Antioxidants and reinforced polymers and oil-in-water emulsions of antioxidants

14 Pages·2013·1.93 MB·English

Unite States Patent [191 [111 4,341,677
Tamosauskas [45] Jul. 27, 1982
[54] ANTIOXIDANTS AND REINFORCED
POLYMERS AND OIL-IN-WATER OTHER PUBLICATIONS
EMULSIONS, OF ANTIOXIDANTS , “Vanderbilt News”, vol. 34, No. 2, 1972, pp. 13-24.
- “Naugard 445” Antioxidant Data Sheets.
[75] Inventor : gibeft E . Tamosauskas’ Plttsburg h, “Ethyl Antl. oxl.d’ ant 330”, Product Li.t erature.
' _ “Irganox 1076”, Product Data Sheets.
[73] Assigrwe? PPG Industries, Inc» Plttsburgh, Pa- “Irganox 1010”, Product Information Bulletin, Apr.
1979.
[ 21 1 AP p l. N o .: 190,153 “Topanol CA Anti.o xi.d ant”, Informati. on Bulleti.n .
[22] Filed: Sep. 24, 1980 “Emulsi?cation of LSU 520”, Product Data Bulletin.
“Emulsi?cable Epoxy Resins”, Bulletin from
Related US. Application Data Ciba-Geigy Corporation.
Division of Ser_ No_ 137,063’ Apr. 3, The Merck Index, Edition, MCl'Ck
& Co., Inc., 1976, p. 1290.
[51] Int. Cl.3 ............................................ .. C08L 63/02 The Condensed Chemical Dictionary’ Tenth Edition,
[52] U.S. Cl. ............................ .._. .... .. 523/421; 65/ 3.43; Revised by Gessner G~ Hawley’ Van Nostrand Reim
428/378; 524/310; 524/110; 524/291; 524/258; hold Company’ p_ 91_
[58] F m f S h ?ll/23623322243132??? Calculation of HLB Values of Non-‘Ionic Surfactants
1e 0 care .............. .. . , . , b ’ Th A ti P f I.’ . 26,
260/294 R; 65/3.43, 3.44; 428/378 Nfay m e m can er ‘me p
[56] References Cited Primary Examiner-Theodore E. Pertilla
U.S. PATENT DOCUMENTS Attorney, Agent, or Firm—Kenneth J. Stachel
2,046,555 7/ 1936 Gill ............ .. ...................... .. 428/375 [57] ABSTRACT
12,269,529 1/1942 Goldsmith .. . 252/310 .1 . 1 . f . .d h . l 1
2,628,930 2/1953 Zentner . . . . . . . . . . . . . . . . .. 167/81 Qljm'water em“ 5101150 “"9” ants avmg 9w "° a‘
2,871,219 1/1959 Baggett et a1_ _ _ 260/459 p t1l1ty' and good thermal resistance are provided for
3,082,183 3/ 1963 Boyd .................... .. 260/296 treatmg ?brous remforcements such as glass ?bers. The
3,249,412 5/ 1966 Kolek et a1. .. 260/292 EP emulsions are comprised of the antioxidant in an'amount
3,285,855 11/ 1966 Dexter et al- -- ------ -- 252/ 57 of about 5 to about 60 weight percent of the emulsion
3,330,859 7/1967 Dexter et al. . . . . . . . . . . .. 260/473 along with an Organic solvent that has a boiling point
Escher et a1‘ ' ‘ above the temperature of use or of preparation and is
3’484’223 11/1969 vaynes '-" """""""" " ' compatible with the antioxidant in an amount in a ratio
, , anderbilt et a1. ..... .. 65/3 . . . -
3,556,754 V1971 Marsden et aL _____ u ' 65/3 of about 05m about 1.5 with the antioxidant and one or
3573594 5/1971 Ddmbrow ________ __ 252/g_9 more emulsi?ers selected from the group consisting of
3,635,834 1/ 1972 Cilento et a1. . 252/314 anionic, and nonionic having a combined HLB (hydro
3,644,141 2/ 1972 Preston --------- 0 117/126 GS philic/lipophilic balance) in the range of about 12 to
about 27. The emulsion can also contain a resin carrier
ghakgni 6t 111- - - - - - - ' - -
4,, 093,, 774 6/1978 Ha0r8tl0e sas eettaal .. . . . . . . . . .. 428/37. 9 slgihsiaileigoxglrgi‘ m and/mas t a “mu' g age“ t we h as
4,134,841 1/1979 Park et a1. ............... .. 252/8.9 P y y P y ' _ _ _
4,177,177 12/1979 Vanderhoff et al. .. 260/292 M An aqueous treating solution for treating ?brous rem
4,2l9,463 8/1980 Minagawa et al. ........ .. 260/4 5-85 B forcement such as a sizing composition for treating glass
?bers to increase the protection of ?ber reinforced pol
FOREIGN PATENT DOCUMENTS ymeric materials against chemical degradation due to
810699 4/1969 Canada .._. ........... ... ............. .. 260/476 the chemistry on the treated glass ?bers or reaction
406642 3/1932 unfted K}ngd°m ' and/or decomposition products of said chemistry is
' comprised of the oil-in-water emulsion, ?lm-former,
1352947 5/1974 United Kingdom _ and couplmg agent and may contain other conventional
United . agents used In Sizing composltlon
1519041 7/1978 United Kingdom .
1565823 4/1980 United Kingdom . 20 Claims, N0 Drawings
4,341,677
1 2
heating source and adding xylol. Then the emulsi?er
ANTIOXIDANTS AND. REINFORCED ‘POLYMERS nonylphenoxy poly(ethyleneoxy)ethanol available from
AND OIL-IN-WATER EMULSIONS OF GAF Corporation Chemical Products under the trade
ANTIOXIDANTS designation “Igepal CO-630” is diluted. Dissolved p0
tassium hydroxide pellets are mixed with the emulsi?er
This is a division of application Ser. No. 137,063, ?led and the mixture is heated to about 88° C. The emulsi?er
Apr. 3, 1980. . mix is then added to the antioxidant mix with vigorous
agitation to produce an emulsion having about 32.1
BACKGROUND OF THE INVENTION
percent oil to 31.8 percent water. Other similar emul
The present invention is directed to approaches to sions and dispersions are available in the publication
increase the performance of ?ber reinforced polymers “Vanderbilt News” volume 34, number 2, 1972, pp
under aging conditions including the use of oil-in-water 13-24.
emulsions of antioxidants that are water insoluble or An emulsion is a two phase system consisting of two
immiscible or have limited water- solubility, wherein the incompletely miscible liquids, the one being dispersed as
emulsions have a small particle size and good stability. b-. 5 ?ne droplets in the other, whereas a suspension is a two
More particularly, ‘the present invention is directed to phase system where the dispersed phase is a solid. As
methods and compositions for increasing the perfor stated above both emulsions and dispersions of antioxi
mance of glass ?ber reinforced polymers under thermal dants have been used in formulations for rubber latices.
aging conditions. Thecompositions include the use of The stability of antioxidant emulsions depends upon the
oil-in-water emulsions of antioxidants that are water 20 factors for emulsions in general: (1) particle size, (2)
insoluble or immiscible or have limited water solubility difference between the densities of the material in the
and that are of low volatility and good thermal stability internal phase, which is the liquid broken into droplets
and non-discoloring for use in treating glass ?bers.The and of the material in the external phase, which is the
oil-in-water emulsion provides a method to reduce surrounding material, (3) the viscosity of the emulsion
chemical degradation of polymers reinforced with glass 25 concentrate, (4) the charges on the particles, (5) choice
?bers containing sizing compositions. ' of emulsi?er type and amount of emulsi?er used, and (6)
In order to stabilize polymers from degradation due the conditions of storage such as agitation, temperature,
to oxygen and ozone, various antioxidants of the hin dilution, and evaporation.
dered phenol and diaryl amines types have been incor Additional applications of antioxidant emulsions may
porated into. polymer formulations. Another type of be developed if the emulsions have a small average
degradation that polymers may encounter is degrada particle size of around 1.5 microns and a suf?ciently
tion due to various chemicals other than oxygen and I narrow particle size distribution. Such additional appli
ozone withwhich the polymers may come in contact. cation can be found in the coating industry where coat
Such chemical degradation may occur when the poly ing or treating solutions for various materials would
mers are reinforced .with material that has been treated 35 bene?t from a small average particle size, fairly narrow
with various chemicals to provide ef?cient processing particle size distribution antioxidant emulsion. Antioxi
of the materials and to provide compatibility of the dants that would be particularly useful in a small aver
materials with the ‘polymers. Care must be taken in age particle size, fairly narrow particle size distribution
producing reinforcement materials containing treat emulsion would be those that are of low volatility, and
ment chemicals, such as sizing compositions for glass 40 /or heat resistant and/or non-discoloring.
?bers, to avoid any problem of interaction between the It is an object of the present invention to provide an
chemistry on the reinforcing material and the polymers. oil-in-water emulsion of an antioxidant and especially
Any possible interaction between the various chemical antioxidants of low ‘ volatility, and/or heat resistant,
agents in the system or reaction or decomposition prod and/or non-discoloring that has an average particle size
ucts of these chemical agents with the polymer may 45 of less than 1.5 microns, a fairly narrow particle size
degrade the polymer to some degree. This degradation distribution, good stability and good dilutability to a
would reduce the mechanical properties of the rein low concentration.
forced polymer over time and especially under thermal It is an additional object of the present invention to
aging conditions. When the reinforced polymer is sub provide a treating composition for glass ?bers that are
jected to elevated temperatures for a period of time, i.e., 50 to be used for reinforcement of various polymeric mate
thermal aging, degradation of the polymer may be ac rials and that reduce degradation of the reinforced poly
celerated due to thermal autooxidation and increased ' mer due to an interaction between the chemicals in the
reaction rates for chemical interaction. This degrada treating composition or their reaction or decomposition
tion shortens the useful properties of the reinforced products and the polymeric material.
polymer which usually have extended properties due to 55 It is a further additional object of the present inven
the presence of the reinforcement. tion to provide a method for reducing degradation of a
Antioxidants that have been added to polymer com glass ?ber reinforced polymer due to any interaction
positions that are to be used in preparing reinforced between the materials present in the sized glass ?ber
polymers have also been added in the form of the anti strand and/or reaction or thermal decomposition prod
oxidant alone as a solid or liquid. Also, antioxidants 60 ucts thereof under thermal aging conditions, thereby
have been added to latex formulations such as rubber reducing any decrease in mechanical properties of the
latices in the form of emulsion and dispersions. For reinforced polymer due to such degradation.
example, the antioxidant “Age RiteResin D” available
SUMMARY OF THE INVENTION
from R. T. Vanderbilt Company, Inc. which is the anti
oxidant polymerized 1,2-dihydro-2,2,4-trimethyl quino 65 In accordance with the present invention, the afore
line can be preparedin a 30% emulsion by melting the mentioned objects and other objects which are inherent
“Age Rite Resin D” antioxidant in lightprocess oil and from the following discussion are achieved by having a
oleic acid at 104° C. and removing the mixture from the method for reducing chemical degradation of polymers
4,341,677
3 4
due to chemical interaction between chemicals'in the porated into the polymer during polymerization and/ or
sizing composition of the reinforcement and/ or chemi dry compounding to prepare the ?ber reinforced poly
cal reaction or thermal decomposition products of said _ mer. This addition is in excess of the usual amount of
chemicals and the polymer by adding. an antioxidant ‘ antioxidant added to the polymer formulations. Usually
either to the treating composition for the reinforcement less than 1 part per hundred parts of polymer up to
or adding an additional amount of one or more antioxi around 3 parts per hundred of polymer are added to
dants with low volatility and good heat resistance to the polymer formulations. This addition protects the poly
polymeric material. mer during processing and in use from degradation due
The treating composition for the reinforcement such to oxygen, ozone and water. The additional amount in
as sizing compositions used with glass ?bers, has the excess of that added for such protection protects a ?ber‘
antioxidant present in the form of an oil-in-water emul reinforced polymer from chemical degradation. The
sion that has a small average particle size and a fairly chemical degradation is that associated with interac
?ne particle size distribution in order that the treating tions of chemicals in treating solutions and/or reaction
composition adequately coats the surface of the rein and/or thermal degradation products thereof vused to
forcement. The treating composition can contain other treat the reinforcement material.
components that are conventionally used in treating
compositions for glass ?bers. Non-exclusive examples DETAILED DESCRIPTION OF THE
of these include coupling agents, ?lm-formers, lubri INVENTION '
cants, surfactants, and the like. Although the theory of the degradation of the rein
The oil-in-water emulsion of the antioxidant allows 20 forced polymer is not completely understood, it is be
for high concentrations, up to about 60 weight percent lieved that there is'a chemical interaction between the
of the aqueous emulsion, of the water immiscible or ' chemical compounds of the sizing composition on the
water insoluble or limited water soluble and miscible glass ?bers or reaction products and/o r thermal decom
hindered phenol or diaryl amine antioxidant with low position products of these chemicals and the polymer.
volatility and good’thermal resistance and good poly 25 This interaction leads to chemical degradation of the
mer compatibility. The emulsion also has an organic polymer over and above any degradation due to oxy
solvent that is fugitive at just above ambient tempera gen,'ozone and/or water. This chemical degradation is
tures to temperatures greater than those just above the especially prevalent when the reinforced polymer is
temperature used to treat and process the reinforcement subjected to elevated temperatures and thermal aging.
treated with the emulsion. The emulsion also has one or It is believed that the degradation is more than thermal
more emulsi?ers or emulsi?er blend wherein the hydro autooxidation, since the molding of the ?ber reinforced
philic/lipophilic balance (HLB) for the emulsi?er or polymers takes place in closed molds that would reduce
blend is in the range of about 12 to about 27. the amount of oxygen present, and since the reinforce
Low volatility refers to the antioxidant having a per ment such as glass fiber contains little, if any, moisture
cent weight loss measured by thermal gravimetric anal 35 because the glass ?bers have been dried to reduce their
ysis (TGA) of less than about 20 percent when about 6 moisture content before the molding operation is per
mg of antioxidant is heated to 250° C. and held for 30 formed. It is further believed that certain types of com
minutes. This assures the presence of a suf?cient pounds present in the treating solution and on the dried
amount of anti-oxidants in the reinforced polymer. treated glass ?bers may be subject to ‘thermal degrada
The good heat or thermal resistance or stability of the 40 tion at conditions that are milder than those conditions
anti-oxidant refers to the antioxidant not decomposing that cause polymer degradation. It is believed that an
in any way to lose its effectiveness at temperatures of example of these compounds are the polyoxyalkylene
less than around 200° F. (93° C.). type compounds that are used as nonionic emulsi?ers in
The compatibility between the antioxidant and the the treating solutions.
polymer to be reinforced refers to the antioxidant hav 45 It has been discovered that the addition or incorpora
ing the capability of forming secondary bonds such as tion of hindered phenolic or diaryl amine antioxidants
hydrogen bonding, Van der Waals bonding, and dipole having low volatility, good thermal stability and good
interactions and ionic bonding with the polymers. If the polymer compatibility into the polymer or into as aque
antioxidant is very compatible with the polymer and has ous sizing composition for treating glass ?bers during
a high degree of at least secondary bonds, the volatility 50 their formation reduces the amount of chemical degra
of the antioxidant can approach the upper limit of dation of the ?ber reinforced polymer. The reduction in
weight loss. chemical degradation extends the mechanical proper
In general, the process of this invention comprises the ties and service life of the ?ber reinforced polymers and
following. The oil-in-water antioxidant emulsion is pre this is especially so under conditions of thermal aging.
pared. The aqueous treating solution containing the 55 The types of hindered phenolic and/or diaryl amine
emulsion is prepared with at least a ?lm-former and antioxidants that can be used include the non-exclusive
coupling agent and optionally a lubricant and other examples of high molecular weight hindered phenolic
conventional sizing additives used to treat glass ?bers. compounds, high molecular weight hindered bis
The glass is formed into glass ?ber strands, and during phenolic compounds, high molecular weight hindered
the formation the aqueous treating solution is applied to 60 phenolic amines, high molecular weight hindered
the glass ?bers. The treating solution, also known as a mono-phenolic compounds; 3,5-di tert butyl-4 hydroxy
sizing composition, in contact with the glass is dried to hydrocinnamic acid triester with l,3,5-tris(2-hydroxy
remove moisture and the fugitive organic solvent. The ethyl)-bis triazine-2,4,6(1H, 3H, 5I-I)-trione; alkylated
dried, treated glass ?bers are used in any form as rein phenols and bis-phenols and phenol condensation prod
forcement for polymeric materials. 65 ucts such as a 3:1 condensate of 3 methyl, 6 tertiary
In addition to incorporating the antioxidant into the butyl phenol with croton-aldehyde; tetra-functional
reinforced polymer by use of the oil-in-water emulsion, hindered phenols such as tetrakis(methylene 3-) 3’, 5’-di
the low volatile, heat resistant antioxidant may be incor t-butyl-4’ hydroxy phenyl (propionate) methane; oc
4,341,677
5 6
tadecyl(di-t-butyl hydroxy phenyl propionate) and present invention, include the non-exclusive examples
other such phenolic compounds having the following of vinyl polymers such as poly-alpha-ole?ns such as
polyethylene, polypropylene, polybutylene, polyiso
structure: g. , ‘
prene and the like including copolymers of poly-alpha
lower alkyl ole?ns; polyurethanes such as are prepared from poly
ols and organic polyisocyanates; polyamides such as
HO Q . (CAHZA)—fl)C —O—(CBH2B)—R 3 polyhexamethylene adipamide; polyesters such as poly
methylene terephthalates and polybutylene terephthal
ates and polyethylene and polypropylene terephthal
10 ates; polycarbonates, poly-acetals, polystyrene, and
lower alkyl
copolymers such as those of a high impact polystyrene
containing copolymers or butadiene and styrene and
wherein A has a value of from 0 to 6 inclusively and B
those formed by the copolymerization of acrylonitrile,
has a value from 2 to 30 inclusively and R is a member
consisting of hydrogen, hydroxy, such as the following butadiene and/or styrene.
compounds 1,2-propylene glycol bis-[3,5-di-t-butyl-4 5 In general, small amounts of the antioxidant stabiliz
hydroxyphenyl)-propionate]; ethylene glycol bis[3-(3,5 ers are added to the polymers during polymerization,
di-t-butyl-4-hydroxyphenyl)propionate]; neopentyl gly although larger amounts are added to polymers during
col bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]; formulations, compoundingv and fabrication and ?nal
ethylene bis (3,5-di-t-butyl-4-hydroxyphenyl acetate; manufacture of the reinforced polymeric material. In
glycerine-[n-octadecanoate-Z,3-bis-(3,5-di-t-butyl-4 general, the antioxidants are employed in an amount of
hydroxyphenyl acetate)]; sorbitol hexa-[3(3,5-di-t-butyl from about 0.005 percent to about 3 percent by weight
4-hydroxyphenyl)propionate]; 2-hydroxyethyl 7-(3 based upon the stabilized composition. In polypropyl
methyl-5-t-butyl-4-hydroxyphenyl)heptanoate; N,N’ ene, amounts of from about 0.01 percent to about 3
hexamethylene bis (3,5-di-tert-butyl;4-hydroxy) percent by weight are advantageous with from about
hydrocinnamamide and the like; polybutyl bisphenol; ' 0.01 to about 1 percent by weight being especially pre
esters of ethoxylated aryl phenols and bis aryl phenols ferred. Therefore, the amount of antioxidant stabilizer
such as the acetate ester of the condensation of 5 moles needed to overcome the chemical degradation of any
of ethylene oxide with 1 mole of benzylphenol; the
compounds on the reinforcement material to be used for
lauric ester of the condensation product of 24 moles of reinforcing the polymer or the reaction and/or decom
ethylene oxide and 1 mole of his benzylphenol; the
position products of the compounds must be an extra
stearate ester of the condensation product of 10 moles of
amount in the range of about 0.25 to about 1.0 part per
ethylene oxide and 1 mole of alpha methyl benzyl
hundred parts of polymer and reinforcement that is
phenol; neutral adipate esters of the condensation prod
added to the polymer that may already have up to 3
uct of 2 moles of ethylene oxide with 1 mole of alpha,
percent of some type of antioxidant. This additional
alpha’ dimethyl benzylphenol; the dipelargonate ester
amount of antioxidant can be added to the polymer to
of the condensation product of 17 moles of ethylene
be reinforced at any time before the ?nal production of
oxide and 1 mole of his methyl benzylphenol; the neu
the reinforced polymeric material. It is most advanta
tral malonate ester of the condensation product of 8
geous to add the additional amount of antioxidant to the
moles of ethylene oxide with 1 mole of alphaphenyl
polymerized polymer that is ready to be compounded
benzyl-phenol; the palmitate ester of the condensation
with the reinforcement, preferably glass ?bers are used
product of 3 moles of ethylene oxide with 1 mole of
to produce the reinforced polymeric material. The anti
alpha methyl benzylphenol and the like; condensation
products of oxalyl dihydrazide and 3-tertiary butyl-4 oxidant can be added in any form such as the solid form,
hydroxy aryl carbonyl compounds such as 3,5-diterti liquid or as an emulsion or dispersion in aqueous or
ary butyl-4-hydroxybenzaldehyde. Especially useful are 45 non-aqueous solvents.
When the additional amount of the antioxidant is
the antioxidants like tetrakis(methylene 3-3’, 5'-di-t
butyl-4' hydroxy phenol)propionate methane, substi incorporated into the aqueous treating solution or sizing
tuted diphenyl amine like 4,4'-[2-(2-phenyl)propyl]di compound placed on the reinforcing material such as
glass ?bers, the antioxidant is added to the treating
phenylamine; a 3:1 condensate of 3 methyl, 6 tertiary
butyl phenol with croton aldehyde and octadecyl 3-(3', solution for the glass ?bers as an oil-in-water emulsion.
5’-di-tert-butyl-4-hydroxy phenyl) propionate and the The aqueous emulsion is necessary in order to provide
like; condensation product of oxalyl dihydrazide and ' near uniform coating of the glass ?bers as they are
3,5-di-tertiary-butyl-4-hydroxy aryl carbonyl com formed. In order to' reduce the amount of degradation
pounds; esters of ethoxylated aryl phenols and 1,3,5 of polymeric materials that are reinforced with ?brous
trimethyl-2,4,6-tris[3,S-di-tert butyl-4-hydroxybenzyl1 reinforcement having chemical agents present that upon
benzene. The aforementioned antioxidants that bene?t thermal aging cause chemical degradation in the poly
most from the present invention are those that are water mer, the amount of antioxidant present in the emulsion
immiscible or water insoluble. should be in the range of about 5 to about 60 weight
When any of the aforementioned antioxidant stabiliz percent of the emulsion.
ers have a high degree of compatibility with monomers 60 The oil-in-water emulsion of the aforementioned anti
polymerized to produce polymers to be reinforced with oxidants that are water immiscible or water insoluble
?brous materials, the antioxidant stabilizer can be added comprises in addition to the antioxidant one or more
directly to the polymer to overcome the chemical deg organic solvents and one or more emulsi?ers.
radation due to chemical compounds present on the The organic solvent will vary with the different anti
?brous reinforcement material or their chemical and/or 65 oxidants used in such a way that if the antioxidant is
thermal degradation products. predominantly aliphatic the organic solvent will have a
Synthetic organic polymeric substances which are to low kauri-butanol value such as from about 10 to about
be reinforced with ?brous materials, useful with the 50 and have a boiling range within the range of from
4,341,677
7 8
ambient temperatures to about 250° C. where the boil erably about 50 to about 60. Less solvent will be needed
ing point is above the temperature of use for the emul if the organic solvent has a higher kauri-butanol number
sion that is the treating of glass ?bers with aqueous when the antioxidant has substantial aromaticity and
sizing compositions. If the antioxidant has more than when the kauri-butanol number approaches 50, when
about 60 percent aromaticity the acceptable organic 5 the antioxidant has a substantial amount of aliphatic
solvent will have a kauri-butanol value of from about 50 character. The amount of the organic solvent used in
to about 100 with a boiling range which lies within the making up the emulsion of the antioxidant will gener
range of about ambient temperature to about 250° C. ally vary within the range of about 1 to about 50 percent
and which is above the temperature of use for the emul by weight of the emulsion. More solvent can always be
sion. The use of organic solvents with a boiling point added, but there is no bene?t to such practice since the
above 250° C. is not advantageous since the solvent is to solvent is usually removed at some later time.
be removed after the reinforcement is treated. When the The one or more emulsi?ers of the present invention
organic solvent has a boiling point below around 100° is selected from nonionic emulsi?ers or a mixture of one
C. to around 150° C., the use of suction equipment to or more nonionic emulsi?ers with an anionic emulsi?er.
control the escaping vapor is necessary. 15 When more than one emulsi?er is used, the emulsi?ers
The kauri-butanol number is a measure of solvent constitute an emulsion blend of at least two emulsi?ers.
power of petroleum thinners where the value is the The emulsi?ers are selected to give a hydrophilic-lipo
number of milliliters of solvent required to cause cloudi philic balance (HLB value) for the emulsi?er or emulsi
ness when added to 20 grams of a solution of kauri gum ?er blend in the range of about 12 to about 27. Non
in butyl alcohol. The solution is prepared in the propor 20 exclusive examples of chemical types of emulsi?ers for
tion of 100 grams of kauri gum and 500 grams of butyl use in the blend of emulsi?ers are nonionic emulsi?ers
alcohol. Solvents of low aromatic content are strong ' such as ethoxylated alcohols, ethoxylated alkyl phenols,
precipitants for the resin, and therefore, give low val ethoxylated fatty acids, ethoxylated fatty esters and oils,
ues. Conversely the solvents having a high aromaticity fatty esters, glycerol esters, glycol esters, monoglycer
give high values. The kauri-butanol numbers are prefer 25 ides and derivatives, sorbitan derivatives, sucrose esters
ably determined against one of two standards where the and derivatives, alkylene glycol ethers, alkyl polyether
one standard is a one degree toluene with a value of 105 alcohol, alkyl aryl polyether alcohol, and polyoxide
used when the organic solvent is a kauri-butanol value alkyl condensates. Non-exclu“sive examples of the ani
over 60, and the other standard is a mixture of 75 per onic emulsi?ers include alkyl sulfonates, phosphate
cent of N-heptane and 25 percent toluene when the 30 esters, polyaminocarboxylic acids and related sequester
organic solvent has a kauri-butanol number of 40. This ing agents, succinates sulfo derivatives, alcohol sulfates,
is discussed in ASTM Standard D.l133-54T. ethoxylated alcohol sulfates, sulfates and sulfonates of
Organic solvents from which the low and high kauri ethoxylated alkyl phenols, oils and fatty esters and the
butanol solvents are selected are solvents such as ali like. The amount of the emulsi?er or emulsi?er blend
phatic hydrocarbons, aromatic hydrocarbons, esters, 35 added to the emulsion is in the range of about 3 to about
ethers, alcohols, ketones, petroleum distillates and coal 15 weight percent of the emulsion.
tar distillates and mixtures thereof. Examples of organic In addition to the antioxidant, organic solvent and
solvents with low kauri-butanol numbers useful when one or more emulsi?ers, the emulsion contains an
the antioxidant has a substantial amount of aliphatic amount of water that is necessary to make the emulsion
components are the isoparaf?nic hydrocarbon solvents. 40 an oil-in-water emulsion which is generally in the range
Suitable examples are those of the series of commer of about 28 to about 70 weight percent. If the emulsion
cially available isoparaf?nic hydrocarbon solvents sold is to be shipped for any considerable distance, it is most
by EXXON Company USA under the trademark “ISO practical to add just the amount of water needed to
PAR” or Philips Petroleum under the trademark “SOL make the emulsion an oil-in-water emulsion that is actu
TROL” which have boiling ranges within the above 45 ally a concentrated emulsion that can be further diluted
ranges. Examples of organic solvents with a high kauri at the location of use.
butanol value include the solvent commercially avail In preparing the emulsion of the present invention,
able under the trade name “HI-SOL-lO” or “HI-SOL one or more of the aforementioned antioxidants is dis
15” available from Ashland Chemical Company, Ohio. solved in one or more of the fugitive organic solvents
The “HI-SOL-lO” solvent has a boiling point of 308° F. 50 suitable for the particular antioxidants involved. Also,
(150° C.) and a flash point of 105° F. (406° C.) and an the antioxidant or antioxidants may be melted and then
evaporation rate of 25.0 using an ether base of 1. Also, added to the fugitive organic solvent. The mixture of
the organic solvent sold by EXXON Company USA,
the one or more antioxidants with one or more organic
Division of EXXON Corp. Co. under the name “SOL solvents may be subjected to moderately elevated tem
VESSO 150” or “SOLVESSO 100” can be used. Addi 55 peratures to facilitate solubilization of the antioxidants.
tional examples of organic solvents that can be used in The mixture of the antioxidant dissolved in the organic
forming the antioxidant oil-in-water emulsion of the solvent has added to it the one or more emulsi?ers, and
present invention are the following non-exclusive exam this mixture is emulsi?ed using standard techniques,
ples xylene, methyl ethyl ketone, cyclohexanone, cyclo conditions and apparatus. Such standard techniques
pentanone, methyl isobutyl ketone, toluol, ethyl cello~ include the direct method of preparing an emulsion or
solve, toluene, butyl carbitolacetate, butyl cellosolve the indirect method of preparing an emulsion wherein
acetate, trichloroethylene, methylene chloride, amy water is added until the oil inverts into an oil-in-water
lacetate, ethyl acetate, and the like. emulsion. The amount of water added to the organic
The ratio of the antioxidant to the organic. solvent solution of the antioxidant and emulsi?er blend is that to
will vary depending on the particular antioxidant and 65 give an emulsion containing from about 28 to about 70
solvent employed, but generally the ratio will be in the percent by weight water. The homogenizing action can
range of at least about 60 to about 40 of antioxidant to be carried out in a variety of equipment which can
solvent and preferably up to about 40:60 and most pref subject the aqueous organic mixture to high shear
4,341,677
9 10
forces. An example of such equipment is an Eppenbach polyole?ns like polyethylene, polypropylene and co
colloid mill with a gap setting at 20. A Manton-Gaulin polymers thereof and the like.
homogenizer can be used- also at pressure of 3000 to
EMBODIMENT
6000 p.s.i. (210 to 420 kg/cmz). The emulsi?er or emul
si?er blend can be added to the mixture of one or more 5 In the preferred embodiment of the present invention,
antioxidants and one or more organic solvents by add the antioxidant'used to- overcome chemical degradation
ing the emulsi?er separately to the mixture or by adding of a reinforced. polymeric material due to chemical
any combination of the emulsi?ers. After the emulsi?ers interaction between chemical compounds present on
are added, the resulting mixture is ‘dilluted slowly with the ?brous reinforcement or the compounds reaction or
water according tov the invert emulsion technique, 10 thermal degradation products and the polymer is added
where the water can be at ambient temperature or ‘at to the aqueous treating solution for the ?brous material
some elevated temperature. The water is added slowly which is preferably glass ?bers. It is preferred to incor
until the emulsioninverts' to an Oll-iIL-W?t?l' emulsion porate the antioxidant into the aqueous treating solution
and then the emulsion is cooled to ambient conditions. by a combination of the oil-in-water antioxidant emul
During the cooling operation or afterwards additional sion with other components to prepare the aqueous
treating solution.
water is added to bring the vemulsion to the desired
In the preferred oil-in-water emulsion the antioxi
concentration. The amount of wateradded to the emul
dants used have fairly low volatility, good thermal sta
sion is at least about-28 weight percent of the emulsion
bility, and good polymer compatibility. The preferred
composition. ' 5 ' emulsion uses about 5 to 60 and most preferably about 5
One usage for the antioxidant emulsion which is par
to about 25 weight percent of octadecyl 3-(3’, 5’-di-tert
ticularly bene?cial is the use in a treating solution for
butyl-4-hydroxyphenyl, propionate) available from
glass ?bers. The emulsion has a ?ne droplet or particle
Ciba Geigy Corporation under the trade designation
size suf?cient to allow for near uniform coating of the
“IRGANOX :1076”. This antioxidant which is a white,
treating solution on the glass ?ber surface. The oil-in
25 crystalline, free-?owing powder with a melting range
water antioxidant emulsion can be formed into an aque
between 50° and 55° C. and a molecular weight of
ous treating'solution or as termed in thevart'a sizing
around 531 is dissolved preferablyin about a l to 1 ratio
composition, for glass ?bers by combining the emulsion
with' xylene. To this mixture there is added about 3 to
with sizing ‘composition ingredients such as ?lm for
about 15 preferably 3 to about 12 weight percent of an
mers, coupling agents, lubricants and perhaps additional
30 emulsi?er blend. It is preferred that the emulsi?er blend
components such ‘as softeners, wetting agents, anti
be a combination of three emulsi?ers that when used in
foaming agents and additional surfactants. This forma
certain weight ratios to each other give a total HLB for
tion can involve slowly adding the emulsion toan aque
the emulsion blend in the range of about 12 to about 27.
ous mixture containing one or more coupling agents and
It is preferred that one emulsi?er have a high HLB
any lubricants or softening agents and ?lm formers and
35 value in the range of about 12 to about 27. Another
the remaining water to make the aqueous sizing compo
emulsi?er hasa lower HLB value in the range of about
sition. It is also possible to add the one or more coupling
6 to about 12 and another emulsi?er has an HLB value
agents, lubricants, ,‘ softening agents, ?lm formers, or in=the middle range of about 9 to about 18. It is 'particu
other sizing agents to a mixture, containing the emulsion larly useful‘to use the emulsi?ers in equal proportions,
alone or the emulsion and any one or more of the afore 40. although any proportion of the various emulsi?ers can
mentioned sizing composition ingredients. Once the
. be used to give the desired HLB range.
emulsion of the present invention is prepared, the aque It is most preferred to have a ?rst emulsi?er which is
ous sizing composition can be made in any manner a trimethyl nonyl polyethyleneglycol ether such as that
known to those skilled in the art. For example, the commercially available from Union Carbide Corpora
amounts of coupling agents, lubricants, ?lm-formers 45 tion under the trade designation “TERGITOL TMN
and other sizing ingredients can generally ' be in the 6” having an HLB of 11.7. This ether is used in an
following ranges. ~ amount of about 1 to about 5 weight percent of the
emulsion. The ether emulsi?ers combined with another
emulsi?er which is nonyl phenoxy polyethyleneoxy
coupling agent about 0.5 to about 10 50 ethanol, commercially available from GAF Corpora
lfuiblrmi-cfaonrtm er ' - aabboouutt 00..50 0t1o taob oaubto u1t5 1 tion Chemical Products under the trade designation
' “IGEPAL CO-630” having an HLB of 13 and used in
an amount of about'l to about 5 weight percent of the
The aqueous sizing composition is applied to individ
aqueous emulsion. These two emulsifying agents are
ual glass ?bers during their formation by any conven
55 combined and stirred until clear. Then another emulsi
tional method of applying sizing compositions to glass
fying agent which is a condensate of ethylene oxide
?bers. The glass ?bers are attenuated from molten with hydrophobic bases formed by condensing propy
streams of glass which can be an E glass or 621 glass lene oxide with propylene glycol and is commercially
composition or any low polluting derivative thereof.
available from BASF Wyandotte Industrial Chemical
Such methods‘ are shown .in (LS. Pat. No. 4,027,071 Corporation under the trade designation “Pluronic-P
(Motsinger) which isincorporated by reference. ‘I , 65” which has an HLB of 17 is used in an amount in the
Sized glass ?bers are dried to remove moisture and range of about 1 to'about 5 weight percent of the aque
the fugitive organic solvent._ The drying can be accom ous emulsion composition.
plished by air drying or drying in a heated over. The It is preferred to add the emulsi?er blend in the fol
dried sized glass ?bers can be used in any form such as 65 lowing manner. A mixture of the ether emulsifying
?bers, strands, wet or dry chopped strands, mats and agent and ethanol emulsifying agent are combined with
the like for reinforcing polymers such as polyamides, the mixture of the antioxidant and organic solvent. The
like Nylon 6; polyesters, like polybutyleneterephthalate, polyoxyalkylene oxide block copolymer emulsi?er is
4,341,677
11 12
split into two portions, preferably arounda 50/50 split BASF Wyandotte Corporation under the trade designa
wherein the ?rst portion is added to the mixture of the tion “Pluronic F-87” having an HLB of 24 and used in
emulsi?ers, antioxidant and solvent, and the second an amount of about 0.5 to about 5 weight percent along
portion is added to water preferably in around a 50/50 with another ethylene oxide-propylene oxide glycol
blend and then this portion of the oxide block copoly condensate available under the trade designation “Plu
mer emulsi?er in water is combined with the emulsi?er, ronic P-65” that has an HLB of 17 and is available in a
antioxidant, solvent mixture. The ?nal mixture is then paste form. Another emulsi?er that is used is the polye
agitated withthe addition of an amount of warm water thoxylated vegetable oil available from GAF under the
of about 25 to about 30° C. in the range of about 15 to trade designation “EMULPHOR EL-7l9” having an
about 30 weight percent of the aqueous emulsion. Then 10 HLB of 13.6. To this mixture there is added a requisite
an amount of cold water is added to give an amount of amount of water by any of the methods discussed above
active antioxidant in the range of about 5 to about 25 for the preferred embodiment.
weight percent to produce the aqueous emulsion. Another alternative embodiment is to use an antioxi
In an alternative embodiment, the antioxidant tet dant that is a 3:1 condensate of 3 methyl-6-tertiary butyl
rakis(methylene-3-3‘,5'-di-t-butyl-4’-hydroxy phenyl) phenol with crotonaldehyde, available from ICI US,
propionate methane available from Ciba Geigy Corpo Inc. under the trade designation “TOPANOL CA” in
ration under the‘trade designation “IRGANOX 1010” an amount in the range of about 5 to about 25 weight
antioxidant is dissolved in an amount of about 5 to about percent of the emulsion. This antioxidant which is a ?ne
20 weight percent of the emulsion in the organic solvent white crystalline powder with a melting point of l82.5°
methyl ethyl ketone. The amount of methyl ethyl ke C. to 188° C. is dissolved in cyclopentanone which is
tone used is in the range of around a l to 1 ratio with the used in an amount of around a l to 1 ratio with the
antioxidant. The emulsifer blend is combined with this ' antioxidant. To this mixture ‘there is added an emulsi?er
mixture by any of the aforementioned manners of addi blend by any of the methods used in the preferred em
tion.’ The emulsi?er- blend comprises the emulsi?er bodiment where the emulsi?er blend comprises an octyl
polyoxyethylene (4) sorbitan monolaurate (Tween 21 25 phenoxy polyethoxyethanol emulsi?er available from
available from ICI Americas, Inc.) wherein the amount Rohm & Haas Company under the trade. designation
of the monolaurate emulsi?er is in the range of about 1 “TRITON X-lOO" which is used in an amount of about
to about 5 weight percent. Another emulsi?er that is 1 to about 5 weight percent of the emulsion. Another
used is a condensate of ethylene oxide with hydrophilic octyl phenoxy polyethoxyethanol emulsi?er that is used
bases formed by condensing propylene oxide and prop 30 is'available from Rohm & Haas Company under the
ylene glycol which is available from BASF Wyandotte trade designation “TRITON X45”, and it is used in the
under the trade designation “Pluronic F-85” having an same amounts as the Triton X-lOO emulsifer. The X-lOO
HLB of 24 and used in an amount of about 1 to about 5 has an HLB of 13.5 and the X-45 has an HLB of 10.4. In
weight percent. Another emulsi?er that is used is the addition to the antioxidant, solvent, emulsi?er blend
polyethoxylated vegetable oil available from GAF Cor mixture an amount of epoxy resin such as Epon 828
poration under the trade designation “EMULPHOR epoxy resin available from Shell Chemical Company
EL-7l9” having an HLB of 13.6 and used in an amount can be added to the emulsion in an amount of up to
of about 1 to about 5 weight percent. In addition to the about 40 weight percent of the emulsion. This mixture is
antioxidant, the methyl ethyl ketone, and the emulsi? then emulsi?ed by the indirect method by adding water
ers, an amount of polyalkylene polyol lubricant avail 40 to invert the oil to an oil-in-water emulsion. The amount
able under the trade designation “.Pluracol V-l0” avail of water that is added and the method it is added is
able from BASF Wyandotte Corporation is added to similar to that discussed for the preferred embodiment.
the emulsion in an amount of about 1 to about 5 weight This emulsion of the antioxidant with the solvent and
percent. This lubricant is added to give the emulsion emulsi?ers and epoxy resins allows for the simultaneous
additional stability. This lubricant can also be added to 45 emulsi?cation of the antioxidant and the epoxy resin.
the sizing composition rather than to the emulsion. The Any of these aforementioned oil-in-water emulsions
polyalkylene glycol “Pluracol V-l0” is a viscous, high and preferably the emulsion having the octadecyl 3
molecular weight, liquid with a speci?c gravity at (3’,5'-di-tert-butyl-4-hydroxyphenyl)propionate antioxi
25/25° C. by BWC Test of 1.089 with a ?ash point by dant can be formulated into a sizing composition for
ASTM D92-52 of 510° F. To the mixture of the antioxi treating glass ?bers. This formulation preferably occurs
dant, methyl ethyl ketone, monolaurate, oxide glycol by adding the oil-in-water emulsion to an aqueous com
condensate and vegetable oil emulsi?ers and polyol position containing a coupling agent that is preferably a
lubricant there is added the requisite water to produce mixture of coupling agents such as an organo diamino
an oil-in-water emulsion as for the preferred antioxidant silane coupling agent and an epoxy containing organo
discussed above. 1 55 silane coupling agent wherein both are present in an
Another alternative embodiment is to use a substi amount of about 0.5 to about 10 weight percent of the
tuted diphenylamine antioxidant 4,4’-[2-(2-phenyl) aqueous sizing composition. To this mixture there is
propyl]diphenylamine available from Uniroyal Chemi also added ?lm-formers like epoxy-containing resin in
cal Corporation under the trade designation “NAU an amount of about 0.5 to about 12 weight percent of
GARD 445” in an amount preferably in the range of 60 the aqueous sizing composition. In an alternative em
about 5 to about 25 weight percent dissolved in acetone bodiment other sizing ingredients may be added like
used in an amount of around a 1 to 1 ratio with the lubricants, such as the Pluracol V-l0 lubricant, wetting
antioxidant. To this mixture of antioxidant and solvent agents, and additional surfactants and cationic agents.
the emulsifier blend is added by any of the methods The amount of water in the aqueous sizing composition
discussed in the preferred antioxidant emulsion. The 65 usually ranges from about 70 to about 99 weight percent
emulsi?ers include the condensate of ethylene oxide of the sizing composition.
with hydrophobic bases formed by condensing propy The aqueous sizing composition is applied to individ
lene oxide and propylene glycol which is available from ual glass ?bers during their formation according to the
4,341,677
13 14
manner illustrated in US. Pat. No. 4,027,071 hereby
incorporated by reference and the sized glass ?bers are
subsequently dried to remove the moisture and organic wt % gm.
solvent. The antioxidant oil-in-water emulsion used A. Epoxy resin (Araldete 540X90) 29.6 685
with the aforementioned sizing composition having a Antioxidant (Naugard 445) 7.8 180
Methyl ethyl ketone 4.3 100
mixture of silanes and a ?lm-former reduces the chemi
Butyl Cellosolve acetate 4.3 100
cal degradation of polymers that are reinforced with 1,1, l-tri-chloroethane 6.0 140
these glass ?bers,-especially at exposures to sever, end B. Nonionic emulsi?er (Pluronic L-35) 3.0 70
use, elevated temperatures. This is particularly bene? Nonionic emulsi?er (Pluronic F-108) 1.6 36
Water 43.3 1000
cial when these sized glass ?bers are used to reinforce
polyesters such as polybutylene terephthalate.
This three solvent blend, dual emulsi?er blend
The aqueous emulsions of the present invention will
yielded an emulsion with good stability.
be further elucidated by making reference to the follow
ing examples.
EXAMPLE 4
15
EXAMPLE 1 Employing the identical preparation procedure as in
Example 1 an emulsion was prepared that had the fol
An emulsion was prepared by the following method.
lowing formulation:
First, 180 grams (8.7 weight percent of the emulsion) of
a 3:1 condensate of 3 methyl-6-tertiary butylphenol
20
with crotonaldehyde antioxidant available from ICI
wt % gm.
US. Inc. as Topanol CA antioxidant was dissolved in
A. Epoxy resin (Araldete 540x90) 25.4 540
an epoxy resin solution at 120° F. (49° C.). The solution Antioxidant (Naugard 445) 8.5 180
contained 540 grams (26.2 wt.%) of epoxy resin avail Methyl carbitol acetate 9.4 200
able from Ciba Products Corporation under the trade 25 methyl ethyl ketone 4.7 100
Nonionic emulsi?er Pluronic L-35 3.3 70
designation “Araldite 540 X90” and 100 grams (4.9
Nonionic emulsi?er Pluronic F-l27 1.6 35
wt.%) of methyl ethyl ketone and 140 (6.8 wt.%) grams Cold Water 47.1 1000
of trichloroethylene.‘ .
Second, two emulsi?ers that are condensates of ethyl
The inversion occurred with the addition of 700
ene oxide with hydrophobic bases formed by condens
grams of water and the entire complement of water was
ing propylene oxide with propylene glycol were
added to produce a stable emulsion.
blended into the antioxidant emulsion. The one emulsi
?er was Pluronic L-35 having an HLB of 18.5 used in an EXAMPLE 5
amount of 66 grams (3.2 wt.%) and the other emulsi?er An amount of 720 grams, 28.8 weight percent, of the
was Pluronic F-127 emulsi?er that has an HLB of 22 35 aqueous emulsion of antioxidant tetrakis[methylene
and used in an amount of 33 grams (1.6 wt.%). Both of 3-(3',5’-di-t-butyl-4'-hydroxyphenyl)propionate]me
these emulsi?ers are available from BASF Wyandotte thane Irganox 1010 was dissolved in 720 grams (25.8
Industrial Chemical Group. The emulsi?er blend had a wt%) of cyclohexane. This dissolution occurred at a
combined HLB of 19.6. The two were blended into the temperature in the range of 802900 F. (26°—33° C.). To
antioxidant mixture until the F-l27 emulsi?er was com this mixture there was blended 45 grams (1.6 wt%) of
pletely melted. the nonionic emulsi?er Tergitol TMN-6 and‘45 grams
‘ The blended mixture was cooled before being ho (1.6 wt%) of the nonionic emulsi?er Igepal CO-630 and
mogenized in an Eppenbach homogenizer with the slow 65 grams (2.3 wt%) of nonionic emulsi?er Triton N
addition of 1000 grams of water at room temperature. 401. The emulsi?er blend had an overall HLB of 19.7.
45
This emulsion could be used in a sizing composition for To emulsify to an oil-in-water emulsion 1200 grams
glass ?bers. (42.9 wt%) of water was added with shear mixing. A
stable emulsion was produced having a ?ne to medium
EXAMPLE 2 particle size distribution with hardly any coarse parti
Using the same preparation procedure another emul cles.
sion was prepared that had the following formulation:
EXAMPLE 6
The emulsion of Example 5 was used in preparing a
wt % grams sizing composition that was used to treat glass ?bers.
The sizing composition contained:
A. Epoxy resin (Araldite 540 X90) 25.4 540 55
Antioxidant (Naugard 445) 8.5 180
trichloroethylene 6.6 140
methyl isobutyl ketone 4.7 100 wt % grns.
Blended with A was
Epoxy resin (Genepoxy 370 H55 55% solids) 8.3 2730
Pluronic Condensate emulsi?er‘
Emulsion (30.6% solids) 6.7 2210
L-35 5.2 110 grams Film-former (polyurethane resin Wyandotte 24.2 7980
F-127 2.4 52 grams
X-l042 50% available from BASF
water 47.1 1000 grams Wyandotte)
diamino organosilane 9.1 3000
water 18.2 6000
EXAMPLE 3 epoxy-containing silane 0.5 150
65 water 32.8 10,800
Using the same preparation procedure as in Example acetic acid .18 60
1 an emulsion was prepared that had the following .01 5
formulation:
4,341, 677
15 16
The sizing composition was prepared by hydrolyzing
EXAMPLE 1 1
the silanes in the indicated amounts of water and com
bining the aqueous solutions of silanes. The antioxidant An oil-in-water emulsion of Irganox 1010 antioxidant
emulsion was combined with the silane mixture and to was prepared by dissolving 160 grams (7.4 wt%) of the
this mixture there was added the polyurethane resin. 5 antioxidant in 160 grams (7.4 wt%) methyl ethyl ketone
The epoxy resin available from General Mills Company at a temperature up to 130° F. (54° C.). To this mixture
was added to the mixture. This sizing composition is there was blended 50 grams of POE (4) sorbitan mono
hereinafter referred to as Size 1. laurate (Tween 21 emulsi?er from ICI Americas Inc.)
The sizing was used to treat K-37 l/O glass ?bers in a and 50 grams of Emulphor EL-719 material, and 50
‘ wet chop process to produce 3" (inch) chopped glass 10 grams of Pluronic P-65 emulsi?er and 50 grams of Plu
?bers. ronic F-87 emulsi?er. The emulsi?er blend had a com
bined HLB of 17.
EXAMPLE 7
Also blended into the mixture was 640 grams (29.3
An amount of 313 grams _(7.9 weight percent of the wt%) of Epon 828 epoxy resin. The total mixture was
emulsion) of antioxidant Naugard 445 was dissolved in 15 emulsi?ed using an Eppenbach mixer with the addition
acetone. The amount of acetone was 500 grams (12.7 of 1000 grams (46.5 wt%) of water.
wt%) which gave a 0.6 to 1 antioxidant solvent ratio. The stability of the emulsion is good on storage of 4
This mixture was added to 1250 grams (31.6 wt%) of hours and 5 days. Although after 5 days of storage some
warm epoxy resin (Epon 828 resin). To this mix there 20 surface ?lm formed which might be due to solvent
was added 48 grams (1.2 wt%) of the nonionic emulsi
evaporation since container was open to the atmo
?er Pluronic F-87 and 82 grams (2.1 wt%) of nonionic . sphere.
emulsi?er Pluronic P-65 and 32 grams (0.8 wt%) of
nonionic emulsi?er Emulphor EL-719. The latter emul EXAMPLE 12
si?er is a polyoxyethylated vegetable oil available from 25
An oil-in-water emulsion of Irganox I076 antioxidant
GAF Corporation. This gives a total HLB for the emul
was prepared by dissolving 160 grams (7.4 wt%) octa
sion blend of 18.4. decyl 3-(3‘,5’-di-tert-butyl-4-hydroxyphenyl)propionate
The mix was heated to remove the acetone although
in 160 grams (7.4 wt%) of toluene solvent at a tempera
the acetone could even be evaporated off before the
ture of 80° to 90° F. (26° C. to 33° C.). To this mixture
‘addition of the emulsi?er blend. 30
there was added 50 grams of POE (4) sorbitan monolau
Once about 90-95% of the acetone was removed,
rate (Tween 21), 50 grams of Emulphor EL-7l9 mate
emulsi?cation was commenced using Eppenbach equip
rial, 50 grams of Pluronic P-65 emulsi?er and 50 grams
ment. The water was added gradually until all of the
of Pluronic F-87 emulsi?er. The emulsi?er blend had a
water was added. The emulsion mix was cooled back to
combined HLB of 17. An epoxy resin, Epon 828 resin,
room temperature. 35
was stirred into the mixture, and the resultant mixture
EXAMPLES 8, 9 AND 10 was emulsi?ed at a temperature of 110° F. (43° C.) with
the addition of 1000 grams of water.
The emulsion of Example 7 was used in preparing
Storability and dilut'ability of the emulsion was good.
three sizing compositions for glass ?bers. These compo
sitions are depicted in Table I below. 40 EXAMPLE 13
TABLE I An oil-in-water emulsion of tetrakis(methylene 3-3'5'
di-t-butyl-4'-hydroxyphenyl)propionate methane was
' Size 2 Size 3 Size 4
Size Formulation gm/wt % gm/wt % gin/Wt % prepared with the following formulation and in the
Emulsion concentrate following manner. An amount of 480 grams of the anti
50% Epoxy Resin/Naugard 445 45 oxidant was dissolved at 120° F. (49° C.) in 480 grams
Antioxidant SOS/8.1 310/85 305/83 methyl ethyl ketone. Blended with this mixture was 150
Film-fonner:
grams of POE (4) sorbitan monolaurate (Tween 21), 150
Urea Melamine Resin
(Resimene resin Monsanto grams of Emulphor EL-7l9 material and 150 grams of
Chem. Co.) 36/ 1.0 ~ — Pluronic P-65 emulsi?er and 50 grams of Pluracol V-10,
Urethane latex 50
a lubricant. The emulsi?er blend had a combined HLB
Witcoband w-zio
of 17 and the lubricant was added to improve the stabil
(Witco Chemical Corp.) ZOO/5.3 - —
Urethane latex ity of the emulsion. After these materials were blended
Nopcothane UOI 1960 grams of Epon 828 epoxy resin were stirred into
(Diamond Shamrock Chemical
the blend. At a temperature of 105° F. (41° C.) the resul
00-) - l00/2.7 _ 55
Urethane latex tant mixture was emulsi?ed with the addition of 6000
Wyandotte X-1042H grams of water.
(BASF Wyandotte Corp.) — — 100/2.7 The dispersibility and stability of the emulsion was
Water 957/255 1000/27.3 1000/27.3 good. The stability was good after two days of storage.
Water 2176/58 2l76/S9.4 2176/59.5
aminosilane 6O
EXAMPLE 14
(A-l 100 Union Carbide Corp.) 60/1.6 60/1.6 60/1.6
Urea 18/05 l8/0.5 l8/O.5 An oil-in-water emulsion of octadecyl 3-(3',5’-di-tert
Total Solids 7.1% 7.0% 6.84% butyl-4-hydroxyphenyl)propionate was prepared in the
same manner as Example 13. The emulsion had a higher
No problems were encountered in using the emul- 65 amount of solids, 34 percent. The only exception to the
sions in Sizings 2, 3 or 4. These sizing compositions manner of preparation was the dissolving of the antioxi
were used to treat glass ?bers made from a glass batch dant in the toluene at room temperature. The formula
marble melter used to make wet chop glass ?bers. tion was:
4,341,677
17 18
temperature was cooled to 90° F. before the addition of
methyl ethyl ketone.
gnis/wt %
To this mixture there was added 45 grams (1.4 wt%)
Octadecyl3-(3’,5'-di-tert-butyl- - I @ of trimethyl no'nylzpolyethylene glycol ethers (Tergitol
4~hydroxyphenyl) propionate 480/ 14.4
TMN-6), and 45 grams (1.4 wt%) of nonylphenox
toluene , v ‘480/ 14.4
POE (4) sorbitan rnonolaurate ' 105/3.l ypolyethyleneoxyethanol (Igepal CO-630) and 65
polyethoxylated vegetable oil ' I grams’ (2.0'wt%) of nonylphenoxypolyethoxyethanol
' (Emulphor Ell/719) - 105/3.1 (Triton N-401 702) *available from’Rohm and Haas Co.
condensates of ethylene oxide and l 3 1' > ,. ‘ The emulsi?er blend had a combined HLB of 15.3.
vpropylene oxide withpropylene glycol v _ v , z ' 10 The resultant ‘mixture was emulsi?ed with the addi
Pluronic P-65 _ , 100/2.9
Pluronic F-87 1 "100/2.9. , tion of 1500 grams (47.2 wt%) of water. '
polyalkylene polyol " '
(Pluracol V-10) ' 50/ 11.5 . EXAMPLE 18
Water . _ 1920/575 ‘I ' ‘ The ‘anti-oxidant which is a three-to-one condensate
15 of ‘3-niethyl,G-tertiarybutylphenol with crotonaldehyde
The emulsion blend had a total HLB of 16.8. The
was emulsi?ed‘ by combining 315 grams or 16.8 weight
emulsion had good stability‘ and dilutability. On storage
percent of the antioxidant with 500 grams or 26.6
for 4 hours and two days the emulsion was good.
Weight percent of cyclohexanone at a temperature of
EXAMPLE 15 around 104° F.‘(40° C.). To this mixture there was
20
added an emulsi?er blend comprising 32 grams or 1.7
An oil-in-water emulsion of an antioxidant of 3:1 weight percent of polyethoxylated vegetable oil (emul
condensate of 3 methyl 6 tertiary "but‘ylphenol with
phor EL 719), and 82 grams or 4.4 weight percent of a
crotonaldehyde'antioxidant was prepared. An amount
condensate of ethylene oxide with hydrophobic bases
of 160 grams (619 wt%) of the antioxidant was dissolved formed by "condensing propylene oxide with propylene
in 160 grams (6.8 wt%) of cyclopentanone. To this 25
glycol (Pluronic P-65) and 48 grams or 2.6 weight per
mixture there was blended 100 grams of POE (4) sorbi cent of another condensate of ethylene oxide with hy
tan monolaurate (Tween 21), and‘ 100 grams of polye drophobic bases formed by condensation of propylene
thoxylated vegetable oil (Emulphor. EL-7‘l9). The
oxide with propylene glycol (Pluronic F-87). The emul
emulsi?er blend had a total HLB of 13.4. I sion blend has a “total HLB of 18.4. The mixture was
To this blended mixture there was added 655 grams 30 cooled back to 80° F. and emulsi?ed while adding 900
(27.9 wt%) of Epon 828 epoxy resin. The resultant grams or-47.9 weight percent water.
mixture was emulsi?ed with the addition of 1175 grams
(50 wt%) of water. . EXAMPLE 19
The emulsion had good dispersibility and good stor
' Another formulation of the 3:1 condensate of 3
35
ageability for 4 hours and one day. ' ' ' methyl;‘6-tertiarybutylphenol with crotonaldehyde anti
oxidant prepared in a similar manner to that of Example
EXAMPLE 16 '
18 is as follows: ' .
An oil-in-water emulsion'of octadecyl-3-(3',5'-di-tert
butyl-4-hydroxyphenyl)propionate was“ prepared. An
amount of 288 grams (17.7 wt%) of the antioxidant was Antioxidant ' 315 Grams 20 Weight Percent
Cyclohexanone Solvent 350 Grams 22.2 Weight Percent
dissolved in 288 grams (17.7 wt%) of xylene at around
Polyethoxylated Vegetable
110° F. (43° C.). To this mixture there was added an
Oil ‘ . 22 Grams 1.4 Weight Percent
emulsi?er blend of 18 grams (1.1 wt%) of ‘trimethyl Condensate of ethylene 54 Grams 3.4 Weight Percent
nonyl polyethylene glycol ethers (Tergitol- TMN-6 Oxide with hydrophobic
45 bases formed by condensing
emulsi?er available from Union Carbide Corp.), and 18
propyleneoxide with propyl
grams (1.1 wt%) of nonyl phenoxypolyethyleneoxye
ene glycol (Pluronic P-65)
thanol (Igepal C0630 from GAF Corp.). Also, 18 Another Condensate of 16 Grams 1 Weight Percent
grams (1.1 wt%) of condensate of ethylene oxide with ethylene Oxide with
hydrophobic bases formed‘by condensing propylene hydrophobic bases formed
by condensing propylene
oxide with propylene glycol (Pluronic P-65 emulsi?er oxide with propylene glycol
available from BASF Wyandotte) was combined with (Pluronic F-77)
200 grams of warm water at 80° F. (27° C.) and added to Pluronic F-77 Emulsion _ 15 Grams 1 Weight Percent
in Water in 500 in
the antioxidant mixture. The emulsi?er blend had a total
_ Grams 31.8 Weight Percent
HLB of 13.7. ‘ ' > . 55 Water to Complete 300 Grams 19.1 Weight Percent
The resulting mixturewa's emulsi?ed vwith the addi Emulsion
tion of 800 grams (49.1 wt%) of water. The emulsion
had good dispersibility and storageability.
The emulsi?er that is a condensate of ethylene oxide
with hydrophilic basis formed by condensing propylene
‘EXAMPLE 17
oxide with propylene glycol and available as Pluronic
The antioxidant tetrakis(methylene-_3-3’,5'¢di-t-butyl
.F-77 was added to the anti-oxidant mixture by adding a
4’-hydroxyphenyl)propionate methane was emulsi?ed ?rst portion of the emulsi?er directly to the antioxidant
in the following manner. An amount of 720 grams (22.7 mixture containing the antioxidant, solvent and other
wt%) was dissolved in a solvent mixture of petroleum emulsi?ers which is preferably a ?fty-?fty split and then
solvent Hi-Sol- 10 available from Ashland Chemical Co. adding the second portion of the emulsi?er to water and
in anamount of 720 grams (22.7 wt%) and 80 grams (2.5 adding the diluted emulsi?er to the antioxidant mixture.
wt%) of methyl ethyl ketone. The temperature was The emulsion had a thin viscosity and blue white
150° F. (66° C.) for dissolution in Hi-Sol-lO and the coloration.