Note: Descriptions are shown in the official language in which they were submitted.
I)ISCUSSION OF TIIE PRIOR ART
The technique of polymerizing or copolymerizing
one or more monomers in the presence of a polymer or a
substrate, "grafting technique," is known and is frequently
called graft polymerization or gra:ft copolymerization. In
this connection, please see "Copolymerization," High Polymers,
~ol. XVIII, Ham, pages 323-324, 335-420 and 573, Interscience
Publishers a division of John Wiley & Sons, New York, 1964;
. "Block ~nd Gra~t Polymers," Burlant and Ho~fman, Reinhold
Publishing Corporationg New York, 1960j "Block And Graft
.. Copolymers," Ceresa, Butterworth & Co. (Publishers) Ltd.,
London, 1962, and "Graf~ Copolymers," Polymer Reviews,
Vol. 16, Battaerd and Tregear, Interscience Publishers, a
i division o~ John Wiley & Sons, ~ew ~orl~, 1967.
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U.S. Patent No. 2,98l~,608 discloses a process
of heating a solid hydrocarbon with a polymerizable monomer
to f`orm a solution which is then cooled to form a gel.
Next, the gel is irradiated to obtain a hard,homogenous,
opa~ue product having properties which are di~erent
substantially ~rom those of the polymer normally obtained
~rom the corresponding monomer. As solid hydrocarbons
there are shown "Vaseline" having a m.p. of 30-~0C.,
chlorinated paraffin and distillation products from tar,
wood, tur~, lignite, and bituminous sha]e having melting
points of 55 to r700 C ~ As monomers there are shown vinyl
acetate, styxene, acrylonitrile and methyl methacrylate.
The parts ratio o~ "graftingl' monomer to solid hydrocarbon
as shown only in -t~e worl~ing examples :LS 100:2 -to lOO:lO.
U.S. Patent No. 3,479,313 discloses a process
for extending latex (e.g., SBR) particles with oil or
plast:icizers by f`orming a charge on the oil which is
dl~ferent from the charge on the latex rubber particles,
the net charge on the latex particles predominating. An
.
acid such as acetic acid may be used to change weak
cation~c surfactants to strorlg sur~ac-tants~ ~nionic~
and cationic sur~actants can be usecl.
~CKCAROUND 0~ rrll~3 INVEN'I'ION
; ~ ~ A carpet or rug, comprising a plurality o~
i~ fibers or tu~ts o~ ~ibers woven with a f`irst or primary
:~:ibrous backing material, is treated with an aqueous
`~ curable adhesive composition such as a rubber latex which
serves to bind those portLo~s of the fibers or tufts
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woven into the back-i~g ~o the backing and is then laminat-
ed b~ pressure to a secondary :~ibrous or woven backing to
force the adhesive at least in part into the ~irst 'backing
arld a'bout the loops of the f'ibers and at least in part into
the second backing. The resulting composite laminate is ;~
then heated or dried to remove the wa-ter and cure the
adhesive to b:ind the ends of the tufts or fibers to the
primary backing and the primary backing to the secondary
backing to ~orm an integral laminate.
Attempts have been made to incorporate rubber
compounding processing and/or extender oils into these
latex carpet backing adhesives to reduce costs. However~
to incorporate useful amounts of these processing oils
into the latices ~las require~ si.gn:L~icant quar~t:i.ti~es o~
various surfactants which have had a deleterious ef~ect
on the adhesive properties o~ the latices.
It, there~ore, is an object o~ this invention
' to avoid the difficulties alluded to ahove and to provide ''
.:
a method of oil extending a latex adhesive useful, among
' ~; ZO~ other things, for carpet backing purposes without appre-
.~
ciahly reducing :its adhesive properties.
It is another obJect o~' this inventlon to provide
a gra~ted rubb~r processing and/or extender oll whlch can
be used f'or extend:Lng latex adhes:ives and f'or other
~ purposes.
'~ ~ A ~urther object is to provide a carpet having
a backing secured to the ~ibers o~ the carpet 'by means of
; ~ an oil extended~adhesive.
These;~and other objects and advantages of the
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present invention will become ~1ore apparent to those skilled in
the art from the following detailed description and working
examples.
According to the invention, there is provided a
method which comprises coating the backing of a carpet comprising
a plurality of fibers or tufts woven with a first fibrous backing
with an aqueous curable adhesive composition and then applying
with pressure a second fibrous backing material to said adhesive
coated first fibrous backing to form a l~ninate, said adhesive
being present in an amount sufficient to secure the ends of said
fibers or tufts to said first backing material and to secure said
second backing material to said first backing material, and then
heating the resulting laminate at a temperature and for a time
suf~icient to dry said adhesive and said secondary backing and
to cure said adhesiYe to bind the ends of the fibers or tufts of
said carpet to said primary backing and said primary backing to
: said secondary backing together into a unitary laminate without
adversely affecting the fibers or tufts of said carpet, said
adhesive in said composition comprising a hlend of a polymer and
20 ~ a minor amount by weight of e~tender ~or said polymer, said ex-
tender comprising a mineral oil containingr per lO0 parts by
weight of saia oil, graft polymerized to said oil from about 2
to 20 parts by we~.ght of an ethylenically unsaturated monomer
having from 2 to 16 carbon atoms and saic~ polymer being a copoly-
mer of a diene selected from the group consisting o butadiene,
isoprene and 2,3-dimethyl butadiene and at least one copolymer-
ized monomer selected from the yroup consistins of acrylic acid,
methacrylic acid,:~maleic acid, maleic anhydride, fumaric acid,
itaconic acid, vinyl benzoic acidr ~-chloro acrylic acid and .
crotonic acid.
In particular, it has been found that a monomer such
f~
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as acrylic acid can be grafted on a rubber compounding process
and/or extender oil. When the grafted oil is emulsified with
ammonium hyd.roxide and water, it can be used to extend a latex
of a carboxylated butadiene-1,3/styrene copolymer to provide a .
latex adhesive which when used as a carpet backing exhibits sub-
stantially the same adhesive properties as a latex which is not
oil extended. This provides a method for lowering the costs of
the adhesive or other latex. Also, it has been found that such
an emulsified grafted oil can be used as an emulsifier or seed in
aqueous a~aline emulsion polymerization in place of more ex-
pensive suffactants or emulsifiers.
The monomers preferred in the practice of the
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present inventiorl are acrylic acld, methacrylic acid,
maleic ac:icl, fuma.r;c acid, vinyl benæoic acid,~ -chloro-
acrylic acld, crotonic acid and itaconic acid. Other
monomers which can be used are ~leic anhydride, methyl
acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate,
ethyl hexyl acrylate, methyl methacrylate, ethyl meth-
acrylate, 2-hydroxy ethyl acrylate, 2-hydroxy propyl
acrylate, hydroxy ethyl methacrylate, hydroxy propyl-
methacrylate, ethylene, butadiene, isoprene, chloroprene,
styrene, alpha methyl sty~rene, vinyl toluene, acrylamide,
methacrylamide, acrylonitrile, methacrylonitrile, diethyl
fumarate, vinyl pyrldine, virlyI chloride, vinylidene
chloride, vinyl acetate, and the like. These monomers
are characterized by having an ethylenic carbon-to-carbon
double bond which can undergo addition polymerization and
~ave from 2 to 16 carbon atoms. Mixtures o~ monomers can
be used. These monomers should be compatible in the sense
that they should not inter~ere with each other during
gra~t pblymerization nor prevent each other from grafting
onto the oi] although they may copolymerize. Moreover,
the monomer may be one wh:ich renders the oi.l compatible
with the polymer wh:ich ls to he extended with the o:Ll as
well as with monomers~ catalysts, and water when used as
a seed or surfactant in an emulsiorl polymerization system.
For example, an acrylic acid grafted oil may be used with
a carboxyl~-ted huta~-lene~-styrene copolymer latex. ~ vinyl
acetate grafted oil may be used with an ethylene-vinyl
acetate copolymer la~tex. A styrene gra~ted oil may be
used with a butadiene-styrene copolymer latex. An
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acry1onitrile grafte~ oil may be used with a butadiene-
acrylonityile copolyrner latex.
~[~ wi:L.l be appY~eciat;ed th3-t an acrylate or maleic
anhydride grafte~l processlng oil can be hydrolyzed and
neutral:ized to ~ree the acid groups although this is not
as convenient as directly grafting an acid such as acrylic
acid onto the oil. A processing oil grafted with an acid
such as acrylic acid or other unsaturated acid can further
be reacted with an epoxide (see U.S. Patent No. 3,873,480).
A processing oil grafted with vinyl acetate can be treated
with alcohol and an acid catalyst to convert some or all
of the ester groups to hydroxyl groups if such reactive or
water sensit;ive groups are desired. See Schildknecht, "V:inyl
And Related Polymers," 1952, John Wiley & Sons, Inc.~ New
York.
The oils to be graftecd are mineral oils. PreP-
erably, the oils to be grafted are rubber compounding
processing or extender oi.ls which also may be considered
sometimes as plastici~ers or sof-teners. These processing
oils may be`o:~ the aromatic including highly aromatic~
naphthenic or paraffinic type ox mixture thereof. The
processing o:lls p:referably should be non-staining, be light
colo:red or c~.~aY 'Wl'leX'C l:L~ht colored proclucts axe des:Lred,
and have low volat:ility. The pour point of the processing
oils should be below about 30C. These processing oils
shollld have a viscos:it~ SUS (Saybolt Universal viscosLty
seconds) at about 3~C. of from about 40 to 27,000 preferably
from about l~o to 7,000 and a molecular weight of from about
220 to 2,l~00, preferably from about 220 to 720. The
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molecular type analysis of these processing oils, clay-gel
weight should be from about 0. to 0.1% asphaltenes, from about
0.2-18% polar compounds, from about 10 to 80~ aromatic com-
pounds, and from about 10 to ~0% of saturates. It is well
known that the polar compounds are designated as such since
their hydrocarbon molecules may contain nitrogen, oxygen and/or
sulfur atoms. The carbon type analyses of these processing
oils show that they contaln from about 3 ~o 47% aromatic
carbon atoms (CA)~ from about 19 to 44% naphthenic carbon atoms
(CN), and from about 31 to 73% paraffinic carbon atoms ~Cp).
Processing or extending oils used in rubber compounding are
well known. See "Plasticizer Technology," Vol. 1, Brulns~
1965, Reinhold Publishing Corporation, New York; "India Rubber
World," Vol. 126, No. 4, July, 1952~ pages 495~499; "Industrial
; And Engineering Chemistry," May, 1953, pages 1035~1053; ASTM
Specification D 2226-70; Sun Oil Company, Industrial Products
Department, Technical Bulletin No. 88, "Rubber Process &
Extender Oils," 12 pages, "Petroleum Oils For The Chemical
Process Industry~" Sun Oil Company, ~ulletin No. Al-1006~
Copyright 1976~ 8 pages; and "Materials, Compoundlng Ingredient~"
And Machlnery For Rubber," 1977, Bill Communications, Inc.,
New York.
Free radical catalysts (free-radical ~ormers or free~
radical-~orming systems) are used in the practice of the present
invention in a minor amount sufficient to provide for poly-
merizatlon of the polymerizable monomers. Oil soluble free
radical catalysts preferably should be employed. Also, the free
radical catalyst should be suf~iciently reactive to polymerize
the monomers and to under~o reaction with the oil or to open up
the double bond of the monomer and to abstract a labile atom
fronl the oil or to open up any~ especially aliphatic, double
bonds o~ the oll. E,xamples of free radlcal catalysts are di
benzogl peroxide3 diacetyl peroxide, didecanoyl peroxide, di-t-
butyl peroxide, dilauroyl peroxide, bis (p-methoxy benzoyl)
peroxide, t-butyl peroxy pivalate, dicumyl peroxide~ percarbonate;,
azobisdimethylvaleronitrile~ 2,2'-azobisisobutyronitrile, 2~2'-
azobls-2-methylbutyronitrlle, 2,2'-azobis(methylisobutyrate) and
the persul~ates like Na, K or ammonium persul~ate, and the like
and mixtures o~ the same.
The grafting process can be conducted in resin
kettles under an atmosphere of an iner~ gas ~uch as
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i~7184
nltrogen, argon, neon, helium and so forth and mixtures
thereof. For reasons of safety it is preferred to use
conventional closed polymerization reactors operating l~der
an atmosphere of the inert gas. Pressure may be used where
the monomer is a gas or is volatile. Temperatures during
; the polymeriæatio~ reaction should be sufficient to decom-
pose the cata]yst to cause polymerizatlon and to maintain
- a fluid polymerization mass. Solvents, also, may be used
to control heat exchange and ~iscosity during graft poly-
merization. They are usually low m.w. hydrocarbons such
as hexane, heptane, benzene, toluene, mixtures thereof
and so forth and may be stripped from the graft polymer
after polymerizat:ion. The solvents should be chosen so as
not to ~orm an azeotrope with the oil or grafted oil. Chain
tran~sfer agents such as mercaptans, also, may be used
durlng grafting. The reactors should be provided with
heating and cooling means, agitators or stirrers, and means
to discharge and charge the reactors. Only a minor amount
of catalyst, enough to cause polymerization, is used
during the grafting process. The amourlt o~ monomer gra:~ted
onto the o:l.1 var:ies from abou-t 2 to 20 paxts by welght,
pre~erab:Ly ~rom about 5 to 15 pa:rts by we:~g~lt, per 100
parts by wei~ht o:~ t~le oil. It will be appreclated that
the grafted oil may inc1ude some homopolymer from the
monomer and that some of the po]ymerizable monomer may
cause cross--linki~g between the oil molecules.
. .
During graft polymerization the mixture pref-
erably shoul~ be well agitated to ensure that the monomers
are well distributed among the oil. molecules or randomly
~ graf~ted on the oll molecule backbone. Where different
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polymerizable monomers are used, it will be appreciated
that copolymers likewise can be formed. The resulting
grafted oil is used in a minor amount by weight as com-
parecl to the latex to be extended (on a dry weigh~ basis)
to extend and/or plasticize the polymer of the latex.
Preferably, the grafted oil is used in an amount of from
about 5 to llo parl;s by weight per 100 parts by weight of
; the polymer which is to be extended (on a dry weight basis).
; While the monomer(s), oil and catalyst may all
be charged at once to the reactor and polymerization
started, it is preferred to mix all of the polymerizable
acid initially with about 75~ by weight o~ the oil and
about 50-600~ hy welght of the catalyst. The remainder
of the oil ancl catalyst are mixed together, and then the
mixture is added in 4 to 5 increments during the poly-
merization. However, other ways o:~ charging and/or
incrementally adding the ingredients may be followed.
After gra~ting the process oil where an acid
such as acrylic acid is used, the grafted oil is treated
with amrnonia or a low molecular wei.ght water soluble
amine such as methyl amine, ethylam:ine, propyl amine,
butyl amlne, triethylamine, anillne or KOH, NaOH, etc. and
mixed with wa~er to ~o.rm an emulslcjn whlch ls compatible
wlth the :latex lo be oll e~tellded such as an aclueous
alkallne~carboxylated butadiene-st~rerle copolymer. Where
a monomer such as styrene is gra~ted onto the oil, the
~ gra~ted oil can be mlxed with water and an e~ulsifier
; and added~to a butadiene-styrene aqueous alkaline latex.
Instead of a fugitlve baæe like ammonla, sodium or
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potassium hydroxide can be used so long as it does not
adversely aI~ect ~he properties of the resulting carpet
or other product. Mlxtures of alkaline materials can
be used.
A feature of the present inven-tion is that the
grafted oil o~ the present inve~tion carl be used as a
seed or emulsifier in aqueous alkaline emulsion poly-
merization of butadiene or isoprene alone or wlth at
least one copolymeriæable monomer such as styrene~ methyl
styrene, methyl acrylate, ethyl acrylate, butyl acrylate,
ethylhexyl acrylate, acrylonitrile, methacrylonitrile,
and so forth and mixtures of the same. Methods for
making such polymers or copolymers are wel.] known t;o -those
skilled in the art.
The grafted oils of the present invention, also,
can be used to extend paper coating latices in the
rnanufacture of paper coatings. See U.S. Patent No.
3,873,480 and the re~erences men-tioned therein.
While the i.nvention has been described with
respect to latices, i.t will be appreciated that the
graf`ted oil carl be mill mixed or Banbury mixed with the
rubber in dry form. Alternati.ve]y, I;he gra~-tcd oil and
the dry rubber can be solvent mlxed and t~le solv~nt
stripped ~rom the same.
, ~
~ llle the process of the present invention can
be applied to the back of any woven or nonwoven carpet
(or rug) material to~secure -the base yarns to the other
- yarns of` the carpet such as Wilton, Axminster~ knitted
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and other carpets, as well as to a secondary 'backing, it
is particularly use:~ul in the manu:facture o~ pilecl or
tufted carpets. ~[n piled or tufted carpe-ts the :Eibers
or yarn is needled or looped through the interstices or
holes in a square woven or nonwoven primar~r cloth such as
cotton, polypropylene, jute or other primary backing
material or other na tural or synthetic fibrous material
or mi~{ture thereof. For a thorough discussion of the
manufacture OI carpets and especially tufted carpel;s please
see ~'C!arpets And Othe:r Textile Floor Coverings, " Robinson,
2nd Ed., 1972, Textile Book Service, Division of Bonn
Industries Inc., The Trinity Press, London.. Please, also,
see "Wel:lington Sears Handbook of Industrial Textiles, "
Kaswell, 1963, Wellington Sears Co., Inc., New York
The yarns o:r tufts Or the carpet can be natural
or synthetic organic ~ibers or mixture thereof. Addi-
tionally, the yarns may vary f rom one t~pe to another
type. Examples: of such yarns are those :Erom silk, cotton,
~: wool, hair, nylon, acrylics ( "Acri1.an';~), polyeater, poly-
vinyl chloride, vinyl chlo:ride-vinyl acetate copolymers,
polyurethanes, rayon, pol~racrylonitriles, ~inyl chloride
or vin;ylidene chloride copolyrnerized w:ith ac:rylonltrile.,
polyvi.nyliclene chloride, polypropylene :fibers and the like.
lass :Eibers may be blended or woven with the natural and/
or synthetic organic :~ibers. These fibers or yarns can
contai.n :Eixe retardarlts, antistatic agents, bacteriostats,
antidegraclants,:~ dyes, pigrnents, optical brightners, and so
~ ~ I orth. :
; The latex adhesive used in the practice OI the
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backing system is generally a water based system o~
polyvinyl acetate, polyacrylates, polyethylene-v:inyl
acetate copolymers, styrene-butadiene copolymers (SBR),
and/or carboxylated styrene-butadiene copolymers.
The latex preferably used in rug or carpe-t
backing operations is an aqueous dispersion o~ a
flexible crosslinkable COOH-containing polymer or mixtures
of polymers. Examples of such polymers are the copolymers
of butadiene, isoprene, 2,3-dimethyl butadiene and other
dienes of 4 to 6 carbon atoms with a copolymeriæable un-
saturated acid such as acrylic acid, methacrylic acid,
maleic acid, maleic anhydride, fumaric acid, itaconic
acid, vinyl benzoi(: acid,~ ~chloro acrylic ac:ld, crotonic
acid, and the like and mixtures thereof. There, also,
may be copolymexized with the diene and acid monomer one
or rnore other copolymerizable monomers such as styrene,
~-methyl styrene, vinyl toluene, acrylonitrile, meth-
acrylorlitrile, methylacrylate, ethylacrylate, butyl
~ ~ acrylatej ethyl hexylacrylate, methyl methacrylate,
hydroxy ethyl acrylate, hydroxy propyl acrylate, hydroxy
ethyl methacxyla~;e, acrylamide, me-t~lacrylamicle, and the
like and mixture ~lereof. Stil~ other polymers can be
used such as the copo:Lymers o:~ one o~ more o~ the above
acrylates and one or more o~ the above acrylic acids. The
addition of the thlrd, ~ourth, etc. monomer wiL1 be
determined by the need for compatibility with the carpet
materials, stif~ness, and the toughness , strength, water
and solvent resistance and so forth desired. Even more
preferred~copolymers to use are the aqueous emulsions of
flexi.b].e carboxylate~cl butadiene styrene copolymers, e.g.,
copo:Lymers oi.~ buta(liene, sty.rene and at least one acld
selected from the group consisting of acrylic, methacrylic,
fumaric, mal.eic, and itaconic acids optionally with a
hydroxy lower alkyl acrylate. These copolymers may be
prepared in aqueous emulsion systems using conventional
emulsifiers, chain transfer agents, antioxidants, short-
stop agents, free radical catalysts and so forth as well
; known to the art. Methods for making these polymers are
disclosed in U.S. Patent Nos. 2,60~,668; 2,669,550;
2,710,292; 2,72~,707; 2,8~9,~26; 2,868,754; 3,392~048;
3,40LI,1].6; 3,~-109,569; and 3,4683833. Please, also~ see
"Rubber World," Sep-tember, 1954, pages 784 to 783 and
"Industrial And Engineering Chemistry," May, 1955, pages
1006 to 1012. See, also, U.S. Patent No. 4,009,310.
The aqueous adhes:ive can have a soli.ds content of from
about 30 to 60~, have a pH of about 7.5 to 11.5 and have
a Brookfielcl viscosity of about 50-350 (LVF Model ~2
Spindle @ 60 rpm) cps at 25 C.
~-Iowever, other polymeYs can be gxaft oil
exte.nded accoYdirlg to the process o~ the present inventlon
such. as polyvlnyl chlo.rlcle, po:Lystyxene, polyvinylldene
chloride, polymethylmethacrylate, polyethylmethacrylate,
polyvinyl chloride~vinylidene chloride, polychloroprene,
butadiene~acrylonitrile copolymers, butadiene-styrene-
acrylonitrile copolymers~ butadiene-styrene-vinyl pyrldine
copolymers, and so forth. Since the grafted oil of the
present invention acts not only as an extender but also
generally as a plasticizex~ it may be desirable to increase
-
the amount of` hard monomer in a copolymer to obtain the
same degree of flexibility. Thus, ln a carboxylated
butadiene-s~yrene copolymer it rnay be desirable to
increase the styrene con-tent from about 50~ to from about
55 ko 90~.
The carboxylated copol~mers are readily cross-
linked by means of polyvalent metal compounds such as the
hydroxides, and oxides of zinc,
magnesium, calciurn, titanium, barium~
strontium, cobalt, tin, iron, lead and others. The chloride,
sul~ate, nitraLe, acetate, and formate salts o~` Ca, Mg,
Sn, Fe, Sr, Ni:, Zn and Co mcay also be used as cross-
linking agents.
Sodium or alkali-metal aluminate may also be used as a
crosslinking agent. Polyamlnes, moreo~er, can be used as
crosslinking agents such as ethylene diamine, 1,3-diamino-
butane, diethylenetri&mine, and the like. Other cross-
llnking agents can be used such as the epoxides, amino-
~ormaldehyde re~sins, phenol-formaldehyde resins, urea~
formaldehyde resins, urea-melamine resins and so forth.
Addi.tionally, sul~llr curing systems can be added to the
copolymer composltion 1~ it conta:Lns sul~ur curable un-
- saturakion; however, such requires extended curing times
~at elevated temperatures and may not be too desirable. In
fact if a pl~nent or ~iller such as limestone~ calcLùm
carbonate, is employed~itshould furnish sufficient divalent
metallic ions durlng the curing step to provide the
necessary crosslinking between the COOH groups of the
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copolymer. Other dlvalent metal carbonates may likewise
be used. Mixtures of -the vari.ous curing or crosslinking
agents can be llS :!à .
In additi.on to the curing agents the aqueous
carboxylated copolymeric latex adhesive composition can
contain the usual antioxida.nts, dispersing agents, clay,
defoamers, urea, rrio2, thickeners, fire retardants,
bacteriostats, pigments or colorants, surfactants, alumina,
alurnlna hydrate, U~V absorbers, ammonia cut ca:seLn, and
so forth.
The compounded aqueous adhesive composition can
contain as high as about 850~ total solids content, and its
initia:l. viscosity can vary from about 9000 to ~0000 cps . or higher.
It can 'be usecl as such or ~rothed with air or other gas
w'hich i s non:reactive under spreading and curing cond:Ltions
ko form a foam containing about 20-65~ gas. p ':"
1'he compounded aqueous adhesive coating com
posikion can 'be applied to the back of the carpet by
air knife coatlng, blade coating, brush-finish coating,
: ~ 20 cast coating, :Elow-on coating, kni:fe coating, machine
coating, polishe~ drum coating, print on coating, roll
coati.ng, spray coaking, wire wound r od coatlng or other
methods known to the art f`or coating the backing ofl a
car.pet;,
The secondary backing material or layer can be
made of any natural or synthetic f'ibers or mixtures
khereof' such as cot ton, rayon, .nylon, polypropylene,
;: acrylics, hair or bast and so forth and is usually made
of square woven: fibers . Bask fibers include ~ute, flax,
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hemp~ sunn, ramie, hena~, urena, nettle and the like. Of
these backing materials it is preferred to use jute ~ibers.
Please see "Matthe~ws' Text:Lle Fibers," Mauersberger, 6th
Edltion, John Wil.ey & Sons, Inc., New York, 1954~ pages
257 to 281. Jute fibers are well known commercially, and
sources of the same can readlly be found in "The Carpet
and Rug Institute Directory and Report," 1974-75,
September, 1975, published by the Carpet and Rug Institute,
Dalton~ Georgia. Prior to the use in the practice o~ the
~resent invention the jute or other backing fiber can be
sized with starch~ treated with antidegradants, fire
retardants, steam or hot water and so f'orth.
To revi~w the process, the carpet lay~r i5 se-
cured on a tenteY (a ~rame or rack wlth hoolcs or clips
along two sides used for drying or stretching cloth) or
other suitable apparatus and ls carried aga:inst a roller
which coats and impregnates the back o~ the carpet with
the aqueous adhesive composltion at ambient temperature.
Then a layer of the second jute backing is roll pressed
~ against~the back o:E' the carpet containing the adhesive
layer and held by the ternter frame to prevent separation
from the adhesive coated and impregnatecl back o~ the
carpet and passed through an a:lr oven at a temperature
and f'or a time su~':E`icient to clry -the laminate and cure the
adhes~ve~pref'erably at a temperature o~ from about 120
~' to 205G. for from about 1 to 30 minutes. This causes evap-
oration o~ the water and curing o~ the polymer to cause
it to adhere~or bind the secondar~ backing to the back of'
the carpet to ~orm a carpet with a secondary backing
- 16 -
:
,:
`~A
8~
integrally bonded ~o the back of the carpet as well as
to bind the fibers of the carpet thereto~ If the adhesive
is a frothed or foamed adhesive, the pressing of the
secondary backing agalnst the back of the carpet causes
collapse of the froth and fur-ther penetration of the
adhe~ive into the back o~ the carpet and into the secondary
jute backing. The adhesive serves to lock the ends of
the tufts or ~i.bers of the carpeting to its cloth or
backing and to the secondary backing.
The temperature during drying and of the adheslve
and secondary backing and crosslinking of the adhesive
should be below that wh;.ch would adversely affect the prop-
erties of the tufts or bulk o~ the fibers of the carpet by
causing loss of strength, melt:ing and so forth.
While the gra~ted olls of thls invention, es-
peclally when emulsified, can be used in extending carpet
backing latex adhesives, they, also, can be used in paper
coating latices. The grafted oi.ls, moreover, can be used
as extenders for the:rubbery pol~ners like SBR rubber,
nitrile rubber, chloropre~ne rubber and so forth a~d as . ~.
plasticizers Por polyvin~l chloride and other plastics.
The gra~ted oils o:~ lhis invention, especially when
emulsi:~`ied, also can be used as emul~i~iers or seeds :in
aqueous alkali.ne emulsion polymerizatl.on and copoly-
merization. .....
.
The following examples will serve to illustrate
the prese.nt inve.ntion wlth more particular~ty to those
:; skilled in the art. In the exarnples all runs were con-
~: : ducted~in sealed polymerization bottles or reactors or in
: .: : ~ ~
. - 17
' ~ : `
resin flas~ first :~lushed wit~ nitrogen and also ~urther
ln an iner~ atmosphere or under a blanket of an inert
atmosphere sucll as nitrogen gas to exclude the air or
oxygen and with agitation. Parts are parts by weight
unless otherwise indicated.
Example l
120 grams of acrylic acid were mixed with 8 grams
o~ "~AZO" and heated to 40o C. to clissolve the
"VAZO". This composition was added to 800 grams
of "Sunpar" 2280 oil, under nitrogen and pre-
heated to 100C., in a resin f'lask in twelve
equal increments at 5 minute intervals. The
resulting mixture was heatecl an addit:Lonal hour at
100C. The results obL;ained were:
Original Oil Viscosity 640
GraftecL Oil. Vlscosity 4250
Exa_ple 2
' ~
120 grams of acrylic acid were mixed with 8 ~rams
of "~MZO" and heated to 40C. to dissolve the
"~AZO". This composltion was addecl to 800 gms.
o~ "Circosol" l~2~0, under nitrogen and pre-
heatecL to 100~., ln a resin ~`lask in eleven
equal increments at ~ive minute intervals. The
resulting mix-ture was reacted one additional hour
at 100C. The results obtained were as follows:
Or:lgin~l OiI Viscosity 380
Grafted Oil Viscosit~ 5000
.
~ ~r ~e ~r 1~ - 18
.~
''' -
- .., : '
Example 3
120 grams of' acrylic acid were mixed with 8 grams
of "VAZ0" and heated to lLOO C . to dissol~e the
"VAZ0". This CompQSitiOn was added to 800 gms.
`~ of "Sundex" 790 oil f`ollowirlg the procedure of
Example 1, above. The results obtained were as
follows:
Original Oil Viscosity 2700
Final Oil Viscosi-ty 750-~
* Viscosity of top layer o~ two phases into which oil
had separated. Bottom phase was a sludge-like
material.
~ .
Examp]e 4
The method o~ Example 1, above, was repeated. The
final Viscosity o~ the oll was 3650. The oil then
separated :into two phases on aging. The bottom oil
phase contained a hard brittle substance.
Example 5
The methocl o~ ~,xample 1~ above, was repeated and the
final oil product separatecl irlto two phase,s on
standing. The viscosities o~ the two phases were
not measured.
. : :
$~
, ~
: ~: :: ~ : : :
, .
`
, ;
~ ~ .
_xample 6
120 grams o~ acrylic acid were mlxed wi~h 8 grams
of "~ZO" and heatecl to L~o - 450C. to dissolve the
"VAZO" and then mixed with 400 grams of "Circosol"
42ll0 oil. This mixture was added to 400 gms. of
; "Circosol" 4240 oil~ preheated to 100C. under
nitrogen in a resin flask,from a separatory fur~nel
wlth vi~orous agitation o~er a one hour period.
~ The reaction was continued an addîtional hour at
; 10 100C. The final viscosity o~ the oil was 5500.
- Example 7
.
Emulsion copolymerization o~ butadiene and styrene
was conducted as follows:
_ Parts
Ingredients Run I Run II
Dlstilled Water118 ml. llo ml.
Solution A 10 ml. 10 ml.
Solution B 10 ml. 10 m]
Styrene ~ 60 gm. 60 gm.
~ "Sulfole" 120 0.1 gm. premixed 0.1 gm. prem:~ed
I Gra~ted Oil. from20 gm.) 20 gm.
Ex. 6, above, 5500
cp., @ 25C.
Butadiene-1,3 20 gm. 20 ~m.
The ingredient~ were placed in 12 oz. polymerizatiorl
bot~tles, capped and rotated in a polymerization bath
to form the copolymer as indi.cated below:
Reaction Temperature 125F. 160~1
Reaction Time ~k 13 to 29 hours5 hours
Final Viscosity 3,1~00 5~850
Total Solids (~) L~2.3 4] ~ 5
p~ 9 5 9 5
# to completion.
:
Tr ~ 2~0 _ ' .
~xample '7 (Cont'cl)
Solution ~
Ammonium Persulfate 5.0 gm.
.~
"Sequestrene" Na3 l.0 gm.
~ater (~/olumetr:ic) to lO0 ml.
Solution B
28% NH3 in I~20 23 gm.
Water (~olumetric) to lO0 ml.
This example shows -that the grafted oil of this
.o invention can be used as an emulsifier or sced in emulsion
polymerization.
. .
Example 8
120 grams of` acrylic acld were mixed with o grams
of "~AZ0" and heated to ca. 40C. to disso]ve the
"VAZ0" and then added to 500 grams of "Sunpar" 2280
oil. This mixture then was added to 300 gms. of
"Sunpar" 2280 oil, preheated to 100C. under
nitrogen in a resin flask, from a separatory funnel
with vigorous ag:Lt,ation over ninety minutes. The
reaction was continued one hour at 100C. after
addition was complete. The viscosity of the final
ol.l was 5000 (2l~C.).
.
~ T~ o~r~ ~
,
:
_ 21 -
, :
. ~ .
: . . -~ . ., : .
~L`137~
Examp:Le 9
120 grams o~ acrylic a,cid were mixed with ll grams
of "V~ZO" and heated to ca. 40 C. to clissolve the
"V~ZO" and then mixed with 500 grams of "Sunpart'
2280 oil. The resulting mixture was next added
to 300 ~ns. of "Sunpar" 2280 oil, preheated to
lOO~C. under nitrogen in a resin flask, from a
separatory funnel with vigorous agitation over
ninety minutes. The reaction was continued one hour
after addition was complete at 100C, The viscosity
of the ~inal product was L~600 (24C.).
:Example 10
150 gram~ of acrylic acld were mixed with 5 grams
of 1'VAZO" and. with 5 grams of benzoyl peroxide.
Thls mixture was heated to Ca. 400 C. to dissolve
the initiators and therl mixed with 625 grams of
"Sunpar" 22~0 oil. The resulting oil mixture was
next added to 375 gms. of "Sunparl' 2ZoO over 105
. ~ minutes following the procedure of Example 9~
above7and heate(l additional~y at 100C. The re
action was continued at 100C. f'o.r additlonal
periods of time. The results obt;a:Lned are shown
below:
R_action~Time (Hours)-~ _scosity
1 3/L~ 6100
2 - 3/11 L~600
3_ 3/L~ L~600
: :: Ll-3/Ll 4600
.Additional~t~ime plus original time.
.
22 -
,:
:
. . . . . . .
7~L8~a
Example l:L
120 grams of acrylic acid were mixed with 8 grams
of "VAZO" and heated to 40~ C. to dissolve the
"VAZO" and then added to 120 grams of "Sunpar"
2280 oil. This mlxture then was added in one
addition to 6~o gms. of "Sunpar" 2280 oil pre-
heated to 100C. under nitrogen with agitation.~
The temperature dropped to 85~C.~ and the reaction
exothermed explosively.
Example 12
;~ Acrylic acid was grafted onto "Sunpar" 2280 oil in
the presence of water and an emulsi~ier.
Ingredients and Parts
"Tamol "
Run Acid l-L20 "~ZO" N Oil
~ 15 15 1~0 1.0 100
! B 15 15 0.5 1.0 100
c 15 7.5 l.o l.o loO
D 15 7.5 0.5 1.0 100
E 10 15 1.0 1.0 100
F ~ ~ 10 15 0.5 1.0 100
G lo 7 . 5 1. 0 1. 0 100
H 10 7.5 0.5 1.0 100
. ,.
The ingredients were mixed ln a ~arlng Blender under
nitrogen ancl reacted at 88qC'. to obtain polymeriæatiotl.
'
,:
:
:
: _ 2 3 -
:
,
8~
Example 12 (Cont'd)
_ Results
Run V:iscosity Sur_ace Tension*
A 6~400 61.2
B llg500 64.8
1~,200 63.8
D 19,800 64.3
E 5,250 64.8
F 5,600 6LI.2
G 5,000 62.7
l~ 6,ll00 62.7
* Tensiometer; after dilution with H20 to 20~ total
solids content (TSC).
Example 13
'
Acrylic acid was grafted onto petroleum oils uslng
a free radical. catalyst at ~C. for 2 hours as
shown below:
I edi.ents and Parts
Acrylic
Run Oil Acid "VAZ0
- "Sunthene" 255
A 400 60 L~ . 6
B 4 oo 50 L~ . 5
C ~ 400 40 4.4
circosol ~l L~2L~o
D l~oo 60 l~.6
I E ll00 50 l~.5
1l.oo 40 11., 4
The reslllt;:l.ng proclllcts w~re diluted wlt;h :t[20, t;reated
- 30 with 287~ NH3 (28~ NH3 in 1120), and maintained o~er~
night at about 880C. Then the viscosity and surface
tension Or the resulting emulsio~ were measured.
rrhe results obtained are shown below:
'.:
e~
.
~ - 24 _
~ 97~
Example 1.3 (Cont'd)
2~/o
NIf3 Visc. S. Tens.
Runin II2o 1~20 p~I(50~ TSC) (25~ TSC)
A 50 L~ 9 1360 64.8
B 42 ll-12 9.05 620 62.2
C 33 l-~ll. 9.0 200 61.2
: D 5 414 9.0 200 57.6
~ 2 l-l-12 9.0 100 56.l~
F 33 411 9.0 60 51.4
Example 14
~ Acr~lic acid was gra~ted onto petroleum oils at
:~ 88C. ~or 2 hours ~ollowing the procedure o~ -
~ Example 13~ above. The ingredients and amounts
.
were as follows:
Ingredient and Amounts
Acrylic
, Run ()il Acid ''V~Z0''
.' ' :
"Sunthene" 255 .
~ 300 30 3-3
B 3 2L~ ~ 3.2
C 300 1~3 3.2
"circoso~ 2L~o
i
~: D 300 30 3.3
E 300 2Ll 3.2 ..
300 18 3.2
A~ter polymerlzatioll, the products obtained were
diluted with watex and the p~l ad~usted to 9 wlth
; ~ammonia water (28~ NH3 in H20) to -~orm emulsions.
rrhe pert.inent data are shown below:
:
~ 25 _
:
~ ;
Examp:le 1l~ (Cont'd)
Results
2~
N~-[3 ~iscosity S. Tens.
Run in M20 H2o (50~ TSC) (50~0rrsc)
__
A 25 305 660 61.6
B 20 30~ 450 65.o
C 15 303 153 63.o
D 25 305 100 49.5
E 20 304 88 52.0
303 68 49.2
Example 15
Following the methods of Examples 13 and 14 various
monomers were graft polymerized onto petrole~n oil
at 880C. ~or 2 hours according to the following
polymerization receipe show:ing parts used:
Oil, ~cryllc Other
Run "Sunthene" Ll2l~0 ~cid "V~ZO" Monomers
~ 100 15 1.0 -~
B 100 12.5 1.0 __
C 100 10 1 . O --
D 100 -- 1.0 Styrene-5.0
E 100 7.5 1.0 Styrene-7.5
F 100 ; __ ~ O Styrene-7.5~0.5
` Sul~ole 120
~;~ G 100 5 1.0 Styrene-5.0
H 100 7.5 1.0 Styrene-2.5
I 100 -- 1.0 1) EIE~-15
J 100 -- 1.0 H~-12.5
K 100 - 1.0 ~EA-10
1) EIydroxy~th~:L acrylate
After polymerization~ the products obta:Lned were
` dlluted with water and treated with NH3 (28~ NH3
in H20), and t,~le results obtained are shown below:
. ~
:
:
~ 26 -
Example 15 (Cont'd)
Run _lscosity (50~ TSC) pH Sur~ace Tension ~0~0 TSC)
A 700 6. r~ 56.2
B 300 7 .1 5L~ . 3
C 200 7.1 53-5
D 700 7.2 L~6~5
E 4~0 7.~ 43.7
F' 300 7.8 40.0
G 220 7.3 L~2.7
: 10 H 400 7.7 48.4
I 3000 3. 5 47.5
J 700 3-7 46. 5
1200 3.7 L~6.5
Example ]6
.~ .
Acrylic aci.d and styrene were graf't polymerized onto
petroleum oil using the procedures of Examples 13 and
14, above, at 88C. ~or 2 hours:
_ Ingredients and Parts
Run "Circosol" ~240 Acr~lic Acid "V~Z0" Styrene
. .
~ 100 10 1.0 --
~' B 100 10 1.0 7.5
' C 100 10 1.O 10
D 100 7 5 1.0 10
E 100: 7.5 1.0 7.5
:
: The products obtained were diluted with water,
treated with ammonla (28~ NH3 in H20) and tested.
The results ob~ained are shown below:
2~3
NEI~ Vlsco,sl.t~
Run H20 :ln II20 pH(50~ TSC)S. Tens~ (20~ TSC)
.~ .
i A :101.5 8.5 6.Z5320 53
: B 109.0 8.5 :6.59000 L~3
: C 111.5 o.5 6.756000 L~
i D 111.1 6, L~ 6.7~3500 L~o
.E, 108.0 6.4 6.751500 44
1 ~ :
_ 27 _
~ .
13xample 17
_. _
The aqueous a,lkaline emulsified grafted oilsof
Example 13, above were used in a process of aqueous
emulsion polymerization of styrene. The poly-
merization charge was set at L~o~ TSC with 0.5 pt.
ammoniurn persulfate, 0.1 "Sequestrene" Na3~ a,nd
varying amounts of' styrene and the grafted oil
(both, dry weights) were added. The pH was
adjusted to abou-t 9 with 28~ NH3 in H20~ and the
polymerization reaction was conducted at 52C.
The results produced are shown below:
;
-~
~*
*
~rl ~)
~Q ~Q O Lr\ O O L5~ LJ~
o E~ I ~ t~ trl t~ t~ tr) r~
C~ I I I I I It~) t~) r~l r~ r-l r-l
~J~ ~. ~
I r~ r~ O O
~rl ~ ~t
O r-l ~
~3 C)
~
4 1 rl ~
H O
r-l ~ 5~J
O bD * F'
P~tl) ~ *
C.) 0 1:) r-l
rl V~ rl
4~ 0 E~ I I I I ~ I t~ ~ ~ t.~l r~ -~ O
~ r
E-l o 'H
C~ t~
':
r~
~
I r-l~ 5~1
~rl r
~I~
rl-rl E~ O o oLl~ L~ L5~ o o o u~
02 ~ ~ ~n I II C~l ~ O t,~l ~O ~O t`O ~ ~ >,
~H r~ O ~ I ~I ~ '~ " '` '~ r~
~ ~ t~ O O t~ ~O t~Or-l r-l O
r-l i~ rl a~ ~ r-l n,
t~ ~ ,1 :
o
rl
tn
r~
Pi II I(~r~ t~ t~ C~ CO ~0 ~ ~0
n~ t~f~; co co CO CO CO CO CO ~ Ci~
. O
r-l L5~
E-~ o o O o o; o r1
~ ) rc~
. ~~rJ ~H
~j O
~ I .
~ ~ cq a) ~
r-l ) ~ O O 0 0 0 0 0 0 0 0 0 0 ~ 1~1
I ~ P~
, ¢ ¢ rq ~ c~ v ~ ~ r~ rr, ~, O
~ ~i
o
~ ~ o o
~ . O O O O O O O O O O O O ~ ~ ~
~o co ~o co ~o co ~ co ~o co ~o co a)
~_ U2 r-l~ ~
r~
a)l Oa) ~n :
m ~ r~ H 1~ ~ ~1 ~ *
: ~ ' :
r-l O
_, .
- - :: . . ,
Example 18
200 grams of acryllc acid were mixed with 22 grams
o~ "VAZ0 and heated to 40C. to dissolve "VAZ0".
The resulting material was mixed with 2000 grams
of "Circosol" 4240 oil and reacted in a one gallon
reactor at 88C. at 500 RPM for two hours. The
resulting material had a viscosity (26C.) of
~ 1320 and a strong odor o~ acrylic acid. 200
; grams of the resu].ting mixture were mixed with
2 grams "~AZ0" in a 12 oz. citrate bottle for
two hours at 190F. to give a material with a
viscosity (2~C.) of 2000 and with a noticeable
but reduced acrylic acid odor.
Example l9
1500 grams of "Circosol" 4240~ 150 grams o~ acrylic
acid and 16.5 grams of "~Z0" were mixed and added
to 88C. (preheated) reactor at 500 RPM. At one
hour added thereto a mixture of 500 grams of
'ICircosol" 42~0, 50 grams of acryllc acid and 5.5
grams of "V~Z0" and the react:ion contlnued ~or an
additional hour at 88C. ~'here was a very strong
acld odor arter l;he additional hour. q'here also
W&S a 150 gram buildup on the agitator.
.
,
:: :
. ,~ .
~ ~ - 30 -
:
., ~
_xarnple 20
1900 grarns of "CLrcosol" 4240, 200 grams of acrylic
acid and 1 G . 5 grams of` "VAZ0" were mixed and placed
in 75C. reactor (preheated) at 500 RPM. The
temperature was increased to 88C. and reacted f`or
; one hour. After one hour there were added 100
grams of "Circosol" 4240 and 5.5 grams of "V~Z0".
I'hen the resu-ting mixture was reacted for one
additional hour at 880C. The final material
had a viscosity o~ 900. There were approximately
80 gm. buildup on the agitator.
Exampl.e 21
Acrylic acid grafted-petroleum oil alkaline emulsions
(50~ TSC) of Example 13, above, were mlxed with
carboxylated lat;:ices (53.2~ TSC~ pH9, aqueous
emulsion terpolymer of about 75~ by weight of
styrene~ 2L~ butadiene-1,3 and 1~ itaconic acld).
;
The viscosities of the resul-ting mixtures were
: tested~ They were then mixed with H20~ fillers
and opt:l.onally a t,hickener a,nd ~urthe~ tested as
to viscos.Lty. ~dhesion tests, al.so~ were con-
ducted~ q.'h~ clata on the same are presented
below:
" ` :
I
: ~ : :
~ 31 -
tf) ~OC-O ~U CU ()')O g r-l c~ L~
r~ r-l CU ~ ' '
~ C~ C~ O
Y~ (r) r~
. . ,
r--l OC~l O :~ L~ O O
~ ~OC~ C~l CU~ O O ~O ~ L~
r-l r~ O r~
C~ D ~ CO
r~
r-l Oc~J O ~ LO O O
*~ (Y) ~OO CU C~ o o ~o r~ r-
~ r~ r~ LO ~ C~\
rl ~~ r1
r1
1:~ :
u~
r-l OC~l O ~ It`\ I O
~) ~OO CU C~l I O I ~I~ CO ~O . .
~13 r l :~¦ ~ L~
.~ O
C~ '
r-l O cu O ~ Ll'~ I O
~ o O CU CU I O I ~O
., r J C~\ _¦-L~
: ~ CO
'~: : O
: ~ :
: ~ ' , - .
, : :
r-l 0 CU O ~ 15~ 0
t`')~O O C~ C\¦ I O I ~0 O ~0
r-l c~ I L~
~O
CU r-l
'
1: ~,
a,
r.--l
,j q_l :
h
.~ E-l-rl c~ h u~ ~ ~rl h~rl
~r,~ ~ rl -~ Oa)~rl ~ h
0 : ~ r~ 0 ~ -~ L~ ~rl C)
C3 a) ~ : ~ LO C.) ~ ~rl ~ O U~
~ ~ c~ D O ~rl ~ L~ r~r~
:.. , : : 0: IC) : ~--~rl I ;~: O~ rl ~rl ~r~
r~l ~1 , ~ r, ~ O ~
: : C~ ~ rl ~ r I ~ ~rl r~ O ~rl
I r~ ) r~ ~ O P L~ i O O r,--I ' ~' ' "
a) ~3 : P~¢ m v ~ r~~ rl CU r I ~rl rl ~r-l X ~ `r') ~) (~ Fl r-l ~D ~ i a): : f ~ U~ \ ~ U~ ~ \
,Q.~ 0: ~1 r-l r-l r-l r-l rl O r~ C~ O :: O ,~ O a) CQ ~ O G~ :r~ P rl~rl ~ V ~ ,C~
tH O : ~ r-l rl ~rl ~ ~ rl r~ i--I ~: O a~ r-l
: X t3 :~ X ~ X X X E-l C~l O ¢~r-l ,51 0 ¢ ~-' ~13 r~ ~ rl `~
) r~ r~ rrl r~ rl ~ r~ rLI 1-
! , . ,, ', ' ~ .' :: . ' , . ' : . :
' ' '' ' : . ': . . ' ,~ '
,11~
Example 21 (Cont'cl)
In the above cotton adhesion test 2 pieces of cottQn
fabric 2" wide x about 6-7" long are used~ A thin
coating of the latex mixture is applied to one
piece, the pi.eces are pressed together and then
cured for 5 minutes at 17~ C. or for 15 minutes
at 177C. The strength of the resulting adheslve
bond in pounds (~rom the latex) is then measured
~: by pulling the cotton pieces apart using an Instron .:
tester at room temperatuxe (about 25C.).
; In the above carpet test, the latex mixture a-t a
coatirlg rate of 32 o~./sq. yd. is applied to the
back o~ the nylon loop carpet conta.ining a p:r:imary
jute backing through which the n~lon yarn is
.. woven and the ,-]ute seconclary layer, both ahout 3" ..
wide x about 6-7" long, ls pressed against the
same. The assembly is then. cured fox 30 mins.
at 17~ ~., and then the adhesive bond in pounds
: is determined hy pulling on the Instron machi~e at
~0 room temperature.
r~xample 22
Carboxylated latlces were mLxed with acr~lic acid
.: : grafted petroleum oil aqueous alkaline emulsions
(50~ q'SC), whiting, water and"Alcogum"and tested
accord-lng to the method of Exa.mple 21 except as
may be noted helow. The data on the same are
presented in t~he followlng tabulatlon
:
i:: : :
~ 33 -
' ~ ~
r
",
~ooLr~ CO ~ ~ ~
C~l (U I r--I ~
r--i i- r-l C~l ~ r i
r-
O L~ ) r--II ~ ~ CO r-i
C\`l C'~l(U C~l I ' ' -
r--i i r--i C~l C'~l ~ lr)
r--Ir--i r--i
.: ~ ' -:
~0 O Ll~1~ 1 0 r--iIrl LO ~ CO
bD ~ i~ C~i C~iI co
~rl ~ -J C\lC\ll r I Jr--i
; .;
m
[q
.,, ~ o Lr~ ~ I o I ~o ~o
~ I ~O ~i C~l OiI cO I
tt r--I ~ r--i C~i CU LO L~
r--I r~
~ '
::
C~l Lr~ r--I C\l ~ I CU C~ --I r-l ~
CO C\J tO C~l I
r--i ~ r--
r--i r--I .
. :.
~'
: ~ '.
:~ O Ll~ ~LS'I L~ I LO r O C~ C~
CO C\~ r--i
r--I : ~ C~ r--I CO O Ll~ CO
,
' '
.,
~ ~rl ~, ~ . ,.
': ~
. i
r~
~ O ~ o ~,
r--l X
-- ~ri O O bD
s:l O r-l~ r-i ~
rl) r,~ r,~ ~rl O a~ C~J -1~ (~i \
: O ~ r-i r-i ~ m-,, LO r-l ~
V tl3 ~ ~r~l t`~) : 1;~ Q) ~3 al a) ,Q
~': ~ ~ ~ ~ C ~ _ ~0 ~ r~ rl r-l ~ r-i
a) a) o ~ o ~ ~ ~ri Qr5~ r ~'
CU :~7 ~ I ~r~i ~rl r~ rlr l ~; ,Q
~` C~J ~ ~d: t~ C~irti ~ Q - p~ ri ~ r,ri r,~ ,~
r-l r~i r-i 1_l U : ~ X X ~ C)
~ PJ ~ ri ~ F.L1L(`\ ~` F~1 ~
: r-i : ~ ~ X ~ ~, tlOUl S:~ : ~ r.
o o ~ o o o
, ,Q OC) C~ ~ O(L~
~.~3 ~ 5-1 r-i r-l ~ ~ r I U~ j $
1~ X tB ~i ~rl ~ri O ~ al ~rl O
: ~ F~ ~ ~ OO ~
~; r~i
17~
~xample 22 (Cont'd)
The cotton a~hesion tests and the dry carpet adhesion
tests were the same as Example 21, above. For the
carpe~ wet test the sample is prepared and cured as
in the dry carpet test, is then immersed in water
for 1 hour at R.T~, squeezed to remove excess
water, and finally tested for pounds aclhesi.on on
the Inst-ron tester. In the tuft lock test the
sample is prepared and cured as in the carpet
test, and then a hook attached to the Instron
tester is placed through a loop on the carpet sample
and pulled to determine the pounds necessary to
pull out the loop.
Carboxylated latex A was an aqueous emu].sion, pH of 9
and TSC of about 55.5~, of a terpolymer of about
5 ~ by weight of styrene, 43~ butadiene-1,3 and
1~ itaconic acid. Carboxylated latex B was an
aqueous emulsion, pH9 and about 55~ TSC, of a ter-
polymer of about 70~ by weight of st~rene, 29~
butadi.ene-~.,3, and 1~ itacon-lc acid. Oil emulsion
A, 50'~ TSC, was Example 13, Run B.
Oil. ernulsLon B~ 50~ TSC~ was E'xamp~.e 13, Run C.
~ .
.
~ 35 -
.
r~.xample 23
_
~rhe metilod oL t~ s exalrlpleWaS the same as t;hose
of Examples 21 and 22. The carboxylated latex C
is an aqueous errlulsion, pH9 and about 53.2~ TSC,
of a terpolymer o~ about 75~ by weight o~ sl;yrene,
24~ butadiene-1,3 and 15~ itaconic acid. The
componen-ts of the cornposition and the test data
are shown below:
Material Parts By Weight
1 2 3 4 5
Carbo}cy:lated latex C 188 169 150 169 150
Oil emulsion A 20 40
(Same as L~x. 22, a~ove)
Oil emulsion B 20 l~o
(Same as L~x. 22, above)
No. 9 NCS ~iting 425 425 425 425 425
Water 25 24 23 24 23
~,
"Alcogum~7 9635 2.9 o . 4 o . 4
Viscosity, x 100 119 164 205 118 122
Cotton, ultimate adh. 12.1 11.8 12.111.9 12.0
(lbs./2" strlp), dry
Carpet, ultimate adh. dry13.9 13.6 12.1~:1.3.2 13.2
(lbs./3" StY'~.p)
Same as above, we(;I~ 6 4.5 IL,4 4.9 5-O
Tu~t, lock 15.9 12.1 11.412.9 14.0
(l~s./tu~t)
.: :
-
~ 36 _
-
;
~: :
r-l CUO r~ r~ C~l ~1 0 ~ ~ Ci~:~C\~l
r ~ (~)~O ~ C\l ' C\l (~) C~
rl r l~ (r~ r l r l r l C~ CO
~: . I
U~ ' $-
æ æ
.~ C\l Or I L(~C3 C\~l C~l C~ ~Lr`i O ~~
Ql (r) ~O C\l ~ ' C~l (r)C~
~1) r I ~ C~J ~I r~ 1~1 0 C~ O ~ r
.~
a) ~
C~l ~ CU O r~ L~O CU ~ ~ ~ ~~ (~)~ ~~ U~
S~ tr) ~C) C~J C\J r~ C~ ' rl
O bO r~ ~~ C\~ r Ir~ r-l 1~ ~ O (r) S
a) r~ 1
~ C~
CU O ~¦ LO~O C\,J O00 L~OO L~ Lf~
(O ~ O c~J c~J C~l~) c~l ~ ~1
~_1 tQ r-l ~ r~ r I r-l r-l r-¦ O O`\ ~)
r~l r~l C~
~d ~d
~i C~l O r~L~ I C\lOLt~O I I O Cr) ~:
~ ~o~u c\
t~l ~1 ~ N(`~1 N ::1- CU ,~
O O
u~ r l
rd
0 N Orl L~ I N L ~ O O I I O r.
.~' (r)~OC\l C~ t~
cula' r-l ~ N(~ 1~) LO (r) ~ I
ra~ ~
O rl LOlS~ O~ C~ LO~ LO C:) I
: CON N ~ I CU t~)r-l . . . U~
~1 : r~l :~ C~l r-l r-l r~ ~~ rl
i ~ ~ ~ ~o
` O
~: uæl ,~
. ~
s o
U~ f~
CJ --~ O ~rl ~rl
r~ N tY~ O O
C~l N r-l Lf~
~: : X ~ X PC ~l a~
h h ~ r~
U~ * `I~ * * ;1: * O ~ rl
;~ 5 ,! rl ¢ V ~ ~ ~ a) ~ ~Uh~r it ~d 'Ci ~: O
1~ rl ~C ~C O O
a) a) ,o ,~ ,o ,L~ ,~ ,n ~ rl U~ ~ ~ r~
~: t~ o a) -~ æ æ æ æ ~ rl O ~ rl
o ~ ~ ~ æ ,~ o ~rl ~1 ~i rd ~ 'C~ P~ rl V ..
a)~ ~ æ : r~ r-l ~ ~ rl ~ O a) ¢ rl Cl~ rl '~
d ~ ~ Ll 4 ~ r ~ LO 1;~ ~H ~ a) ~ ~ : -
'd ~ C ~ r~~rl r~
~ C) r-æ4 ~r~ ,~ h " '`P=C~P ,r, CB
a) ~ rl ~rl t ~ U~ \ o
: ~ a) O ~ rl r-l r I ~i rl r-l~ h C~ O O O~ O ,S~ O U~ ~ a) tn ~ :
Q '1~ r æ C) C) l ~t ~ r~ rl ~ ¢
~ æ ~ X ~ X X X ~ O CL~ rl ~r~ C\~l C~l O ~' ~ tB ~~ ~
v v r~ rLl rll rll rLl r~ p p ~ ~Q V CQ *
O
~7~
Example 2LL ( Cont'd)
With respect -to viscosity stability, portions o~
the mixtures are aLlowed to stand ~or 24 hours
and then the viscosity is determined. After such
standing other portions of the mixtures are stirred
; for ~rom 4 tO 5 minutes, and then their viscosities
are determined.
In the foregoing working examples the viscosities
were Brook~ield viscosities LVT in centipoises (cps) No~
3 spindle, 50-60 r.p.m. for
compositions without filler, e.g. whiting. The
~illed or thîckened viscosities were Brookfield
viscosities RVT in centîpoises, No. 5 spindle, 20
r.p.m. ~or compositions with the
~iller. All viscosities were at room temperature
(R.T.), about 25C., except where noted.
Notes: ~Iv~zo~ - "V~ZO" 6L~, azobisisobu-tyronitrile.
A ~liny1 polymerization catalyst~ Melts at
105C. E.I. du Pont dQ Nemours and Co.
(Inc.).
`~ "Sunpar" 2280 - Rubber process and extender
oi:L. Para~finic. Viscosity sus/3'7.780c. o~`
26L~2., m~w. of 720, 0~ asphaltenes, 1.5~
polar compounds~ 22~ aromatics, 76.5'~ ;
saturates; carbon type analysis, ~, C~-4,
CN-25, and Cp-71; ASTM D 2226 Type 104 B.
Sun Oil Co.
.
;~ - 3~ -
i; : :
. :
:
..
Notes (Cont'd)
"Circosol" 42LIO _ Rubber process and extender
oil. Naphthenic. Viscosity SUS/37 . 78 C . of
2525~ m.w. o~ 395, 0~ asphaltenes, 2.7~ polar
cornpounds, 44.8~ aromatics, 52.5~o saturates;
carbon type analysis, ~, CA-21, CN-393 and
Cp-40; ASTM D-2226 Type 103. Sun Oil ~o.
"Sundex" 790 - Rubber process and extender
oil. Aromatic. Viscoslty SUS~37 . 70 C . Of'
3500~ m.w. o~ 375~ O.l~ asphaltenes, 10.
polar compounds, 73.2~o aromatics, 16,3
saturates; carbon type analysis, ~o, C~-37l
C~-28~ and Cp-35. ASTM D-2226 Type 102. Sun
Oil (~O.
"Sul:~ole" 120 - t-dodecyl mercaptan. Av.
mol. wt. 198. Calc. purity, wgt. ~, 96.3.
Phillips Petroleum Company.
"Sequestrene" Na3 - Trisodium salt Of' ethylerle-
d:iamine tetra acetic acid. Ci.ba-Geigy.
,
"'I'amol" N - D:lspersanl;. Sodlum salt o~
condensed naphthalene sulfcnic acid. Rohm
;~ & Haas Co.
.
.
:
:
~ - 39 -
. '
,. ~
Notes (Cont'd)
"Sunthene" 255 - Rubber process and extender
oil. Naphthenic. Viscosity SUS/37.78C.-420,
m.w. of 440. o~ asphaltenes, o.6~ polar
compounds, 27.l-~% aromatics, 72~ saturates;
ca.rbon -type analysis, ~0, C~-9, CN-33
Cp-5$. Sun Oil Co.
"Sunthene" 4240 - Rubber process and extender
oil. Naphthenic. Viscosity SUS/37.78C. of
2206. m.w. of 400. 0~ asphaltenes, 1.1~
polar compounds, 43 9/ aromatics, 55~0 saturates;
. carbon type analysis, ~, C~-18, CN-41 and
Cp-l~l. ASTM ~-2226 Type 103. Sun Oil Co.
No. 9 NCS Whiting - No color standard,
medium ground whiting. 9~0 calcium
: carbonate (mi.n.) of which 93~ ~ 2~ is ~iner
: ~ than 325 mesh USS screen. Georgia Marble
.; ~o. ..
"Alc.ogum" 9635 - ~ sodium polyacrylate
t:hlckener. Alco Chemlcal Co.
~ ` ,.' .
:
~ 40
.~ , ' '~ ' ' , ,
_ample 25
8 parts by weight of an aqueous solution of poly
acrylic aci.d (TSC 50l l~o in H20, molecular weight
o~ about 5~000, high purity ~.~0 soluble polyacrylic
acid, pH 1.5 to 2~ "Good-ri.t~' 732, The B.F. Goodrich
Company) were mi.xed with varying amounts o~ "Circosol"
~240 oll and water containing NH40H to give alkaline
aqueous mixtures (pH9). The total solids content of
the aqueous mixtures was about 17.5-18.5~. In the
mixtures the dr~ .ratio of the oil to the polyacrylic
acid was about 100/4.2, 100/8.1~, 100/12.6 and 100/16.8.
The resultlng mi.xtures did not form stable emuls:ions,
e.g., they separa-ted i~to two layers.
Example 2~
~,:
The procedure of Examp]e 25, above, was followed
except that the polyacrylic acid used had a higher
:~ molecular weight (m.w. of about 90~000 in H20, TSC
25+ 1~, pH2 to 3,~"Good-rite" 702, The B.F. Goodrich
Co.). The resulting aqueous mixtures had a total
solids content o~ about 18-18.5~. In the mixtures the
ratio on a dx~ basls o~ the o:Ll to the polyacr~li.c
acid was about 100/3, 100/6, 100/9 and 100/12. The
~inal alkaline oil-acid aqueous emulsions were
semistable.
These oil-acicl aqueous mixtures were mixed with
butadiene-1,3 a.nd styrene and enough water to make a
total so1ids c~ontent~of about ~2-43~ In the
' -
- ~1 - .
37~
Example 26 (Cont'd)
resulting polymeriæation mixture on a dry weight
basis the ratio of oil to styrene to butadiene was
30/50/20, the acid being an addition in the ratio
as shown above. To these were added catalyst but no
Sulfole,and copolymerizationswere attempted according
to the general method of Example 7, above, except
that the grafted oil of Example 6 was omitted~ The
resulting latices either coagulated or formed a sludge.
The results of Examples 25 and 26 would indicate
that mixtures of polyacrylic acids and petroleum
oils do not form satisfactory emulsions.
: '
'
2 -
