Note: Descriptions are shown in the official language in which they were submitted.
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POLYMER LA'I'EXES PREPARED FROM ETIIYL.ENICALLY L1NSATURA'I'ED AMINE SALTS
S
BACKGROUND OF THE INVENTION
Field of the Invention:
The present invention relates to an improved agricultural formulations derived
from
polymer latexes prepared by emulsion polymerization processes which utilize
ethylenically
unsaturated amine salts of sulfonic, phosphoric and carboxylic acids. More
specifically, the
invention relates to latex-based agricultural formulations produced from
emulsion
polymerization processes which utilize ethylenically unsaturated amine salts
of alkylbenzene
sulfonic acids, alkyl olefin sulfonic acids, alkyl alcohol sulfuric acid
esters, or alkoxylated
alkyl alcohol sulfuric acid esters, fatty acids, and fatty phosphate acid
esters, or mixtures
thereof, to form polymers, discrete solid polymeric particles and latexes. The
agricultural
formulations of the present invention typically comprise a stable mixture of a
polymer latex
and a pesticide, herbicide, fungicide, or insecticide. A method for using
novel polymer
latexes as delivery systems for pesticides is provided, wherein such systems
show excellent
stability, dispersion and dilution properties.
Description of the Related Art
The emulsion polymerization of ethylenically unsaturated monomers to form
discrete
solid polymeric particles for use in coating, sealant, adhesive and/or
elastomer (CASE)
applications is well known to the art. These polymeric latexes have found wide
spread use in
the preparation of a variety of agricultural formulations, including
herbicidal,
pesticidal/insecticial, and fungicidal formulations. Conventional emulsion
polymerization of
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ethylenically unsaturated monomers employs one or more water soluble
surfactants to
emulsify the monomers and the resulting polymer products, i.e., latexes. The
monomers used
in emulsion polymerization reactions are generally water-insoluble, but in
some cases may be
water-soluble. During a typical emulsion polymerization, a surfactant is used
to suspend
small portions of monomer in a continuous or semi-continuous aqueous phase.
Typically, the
monomer molecules are suspended as small spheres in the aqueous phase, wherein
the
polymerization takes place within the small spheres. The water soluble surface
active agents,
i.e., surfactants, typically utilized in emulsion polymerization reactions are
anionic, nonionic,
and cationic surfactants or a mixture thereof.
The polymeric particles formed by the emulsion polymerization process are
typically
utilized in coating, sealant, adhesive and/or elastomer (CASE) applications
and agricultural
applications and formulations. In a traditional emulsion polymerization
reaction, the
surfactant does not become chemically bonded to the polymeric particles by
carbon-carbon
bond formation but rather remains in the polymeric particle product solution
after the
emulsion polymerization reaction is complete, i.e., all of the monomers) is
reacted. The
unreacted surfactant can have a detrimental effect on the polymer product
solution, as it can
interfere with the performance of such polymerization products in CASE
applications and
agricultural formulations; the suspension of polymeric particles and/or
agricultural technical
may become destabilized over time and undergo unwanted coagulation and/or
phase
separation.
Several proposals have been made in the prior art to employ a polymerizable
surfactant as the surface active agent during an emulsion polymerization
reaction. U.S. Pat.
No. 5,478,883 (incorporated herein by reference in its entirety) describes the
use of
ethylenically unsaturated polymerizable water-soluble nonionic surfactants
formed by the
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reaction of a diallylamine compound with ethylene oxide, propylene oxide or
butylene oxide,
in emulsion polymerization reactions. Similarly, U.S. Pat. No. 5,162,475
(incorporated herein
by reference) provides alpha-beta ethylenically unsaturated poly(alkylenoxy)
polymerizable
surface active compounds for use in emulsion polymerization. For additional
examples of
polymerizable surfactants for use in emulsion polymerization processes, see
U.S. Pat. Nos.
4,377,185 and 4,049,608.
Non-polymerizable surfactant solutions to the traditional problems encountered
in
performing an emulsion polymerization process are numerous. U.S. Pat. No.
3,941,857
describes the use of epoxy resins which react with the residual anionic,
cationic or nonionic
surfactant. Polymerizable compounds such as allyl alcohol (and esters thereof)
have been
found to be ineffective due to the formation of undesirable high levels of
coagulum in the
final emulsion polymerization product. Additionally, see U.S. Pat. No.
4,224,455.
Also, particularly with respect to agricultural formulations, see far example,
U.S. Pat.
No. 3,156,661, describing water insoluble pesticides lindane and dieldrin
incorporated into
floor wax formulations using styrene and acrylic resinous materials; the final
compositions
are water-based and form coatings of flooring materials. U.S. Pat. No.
4,303,642 discloses
stable latexes comprising polymers containing chlorpyrifos or chlorpyrifos-
methyl insecticide,
which are prepared by mixing the latex with the insecticide. U.S. Pat. No.
4,304,769 describes
a process of blending a loadable polymeric latex into a solution of a
hydrophobic material
(i.e. a pesticide) dissolved in a water-miscible solvent or the particles of
the latex. U.S. Pat.
No. 4,336,173 involves a pre-emulsification, with a homogenizes, of a water
insoluble
substance with emulsifier, then combining the emulsion with a seed latex and a
water soluble
solvent. EP 0 381 691 B 1 discloses a method of reducing or eliminating
incompatibility
between two pesticidal active ingredients, by incorporating one pesticide in a
dispersed latex
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phase and the other ingredient within the continuous aqueous phase. U.S. Pat.
No. 5,188,824
discloses stable aqueous emulsion formulations of water-insoluble organic
pesticides which
are formed from a mixture of organic pesticide, structured particle latex and
optionally a
cosolvent and/or a cosurfactant. U.S. Pat. No. 5,260,259 discloses a
controlled release and
delivery system for a hydrophobic, water sensitive herbicide, produced by
mixing a pesticide
dissolved in water-immiscible solvent, with a latex dispersion until the latex
particles absorb
the herbicide. U.S. Pat. No. 5,321,049 discloses a water dilutable pesticidal
composition,
prepared by combining a pesticidal substance dissolved in a water-immiscible
solvent, with an
emulsifier and polymer latex to form a dispersion in water. WO 96/02136
discloses a method
of controlling the particle size and distribution of an aqueous emulsion using
dispersions of
templating agents and surfactants; polymer latexes are used as examples of
template agents
for controlling particle size of the emulsions.
It is generally desired of such pesticidal compositions that they should be
easy to
handle, and easy to apply in any desired concentration. For this reason,
herbicidal
compositions are generally supplied in the form of wettable powders,
emulsifiable
concentrates and the like. In the formulation of emulsifiable concentrates, it
is generally
necessary to incorporate substantial quantities of organic solvents, and this
can result in
substantial problems of dern~al toxicity and flammability. Furthermore,
because of the
presence of organic solvents, it is not possible, for many emulsifiable
concentrate
compositions, to utilize containers of conventional plastics materials, such
as high density
polyethylene (HDPE). Instead, such concentrates have to be contained within
specially
designed containers, which are resistant to the solvents used. In addition,
the incorporation of
high levels of organic solvents in emulsifiable concentrates gives rise to
problems of
phytotoxicity to crops when the pesticidal substances are utilized.
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Much of the related are requires the use of heat to incorporate the
agricultural
technical in to the polymer latex, i.e. to make the mixture a single phase
mixture. Heat is
generally necessary to drive the incorporation of the technical actives into
the polymer latex.
Additionally, these disclosures describe agricultural formulations which may
phase separate
upon extended storage. Many of these formulations have the distinct
disadvantage of
requiring the use of water-miscible solvents to help transport the oil phase
through the
aqueous phase and into the latex particles. Typically, the use of such
solvents requires
subsequent removal of the solvent when preparing a finished agricultural
formulation. Such
removes is costly, time consuming and presents a disposal concern. Several of
the suggested
methods above have the draw-back of requiring the use of co-solvents, such as
methyl laurate,
to aid in the absorption of agricultural active ingredients into the latex
polymer particles.
Additionally, the above approaches often may not allow for dilution stability.
Several
of the above approaches are oil in water emulsions which must be prepared
under high shear
prior to blending with the latex.
I 5 Thus there exists a need for stable, easy to prepare agricultural latex-
based
formulations which overcome or decrease the afforementioned difficulties.
Agricultural
latex-based formulations which are solvent/co-solvent free and do not require
the use of
excessive heat to prepare, i.e. drive the actives into the latex, arc highly
desireable.
Additionally, these formulations would desireabally would not contain water-
miscible
solvents to help transport the oil phase through the aqueous phase and into
the latex particles.
It is highly desirable to develop a latex-based agricultural formulation which
does not require
the formation of an oil in water emulsion prior to mixing with the polymer
latex. A need
exists in the art for agricultural latex-based formulations which high
dilution stability are also
highly desirable.
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SUMARY OF THE INVENTION
The present invention utilizes a novel group of compounds in the form of
ethylenically
unsaturated amine salts of sulfonic, phosphoric and carboxylic acids, which
display surface
activity, i.e. they are surfactants. It has been discovered that these
compounds function as
reactive surfactants, i.e. surface active agents in polymerization processes,
particularly
emulsion polymerization processes. The surface active agents of the present
invention are
capable of polymerizing with themselves (to form homopolymeric surface active
agents)
and/or are capable of co-polymerizing with other ethylenically unsaturated
monomers of the
type which arc commonly employed in polymerization processes. The
polymerizable surface
active agents utilized in the present invention are prepared from readily
available, economical
raw materials, and generally, their preparation does not require any special
handling or
equipment.
The surface active agents of the present invention are prepared from readily
available,
economical raw materials, and generally, their preparation does not require
any special
handling or equipment. The polymerizable surface active agents may be prepared
in a batch
mode or a continuous mode; they may be prepared by contacting the
ethylenically unsaturated
amine with the acid or contacting the acid with the ethylenically unsaturated
amine. By
contacting it is meant that the acids) is added to the ethylenically
unsaturated amines) and
the components are mixed, or the ethylenically unsaturated amines) is added to
the acids)
and the components are mixed. Typically, upon mixing, the acid and the base
combine to
form an amine salt. As known by one skilled in the art, upon mixing the acid
and
nitrogenous base together, the nitrogenous base becomes a conjugate acid and
the acid
becomes a conjugate base.
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Accordingly, an improved method is provided for forming agricultural
formulations
comprising an agricultural technical (i.e. a herbicide, pesticide/insecticide,
or fungicide) and
latex polymers derived from polymerizable surface active agents detailed
herein. Generally,
the improved method comprises:
a) preparing a mixture comprising:
i) at least one ethylenically unsaturated monomer;
ii) at least one polymerizable, surface active agent;
wherein the polymerizable, surface active agent is an amine salt or quaternary
nitrogen
compound comprising:
a) at least one acid, wherein the acid is a sulfonic acid, a carboxylic acid,
or a
phosphoric acid, or a mixture thereof; and
b) at least one nitrogenous base, wherein the nitrogenous base contains at
least one
nitrogen atom and at least one ethylenically unsaturated moiety; and
b) polymerizing the mixture to form a polymer latex;
c)adding to the polymer latex an agricultural technical;
wherein the polymerizable, surface active agent is capable of polymerization
with itself,
polymerization with the ethylenically unsaturated monomer or co-polymerization
with a
partially polymerized polymer particle. Somewhat preferably, the nitrogen atom
is linked
covalently, directly or indirectly, to the ethylenically unsaturated moiety of
the nitrogenous
base. Also preferably, the polymerizable surface active agent is in the form
of an amine salt,
rather than a quaternary nitrogen compound. Additionally, although somewhat
less preferred,
the agricultural technical may be added before or during the polymerization.
The invention
relates to agricultural formulations, and in particular to herbicidal,
fungicidal and
pesticidal/insecticidal compositions for both pre-emergence and post-emergence
application.
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As used herein, the terms pesticide (or pesticidal) and insecticide (or
insecticidal) are
interchangable.
The polymers prepared utilizing the polymerizable surface active agents of the
present
invention may be used as the primary resin component or a minor resin
component of a resin
mixture which is used to prepare latexes, coatings, adhesives, seaIants,
elastomers, binders,
inks, floor finishes and the like. A polymer is defined herein as a product
produced by
polymerizing two or more monomers, which may be the same or different.
Additionally, the
polymer may have incorporated into it, surface active agent monomers and/or
homopolymeric
surface active agents. The various final compositions, application and polymer
products
described herein may contain various optional ingredients such as fillers,
pigments, colorants,
solvents, plasticizers, antioxidants, curing agents, thickeners, non-
polymerizable surface
active agents (surfactants), preservatives, wet strength additives, and the
like.
The present invention provides an improved polymerization process for forming
polymers, wherein the polymerizable surface active agent used in the
polymerization reaction
does not interfere with the quality of the CASE applications or the
agricultural formulations.
The present invention provides an improved polymerization process, wherein
agricultural formulations prepared, using the polymers of the present
invention, remain
uniform and stable upon the passage of time.
The present invention provides polymers suitable for use in coating, adhesive,
sealant
and/or elastomer (CASE) applications and agricultural formulations. The
polymers may be in
a variety of forms, such as, for example, solids, flakes, powders, semi-
solids, thick pastes,
flowable/pumpable pastes (i.e. G-phase pastes), liquids, gels, "ringing" gels,
dilute or
concentrated solutions and the like. The polymers may be spray dried, flaked,
extruded, or
the like.
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The present invention additionally provides homopolymeric surface active
agents
comprised of polymerized, polymerizable surface active agents or blends of
polymerizable
surface active agents. These homopolymeric surface active agents are useful in
the
polymerization processes detailed herein. The present invention further
provides
homopolymeric surface active agent/polymerizable surface active agent blends
comprised of
partially polymerized, polymerizablc surface active agents and non-
polymerized,
polymerizable surface active agents. These hornopolymeric/polymerizable
surface active
agent blends arc also useful in the polymerization processes detailed herein.
The improved polymerization process of the present invention preferably does
not
require the use of a surfactant which contains residual formaldehyde or other
low molecular
weight volatile organic compounds. However, while not usually desirable, low
molecular
weight volatile organic compounds and/or residual formaldehyde may be present
in the
polymerization products of the present invention. Further, the polymerization
process of the
present invention provides latexes with improved shear stability, improved pH
stability,
improved shelf storage stability and improved ease of viscosity modification.
The polymerizable surface active agent may be added to the mixture in a batch
mode
(i.e. all at once), a continuous mode (i.e. by addition of an amount of the
polymerizable
surface active agent throughout the polymerization) or in a semi-continuous
mode (i.e.
addition of portions of the polymerizable surface active agent at various
times during the
polymerization).
The polymerizable surface active agents utilized in the present invention are
generally
formed by combining at least one acid, wherein the acid is a sulfonic acid, a
carboxylic acid,
or a phosphoric acid, or a mixture thereof, with a nitrogenous base, wherein
the nitrogenous
base contains at least one nitrogen atom and at least one ethylenically
unsaturated moiety.
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The polymerizable surface active agents of the present invention are
preferably in the form of
amine salts. The surface active agents of the present invention are prepared
from readily
available, economical raw materials, and generally, their preparation does not
require any
special handling or equipment. The polymerizable surface active agents may be
prepared in a
batch mode or a continuous mode; they may be prepared by contacting the
ethylenically
unsaturated amine with the acid or contacting the acid with the ethylenically
unsaturated
amine. By contacting it is meant that the acids) is added to the ethylenically
unsaturated
amines) and the components are mixed, or the ethylenically unsaturated amines)
is added to
the acids) and the components are mixed. Typically, upon mixing, the acid and
the base
combine to form an amine salt. As known by one skilled in the art, upon mixing
the acid and
nitrogenous base together, the nitrogenous base becomes a conjugate acid and
the acid
becomes a conjugate base.
The polymerizable surface active agents may alternatively be prepared by
contacting
the ethylenically unsaturated amine with an alkaline earth or ammonium salt of
the acid (e.g.,
I S the sodium, potassium, magnesium, calcium, ammonium, or ethoxylatcd
ammonium salts of
the acid), whereby the polymerizable surface active agent is formed in situ.
The surface active agents and blends of surface active agents may be prepared
in a
variety of forms, including but not limited to, liquids, solutions, solids,
powders, flakes, semi-
solids, gels, "ringing" gels, G-phase liquids, hexagonal phase solids, or
thick pastes. The
surface active agents may be spray dried, flaked, extruded, and the like.
Although not critical
to the present invention, the polymerizable, surface active agents may be
prepared "neat" or in
a conventional solvent such as water, low molecular weight alcohol or
hydrocarbon, or a
mixture thereof, to produce a solution of the surface active agent. The
present invention
encompasses surface active agents as salts in dry form and as aqueous
solutions. Salts of the
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surface active agents may be isolated by drying a solution of the surface
active agents; a
solution of surface active agents may be prepared by dissolving the salt of
the surface active
agent in water, low molecular weight alcohol or hydrocarbon, or a mixture
thereof.
Individual surface active agents of the present invention may be prepared and
mixed
together to produce a surface active mixture comprising "neat" surface active
agents or an
aqueous surfactant blend. Additionally, neat or aqueous blends of the surface
active agents
may be prepared by contacting a blend of two or more ethylenically unsaturated
amines with
one acid, or by contacting a blend of two or more ethylenically unsaturated
amines with a
blend of 2 or more acids. Conversely, blends of the surface active agents may
be prepared by
contacting a blend of two or more acids with one ethylenically unsaturated
amine, or by
contacting a blend of two or more acids with a blend of two or more
ethylenically unsaturated
amines.
In accordance with a first aspect of the present invention, there is provided
a stabilized
water dilutable agricultural composition which has been prepared by forming a
mixture of a
1 S polymer latex and a herbicide, pesticide or fungicide, which is not freely
soluble in water but
has a water solubility of at least 500 parts per billion by weight, wherein
the mixture is
generally dilutable in water, at least to a dilution of 50:1 by weight.
The term "latex" as used herein is intended to include any polymeric product
produced
as an aqueous suspension emulsion polymerization process and includes within
its scope both
synthetic latexes and natural latexes. The term "water dilutable" as used
herein is intended to
mean that the agricultural formulation or composition may effectively be
diluted in water to
any desired dilution e.g. to a dilution of at least 50:1 (water:composition)
by weight, typical
500:1, without flocculation or coagulation. In preferred examples of the
composition of the
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invention the water dilutability of the composition is retained, even in the
presence of
electrolytes, such as ionic fertilizers or pesticides.
These and other objects and advantages, as well as the scope, nature, and
utilization of
the claimed invention will become apparent to those skilled in the art from
the following
detailed description and claims.
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DETAILED DESCRIPTION OF THE INVENTION
A method is provided for forming agricultural formulations using latex
polymers
prepared from monomers and polymerizablc surface active agents, wherein the
method
comprises: ( 1 ) preparing a mixture comprising at least one ethylenicaily
unsaturated
monomer and at least one polymerizable surface active agent; (2) polymerizing
the mixture to
form polymer latex; and (3) adding an agricultural technical to the polymer
latex. Generally,
any ethylenically unsaturated monomer that is capable of undergoing
polymerization may be
utilized in the present invention. The method of the present invention is
particularly well
suited to emulsion polymerization but may also be conducted as a solution
polymerization,
suspension polymerization, micro emulsion polymerization or inverse emulsion
polymerization. The polymerization may be conducted in any manner known to the
art,
including but not limited to, free-radical initiated polymerization, thermal
initiated
polymerization and redox initiated polymerization using, for example, batch,
continuous, or
controlled monomer feed processes, known conditions of stirnng time and
temperature, and
I ~ known kinds of additives such as initiators, surfactants, electrolytes, pH
adjusting agents,
buffering agents, protective colloids and the like. In general, the
polymerization process of
the present invention will be carried out from about 20°C to about
120°C (e.g., between about
50°C and about 110°C). These polymerization temperatures will
vary with respect to the
reactivity and concentration of the polymerization initiator being used. Batch
polymerization
times may vary depending on the method of polymerization and the monomers
being
polymerized. Such times may vary from about 10 minutes to about 10 hours. In
general, the
mixture may be a solution, emulsion, suspension or dispersion of the
ethylenically unsaturated
monomer and the polymerizable surface active agent. Further, the polymerizable
surface
active agent may be provided to the mixture as an aqueous solution.
Additionally, although
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somewhat less preferred, the agricultural technical may be added before or
during the
polymerization.
In accordance with the present invention, polymerization may occur
simultaneously as
the mixture is being formed (i.e. as the monomer and the polymerizable surface
active agent
come in contact, a self initiating polymerization occurs). Accordingly, the
present invention
also encompasses a method for continuous polymerization, utilizing at least
one ethylenically
unsaturated monomer and at least one polymerizable surface active agent.
The polymerizable, surface active agents utilized in the present invention are
preferably amine salts (or somewhat less preferably quaternary nitrogen
compounds)
comprising:
a) at least one acid, wherein the acid is a sulfonic acid, a carboxylic acid,
or a
phosphoric acid, or a mixture thereof; and
b) at least one nitrogenous base, wherein the nitrogenous base contains at
least one
nitrogen atom and at least one ethylenically unsaturated moiety.
The polymerizable surface active agents are generally capable of
polymerization with
themselves, polymerization with the ethylenically unsaturated monomer or co-
polymerization
with a partially polymerized polymer particle. 1n a somewhat preferred
embodiment, the
polymerizable surface active agent is partially (i.e. 1-SO percent by weight
of the
polymerizable surface active agent) consumed by polymerization with itself, co-
polymerization with the monomer and/or co-polymerization with a partially
polymerized
polymer particle. In a more preferred embodiment, the polymerizable, surface
active agent is
substantially (i.e. 50-90 percent by weight of the polymerizable surface
active agent)
consumed by polymerization with itself, co-polymerization with the monomer
and/or co-
polymerization with a partially polymerized polymer particle. In a most
preferred
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embodiment, the polymerizable, surface active agent is substantially
completely (i.e. greater
than 9(? percent by weight of the polymerizable surface active agent) consumed
by
polymerization with itself, co-polymerization with the monomer and/or co-
polymerization
with a partially polymerized polymer particle.
The polymerizable surface active agent and the ethylenically unsaturated
monomer are
in a ratio of about 0.01:1 to about 3:1 on a weight basis, prior to
polymerization. In a
preferred embodiment, the polymerizable surface active agent is present in the
mixture in a
concentration of about 1-100 weight percent, based on the total weight of the
ethylenicaliy
unsaturated monomer present in the mixture. In a more preferred embodiment,
the
polymerizable surface active agent is present in the mixture in a
concentration of about 1-20
weight percent, based on the total weight of the ethylenically unsaturated
monomer present in
the mixture. In another embodiment, the polymerizable surface active agent
comprises about
0.1-10 weight percent of the polymer, more preferably 0.5-3.0, based on the
total weight of
the ethylenically unsaturated monomer present prior to polymerization.
In general, the method of preparing polymers in accordance with the present
invention does not require the use of a non-polymerizable surfactant, i.e. the
mixture is
substantially free of non-polymerizable, surface active agents. However, in a
somewhat less
preferred embodiment, the mixture further comprises a supplemental, non-
polymerizable
surfactant (iii); wherein the supplemental surfactant is a sodium, potassium,
calcium,
magnesium, or ammonium salt of a substantially saturated anionic surfactant,
or a nonionic,
cationic, or amphoteric surfactant, or a mixture thereof; and wherein the
supplemental
surfactant is provided in a concentration of about 0.01 to about 20.0 percent
by weight, based
on the total weight of polymerizable surface active agent and supplemental
surfactant
provided in the reaction zone.
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The present invention provides pre-polymerization mixtures comprising (I) at
least
one ethylenically unsaturated monomer; (2) at least one polymerizable surface
active agent;
and (3) an agricultural technical.
wherein the ethylenically unsaturated monomer, the polymerizable surface
active agent, and
the agricultural technical are defined as above or below. This pre-
polymerization mixture
may be polymerized by a variety of initiation methods known to the art.
The present invention provides agricultural formulations comprising an
agricultural
technical and polymers comprising: (1) at least one monomer unit; and (2) at
least one
surface active agent unit; wherein the monomer unit is derived from an
ethylenically
unsaturated monomer; wherein the surface active agent is derived from a
polymerizable
surface active agent; and wherein the ethylenically unsaturated monomer and
the
polymerizable surface active agent have co-polymerized to form the polymer.
In another embodiment, the present invention provides a method for forming
agricultural formulations wherein the method comprises ( 1 ) preparing a
mixture comprising at
least one ethylenically unsaturated monomer, at least one acid, wherein the
acid is a sulfonic
acid, a carboxylic acid, or a phosphoric acid, or a mixture thereof; and at
least one
nitrogenous base, wherein the nitrogenous base contains at least one nitrogen
atom and at
feast one ethylenically unsaturated moiety; (2) polymerizing the mixture to
form a polymer
latex; and (3) adding an agricultural technical to the polymer latex. In
accordance with this
embodiment, the acid and the nitrogenous base may form a polymerizable,
surface active
agent in situ; wherein the polymerizable, surface active agent is an amine
salt (or somewhat
less preferably a quaternary nitrogen compound); wherein the polymerizable
surface active
agent is capable of polymerization with itself, copolymerization with the
ethylenically
unsaturated monomer and/or co-polymerizing with a partially polymerized
polymer particle;
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and wherein the polymerizable, surface active agent is substantially
completely consumed by
polymerization with itself, co-polymerization with the monomer and/or co-
polymerization
with a partially polymerized polymer particle. In one alternative, the
nitrogenous base may
partially or completely co-polymerize with the ethylenically unsaturated
monomer, followed
by formation of a surface active agent (i.e. complexation/salt formation with
the acid).
Without being bound by any particular theory, it is believed that the
nitrogenous base is
incorporated into the polymer back-bone and the acid forms an ion pair, i.e. a
salt, with the
nitrogen atom of the nitrogenous base, thereby adhering to the polymer and
forming a
positively charged nitrogen atom. In another alternative within the purview of
this
embodiment, a portion of the nitrogenous base may polymerize with itself, co-
polymerizes
with the ethylenically unsaturated monomer or co-polymerize with a partially
polymerized
polymer, followed by complexation/salt formation with the acid. In another
alternative, the
nitrogenous base may partially or completely co-polymerize with a
homopolymeric
surfactant, followed by complexation/salt formation with the acid.
The present invention provides agricultural formulations comprising an
agricultural
technical and polymers comprising: ( 1 ) at least one monomer unit; (2} at
least one acid,
wherein the acid is a sulfonic acid, a carboxylic acid, or a phosphoric acid,
or a mixture
thereof; and at least one nitrogenous base, wherein the nitrogenous base
contains at least one
nitrogen atom and at least one ethylenically unsaturated moiety; wherein the
monomer unit is
derived from an ethylenically unsaturated monomer; wherein the nitrogenous
base is
homopolymerized, co-polymerized with the monomer, and/or polymerized with a
partially
polymerized polymer, wherein the acid complexes to the nitrogen atom(s), to
form an amine
salt- or a quaternary nitrogen-containing polymer.
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In another embodiment, the present invention provides a method for forming
agricultural formulations, wherein the method comprises: ( 1 ) preparing a
mixture comprising
at least one ethylenically unsaturated monomer and at least one homopolymeric
surface active
agent, the homopolymeric surface active agent being a polymer formed by
polymerizing at
feast one polymerizable, surface active agent; wherein the polymerizable,
surface active agent
is an amine salt or quaternary nitrogen compound comprising at least one acid,
wherein the
acid is a sulfonic acid, a carboxylic acid, or a phosphoric acid, or a mixture
thereof, and at
least one nitrogenous base, wherein the nitrogenous base contains at least one
nitrogen atom
and at least one ethylenically unsaturated moiety; (2) polymerizing the
mixture to form a
polymer latex; and (3) adding an agricultural technical to the polymer latex.
The present invention provides homopolymeric surface active agents. These
homopolymeric surface active agents are formed by polymerizing at least one
polymerizable,
surface active agent, wherein the polymerizable, surface active agent is an
amine salt or
quaternary nitrogen compound comprising at least one acid, wherein the acid is
a sulfonic
acid, a carboxylic acid, or a phosphoric acid, or a mixture thereof; and at
least one nitrogenous
base, wherein the nitrogenous base contains at least one nitrogen atom and at
least one
ethylenically unsaturated moiety. Optionally, the homopolymeric surface active
agents may
be formed by partially or completely polymerizing the nitrogenous base,
followed by
complexation of the resulting polymer with the acid, wherein the acid
complexes to the
nitrogen atom(s), to form an amine salt- or a quaternary nitrogen-containing
homopolymeric
surface active agent.
The homopolymeric surface active agents of the invention arc generally capable
of
polymerization with themselves, co-polymerization with the monomer or co-
polymerization
with a partially polymerized polymer.
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In another embodiment, the present invention provides a method for forming
agricultural formulations, wherein the method comprises: (1) partially
polymerizing at least
one ethyienically unsaturated monomer to form a partially polymerized
polymer/monomer
mixture; (2} adding to the partially polymerized polyrner/monomer mixture at
least one
polymerizable surface active agent and/or at least one homopolymeric surface
active agent, to
form a partially polymerized polymer/monomer/surface active agent mixture; (3)
polymerizing the partially polymerized polymer/monomer/surface active agent
mixture to
form a polymer latex; and (4) adding an agricultural technical to the polymer
latex; wherein
the homopolymcric surface active agent being a polymer formed by polymerizing
at least one
polymerizable, surface active agent; wherein the polymerizable, surface active
agent is an
amine salt or quaternary nitrogen compound comprising at least one acid,
wherein the acid is
a sulfonic acid, a carboxylic acid, or a phosphoric acid, or a mixture
thereof, and at least one
nitrogenous base, wherein the nitrogenous base contains at least one nitrogen
atom and at
least one ethylenically unsaturated moiety.
In another embodiment, the present invention provides a method for forming
agricultural formulations, wherein the method comprises: ( 1 ) preparing a
mixture comprising
at least one ethylenically unsaturated monomer and at least one non-
polymerizable,
supplemental surface active agent; (2) partially polymerizing the mixture to
form a partially
polymerized polymer/monomer/supplemental surface active agent mixture; (3)
adding to the
partially polymerized polymer/monomer/supplemental surface active mixture at
least one
polymerizable surface active agent and/or at least one homopolymeric surface
active agent, to
form a partially polymerized polymer/monomer/supplemental surface active
agent/polymerizable surface active agent mixture; and (4) polymerizing the
partially
polymerized polymer/monomer/surface active agent/polymerizable surface active
agent
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mixture to form a polymer latex; and (5) adding an agricultural technical to
the polymer latex;
wherein the homopolymeric surface active agent being a polymer formed by
polymerizing at
least one polymerizable, surface active agent; wherein the polymerizable,
surface active agent
is an amine salt or quaternary nitrogen compound comprising at least one acid,
wherein the
acid is a sulfonic acid, a carboxylic acid, or a phosphoric acid, or a mixture
thereof, and at
least one nitrogenous base, wherein the nitrogenous base contains at least one
nitrogen atom
and at least one ethylenically unsaturated moiety; and wherein the
supplemental surface active
agent is generally non-polymerizable and is defined herein.
In another embodiment, the present invention provides a method for forming
agricultural formulations, which contain suspensions or dispersions of
polymers of the instant
invention, wherein the method comprises: ( 1 ) preparing a mixture comprising
at least one
ethylcnically unsaturated monomer and at least one non-polymerizable,
supplemental surface
active agent; (2) polymerizing the mixture to form a polymer latex; (3) adding
at least one
polymerizable surface active agent and/or at least one homopolymeric surface
active agent to
the polymer latex; and (4) adding an agricultural technical to the polymer
latex; wherein the
homopolymeric surface active agent being a polymer formed by polymerizing at
least one
polymerizable, surface active agent; wherein the polymerizablc, surface active
agent is an
amine salt or quaternary nitrogen compound comprising at least one acid,
wherein the acid is
a sulfonic acid, a carboxylic acid, or a phosphoric acid, or a mixture
thereof, and at least one
nitrogenous base, wherein the nitrogenous base contains at least one nitrogen
atom and at
least one ethylenically unsaturated moiety.
The present invention encompasses polymers prepared by any of the methods or
processes described herein. Generally, the methods of the present invention
encompass,
emulsions, suspensions or dispersion of polymers obtained therefrom.
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Ethylenically Unsaturated Monomers
The ethylenically unsaturated monomer or monomers that may be polymerized or
copolymerized according to the present invention are known to the art and are
described
below in a representative manner. Examples of suitable ethylenically
unsaturated monomers
are, for example, mono- and polyunsaturated hydrocarbon monomers, vinyl esters
(e.g., vinyl
esters of C, to C~, saturated monocarboxylic acids), vinyl ethers,
monoethylenically
unsaturated mono- and polycarboxylic acids and there alkyl esters (e.g.,
acrylic acid esters
and methacrylic acid esters, particularly the C~ to C,~ alkyl, and more
particularly the C, to Ca
alkyl esters), the nitriles, vinyl and vinylidene halides, and amides of
unsaturated carboxylic
acids and amino monomers.
Examples of suitable hydrocarbon monomers for use in the present invention
include
styrene compounds (e.g., styrene, carboxylated styrene, and alpha-methyl
styrene), ethylene,
propylene, butylene, and conjugated dimes (e.g., butadiene, isoprene and
copolymers of
butadiene and isoprene). Examples of vinyl and vinylidene halides include
vinyl chloride,
vinylidene chloride, vinyl fluoride and vinylidene fluoride.
Examples of acrylic esters and methacrylic esters suitable for use in the
present
invention include C,-C,z (e.g., C,-C4) alkyl acrylates and methacrylates.
Typical alkyl esters
and methacrylic esters include methyl acrylate, methyl methacrylate, ethyl
acrylate, ethyl
methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-
butyl
methacrylate, isobutyl acrylate, isobutyl methacrylate, hexyl acrylate, 2-
ethylhexyl acrylate,
2-ethylhexyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 3,3-
dimethylbutyl acrylate,
3,3-dimethyl butyl methacrylate, and lauryl acrylate.
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Suitable vinyl esters for use in the present invention include aliphatic vinyl
esters,
such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl
isobutyrate, vinyl
valerate, and vinyl caproate, and allyi esters of saturated monocarboxylic
acids, such as allyl
acetate, allyl propionate and ally lactate.
Vinyl ethers suitable for use in the present invention include methylvinyl
ether,
ethylvinyl ether and n-butylvinyl ether. Typically vinyl ketones include
methylvinyl ketone,
ethylvinyl ketone and isobutyivinyl ketone. Suitable dialkyl esters of
monoethylenically
unsaturated dicarboxyiic acids include dimethyl maleate, diethyl malcate,
dibutyl maleate,
dioctyl maleate, diisooctyl maleate, dinonyl maleate, diisodecyl maleate, ditr-
idecyl maleate,
! 0 dimethyl fumarate, diethyl fumarate, dipropy! fumarate, dibutyl fumaratc,
dioctyl fumarate,
diisooctyl fumarate, didecyl fumarate, dimethyl itaconate, diethyl itaconate,
dibutyl itaconate,
and dioctyl itaconate.
Monoethylenically unsaturated monocarboxylic acids suitable for use in the
present
invention include acrylic acid, methacrylic acid, ethacryiic acid, and
crotonic acid. Suitable
monocthylenically unsaturated dicarboxylic acids include malefic acid, fumaric
acid, itaconic
acid and citraconic acid. Suitable monoethylenically unsaturated tricarboxylic
acids include
aconitic acid and the halogen-substituted derivatives (e.g., alphachloracylic
acid), and the
anhydrides of these acids (e.g., malefic anhydride and citraconic anhydride).
Nitrites of the above ethylenically unsaturated mono-, di- and tricarboxylic
acids
which are suitable monomers include acrylonitrile, alpha-chloroacrylonitrile
and
methacrylonitrile. Suitable amides of these carboxylic acids include
unsubtituted amides such
as acrylamide, methacrylamide and other alpha-substituted acrylamides and N-
substituted
amides obtained by the reaction of the amides of the aforementioned mono- and
polycarboxylic acids with and aldehyde (e.g., formaldehyde). Typical N-
substituted amides
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include N-methylolacrylamide, N-methylolmethacrylamide alkylated N-
methylolacrylamides
and N-methylolmethacrylamides (e.g., N-methyoxymethylacrylamide and N-
methoxymethylmethacrylamide).
Amino monomers useful in the present invention include substituted and
unsubstituted
aminoalkyl acrylates, hydrochloride salts of amino monomers and methacrylates,
such as
beta-aminoethylacrylate, beta-amino-ethylmethacrylate,
dimethylaminomethylacrylate, beta-
methylaminoethylacrylate, and dimethylaminomethylmethacrylate.
Hydroxy-containing monomers useful in the present invention include beta-
hydroxyethylacrylate, beta-hydroxypropylacrylate, gamma-hydroxypropylacrylate
and beta-
hydroxyethylmethacrylate.
Monomers useful in the present invention may be homopolymerizcd or
copolymerized, i.e., one or more different monomers capable of polymerization
may be used.
Polymerizable Surface Active Agents
1 S The polymerizable surface active agents utilized in the present invention
arc amine
salts or quaternary nitrogen compounds comprising at least one acid, wherein
the acid is a
sulfonic acid, a carboxylic acid, or a phosphoric acid, or a mixture thereof,
and at least one
nitrogenous base, wherein the nitrogenous base contains at least one nitrogen
atom and at
least on cthylenically unsaturated moiety. In a preferred embodiment of the
present invention,
the polymerizable surface active agents used are in the form of amine salts.
The
polymerizable surface active agents is usually present in the mixture in a
concentration from
about 0.01-100.0 percent by weight based on the total weight of the
ethylenically unsaturated
monomer. In general, although not required, the polymerizable surface active
agents have a
hydrophilic/Iipophilic balance (HLB) of less than about 45. In a somewhat more
preferred
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embodiment, the polymerizable surface active agents have an HLB of about S-40.
The
polymerizable surface active agents are generally capable of polymerization
with themselves,
co-polymerization with the ethylenically unsaturated monomer, or co-
polymerization with a
partially polymerized polymer.
The polymerizable surface active agents of the present invention are prepared
from
readily available, economical raw materials, and generally, their preparation
does not require
any special handling or equipment. The polymerizable surface active agents may
be prepared
in a batch mode or a continuous mode; they may be prepared by contacting
nitrogenous base
with the acid or contacting the acid with the nitrogenous base. By contacting
it is meant that
the acids) is added to the nitrogenous base and the components are mixed, or
the
ethylenically unsaturated amines) is added to the acids) and the components
are mixed.
The surface active agents and blends of surface active agents may be prepared
in a
variety of forms such as, for example, liquids, solutions, solids, powders,
flakes, semi-solids,
gels, "ringing" gels, G-phase liquids, hexagonal phase solids, or thick
pastes. The surface
active agents may be spray dried, flaked, extruded, and the like. Although not
critical to the
present invention, the polymerizable surface active agents may be prepared
"neat" or in a
conventional solvent such as water, low molecular weight alcohol or
hydrocarbon, or a
mixture thereof, to produce a solution of the polymerizable surface active
agent. The present
invention encompasses polymerizable surface active agents as salts in dry form
and as
aqueous solutions. The polymerizable surface active agents may be isolated by
drying a
solution of the surface active agents; a solution of polymerizable surface
active agents may be
prepared by dissolving a solid form of the polymerizable surface active agent
(i.e. an amine
salt) in water, low molecular weight alcohol or hydrocarbon, or a mixture
thereof.
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Polymerizable surface active agents of the present invention may be prepared
and
mixed together to produce a surface active mixture comprising "neat" surface
active agents or
an aqueous surfactant blend. Additionally, neat or aqueous blends of the
polymerizable
surface active agents may be prepared by contacting a blend of two or more
nitrogenous bases
S with one acid, or by contacting a blend of two or more nitrogenous bases
with a blend of 2 or
more acids. Conversely, blends of the polymerizable surface active agents may
be prepared
by contacting a blend of two or more acids with one nitrogenous base, or by
contacting a
blend of two or more acids with a blend of two or more nitrogenous bases.
The polymerizable surface active agents utilized in the present invention may
be
homopolymerized (i.e. polymerized with themselves), or partially
homopolymerized, prior to
use in the polymerization, to form a homopolymeric surface active agent or a
blend of
homopolymeric surface active agents) and polymerizable surface active agents.
The acids useful in the present invention are generally sulfonic acids,
polysulfonic
acids, sulfonic acids of oils, paraffin sulfonic acids, lignin sulfonic acids,
petroleum sulfonic
acids, tall oil acids, olefin sulfonic acids, hydroxyolefin sulfonic acids,
polyolefin sulfonic
acids, polyhydroxy polyolefin sulfonic acids, carboxylic acids, perfluorinated
carboxylic
acids, carboxylic acid sulfonates, alkoxylated carboxylic acid sulfonic acids,
polycarboxylic
acids, polycarboxylic acid polysulfonic acids, alkoxylated polycarboxylic acid
polysulfonic
acids, phosphoric acids, alkoxylated phosphoric acids, polyphosphoric acids,
and alkoxylated
polyphosphoric acids, fluorinated phosphoric acids, phosphoric acid esters of
oils, phosphinic
acids, alkylphosphinic acids, aminophosphinic acids, polyphosphinic acids,
vinyl phosphinic
acids, phosphonic acids, polyphosphonic acids, phosphonic acid alkyl esters, a-
phosphono
fatty acids, oragnoamine polymethylphosphonic acids, organoamino dialkylene
phosphonic
acids, alkanolamine phosphonic acids, trialkyledine phosphonic acids,
acylamidomethane
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phosphonic acids, alkyliminodimethylene diphosphonic acids, polymethylene-
bis(nitrilo
dimethylene)tetraphosphonic acids, alkyl bis(phosphonoalkylidene) amine oxide
acids, esters
of substituted aminomethylphosphonic acids, phosphonamidic acids, acylated
amino acids
(e.g., amino acids reacted with alkyl acyl chlorides, alkyl esters or
carboxylic acids to produce
N-acylamino acids), N-alkyl acylamino acids, and acylatcd protein
hydrolysates, and mixtures
thereof.
Other acids which are useful in the present invention are selected from the
group
comprising linear or branched alkylbenzene sulfonic acids, alkyl sulfuric acid
esters,
alkoxylated alkyl sulfuric acid esters, a-sulfonated alkyl ester acids, a-
sulfonated ester
diacids, alkoxylated a-sulfonated alkyl ester acids, a-sulfonatcd dialkyl
diester acids, di-a-
sulfonated dialkyl diestcr acids, a-sulfonated alkyl acetate acids, primary
and secondary alkyl
sulfonic acids, perfluorinated alkyl sulfonic acids, sulfosuccinic mono- and
diestcr acids,
polysulfosuccinic polyester acids, sulfoitaconic diester acids,
sulfosuecinamic acids,
sulfosuccinic amide acids, sulfosuccinic imide acids, phthalic acids,
sulfophthalic acids,
sulfoisaphthalic acids, phthalamic acids, sulfophthalamic acids, alkyl ketone
sulfonic acids,
hydroxyaikane-l-sulfonic acids, lactone sulfonic acids, sulfonic acid amides,
sulfonic acid
diamidcs, alkyl phenol sulfuric acid esters, alkoxylated alkyl phenol sulfuric
acid esters,
alkylated cycloalkyl sulfuric acid esters, alkoxylated alkylated cycloalkyl
sulfuric acid esters,
dendritic polysulfonic acids, dendritic polycarboxylic acids, dendritic
polyphosphoric acids,
sarcosinic acids, iscthionic acids, and tauric acids, and mixtures thereof.
Additionally in accordance with the present invention, suitable acids of the
present
invention include fluorinated carboxylic acids, fluorinated sulfonic acids,
fluorinated sulfate
acids, fluorinated phosphonic and phosphinic acids, and mixtures thereof.
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Due to their inherent hydrolytic instability, the sulfuric acid esters are
preferably
immediately converted to ethylenically unsaturated amine salts. For example,
linear dodecyl
alcohol is sulfated with S03 to produce an intermediate, hydrolytically
unstable, dodecyl
alcohol sulfate acid as shown in Scheme I below. The intermediate acid is
neutralized with an
ethylenically unsaturated nitrogenous base, such as allyl amine, to produce a
dodecyl sulfate
ethylenically unsaturated amine salt.
Scheme I' Formation of Dodecyl Sulfate Ethylenically Unsaturated Amine Salt
CH~(CH~)"OH + S03 ~ [CH3(CHZ)"OSO,H] + H~NCHzCH=CHI ~
[CH~(CH~)"OS03]~[NH ~CHZCH=CHZ]+
Additionally, for example, methyl laurate is sulfonated with SO~ to produce an
intermediate a-sulfonated lauryl methyl ester acid, as shown in Scheme II
below. This acid is
neutralized with an ethylenically unsaturated nitrogenous base, such as allyl
amine, to
produce an a-sulfonated lauryl methyl ester ethylenically unsaturated amine
salt.
Additionally, an a-sulfonated lauryl methyl ester ethylenically unsaturated
amine di-salt may
be produced as shown below in Scheme III. The a-sulfonatcd lauryl methyl ester
ethylenically unsaturated amine salt and the a-sulfonated lauryl fatty acid
ethylenically
unsaturated amine di-salt may be formed as a mixture depending on the
sulfonation conditions
employed. The ratio of unsaturated amine salt to unsaturated amine di-salt is
readily
controlled by suifonation conditions, well known to those skilled in the art.
Scheme II' Formation of a-Sulfonated Lauryl Methyl Ester Ethylenically
Unsaturated Amine
Salt
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0
0 0
H3C SOI HZN
OMe
HOC g OMe H3C Q OMe
_+
S03H SO~ NHS
Scheme III: Formation of a-Sulfonated Laurel Methvi Ester Ethylenically
Unsaturated
Amine Di-Salt
p O o
H 3C S03 H2N ~ _ + ~ /
OMe ~ HOC 9 OSOyOMe ~' t~3C ~ O NHS
(-IISO~OMe) _ + ~ /
SOyH SO~ NHS
Ethylenically unsaturated amine salts of sulfosucinnate ester acids are
typically
produced by sulfitation of a succinic acid alkyl diester with sodium
bisulfate, followed by, for
l0 example, ionic exchange with an ethylenically unsaturated nitrogenous base,
such as ally!
amine, as shown in Scheme 1V below.
Scheme IV: Formation of a Sulfosuccinate Ester Ethylenically Unsaturated Amine
Salt
O
O O
RO \ N3FISC)~ RO RZN~ RO
FOR ~ ~OR ~ \OR
O O SO~Na NaOH O SO~ NHS
The sarcosinic acid ethylenically unsaturated amine salts are prepared by the
amidation of a fatty acid, a fatty acid alkyl ester or a fatty acid chloride
with sarcosine,
followed by addition of an ethylenically unsaturated nitrogenous base, such as
ally! amine, as
shown in Scheme V below. Optionally, and somewhat less preferably, the
ethylenically
unsaturated nitrogenous base is combined with sarcosine to produce the
corresponding
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sarcosine salt, which is then be used to amidate the fatty acid, fatty acid
alkyl ester or fatty
acid chloride.
Scheme V' Formation Of A Fatty Sarcosinate Acid Ethylenicallv Unsaturated
Amine Salt
0 0 0 0
\~IIII ~ /jj\ H2N
R~OH ~ CH3~ ~OH ~ R N~~OH
O 0
R~N~~O ~N Ij
S
The isethionic acid ethylenically unsaturated amine salts may be prepared by
the
esterification of a fatty acid, a fatty acid alkyl ester or a fatty acid
chloride with iscthionic
acid, followed by addition of an ethylenically unsaturated nitrogenous base,
such as allyl
amine, as shown in Scheme VI below. Additionally, isethionic acid
ethylenically unsaturated
amine salts may be prepared by esterifying a fatty acid, a fatty acid alkyl
ester or a fatty acid
chloride with the sodium salt of isethionic acid, followed by ion exchange
with the
ethylenically unsaturated nitrogenous base, such as allyl amine. Optionally,
isethionic acid,
or its sodium salt, may be combined with the ethyienically unsaturated
nitrogenous base, such
as allyl amine, to produce the isethionic acid allyl amine salt, which may
then be estcrified
1 S with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
Scheme VI~ Formation Of An Isethionic Acid Ethylenically Unsaturated Amine
Salt
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0 0
HO ~ ~SO~H H N
R OH ~ ~SO H R O
9
O
-+ ~ ~
~SO~ NHS
R~O
The preferred acids of the present invention are branched or linear
alkylbenzene
sulfonic acids, alkyl sulfuric acid esters, alkoxylated alkyl sulfuric acid
esters, a-sulfonated
S alkyl ester acids, fatty carboxylic acids and phosphoric acid esters, and
mixtures thereof. The
most preferred acids of the present invention are branched or linear
alkylbenzene sulfonic
acids, alkyl sulfuric acid esters, and alkoxylated alkyl sulfuric acid esters,
and mixtures
thereof.
Other useful surfactants in accordance with the present invention include
sulfonic acid
l0 salts of ethylenically unsaturated amines, derived from sultone precursors,
such as cyclic alkyl
sultones. Examples of these sultone-derived sulfonic acid salts (e.g., allyl
amine salts) include
2-acetamidoalkyl-1-sulfonates and amino carboxy acid alkyl sulfonates, as
shown in Scheme
VII and Scheme VIII below.
1 S Scheme VII' 2-Acetamidoalkyl-1-Sulfonic Acid Allvl Amine Salts
R
~ ~ R /~ ~
CHIC-N ~ NHy~ S03 rNH~~
N SOy
O-SOy HN
O
O
where R is C4_za alkyl.
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Scheme VIII' Amino Carboxy Acid Alkyl Sulfonic Acid Allvl Amine Salts
R
R OH
NH3
S03 + CI
O-SOZ
NH3' O
HzN
R ~ ~
O S03 'NH3'~
\ NH
~NH3+ O
where R is C:,_z.~ alkyl.
In general, nitrogenous bases which are useful in the present invention are
any
nitrogenous base which contains an ethylenically unsaturated moiety, including
various vinyl
amines. The nitrogenous base useful in accordance with the present invention
is a compound
of the formula
R,
/N~
R~ RZ
wherein R~, Rz and R3 are independently hydrogen or organic groups containing
an
ethenylene group, provided that at least one of R,-R3 is a straight or
branched chain alkyl
group containing 1-8 carbon atoms and an ethenylene functionality.
Additionally, other examples of nitrogenous bases that are useful in the
present
invention are ethylenically unsaturated amines selected from the group
comprising vinyl
amine, N-methyl N-allyl amine, C,-Cz4 alkyl allyl amine, C~-CZa alkyl
ethoxylated and/or
propoxylated allyl amine, Ci-C24 dialkyl allyl amine, ethoxylated and/or
propoxylated allyl
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amine diallyl amine, Ci-CZa alkyl diallyl amine, ethoxylated and/or
propoxylated diallyl
amine, triallyl amine, 1,2-diaminoethene, aminocrotonitrile,
diaminomaleonitrile, N-
allylcyclopentylamine, N-allylaniline, allylcyclohexylamine, [ 1-(2-
allylphenoxy)-3-
{isopropylamino)-2-propanol], 3-amino-2-butenethioamide, bis[4-(dimethylamino)-
S benzylidene]acetone, 1,4-butanediol bis(3-aminocrotonate), 3-amino-1-
propanol vinyl ether,
2-(diethylamino)ethanol vinyl ether, 4-(diethylamino)cinnamaldehyde, 4-
(diethylamino)cinnamonitrile, 2-(diethylamino)ethyl methacrylate, diethyl (6-
methyl-2-
pyridylaminomethylene)maleate, 3-(dimethylamino)acrolein, 2-
(dimethylamino)ethyl
methacrylatc, 4-dimethylaminocinnamaldehydc, 2-(dimethylamino)ethyl acrylate,
3-
(dimethylamino)-2-methyl-2-propenal, 9-vinylcarbazole, N-vinylcaprolactam, 1-
vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, allylcyclohexylamine, N-
allylcyclopentylamine, allyl(diisopropylamino)dimethylsilane, 1-
allylimidazole, 1-vinyl-2-
pyrrolidinone, N-[3-(dimethylamino)propyl]mcthacrylamide, 4-[4-
(dimethylamino)styryl]pyridine, 2-[4-(dimethylamino)styrylJpyridine, 2-[4-(1,2-
diphenyl-1-
I S butenyl)phenoxy]-N,N-dimethylethylamine, 2-[4-dimethylamino)styryl)-
benzothiozole, S-[4-
(dimethylamino)phenyl]-2,4-pentandienal, (dimethylamino-
methylene)malononitrile, 4-
dimethylaminocinnamonitrile, 4-(dimethylamino)chalcone, [6-(3,3-
dimethylallylamino-purine
riboside, 3,7-dimethyl-2,~-octadien-1-ylamine, 2-isopropenylaniline, isopropyl
3-
aminocrotonate, S-{2-[3-(hexyloxy)bcnzoylJ-vinyl}glutathione, methyl 3-
aminocrotonate, N-
methylallylamine, N-methyl-1-(methylthio)-2-nitroetheneamine, oleylamine,
tetrakis(dimethylamino)ethylene, 5-[(6,7,8-trimethoxy-4-quinazolinyl)amino]-1-
pentanol
nitrate ester, tris(2-methylallyl)amine, N,N,N',N'-tetramethyl-2-butene-1,4-
diamine, S-{2-[3-
(octyloxy)benzoyl]vinyl}-glutathione, 4,4'-vinylidene-(N,N-dimethylaniline),
2',S'-
dimethoxy-4-stilbenamine, 3-(dimethylamino)propyl acrylate, 3-
dimethylaminoacrylonitrile,
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4-(dimethylamino)-cinnamic acid, 2-amino-1-propene-I,1,3-tricarbonitrile, 2-
amino-4-
pentenoic acid, N, N'-diethyl-2-butene-1,4-diamine, 10,11-dihyro-N,N-dimethyl-
S-
methylene-SH-dibenzo[a,dJ-cyclohepene-10-ethanamine maleate, 4-
(dicyanomethylene)-2-
methyl-6-(4-dimethyl-aminostyryl)-4H-pyran, N-ethyl-2-methylallylamine, ethyl
3-
S aminocrotonate, ethyl-a-cyano-3-indoleacrylate, ethyl-3-amino-4,4-dicyano-3-
butenoate, 1,3-
divinyl-1,1,3,3-tetramcthyldisilazane, N-(4,S-dihydro-S-oxo-1-phenyl-1H-
pyrazol-3-yl)-9-
octadecen-amide, and N-oleoyl-tryptophan ethyl ester, and mixtures thereof.
More preferred nitrogenous bases of the present invention are allyl amine,
diallyl
amine, triallyl amine, methylallyl amine, N-allyl-N,N-dimethyl amine, methyl 3-
amino
crotonate, 3-amino crotononitrile, 3-amino-1-propanol vinyl ether, N-methyl N-
allyl amine, 2-
(dimcthylamino)ethyl acrylate, or 1,4-diamino-2-butene, and mixtures thereof.
The most
preferred nitrogenous bases of the present invention are allyl amine, diallyl
amine, triallyl
amine, methallyl amine, N-methyl N-allyl amine, and 2-(dimethylamino)ethyl
acrylate, and
mixtures thereof.
1 S In the methods and compositions of the invention, amine salts are
generally preferred
over quaternary ammonium compounds.
Accordingly, the present invention utilizes surface active agents of the
formula:
(R i )~-~( S03-M+)~,
wherein R, is a saturated or unsaturated hydrocarbon group having from about 1-
24 carbon
atoms; wherein Ar is a phenyl, polyphenyl, napthyl, polynapthyl, styryl, or
polystyryl group,
or a mixture thereof; wherein M+ is a conjugate acid of the nitrogenous base;
wherein n is an
integer of from 1-S and m is an integer of from 1-8; and wherein the total
number of carbon
atoms represented by (R,)~ is at least S. In a preferred embodiment R, is a
saturated or
unsaturated hydrocarbon group having from about 6-24 carbon atoms, Ar is a
phenyl, M+ is a
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conjugate acid of the nitrogenous base, the nitrogenous base selected from the
group
consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-
methyl N-allyl
amine or 2-(dimethylamino)ethyl acrylate, and mixtures thereof and n is 1 and
m is 1. In
another preferred embodiment, the surface active agent is of the formula:
CH~(CHZ)m
S03 ~NH3~
R'
wherein nl = 4 -18; and wherein R' is hydrogen or saturated or unsaturated
hydrocarbon
group having from about 1-8 carbon atoms.
The present invention further utilizes surface active agents of the formula
(Ri)m-~~(s~3 M+)mi }-~-tAr(SO,-M+)mzt-(Rz)~z
wherein R, and Rz are independently hydrogen, or saturated or unsaturated
hydrocarbon
groups having from about 1-24 carbon atoms; wherein Ar is a phenyl,
polyphenyl, napthyl,
polynapthyl, styryl, or polystyryl group, or a mixture thereof; wherein M+ is
a conjugate acid
of the nitrogenous base; wherein nl and n2 are independently 0-5, provided
that nl and n2 are
not both equal to zero; and wherein m 1 and m2 are independently 0-8, provided
that m 1 and
m2 are not both equal to zero. In a preferred embodiment, R, is hydrogen and
Rz is a
saturated or unsaturated hydrocarbon group having from about G-24 carbon
atoms, Ar is
phenyl, M+ is a conjugate acid of the nitrogenous base, the nitrogenous base
selected from the
group consisting of allyi amine, diallyl amine, triallyl amine, methallyl
amine, N-methyl N-
allyl amine or 2-(dimethylamino)ethyl acrylate, and mixtures thereof, nl = 4,
n2 = l, and ml
and m2 both equal one. In another preferred embodiment, R, and Rz are
independently
saturated or unsaturated hydrocarbon groups having from about 6-24 carbon
atoms, Ar is
phenyl, M+ is a conjugate acid of the nitrogenous base, the nitrogenous base
selected from the
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group consisting of allyl amine, diallyl amine, triallyl amine, methallyl
amine, N-methyl N-
allyl amine, or 2-(dimethylamino)ethyl acrylate, and mixtures thereof, nl and
n2 both equal
one, and m 1 and m2 both equal one. In another preferred embodiment, the
surface active
agent is of the formula:
(CHz)n.CH3
CH3(CH,)"
R. O R..
S03 iNH3 S03 +NH3
wherein n and n' are independently 4-18; and wherein R' and R" are
independently
hydrogen, methyl, ethyl or propyl.
The present invention further utilizes surface active agents of the formula:
R, -CH(S03-M+)COzR2
wherein R, and R~ are independently saturated or unsaturated hydrocarbon
groups having
from about 1- 24 carbon atoms; and wherein M+ is a conjugate acid of the
nitrogenous base.
In a preferred embodiment, R, is a saturated or unsaturated hydrocarbon group
having from
about 6-24 carbon atoms, R2 is methyl, ethyl, or propyl, or a mixture thereof,
and M+ is a
conjugate acid of the nitrogenous base, the nitrogenous base selected from the
group
consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-
methyl N-allyl
amine, or 2-(dimethylamino)ethyl acrylate, and mixtures thereof. In another
preferred
embodiment, the surface active agent is of the formula:
0
CHa v ~ " ~OCH~
~NH3
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wherein n = 3-18.
The present invention further utilizes surface active agents of the formula:
R,-CH(S03-M+)COZM+
wherein R, is a saturated or unsaturated hydrocarbon group having from about 3-
24 carbon
atoms; and wherein M+ is a conjugate acid of the nitrogenous base. In a
preferred
embodiment, R, is a saturated or unsaturated hydrocarbon group having from
about G-24
carbon atoms, M' is a conjugate acid of the nitrogenous base, the nitrogenous
base selected
from the group consisting of allyl amine, diallyl amine, triallyl amine,
methallyl amine, N-
methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and mixtures
thereof. In another
preferred embodiment, the surface active agent is of the formula:
0
hi C O- ;Nhi3
S03 +NH3~
wherein n = 3-18.
The present invention further utilizes surface active agents of the formula:
R,-CH(SO~-M+)C(O)O(CHZCH(R')O)~ Rz
wherein R, and Rz are independently saturated or unsaturated hydrocarbon
groups having
from about 1- 24 carbon atoms; wherein R' is methyl or hydrogen; wherein n is
an integer of
from 1-100; and wherein M+ is a conjugate acid of the nitrogenous base. In a
preferred
embodiment, R, is a saturated or unsaturated hydrocarbon group having from
about 4-24
carbon atoms, R' is methyl or hydrogen, Rz is methyl, ethyl, or propyl, and
mixtures thereof,
M+ is a conjugate acid of the nitrogenous base, the nitrogenous base selected
from the group
consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-
methyl N-allyi
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amine, or 2-(dimethylamino)ethyl acrylate, and mixtures thereof, and n = 1-
100. In another
preferred embodiment, the surface active agent is of the formula:
0
CH3 ~ ' "p - ~ O(CHzCHzO)"zMe
IS03 'NH3~
wherein nl = 2-18; and wherein n2 = 1 -20.
The present invention further utilizes surface active agents of the formula:
R,-(S03-M+)
wherein R, is a saturated or unsaturated hydrocarbon group having from about 6-
24 carbon
atoms and wherein M+ + is a conjugate acid of the nitrogenous base. In a
preferred
embodiment, R, is a saturated or unsaturated hydrocarbon group having from
about 6-24
carbon atoms, and M+ is a conjugate acid of the nitrogenous base, the
nitrogenous base
selected from the group consisting of allyl amine, diallyl amine, triallyl
amine, methallyl
amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and
mixtures thereof. In
another preferred embodiment, the surface active agent is of the formula:
CH3(CH,)"S03 +NH3
wherein n = 5-17.
The present invention further utilizes surface active agents of the formula:
R~ COz(CHZ)~CH(SO;'M+)COZRZ
wherein R, and RZ are independently saturated or unsaturated hydrocarbon
groups having
from about 1- 24 carbon atoms; wherein n is zero or an integer of from 1-10;
and wherein M+
is a conjugate acid of the nitrogenous base. In a preferred embodiment, R, and
Rz are
independently saturated or unsaturated hydrocarbon groups having from about 1-
24 carbon
atoms, n = 1-6, and M+ is a conjugate acid of the nitrogenous base, the
nitrogenous base
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selected from the group consisting of allyl amine, diallyl amine, triallyl
amine, methallyl
amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and
mixtures thereof. In
another preferred embodiment, the surface active agent is of the formula:
0
cH,o
O(CHZ)",CH,
O SO, ~NH,~
wherein nl is zero or an integer of from I- 17
The present invention further utilizes surface active agents of the formula:
R, COZ(CHZ)"S03-M+
wherein R, is a saturated or unsaturated hydrocarbon group having from about 1-
24 carbon
atoms; wherein n = 1-10; and wherein M+ is a conjugate acid of the nitrogenous
base. In a
preferred embodiment, R, is a saturated or unsaturated hydrocarbon group
having from about
6-24 carbon atoms, n = I-5, and M+ is a conjugate acid of the nitrogenous
base, the
nitrogenous base selected from the group consisting essentially of allyl
amine, diallyl amine,
triallyl amine, methallyl amine, N-methyl N-allyl amine, or 2-
(dimethylamino)ethyl acrylate,
or a mixture thereof. In another preferred embodiment, the surface active
agent is of the
l5 formula:
0
-+ ~
CH3 ~S03 NH3
O
nl
wherein nl = 2 -18.
The present invention further utilizes surface active agents of the formula:
(Ri )~-Ar-O(CHZCH(R')O)mS03-M+
wherein R, is a saturated or unsaturated hydrocarbon group having from about I-
24 carbon
atoms; wherein Ar is a phenyl, polyphenyl, napthyl, polynapthyl, styryl, or
polystyryl group,
and mixtures thereof; wherein R' is methyl or hydrogen; wherein M+ is a
conjugate acid of
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the nitrogenous base; wherein n = 1-5; wherein the total number of carbon
atoms represented
by (R, )" is at least 5; and wherein m is zero or an integer of from 1-100. In
a preferred
embodiment, R, is a saturated or unsaturated hydrocarbon group having from
about 6-24
carbon atoms, Ar is phenyl; M+ is a conjugate acid of the nitrogenous base,
the nitrogenous
S base selected from the group consisting of allyl amine, diallyl amine,
triallyl amine, methallyl
amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and
mixtures thereof, n =
l, and m is zero or an integer of from 1-100. In another preferred embodiment,
the surface
active agent is of the formula:
O S03 ;NH3'
CH3 nl O
n2
wherein nl = 5 -18; and wherein n2 = 0-20.
The present invention further utilizes surface active agents of the formula:
R~O(CH~CH(R')O)nS03-M+
wherein R, is a saturated or unsaturated hydrocarbon group having from about 1-
24 carbon
atoms; wherein R' is methyl or hydrogen; wherein n = 0-100; and wherein M+ is
a conjugate
acid of the nitrogenous base. In a preferred embodiment, R, is a saturated or
unsaturated
hydrocarbon group having from about 6- 24 carbon atoms, R' is methyl or
hydrogen, n = 0-
100, and M+ is a conjugate acid of the nitrogenous base, the nitrogenous base
selected from
the group consisting of allyl amine, diallyl amine, triallyi amine, methallyl
amine, N-methyl
N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and mixtures thereof. In
another preferred
embodiment, the surface active agent is of the formula:
CH3(CH2)n1~S03_ +NH3
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wherein nl = 5-18. In another preferred embodiment, the surface active agent
is of the
formula:
/O S03 +NH3
CH3(CHZ)m
n
wherein nl = S-18; and wherein n = 1-20.
The present invention further utilizes surface active agents of the formula:
R, COZ~M+
wherein R, is a saturated or unsaturated hydrocarbon group having from about 4-
24 carbon
atoms; and wherein M+ is a conjugate acid of the nitrogenous base. In a
preferred
embodiment, Ri is a saturated or unsaturated hydrocarbon group having from
about 6-24
carbon atoms, and M+ is a conjugate acid of the nitrogenous base, the
nitrogenous base
selected from the group consisting of allyl amine, diallyl amine, tria11y1
amine, methallyl
amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and
mixtures thereof. In
another preferred embodiment, the surface active agent is of the formula:
CH3(CII~)nCO, NH3
wherein n = 5-18.
The present invention further utilizes surface active agents of the formula:
R, CON(R')(CHZ)"COZ-M+
wherein R, is a saturated or unsaturated hydrocarbon group having from about 1-
24 carbon
atoms; wherein R' is methyl, ethyl, propyl or hydrogen; wherein M+ is a
conjugate acid of the
nitrogenous base; and wherein n = 1-10. In a preferred embodiment, M+ is a
conjugate acid
of the nitrogenous base, the nitrogenous base selected from the group
consisting of allyl
amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine,
or 2-
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(dimethylamino)ethyl acrylate, and mixtures thereof, R' is methyl, ethyl,
propyl or hydrogen,
and n = 2-S. In another preferred embodiment, the surface active agent is of
the formula:
0
CH3 ~COz +NH3%~
nl N
wherein nl = 2-18.
The present invention further utilizes surface active agents of the formula:
R,CON(R')(CHz)"SO~M+
wherein R, is a saturated or unsaturated hydrocarbon group having from about 1-
24 carbon
atoms; wherein R' is methyl, ethyl, propyl or hydrogen; wherein M+ is a
conjugate acid of the
nitrogenous base; and wherein n = 1-10. In a preferred embodiment, M+ is a
conjugate acid of
the nitrogenous base, the nitrogenous base selected from the group consisting
of allyl amine,
diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or 2-
(dimethylamino)ethyl acrylate, and mixtures thereof, R' is methyl, ethyl,
propyl or hydrogen,
and n = 2-5. In another preferred embodiment, the surface active agent is of
the formula:
0
-+ /
CH3 ~SOg NH3
nt N
1 S wherein nl = 2-18.
The present invention further utilizes surface active agents of the formula:
R~O(CHZCH(R')O)~COCHzS03-M+
wherein R, is a saturated or unsaturated hydrocarbon group having from about 1-
24 carbon
atoms; wherein R' is methyl or hydrogen; wherein n = 0-100; wherein M+ is a
conjugate acid
of the nitrogenous base. In a preferred embodiment, R, is a saturated or
unsaturated
hydrocarbon group having from about 6-24 carbon atoms; R' is methyl or
hydrogen, M+ is a
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conjugate acid of the nitrogenous base, the nitrogenous base selected from the
group
consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-
methyl N-allyl
amine, or 2-(dimethylamino)ethyl acrylate, and mixtures thereof; and n = 0-
100. In another
preferred embodiment, the surface active agent is of the formula:
0
_+
CH3 ~O~\~~ S03 NH3
$ nl n
wherein nl = $-17; and wherein n = 0-20.
The present invention further utilizes surface active agents of the formula:
R, O(PO;)x-M+y
wherein R, is a saturated or unsaturated hydrocarbon group having from about 1-
24 carbon
atoms, phenyl, polyphenyl, napthyl, polynapthyl, styryl, or polystyryl group,
an
alkyl/alkoxylate substituted phenyl, an alkyl/alkoxylate substituted or poly-
substituted
polyphenyl, an alkyl/alkoxylate substituted or poly-substituted napthyl, an
alkyl/alkoxylate
substituted or poly-substituted polynapthyl, an alkyl/alkoxylate substituted
or poly-substituted
styryl, or an alkyl/alkoxylate substituted or poly-substituted polystyryl
group, and mixtures
1$ thereof; wherein M+ is a conjugate acid of the nitrogenous base; wherein x
= 1 or 2; and
wherein y = 1 or 2.
The present invention further utilizes surface active agents of the formula:
[Ri0(CHzCH(R')O)m]nP(O)Px-M+Y
wherein R, is a saturated or unsaturated hydrocarbon group having from about 1-
24 carbon
atoms; wherein R' is methyl or hydrogen; wherein M+ is a conjugate acid of the
nitrogenous
base, the nitrogenous base selected from the group consisting of allyl amine,
diallyl amine,
triallyl amine, methallyi amine, N-methyl N-allyl amine, or 2-
(dimethylamino)ethyl acrylate,
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and mixtures thereof; m = 0 -100; wherein n = 1 or 2; wherein p = 2 or 3;
wherein x = 1 or 2;
and wherein y = 1 or 2.
The present invention further utilizes surface active agents of the formula:
L(R,)~ArO(CHzCH(R')(J)m]qP(O)~," M+Y
wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1-
24 carbon
atoms; wherein Ar is phenyl; wherein R' is methyl or hydrogen; wherein M+ is a
conjugate
acid of the nitrogenous base, the nitrogenous base selected from the group
consisting of allyl
amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine,
or 2-
(dimethylamino)ethyl acrylate, and mixtures thereof; wherein n = 1-4; wherein
m = 0 -100;
wherein q = 1 or 2; wherein p = 2 or 3; wherein x = 1 or 2; and wherein y = 1
or 2.
Although less preferred, the present invention may utilizes polymerizable
surface
active agents which are quaternary ammonium salts of the general formula:
R~
i R3 X_
R2/~ \ Ra
wherein R,, R2, R3, and R~ are independently, substituted or unsubstituted
hydrocarbyl groups
of from about 1 to about 30 carbon atoms, or hydrocarbyl groups having from
about 1 to
about 30 carbon atoms and containing one or more aromatic, ether, ester,
amido, or amino
moieties present as substituents or as linkages in the radical chain, wherein
at least one of the
R,-R4 groups contains at least one or more ethenylene groups; and wherein X-
is an anion
group selected from the group consisting of sulfonate, sulfate, sulfinate,
sulfenate, phosphate,
carboxylate, nitrate, and acetate. Additionally, useful polymerizable surface
active agents
include those of the above general formula in the form of ring structures
formed by covalently
linking two of the R,-R4 groups. Examples include unsaturated imidazolines,
imidazoliniums,
and pyridiniums, and the like. These quaternary ammonium salts may be prepared
by a
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variety of methods known to the art, for example, halide exchange; wherein a
halide based
quaternary ammonium compound is ion exchanged with X-, where X- is defined
above.
The present invention encompasses amine oxide-derived polymerizable surface
active
agents, formed as shown in Scheme IX, wherein R,, R2, R3 are independently,
substituted or
S unsubstituted hydrocarbyl groups of from about 1 to about 30 carbon atoms,
or hydrocarbyl
groups having from about 1 to about 30 carbon atoms and containing one or more
aromatic,
ether, ester, amido, or amino moieties present as substituents or as linkages
in the radical
chain, wherein at least one of the R,-R; groups contains at least one or more
ethenylene
groups; and wherein X- is an anion group selected from the group consisting of
sulfonate,
sulfate, sulfinate, sulfenate, phosphate, carboxylate, nitrate, and acetate.
Additionally, useful
polymerizable surface active agents include those of the above general Formula
in the form of
ring structures formed by covalently linking two of the R,-R4 groups. Examples
include
unsaturated imidazolines, imidazoliniums, and pyridiniums, and the like.
I S Scheme IX: Amine Oxide-Derived Polymerizable Surface Active Agents
R~
R~ Ri
HaO, ( X I _
N -~--~- ~ O ~ ~ O H
X
Rz~ ~R3 ~N~ ~N~
R2 R3 R2 R3
The present invention further encompasses quaternary halide-derived
polymerizable
surface active agents, formed as shown in Scheme X, wherein Ri, R2, R3 are
independently,
substituted or unsubstituted hydrocarbyl groups of from about I to about 30
carbon atoms, or
hydrocarbyl groups having from about 1 to about 30 carbon atoms and containing
one or more
aromatic, ether, ester, amido, or amino moieties present as substituents or as
linkages in the
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radical chain, wherein at least one of the R~-R~ groups contains at least one
or more
ethenylene groups; and wherein X- is an anion group selected from the group
consisting of
sulfonate, sulfate, sulfinate, sulfenate, phosphate, carboxylate, nitrate, and
acetate.
Additionally, useful polymerizable surface active agents include those of the
above general
formula in the form of ring structures formed by covalently linking two of the
R,-R,~ groups.
Examples include unsaturated imidazolincs, imidazoliniums, and pyridiniums,
and the like.
The present invention further encompasses polymerizable opium compounds,
particularly ammonium salts, sulfonium salts, sulfoxonium salts, oxonium
salts, nitronium
salts, and phosphonium salts of various anions, including for example, anions
group selected
from the group consisting of sulfonate, sulfate, sulfinate, sulfenate,
phosphate, carboxylate,
nitrate, acetate and various halides; wherein the opium compound contains at
least one
ethenylcne functionality.
"Reverse" Polymerizable Surface Active Agents
1 S Although somewhat less preferred, the polymerizable, surface active agents
utilized in
the present invention may be "reverse" polymerizablc surface active agents.
Reverse
polymerizable surface active agents utilized in the present invention are
amine salts or
quaternary nitrogen compounds comprising: ( 1 } at least one ethylenically
unsaturated acid,
wherein the acid contains at least one ethyienically unsaturated moiety and is
a sulfonic acid,
a carboxylic acid, or a phosphoric acid, or a mixture thereof; and (2) at
least one substantially
saturated nitrogenous base, wherein the nitrogenous base contains at least one
nitrogen atom
and a C,-CZa alkyl group. By substantially saturated nitrogenous base, it is
meant that the
nitrogenous base contains less than about 5% unsaturation in the alkyl
group(s).
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In general, the ethylenically unsaturated acids of the present invention are
any sulfonic
acids, carboxylic acids, or phosphoric acids which contain at least one
unsaturated moiety.
More specifically, the ethylenically unsaturated acids useful in the present
invention are
generally vinyl sulfonic acids, vinyl sulfinic acids, vinyl sulfenic acids,
vinyl sulfonic acid
esters, vinyl carboxylic acids, vinyl, phosphoric acids, vinyl phosphonic
acids, vinyl
phosphinic, vinyl phosphenic acids, unsaturated sulfonic acids, unsaturated
polysulfonic
acids, unsaturated suIfonic acids of oils, unsaturated paraffin sulfonic
acids, unsaturated lignin
sulfonic acids, unsaturated petroleum sulfonic acids, unsaturated tall oil
acids, unsaturated
olefin sulfonic acids, unsaturated hydroxyolefin sulfonic acids, unsaturated
polyolefin
sulfonic acids, unsaturated polyhydroxy polyolefin sulfonic acids, unsaturated
carboxylic
acids, unsaturated perfluorinated carboxylic acids, unsaturated carboxylic
acid sulfonates,
unsaturated alkoxylated carboxylic acid sulfonic acids, unsaturated
polycarboxylic acids,
unsaturated polycarboxylic acid polysulfonic acids, unsaturated alkoxylated
polycarboxylic
acid polysulfonic acids, unsaturated phosphoric acids, unsaturated alkoxylated
phosphoric
acids, unsaturated polyphosphoric acids, and unsaturated alkoxylated
polyphosphoric acids,
unsaturated fluorinated phosphoric acids, unsaturated phosphoric acid esters
of oils,
unsaturated phosphinic acids, unsaturated alkylphosphinic acids, unsaturated
aminophosphinic acids, unsaturated polyphosphinic acids, unsaturated vinyl
phosphinic acids,
unsaturated phosphonic acids, unsaturated polyphosphonic acids, unsaturated
phosphonic acid
alkyl esters, unsaturated a-phosphono fatty acids, unsaturated oragnoamine
polymethylphosphonic acids, unsaturated organoamino dialkylene phosphonic
acids,
unsaturated alkanolamine phosphonic acids, unsaturated trialkyledinc
phosphonic acids,
unsaturated acylamidomethane phosphonic acids, unsaturated
alkyliminodimethylene
diphosphonic acids, unsaturated polymethylene-
bis(nitrilodimethylene)tetraphosphonic acids,
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unsaturated alkyl bis(phosphonoalkylidene} amine oxide acids, unsaturated
esters of
substituted aminomethylphosphonic acids, unsaturated phosphonamidic acids,
unsaturated
acylated amino acids (e.g., amino acids reacted with alkyl acyl chlorides,
alkyl esters or
carboxylic acids to produce N-acylamino acids), unsaturated N-alkyl acylamino
acids, and
unsaturated acylated protein hydrolysates, and mixtures thereof.
Other ethylenically unsaturated acids which are useful in the present
invention are
selected from the group comprising unsaturated linear or branched alkylbenzene
sulfonic
acids, unsaturated alkyl sulfuric acid esters, unsaturated alkoxylated alkyl
sulfuric acid esters,
unsaturated cx-sulfonated alkyl ester acids, unsaturated a-sulfonated ester
diacids, unsaturated
alkoxyiated a-sulfonated alkyl ester acids, unsaturated a-sulfonated dialkyl
diester acids,
unsaturated di-a-sulfonated dialkyl diester acids, unsaturated a-sulfonated
alkyl acetate acids,
unsaturated primary and secondary alkyl sulfonic acids, unsaturated
perfluorinated alkyl
sulfonic acids, unsaturated sulfosuccinic mono- and diester acids, unsaturated
polysulfosuccinic polyester acids, unsaturated sulfoitaconic diester acids,
unsaturated
sulfosuccinamic acids, unsaturated sulfosuccinic amide acids, unsaturated
sulfosuccinic imide
acids, unsaturated phthalic acids, unsaturated sulfophthalic acids,
unsaturated sulfoisophthalic
acids, unsaturated phthalamic acids, unsaturated sulfophthalamic acids,
unsaturated alkyl
ketone sulfonic acids, unsaturated hydroxyalkane-1-sulfonic acids, unsaturated
lactone
sulfonic acids, unsaturated sulfonic acid amides, unsaturated sulfonic acid
diamides,
unsaturated alkyl phenol sulfuric acid esters, unsaturated alkoxylated alkyl
phenol sulfuric
acid esters, unsaturated alkylatcd cycloalkyl sulfuric acid esters,
unsaturated alkoxylated
alkylated cycloalkyl sulfuric acid esters, unsaturated dendritic polysulfonic
acids, unsaturated
dendritic polycarboxylic acids, unsaturated dendritic polyphosphoric acids,
unsaturated
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sarcosinic acids, unsaturated isethionic acids, and unsaturated tauric acids,
and mixtures
thereof.
Additionally in accordance with the present invention, suitable ethylenically
unsaturated acids of the present invention include unsaturated fluorinated
carboxylic acids,
unsaturated fluorinated sulfonic acids, unsaturated fluorinated sulfate acids,
unsaturated
fluorinated phosphonic and phosphinic acids, and mixtures thereof.
In general, the substantially saturated nitrogenous bases of the present
invention are
any bases which contain at least one nitrogen atom, and are capable of forming
a salt with the
ethylenically unsaturated acid. The saturated nitrogenous bases suitable for
use in the present
invention include any primary, secondary or tertiary amine, which has at (east
one Ci-Cza
alkyl group. Preferably, the alkyl groups of such amines have from about 12 to
about 22
carbon atoms, and may be substituted or unsubstituted. Such amines, include
for example,
stearamido propyl dimethyl amine, diethyl amino ethyl stearamide, dimethyl
stearamine,
dimethyl soyamine, soyamine, myristyl amine, tridecyl amine, ethyl
stearylamine, N-
tallowpropane diamine, ethoxylated (5 moles E.O.) stearylamine, dihydroxy
ethyl
stearylamine, and arachidyibehenylamine and mixtures thereof.
Auxiliary Polymerizable Surface Active Agents
The present invention encompasses the use of auxiliary polymerizable surface
active
agents, i.e. polymerizable surface active agent known to those skilled in the
art, in
combination with the polymerizable surface active agents, homopolymeric
surface active
agents, and supplemental surface active agents described herein. Examples of
auxiliary
polymerizable surface active agents useful in the present invention are shown
below in Table
I.
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Table I: Auxiliary Polymerizable Surface Active Agents
CH3
Diallyl Amine Pluronics - BASF ~ N ~p~p~0~ ~~
'' HI
m
Linoleic Alcohol Derivatives -
IICI IR n O
Allyl Alkyl Phenol Derivatives
DKS (Japan) '
o~o~'o~x
n J
Derivatives - PPG O
O~/O. Rt
l
Allyl Alcohol Alkenyl Succinic , ° °
Anhydride Derivatives - KAO "o 0
(Japan)
Polystep RA Series (Malefic ~ o o so,Na ,
Derivatives) - Stepan Co.
Malefic Derivatives - Rhone o
Poulenc R~o~so3Na
n ,
Trem LF-40 Allyl
Sulfosuccinate Derivatves -
Henkel
Additional auxiliary polyrnerizable surfactants useful herein, for example,
are generally
disclosed in Polymerizable Surfactants Guyot, A. Current Opinions in Colloid
and Sa~rface
Science, 1996, pg. 580-585; Reactive Surfactants in Emulsion Polymerization
Guyot, A.; et.
al; Advances in Polymer Science, Vol. 11, Springer-Verlag, Berlin, 1994, pg.43-
65; and
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Polymerizable Surfactant, Holmberg, K., Progress in Organic Coatings, 20
(1992) 325-337
(all incorporated herein in their entirety).
Suaplemental Surface Active Agents
S Generally, optional non-polymerizable surface active agents may be utilized
in the
present invention. These supplemental surfactants are generally combined with
the
agricultural technical to for the oil phase of the formulation. The
supplemental surface active
agents are generally anionic, nonionic, cationic or amphoteric surfactants or
mixtures thereof,
and are typically used as in a concentration of about 0.01 to about 20.0
percent by weight,
based on the total weight of surface active agents (i.e. both polymerizable
and non-
polymcrizable). Somewhat more preferably, the supplemental surface active
agents are used
in a concentration of about 0.01 to about 5.0 percent by weight, based on the
total weight of
surface active agents (i.e. both polymerizable and non-polymerizable).
Suitable supplemental nonionic surface active agents are generally disclosed
in U.S.
i 5 Pat. No. 3,929,678, Laughlin et al., issued Dec. 30, 1975, at column, 13
line 14 through
column 16, line 6, incorporated herein by reference. Generally, the
supplemental nonionic
surface active agent is selected from the group comprising polyoxyethylenated
alkylphenols,
polyoxyethyleneated straight chain alcohols, polyoxyethyleneated branched
chain alcohols,
polyoxyethyleneated polyoxypropylene glycols, polyoxyethyIeneated mercaptans,
fatty acid
esters, glyceryl fatty acid esters, polyglyceryl fatty acid esters, propylene
glycol esters,
sorbitol esters, polyoxyethyleneated sorbitol esters, polyoxyethylene glycol
esters,
polyoxyethyleneated fatty acid esters, primary alkanolamides, ethoxylated
primary
alkanolamides, secondary alkanolamides, ethoxylated secondary alkanolamides,
tertiary
acetylenic glycols, polyoxyethyleneated silicones, N-aIkyIpyrrolidones,
alkylpolyglycosides,
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alkylpolylsaccharides, EO-PO block polymers, polyhydroxy fatty acid amides,
amine oxides
and mixtures thereof. Further, exemplary, non-limiting classes of useful
supplemental
nonionic surface active agents are listed below:
1. The polyethylene, polypropylene, and polybutylene oxide condensates of
alkyl
S phenols. In general, the polyethylene oxide condensates are preferred. These
compounds include the condensation products of alkyl phenols having an alkyl
group
containing from about 6 to 12 carbon atoms in either a straight or branched
chain
configuration with the alkylene oxide. In a preferred embodiment, the ethylene
oxide
is present in an amount equal to from about 1 to about 25 moles of ethylene
oxide per
mole of alkyl phenol. Commercially available nonionic surfactants of this type
include Igepal~ CO-G30, marketed by Stepan Company, Canada; and Triton~ X-45,
X-114, X-100 and X-102, all marketed by the Union Carbide Company.
2. The condensation products of aliphatic alcohols with from about 1 to about
25
moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either
be straight
or branched, primary or secondary, and generally contain from about 8 to about
22
carbon atoms. Particularly preferred are the condensation products of aicohols
having
an alkyl group containing from about G to about 1 1 carbon atoms with from
about 2 to
about 10 moles of ethylene oxide per mole of alcohol. Examples of commercially
available nonionic surfactants of this type include Tergitol~ 15-S-9 (the
condensation
products of Ci~-C~5 linear alcohol with 9 moles of ethylene oxide), Tergitol~
24-L-G
NMW (the condensation products of C,z-C,4 primary alcohol with G moles of
ethylene
oxide with a narrow molecular weight distribution), both marketed by Union
Carbide
Corporation; Neodol~ 91-8 (the condensation product of C9-C" linear alcohol
with 8
moles of ethylene oxide), Neodol~ 23-G.5 (the condensation product of C, 2-C,
3 linear
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alcohol with 6.5 moles of ethylene oxide), Neodol~ 45-7 (the condensation
product of
C,4-C,5 linear alcohol with 7 moles of ethylene oxide}, Neodol~ 91-6 (the
condensation product of C~-C, i linear alcohol with 6 moles of ethylene
oxide),
marketed by Shell Chemical Company, and Kyro~ EOB (the condensation product of
C,3-C,5 linear alcohol with 9 moles of ethylene oxide), marketed by the
Procter and
Gamble Company.
3. The condensation products of ethylene oxide with a hydrophobic base formed
by
the condensation of propylene oxide with propylene glycol. The hydrophobic
portion of these compounds preferably has a molecular weight of from about
1500 to about 1880 and exhibits water insolubility. The addition of
polyoxyethylene
moieties to this hydrophobic portion tends to increase the water solubility of
the
molecule as a whole, and the liquid character of the product is retained up to
the point
where the polyoxyethylene content is about SO% of the total weight of the
condensation product, which corresponds to condensation with up to about 40
moles
1 S of ethylene oxide. Examples of compounds of this type include certain of
the
commercially available Pluronic~ surfactants, marketed by BASF.
4. The condensation products of ethylene oxide with the product resulting from
the
reaction of propylene oxide and ethylenediamine. The hydrophobic moiety of
these
products consists of the reaction product of ethylenediamine and excess
propylene
oxide, and generally has a molecular weight of from about 2500 to about 3000.
This
hydrophobic moiety is condensed with ethylene oxide to the extent that the
condensation product contains from about 40 % to about 80 % by weight of
polyoxyethylene and has a molecular weight of from about 5,000 to about
11,000.
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Examples of this type of nonionic surfactant include certain of the
commercially
available Tetronic~ compounds, marketed by BASF.
5. Semi-polar nonionic surfactants are a special category of supplemental
nonionic
surface active agents which include water-soluble amine oxides containing on
alkyl
moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from
the
group comprising alkyl groups and hydroxyalkyl groups containing from about 1
to
about 3 carbon atoms; and water-soluble sulfoxides containing alkyl moieties
of from
about 10 to about 18 carbon atoms and a moiety selected from the group
comprising
alkyl groups and hydroxyalkyl groups of from about 1 to about 3 carbon atoms.
6. Alkylpolysaccharides disclosed in U.S. Pat. No. 4,565,647, Lenado, issued
Jan. 21,
1986, incorporated herein by reference, having a hydrophobic group containing
from
about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon
atoms
and a polysaccharide, e.g., a polyglucoside, hydrophilic group containing from
about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably
from
about 1.3 to about 2.7 saccharide units. Any reducing saccharide containing 5
or 6
carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can
be
substituted for the glucosyl moieties. (Optionally, the hydrophobic group is
attached
at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as
opposed to a
glucoside or galactoside.) The intersaccharide bonds can be, e.g., between the
one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6-
positions on
the preceding saccharide units.
7. An ethyl ester ethoxylate and/or alkoxylate such as those described in U.S.
Pat. No.
5,220,046, incorporated herein by reference. These material may be prepared
according to the procedure set forth in Japanese Kokai patent application No.
HEI S
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[1993]-222396. For example, they may be prepared by a one-step
condensation reaction between an alkyl ester and an alkylene oxide in the
present of a
catalytic amount of magnesium together with another ion selected from the
group of
Al+3, Ga+3, In+3, Co+3, Sc+3, La+; and Mn+3. Optionally, and less desirably,
there can
be a polyalkyleneoxide chain joining the hydrophobic moiety and the
polysaccharide
moiety. The preferred alkyleneoxide is ethylene oxide. Typical hydrophobic
groups include alkyl groups, either saturated or unsaturated, branched or
unbranched,
containing from about 8 to about 18, preferably from about 12 to about 14
carbon
atoms; n is 2 or 3, preferably 2; t is from about 0 to about 10, preferably 0;
and x is
from about 1.3 to about 10, preferably from about 1.3 to 3, most preferably
from about
1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare
these
compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then
reacted
with glucose, or a source of glucose, to form the glucoside (attachment at the
t-
position). The additional glucosyl units can then be attached between their I-
position
I S and the preceding glycosyl units 2-, 3-, 4-, and/or O-position, preferably
predominately the 2-position.
Examples of suitable supplemental amphotcric surface active agents are
selected from
the group comprising alkyl glycinates, propionates, imidazolines,
amphoalkylsulfonates sold
as "Miranol"~ by Rhone Poulenc, N-alkylaminopropionic acids, N-
alkyliminodipropionic
acids, imidazoline carboxylates, N-alkylbetaines, amido propyl betaines,
sarcosinates,
cocoamphocarboxyglycinates, amine oxides, sulfobetaines, sultaines and
mixtures thereof.
Additional suitable amphoteric surfactants include cocoamphoglycinate,
cocoamphocarboxyglycinate, lauramphocarboxyglycinate, cocoamphopropionate,
lauramphopropionate, stearamphoglycinate, cocoamphocarboxy-propionate,
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tallowamphopropionate, tallowamphoglycinate, oleoamphoglycinatc,
caproamphoglycinate,
caprylamphopropionate, caprylamphocarboxyglycinate, cocoyl imidazoline, lauryi
imidazoline, stearyl imidazoline, behenyl imidazoline, behenylhydroxyethyl
imidazoline,
caprylamphopropylsulfonate, cocamphopropylsulfonate, stearamphopropyl-
sulfonate,
oleoamphopropylsulfonate and the like.
Examples of supplemental amine oxide surface active agents which are generally
suitable for use in the present invention are alkylamine and amidoamine
oxides. Examples of
supplemental betaine and sultaine surface active agents which are suitable for
use in the
present invention arc alkyl betaines and sultaines sold as "Mirataine"~ by
Rhone Poulenc ,
"Lonzaine"~ by Lonza, Inc., Fairlawn, N.J. Examples of supplemental betaincs
and sultaines
are cocobetaine, cocoamidoethyl betaine, cocoamidopropyl betaine, lauryl
betaine,
lauramidopropyl betaine, palmamidopropyl betaine, stearamidopropyl betaine,
stearyl bctaine,
coco-sultainc, lauryl sultaine, tallowamidopropyl hydroxysultaine and the
like.
Examples of supplemental cationic surface active agents useful in the present
invention arc fatty amine salts, fatty diamine salts, polyamine salts,
quaternary ammonium
compounds, polyoxyethyleneated fatty amines, quaternized polyoxycthylcncated
fatty amines,
amine oxides and mixtures thereof.
Examples of suitable supplemental cationic surface active agents are disclosed
in the
following documents, all incorporated by reference herein: M. C. Publishing
Co.,
,'I~IcC'utcheon 's Detergents & Emulsifiers, (North American Ed., 1993);
Schwartz et al.,
Sitrjace Active Agents, Their Chemistry and Technology, New York; Interscience
Publisher,
1949; U.S. Pat. No. 3,155,591, Hilfer, issued Nov. 3, 1964; U.S. Pat. No.
3,929,678, Laughlin
et al., issued Dec. 30, 1975; U.S. Pat. No. 3,959,461, Bailey et al., issued
May 25, 1976; and
U.S. Pat. No. 4,387,090, Bolich, Jr., issued June 7, 1983.
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Examples of supplemental cationic surface active agents in the form of
quaternary
ammonium salts include dialkyldiethyl ammonium chlorides and trialkyl methyl
ammonium
chlorides, wherein the alkyl groups have from about 12 to about 22 carbon
atoms and are
derived from long-chain fatty acids, such as hydrogenated tallow fatty acid
(tallow fatty acids
yield quaternary compounds wherein Ri and RZ have predominately from about 16
to about
18 carbon atoms). Examples of supplemental quaternary ammonium salts useful
herein
include ditallowdimethyl ammonium chloride, ditallowdimethyl ammonium methyl
sulfate,
dihexadecyl dimethyl ammonium chloride, di-(hydrogenated tallow} dimethyl
ammonium
chloride, dioctadecyl dimethyl ammonium chloride, dieicosyl dimethyl ammonium
chloride,
didocosyl dimethyl ammonium chloride, di-(hydrogenated tallow) dimethyl
ammonium
acetate, dihexadecyl dimethy! ammonium chloride, dihexadecyl dimethyol
ammonium
acetate, ditallow dipropyl ammonium phosphate, ditallow dimethyl ammonium
nitrate, di-
(coconutalkyl) dimethyl ammonium chloride, and stearyl dimethyl benzyl
ammonium
chloride.
Salts of primary, secondary and tertiary fatty amines are also suitable
supplemental
cationic surface active agents. The alkyl groups of such supplemental amines
preferably have
from about 12 to about 22 carbon atoms, and may be substituted or
unsubstituted. Such
amines, useful herein, include stearamido propyl dimethyl amine, diethyl amino
ethyl
stearamide, dimethyl stearamine, dimethyI soyamine, soyamine, myristyl amine,
tridecyl
amine, ethyl stearylamine, N-tallowpropane diamine, ethoxylated (5 moles E.O.)
stearylamine, dihydroxy ethyl stearylamine, and arachidylbehenylamine.
Suitable
supplemental amine salts include the halogen, acetate, phosphate, nitrate,
citrate, lactate and
alkyl sulfate salts. Such supplemental salts include stearylamine hydrogen
chloride, soyamine
chloride, stearylamine formate, N-tallowpropane diamine dichloride and
stearamidopropyl
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dimethylamine citrate. Supplemental cationic amine surfactants included among
those useful
in the present invention are also disclosed in U.S. Pat. No. 4,275,055,
Nachtigal, et al., issued
June 23, 1981, inco~orated herein by reference.
Supplemental cationic surface active agents which are especially useful are
quaternary
ammonium or amino compounds having at least one N-radical containing one or
more
nonionic hydrophilic moieties selected from the group comprising alkoxy,
polyoxyalkylene,
alkylamido, hydroxyalkyl, and alkylester moieties, and combinations thereof.
The
compounds contain at least one hydrophilic moiety within 4, preferably within
3, carbon
atoms (inclusive) of the quaternary nitrogen or cationic amino nitrogen.
Additionally, carbon
atoms that are part of a hydrophilic moiety, e.g., carbon atoms in a
hydrophilic
polyoxyalkylene (e.g.,-CHZ-CHZ-O-), that are adjacent to other hydrophilic
moieties are not
counted when determining the number of hydrophilic moieties within 4, or
preferably 3,
carbon atoms of the cationic nitrogen. In general, the alkyl portion of any
hydrophilic moiety
is preferably a C,-C~ alkyl. Suitable hydrophile-containing radicals include,
for example,
l5 cthoxy, propoxy, polyoxyethylenc, polyoxypropylene, ethylamido,
propylamido,
hydroxymethyl, hydroxyethyl, hydroxypropyl, methyl ester, ethyl ester, propyl
ester, or
mixtures thereof, as nonionic hydrophile moieties.
Among the supplemental cationic surface active agents useful herein are those
of the
general formula:
R~
R3 X.
Rz~ ~Ra
wherein R,, R2, R3, and R4 comprise, independently, substituted or
unsubstituted substantially
saturated hydrocarbyl chains of from about 1 to about 30 carbon atoms, or a
hydrocarbyl
having from about I to about 30 carbon atoms and containing one or more
aromatic, ether,
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ester, amido, or amino moieties present as substituents or as linkages in the
radical chain,
wherein at least on of the R,-R.~ groups contains one or more hydrophilic
moieties selected
from the group comprising alkoxy (preferably C,-C~ alkoxy), polyoxyalkylene
(preferably C,-
C3 polyoxyalkylene), alkylamido, hydroxyalkyl, aikylester and combination
thereof.
Preferably, the cationic conditioning surfactant contains from about 2 to
about 10 nonionic
hydrophile moieties located within the about stated ranges. For purposes
herein, each
hydrophilic amido, alkoxy, hydroxyalkyl, alkylester, alkylamido or other unit
is considered to
be a distinct nonionic hydrophile moiety. X- is a substantially saturated
soluble salt forming
anion preferably selected from the group comprising halogens (especially
chlorine), acetate,
phosphate, nitrate, sulfonate, and alkyl sulfate radicals.
Preferred supplemental cationic surface active agents include polyoxycthylene
(2)
stcaryl methyl ammonium chloride, methyl bis-(hydrogenated tallowamidoethyl) 2-
hydroxyethyl ammonium methyl sulfate, polyoxypropylene (9) diethyl methyl
ammonium
chloride, tripolyoxyethylene (total PEG-10) stearyl ammonium phosphate, bis-(N-
hydroxyethyl-2-oleyl imidazolinium chloride) polyethylene glycol (1), and
isododecylbenzyl
triethanolammonium chloride.
Other supplemental ammonium quaternary and amino surface active agents include
those of the above general formula in the form of ring structures formed by
covalently linking
two of the radicals. Examples include imidazolines, imidazoliniums, and
pyridiniums, etc.,
wherein said compound has at least one nonionic hydrophile-containing radical
as set forth
above. Specific examples include 2-heptadecyl-4,5-dihydro-1H-imidazol-1-
ethanol, 4,5-
dihydro-1-(2-hydroxyethyl)-2-isoheptadecyl-1-phenylmethylimidazolium chloride,
and I-[2-
oxo-2-[[2-[(1-oxoctadecyl)oxy]ethyl]amino]ethyl] pyridinium chloride.
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Salts of primary, secondary and tertiary fatty amines are also preferred
supplemental
cationic surfactant materials. The alkyl groups of such amines preferably have
from about 1
to about 30 carbon atoms and must contain at least one, preferably about 2 to
about 10,
nonionic hydrophilic moieties selected from the group comprising alkoxy,
polyoxyalkylene,
alkylamido, hydroxyalkyl, and alkylester groups, and mixtures thereof.
The supplemental anionic surface active agents suitable for use in the present
invention are generally the sodium, potassium, calcium, ammonium or
alkanolamine salts of
any substantially saturated sulfonic acid, carboxylic acid, or phosphoric
acid, or a mixture
thereof. More specifically, supplemental anionic surface active agents
suitable for use in the
present invention are generally the sodium, potassium, calcium, ammonium or
alkanolamine
salts of saturated sulfonic acids, sulfinic acids, sulfenic acids, sulfonic
acid esters, carboxylic
acids, phosphonic acids, phosphinic, phosphenic acids, polysulfonic acids,
sulfonic acids of
oits, paraffin sulfonic acids, lignin sulfonic acids, petroleum sulfonic
acids, tall oil acids,
olefin sulfonic acids, hydroxyolefin sulfonic acids, polyolefin sulfonic
acids, polyhydroxy
polyolefin sulfonic acids, carboxylic acids, perfluorinated carboxylic acids,
carboxylic acid
sulfonates, alkoxylated carboxylic acid sulfonic acids, polycarboxylic acids,
polycarboxylic
acid polysulfonic acids, alkoxylated polycarboxylic acid polysulfonic acids,
phosphoric
acids, alkoxylated phosphoric acids, polyphosphoric acids, and alkoxylated
polyphosphoric
acids, fluorinated phosphoric acids, phosphoric acid esters of oils,
phosphinic acids,
alkylphosphinic acids, aminophosphinic acids, polyphosphinic acids, vinyl
phosphinic
acids, phosphonic acids, polyphosphonic acids, phosphonic acid alkyl esters, a-
phosphono
fatty acids, oragnoamine polymethylphosphonic acids, organoamino dialkylene
phosphonic
acids, alkanolamine phosphonic acids, triaIkyledine phosphonic acids,
acylamidomethane
phosphonic acids, alkyliminodimethylene diphosphonic acids, polymethylene-
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bis(nitrilodimethylene)tetraphosphonic acids, alkyl bis(phosphonoalkylidene)
amine oxide
acids, esters of substituted aminomethylphosphonic acids, phosphonamidic
acids, acylated
amino acids (e.g., amino acids reacted with alkyl acyl chlorides, alkyl esters
or carboxylic
acids to produce N-acylamino acids), N-alkyl acylamino acids, and acylated
protein
hydrolysatcs, and mixtures thereof.
Other supplemental anionic surface active agents suitable for use in the
present
invention are the sodium, potassium, calcium, ammonium or alkanolamine salts
of saturated
linear or branched alkylbenzene sulfonic acids, alkyl sulfuric acid esters,
alkoxylated alkyl
sulfuric acid esters, a-sulfonated alkyl ester acids, a-sulfonated ester
diacids, alkoxylated
f 0 cx-sulfonated alkyl ester acids, a-sulfonated dialkyl diester acids, di-a-
sulfonated dialkyl
diester acids, cx-sulfonated alkyl acetate acids, primary and secondary alkyl
sulfonic acids,
perfluorinated alkyl sulfonic acids, sulfosuccinic mono- and diester acids,
polysulfosuccinic
polyester acids, sulfoitaconic diester acids, sulfosuccinamic acids,
sulfosuecinic amide
acids, sulfosuccinic imidc acids, phthalic acids, sulfophthalic acids,
sulfoisophthalic acids,
phthalamic acids, sulfophthalamic acids, alkyl ketone sulfonic acids,
hydroxyalkane-1-
sulfonic acids, lactone sulfonic acids, sulfonic acid amides, sulfonic acid
diamidcs, alkyl
phenol sulfuric acid esters, alkoxylatcd alkyl phenol sulfuric acid esters,
alkylated cycioalkyl
sulfuric acid esters, alkoxylated alkylated cycloalkyl sulfuric acid esters,
dendritic
poiysulfonic acids, dendritic polycarboxylic acids, dendritic polyphosphoric
acids,
sarcosinic acids, isethionic acids, and tauric acids, and mixtures thereof.
Additionally in accordance with the present invention, supplemental anionic
surface
active agents suitable for use in the present invention are generally the
sodium, potassium,
calcium, ammonium or alkanolamine salts of saturated fluorinated carboxylic
acids,
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fluorinated sulfonic acids, fluorinated sulfate acids, fluorinated phosphonic
and phosphinic
acids, and mixtures thereof.
In a preferred embodiment of the present invention, the polymerization process
is
conducted in the absence of any non-polymerizable, supplemental surfactant, as
the
polymerizable surface active agents of the present invention display excellent
capacity for
producing emulsion stability characteristics in an emulsion polymerization.
In another embodiment of the present invention, the polymerizable surface
active
agents of the present invention may be used as co-monomers with the
ethylenically
unsaturated monomers) to modify the physical properties of the resulting
polymer. In this
embodiment, supplemental surface active agents also may be used as additives
to the
polymerization, e.g., in amounts of from about 3 to 6 weight percent, based on
the total
weight of monomer. Although somewhat less preferred, in a further embodiment
of the
present invention, any conventional organic solvent, which may be a solvent
for both the
monomers) and/or polymer, or just the monomers) may be used.
Initiators and Additives
Organic or inorganic initiators may be used to initiate the polymerization
reaction. A
sufficient quantity of a polymerization initiator (such as a conventional free
radical initiator)
is typically introduced into the polymerization medium to cause polymerization
of the
monomers) at the particular temperatures employed. Initiators used in
polymerization
processes may be of the type which produce free radicals and conveniently are
peroxygen
compounds, for example: inorganic peroxides such as hydrogen peroxide and
inorganic
persulfate compounds such as ammonium persulfate, sodium persulfate and
potassium per-
sulfate; organic hydroperoxides such as cumene hydroperoxide and tertiary
butyl
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hydroperoxide; organic peroxides such as benzoyl peroxide, acetyl peroxide,
lauroyl peroxide,
peroxydicarbonate esters such as diisopropyl peroxydicarbonate, peracetic acid
and per-
benzoic acid, sometimes activated by water-soluble reducing agents such as
ferrous
compounds, sodium bisulfite or hydroxylamine hydrochloride, and other free
radical
producing materials such as 2,2'-azobisisobutyronitrile.
A further additive which may be added to the mixture contents is a
conventional chain
transfer agent, such as an alkyl polyhalide or mercaptan. Examples of suitable
chain transfer
agents include bromoform, carbon tetrachloride, carbontetrabromidc,
bromoethane, C,-C,Z
alkyl mercaptans, e.g., dodecylmercaptan, thiophenol, and hydroxyalkyl
mercaptans, e.g.,
mercaptoethanol.
Optional Water Immicsible Solvents
Although less preferable, small amounts of water-immiscible solvents may be
used in
the agricultural formulations of the present invention. Specific examples of
these water-
immiscible solvents are the aromatic liquids, particularly alkyl substituted
benzenes such as
1 S xylene or propyl benzene fractions, and mixed naphthalene and alkyl
naphthalene fractions;
mineral oils, substituted aromatic organic liquids such as dioctyl phthalate;
kerosene,
polybutenes; diaikyl amides of various fatty acids, particularly the dimethyl
amides of fatty
acids such as the dimethyl amide of caprylic acid; chlorinated aliphatic and
aromatic
hydrocarbons such as l, l, 1-trichloroethane and chlorobenzene, esters of
glycol derivatives,
such as the acetate of the n-butyl, ethyl, or methyl ether of diethylene
glycol, the acetate of the
methyl ether of dipropylene glycol, ketones such as isophorone and trimethyl
cyclohexanone
(dihydroisophorone) and the acetate products such as hexyl, or heptyl acetate.
The preferred
organic liquids are xylene, propyl benzene fractions, dihydroisophorone, and
alkyl acetates.
Agricultural Tcchnicals
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Agriculatural technicals useful in the present invention include pesticides,
herbicides
and fungicides. Pesticidal substances suitable for use in the composition in
accordance with
the invention include, for example, amitraz, bromophos, azinphos-ethyl,
bromopropylate,
azinphos-methyl, butocarboxin, *benzoximate, butoxycarboxin, bifenthrin,
chlordimeform,
binapacryl, chlorobenzilate, bioresmethrin, chloropropylate, chlorpyrifos,
chlorphoxim,
chlorpyrifos-methyl, fenamiphos, cyanophos, fenobucarb, *cyfluthrin, gamma-
HCH,
*cypermethrin, methidathion, *deltamethrin, parathion methyl, *dicofol,
phosalone,
dioxabenzafos, phosfolan, dioxacarb, phosmet, *endosulfan, promecarb, EPN,
quinaIphos,
Ethiofencarb, resmethrin, dinobuton, temephos, tetradifon, tetramethrin,
tralomethrin,
xylylcarb, N-2,3-dihydro-3-methyl-1,3-thiazol-2-ylidene-2,4- xylidine (wherein
compounds
denoted with a "*" correspond to 1-[3,5-dichloro-4-(1,1,2,2-tetrafluoro ethoxy
phenylJ-3-(2,6-
difluorobenzoyl) urea), and mixtures thereof. Other pesticidal materials
include acylurea
insecticides, organophosphorous insecticides, pyrethroid insecticides,
aryloxyaryl herbicides
and sulfonamide herbicides. Examples of such pesticides include the acylurea
insecticides
described in U.S. Pat. Nos. 4,148,902: 4,173,637 and Re. 30,563, which are
incorporated
herein by reference, and 1-[3,5-dichloro-4-((5-trifluoromethyl)-3-chloro-2-
pyridyloxy)phenylJ-3-(2,6-difluorobenzoyl) urea (common name Chlorfluazuron):
the
organophosphorous insecticides described in U.S. Pat. Nos. 3,244,586;
4,429,125; 4,654,329
and 4,729,987 which are incorporated herein by reference, chlorpyrifos and
chlorpyrifos
methyl: the pyrethroid insecticides such as cyperrnethrin, permethrin and
fenvalerateahe
aryloxyaryl herbicides described in U.S. Pat. Nos. 4,550,192: 4,551,170 and
4,750,931 which
are incorporated herein by reference, 2-(4-((5-trifluoromethyl)-2-
pyridinyl)oxy)phenoxy)propanoic acid; 2-(4-((3-chloro-5-trifluoromethyl)-2-
pyridinyl)oxy)phenoxy)propanoic acid, methyl ester: 2-(4-((3-chloro-5-
trifluoromethyl)-2-
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pyridinyl)oxy)phenoxy)propanoic acid, ethyl ester: and 2-(4-((3-fluoro-5-
trifluoromethyl)-2-
pyridinyl)oxy)phenoxy)propanoic acid, methyl ester: and the sulfonamide
herbicides
described in U.S. Pat. Nos. 4,731,446: 4,740,233: 4,741,764 and 4,755,212
which are
incorporated herein by reference, especially N-(2,6-dichlorophenyl)-5,7-
dimethoxy-1,2,4-
S triazolo (l,Sa)pyrimidine-2-sulfonamide: N-(2,6-dichloro-3-methylphenyl)-5,7-
dimethoxy-
1,2,4-triazolo (1,5a)-pyrimidine-2-sulfonamide; N-(2,6-dichloro-phenyl)-5-
methyl-7-
methylthio-1,2,4-triazolo (l,Sa)pyrimidine-2-sulfonamide; N-(2-
trifluoromethylphenyl)-5-
methyl-7-methylthio-1,2,4-triazolo-(1, Sa) pyrimidine-2-sulfonamide: N-(2,6-
dichloro-3-
mcthylphenyl)-7-methoxy-5-methyl-1,2,4-triazolo (1,5a)-pyrimidine-2-
sulfonamide: and N-
(2,6-dichloro-3-methylphenyl)-7-ethoxy-S-methyl-1,2,4-triazolo
(1,5a)pyrimidine-2-
sulfonamide.
Fungicidal substances suitable for use in the composition in accordance with
the
invention include, for example
benalaxyl myclobutanil
bupirimate nuarimol
carboxin oxycarboxin
dodemorph ergosterol
dodine fenarimol
ditalimfos penconazole
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prochIoraz tolclofos-methyl
triadimefon triadimenol
and mixtures thereof.
Herbicidal substances
suitable for use
in the composition
in accordance with
the
invention include,
for example
aclonifen chlorpropham
alachlor cycloxydim
anilophos diclofop-methyl
bcnfluralin diethatyl
bensulide dimethachlor
benzoylprop-ethyl dinitramine
bifenox ethalfluralin
bromoxynil ethofumesate
butralin fenoxaprop ethyl
flurochloridone flamprop-methyl
fluchloralin phenisopham
flumetralin phenmedipham
fluorodifen profluralin
fluoroglycofen
ethyl
propachlor
flurecol butyl propanil
fluoroxypyr ester pyridate
haloxyfop-methyl *quizalafop-ethyl
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haloxyfop ethoxyethyl
tridiphane
monalidc *trifluralin
napropamide
nitrofen
oxadiazon
*oxyfluorfen
*pendimethalin.
and mixtures thereof.
Of the above active materials, those indicated * have a water solubility of
less than
500 ppb, and thus are of direct relevance only to those aspects of the
invention concerned with
the nature of the polymeric latex.
Other pesticides such as the nitrification inhibitor nitrapyrin may al be
employed. The
pesticide may be an organosoluble derivative of a pesticidal compound which is
itself poorly
organosoluble or insoluble, such as cyhexatin dodecylbenzene sulphonate.
The compositions of the invention may also include optional adjuvants such as
freezing point depressants preferably in amounts of 0-15%, flow aids to
prevent caking or aid
in the redispersion of bottom sediment preferably in amounts of 0-5%,
thickening agents
preferably amounts of 0-3% and defoamers preferably 0-1% to improve the
overall properties
under field storage and use conditions.
Similarly conventional pesticide additives such as adjuvant solvents,
surfactants for
increasing penetration of the active substances or salts may be incorporated
into the
compositions to maintain or improve biological efficacy of the composition.
These may be
incorporated into the oil phase or aqueous phase as appropriate.
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All documents, e.g., patents and journal articles, cited above or below are
hereby
incorporated by reference in their entirety.
In the following examples, all amounts are stated in percent by weight unless
indicated
otherwise.
One skilled in the art will recognize that modifications may be made in the
present
invention without deviating from the spirit or scope of the invention. The
invention is
illustrated further by the following examples which are not to be construed as
limiting the
invention or scope of the specific procedures or compositions described
herein. All
documents, e.g., patents and journal articles, cited above or below are hereby
incorporated by
reference in their entirety.
As used in the Examples appearing below, the following designations, symbols,
terms
and abbreviations have the indicated meanings:
Material Definition
I S Polystep~ A-13 Linear dodecylbenzene sulfonic acid (commercially available
from
Stepan Company, Northfield Illinois)
Polystep~ A-16 Branched dodecylbenzene sulfonic acid, sodium salt
(commercially
available from Stepan Company, Northfield Illinois)
Polystep~ A-17 Branched dodecylbenzene sulfonic acid (commercially available
from
2a Stepan Company, Northfield Illinois)
Cedephos CP-610 Nonyl Phenol 9-EO Phosphoric Acid Ester (commercially
available
from Stepan Company, Northfield Illinois)
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The amount of agglomerated polymers, or "coagulum", in the resulting lattices
at the
conclusion of the polymerization is determined by collecting the agglomerated
polymers
using a 20 mesh screen that has openings sufficiently large enough to allow
the discrete un-
agglomerated polymers to pass, rinsing the collected agglomerated polymers
with water, and
weighting the remaining agglomerated polymers trapped on the screen. The
percent
coagulum is calculated by dividing the weight of the coagulum by the
theoretical weight of
the entire latex based upon the weights of the ingredients used for the
polymerization reaction.
The viscosity of the resulting lattices following polymerization is determined
by using
a RV Brook field synchro-lechtric viscometer equipped with a No. 3 spindle.
During such
determinations )50 ml of each latex is placed in a 1000 ml beaker and the
viscometer
operated at 25°C and 60 rpm.
The mechanical stability of the lattices following exposure to mechanical
stress is
evaluated to determine the extent to which there is a change in the viscosity
andlor the visual
presence of coagulum. More specifically, two cups of each latex are placed in
a five-cup
stainless steel Hamilton Beach blender, and the blender operated at medium
speed until the
latex coagulates. Failure of the latex is the point at which coagutum
separation can be visually
observed; a longer time of blending at medium speed without coagulum
separation, i.e. a
longer time before failure, is a highly desirable characteristic of a latex.
Solids of lattices were determined by concentrating the latex at 120°C
in an oven to
remove all volitiles, and subsequently weighing the residue. The pH of each
solution was
measured using an Orion 210 pH meter. Particle size was measured using a
Nicomp 370,
[submicron analyzer , (up to 2 microns)].
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The particle size of the resulting lattices is determined with a NICOMP 370C
Auto-
dilution particle size analyzer using standard methods and procedures for
operation of such
equipment and such data recorded for 50% volume in units of nano-meters.
The water sensitivity, e.g. hydrophobicity, of the resulting lattices was
determined by
ASTM D724-45.
The allylamine and propyl amine may be obtained from Aldrich Chemical Company
(USA).
In the following examples, all amounts are stated in percent by weight of
active
material unless indicated otherwise. One skilled in the art will recognize
that modifications
may be made in the present invention without deviating from the spirit or
scope of the
invention. The invention is illustrated further by the following examples
which are not to be
construed as limiting the invention or scope of the specific procedures or
compositions
described herein.
Latex Examples
1S
Example 1:
A methylmethacrylate/butylacrylate/methacrylic acid (MMA/BA/MMA) co-polymer
(in a weight ratio of about 48:49:3), in combination with the allylamine salt
of
dodecylbenzenesulfonic acid (ADDBS), is prepared as follows. About 254 g of
deionized
water and about 10.6 g of ADDBS (as a 22% active aqueous solution), are placed
in a reactor
suitable for emulsion polymerization, equipped with agitation means, heating
means and
cooling means. With agitation, the reactor is purged with nitrogen (99% pure),
and heated to
about 80-82°C. The temperature of the reactor contents is adjusted to
about 77-79°C, and
about 7S g of the monomer mixture (20% of a total of 374 g of the MMA/BA/MMA
2S monomer mixture in the ratio above) is added to the reactor. After 10
minutes, 16.9 g of a
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solution of ammonium persulfate (20% of the total solution of 1.9 g of
ammonium persulfate
dissolved in 82.5 g of water) is added to the reactor over a period of about 7
minutes with
continued agitation, during which time there is an exotherm of about 7-
10°C. After the
exotherm is complete, about 299 g of the monomer mixture (the remaining 80%
MMA/BA/MMA monomer mixture), 64.5 g of the ammonium persulfate solution (the
remaining 80 %) , and 15.55g of ADDBS (as the 22% active aqueous solution) are
simultaneously charged to the reactor over a period of 2 hours with continued
agitation, while
keeping the reactor contents at a temperature of about 78-81 °C. The
reactor temperature is
then elevated to about 82-84°C with continued agitation, for about 15
minutes. After this 15
minute period, the reactor is cooled to about 30°C. The resulting latex
product is completely
removed from the reactor and gravity filtered using a first 20 mesh screen and
then a second
250 mesh screen. The total latex coagulum (i.e. solids) from both mesh screens
is collected,
combined and weighed. Various physiochemical properties of the latex are
reported in Table
Example 2 ~Comparativc Example):
A methylmethacrylate/butylacrylate/methacrylic acid (MMA/BA/MMA) co-polymer
(in a weight ratio of about 48:49:3), in combination with the propylamine salt
of
dodecylbenzenesulfonic acid (PDDBS), is prepared as follows. About 330 g of
deionized
water and about 25 g of PDDBS (as a 20% active aqueous solution) are placed in
a reactor
suitable for emulsion polymerization, equipped with agitation means, heating
means and
cooling means. With agitation, the reactor is purged with nitrogen (99% pure),
and heated to
about 80-82°C. The temperature of the reactor contents is adjusted to
about 77-79°C, and
about 75 g of the monomer mixture (20% of a total of 374 g of the MMA/BA/MMA
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monomer mixture in the ratio above) is added to the reactor. After 10 minutes,
15.5 g of a
solution of ammonium persulfate (20 % of the total solution of 1.9 g of
ammonium persulfate
dissolved in 75.6 g of water), is added to the reactor over a period of about
5 minutes with
continued agitation, during which time there is an exotherm of about 3-
5°C. After the
S exotherm is complete, about 299 g of the monomer mixture (the remaining 80%)
and 62 g of
the ammonium persulfate solution (the remaining 80%) are simultaneously
charged tot he
reactor over a period of 2 hours with continued agitation, while keeping the
reactor contents at
a temperature of about 78-82°C. The reactor temperature is then
elevated to about 82-84°C
with continued agitation, for about 15 minutes. After this 15 minute period,
the reactor is
cooled to about 30°C. The resulting latex product is completely removed
from the reactor and
gravity filtered using a first 20 mesh screen and then a second 250 mesh
screen. The total
latex coagulum (i.e. solids) from both mesh screens is collected, combined and
weighed.
Various physiochemical properties of the latex are reported in Table II.
1 S Example.3:
A methylmethacrylate/butylacrylate/methacrylic acid (MMA/BA/MMA) co-polymer
(in a weight ratio of about 46.1:50.8:3.1 ) in combination with the allylamine
salt of nonyl
phenol 9-EO phosphate acid ester (Cedephos CP-610) is prepared as follows.
About 249 g of
deionized water and about 11.0 g of the allyl amine salt of Cedephos CP-610
(as a 20%
active aqueous solution), are placed in a reactor suitable for emulsion
polymerization,
equipped with agitation means, heating means and cooling means. With
agitation, the reactor
is purged with nitrogen (99% pure), and heated to about 75 77°C. The
temperature of the
reactor contents is adjusted to about 71-74°C, and about 74 g of the
monomer mixture (20%
of a total of 371 g of the MMA/BA/MMA monomer mixture in the ratio above) is
added to
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the reactor. After 10 minutes, 15 g of a solution of ammonium persulfate (20%
of the total
solution of 1.9 g of ammonium persulfate dissolved in 74.0 g of water) is
added to the reactor
over a period of about 10 minutes with continued agitation, during which time
there is an
exotherm of about 5-8°C. After the exotherm is complete, about 299 g of
the monomer
S mixture (the remaining 80% MMA/BA/MMA monomer mixture), 60.7 g of the
ammonium
persulfate solution (the remaining 80 %), and 15.3 g of the allyl amine salt
of Cedephos CP-
610 (as a 20% active aqueous solution) are simultaneously charged to the
reactor over a
period of 2 hours with continued agitation, while keeping the reactor contents
at a
temperature of about 78-81 °C. The reactor temperature is then elevated
to about 82-84°C
with continued agitation, for about 15 minutes. After this 15 minute period,
the reactor is
cooled to about 30°C. The resulting latex product is completely removed
from the reactor and
gravity filtered using a first 20 mesh screen and then a second 250 mesh
screen. The total
latex coagulum (i.e. solids) from both mesh screens is collected, combined and
weighed.
Various physiochemical properties of the latex are reported in Table II.
Fxamnle 4 (Comparative Example):
A methylmethacrylate/butylacrylate/methacrylic acid (MMA/BA/MMA) co-polymer
(in a weight ratio of about 46:51:3), in combination with the propylamine salt
of nonyi phenol
9-EO phosphate acid ester (Cedephos CP-610) is prepared as follows. About 251
g of
deionized water and about 10.2 g of propylamine salt of Cedephos CP-610 (as a
20% active
aqueous solution), are placed in a reactor suitable for emulsion
polymerization, equipped with
agitation means, heating means and cooling means. With agitation, the reactor
is purged with
nitrogen (99% pure), and heated to about 75 77°C. The temperature of
the reactor contents is
adjusted to about 71-74°C, and about 75 g of the monomer mixture (20%
of a total of 375 g of
the MMA/BAIMMA monomer mixture in the ratio above) is added to the reactor.
After 10
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minutes, 15 g of a solution of ammonium persulfate (20% of the total solution
of 1.9 g of
ammonium persulfate dissolved in 75.0 g of water) is added to the reactor over
a period of
about 10 minutes with continued agitation, during which time there is an
exotherm of about 8-
10°C. After the exotherm is complete, about 300 g of the monomer
mixture (the remaining
80% MMA/BA/MMA monomer mixture), 61.5 g of the ammonium persulfate solution
(the
remaining 80%), and 15.3 g of the propylamine salt of Cedephos CP-610 (as a
20% active
aqueous solution) are simultaneously charged to the reactor over a period of 2
hours with
continued agitation, while keeping the reactor contents at a temperature of
about 78-80°C.
The reactor temperature is then elevated to about 82-84°C with
continued agitation, for about
15 minutes. After this 15 minute period, the reactor is cooled to about
30°C. The resulting
latex product is completely removed from the reactor and gravity filtered
using a first 20 mesh
screen and then a second 250 mesh screen. The total latex coagulum (i.e.
solids) from both
mesh screens is collected, combined and weighed. Various physiochemical
properties of the
latex are reported in Table II.
Example 5
A methylmethacrylate/butylacrylate/methacrylic acid (MMA/BA/MMA) co-polymer
(in a weight ratio of about (48:49:3), in combination with the allylamine salt
of lauric acid
(ALA) is prepared as follows. About 205 g of deionized water and about 1.6 g
of ALA (as a
20% active aqueous solution), are placed in a reactor suitable for emulsion
polymerization,
equipped with agitation means, heating means and cooling means. With
agitation, the reactor
is purged with nitrogen (99% pure), and heated to about 70-73°C. The
temperature of the
reactor contents is adjusted to about 71-73°C, and about 75 g of the
monomer mixture (20%
of a total of 374 g of the MMA/BA/MMA monomer mixture in the ratio above) is
added to
the reactor. After 10 minutes, 15 g of a solution of ammonium persulfate (20%
of the total
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solution of 1.8 g of ammonium persulfate dissolved in 75.0 g of water) is
added to the reactor
over a period of about 10 minutes with continued agitation, during which time
there is an
exotherm of about 2-3°C. After the exotherm is complete, about 299 g of
the monomer
mixture (the remaining 80% MMA/BA/MMA monomer mixture), 61.5 g of the ammonium
persulfate solution (the remaining 80%), and 29.2 g of the ALA (as a 20%
active aqueous
solution) are simultaneously charged to the reactor over a period of 2 hours
with continued
agitation, while keeping the reactor contents at a temperature of about 78-
81°C. The reactor
temperature is then elevated to about 83-85°C with continued agitation,
for about I S minutes.
After this 15 minute period, the reactor is cooled to about 30°C. The
resulting latex product is
completely removed from the reactor and gravity filtered using a first 20 mesh
screen and
then a second 250 mesh screen. The total latex coagulum (i.c. solids) from
both mesh screens
is collected, combined and weighed. Various physiochemical properties of the
latex are
reported in Table II.
Example 6 (Comparative Example):
A methylmethacrylate/butylacrylate/methacrylic acid (MMA/BA/MMA) co-polymer
(in a weight ratio of about (48:49:3), in combination with the propylamine
salt of lauric acid
(PLA) is prepared as follows. About 206 g of deionized water and about 1.6 g
of PI_A (as a
20% active aqueous solution), are placed in a reactor suitable for emulsion
polymerization,
equipped with agitation means, heating means and cooling means. With
agitation, the reactor
is purged with nitrogen (99% pure), and heated to about 75-77°C. The
temperature of the
reactor contents is adjusted to about 71-73°C, and about 7 g of the
monomer mixture (2% of a
total of 373 g of the MMA/BA/MMA monomer mixture in the ratio above) is added
to the
reactor. After 10 minutes, 15 g of a solution of ammonium persulfate (20% of
the total
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solution of 1.8 g of ammonium persulfate dissolved in 75.0 g of water) is
added to the reactor
over a period of about 10 minutes with continued agitation, during which time
there is an
exotherm of about 2-3°C. After the exotherm is complete, about 366 g of
the monomer
mixture (the remaining 98% MMA/BA/MMA monomer mixture), 61.5 g of the ammonium
persulfate solution (the remaining 80%), and 28.4 g of the PLA (as a 20%
active aqueous
solution) are simultaneously charged to the reactor over a period of 2 hours
with continued
agitation, while keeping the reactor contents at a temperature of about 79-
82°C. The reactor
temperature is then elevated to about 83-85°C with continued agitation,
for about 15 minutes.
After this 15 minute period, the reactor is cooled to about 30°C. The
resulting latex product is
completely removed from the reactor and gravity filtered using a first 20 mesh
screen and
then a second 250 mesh screen. The total latex coagulum (i.e. solids) from
both mesh screens
is collected, combined and weighed. Various physiochemical properties of the
latex are
reported in Table II.
Table II:
Latexes of
MethylmethacrytatelButytacrylatelMethacrylic
Acid
Mechanical
Particle
Contact Method
Coagulum Viscosity
Stability
Size Angle
of
Surfactant
(%) (CPS)
(min) (microns)
(deg.) pH
Solids (%)
Initiation
Polymerizable
Surfactant
ADDBS
Ex.1 <0.2 11 8 120.5 125 2.4346.9 Thermal
Non-Polymerizable
Surfactant
PDDBS
Com artive <0.03 220 5 122.5 98 2.2344 Thermal
Ex. 2
Polymerizable
Surfactant
Allylamine-
Cede hos Ex.3<0.67 90 ND 135 126 3.2546.6 Thermal
Non-Polymerizable
Surfactant
PDDBS
Com artive <0.52 115 ND 149 104 2.9247.7 Thermal
Ex. 4
Polymerizable
Surfactant <0.67 50 >15 1191 ND 5.7 49.7 Thermal
ALA Ex. 5
Non-Polymerizable
Surfactant
PLA ~
(Comparative <0.52 50 >15 1197.7 N 6.1 48.8 Thermal
Ex. 6)
I5
Example 7:
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A vinylacetate/butyl acrylate (VA/BA) co-polymer (in a weight ratio of about
78.9:21.1 ), in combination with the allylamine salt of dodecylbenzenesulfonic
acid (ADDBS)
and propylamine salt of dodecylbenzenesulfonic (PDDBS) is prepared as follows.
About 245
g of deionized water and about 1.5 g of ADDBS (as a 20% active aqueous
solution), 1.5 g of
S PDDBS (as a 23 % active aqueous solution), and 1.0 g of sodium sulfate are
placed in a
reactor suitable for emulsion polymerization, equipped with agitation means,
heating means
and cooling means. With agitation, the reactor is purged with nitrogen (99%
pure), and heated
to about 65-68°C. The temperature of the reactor contents is adjusted
to about 63-65°C, and
about 73.7 g of the monomer mixture (20% of a total of 369 g of the VA/BA
monomer
mixture in the ratio above) is added to the reactor. After 10 minutes, 15 g of
a solution of
ammonium persulfate (20% of the total solution of 1.8 g of ammonium persulfate
dissolved in
75.0 g of water) is added to the reactor over a period of about 5 minutes with
continued
agitation. The temperature of the reactor is increased to about 82-
84°C. Evidence of
polymerization is observed by the appearance of blue tint in the reaction
contents and a slight
I S exotherm of 1 -2°C. The temperature of the reaction contents is
adjusted to about 76-78°C
and about 294g of the BA/VA monomer mixture (the remaining 80 %), 61.5 g of
the
ammonium persulfate solution (the remaining 80%), 27.46 g ADDBS (as a 20%
active
aqueous solution), and 8.59 g PDDBS (as a 23 % active aqueous solution) are
simultaneously charged to the reactor over a period of 4 hours with continued
agitation, while
keeping the reactor contents at a temperature of about 78-82°C. The
reactor temperature is
then elevated to about 82-84°C with continued agitation, for about 1 S
minutes. After this 15
minute period, the reactor is cooled to about 30°C. The resulting latex
product is completely
removed from the reactor and gravity filtered using a first 20 mesh screen and
then a second
250 mesh screen. The total latex coagulum (i.e. solids) from both mesh screens
is collected,
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combined and weighed. Various physiochemical properties of the latex are
reported in Table
III.
Example 8 (Comparative Examvle):
A vinylacetate/butyl acrylate (VA/BA) co-polymer (in a weight ratio of about
79.1:20.9), in combination with the propyl amine salt of
dodecylbenzenesulfonic acid
(PDDBS) is prepared as follows. About 162 g of deionized water and about 5.4 g
of PDDBS
(as a 23% active aqueous solution) are placed in a reactor suitable for
emulsion
polymerization, equipped with agitation means, heating means and cooling
means. With
agitation, the reactor is purged with nitrogen (99'% pure), and heated to
about 6S-68°C. The
temperature of the reactor contents is adjusted to about 62°C, and
about S.0 g of the monomer
mixture (2% of a total of 24S g of the VA/BA monomer mixture in the ratio
above) is added
to the reactor. After 10 minutes, 10.1 g of a solution of ammonium persulfate
(20% of the
total solution of 1.8 g of ammonium persulfate dissolved in 75.0 g of water)
is added to the
1 S reactor over a period of about 1 S minutes with continued agitation. The
temperature of the
reactor is increased to about 82-84°C. Evidence of polymerization is
observed by the
appearance of blue tint in the reaction contents and a slight exotherm of 2-
4°C. The
temperature of the reaction contents is adjusted to about 76-78°C and
about 240 g of the
BA/VA monomer mixture (the remaining 80 %), 40.7 g of the ammonium persulfate
solution
(the remaining 80%), 16.8 g PDDBS (as a 23% active aqueous solution) are
simultaneously
charged to the reactor over a period of 4 hours with continued agitation,
while keeping the
reactor contents at a temperature of about 78-80°C. The reactor
temperature is then elevated
to about 82-84°C with continued agitation, for about 1 S minutes. After
this 1 S minute period,
the reactor is cooled to about 30°C. The resulting latex product is
completely removed from
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the reactor and gravity filtered using a first 20 mesh screen and then a
second 250 mesh
screen. The total latex coagulum (i.e. solids) from both mesh screens is
collected, combined
and weighed. Various physiochemical properties of the latex are reported in
Table III.
Example 9:
A vinylacetatelbutyl acrylate (VA/BA) co-polymer (in a weight ratio of about
78.9:21.1 ), in combination with the allylamine salt of dodecylbenzenesulfonic
acid (ADDBS)
and the ammonium salt of lauryl ether sulphate with 30 EO groups (ALSE) is
prepared as
follows. About 245 g of deionized water and about 1.5 g of ADDBS (as a 19%
active
IO aqueous solution) and 1.0 g of sodium sulfate are placed in a reactor
suitable for emulsion
polymerization, equipped with agitation means, heating means and cooling
means. With
agitation, the reactor is purged with nitrogen (99% pure), and heated to about
65-68°C. The
temperature of the reactor contents is adjusted to about 60-63°C, and
about 73.7 g of the
monomer mixture (20% of a total of 369 g of the VA/BA monomer mixture in the
ratio
above) is added to the reactor. After 10 minutes, 1 S g of a solution of
ammonium persulfate
(20% of the total solution of 1.8 g of ammonium persulfate dissolved in 75.0 g
of water) is
added to the reactor over a period of about 5 minutes with continued
agitation. The
temperature of the reactor is increased to about 82-84°C. Evidence of
polymerization is
observed by the appearance of blue tint in the reaction contents and a slight
exotherm of 1 -
2°C. The temperature of the reaction contents is adjusted to about 78-
81 °C and about 294g
of the BA/VA monomer mixture (the remaining 80 %), 61.4 g of the ammonium
persulfate
solution (the remaining 80%), 27.8 g ADDBS (as a 20% active aqueous solution),
and 6.3 g
ALSE (as a 30 % active aqueous solution) are simultaneously charged to the
reactor over a
period of 4 hours with continued agitation, while keeping the reactor contents
at a
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temperature of about 78-82°C. The reactor temperature is then elevated
to about 82-84°C
with continued agitation, for about 15 minutes. After this 1 S minute period,
the reactor is
cooled to about 30°C. The resulting latex product is completely removed
from the reactor and
gravity filtered using a first 20 mesh screen and then a second 250 mesh
screen. The total
S latex coagulum (i.e. solids) from both mesh screens is collected, combined
and weighed.
Various physiochemical properties of the latex are reported in Table III.
Example 10
A vinylacetate/butyl acrylate (VA/BA) co-polymer (in a weight ratio of about
78.9:21.1 ), in combination with the allylamine salt of dodecylbenzenesulfonic
acid (ADDBS)
and propylamine salt of dodecylbenzenesulfonic (PDDBS) is prepared, using
redox couple
as initiators, as follows. About 251 g of deionized water and about I.5 g of
ADDBS (as a
19% active aqueous solution), 0.9 g of PDDBS (as a 23 % active aqueous
solution), and 0.3 g
of sodium hydrogen carbonate are placed in a reactor suitable for emulsion
polymerization,
equipped with agitation means, heating means and cooling means. With
agitation, the reactor
is purged with nitrogen (99% pure), and heated to about 65-68°C. The
temperature of the
reactor contents is adjusted to about 63-65°C, and about 10.3 g of the
monomer mixture (2%
of a total of 513 g of the VA/BA monomer mixture in the ratio above) is added
to the reactor.
After I S minutes, I3.7 g of a solution of ammonium persulfate (20% of the
total solution of
2.0 g of ammonium persulfate dissolved in 66.5 g of water) and 13.7 g of a
solution of sodium
metabisulfite (20% of the total solution of 0.83 g of sodium metabisulfite
dissolved in 67.8 g
of water) is added to the reactor over a period of about 5 minutes with
continued agitation.
Evidence of polymerization is observed by the appearance of blue tint in the
reaction contents
and a slight exotherm of 1 -2°C. The temperature of the reaction
contents is adjusted to about
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68-72°C, and 54.9 g of the sodium metabisulphite solution (the
remaining 80%), 54.8 g of the
ammonium persulfate solution (the remaining 80%), 503 g of the BANA monomer
mixture
(the remaining 98 %), 29.3 g of ADDBS (as a 19 % active aqueous solution), and
10.3 g of
PDDBS (as a 23 % active aqueous solution) are simultaneously added over a
period of three
hotus with continued agitation, while keeping the reactor contents at a
temperature of about
68 - 72°C. The reactor temperature is then elevated to about 75 -
78°C with continued
agitation, for about 15 minutes. After this 15 minute period, the reactor is
cooled to about
30°C. The resulting latex product is completely removed from the
reactor and gravity filtered
using a first 20 mesh screen and then a second 250 mesh screen. The total
latex coagulum
(i.e. solids) from both mesh screens is collected, combined and weighed.
Various
physiochemical properties of the latex are reported in Table III.
Table III:
Latexes of
VinylacetatelButylacrylate
Mechanical
Particle
Contact Method
Coagutum Viscosity
Stability
Sfze Angle
of
Surfactant
'/. CPS min
microns d
H Solids
('/. tnitiatfon
PolymerizabIeINon-
Polymerizable
Surfactants
ADDBS
PDDBS Ex.7 <0. 220 >13 266176786 2.2345.1 Thermal
9
Non-Polymerizable
Surfactant
PDDBS
Com artive <0.05 50 6 98.3 104 2.4841.2 Thermal
Ex. 8
PolymenzablelNon-
Polymerizable
Surfactants
ADDBS
ALSE Ex.9 <0.03 50 ND 1599 ND 2.6345.3 Thermal
PolymerizabIeINon-
Poiymerizable
Surfactants
ADDBS
PDDBS Ex.lO <0.06 220 ND 410 ND 5.2346.6 Redox
Example 11
A methylmethacrylate/butylacrylate/methacrylic acid (IvL~iA/BAJMMA) co-polymer
(in a weight ratio of about 48:49:3), in combination with the allylamine salt
of laureth-3E0-
SUBSTITUTE SHEET (RULE 26)
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sulfate (AES-3), is prepared as follows. About 205 g of deionized water and
about 1.6 g of
AAES-3 (as a 25.5% active aqueous solution), are placed in a reactor suitable
for emulsion
polymerization, equipped with agitation means, heating means and cooling
means. With
agitation, the reactor is purged with nitrogen (99% pure), and heated to about
77 - 79°C.
Next, about 75 g of the monomer mixture (20% of a total of 376 g of the
MMA/BA/MMA
monomer mixture in the ratio above) is added to the reactor. After 10 minutes,
15.0 g of a
solution of ammonium persulfate (20% of the total solution of 1.9 g cf
ammonium persulfate
dissolved in 72.9 g of water) is added to the reactor over a period of about 4
minutes with
continued agitation, during which time there is an exotherm of about 12-
14°C. After the
exotherm is complete, about 301 g of the monomer mixture (the remaining 80%
MMA/BA/MMA monomer mixture), 59.8 g of the ammonium persulfate solution (the
remaining 80 %) , and 22.0 g of AAES-3 (as the 22% active aqueous solution)
are charged to
the reactor over a period of 2 hours with continued agitation, while keeping
the reactor
contents at a temperature of about 78 - 82°C. The reactor temperature
is then elevated to
about 82 - 84°C with continued agitation, for about 15 minutes. After
this 15 minute period,
the reactor is cooled to about 30°C. The resulting latex product is
completely removed from
the reactor and gravity filtered using a first 420 mesh screen and then a
second 250 mesh
screen. The total latex coagulum (i.e. solids) from both mesh screens is
collected, combined
and weighed. The resulting latex has the following charateristics:
Solids 48.41
Particle size (nm) Vol (50%) 95nm.
pH 2.43
Visc.(3/60) 140.00 (centipoise)
Coagulum 0.36g (<0.05% on total batch weight).
Example 12
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A methylmethacrylate/butylacrylate/methacrylic acid (MMA/BA/MMA) co-polymer
(in a weight ratio of about 48:49:3), in combination with the allylamine salt
of lauryl sulfate
(AS}, is prepared as follows. About 222 g of deionized water and about 2.3 g
of AS (as a
17.2% active aqueous solution), are placed in a reactor suitable for emulsion
polymerization,
equipped with agitation means, heating means and cooling means. With
agitation, the reactor
is purged with nitrogen (99% pure), and heated to about 77 - 79°C.
Next, about 77 g of the
monomer mixture (20% of a total of 378 g of the MMA/BA/MMA monomer mixture in
the
ratio above) is added to the reactor. After 10 minutes, 15.4 g of a solution
of ammonium
persulfate (20'% of the total solution of 1.9 g of ammonium persulfate
dissolved in 75.0 g of
water) is added to the reactor over a period of about 4 minutes with continued
agitation,
during which time there is an exotherm of about 7-8°C. After the
exotherm is complete,
about 301 g of the monomer mixture (the remaining 80% MMA/BA/MMA monomer
mixture), 61.6 g of the ammonium persulfate solution (the remaining 80 %) ,
and 33.7 g of
AS (as the 17.2% active aqueous solution) are charged to the reactor over a
period of 2 hours
with continued agitation, while keeping the reactor contents at a temperature
of about 78 -
82°C. The reactor temperature is then elevated to about 82 -
84°C with continued agitation,
for about 15 minutes. After this 15 minute period, the reactor is cooled to
about 30°C. The
resulting latex product is completely removed from the reactor and gravity
filtered using a
first 420 mesh screen and then a second 250 mesh screen. The total latex
coagulum (i.e.
solids) from both mesh screens is collected, combined and weighed. The
resulting latex has
the following charateristics:
Solids 48.41
Particle size (nm) Vol (SO%) 95nm.
pH 2.43
Visc.(3/60) 140.00 (centipoise)
Coagulum 0.368 (<0.05% on total batch weight)
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The hydrophobicity of a latex prepared using a typical non-polymerizable
surfactant
was compared to that of a latex prepared using a representative polymerizable
surfactant of
the present invention. It has been discovered that the latex prepared in
Example 1 (using
ADDBS) possess remarkable hydrophobicity, as compared to the latex prepared
according to
Example 1 (using the ammonium salt of dodecylbenzene sulfonic acid, AmDDBS).
[Need to
insert ASTM method and description here.) The change in contact angle as a
function of time
for a water droplet at each of the latex film surfaces was measured; the
results are shown
below.
15
Time (Seconds)
Latex Surfactant 5 20 40 60
AmDDBS (non-polymerizable) (Contact Angle) 98° 74° 51
° 27°
ADDBS (polymerizable) (Contact Angle) 125° 125° 125°
125°
Without being bound by any particular theory, a rapidly increasing contact
angle as observed
from a latex film indicates that the water droplet is penetrating the film due
to surfactant
related imperfections of the film. A constant water droplet contact angle, as
in the case of the
ADDBS derived latex, indicates the desirable result whereby water is unable to
penetrate the
hydrophobic film.
In a test similar to the contact angle measurements, the hydrophobicity of a
latex
prepared using a typical non-polymerizable surfactant was compared to that of
a latex
prepared using a representative polymerizable surfactant of the present
invention, whereby the
different latex films were coated and heat cured onto porous filter paper and
treated with
water. As observed in the results shown below, water undesirably, readily
penetrated through
the film and absorbed into the paper in a few seconds for the latex derived
from the AmDDBS
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surfactant. However, the latex film derived from the ADDBS surfactant, did not
allow the
water to penetrate or absorb; the water droplet maintained its original shape
on the latex film,
prior to being influenced by evaporation effects (at least thirty minutes).
Time (Seconds)
Latex Surfactant S 20 40 60
AmDDBS (non-polymerizable) (penetration/absorption) slight total total total
ADDBS (polymerizable) (penetration/absorption) none none none
none
The adhesion properties of a latex prepared using a typical non-polymerizable
surfactant were compared to that of a latex prepared using a representative
polymerizable
surfactant of the present invention. It has been discovered that the latex
prepared in Example
1 (using ADDBS) possess a vastly superior adhesion profile, as compared to the
latex
prepared according to Example 1 (using the ammonium salt of dodecylbenzene
sulfonic acid,
AmDDBS). Adhesion data were collect for each latex acrylic lattice using ASTM
method
D897. This test method is a standard test for adhesion called "block pull";
results from the
test are indicated in pounds per square inch (p.s.i.), wherein the higher the
p.s.i. obtained, the
better the adhesion properties of the latex. Adhesive failure is defined as
the point at which
the latex, upon application of a pulling force, no longer adheres to the
surface of the substrate.
Cohesive failure is defined as the point at which the latex itself fails, i.e.
where the latex splits
into two or more portions, but remains bound to the substrate. The adhesion
tests were
conducted using an Instron Model 1123, with a 5000 pound load cell, a sample
size of 0.5 g of
latex, a surface area of 4 inz, whereby the treated sample blocks were allowed
to dry at room
temperature (i.e. 25°C) for three days under 0.25 p.s.i. external
pressure. Aluminum and steel
blocks were prepared by sanding with extra fine 220 grit paper until smooth to
the touch. A
weighed amount of each latex (0.5 g) was placed on one surface of one block
and another
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black place on top for three days. Failure was determined by visual
inspection, with the
results indicated below.
Latex Surfactant Adhesive Failure (~.s.i.)
AmDDBS (non-polymerizable) 65
ADDBS (polymerizable) 170
The latex film yellowing properties of a latex prepared using a typical non-
polymcrizable surfactant were compared to that of a latex prepared using a
representative
polymerizable surfactant of the present invention. It has been discovered that
the latex
prepared in Example 1 (using ADDBS) possess a greatly improved film yellowing
profile, as
compared to the latex prepared according to Example 1 (using the ammonium salt
of
dodecylbenzene sulfonic acid, AmDDBS). Latex film yellowing was compared after
aging
the films six months at room temperature, at approximately standard
atmospheric conditions.
It is highly desirable, as known by one skilled in the art, to produce a latex
film which does
not yellow upon application to a surface, with the passage of time. After a
period of 6
months, the ADDBS-derived latex was plainly observed to be significantly
lighter color than
the AmDDBS-derived latex. Absorbence measurements were taken for each latex at
350 nm
and 420 nm; the lower the absorbance at a given wave length, the lighter the
latex (i.e. the less
yellow the latex). Results of the measurements for the two latexes are shown
below.
Latex Absorbance
Latex Surfactant 350 nm 420 nm
AmDDBS (non-polymerizable) 16.9 5.3
ADDBS (polymerizable) 10.0 2.5
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The scrubability properties of a latex prepared using a typical non-
polymerizable
surfactant were compared to that of a latex prepared using a representative
polymerizable
surfactant of the present invention. It has been discovered that the latex
prepared in Example
1 (using ADDBS) possess improved scrubability characteristics, as compared to
the latex
prepared according to Example 1 (using the ammonium salt of dodecylbenzene
sulfonic acid,
AmDDBS). Scrubability of the latexes was evaluated using ASTM scrub test
D2486. Seven
Star Acrylic Flat House Paint, 103A100 White, from Ace Hardware was utilized
in the
testing. The ADBBS- and AmDDBS-derived latexes were individually added to the
paint in a
ratio of 2:1 (latex:paint).
FTIR comparisons were conducting by casting latex films on glass, derived from
both
ADDBS and AmDDBS. The films were dried at room temperature for several days,
removed
from the glass and aged at room temperature, at approximately standard
atmospheric
conditions, for six months. The films were individually placed on a ZnSe
plates and the FTIR
spectra recorded. Peak heights were measured on the absorbance peak located at
1035 cm-~
1 S (i.e. the S=O stretch peak) for each film. It has been discovered that the
latex prepared in
Example 1 (using ADDBS) possess a much lower peak height absorbance in the
FTIR
spectrum, as compared to the latex prepared according to Example I (using the
ammonium
salt of dodecylbenzene sulfonic acid, AmDDBS). Without being bound by any
particular
theory, a lower the peak height absorbance indicates a desirable
characteristic of the latex,
whereby the individual surfactant molecules are not present at the surface of
the latex film,
i.e. they have not migrated to the surface of the film.
Latex Surfactant Latex FTIR Absorbance (x 10~°l
AmDDBS (non-poIymerizable) 73
ADDBS (polymerizable) 29
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Agricultural Formulations
The oil phase (i.e. agricultural technical + optional supplemental surface
active agent;
i.e. co-surfactant, and optional water immissible solvent) may contain from 10
to 80% w/v of
the agricultural technical, preferably 10 to 60% and most preferably 20 to SO%
w/v. The latex
content of the composition will depend upon the latex type as well as the
pesticide and
surfactant type but may vary from 5% w/v to 80% w/v, preferably 5 to 60% w/v
and most
preferably 10 to 50% w/v.
The amount of the latex to be employed in the compositions in the present
invention
should be as low as possible, provided that it is sufficient to stabilize the
emulsion. Not only
is the use of excess polymer latex generally uneconomical, it also means that
the resulting
composition is unable to carry such a high loading of active ingredient, which
makes the
resulting compositions unattractive to the purchaser.
A variety of stirring methods may be employed, from simple shaking, stirring
through
to sonication and high shear emulsification, including bead milling. The
aqueous dispersions
in accordance with at least the preferred embodiments of the invention are
useful for the
control of a wide variety of target organisms, being advantageously employed
wherever a
conventional emulsifiable concentrate finds use, but having the advantages of
being water
based and therefore of low flammability, lower dermal toxicity in many cases,
ability to be
packed in HDPE and being at least as efficacious as an emulsifiable
concentrate counterpart.
They also have the ability in many cases, since they contain film-forming
latexes, to be
utilized in those areas where film forming is a desirable effect, such as in
seed treatments and
pest control in dwelling places.
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They are however particularly suitable for an intended for use on growing
crops, and
to locations in which agricultural crops are to be grown, particulary cereals
and the like.
Agricultural compositions of the invention show improved long term stability,
as compared
with the compositions of EP 0080516.
Example 1
Formulations of NMS (non-migrating surfactnat: polymerizable surface active
agent-
derived) latex show superior physical stability compared to migrating latexes.
Acetochlor
latex formulations were prepared by adding 12.5 g of acetochlor technical and
1.39 g of
Makon 10 (optional co-surfactant) to 25 g of either a migrating latex prepared
according to
Latex Example #1, using lauryl alcohol 3-mole ethylene oxide, ether sulfate
allyl amine salt (a
NMS latex; also called AU-7 latex) and Latex Example #2, using lauryl alcohol
3-mole
ethylene oxide, ether sulfate sodium salt (a traditional surfactant latex;
also called B-330A
latex). 1 S g of DI water was blended into each latex prior to addition of the
pesticide + co-
surfactant. The oil phase was added slowly to the latex and water solution
while the latex was
being stirred using a magnetic stir bar and stir plate. After oil phase
addition was complete,
each mixture was stirred for 5 minutes, and then transferred to 100 mL conical
centrifuge
tubes. After 24 hours, the separation was measured. The results arc in the
following table:
Traditional Latex NMS Latex
mL of separation @ 24 hrs. 0.25 0.01
Description of separation: Oil creamy
The samples were monitored for another 13 days, at which time the traditional
latex
formulation had formed 0.7 mL of oily separation, but the NMS latex had not
formed any oily
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separation. The NMS latex had formed some layers of creamy stratification but
when the
tube was inverted through 10 inversions the mixture was uniform. The 0.7 mL of
oily
separation in the traditional surfactant latex did not go into solution even
after more than 20
inversions of the tube. Formulations of NMS latex show superior physical
stability compared
S to migrating iatexes.
Example 2
Formulations of traditional migrating (Latex Example #2, using lauryl alcohol
3-mole
ethylene oxide, ether sulfate sodium salt) and NMS latexes (Latexes prepared
according to
Latex Example #l, also called AU-1 latex, and Latex Example #3, also called AU-
9 latex)
containing chlorpyrifos as the active ingredient were prepared by the
previously described
technique. The chlorpyrifos was dissolved in Aromatic 150 solvent plus 10% w/w
Makon 10.
The concentration of chlorpyrifos in the solvent plus co-surfactant solution
was 65% w/w.
Each formulaton contained 25 g of the latex, 15 g. of chlorpyrifos solution,
and 10 g of DI
water. The formulations were then stored in 2 oz glass bottles with nylene
caps, at SOC for 60
days. After 60 days of storage, there were noticeable changes in the migrating
surfactant
containing latexes. Both samples developed a thick layer of yellow colored
coagulum on the
bottom of the bottles. The coagulum was removed, drained and weighed. The
results are in
the following table.
Formulation / surfactant Residue wt. (g) Particle Size of latex
Latex Example #1-Derived 0 98 nm
Traditional Surfactant 2.23 157 nm
Latex Example #3-Derived 0 95 nm
Traditonal Surfactant 6.21 91 nm
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Both of the NMS latex samples remained uniform, and had excellent dispersion
properties after the 60 day storage time.
Examgle 3
It is possible to achieve a higher active ingredient content product using non-
migrating
latexes in pesticide formulations instead of traditional type latexes. The
higher concentration
products also surprisingly have much more rapid dispersion properties when
diluted compared
to high concentration traditional latex pesticide formulations. The
formulations were made by
blending acetochlor technical with 10% (relative to the acetochlor) Makon 10
and mixing
until uniform. To a beaker was added 12.5 g. of latex (migrating or non-
migrating), and 5 g
of DI water. The latex and water were stirred with a magnetic stir bar until
uniform, then the
acetochlor solution was added to the latex until the viscosity was too high to
permit agitation.
The amount of acetochlor that was added, and the number of inversions required
to
disperse 1 g. of product in 99 mL of 1000 ppm (as CaC03) test water is in the
table that
follows.
Traditional Surfactant
Latex Latex Example #3 Latex
Weight of Latex: 12.5 g 12.5 g
Oil phase weight added: 21.35 g 26.95 g
Ratio of oil phase to
polymer solids: 3.7:1 4.7:1
# inversions needed to
disperse 1 g. in 99 mL
of test water: 45 12
The dispersions show only a trace of creamy separation after 1 hour at room
temp erature.
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Example 4
NMS latexes show superior dilution stability compared to tradional type
latexes.
Samples of a migrating type latex B-330A , and a non-migrating type latex AU-
7, were each
diluted 1:50, 1:100, 1:1000 in 100 mL conical centrifuge tubes. The dilutions
were made in
WHO 342 ppm test water, and the separation was noted after 10 days. All of the
B-330A
samples showed traces of separation at the bottom of the tubes, whereas the AU-
7 samples
showed no separation.
Example 5
A formulation was prepared to contain propanil, by adding 20 g of a 36% ai
stock
solution, containing 1.5 g of Makon 10 as co-surfactant, to 20 g of AU-9 latex
containing 10 g
of additional DI water. The oil phase was added to the latex and water
solution gradually
while the mixture was being stirred with a magnetic stir bar. The formulation
formed was
uniform, and physically stable, showing no separation after 3 months.
Example 6
Stable formulations of trifluralin and metolachlor were prepared using AU-7
latex, by
blending oil phase into water plus latex and stirring until a uniform mixture
was achieved.
The oil phase was mixed with Makon 10 as co-surfactant prior to adding the oil
to the latex.
The trifluralin was dissolved in Aromatic 150 solvent to form a 45% AI stock
solution on a
weight/weight basis. The metolachlor technical was used as-is with no
dilution.
The formulation compositions are below:
Ingredient Formulation Formulation
Latex 25 g 25 g
DI water 15 g 15 g
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Metolachlor TG 12.5 g
Trifluralin Stock Solution 12.5 g
Makon 10 1.39 g 1.39 g
These formulations remained stable, showing no separation for 4 months at room
temperature.
Example 7
NMS latex formulations show excellent dilution stability. Formulations that
had been
prepared previously were diluted 5 mL of formulation to 95 mL of 342 ppm WHO
test water,
and mixed in a 100 mL stoppered mixing cylinder. After the dispersions were
formed, the
cylinders were stored in a rack at room temperature for 14 days. At the end of
14 days, the
amount of separation was recorded. The data are below:
Active Ingredient 14 day separation Latex
acetochlor trace AU-7
chlorpyrifos slight trace AU-7
trifluralin trace AU-7
metolachlor slight trace AU-7
The separation rates shown above are what typically would show up after 24
hours for an
emulsifiable concentrate type formulation.
Example 8
NMS latex formulations show exellent dilution stability when diluted below
1:50.
Formulations were prepared with two non-migrating latexes for each of three
pesticide active
ingredients. The latexe (either AU-1 or AU-9) formulations and were diluted
1:200 in 50 mL
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mixing cylinders containing 1000 ppm (as CaC03) testwater. After 5 days, the
separation
was measured. The basic formulation is below, as is the composition of all
stock solutions
and the separation data.
Basic formulation: 50% Latex (AU-1 or AU9); 30% Oil phase (stock solution
containing
10% Makon 10); and 20% DI water.
Chlorpyrifos stock solution contained 67% technical, 23% Aromatic 150, 10%
Makon 10.
Metolachlor stock solution contained 90% technical, 10% Makon 10. Acetochlor
stock
solution contained 90% technical, 10% Makon 10.
The formulations were made by adding the water phase and latex to a 2 oz vial,
then
the oil phase was added. The vials were immediately mixed using a vortex
mixer. Dilution
stability results after1:200 in 1000 ppm
5 days, test water:
Active Ingredient Latex Separation
Metolachlor AU-1 None
Metolachlor AU-9 Slight
trace
Acetochlor AU-1 Slight
trace
Acetochlor AU-9 Slight
trace
Chlorpyrifos AU-1 Slight
trace
Chlorpyrifos AU-9 None
Example 9
NMS latexes show excellent stability at dilutions below 1:200. Chlorpyrifos
formulations were prepared by blending a chlorpyrifos stock solution
containing 67%
pesticide technical, 10% Makon 10 and 23% Aromatic 150 solvent, with an AU-1
or AU-9
latex and water. The formulations contained 30% stock solution, 20% DI water
and 50%
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latex. Both formulations were then diluted serially from 1 % down to 0.001 %
in tap water,
and then the separation was measured after 3 hours. The results are below:
Dilution AU-1 Latex AU-9 Latex
1% 0 0
0.1 % 0 0
0.01 % 0 0
0.001 % 0 0
Example 10
NMS latex pesticide formulations show excellent stability under shear
conditions. A
metolachlor NMS latex formulation was prepared and compared with an EC
formulation of
the same active ingredient for dispersion stability under shear conditions
similar to those
expected under normal agricultural sprayer conditions. Both formulations were
diluted to a
use rate of 3.6 g. active ingredient per liter of spray solution, in a 2 liter
laboratory spray
1 S apparatus. The test emulsions / dispersions were recirculated through a
centrifugal pump
system at 20 psi initial pressure. Every 10 minutes a 100 mL aliquot was
removed through a
Teejet SS8003 nozzle. The test was run for 60 minutes for each formulation,
and readings
from the pressure guage (indicating the in-line 100 mesh strainer was being
clogged) were
recorded. 30 minutes after each aliquot was removed, the separation in the 100
mL cylinder
was measured. Equal separation over time and no significant increase in the
pressure reading
over time indicates a stable system. The results for both types of
formulations are below. The
test was run in 342 WHO water.
Pressure and separation readings for the Metolachlor EC
Time (Min.) Pressure (PSI) Separation @ 30 minutes
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0 20 SI. Trace
20 Sl. Trace
19 SI. Trace
18.5 Sl. Trace
5 40 18 Sl. Trace
50 18 S1. Trace
60 18 SI. Trace
Separation and pressure readings for Metolachlor latex formulation NMS-based
10 Time (Min.) Pressure (PSI) Separation @ 30 minutes
0 20 0
10 20 0
20 20 0
30 20 0
I S 40 19.5 0
50 19 0
60 19 0
Example I 1
20 NMS latex formulations show excellent physical stability. An acetochlor
formulation
was prepared by blending 25 g of AU-9 latex (2157-24) with 10 g of DI water
then adding 15
g of a 90/10 solution of acetochlor/Makon 10. The mixture was blended with a
magnetic stir
plate apparatus until uniform. 2.5 mL of the sample was dispersed in 47.5 mL
of 342 ppm
WHO water in a mixing cylinder. The mixing cylinder was inverted 10 times and
then the
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separation was recorded at 3 hours. The remainder of the sample was stored at
SOC for 60
days. At 30 and 60 days, the sample was removed from the oven and allowed to
equilibrate to
room temperature. At that time, the product was observed for any changes in
appearance and
the dispersion check was once again performed. At no time during the study
were any
physical changes detected. The dispersion stability was also very good,
showing no more
than a trace of separation after 3 hours. When the cylinder was re-inverted
after the
separation reading, the residue was easily re-dispersible.
From the foregoing, it will be appreciated that although specific embodiments
of the
invention have been described herein for purposes of illustration, various
modifications may
be made without deviating from the spirit or scope of the invention.
