commercially available glass fibers. The results are shown in Table II.
- 38 -
5 9 9 3
!Z ~ cn u~ ~ ~ ~ ~ O O
C' CO ~ ~ ~ ~t. g
D ~ X ~.~D
P P)
~ g
3~
co ~ ~ _l ~ ~I o~9 ~ ~ ,_ rt ~. ~
~, ~~ ~ ~~ ~ Y
U~ ~$
Y
(D O
.
y
~I co O ~n co ~ 1-- ~ ~D
5 ,~
n
~ 3 p~ 3
O~ D O O O ~--' O ~ ~ ~ " ~ ' ~ D~
~ ~~ ~ CO ~ ~n O ~ I~ ~ ~ D ~
O ~ W ~ D5 ~D Y '1~
Il)
p
~n
O~ ~-3 N
O O ~ ~ U~ ~ ~ ~ ~ ~ ~. (D
W 0~ ~I CO 0~ ~I W N
-- 00 ~ ~O 1-- ~~I O Cr~ I-- ~ 5
cr~ ~ o ~ ~ ~ w~ ~ ~ ~
1~ _ _ _ ,~ 4_ _ _ Ul N
1-- Vl ~D Ul Y 1-- CS` 00 0 C:' ~
O oo.~ ~ w
O~
4 _ _ 4 .. ~ _ U~
n Y W ~ O ~ r~
W ~I ~n o u- ~ ID
:r
y
Ul ~ D 00 0 Y Y Y~0 ~ r~ p N
O ~ ~ tn U~ Il)
W ~n o t-- o oo ~ ~ o ul ~ Oq ~ ~n
~ O ~ ~ ~ ~ 5
-- 39 --
~, ~
9 9 3
Table II shows the reinforced polybutylene terephthalate that is
reinforced with glass fibers treated with a sizing composition having the
antioxidant emulsion of the present invention outperforms the commercial
material. This better performance can be higher original and first couple
weeks tensile strength values and similar values after several weeks and/or
similar original values and higher values after several weeks.
Example 24
Dry Blending E _mples
In addition to testing the mechanical properties after accel-
erated aging tests for fiber glass reinforced polybutylene terephthalate
where the glass fibers were treated with a sizing composition containing
the antioxidant emulsion, dry blending accelerated aging studies were
conducted. In the dry blending studies, the antioxidant was added to the
polybutylene terephthalate and this polymer was compounded with 30 parts of
chopped glass fibers commercially available from PPG Industries, Inc. The
antioxidant added to the polymer represents an extra amount to that amount
which is already present in the commercial polymer. The glass fiber poly-
butylene terephthalate antioxidant mixture was molded by injection molding
in the same Newbury molder used in the previous examples.
2~ The tensile bars prepared by injection molding were subjected to
accelerated aging in a similar manner as previous examples at a temperature
usually of 200C. ~ 1C. for test 1 and 2 and 190C. ~ 1C. for tests
3-6 of Table III. Table III shows results of the mechanical property of
tensile strength ;n pounds per square inch for the samples after various
times under the accelerated aging conditions. Specimens 4, 5 and 6 were
compared with specimens 2 and 3 that had glass fiber reinforced polybutylene
terephthalate where the glass fibers used are commercially available from
PPG Industries, Inc. Specimen number 1 was prepared in the same manner as
the other speciments except no glass fibers were incorporated into the
polymer.
- 40 -
~ ~ ~5~39 3
3 ~ 3 s P~ p~ P~ n r--
c~. r~ r-~ tD rl c~ rt X p~ . rl 13 ~ rl 3 P rt ~
~ O 1 3 ~ ~ r~ r--
r~ ~ 3 s r- 3
N ~ _~ O r~ r-- c n rn ~ O O ~~ O O O ~ cr z n c~ ~D
r~ n ~ rl~ r~ rt r- r~
O ~ ~ 3 ~ r~ O ~ r~
o r r ~ 0 P ~ O O ,_ 0 ~ r~ ~ 0~ C) 0 0
c~ X X ~ cr 7i~ ~ rn t-~ ~ ~ c
t~ ~ ~ ~ n~ ~ ~_ O rd ~ P C (D ~ 0~ ~ :1 0 '~:1 C
rt~ ~n r~ I c O ^ Oc~ ~3 0 c O tD ~: C ~ tD c n r~ `~
~_ r~ a ~ X w ~ r~ u~ r r~ ~ r
P~ 3- 1 0 I V~ ~0 ~ 3 ~ t~l O ID rt o
~ ~ ~ ~ I Z ~ ~D ~ I ~ rt y fi
r~ 1 ~ ~ . p~ a. r~ ~ - rD
rl ~ O p~
I_
O
~~ O O O r- _l r
O ~ _ :~
W ~ C~ ~ O ~ P~
Co ~D ~ ~ O U~ ~_
r-- r~ rt
O ~--
r~
¢~ g o~ ~ 00 CO ~ S
(~ r~
C~ ~
tD r1 rn 3
.~ ~J O O Oq
. _ _ :~ rl~ n C:~
0 ~ ~ us,a o~
O C0 ~ e ~ ::1 r-3
r~ r~ . I~ W
;~ 3 :1 ~ r3 r
r~ ~ P~ :~
r,~ r . r
0
~_ ~_. ~ 0 U~
~ W 0~ r~ C rt
`~ _ _ ~ ~:b r~
0~ `D ~ ~ (D
~n ~
tD ~. n
:~ r~
rr~3 '
r~ ~_ C ID
O rn
. S
W
rn
., O 5
O :~
O ~D
7i'
~ 1 65993
Table III shows the improved property of tensile strength at
longer times under thermal aging conditions obtained by addition of extra
antioxidant that has low volatility, good heat stability and good polymer
compatibility.
The foregoing has described oil-in-water antioxidant emulsions,
aqueous treating compositions for treating fibrous reinforcement containing
the antioxidant emulsions, and a method of reducing chemical degradation
of polymers reinforced with fibrous materials. The aqueous emulsions com-
prise the antioxidant, organic solvents, one or more emulsifiers having an
HLB in the range of about 12 to about 27. ~The aqueous treating solutions
for treating fibrous materials to be used as reinforcement in polymers,
particularly glass fibers, comprises the antioxidant emulsion along with a
film former and coupling agent althou~h other sizing ingredients well known
to those skilled in the art may also be used. The method of reducing the
amount of chemical degradation of reinforced polymers, wherein the chemical
degradation is due to an interaction between the chemistry and/or reaction
and/or thermal decomposition products thereof of the reinforcement and the
polymer involves the addition of an amount of antioxidant in excess of
three parts per hundred parts of resin to the polymer or by adding an
amount of antioxidant in an oil-in-water emulsion in the range of about 5
to about 60 weight percent of the emulsion to the aqueous treating solution
for the fibrous materials.
- 42 -
