Note: Descriptions are shown in the official language in which they were submitted.
CA 02297987 2000-02-04
DIOL LATEX COMPOSITIONS
Cross Reference to Related AR ' ti
This application claims priority to U.S. provisional application Serial No.
60/057,714 filed on August 28, 1997, and U.S. provisional application Serial
No.
60/058,008 filed on August 28, 1997, and 'the 60/057,714 and 60/058,008
applications
are herein incorporated by this reference in their entirety.
Field of the Invention
The present invention relates to diol latex compositions, and methods for
making such diol latex compositions. The diol latex compositions are
preferably
produced with diol as the major component of the continuous phase.
The present invention further relates to condensation polymers, and methods
for
making such polymers. The condensation polymers are produced using a polymer
colloid system preferably comprising a diol component. In a preferred
embodiment,
the polymer colloid system is the diol latex composition. The condensation
polymers
produced according to the methods of the invention are heterophase materials.
Background of the Invention
With regard to the first major embodiment of the present invention, latex
polymers are utilized in a variety of products due to the unique features of
their delivery
system. Latex polymers, by nature, have lower viscosities than their solution
counterparts. This lower viscosity allows for higher polymer concentrations to
be
delivered in an application without encountering the numerous problems
associated
with high viscosity fluids. The reason for the unique viscosity behavior of
latex
polymers stems from the heterogeneity of the system. The fact that the latex
polymers
are dispersed, rather than dissolved, in a continuous low viscosity media
reduces the
influence of the latex polymer on the viscosity of the media. Therefore, the
continuous
CA 02297987 2000-02-04
-1-
phase or solvent of the latex is the dominant component affecting the
viscosity of the
system.
Typically, the continuous phase of most commercial latexes is water. This is
beneficial in that water has low toxicity and is not flammable. Water is a
good choice
when the continuous phase is to be used as a delivery system for the polymer.
In some
circumstances, however, water may be detrimental to the substrate, or it may
be
necessary to change the drying characteristics of the latex.
Solvents other than water may be used in the continuous phase. For example,
the addition of diol solvents in minor amounts is lrnown. JP 04335002 teaches
the
addition of alcohol(s) as an antifreeze agent for the production of vinyl
ester emulsions
at low temperatures. The amount of the diol solvent disclosed is below 50 wt.
%. JP
63186703 teaches the addition of film forming agents and plasticizers in an
amount up
to 10 wt % of the solid component to effect film formation properties of the
resulting
emulsion. JP06184217 teaches the addition of polyols and water-soluble
inorganic
salts to vinyl chloride suspension polymerizations to produce vinyl chloride
polymers
that have good powder fluidity. EP 255137 teaches the use of water soluble
alcohol in
a water/alcohol level of 100/0 to 50/50 for producing polyvinylester with a
high degree
of polymerization.
US 3,779,969 describes the use of propylene diol or diethylene diol in amounts
of 10-50 wt% of the emulsion. The ethylene diol is added to impart improved
wetting
properties of the emulsion.
US 4,458,050 describes a process for the manufacturing of polymer dispersions
in diol chain extenders. The patent relates to the production o~polymers which
have
low viscosity for the preparation of polyurethanes. The '050 patent does not
teach
compositions which lead to stabilized latexes in diol solvents. The patent
also teaches
large amounts ofpolymeric stabilizers to produce the dispersion polymer.
CA 02297987 2000-02-04
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JP 60040182 and JP 64001786 teach compositions for water-oil repellency for
fabric treatment. The compositions are aimed at producing fluoropolymer
emulsions in
a mixture of diol solvents. Such fluoropolymers are not the subject of this
invention.
US 4,810,763 teaches suspension polymerization in an organic medium for the
preparation of pressure sensitive adhesives. The compositions described in the
'763
patent are specifically aimed at producing large particle size dispersions.
This patent
does not disclose compositions which produce particle size latexes having a
particle
size below 1000 nm. This reference also does not disclose emulsion
polymerization.
US 4,885,350 and US x,061,766 teach the dispersion polymerization of vinyl
monomers in hydrophillic organic liquids. To produce the dispersion polymer,
large
amounts of polymeric dispersion stabilizers are taught.
Prior to the present invention, it had not been previously known to utilize
40%,
more preferably 60% or greater, of diol, by weight of the continuous phase, in
the
continuous phase of a latex polymer. This amount of diol gives certain
advantages to a
Iatex composition, such as improved compatibility with a particular substrate,
better
drying characteristics of the latex, or use in the second major embodiment of
the
invention (production of a condensation polymer/first polymer matrix).
With regard to the second major embodiment of the present invention, it is
known to modify condensation polymers by blending the condensation polymer
with
another polymer in an extruder. For example, to improve the impact properties
of a
polyester, a low Tg elastomer is typically added to the polyester in a twin-
screw
'- extruder. Japan Kokai J$ 02155944 describes compounds for moldings
comprising
physical blends of saturated polyester with polystyrene polymers containing 1-
100 phr
glycidylamido-grafted olefin polymers of glycidyl methacrylate-graft olefin
polymers.
Jpn. Kokai JP 02016145, JP 02024346, JP Ol 123854, JP 01153249 and JP 01163254
all teach the blending of aromatic polyesters with resins prepared by graft
emulsion
copolymerization. The size of the dispersed phase is critical in attaining
good
CA 02297987 2000-02-04
f
-4-
properties. This is an energy intensive process sometimes resulting in the
reduction of
the physical properties of the polymer, in particular the molecular weight,
and it
requires a blending step, which utilizes more resources and more time.
U.S. Patents 5,652,306, 4,180,494 and 5,409,967 disclose compositions for
impact modification of aromatic polyesters that involve blending an acrylic or
polybutadiene/acrylic rubber powder with polylethylene terephthalate (PET).
The
acrylic rubber particles are prepared by typical core/shell emulsion
polymerization and
then harvested by spray drying the latex. The procedure for latex harvesting
is outlined
in U.S. patent 3,895,703.
The extrusion blending of an elastomer and a plastic is labor intensive and
time
consuming. Typically, polybutadiene or poly(butyl acrylate) are used as the
low Tg
polymer to impact modify the polyester. These low Tg elastomers are difficult
to
handle and require that a second monomer, typically poly(methyl methacrylate)
be
utilized as a "shell" surrounding the low Tg polymer "core" so that the low Tg
polymer
may be handled. The core-shell polymer is isolated, dried and then added to
the
polyester in an extruder.
There exists a need for a process for producing a polymer blend by more
economical methods. It would also be desirable be able to utilize both core
shell and/or
non core shell polymers in a process for producing a polymer blend. Such a
need has
been solved by the present invention, which can achieve such a blend in a
polymerization reactor, wherein the physical properties of the condensation
polymer are
maintained or improved.
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Summary of the Invention
In a first major aspect, the invention concerns a diol latex composition
comprising:
(a) latex polymer particles comprising a residue of an ethylenically
unsaturated monomer, wherein the latex polymer particles have a size
below 1000 nm;
(b) a surfactant; and
(c) a continuous liquid phase comprising a diol component, wherein the
I 0 diol component comprises from 60 to 100% by weight of the
continuous phase;
In a second major aspect, the invention concerns a method of making a
condensation polymer/ first polymer matrix comprising the steps of
(a) preparing a polymer colloid system comprising a first polymer dispersed
in a liquid continuous phase; and
(b) introducing the polymer colloid system into a condensation reaction
medium prior to or during the condensation reaction, wherein the
condensation reaction medium comprises (1) a diacid, di-isocyanate,
dialkyl carbonate, diaryl carbonate, dihalo carbonate or a mixture
thereof,
wherein the liquid continuous phase, the condensation reaction medium or both
comprises a diol component, thereby forming a condensation polymer / first
polymer
matrix.
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Detailed Description of the Invention
The present invention may be understood more readily by reference to the
following detailed description of preferred embodiments of the invention and
the
Examples included therein.
Before the present compositions of matter and methods are disclosed and
described, it is to be understood that this invention is not limited to
specific synthetic
methods or to particular formulations, as such may, of course, vary. It is
also to be
understood that the terminology used herein is for the purpose of describing
particular
embodiments only and is not intended to be limiting.
In this specification and in the claims which follow, reference will be made
to a
number of terms which shall be defined to have the following meanings:
The singular forms "a," "an" and "the" include plural referents unless the
context clearly dictates otherwise.
"Optional" or "optionally" means that the subsequently described event or
circumstances may or may not occur, and that the description included
instances where
said event or circumstance occurs and instances where it does not.
"Latex" is herein defined as a dispersion of polymeric particles in a
continuous
phase, the polymeric particles preferably having a size range of from 10 to
1000 iun.
The polymeric particles are produced through emulsion polymerization. "Latex
particle" is herein defined as such a polymeric particle, which is dispersed
in a
continuous phase.
"Diol" is a synonym for glycol or dihydric alcohol. "Polyol" is a polyhydric
alcohol containing three or more hydroxyl groups.
_ CA 02297987 2000-02-04
Throughout this application, where publications are referenced, the
disclosures
of these publications in their entireties are hereby incorporated by reference
into this
application in order to more fully describe the state of the art to which this
invention
pertains.
In a first major aspect, the invention concerns a diol latex composition
comprising:
(a) latex polymer particles comprising a residue of an ethylenically
unsaturated monomer, wherein the latex polymer particles have a size
below 1000 nm;
(b) a surfactant; and
(c) a continuous liquid phase comprising a diol component, wherein the
diol component comprises from 60 to 100% by weight of the
continuous phase;
In a second major aspect, the invention concerns a method of making a
condensation polymer/ first polymer matrix comprising the steps of:
(a) preparing a polymer colloid system comprising a first polymer dispersed
in a liquid continuous phase; and
(b) introducing the polymer colloid system into a condensation reaction
medium prior to or during the condensation reaction, wherein the
condensation reaction medium comprises ( 1 ) a diacid, di-isocyanate,
dialkyl carbonate, diaryl carbonate, dihalo carbonate or a mixture
thereof,
wherein the liquid continuous phase, the condensation reaction medium or both
comprises a diol component, thereby forming a condensation polymer / first
polymer
matrix.
____. CA 02297987 2000-02-04
_8_
In the first major aspect, the present invention concerns a diol latex
composition
and methods for making such diol latex compositions, in which the diol latex
compositions comprise a latex polymer derived from a polymerization of an
ethylenically unsaturated monomer in the presence of a free radical initiator,
a suitable
surfactant and a diol continuous phase in which the polymer is not soluble.
The diol
latex composition is produced through an emulsion polymerization, in which the
continuous phase of the emulsion comprises a diol component or a combination
of
diol(s) with other (co) solvents.
In the second major aspect, the invention is concerned with the introduction
of
polymer colloid systems, preferably comprising a diol component as a co-
reactant, in a
condensation polymerization. The diol component may be used as a co-reactant
in
condensation polymerizations to produce polyesters, polycarbonates,
polyurethanes, or
any other condensation polymerization in which diols are employed.
More particularly, this second major aspect of the invention includes methods
and composition for entrapping polymer particles during a diol containing
condensation polymerization, by introducing a polymer colloid system into the
condensation reaction. In one embodiment of the invention, the polymer colloid
system
is the diol latex composition of the first invention aspect, in which the
continuous phase
comprising the diol component is a source of the diol in the condensation
polymerization. In another embodiment, the polymer colloid system comprises a
water
based continuous phase. The water based continuous phase may or may not
contain a
diol component. In a further embodiment, the polymer colloid system comprises
a diol
based continuous phase. If the polymer colloid system is properly stabilized,
the
polymer colloid system retains its integrity and remains a dispersed phase
within the
resulting condensation polymer matrix. Depending on the nature of the polymer
particles, the physical characteristics of the condensation polymer can be
modified.
This invention includes compositions and methods useful for producing polymers
in
which a first polymer, the polymer comprising the polymer colloid system, is
incorporated during the polymerization of second polymer, the condensation
polymer.
--------- -- CA 02297987 2000-02-04
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The resulting condensation polymer then contains the polymer particles
comprising the polymer colloid system wherein the polymer particles are
preferably
dispersed in the solid condensation polymer continuous phase. This provides
polymer
blends with improved physical properties. For example, if the diol latex
polymer is a
low Tg rubber and the condensation polymer is a polyester, such as
polyethylene
terephthalate) (PET), the resultant condensation polymer blend could have
improved
impact resistance. Moreover, the need for a core-shell system for the low Tg
rubber as
used in the prior art is avoided.
I. The Diol Latex Compositions
As mentioned, in a first major aspect, this invention concerns the preparation
of
a diol latex composition through emulsion polymerization, wherein the
continuous
phase comprises a diol component. The diol latex composition may be used for a
variety of purposes, including, but not limited to, ink compositions, pigment
concentrates, coatings, and as reactants in condensation polymerizations. The
diol latex
composition comprises a latex polymer and a continuous phase, the continuous
phase
comprising a diol component.
Diol components useful for the continuous phase of the diol latex compositions
include, but are not limited to, any aliphatic or cycloaliphatic diol having
from about 2
to about 10 carbon atoms and mixtures thereof. Preferred diols include
ethylene diol,
1,3-trimethylene diol, propylene diol, tripropylene diol, 1,4-butanediol, 1,5-
pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol,
neopentyl
diol, cis- or traps- cyclohexanedimethanol, cis- or traps- 2,2,4,4-tetramethyl-
1,3-
- cyclobutanediol, diettiylene diol, 2-methyl-1,3-propanediol, 2-methyl-1,3-
pentanediol,
2,2,4-trimethyl-1,3-pentanediol or mixtures thereof; more preferred diols
include
ethylene diol, propylene diol, tripropylene diol, 1,4-butanediol, diethylene
diol,
neopentyl diol, cis and traps- cyclohexanedimethanol and mixtures thereof;
even more
preferred diols include neopentyl diol, ethylene diol, cis or traps
cyclohexanedimethanol, 1,4 butanediol, or a mixture thereof.
02297987 2000-02-04
- 10-
In addition to the diol component, the continuous phase may contain one or
more polyol components. Representative polyol components that may be used in
the
continuous phase include, but are not limited to, glycerol,
trimethylolpropane,
pentaerythritol, 1,2,6-hexanetriol, sorbitol, 1,1,4,4-
tetrakis(hydroxymethyl)cyclohexane, tris-(2,hydroxyethyl)isocyanurate,
dipentaerythritol and mixtures thereof. In addition to low molecular weight
polyols,
higher molecular weight polyols (MW 400-3000), preferably triols derived by
condensing alkylene oxides having from 2 to 3 carbons, e.g., ethylene oxide or
propylene oxide, with polyol initiators, having from 3 to 6 carbons, e.g.,
glycerol, can
also be used.
The continuous phase may also comprise a cosolvent. These cosolvents
include, but are not limited to water, methanol, ethanol, propanol, n-butanol,
and
mixtures thereof. The cosolvent may be present in the amount of less than 60%
by
weight, more preferably less than 40% by weight, based on the total weight of
the
continuous phase.
As used throughout, the total weight of the continuous phase includes the
weight of the diol component, polyol component, and co-solvent. The weight of
any
surfactant is not included in the total weight of the continuous phase.
In one embodiment, the diol component is present in an amount of from 60 to
100% by weight, based on the total weight of the continuous phase, preferably
from 65
to 100% by weight, based on the total weight of the continuous phase, more
preferably,
from 75 to 100% by weight, based on the total weight of the continuous phase,
more
preferably, from 90 to 100% by weight, based on the total weight of the
continuous
phase, and even more preferably, 100% by weight, based on the total weight of
this
continuous phase. In a further embodiment, the diol containing phase consists
essentially of the diol component.
02297987 2000-02-04
-11-
In an alternative embodiment, the diol component is present in an amount of
from 40 to 100% by weight, based on the total weight of the continuous phase,
preferably from 50 to 100 % by weight, based on the total weight of the
continuous
phase, more preferably, from 65 to 100% by weight, based on the total weight
of the
continuous phase and even more preferably, from 90 to 100% by weight, based on
the
total weight of the continuous phase. In a further embodiment, the continuous
phase
consists essentially of the diol component. The total weight of the continuous
phase
includes the weight of the diol component, polyol component and co-solvent.
The
weight of any surfactant is not included in the total weight of the continuous
phase. In
this embodiment, the diol component consists essentially of tripropylene
glycol, 1,4-
butanediol, neopentyl glycol, cyclohexanedimethanol or a mixture thereof.
The diol latex compositions of this invention are prepared by emulsion
polymerization. The solids content of the reaction is preferably from 5 to 60%
by
weight but more preferably from 20 to 50% by weight. The particle size of the
latex
polymer particles of the diol latex composition is preferably below 1000 nm;
more
preferably from 20 to 700 nm, even more preferably from 60 to 250 nm. The
temperature of the reaction is preferably from 0 to 190 °C, more
preferably from 60 to
90°C.
A surfactant is preferably used to prepare the diol latex compositions. The
type
and amount of surfactant used in the emulsion polymerization depends on the
monomer
combinations and the polymerization conditions. Typical surfactants used in
the
emulsion polymerization are anionic, cationic,'or nonionic surfactants.
Anionic
surfactants that may be used in the invention include surfactants such as
alkali metal or
ammonium salts of alkyl, aryl or alkylaryl sulfonates, sulfates, phosphates
and mixtures
thereof. Suitable nonionic surfactants include, but are not limited to, alkyl
and
alkylaryl polydiol ethers, such as ethoxylation products of lauryl, oleyl and
stearyl
alcohols; alkyl phenol glycol ethers, including but not limited to,
ethoxylation products
of octyl or nonylphenol. Suitable surfactants may be found in McCutheon's
Volume l:
Emulsifiers and Detergents 1996 North American Edition, MC Publishing Co, Glen
--------------- CA 02297987 2000-02-04
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Rock, NJ, 1996. The surfactant may or may not be reactive in the
polymerization. In
one embodiment, useful surfactants are the sulfate/sulfonate salts of nonyl
phenol and
alkyl alcohol ethoxylates. Preferred surfactants include, but are not limited
to,
polymerizable or nonpolymerizable alkyl ethoxylate sulfates, alkyl phenol
ethoxylate
sulfates, alkyl ethoxylates, alkyl phenol ethoxylates or mixtures thereof.
The latex polymers of the diol latex compositions may be prepared by any
conventional means known in the art. The monomers that are used to form the
latex
polymers may be broadly characterized as ethylenically unsaturated monomers.
These
include, but are not limited to, non-acid vinyl monomers, acid vinyl monomers
and/or
mixtures thereof. The latex polymers of the invention may be copolymers of non-
acid
vinyl monomers and acid monomers, mixtures thereof and their derivatives. The
latex
polymers of the invention may also be homopolymers of ethylenically
unsaturated
monomers.
Suitable non-acid vinyl monomers that may be used to prepare the latex
polymer include, but are not limited to; acetoacetoxy ethyl methacrylate,
acetoacetoxy
ethyl acrylate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl
methacrylate,
butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate,
ethylhexyl
acrylate, 2-ethylhexyl methacrylate, 2-ethyl hexyl acrylate, isoprene, octyl
acrylate,
octyl methacrylate, iso-octyl acrylate, iso-octyl methacrylate,
trimethyolpropyl
triacrylate, styrene, «-methyl styrene, glycidyl methacrylate, carbodiimide
methacrylate, C,-C,g alkyl crotonates, di-n-butyl maleate, a or-~3-vinyl
naphthalene, di-
octyhnaleate, allyl methacrylate, di-allyl maleate, di-allylmalonate,
methyoxybutenyl
methacrylate, isobornyl methacrylate, hydroxybutenyl methacrylate,
hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, acrylonitrile, vinyl
chloride, -
vinylidene chloride, vinyl acetate, vinyl ethylene carbonate, epoxy butene,
3,4-
dihydroxybutene, hydroxyethyl(meth)acrylate, methacrylamide, acrylamide, butyl
acrylamide, ethyl acrylamide, butadiene, vinyl ester monomers,
vinyl(meth)acrylates,
isopropenyl(meth)acrylate, cycloaliphaticepoxy(meth)acrylates, ethylformamide,
4-
vinyl-1,3-dioxolan-2-one, 2,2-dimethyl-4 vinyl-1,3-dioxolane, and 3,4-di-
acetoxy-1-
CA 02297987 2000-02-04
-13-
butene or a mixture thereof. Suitable monomers are described in "The Brandon
Associates," 2nd edition, 1992 Merrimack, New Hampshire, and in "Polymers and
Monomers," the 1966-1997 Catalog from Polyscience, Inc., Warrington,
Pennsylvania,
U.S.A.
Acid vinyl monomers that may be used to prepare the latex polymer include, but
are not limited to, acrylic acid, methacrylic acid, itaconic acid, crotonic
acid, and
monovinyl adipate.
Preferred monomers useful for making the latex polymer/(co)polymer are
ethylenically unsaturated monomers including, but not limited to, acrylates,
methacrylates, vinylesters, styrene, styrene derivatives, vinyl chloride,
vinylidene
chloride, acrylonitrile, isoprene and butadiene. In a more preferred
embodiment, the
latex polymer comprises (co)polymers of 2-ethyl-hexyl acrylate, styrene,
butylacrylate,
butylmethacrylate, ethylacrylate, methylmethacrylate, butadiene and isoprene.
In a preferred embodiment, the molecular weight of the latex polymer is a
weight average molecular weight (Mw) of from 1,000 to 1,000,000 as determined
by
gel permeation chromatography (GPC), more preferably a weight average
molecular
weight of from 5000 to 250,000. In one embodiment, the glass transition
temperature
(Tg) of the latex polymer is then that or equal to about 170 °C.
The diol latex compositions of this invention may be characterized as
stabilized
latexes in a continuous phase comprising a diol component. A stable latex is
defiiled
for the purposes of this invention as one in which the particles are
colloidally stable,
_.
i.e., the latex particles remain dispersed in the continuous phase for long
periods of
time, such as 24 hours, preferably 48 hours, even more preferably, one week.
The latex polymer particles generally have a spherical shape. The latex
polymer may be a core shell polymer or a non core shell polymer. It is
possible to
prepare the polymers in a corelshell fashion by staging the monomer addition.
For
--CA 02297987 2000-02-04
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example, the composition of the monomer feed of the polymerization may be
changed
over the course of the reaction in an abrupt fashion, resulting in a distinct
core and shell
portion of the polymer. The core/shell polymer particles may also be prepared
in a
multilobe form, a peanut shell, an acorn form, or a raspberry form. That in
such
particles, the core portion can comprise from about 20 to about 80 percent of
the total
weight of said particle and the shell portion can comprise from about 80 to
about 20
percent of the total weight volume of the particle.
In one embodiment, chain transfer agents are used in the emulsion
polymerization. Typical chain transfer agents are those Irnown in the art.
Chain
transfer agents that may be used in the emulsion polymerization reaction to
form the
diol latex compositions include, but are not limited to, butyl mercaptan,
dodecyl
mercaptan, mercaptopropionic acid, 2-ethylhexyl-3-mercaptopropionate, n-butyl-
3-
mercaptopropionate, octyl mercaptan, isodecyl mercaptan, octadecyl mercaptan,
mercaptoacetate, allyl mercaptopropionate, allyl mercaptoacetate, crotyl
mercaptoproprionate, crotyl mercaptoacetate, and the reactive chain transfer
agents
disclosed or described in U.S. Patent No. 5,247,040, which is incorporated
herein by
this reference. Preferably the chain transfer agent is selected from the
mercaptans and
various alkyl halides, including but not limited to carbon tetrachloride; more
preferably
the chain transfer agent is 2-ethylhexyl-3-mercaptopropionate. Chain transfer
agents
can be added in amounts from 0 to 2 parts per hundred monomer (phm), more
preferably 0 to 0.5 phm.
The latex polymers of the invention can be uncrosslinked or crosslinked. When
crosslinked, suitable crosslinking agents include multifunctional unsaturated
compounds including, hut not limited to, divinyl benzene, allyl methacrylate,
allyl
acrylate, multifunctional acrylates and mixtures thereof. Suitable
multifunctional
acrylates include, but are not limited to, ethylene diol dimethacrylate,
ethylene diol
diacrylate, trimethylolpropane triacrylate, trimethylolpropane
trimethacrylate,
pentaerythritoltetraacrylate and mixtures thereof. The amount of the
crosslinking
monomer in the emulsion polymerization can be controlled to vary the gel
fraction of
02297987 2000-02-04
-15-
the latex from 20 to 100 percent. The gel fraction is the amount that will not
dissolve
in a good solvent.
The latex particles may be functionalized by including monomers with pendent
functional groups. Functional groups that may be incorporated in the latex
particle
include, but are not limited to, epoxy groups, acetoacetoxy groups, carbonate
groups,
hydroxyl groups amine groups, isocyanate groups, amide groups, and mixtures
thereof.
The functional groups may be derived from a variety of monomers, including,
but not
limited to, glycidyl methacrylate, acetoacetoxy ethyl methacrylate, vinyl
ethylene
carbonate, hydroxyl ethyl methacrylate, t-butylaminoethyl methacrylate,
dimethylamino methacrylate, m-isopropenyl-alpha,alpha-dimethylbenzyl
isocyanate,
acrylamide and n-methylolacrylamide. The addition of functional groups allows
for
further reaction of the polymer after latex synthesis. The functionality may
be useful to
impart latent crosslinking or it may be used to react with condensation
polymers as
discussed in Section II, below.
Initiators can be used in the emulsion polymerization to form the diol latex
compositions, which include, but are not limited to salts of persulfates,
water or diol
soluble organic peroxides and azo type initiators. Prefen:ed initiators
include, but are
not limited to hydrogen peroxide, potassium or ammonium pemxydisulfate,
dibenzoyl
peroxide, lauryl peroxide, ditertiary butyl peroxide, 2,2'-
azobisisobutyronitrile, t-butyl
hydroperoxide, benzoyl peroxide, and mixtures thereof. Redox initiation
systems
(Reduction Oxidation Initiation) such as iron catalyzed reaction of t-butyl
hydroperoxide with isoascorbic acid are also useful. It is preferable not to
use initiators
capable of generating a stmng acid as a by-product. This avoids possible side
reactions
"- of the diol component of~'the solvent with the acid. Initiators can be
added in amounts
from 0.1 to 2 phm, more preferably from 0.3 to 0.8 phm.
Reducing agents may also be used in the emulsion polymerization. Suitable
reducing agents are those that increase the rate of polymerization and
include, for
example, sodium bisulfate, sodium hydrosulfite, sodium formaldehyde
sulfoxylate,
02297987 2000-02-04
-16-
ascorbic acid, isoascorbic acid and mixtures thereof. If a reducing agent is
introduced
into the emulsion polymerization, it is preferably added in an amount of 0.1
to 2 phm,
more preferably 0.3 to 0.8 phm. It is preferable to feed the reducing agent
into the
reactor over time.
Buffering agents may also be used in the diol containing emulsion
polymerization to control the pH of the reaction. Suitable buffering agents
include, but
are not limited to, ammonium and sodium salts of carbonates and bicarbonates.
It is
preferred that the buffering agents be included when using acid generating
initiators,
including, but not limited to, the salts of persulfates.
Polymerization catalysts may also be used in the emulsion polymerization.
Polymerization catalysts are those compounds that increase the rate of
polymerization
and which, in combination with the above described reducing agents, may
promote
decomposition of the polymerization initiator under the reaction conditions.
Suitable
catalysts include, but are not limited to, transition metal compounds such as,
for
example, ferrous sulfate heptahydrate, ferrous chloride, cupric sulfate,
cupric chloride,
cobalt acetate, cobaltous sulfate, and mixtures thereof.
The diol latex composition is prepared by first forming an emulsion or
solution
comprising monomers, an initiator, a surfactant and a continuous phase. In one
embodiment, the continuous phase comprises 60 to 100% by weight of the diol
component. The mixture is then heated which causes the monomer to polymerize
and
form the latex polymers. Typically, the monomer is fed into the reactor over a
period
of time, and a separate initiator feed is also fed into the reactor over time.
_.
The diol latex composition may contain a stabilizer or a stabilizer does not
have
to be present. Stabilizers suitable for use in the diol latex composition
include, but are
not limited to an anionic stabilizer, a nonionic suspension stabilizer, an
amphoteric
suspension stabilizer or a mixture thereof. The suspension stabilizer must be
soluble in
the continuous phase, but substantially insoluble with the monomers. If
present, the
02297987 2000-02-04
-17-
concentration of the suspension stabilizer is from 3 to 15 percent by weight
of the
monomers; preferably from 7 to 8 percent by weight of the monomers.
As the diol concentration in the continuous phase approaches 100%, the wetting
properties of the diol latex composition for hydrophobic surfaces improve, and
the diol
latex composition is less volatile. The reduced volatility of the diol latex
composition
is especially advantageous when the diol latex composition is used in a
condensation
reaction as disclosed in Section II, below.
The polymers produced by this invention are useful for thermoplastic
engineering resins, elastomers, filins, sheets and container plastics. The
diol latex
compositions of the invention are useful in a variety of coating compositions
such as
architectural coatings, maintenance coatings, industrial coatings, automotive
coatings,
textile coatings, inks, adhesives, and coatings for paper, wood, and plastics.
Accordingly, the present invention further relates to such coating
compositions
containing a diol latex composition of the invention. The diol latex
composition of the
invention may be incorporated in those coating compositions in the same manner
as
known polymer latexes and used with the conventional components and/or
additives of
such compositions. The coatings may be clear or pigmented.
Upon formulation, a coating composition containing a diol latex composition of
the invention may then be applied to a variety of surfaces, substrates, or
articles, e.g.,
paper, plastic, steel, aluminum, wood, gypsum board, or galvanized sheeting
(either
primed or unprimed). The type of surface, substrate or article to be coated
generally
determines the type of coating composition used. The coating composition may
be
applied using means known in tl~e art. For example, a coating composition may
be
applied by spraying or by coating a substrate. In general, the coating may be
dried by
heating but preferably is allowed to air dry.
The coating composition contains the diol latex composition of the invention,
and may further contain water, a solvent, a pigment (organic or inorganic)
and/or other
02297987 2000-02-04
-18-
additives or fillers known in the art. Such additives or fillers, include, but
are not
limited to, leveling, rheology, and flow control agents such as silicones,
fluorocarbons,
urethanes, or cellulosics, extenders, reactive coalescing aids such as those
described in
U.S. Patent No. 5,349,026, flatting agents, pigment wetting and dispersing
agents and
surfactants, ultraviolet absorbers, ultraviolet light stabilizers, tinting
pigments,
extenders, defoaming and antifoaming agents, anti-settling, anti-sag and
bodying
agents, anti-skinning agents, anti-flooding and anti-floating agents,
fungicides and
mildewcides, corrosion inhibitors, thickening agents, plasticizers, reactive
plasticizers,
curing agents or coalescing agents. Specific examples of such additives can be
found in
Raw Materials Index, published by the National Paint & Coatings Association,
1500
Rhode Island Avenue, NW, Washington, DC 20005, U.S.A.
The diol latex composition of the present invention can be utilized alone or
in
conjunction with other conventional polymers. Such polymers include, but are
not
limited to, polyesters, such as terephthalate based polymers, polyesteramides,
cellulose
esters, alkyds, polyurethanes, polycarbonates, epoxy resins, polyamides,
acrylics, vinyl
polymers, styrene-butadiene polymers, vinylacetate-ethylene copolymers, and
mixtures
thereof.
The diol latex compositions of the invention are also useful as reactants in
condensation polymerizations. As reactants in condensation polymerizations,
the diol
latex compositions of this invention can be used to modify thermoplastic
condensation
polymers by coreacting the latex diols with diacids, diisocyanates, and
dialkyl, diaryl-
or dihalo- carbonates. Section II below, describes, as one of its embodiments,
such a
use of the diol latex composition as a reactant in a condensation
polymerization. In
addition, the invention can act as a convenient delivery method to deliver the
latex
polymer into the thermoplastic condensation polymer.
02297987 2000-02-04
- 19-
II. Modified Condens9tinr polxmer Matrix
In a second major embodiment, the invention concerns the introduction of a
polymer colloid system into a reaction that forms a condensation polymer,
resulting in a
S product having polymer particles entrapped in a condensation polymer matrix.
The
polymer colloid system that is introduced into the polymerization reaction is
herein
defined as polymer particles dispersed in a continuous phase, the polymer
particles
preferably having a particle size in the range of from 0.020 microns to 1000
microns.
The continuous phase may contain small amounts of unreacted monomer,
surfactant,
etc. The polymer particles suitable for use in the polymer colloid system,
which are
herein defined as the first polymer, comprise that same polymers made from the
same
ethylenically unsaturated monomers as those described in connection with the
diol latex
composition described in Section I, above, and may be fimctionalized or
crosslinked in
the same manner as that disclosed for the latex polymers of Section I. If
fimctionalized,
1 S it is preferred that the functional groups include groups capable of
reacting with a
diacid, diisocyanate, diarylcarbonate, dialkylcarbonate, dihalocarbonate, or a
diol
component. These fimctional groups include, but are not limited to, epoxy,
acid,
hydroxyl, isocyanate, amine, amide, and carbonate groups or a mixture thereof.
In
addition the first polymer may be a core-shell or non core-shell polymer.
The polymer colloid system may be prepared by a variety of methods,
including, but not limited to, emulsion, suspension, dispersion polymerization
and
mechanical emulsification. In general, dispersion and suspension
polymerization
produce larger particle sizes, typically in the range of 1 to 500 microns,
while emulsion
polymerization produces particles of smaller sizes, typically in the range of
10 to 1000
nanometers.
In a preferred embodiment, the first polymer is a non core-shell polymer, and
the first polymer of the polymer colloid system comprises from 50 to 100%,
preferably
70 to 100%, even more preferably from 80 to 100% of the residues of one of the
CA 02297987 2000-02-04
-20-
following monomers: ?-ethyl hexyl acrylate, butyl acrylate, isoprene, styrene,
butadiene, or acrylonitrile.
Emulsion, suspension, dispersion and mechanical emulsification polymerization
are lrnown techniques of forming polymer colloid systems. If dispersion
polymerization is selected to prepare the polymer colloid system that is
introduced into
the condensation polymerization reaction, processes similar to those described
in U.S.
Pat No. 4,885,350 and U.S. Pat No. 5,061,766 may be used to prepare polymer
colloid
systems having a particle size range of 1 micron to 100 microns. If mechanical
emulsification is used, processes similar to those described in U.S. Patent
No.
4,177,177, U.S. Patent No. 5,358,981 and U.S. Patent No. 5,612,407.
For either the emulsion, suspension, dispersion or mechanical emulsification
polymerized polymer colloid system, formed as a precursor to be introduced
into the
condensation reaction, the solvent or continuous phase may be water or diol
based. It is
preferred, however, that the continuous phase be diol based, so that the diols
in the
continuous phase of the polymer colloid system may participate in the
condensation
polymerization reaction. In a particularly preferred embodiment, the polymer
colloid
system is the diol latex composition described in Section I, above. Further,
the
continuous phase of each polymer colloid system may consist essentially of or
consist
of either water or diol; or comprise any proportion of either component.
In the polymer colloid system having a diol based continuous phase, the diols
in
the continuous phase co-react with the diacids, diisocyanates, dialkyl or
diaryl or dihalo
carbonates, or mixtures thereof that comprise the reaction medium which forms
the
- condensation polymer. 'fin this embodiment, the diol component preferably
comprises
25 to 100% by weight of the continuous phase; preferably 50 to 100% by weight
of the
continuous phase; more preferably from 70 to 100% by weight of the continuous
phase;
even more preferably from 90 to 100% by weight of the continuous phase. In a
preferred embodiment, the continuous phase consists essentially of the diol
component.
02297987 2000-02-04
-21 -
Suitable diol components for the diol based continuous phase of the polymer
colloid
system include, but are not limited to, the diol components described in
Section I.
The diol component may be present in either the continuous phase, the
condensation reaction medium, or both. The diol concentration present in the
original
reaction medium may be adjusted to account for the diol concentration in the
polymer
colloid system. The polymer colloid system may be introduced into the
condensation
polymerization at various stages of the polymerization. For example, in a
polyethylene terephthalate) (PET) polymerization, dimethyl terephthalate
(DMT),
ethylene diol (EG) and catalyst metals are placed in a flask and polymerized.
The latex
can be added 1 ) "up front", i.e. with the other materials at the start, 2)
after the other
starting materials have melted and formed a homogeneous solution, 3) after the
DMT
and EG have reacted in the first stage and given off MeOH, 4) right before NZ
is turned
off and vacuum applied, 5) sometime during the final "polycondensation phase,"
or
anywhere in between, i.e. during the ester exchange phase. The final blend can
be
affected by the time the latex is added to the condensation polymer. While not
wishing
to be bound by any mechanism, it is understood that the size and shape of the
emulsion
polymer in the condensation polymer matrix can be affected by the time of the
addition.
Also, particular chemical interaction between emulsion polymers and
condensation
polymers are affected by time of addition, and they in consequence, affect
final blend
properti es.
The process of the invention does not require the isolation of the polymer
iwthe
polymer colloid system. Thus the present invention overcomes the necessity of
preparing a core shell polymer or the necessity of harvesting the polymer from
the
emulsion. Further, since blending takes place during the condensation polymer
preparation, there is no need for a polymer/polymer post blending step that is
energy
intensive, expensive and often leads to the reduction of the molecular weight
of the
condensation polymer.
02297987 2000-02-04
-22-
In a preferred embodiment, the reaction medium in which the polymer colloid
systems of the invention are introduced forms polyesters. The term
"polyester," as used
herein, refers to any unit-type of polyester falling within the scope of the
polyester
portion of the blend, including, but not limited to, homopolyesters, and
copolyesters
(two or more types of acid and/or diol residues of monomeric units). The
polyesters of
the present invention comprise an acid residue and a diol residue. The acid
residues of
the polyesters of the present invention total 100 mol% and the diol residues
of the
polyesters of the present invention total 100 mol%. It should be understood
that use of
the corresponding derivatives, specifically acid anhydrides, esters and acid
chlorides of
these acids is included throughout the application in the term "acid residue."
In
addition to the acid residue and the diol residue, the polyester may comprise
other
modifying residues. These modifying residues include, but are not limited to,
a
diamine, which would result in a polyester/amide.
The polyesters preferably comprise residues of dicarboxylic acids or esters,
including, but not limited to, aromatic dicarboxylic acid or ester residues,
preferably
having from 8 to 14 carbon atoms, aliphatic dicarboxylic acid or ester
residues,
preferably having from 4 to 12 carbon atoms, or cycloaliphatic dicarboxylic
acid or
ester residues, preferably having from 8 to 12 carbon atoms. The acid or ester
residue
that comprise the acid moiety of the polyester preferably include residues of
phthalic
acid; terephthalic acid, naphthalenedicarboxylic acid, isophthalic acid;
cyclohexanediacetic acid; diphenyl 4,4'-dicarboxylic acid; succinic acid;
glutaric acid;
adipic acid; fumaric acid; azelaic acid; resorcinoldicetic acid; didiolic
acid; 4,4'-
oxybis(benzoic) acid; biphenyldicarboxylic acid; 1,12-dodecanedicarboxylic
acid; 4,4'-
sulfonyldibenzoic acid; 4,4'-methyldibenzoic acid; trans 4,4'-
stilbenedicarboxylic acid;
1,2-, 1,3-, and 1,4-cyclohexanedicarboxylic acids; and mixtures thereof. The
polyester
may be prepared from one or more of the above dicarboxylic acids.
Preferred examples of dicarboxylic acids or derivatives used to prepare the
polyester are terephthalic acid or ester and 2,6-napthalenedicarboxylic acid
or ester,
succinic, isophthalic, glutaric, adipic acid or ester. Other
naphthalenedicarboxylic acids
-.CA 02297987 2000-02-04
- 23 -
or their esters may also be used. These include the 1,2-; 1,3-; 1,4-; 1,5-;
1,6-; 1,7-; 1,8-;
2,3-; 2,4-; 2,5-; 2,6-; 2,7-; and 2,8- naphthalenedicarboxylic acids, and
mixtures thereof.
Even more preferred is the 2,6- napthalenedicarboxylic acid as the modifying
acid.
5 The diol component of the polyester comprises residues of diols preferably
selected from cycloaliphatic diols preferably having from 6 to 20 carbon atoms
or
aliphatic diols preferably having from 2 to 20 carbon atoms. Examples of such
diols
include ethylene diol, diethylene diol, triethylene diol, neopentyl diol, 1,4
butanediol,
1,6 hexanediol 1,4-cyclohexanedimethanol, 1,3-propanediol, 1,10-decanediol,
2,2,4,4,-
10 tetramethyl-1,3-cyclobutanediol, 3-methyl-2,4-pentanediol, 2-methyl-1,4-
pentanediol,
2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1-1,3-hexanediol, 2,2-diethyl-1,3-
propanediol,
1,3-hexanediol, 1,4-bis-(hydroxyethoxy)benzene, 2,2-bis-(4-hydroxycyclohexyl)-
propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutaine, 2,2-bis-(3-
hydroxyethoxyphenyl)propane, 2,2-bis-(4-hydroxypropoxyphenyl)propane and
15 mixtures thereof. The diol component is more preferably selected from
ethylene diol,
1,4-butanediol, neopentyl diol, cyclohexanedimethanol, diethylene diol and
mixtures
thereof. The diols may be modified with up to about 50 mol % and more
preferably up
to about 20 mol % of any of the other diols disclosed herein.
20 It is preferred that the polyesters of the invention are essentially
linear. The
polyesters may be modified with low levels of one or more branching agents. A
branching agent is herein defined as a molecule that has at least three
functional groups
that can participate in a polyester forming reaction, such as hydroxyl,
carboxylic acid,
carboxylic ester, phosphorous based ester (potentially trifunctional) and
anhydride
25 (difunctional).
Branching agents useful in preparing the polyester of the invention include,
but
are not limited to glycerol, pentaerythritol, trimellitic anhydride,
pyromellitic
dianhydride, tartaric acid, and mixtures thereof. If branching agents are used
in the
30 condensation reaction, a preferred range for the branching agent is from
0.1 to 2.0
02297987 2000-02-04
-24-
weight %, more preferably from about 0.2 to 1.0 weight %, based on the total
weight of
the polyester.
Addition of branching agents at low levels does not have a significant
detrimental effect on the physical properties of the polyester and provides
additional
melt strength which can be very useful in film extruding operations. High
levels of
branching agents incorporated in the copolyesters results in copolyesters with
poor
physical properties, for example low elongation.
An agent comprising one or more ion-containing monomers may be added to
increase the melt viscosity of the polyesters. The ion-containing monomers
useful in
the invention, include, but are not limited to alkaline earth metal salts of
sulfisophthalic
acid or a derivative thereof. The preferred weight percentage for ion-
containing
monomers is from about 0.3 to 5.0 mole%, preferably from about 0.3 to 3.0
mole%.
The ion containing monomers also increase the melt viscosity of the polyesters
and do
not reduce the elongation of the films to substantially low levels.
The homo or copolyesters of the invention are preferably prepared in reaction
carried out using diols and diacids (or diesters or anhydrides) at
temperatures from
about 150°C to about 300°C in the presence ofpolycondensation
catalysts, including,
but not limited to, titanium tetrachloride, titanium tetraisopropoxide,
manganese
diacetate, antimony oxide, antimony triacetate, dibutyl tin diacetate, zinc
chloride, or a
mixture thereof. The catalysts are typically employed in amounts between 10 to
1000 ppm, based on the total weight of the reactants. The final stage of the
reaction is
generally conducted under high vacuum (<1 Omm of Hg) in order to produce a
high
molecular weight polyester.
The invention also relates to the modification, as discussed herein, of high
molecular weight homo or copolyesters prepared by a method comprising the
following steps:
02297987 2000-02-04
- 25 -
(I) combining the diols and diacids as described herein, with a catalyst
system,
(II) in a first stage, heating said reaction mixture at from 190 ° C
and 220 ° C,
at or slightly above atmospheric pressure, and
(III) in a second stage adding a phosphorous based additive, heating the
reaction mixture between 220°C and 290°C under a reduced
pressure of
0.05 to 2.00 mm of Hg.
These polyesters are best prepared with one of the above named catalyst
systems in the presence of a phosphorous based additive. The preferred
concentration
of catalyst in the reaction is about 5 to about 220 ppm, with the most
preferred
concentration being about 20 to about 200 ppm. This reaction is best carried
out in the
two stages as described above.
In another embodiment of the invention, a polycarbonate may be modified by
introduction of the polymer colloid system into the reaction medium. The
polycarbonates that may be modified, include, but are not limited to,
homopolymers,
copolymers and mixtures thereof that are prepared by reacting a dihydric
phenol with a
carbonate precursor. The dihydric phenols which may be used to produce the
carbonate, include, but are not limited to bisphenol-A, (2,2-bis(4-
hydroxyphenyl)propane), bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxy-3-
methyl-
phenyl)propane, 4,4-bis(4-hydroxyphenyl heptane, 2,2-(3,5,3',5'-tetrachloro-
4,4'-
dihydroxydiphenyl)propane, 2,2-(3,5,3',5'-tetrabromo-
4,4'dihydroxydiphenyl)propane,
(3,3'-dichloro-4,4'-dihydroxydiphenyl) methane, and mixtures thereof.
Branching
agents useful in preparing the polycarbonate of the invention include, but are
not
limited to glycerol, pe~taerythritol, trimellitic anhydride, pyromellitic
dianhydride,
tartaric acid, and mixtures thereof. If branching agents are used in the
condensation
reaction, a preferred range for the branching agent is fibm 0.1 to 2.0 weight
%, more
preferably from about 0.2 to 1.0 weight %, based on the total weight of the
polyester.
02297987 2000-02-04
-26-
In another embodiment of the invention, the thermoplastic condensation
polymer to be modified by introduction of the polymer colloid system may
comprise a
polyurethane. The polyurethane that may be modified comprises residues of a
diol or
diols and residues of a di-isocyanante or di-isocyanates. The diol residues of
the
polyurethane may be derived from diols including but not limited to, 1,3-
cyclobutanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-
cyclohexanediol, 1,4-
cyclohexanediol, 2-cyclohexane-1,4-diol, 2-methyl-1,4-cyclohexanediol, 2-ethyl-
1,4
cyclohexanediol, 1,3-cycloheptanediol, 1,4 cycloheptanediol, 2-methyl-1,4
cycloheptanediol, 4-methyl-1,3-cycloheptanediol, 1,3-cyclooctanediol, 1,4
cyclooctanediol, 1,5 cyclooctanediol, 5-methyl-1,4-cyclooctanediol, 5-ethyl-
1,4-
cyclooctanediol, 5-propyl-1,4 cyclooctanediol, 5-buty1,1,4-cyclooctanediol, 5-
hexyl-
1,4-cyclooctanediol, 5-heptyl-1,4-cyclooctanediol, 5-octyl-1,4
cyclooctanediol, 4,4'
methylenebis(cyclohexanol), 4,4'-methylenebis(2-methylcyclohexanol), 3,3'-
methylenebis(cyclohexanol), 4,4' ethylenebis(cyclohexanol),
4,4'propylenebis(cyclohexanol), 4,4' butylenebis(cyclohexanol), 4,4'
isopropylidenebis(cyclohexanol), 4,4' isobutylenebis(cyclohexanol), 4,4'
dihydroxydicyclohexyl, 4,4' carbonylbis(cyclohexanol), 3,3'-
carbonylbis(cyclohexanol), 4,4'sulfonylbis(cyclohexanol), 4,4'-
oxybis(cyclohexanol),
and mixtures thereof.
The polyurethanes of the invention can be prepared using any known methods
for bringing together, in the presence or absence of solvents,
polyisocyanates,
extenders, and optionally, high molecular weight polyols. This includes manual
or
mechanical mixing means including casting, reaction extrusion, reaction
injection
molding and related processes. Typical preparative methods useful in the
instant
invention are disclosed in U.S. Patent Nos. 4,376,834 and 4,567,236,
incorporated
herein by reference, whose disclosures relate to polyurethane plastic forming
ingredients and preparative procedures.
The mixing of the reactants may be carried out at ambient temperature, i.e at
a
temperature from 20°C to 25°C. The resulting mixture is
preferably heated to a
02297987 2000-02-04
-27-
temperature from 40°C to 130°C, more preferably from 50°C
to 100°C; preferably one
or more of the reactants is heated to a temperature within these ranges before
admixing. .
A catalyst may optionally be included in the reaction mixture which is used to
prepare the polyurethanes. Any of the catalysts conventionally employed in the
art to
catalyze the reaction of an isocyanate with a reactive hydrogen containing
compound
may be used for this purpose. Suitable catalyst are disclosed in U.S. Patent
No.
4,202,957 at column 5, lines 45 to 67, incorporated herein by this reference.
The
amount of catalysts used is preferably within the range of about 0.02 to 2.0
percent by
weight, based on the total weight of the reactants. In a particular embodiment
of the
one-shot procedure, the reaction is carried out on a continuous basis using
apparatus
and procedures such as that disclosed in U.S: Patent No. 3,642,964.
The polyurethanes of this invention include both thermoplastic injection-
moldable and thermoset resins. The thermoplastic resins are obtained by
employing
substantially difunctional polyisocyanates and difunctional extenders, and a
polyol
having a functionality preferably not exceeding 4, although polyols having
higher
functionalities may be employed where the weigh proportion used in a low
range. As
will be recognized by one skilled in the art, this limit will vary according
to the nature
of the polyol, the molecular weight of the polyol, and the amount of polyol
used. In
general, the higher the molecular weight of the polyol the higher the
functionality
which can be employed without losing the thermoplastic properties in the
polyurethane
product.
The di-isocyanante residue may be derived from di-isocyanates, including, but
not limited to methylenebis(phenyl isocyanate) including the 4,4'-isomer, the
2,4'
isomer and mixtures thereof, m-and p-phenylene diisocyanates, chlorophenylene
diisocyanates, a,a'-xylylene diisocyanate, 2,4-and 2,6-toluene diisocyanates
and
mixtures of these latter two isomers, tolidine diisocyanate, hexamethylene
diisocyanate,
1,5-naphthalene diisocyante, isophorone diisocyanate and the like,
cycloaliphatic
diisocyanates such as methylenebis(cyclohexyl isocyanate) including the 4,4'
isomer,
02297987 2000-02-04
-28-
the 2,4' isomer and mixtures thereof, and all the geometric isomers thereof
including
trans/trans, cis/trans, cis/cis and mixtures thereof, cyclohexylene
diisocyanantes (1,2,
1,3 or 1,4-), 1-methyl-2,5-cyclohexylene diisocyanate, 1-methyl-2,4
cyclohexylene
diisocyante, 1-methyl-2,6-cyclohexyl diisocyanate, 4,4'-
isopropylidenebis(cyclohexyl
isocyanate), 4,4'-diisocyanatodicyclohexyl and all geometric isomers and
mixtures
thereof. Also included are the modified forms of
methylenebis(phenylisocyanate). By
the latter are meant those forms of methylenebis(phenyl isocyanate) which have
been
treated to render them stable liquids at ambient temperature. Such products
include
those which have been reacted with a minor amount (up to about 0.2 equivalents
per
equivalent of polyisocyanate) of an aliphatic diol or a mixture of aliphatic
diols such as
the modified methylenebis(phenyl isocyanates) described in U.S. Pat. Nos.
3,394,164;
3,644,457; 3,883,571; 4,031,026; 4,115,429; 4,118,411; and 4,299,347.
The modified methylenebis(phenyl isocyanates) also include those which have
been treated so as to convert a minor proportion of the diisocyanate to the
corresponding carbodiimide which then interacts with further diisocyanate to
form the
aeration-imine groups, the resulting product being a stable liquid at ambient
temperatures as described, for example in U.S. Pat. No. 3,384,653. Mixtures of
any of
the above-named polyisocyanates can be employed if desired. Further in the
case of the
preparation of those polyurethanes of the invention which are thermoset, it is
possible
to introduce into the polyisocyanate component employed in the reaction minor
amounts (up to 30 percent by weight) of polymethylene polyphenyl
polyisocyanates.
The latter are mixtures containing from about 20 to 90 percent by weight of
methylenebis(phenyl isocyanate) the remainder of the mixture being
polymethylene
polyphenyl polyisocyanates of functionality higher than 2Ø Such
polyiscoyanates and
methods for their prep~ra~ion are well lrnown in the art; see for example,
U.S. Pat. Nos.
2,683,730; 2,950,263; 3,012,008 and 3,097,191. Branching agents useful in
preparing
the polyurethane of the invention include, but are not limited to glycerol,
pentaerythritol, trimellitic anhydride, pyromellitic dianhydride, tartaric
acid, and
mixtures thereof. If branching agents are used in the condensation reaction, a
preferred
02297987 2000-02-04
-29-
range for the branching agent is from 0.1 to 2.0 weight %, more preferably
from about
0.2 to 1.0 weight %, based on the total weight of the polyester.
Other ingredients may optionally be added to the compositions of the present
invention to enhance the performance properties of the condensation polymer /
latex
polymer matrix . For example, surface lubricants, denesting agents,
stabilizers,
antioxidants, ultraviolet light absorbing agents, mold release agents, metal
deactivators,
colorants such as black iron oxide and carbon black, nucleating agents,
phosphate
stabilizers, zeolites, fillers, mixtures thereof, and the like, can be
included herein. All
of these additives and the use thereof are well known in the art. Any of these
compounds can be used so long as they do not hinder the present invention from
accomplishing its objects.
End-use applications for the compositions of the condensation polymers
produced according to the instant invention include impact-modified polymers,
elastomers, high barrier films and coatings, improved barrier polymers, and
polymers
having improved mechanical properties, such as improved tensile strength,
improved
elongation at break, better weathering properties, and improved flexural
strength. Other
end-use applications include engineering resins, coatings, containers for
barrier
applications and molding plastics. In addition, powder coatings may be
produced form
the modified condensation polymers produced according to the invention. The
polymers produced by this invention are useful for thermoplastic engineering
resins,
elastomers, films, sheets and container plastics.
In a preferred embodiment, an impact modified polyester is prepared
comprising a non core shell first polymer derived from a polymer colloid
system. In
another preferred embodiment, a hydroxyl functionalized polyester coating is
prepared
comprising a non core shell first polymer derived from a polymer colloid
system.
In one embodiment of the invention, a modified condensation polymer ,
including, but not limited to, an impact modified plastic, is produced from a
polymer
CA 02297987 2000-02-04
-30-
colloid system comprising first polymers which are non core shell polymers,
and a
condensation polymer. The polymer colloid in this embodiment has a Tg less
than
40°C, while the condensation polymer has a Tg greater than 40°C.
The impact
modified plastic is preferably prepared from a polymer colloid system
comprising a
first polymer which comprises residues of 2-ethyl hexyl acrylate, butyl
acrylate,
isoprene, butadiene, lauryl acrylate, acrylonitrile, vinylidene chloride, or a
mixture
thereof.
In another embodiment of the invention, a modified condensation polymer,
including but not limited to, a thermoplastic elastomer, is produced from a
polymer
colloid system comprising first polymers which are non core shell polymers.
The
polymer colloid in this embodiment has a Tg greater than 40°C, and the
condensation
polymer has a Tg less than 40°C and preferably has essentially no
crystallinity. The
thermoplastic elastomer is preferably prepared from a polymer colloid system
comprising a first polymer comprising residues of vinyl chloride, styrene, a-
methyl
styrene, methyl methacrylate, vinyl naphthalene, isobomyl methacrylate or a
mixture
thereof.
Elastomers are finding increasing utility, in particular thermoplastic
elastomers
(TPE's) that are elastomeric at use temperature, but can be proccssed as a
plastic (e.g.
injection molding, extruded) at appropriate temperatures. An elastomer may be
prepared according to the process of the invention. For example, a
condensation
polymer that is amorphous and has a low Tg may be a viscous fluid that is not
useful as
a plastic or elastomer. This low Tg viscous polymer may be used to make an
elastomer
by adding a second polymer, in the form of a polymer colloid system, that acts
as a
' physical cross-linker and is a tie-point for the viscous polymer chains. A
phase
separated polymer blend will result that has elastomeric properties.
CA 02297987 2000-02-04 --
-31 -
The following examples are put forth so as to provide those of ordinary skill
in
the art with a complete disclosure and description of how the compositions of
matter
and methods claimed herein are made and evaluated, and are not intended to
limit the
scope of what the inventors regard as their invention. Efforts have been made
to insure
accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some
errors and
deviations should be accounted for. Unless indicated otherwise, parts are by
weight,
temperature is in ° C or is at room temperature and pressure is at or
near atmospheric.
The materials and testing procedures used for the results shown herein are as
follows:
Inherent viscosity (Ih.V.) was determined at 25 °C with a 0.50 gram
sample in
100 mL of 60/40 by weight solution of phenol/tetrachloroethane.
Molecular weight distributions were determined by gel permeation
chromatography (GPC). Solutions were made by dissolving 4 mg of polymer in a
30/70 by weight solution of hexafluoroispropanol/methylene chloride containing
10%
by volume toluene as a flow rate marker. The system was calibrated using a
series of
narrow molecular weight polystyrene standards. The molecular weights were
reported
in absolute molecular weight values determined from a set of Mark-Houwink
constants
that relate PET to polystyrene.
Thermal transitions were determined by differential scanning calorimetry (DSC)
on a DuPont instruments 2200 DSC. Percent crystallinity was also determined by
DSC. DSC was performed using a scan rate of 20 °C/minute aRer the
sample was
heated above its melting temperature and rapidly quenched below its glass
transition
temperature.
CA 02297987 2000-02-04-------- w ---------
-32-
Films were prepared by compression molding the dried polymer. Drying was
accomplished in a 120 °C vacuum oven (20 mm Hg) overnight. The dried
polymers
were compression molded at Tm + 30 to 50°C into a 6" x 6" film by
pressing between
two metal plates with a 15 mil shim on a Pasadena Hydraulics Inc. press.
Pressure was
gradually applied for 2 minutes before ultimately reaching 15,000 ram force
pounds
and holding for 1 minute. After compression molding, the films were quickly
dipped
into an ice bath to quench. Instrumented impact testing of the filins was done
according to ASTM method D3763, "High Speed Puncture Properties of Plastics
Using
Load and Displacement Sensors." Testing was done at 23 °C on a Ceast
Fractovic
testing machine. Film thickness ranged from 0.33-0.38 mm. Films were placed
over a
hole with a 76 mm insert diameter while the films were hit with a 0.5"
diameter striker
with a velocity of 11.1 f3/s. Failure was classified as brittle if the film
shattered or
fractured into pieces; while a ductile failure was reported if a hole was
created in the
film.
Transmission Electron Microscopy. Thin cross sections were made on a Cryo-
Ultramicrotome operated at -105 °C. The sections were examined in a
Philips CM12
TEM operated at 80kV. The contrast was natural without the use of stains.
Optical Microscopy. Thin cross sections were made at -60°C and
examined
using a Zeiss light microscope.
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
'~ stirrer, 300 g of ethylene diol and 2.33 g of Hitenol A-10, a polymerizable
polyoxyethylene alkyl phenyl ether ammonium sulfate, manufactured by DKS
International, were added. The contents of the reactor were heated to 80
°C. In a
separate 500 ml flask, a monomer/surfactant mix of 118.75 g 2-
ethylhexylacrylate, 6.25
g of trimethylolpropane-triacrylate and 3.60 g of Hitenol A-10 was prepared.
To the
heated reactor, 12.85 g of the monomer/surfactant mix was added. After
allowing the
CA 02297987 2000-02-04
-33-
contents of the reactor to re-equilibrate, 3.0 g of sodium persulfate
dissolved in 15 g of
water was added to the reactor. After a few minutes, the reactor appearance
changed
from clear to a bluish white tint indicating the formation of small particles.
The
remaining monomer mix was fed into the reactor over a period of 39 minutes. At
the
same time the monomer was being added to the reactor, 1.50 g of sodium
persulfate
dissolved in 50 g of water was fed into the reactor. After all the monomer was
added,
the reaction was held at 80 °C for an additional hour at which point
the reactor was
cooled to room temperature.
The resulting latex was filtered through a 100 mesh screen. The dried scrap
collected on the screen was 0.815g. The latex was evaluated for the solids
content
using a CEM microwave drier and contained 28.1 % solids. The effective
diameter as
measured by dynamic light scattering was 181 nm.
I S Exams
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer, 300 g of ethylene diol and 2.3 g of Hitenol A-10 were added. The
contents of
the reactor were heated to 70 °C. In a separate 500 ml flask, a
monomer/surfactant mix
of 118.75g 2-ethylhexylacrylate, 6.25g of trimethylol-propanetriacrylate and
3.60 g of
Hitenol A-10 was prepared. To the heated reactor, 12.85 g of the
monomer/surfactant
mix was added. After allowing the contents of the reactor to re-equilibrate,
3.0 g of
azobisisovaleric acid slurried in 15g of ethylene diol was added to the
reactor. After a
few minutes, the reactor appearance changed from clear to a bluish white tint
indicating
the formation of small particles. The remaining monomer mix was fed into the
reactor
over a period of 58 minutes. After all the monomer was added the reaction was
held at
70 °C for an additional hour and a half at which point the reactor was
cooled to room
temperature.
The resulting latex was filtered through a 100 mesh screen. The dried scrap
collected on the screen was 0.741 g. The latex was evaluated for the solids
content
02297987 2000-02-04
-34-
using a CEM microwave drier and contained 27.6% solids. The effective diameter
as
measured by dynamic light scattering was 122 nm.
5
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer, 272 g of ethylene diol, 0.839 g of sodium formaldehyde sulfoxylate
and 5.04 g
of Hitenol A-10 were added. The contents of the reactor was heated to 65
°C. In a
separate SOOmI flask, a monomer/surfactant mix of 132.81 g 2-
ethylhexylacrylate, 6.99
10 g of trimethylolpropanetriacrylate, 35.66 g of ethylene diol and 2.88 g of
Hitenol A-10
was prepared. To the heated reactor, 17.8 g of the monomer/surfactant mix was
added.
After allowing the contents of the reactor to re-equilibrate, 0.777 g of 90
wt. % t-butyl
hydroperoxide dissolved in 15 g of ethylene diol was added to the reactor.
After a few
minutes, the reactor appearance changed from clear to a bluish white tint
indicating the
15 formation of small particles. The remaining monomer mix was fed into the
reactor over
a period of 58 minutes. After all the monomer was added, the reaction was held
at 65
°C for an additional one half hour at which point the reactor was
cooled to room
temperature.
20 The resulting latex was filtered through a 100 mesh screen. The dried scrap
collected on the screen was 0.8378. The latex was evaluated for the solids
content
using a CEM microwave drier and contained 25.2% solids. The effective diameter
as
measured by dynamic light scattering was 126 nm.
25 Exams
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer; 379.25 g of ethylene diol and 24.65 g of Disponil FES 77, an alkyl
ethoxylate
sodium sulfate, ( 30 % active in water) manufactured by Henkle were added. The
30 contents of the reactor were heated to 65 °C. In a separate 500 ml
flask, a
monomer/surfactant mix of 191.55 g 2-ethylhexylacrylate, 22.54 g of styrene,
11.27 g
02297987 2000-02-04
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of allyl methacrylate, 47.89 g of ethylene diol and 14.09 g of Disponil FES77
was
prepared. To the heated reactor, 28.7 g of the monomer/surfactant mix was
added.
After allowing the contents of the reactor to re-equilibrate, 0.751 g of 90
wt. % t-butyl
hydroperoxide (t-BHP) dissolved in 11 g of ethylene diol was added to the
reactor
followed by 0.255 g of sodium formaldehyde sulfoxylate (SFS) dissolved in 11 g
of
Distilled water. After a few minutes, the reactor appearance changed from
clear to a
bluish white tint indicating the formation of small particles. The remaining
monomer
mix was fed into the reactor over a period of 195 minutes. During the same
time
period, 0.901 g of SFS dissolved in 28 g of distilled water was fed into the
reactor.
also, 0.501 g of 90 wt. % t-BHP dissolved in 56 g of ethylene diol was fed
into the
reactor. After all the monomer was added, the reaction was held at 65
°C for an
additional one half hour at which point the reactor was cooled to room
temperature.
The resulting emulsion was filtered through a 100-mesh screen. The emulsion
contained 27.5 % solids and the particle size was 184 nm as measured by
dynamic light
scattering.
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer; 396.01 g of ethylene diol and 7/89 g of Hitenol HS-20, polymerizable
polyoxyethylene alkyl phenyl ether ammonium sulfate, manufactured by DKS
International, were added. The contents of the rcactor were heated to 65
°C. In a
separate 500 ml flask, a monomer/surfactant mix of 112.68 g 2-
ethylhexylacrylate,
112.68 g of vinyl acetate, 57.46 g of ethylene diol and 4.51 g of Hitenol HS-
20 was
prepared. To the heated reactor, 28.7 g of the monomer/surfactant mix was
added.
After allowing the contents of the reactor to re-equilibrate, 0.751 g of 90
wt. % t-butyl
hydroperoxide (t-BHP) dissolved in 11 g of ethylene diol was added to the
reactor
followed by 0.255 g sodium formaldehyde sulfoxylate (SFS) dissolved in 11 g of
Distilled water. After a few minutes, the reactor appearance changed from
clear to a
bluish white tint indicating the formation of small particles. The remaining
monomer
CA 02297987 2000-02-04
-36-
mix was fed into the reactor over a period of 195 minutes. During the same
time
period, 0.901 g of SFS dissolved in 28 g of distilled water was fed into the
reactor.
Also, 0.501 g of 90 wt. % t-BHP dissolved in 56 g of ethylene diol was fed
into the
reactor. After all the monomer was added, the reaction was held at 65
°C for an
S additional one half hour at which point the reactor was cooled to room
temperature.
The resulting emulsion was filtered through a 100 mesh screen. The emulsion
contained 23.18 % solids and the particle size was 114 nm as measured by
dynamic
light scattering.
ExamRl_e~
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer; 396.01 g of ethylene diol and 7.89 g of Hitenol HS-20 were added. The
contents of the reactor were heated to 65 °C. In a separate 500 ml
flask, a monomer/
surfactant mix of 169.01 g of n-butylacrylate, 4.507 g of Hitenol HS-20 was
prepared.
To the heated reactor, 28.7 g of the monomer/surfactant mix was added. After
allowing
the contents of the reactor to re-equilibrate, 0.751 g of 90 wt. % t-butyl
hydroperoxide
(t-BHP) dissolved in 11 g of ethylene diol was added to the reactor followed
by 0.255 g
sodium formaldehyde sulfoxylate (SFS) dissolved in 11 g of Distilled water.
After a
few minutes, the reactor appearance changed from clear to a bluish white tint
indicating
the formation of small particles. The remaining monomer mix was fed into the
reactor
over a period of 195 minutes. During the same time period, 0.901 g of SFS
dissolved
in 28 g of distilled water was fed into the reactor. Also, 0.501 g of 90 wt. %
t-BHP
dissolved in 56 g of ethylene diol was fed into the reactor. After all the
monomer was
added, the reaction was held at 65 °C for an additional one half hour
at which point the
reactor was cooled to room temperature.
The resulting emulsion was filtered through a 100 mesh screen. The emulsion
contained 27.5 % of solids and the particle size was 102 nm as measured by
dynamic
light scattering.
~'A 02297987 2000-02-0
-37-
xam le 7
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer; 396.01 g of ethylene diol and 7.89 g of Hitenol HS-20 were added. The
contents of the reactor were heated to 65 °C. In a separate 500 ml
flask, a
monomer/surfactant mix of 169.01 g 2-ethylhexylacrylate, 45.07 g of methyl
methacrylate, 11.27 g of allyl methacrylate, 57.46 g of ethylene diol and 4.51
g of
Hitenol HS-20 was prepared. To the heated reactor, 28.7 g of the
monomer/surfactant
mix was added. After allowing the contents of the reactor to re-equilibrate,
0.71 g of 90
wt. % t-butyl hydroperoxide (t-BHP) dissolved in 11 g of ethylene diol was
added to
the reactor followed by 0.255 g sodium formaldehyde sulfoxylate (SFS)
dissolved in 11
g of distilled water. After a few minutes, the reactor appearance changed from
clear to
a bluish white tint indicating the formation of small particles. The remaining
monomer
mix was fed into the reactor over a period of 195 minutes. During the same
time
period, 0.901 g of SFS dissolved in 28 g of distilled water was fed into the
reactor.
Also, 0.501 g of 90 wt. % t-BHP dissolved in 56 g of ethylene diol was fed
into the
reactor. After all the monomer was added, the reaction was held at 65
°C for an
additional one half hour at which point the reactor was cooled to room
temperature.
The resulting emulsion was filtered through a 100 mesh screen. The emulsion
contained 27.0 % solids and the particle size was 140 nm as measured by
dynamic light
scattering.
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer; 267.5 g of ethylene diol and 1.74 g of Hitenol HS-20 were added. The
contents
of the reactor were heated to 65 °C. In a separate 500 ml flask, a
monomer/surfactant
mix of 295.65 g 2-ethylhexylacrylate, 34.78 g of styrene, 17.39 g of allyl
methacrylate,
88.70 g of ethylene diol and 6.96 g of Hitenol HS-20 was prepared. To the
heated
reactor, 44.3 g of the monomer/surfactant mix was added. After allowing the
contents
~'A 02297987 2000-02-04
-38-
of the reactor to re-equilibrate, 1.16 g of 90 wt. % t-butyl hydroperoxide (t-
BHP)
dissolved in 9 g of ethylene diol was added to the reactor followed by 0.348 g
sodium
formaldehyde sulfoxylate (SFS) dissolved in 9 g of distilled water. After a
few
minutes, the reactor appearance changed from clear to a bluish white tint
indicating the
formation of small particles. The remaining monomer mix was fed into the
reactor over
a period of 220 minutes. During the same time period, 1.391 g of SFS dissolved
in 22
g of distilled water was fed into the reactor. Also, 0.773 g of 90 wt. % t-BHP
dissolved
in 44 g of ethylene diol was fed into the reactor. After all the monomer was
added, the
reaction was held at 65 °C for an additional one half hour at which
point the reactor was
cooled to room temperature.
The resulting emulsion contained 41.78 % solids and the particle size was 337
nm as measured by dynamic light scattering.
1 S Exams
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer; 267.5 g of ethylene diol, 7.85 g of Hitenol HS-20, 0.0898 g of a 1
wt.
ammonium iron sulfate solution in water and 0.449 g of a 1% solution of
ethylenediamine tetraaceticacid in water were added. The contents of the
reactor were
heated to 65 °C. In a separate 500 ml flask, a monomer/surfactant mix
of 190.82 g 2-
ethylhexylacrylate, 22.45 g of styrene, 11.2 g of allyl methacrylate, 57.25 g
of ethylene
diol and 4.49 g of Hitenol HS-20 was prepared. To the heated reactor, 28.8 of
the
monomer/surfactant mix was added. After allowing the contents of the reactor
to re-
equilibrate, 1.25 g of a 90 wt. % t-butyl hydroperoxide (t-BHP) dissolved in
11 g of
_ .~ _
ethylene diol was added to the reactor followed by 0.449 g d-isoascorbic acid
dissolved
in 11 g of ethylene diol. After a few minutes, the reactor appearance changed
from
clear to a bluish white tint indicating the formation of small particles. The
remaining
monomer mix was fed into the reactor over a period of 195 minutes. During the
same
time period, 1.247 g of d-isoascorbic acid dissolved in 22 g of ethylene diol
was fed
into the reactor. Also, 0.773 g of 90 wt. % t-BHP dissolved in 44 g of
ethylene diol
02297987 2000-02-04
-39-
was fed into the reactor. After all the monomer was added, the reaction was
held at 65
°C for an additional one half hour at which point the reactor was
cooled to room
temp erature.
The resulting emulsion contained 27 % solids and the particle size was 127 nm
as measured by dynamic light scattering.
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer; 424.7 g of a 75 wt. percent propylene diol/ water solution and 7.78 g
of Hitenol
HS-20 were added. The contents of the reactor were heated to 65 °C. In
a separate 500
ml flask, a monomer/surfactant mix of 188.9 g 2-ethylhexylacrylate, 22.22 g of
styrene,
11.11 g of allyl methacrylate, 56.67 of a 75 wt. percent propylene diol/ water
solution
and 4.44 g of Hitenol HS-20 was prepared. To the heated reactor, 28.3 g of the
monomer/surfactant mix was added. After allowing the contents of the reactor
to re-
equilibrate, 1.73 g of 90 wt. % t-butyl hydroperoxide (t-BHP) dissolved in 11
g of
ethylene diol was added to the reactor followed by 0.23 g sodium formaldehyde
sulfoxylate (SFS) dissolved in 11 g of distilled water. After a few minutes,
the reactor
appearance changed from clear to a bluish white tint indicating the formation
of small
particles. The remaining monomer mix was fed into the reactor over a period of
195
minutes. During the same time period, 0.95 g of SFS dissolved in 22 g of
distilled
water was fed into the reactor. Also, 0.741 g of 90 wt. % t-BHP dissolved in
44 g of
ethylene diol was fed into the reactor. After all the monomer was added, the
reaction
was held at 65 °C for an additional one half hour at which point the
reactor was cooled
to room temperature. .
The resulting emulsion was filtered through a 100 mesh screen. This emulsion
contained 27.1 % solids and the particle size was 196 nm as measured by
dynamic light
scattering.
CA 02297987 2000-02-0
-40-
exam lp a 11
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer; 424.7 g of a 50:50 wt. percent propylene diol: Ethylene diol mixture
and 7.78 g
of Hitenol HS-20 were added. The contents of the reactor were heated to 65
°C. In a
separate 500 ml flask, a monomer/surfactant mix of 188.9 g 2-
ethylhexylacrylate, 22.22
g of styrene, 11.11 g of allyl methacrylate, 56.67 g of a 50:50 wt. percent
propylene
diol: Ethylene diol mixture and 4.44 g of Hitenol HS-20 was prepared. To the
heated
reactor, 28.3 g of the monomer/surfactant mix was added. After allowing the
contents
of the reactor to re-equilibrate, 1.73 g of t-butyl hydroperoxide (t-BHP)
dissolved in 11
g of ethylene diol was added to the reactor followed by 0.23 g Sodium
Formaldehyde
Sulfoxylate (SFS) dissolved in 11 g of Distilled water. After a few minutes,
the reactor
appearance changed from clear to a bluish white tint indicating the formation
of small
particles. The remaining monomer mix was fed into the reactor over a period of
195
minutes. During the same time period, 0.95 g of SFS dissolved in 22 g of
distilled
water was fed into the reactor. Also, 0.741 g of 90 wt. % t-BHP dissolved in
44 g of
ethylene diol was fed into the reactor. After all the monomer was added, the
reaction
was held at 65 °C for an additional one half hour at which point the
reactor was cooled
to room temperature.
The resulting emulsion was filtered through a 100 mesh screen. This emulsion
contained 27.6% solids and the particle size was 332 nm as measured by dynamic
light
scattering.
ZS Exam In a 12
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer; 394.05 g of a 75 wt. percent diethylene diol water solution and 1.15
g of Hitenol
HS-20 were added. The contents of the reactor were heated to 65 °C. In
a separate 500
ml flask, a monomer/surfactant mix of 195.22 g 2-ethylhexylacrylate, 22.97 g
of
styrene, 11.48 g of allyl methacrylate, 58.56 g of a 75 wt. percent diethylene
diol water
CA 02297987 2000-02-0
-41 -
solution and 4.59 g of Hitenol HS-20 was prepared. To the heated reactor, 29.3
g of the
monomer/surfactant mix was added. After allowing the contents of the reactor
to re-
equilibrate, 0.984 g of 90 wt. % t-butyl hydroperoxide (t-BHP) dissolved in 11
g of a
75 wt% diethylene diol/water solution was added to the reactor followed by
0.689 g
Sodium Formaldehyde Sulfoxylate (SFS) dissolved in 11 g of Distilled water.
After a
few minutes, the reactor appearance changed from clear to a bluish white tint
indicating
the formation of small particles. The remaining monomer mix was fed into the
reactor
over a period of 195 minutes. During the same time period, 1.605g of SFS
dissolved in
28 g of distilled water was fed into the reactor. Also, 2.297 g of 90 wt. % t-
BHP
dissolved in 56 g of a 75 wt % diethylene diol/water solution was fed into the
reactor.
After all the monomer was added, the reaction was held at 65 °C for an
additional one
half hour at which point the reactor was cooled to room temperature.
The resulting emulsion was filtered through a 100 mesh screen. This emulsion
contained 25.6 % solids and the particle size was 302 nm as measured by
dynamic light
scattering.
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer; 394.05 g of a 50:50 wt. percent diethylene diol:ethylene diol mixture
and 1.15 g
of Hitenol HS-20 were added. The contents of the reactor were heated to 65
°C. In a
separate 500 ml flask, a monomer/surfactant mix of 195.22 g 2-
ethylhexylacrylate,
22.97 g of styrene, 11.48 g of allyl methacrylate, 58.56 g of a 50:50 wt.
percent
diethylene diol:ethylene diol and 4.59 g of Hitenol HS-20 was prepared. To the
heated
reactor, 29.3 g of the monomer/surfactant mix was.added. After allowing the
contents
of the reactor to re-equilibrate, 0.984 g of a 70wt %t-butyl hydroperoxide (t-
BHP)
dissolved in 11 g of ethylene diol was added to the reactor followed by 0.689
g Sodium
Formaldehyde Sulfoxylate (SFS) dissolved in 11 g of Distilled water. After a
few
minutes, the reactor appearance changed from clear to a bluish white tint
indicating the
formation of small particles. The remaining monomer mix was fed into the
reactor over
CA 02297987 2000-02-04
-42-
a period of 195 minutes. During the same time period, 1.608 g of SFS dissolved
in 28
g of distilled water was fed into the reactor. Also, 2.297 g of a 70 wt% t-BHP
dissolved
in 56 g of ethylene diol was fed into the reactor. After all the monomer was
added the
reaction was held at 65 °C for an additional one half hour at which
point the reactor was
cooled to room temperature.
The resulting emulsion was filtered through a 100 mesh screen. The particle
size
of the emulsion was 497 run as measured by dynamic light scattering.
exam tp a 14
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer; 75.70 g of a 50 wt. percent tripropylene diol water solution and 4.49
g of
Hitenol HS-20 were added. The contents of the reactor were heated to 65
°C. In a
separate SOOmI flask, a monomer/surfactant mix of 190.65 g 2-
ethylhexylacrylate,
22.43 g of styrene, 11.21 g of allyl methacrylate, 376.94 g of the 50 wt.
percent
tripropylene diol water solution and 6.73 g of Hitenol HS-20 was prepared. To
the
heated reactor, 29.3 g of the monomer/surfactant mix was added. After allowing
the
contents of the reactor to re-equilibrate, 0.984 g of t-butyl hydroperoxide (t-
BHP)
dissolved in 11 g of 50 wt % tripropylene diol/water solution was added to the
reactor
followed by 0.689 g sodium formaldehyde sulfoxylate (SFS) dissolved in 11 g of
Distilled water. After a few minutes, the reactor appearance changed from
clear to
white with a bluish white tint indicating the formation of small particles.
The
remaining monomer mix was feed into the reactor over a period of 195 minutes.
During
the same time period, 1.608 g of SFS dissolved in 28 g of distilled water was
feed into
the reactor. Also, 2.29Tg of 70 wt. % t-BHP dissolved in 56 g of 50 wt%
tripropylene
diol/water solution was fed into the reactor. After all the monomer was added
the
reaction was held at 65 °C for an additional one half hour at which
point the reactor
was cooled to room temperature.
CA 02297987 2000-02-04
-43-
The resulting emulsion was filtered through a 100 mesh screen. The particle
size of the emulsion was 144 nm as measured by dynamic light scattering.
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer; 322.13 g of a 75 wt. percent ethylene diol/ water solution and 26.71
g of
Disponil FES 77 surfactant were added. The contents of the reactor were heated
to
65 °C. In a separate 500 ml flask, a monomer mix of 307.69 g 2-
ethylhexylacrylate,
34.19 g of styrene, was prepared. To the heated reactor, 34.19 g of the
monomer mix
was added. After allowing the contents of the reactor to re-equilibrate, 0.76
g of a
90 wt% t-butyl hydroperoxide (t-BHP) dissolved in 8.8 g of the 75% ethylene
diol/water mixture was added to the reactor followed by 0.34 g sodium
formaldehyde
sulfoxylate (SFS) dissolved in 11 g of distilled water. After a few minutes,
the reactor
appearance changed from clear to white with a bluish white tint indicating the
formation of small particles. The remaining monomer mix was feed into the
reactor
over a period of 195 minutes. During the same time period, 1.03 g of SFS and
22.79 g
of the Disponil FES77 surfactant dissolved in 22 g of distilled water was feed
into the.
reactor. Also, 0.76 g of 90 wt. % t-BHP dissolved in 44 g of 75 % ethylene
diol/water
was feed into the reactor. After all the monomer was added the reaction was
held at
65 °C for an additional one half hour at which point the reactor was
cooled to room
temperature.
The resulting emulsion was filtered through a 100 mesh screen. This emulsion
contained 45 % solids and the particle size was 63 nm as measured by dynamic
light
scattering.
To a 1 L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer; 395.38 g of a 50 wt. percent cyclohexanedimethanol (CHDM) water
solution
CA 02297987 2000-02-04
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and 5.70 g of Hitenol HS-20 were added. The contents of the reactor were
heated to
65 °C. In a separate 500 ml flask, a monomer/surfactant mix of 193.73 g
2-
ethylhexylacrylate, 34.19 g of styrene, 58.12 g of the 50 wt. percent
CHDM:water
solution and 4.56 g of Hitenol HS-20 was prepared. To the heated reactor, 29.1
g of the
S monomer/surfactant mix was added. After allowing the contents of the reactor
to re-
equilibrate, 0.51 g a 90 wt % of t-butyl hydroperoxide (t-BHP) dissolved in 11
g of
50% wt% CHDM/Water solution was added to the reactor followed by 0Ø23 g
sodium
formaldehyde sulfoxylate (SFS) dissolved in 11.2 g of distilled water. After a
few
minutes, the reactor appearance changed from clear to white with a bluish
white tint
indicating the formation of small particles. The remaining monomer mix was
feed into
the reactor over a period of 195 minutes. During the same time period, 0.68 g
of SFS
dissolved in 28 g of distilled water was feed into the reactor. Also, 0.50 g
of 90 wt.
t-BHP dissolved in 56 g of 50% wt%CHDM/Water solution was feed into the
reactor.
After all the monomer was added the reaction was held at 65 °C for an
additional one
half hour at which point the reactor was cooled to room temperature.
The resulting emulsion was filtered through a 100 mesh screen. The particle
size of the emulsion was 225 nm as measured by dynamic light scattering.
Example 17
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer; 395.38 g of a 25wt. percent cyclohexanedimethanol (CHDM) in ethylene
diol
and 5.70 g of Hitenol HS-20 were added. The contents of the reactor were
heated to
65 °C. In a separate SOOmI flask, a monomer/surfactant mix of 193.73 g
2-
ethylhexylacrylate, 34.19 g of styrene, 58.12 g of 25 wt% CHDM/EG solution and
4.56
g of Hitenol HS-20 was prepared. To the heated reactor, 29.1 g of the
monomer/surfactant mix was added. After allowing the contents of the reactor
to re-
equilibrate, 0.51 g of a 90 wt% t-butyl hydroperoxide (t-BHP) dissolved in 11
g of 25%
CHDM/EG solution was added to the reactor followed by 0Ø23 g Sodium
Formaldehyde Sulfoxylate (SFS) dissolved in 11.2 g of Distilled water. After a
few
_- __--__---.--_-__-CA 02297987 2000-02-04
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minutes, the reactor appearance changed from clear to white with a bluish
white tint
indicating the formation of small particles. The remaining monomer mix was
feed into
the reactor over a period of 195 minutes. During the same time period, 0.68 g
of SFS
dissolved in 28 g of distilled water was feed into the reactor. Also, 0.51
grams of 90
wt. % t-BHP dissolved in 56 g of 25% CHDM/EG solution was feed into the
reactor.
After all the monomer was added the reaction was held at 65 °C for an
additional one
half hour at which point the reactor was cooled to room temperature.
The resulting emulsion was filtered through a 100 mesh screen. This emulsion
contained 28% solids and the particle size was 310 nm as measured by dynamic
light
scattenng.
Examp,~e 18
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer; 395.38 g of a 60 wt. percent neopentyl diol (NPG) water solution and
5.70 g of
Hitenol HS-20 were added. The contents of the reactor were heated to 65
°C. In a
separate SOOmI flask, a monomer/surfactant mix of 186.89 g_2-
ethylhexylacrylate,
27.35 g of styrene, 6.84 g of allyl methacrylate, 6.84 g of methacrylic acid
58.12 g of
the 60 wt. percent 1~'PG/Water solution and 4.56 g of Hitenol HS-20 was
prepared. To
the heated reactor, 29.1 g of the monomer/surfactant mix was added. After
allowing
the contents of the reactor to re-equilibrate, 0.51 g of t-butyl hydroperoxide
(t-BHP)
dissolved in 11 g of 50% NPG/Water solution was added to the reactor followed
by
0Ø23 g sodium formaldehyde sulfoxylate (SFS) dissolved in 11.2 g of
Distilled water.
After a few minutes, the reactor appearance changed from clear to white with a
bluish
white tint indicating ihe~formation of small particles. The remaining monomer
mix was
feed into the reactor over a period of 195 minutes. During the same time
period, 0.68 g
of SFS dissolved in 28 g of distilled water was feed into the reactor. Also,
0.51 g of
90 wt. % t-BHP dissolved in 56 g of 60wt% NPG/Water solution was feed into the
reactor. After all the monomer was added the reaction was held at 65 °C
for an
additional one half hour at which point the reactor was cooled to room
temperature.
CA 02297987 2000-02-04
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The resulting emulsion was filtered through a 100 mesh screen. The particle
size of the emulsion was 691 nm as measured by dynamic light scattering.
S
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer, 392.54 g of a 75 wt. percent ethylene diol:water solution and 11.29 g
of Tergitol
I S-S-40, a secondary alcohol ethoxylate (70wt% in water), manufactured by
Union
Carbide, were added. The contents of the reactor were heated to 65 °C.
In a separate
SOOmI flask, a monomer/surfactant mix of 203.20 g 2-ethylhexylacrylate, 22.58
g of
styrene, 58.64 g of the 75 wt. percent EG:water solution and 6.45 g of
Tergitol 15-S-
40 was prepared. To the heated reactor, 28.79 g of the monomer/surfactant mix
was
added. After allowing the contents of the reactor to re-equilibrate, 0.50 g of
a 90 wt% t-
butyl hydroperoxide (t-BHP) dissolved in 11 g of the 75 wt.% EG:water solution
was
added to the reactor followed by 0.23 g sodium formaldehyde sulfoxylate (SFS)
dissolved in 11.2 g of Distilled water. After a few minutes, the reactor
appearance
changed from clear to white with a bluish white tint indicating the formation
of small
particles. The remaining monomer mix was feed into the reactor over a period
of 195
minutes. During the same time period, 0.68 g of SFS dissolved in 28 g of
distilled
water was feed into the reactor. Also, 0.50 g of 90 wt. % t-BHP dissolved in
56 g of
75% EG:water solution was feed into the reactor. After all the monomer was
added the
reaction was held at 65 °C for an additional one half hour at which
point the reactor
was cooled to room temperature.
The resulting emulsion was filtered through a 100 mesh screen. The particle
'T size of the emulsion was I18 run as measured by dynamic light scattering.
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer, 229.91 g of ethylene diol and 3.62 g of Hitenol HS-20 were added and
0.72 g of
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a 1 % ammonium iron (II) sulfate solution in water. The contents of the
reactor were
heated to 65 °C. In a separate 500m1 flask, a monomer/surfactant mix of
65.02 g
isoprene, 62.48 g of styrene, and 2.60 g of methacrylic acid was prepared. To
the
heated reactor, 14.17 g of styrene and 0.29 g of methacrylic acid were added.
After
allowing the contents of the reactor to re-equilibrate, 0.21 g of 70 wt.% t-
butyl
hydroperoxide (t-BHP) dissolved in 11 g of EG was added to the reactor
followed by
0.14 g sodium formaldehyde sulfoxylate (SFS) dissolved in 11.2 g of Distilled
water.
After a few minutes, the reactor appearance changed from clear to white with a
bluish
white tint indicating the formation of small particles. After allowing the
styrene/methacrylic acid to react for 30 minutes, the monomer mix was feed
into the
reactor over a period of 150 minutes. During the same time period, 0.72 g of
SFS
dissolved in 52.50 g of distilled water was feed into the reactor. Also, 1.02
g of 70 wt.
t-BHP dissolved in 52.5 g of EG was feed into the reactor. After all the
monomer
was added the reaction was held at 65 °C for an additional one half
hour at which point
the reactor was cooled to room temperature.
The resulting emulsion was filtered through a 100 mesh screen. This emulsion
contained 18% solids and the particle size was 109 nm as measured by dynamic
light
scattenng.
Examyle 21
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer, 338.66 g of 1,4-butanediol (1,4-BD) and 127.56 g of water solution
and 7.90 g
of Hitenol HS-20 were added. The contents of the reactor were heated to 65
°C. In a
separate 500m1 flask, a~monomer/surfactant mix of 191.91 g 2-
ethylhexylacrylate,
22.58 g of styrene, 11.29 g allyl methacrylate and 4.52 g of Hitenol HS-20 was
prepared. To the heated reactor, 23.03 g of the monomer/surfactant mix was
added.
After allowing the contents of the reactor to re-equilibrate, 0.65 g of t-
butyl
hydroperoxide (t-BHP) dissolved in 9.03 g of 1,4-BD was added to the reactor
followed
by 0.23 g sodium formaldehyde sulfoxylate (SFS) dissolved in 11.2 g of
distilled water.
_ __._____.___ ___CA 02297987 2000-02-04
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After a few minutes, the reactor appearance changed from clear to white with a
bluish
white tint indicating the fonmation of small particles. The remaining monomer
mix was
feed into the reactor over a period of 195 minutes. During the same time
period, 0.68 g
of SFS dissolved in 28 g of distilled water was feed into the reactor. Also,
0.65g of 90
S wt. % t-BHP dissolved in 45.16 g of 1,4-BD was feed into the reactor. After
all the
monomer was added the reaction was held at 65 °C for an additional one
half hour at
which point the reactor was cooled to room temperature.
The resulting emulsion was filtered through a 100 mesh screen. This emulsion
contained 28% solids and the particle size was 174.9 nm as measured by dynamic
light
scattering.
TABLE I
Ex. Continuous Monomers Surfactant InitiatorReductant
Phase
1 EG 2-EHA,TMPTA Hitenol A-10 NaPS --
2 EG 2-EHA,TMPTA Hitenol A-10 ABVA -
3 EG 2-EHA,TMPTA Hitenol A-10 t-BHP SFS
4 EG 2-EHA,Sty,ALMA FES 77 t-BHP SFS -
5 EG Z-EHA,Vac Hitenol HS-20t-BHP SFS
6 EG Sty,BA,ALMA Hitenol HS-20t-BHP SFS
7 EG MIvIA,2-EHA,ALMAHitenol HS-20t-BHP SFS
8 EG 2-EHA,Sty,ALMA Hitenol HS-20t-BHP SFS
9 EG 2-EHA,Sty,ALMA Hitenol HS-20t-BHP IAA
10 PG/Water 2-EHA,Sty,ALMA Hitenol HS-20t-BHP SFS
I 1 PGBG 2-EHA,Sty,ALMA Hitenol HS-20t-BHP SFS
12 DEG/Water 2-EHA,Sty,ALMA Hitenol HS-20t-BHP SFS
-
13 DEG/EG 2-EHA,Sty,ALMA Hitenol HS-20t-BHP SFS
14 TPG/Water 2-EHA,Sty,ALMA Hitenol HS-20t-BHP SFS
_ 15 EG/Water 2-EHA,Sty FES 77 t-BHP SFS
.
16 CHDM/Water 2 EHA,Sty Hitenol HS-20t-BHP SFS
17 CHDMBG 2-EHA,Sty Hitenol HS-20t-BHP SFS
18 NPG/Water 2-EHA,Sty,MAA Hitenol HS-20t-BHP SFS
19 EG/Water 2-EHA,Sty Tergito115-S-40t-BHP SFS
EG Sty,isoprene,MAAHitenol HS-20t-BHP SFS
21 1,4BD/Water2-EHA,Sty,MAA Hitenol HS-20t-BHP SFS
CA 02297987 2000-02-04
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Examzzles for Modified Condensation Polymer
Example 22 (Comparative Example)
PET homopolymer was prepared by the following procedure. Dimethyl
terephthalate (0.5 moles, 97 grams), ethylene diol (1.0 moles, 62 grams) and
catalyst
metals were placed in a 0.5 L polymerization reactor under a 1 atmosphere
nitrogen
atmosphere. The mixture was heated with stirring at 200 °C for 1 hour
and then 210 °C
for 3 hours. The temperature was increased to 280 ° C, the nitrogen
flow was stopped
and vacuum applied. The polymer was stirred under vacuum (0.2-0.3 Torr) for 1
hour.
The polymer was allowed to cool and ground. After grinding, some of the
polymer was
utilized to melt press polymer films that could be used for physical property
testing.
The characterization data is listed in Table 2.
Exam lp a 23
The blend was prepared by the following procedure. Dimethyl terephthalate
(0.5 moles, 97 grams), ethylene diol (10 moles, 62 grams) and catalyst metals
were
placed in a 0.5 L polymerization reactor under a nitrogen atmosphere. The
mixture was
heated with stirring at 200 °C for 1 hour and then 210 °C for 3
hours. The temperature
was increased to 275 °C and held there for 30 minutes. Nitrogen flow
was stopped and
vacuum was applied (5 Torr) for five minutes. After this time the temperature
of the
polymerization was decreased to 240 °C and pressure was increased to
300 Torr. 1 mL
of the emulsion of Example 1 was syringed into the polymerization flask which
dispersed into the polymer melt. The temperature was increased to 275
°C and pressure
dropped to 10 Torr. After five minutes, the pressure was increased to 300 Torr
and an
additional 2 mL Example 1 emulsion was added. Vacuum was increased to 0.2-0.3
Torr for 45 minutes at a stir rate decreasing from 200 to 50 rpms. The melt
appeared
homogeneous but with some opacity. Heating and stirring were removed and the
blend
crystallized to a white opaque solid in 15 minutes. The polymer was allowed to
cool
and ground. After grinding, some of the polymer was utilized to melt press
polymer
CA 02297987 2000-02-04
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films that could be used for physical property testing. The characterization
data is
listed in Table 2. Transmission Electron Microscopy of a melt pressed film
showed
that the rubber particles were dispersed in a polyester matrix. Particle sizes
ranged
from 50-300 nm.
5
Example 24
The blend was prepared by the following procedure. Dimethyl terephthalate
(0.5 moles, 97 grams), ethylene diol (1.0 moles, 52 grams) and catalyst metals
were
10 placed in a 0.5 L polymerization reactor under a nitrogen atmosphere. The
mixture was
heated with stirring at 200 °C for 1 hour and then 210 °C for 3
hours. The temperature
was increased to 280 °C and held there for 20 minutes. Nitrogen flow
was stopped and
vacuum was applied (5 Torr) for five minutes. Pressure was increased to 300
Torr. 10
mL of the emulsion of Example 1 was syringed into the polymerization flask
which
15 dispersed into the polymer melt. Vacuum was increased to 0.2-0.3 Torr for
60 minutes
at a stir rate decreasing from 200 to 50 rpms. The melt appeared homogeneous
but with
some opacity. Heating and stirring were removed and the blend crystallized to
a white
opaque solid in 30 minutes. The polymer was allowed to cool and ground. After
grinding, some of the polymer was utilized to melt press polymer films that
could be
20 used for testing. The characterization data is listed in Table 1.
Transmission Electron
Microscopy of a melt pressed film showed that the rubber particles were
dispersed in a
polyester matrix. Particle sizes were from 100-400 nm.
__.___---------~A 02297987 2000-02-04
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TABLE 2 - Properties of impact modified PET using acrylate emulsions in EG.
PET 1 % Acrylate 3.5 % Acrylate
Properties Polymer Film Polymer Filin Polymer Film
Ih V. (dl/g)0.61 0.58 0.64 0.60 0.73 0.67
Tch, none 142 none 1334 none 135
Tm, 254 257 250 251 239 238
(Hf-12.82)(H~10.79)(H,=11.56)(H,~9.08)(H~8.40)(Hf-7.31)
Tg 81 78 78 77 73 72
Tchz 152 137 161 149 162 150
TmZ 257 257 252 251 240 240
(H~-9.89)(H,~12.70)(H~10.20)(H~10.92)(H~.=7.97)(H~9.61)
Tcc 161 193 158 178 none 154
Film % NT 7.84 NT 5.6 NT 2.68
Xtal
M~ 12300 11600 12800 11800 13600 13000
M". 39900 35900 40300 37500 49200 46400
M= 67000 59800 64500 60600 81000 76400
Film ImpactNT 2.36 NT 2.60 NT 2.74
(ft-Ibs)
Failure -- brittle -- ductile -- ductile
Mode
NT - not tested
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer, 394.63 g of water and 2.31 g of Hitenol HS-20 were added. The
contents of the
reactor were heated to 65 °C. In a separate SOOml flask, a
monomer/surfactant mix of
196.15 g butylacrylate, 23.08 g of styrene, 11.54 g of allyl methacrylate
58.85 g of
water and 4.62 g of Hitenol HS-20 was prepared. To the heated reactor, 29.4 g
of the
monomer/surfactant mix was added. ARer allowing the contents of the reactor to
re-
equilibrate, 0.77 g of t-butyl hydroperoxide (t-BHP) dissolved in 11.2 g of
distilled
CA 02297987 2000-02-04
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water was added to the reactor followed by 0.23 g Sodium Formaldehyde
Sulfoxylate
(SFS) dissolved in 11.2 g of distilled water. After a few minutes, the reactor
appearance changed from clear to white with a bluish white tint indicating the
formation of small particles. The remaining monomer mix was feed into the
reactor
over a period of 195 minutes. During the same time period, 0.92 g of SFS
dissolved in
28 g of distilled water was feed into the reactor. Also, 0.51 g of 90 wt. % t-
BHP
dissolved in 56 g of water was feed into the reactor. After all the monomer
was added
the reaction was held at 65 °C for an additional one half hour at which
point the reactor
was cooled to room temperature.
The resulting emulsion was filtered through a 100 mesh screen. This emulsion
contained 28.5 % solids and the particle size was 63 nm as measured by dynamic
light
scattering.
Exam l~e 26
The blend was prepared by the following procedure. Dimethyl terephthalate
(0.5 moles, 97.0 grams), ethylene diol (1.0 moles, 62.0 grams), 15.0 grams of
the
emulsion of Example 25, and catalyst metals were placed in a O.SL
polymerization
reactor under a 1 atmosphere nitrogen atmosphere. The mixture was heated with
stirring under a slow nitrogen purge at 200 °C for 1 hour and then 2
hours at 210 °C.
The temperature was increased to 275 °C, the nitrogen flow was stopped
and vacuum
applied. The polymer was stirred under vacuum (0.1-0.3 Torr) for 60 minutes
and then
stirring was stopped and heat removed. The polymer was allowed to cool and
ground.
The Ih.V. was 0.50 dL/g, the Mw was 32,200 grams/mole, the Tg was 86.0
°C.
Exam In a 27
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer; 395.93 g of ethylene diol (EG) and 7.90 g of Hitenol HS-20 were
added. The
contents of the reactor were heated to 65 °C. In a separate SOOmI
flask, a
monomer/surfactant mix of 182.88 g 2-ethylhexylacrylate, 31.61 g of styrene,
11.29 g
CA 02297987 2000-02-04
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of allyl methacrylate, 57.57 g of EG and 4.52 g of Hitenol HS-20 was prepared.
To the
heated reactor, 28.79 g of the monomer/surfactant mix was added. After
allowing the
contents of the reactor to re-equilibrate, 0.50 g of 90 % t-butyl
hydroperoxide (t-BHP)
dissolved in 11.2 g of EG was added to the reactor followed by 0.23 g Sodium
Formaldehyde Sulfoxylate (SFS) dissolved in 11.2 g of distilled water. After a
few
minutes, the reactor appearance changed from clear to white with a bluish
white tint
indicating the formation of small particles. The remaining monomer mix was
feed into
the reactor over a period of 195 minutes. During the same time period, 0.68 g
of SFS
dissolved in 28 g of distilled water was feed into the reactor. Also, 0.50 g
of 90 wt.
t-BHP dissolved in 56-g of EG was feed into the reactor. After all the monomer
was
added the reaction was held at 65 °C for an additional one half hour at
which point the
reactor was cooled to room temperature.
The resulting emulsion was filtered through a 100 mesh screen. This emulsion
1 S contained 28.4% solids and the particle size was 120 nm as measured by
dynamic light
scattering.
Examyle 28
The blend was prepared by the following procedure. biphenyl carbonate (0.30
moles, 64.20 grams), bisphenol A (0.30 moles, 68.40 grams, and catalyst metals
were
placed in a O.SL polymerization reactor under a 1 atmosphere nitrogen
atmosphere.
The mixture was heated with stirring under a slow nitrogen purge at 200
°C for 0.5
hour, 220 °C for 20 minutes, 24°C for 30 minutes, 260 °
for 30 minutes; and was raised
to 280°C. At this point 13.4 grams of the emulsion of Example 27 was
slowly added
'- via a 125 mL pressure-equalizing funnel over a period of 2 minutes and
continued
heating at 280 °C under an atmosphere of nitrogen. Over a period of 15
minutes the
pressure in the flask was reduced from 1 atmosphere to 0.35 Torr with the
application
of vacuum. The temperature was increased to 290 °C for 30 minutes, to
300 °C for 1.5
hours and then 320 °C for 20 minutes. Heat and stirring were removed
from the
viscous melt and the polymer was allowed to cool. The Tg was 135 °C and
Ih.V. was
CA 02297987 2000-02-04
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0.29dL/g. Particles up to 30 microns in size are dispersed in the
polycarbonate matrix
(optical microscopy).
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer, 395.33 g of ethylene diol and 5.50 g of Hitenol HS-20 were added. The
contents of the reactor were heated to 65 °C. In a separate 500m1
flask, a
monomer/surfactant mix of 194.84 g 2-ethylhexylacrylate, 22.92 g of styrene,
11.46 g
of allyl methacrylate, 47.89 g of ethylene diol and 3.44 g Hitenol HS-20 was
prepared.
To the heated reactor, 29.1 g of the monomer/surfactant mix was added. After
allowing
the contents of the reactor to re-equilibrate, 0.51 g of 90 wt.% t-butyl
hydroperoxide (t-
BHP) dissolved in 11.2 g of ethylene diol was added to the reactor followed by
0.23 g
Sodium Formaldehyde Sulfoxylate (SFS) dissolved in 11.2 g of Distilled water.
After a
few minutes, the reactor appearance changed from clear to a bluish white tint
indicating
the formation of small particles. The remaining monomer mix was feed into the
reactor~
over a period of 195 minutes. During the same time period, 0.68 g of SFS
dissolved in
28 g of distilled water was feed into the reactor. Also, 0.51 g of 90 wt.% t-
BHP
dissolved in 56 g of ethylene diol was feed into the reactor. After all the
monomer was
added the reaction was held at 65 °C for an additional one half hour at
which point the
reactor was cooled to room temperature.
The resulting emulsion was filtered through a 100-mesh screen. The emulsion
contained 27.5 % solids and the particle size was 164 nm as measured by
dynamic light
scattering.
CA 02297987 2000-02-04
-$5-
Exam In a 30
The blend was prepared by the following procedure. Dimethyl terephthalate
(0.5 moles, 97.0 grams), 1,4-cyclohexanedimethanol (0.75 moles, 108 grams),
and
catalyst metals were placed in a O.SL polymerization reactor under a 1
atmosphere
nitrogen atmosphere. The mixture was heated with stirring under a slow
nitrogen purge
at 310 °C for 10 minutes and the solution was homogeneous. 30 grams of
the emulsion
of Example 29 and 1.5 mL of the antifoaming agent DC-7 (Dow Corning) were
added
over a 1 S minute period and the reaction was heated under an atmosphere of
nitrogen
for 45 more minutes. At this point vacuum was added and the pressure was
lowered to
200 Torr and then (within a minute) the pressure was decreased to 0.3-0.5 Torr
and
stirred for 1 hour giving a viscous polymer solution. Heat was removed and the
polymer was allowed to cool and then ground. The Ih.V. was 0.65 dL/g, the Tg
was
91.4 (2"° cycle) and the Tm was 274.4 °C (2"° cycle).
Exam l
The polymer was prepared by the following procedure. Dimethyl terephthalate
(0.5 moles, 97.0 grams), 1,4-butanediol (0.75 moles, 67.5 grams), and catalyst
metals
were placed in a O.SL polymerization reactor under a 1 atmosphere nitrogen
atmosphere. The mixture was heated with stirring under a slow nitrogen purge
at 200
°C for 1 hour, at for 2 hours and then the temperature was increased to
255 °C and
held for 15 minutes. At this point vacuum was added and the pressure was
lowered to
200 Torr and then (within a minute) the pressure was decreased to 0.3-0.5 Torr
and
stirred for 1 hour giving a viscous polymer solution. Heat was removed and the
.
polymer was allowed to cool and then ground. The Ih.V. was 0.94 dI,/g, the Tg
was
45.6 (2"° cycle) and the 'Fm was 224.0 °C (2"° cycle). Mn
was 13,000 and Mw was
35,400.
02297987 2000-02-04
-56-
Exam In a 32
The blend was prepared by the following procedure. Dimethyl terephthalate
(0.5 moles, 97.0 grams), 1,4-butanediol (0.75 moles, 67.5 grams), and catalyst
metals
were placed in a O.SL polymerization reactor under a 1 atmosphere nitrogen
atmosphere. The mixture was heated with stirring under a slow nitrogen purge
at 200
°C for about fifteen minutes and then 30 mL of emulsion of Example 29
was added to
the reaction vessel over a 2 minute period. The reaction mixture was heated
for another
45 minutes at 200 °C and then 210 °C for 2 hours. The
temperature was raised to 255
°C and held for fifteen minutes before vacuum (200 Torr) was applied
and then (within
a minute) the pressure was decreased to 0.3-0.5 Torr and stirred for 1 hour
giving a
viscous polymer melt. Heat was removed and the polymer was allowed to cool and
then ground. The Ea.V. was 0.58 dL/g, the Tg was 42.3 (2"~ cycle) and the Tm
was
178.8 °C (2"~ cycle).
The blend was prepared by the following procedure. Dimethyl terephthalate
(0.5 moles, 97.0 grams), ethylene diol (1.0 moles, 62.0 grams), and catalyst
metals were
placed in a O.SL polymerization reactor under a 1 atmosphere nitrogen
atmosphere.
The mixture was heated with stirring under a slow nitrogen purge at 200
°C for about
10 minutes until the mixture was homogeneous. Over a 20 minute period, 56.5
grams
of the emulsion of Example 27 was added with a 125 mL pressure-
equalizing,fiumel
and the reaction was heated for 45 minutes longer at 200 ° C, for two
hours at 210 ° C
and then raised to 280 °C. At this point vacuum was added and the
pressure was
lowered to from 1 atmosphere 0.3-0.5 Torr over the period of 35 minutes.
Pressure of
0.3-0.5 Torr was maintained for 45 minutes as the viscous melt was stirred.
Heat was
removed and the polymer was allowed to cool and then ground. A tough (tan-
colored)
translucent film was melt-pressed at 200 °C for 15 seconds. The Ih.V.
was 0.59 dL/g,
the Tg was 28 °C (2"° cycle). Particles up to 30 microns in size
were dispersed in the
polyester matrix. (optical microscopy)
02297987 2000-02-04
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xamgle 34
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
5 stirrer; 406.17 g of a ethylene diol (EG) water solution and 4.58 g of
Hitenol HS-20
were added. The contents of the reactor were heated to 65 °C. In a
separate 500m1
flask, a monomer/surfactant mix of 206.11 g of styrene, 22.90 g of divinyl
benzene,
68.70 g of EG and 4.58 g of Hitenol HS-20 was prepared. To the heated reactor,
30.23
g of the monomer/surfactant mix was added. After allowing the contents of the
reactor
10 to re-equilibrate, 0.51 g of 90 % t-butyl hydroperoxide (t-BHP) dissolved
in 11.45 g of
EG was added to the reactor followed by 0.23 g Sodium Formaldehyde Sulfoxylate
(SFS) dissolved in 11.2 g of distilled water. ARer a few minutes, the reactor
appearance changed from clear to white with a bluish white tint indicating the
formation of small particles. The remaining monomer mix was feed into the
reactor
15 over a period of 195 minutes. During the same time period, 0.69 g of SFS
dissolved in
28 g of distilled water was feed into the reactor. Also, 0.51 g of 90 wt. % t-
BHP
dissolved in 34.35 g of EG was feed into the reactor. After all the monomer
was added
the reaction was held at 65 °C for an additional one half hour at which
point the reactor
was cooled to room temperature.
20
The resulting emulsion was filtered through a 100 mesh screen. This emulsion
contained 28.0 % solids and the particle size was 174 nm as measured by
dynamic light
scattenng.
25 Examcile 35
The blend was prepared by the following procedure. Dimethyl terephthalate
(0.5 moles, 97.0 grams), ethylene diol (1.0 moles, 62.0 grams), and catalyst
metals were
placed in a 0.5L polymerization reactor under a 1 atmosphere nitrogen
atmosphere.
30 The mixture was heated with stirring under a slow nitrogen purge at 200
°C for 1 hour
and then 210 °C for two hours. Over a 17 minute period, 56.5 grams of
the emulsion of
02297987 2000-02-04
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Example 34 was added with a 125 mL pressure-equalizing funnel and then the
reaction
mixture was raised to 280 °C. At this point vacuum was added and the
pressure was
lowered to from 1 atmosphere to 0.3-0.5 Torr over a period of 11 minutes.
Pressure of
0.3-0.5 Torr was maintained for 1 hour as the viscous melt was stirred. Heat
was
removed and the polymer was allowed to cool and then ground. A tough film was
melt-pressed at 280 °C for 15 seconds. The Ih.V. was 0.54 dL/g, the Tg
was 57 °C (2~d
cycle), the Tm was 200 °C (2"~ cycle). Optical microscopy showed that
the particles
were somewhat agglomerated and up to about 30 microns in size.
Exam In a 36
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer; 406.17 g of a ethylene diol (EG) water solution and 4.58 g of Hitenol
HS-20
were added. The contents of the reactor were heated to 65 °C. In a
separate SOOmI
flask, a monomer/surfactant mix of 183.21 g of 2-ethylhexylacrylate, 18.32 g
of
styrene, 27.48 g of trimetylolpropane triacrylate, 68.70 g of EG and 4.58 g of
Hitenol
HS-20 was prepared. To the heated reactor, 30.23 g of the monomer/surfactant
mix
was added. After allowing the contents of the reactor to re-equilibrate, 0.51
g of 90
t-butyl hydroperoxide (t-BHP) dissolved in 11.45 g of EG was added to the
reactor
followed by 0.23 g Sodium Formaldehyde Sulfoxylate (SFS) dissolved in 11.2 g
of
distilled water. After a few minutes, the reactor appearance changed from
clear to
white with a bluish white tint indicating the formation of small particles.
The
remaining monomer mix was feed into the reactor over a period of 195 minutes.
During the same time period, 0.69 g of SFS dissolved in 28 g of distilled
water vvas
feed into the reactor. Also, 0.51 g of 90 wt. % t-BHP dissolved in 34.35 g of
EG was
feed into the reactor. After all the monomer was added the reaction was held
at 65 ° C
for an additional one half hour at which point the reactor was cooled to room
temperature.
The resulting emulsion was filtered through a 100 mesh screen.
02297987 2000-02-04
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Exam 1R a 37
The blend was prepared by the following procedure. Dimethyl terephthalate
(0.5 moles, 97.0 grams), ethylene diol (1.0 moles, 62.0 grams), and catalyst
metals were
placed in a O.SL polymerization reactor under a 1 atmosphere nitrogen
atmosphere.
The mixture was heated with stirring under a slow nitrogen purge at 200
°C for 1 hour
and then 210 °C for two hours. Over a 21 minute period, 56.5 grams of
the emulsion of
Example 36 was added with a 125 mL pressure-equalizing funnel and then the
reaction
mixture was raised to 280 °C. At this point vacuum was added and the
pressure was
lowered to from 1 atmosphere to 0.3-0.5 Toa over a period of 11 minutes.
Pressure of
0.3-0.5 Torr was maintained for 1 hour as the viscous melt was stirred. Heat
was
removed and the polymer was allowed to cool aad then ground. A tough film was
melt-pressed at 280 °C for 15 seconds. The Ih.V~. was 0.66 dL/g, the Tg
was 51 °C (2~d
cycle), the Tm was 200 °C (2'~ cycle). Optical microscopy showed that
the particles
were somewhat agglomerated and up to about 30 microns in size.
Exams
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer; 338.86 g of 1,4-butanediol (1,4-BD), 127.56 g of distilled water and
7.90 g of
Hitenol HS-20 were added. The contents of the reactor were heated to 65
°C. In a
separate SOOmI flask, a monomer/surfactant mix of 191.91 g of 2-
ethylhexylacrylate,
22.58 g of styrene, 11.29 g of allyl methacrylate, and 4.52 g of Hitenol HS-20
was
prepared. To the heated reactor, 23.03 g of the monomer/surfactant mix was
added.
After allowing the contents of the reactor to re-equilibrate, 0.65 g of 70 % t-
butyl
hydroperoxide (t-BHP) dissolved in 9.03 g of 1,4-BD was added to the reactor
followed
by 0.23 g Sodium Formaldehyde Sulfoxylate (SFS) dissolved in 11.2 g of
distilled
water. After a few minutes, the reactor appearance changed from clear to white
with a
bluish white tint indicating the formation of small particles. The remaining
monomer
mix was feed into the reactor over a period of 195 minutes. During the same
time
period, 0.68 g of SFS dissolved in 28 g of distilled water was feed into the
reactor.
CA 02297987 2000-02-04
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Also, 0.65 g of 70 wt. % t-BHP dissolved in 45.16 g of 1,4-BD was feed into
the
reactor. ARer all the monomer was added the reaction was held at 65 °C
for an
additional one half hour at which point the reactor was cooled to room
temperature.
5 The resulting emulsion was filtered through a 100 mesh screen. Particle size
of
the resulting latex was measured to be 175 nm by dynamic light scattering.
10 The blend was prepared by the following procedure. Dimethyl terephthalate
(0.40 moles, 77.6 grams), 1,4-butanediol (0.60 moles, 54.0 grams), and
catalyst metals
were placed in a 0.5L polymerization reactor under a 1 atmosphere nitrogen
atmosphere. The mixture was heated with stirring under a slow nitrogen purge
at 200
°C for 1 hour and then 210 °C for one hour. Over a 36 minute
period, 51.8 grams of
15 the emulsion of Example 38 were added with a 125 mL pressure-equalizing
fixnnel and
then the reaction mixture was raised to 255 °C. At this point vacuum
was added and
the pressure was lowered to from 1 atmosphere to 0.3-0.5 Torr over a period of
I O
minutes. Pressure of 0.3-0.5 Torr was maintained for 1 hour as the viscous
melt was
stirred. Heat was removed and the polymer was allowed to cool and then ground.
A
20 very tough film was melt-pressed at 260 °C for 15 seconds. The Ih.V.
was 0.58 dL/g,
the Tg was 25 °C (2"~ cycle), the Tm was 220°C (2"~ cycle).
Optical microscopy
showed that the particles were somewhat agglomerated and up to about 30
microns in
size.
25 Exam 1~0_
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer, 395.38 g of a 60 wt. percent Neopentyl diol (NPG) water solution and
5.70 g of
Hitenol HS-20 were added. The contents of the reactor were heated to 65
°C. In a
30 separate 500m1 flask, a monomer/surfactant mix of 186.89 g 2-
ethylhexylacrylate,
27.35 g of styrene, 6.84 g of allyl methacrylate, 6.84 g of methacrylic acid,
58.12 g of
02297987 2000-02-04-
-61 -
the 60 wt. percent NPG/Water solution and 4.56 g of Hitenol HS-20 was
prepared. To
the heated reactor, 29.1 g of the monomer/surfactant mix was added. After
allowing
the contents of the reactor to re-equilibrate, 0.51 g of t-butyl hydroperoxide
(t-BHP)
dissolved in 11 g of 60% NPG/Water solution was added to the reactor followed
by
0Ø23 g Sodium Formaldehyde Sulfoxylate (SFS) dissolved in 11.2 g of
Distilled
water. After a few minutes, the reactor appearance changed from clear to white
with a
bluish white tint indicating the formation of small particles. The remaining
monomer
mix was feed into the reactor over a period of 195 minutes. During the same
time
period, 0.68 g of SFS dissolved in 28 g of distilled water was feed into the
reactor.
Also, 0.51 g of 90 wt. % t-BHP dissolved in 56 g of 60% NPG/Water solution was
feed
into the reactor. After all the monomer was added the reaction was held at 65
°C for an
additional one half hour at which point the reactor was cooled to room
temperature.
The resulting emulsion was filtered through a 100 mesh screen. The particle
size of the resulting latex was bimodal with sizes of 691 nm and 211 nm as
measured
by dynamic light scattering.
ExamQle 41
In a 2L reaction kettle equipped with steam jacketed condenser, a water cooled
condenser and a Dean-Stark trap was placed 496 g of neopentyldiol (NPG), 86 g
of
trimethylolpropane (TMP) and 460 g of isophthalic acid (IPA). To this was
added 250
g of the NPG containing latex Example 40. The reaction was heated to 150
°C. After
reaching 150 °C, 1.5 g of Fastcat 4100 (Sn Catalyst) was added. After 1
hour, the
temperature was increased to 220 °C and held at this temperature for 3
hours. A total
of 140 ml of water was collected in the distillate. The reactor was then
cooled to
120 °C and 477 g of 1,4-cyclohexane dicarboxylic acid (1,4-CHDA) was
added and the
temperature was increased to 230 °C. The reaction was held at 230
°C for 2 and one-
half hours and then cooled. A total of 241 ml of water was collected over the
entire
reaction period (88 % of theoretical amount). 325 g of xylene was then added
to the
02297987 2000-02-04-._ ___-___..-.- _._ _ _ ___
-62-
resin. The resin retained the hazy nature of the latex. No signs of coagulated
acrylic
rubber were observed.
Enamels were prepared from the latex-containing polyester resin and Resimene
745 (hexamethoxymethyl melamine). Resin/crosslinker weight ratio was 70/30.
0.3%
pTSA was used as catalyst and 0.4% FC430 was used as a flow aid. Coatings were
drawn down on Bonderite 1000 panels using a wire wound bar. Panels were baked
at
160 degrees C for 30 minutes. Coating had over 500 MEK double rubs indicating
good
cure.
The blend is prepared by the following procedure. Dimethyl glutarate (1 mole),
ethylene glycol (1.5 moles), diethylene glycol (0.5 moles) and titanium
tetraisopropoxide (100 ppm based on the final polymer weight) are placed in a
0.5 L
polymerization reactor under a 1 atmosphere nitrogen atmosphere. The mixture
is
heated with stirring under a slow nitrogen purge at 200 °C for about 10
minutes until
the mixture is homogeneous. Over a 20 minute period, 100 grams of an ethylene
glycol
based polystyrene (95 mol%)-co-glycidyl methacrylate (5 mole%)) emulsion is
added
to the reaction and heated for 45 minuted longer at 200 °C, for two
hours at 210 °C and
then raided to 250 °C. At this point, vacuum is added ant the pressure
is lowered to
from 1 atmosphere, 0.3-0.5 Torr over the period of 35 minutes. Pressure of 0.3
to 0.5
Torr is maintained for 45 minuted as the viscous melt is stirred. Heat is
removed and
the polymer is allowed to cool. An elastomeric polymer is isolated.
The invention fias been described in detail with particular reference to
preferred
embodiments thereof, but it will be understood that variations and
modifications can be
effected within the spirit and scope of the invention.
02297987 2000-02-04
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Example 43
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer; 341.88 g of a ethylene diol and 37.99 g of 15 wt. % Rhodafac RE-610
(phosphate surfactant from Rhone Poulenc) were added. The contents of the
reactor
were heated to 65 °C. In a separate 500 ml flask, a monomer/surfactant
mix of 182.34
g 2-ethylhexylacrylate, 27.35 g of styrene, 18.23 g of glycidyl methacrylate,
30.39 g of
Rhodafac RE-610 and 45.58 g of ethylene diol was prepared. To the heated
reactor,
30.39 g of the monomer/surfactant mix was added. After allowing the contents
of the
reactor to re-equilibrate, 0.51 g of t-butyl hydroperoxide (t-BHP) dissolved
in 11 g of
ethylene diol was added to the reactor followed by 0.23 g Sodium Formaldehyde
Sulfoxylate (SFS) dissolved in 11.2 g of Distilled water. After a few minutes,
the
reactor appearance changed from grayish white to white with a slight bluish
tint
indicating the formation of particles. The remaining monomer mix was fed into
the
reactor over a period of 215 minutes. During the same time period, 0.68 g of
SFS
dissolved in 28 g of distilled water was fed into the reactor. Also, 0.65 g of
70 wt. % t-
BHP dissolved in 45.6 g of EG was fed into the reactor. After all the monomer
was
added, the reaction was held at 65 °C for an additional one half hour
at which point the
reactor was cooled to room temperature. The resulting emulsion was filtered
through a
100 mesh screen.
Exam In a 44
A urethane/acrylic composite was prepared by the following procedure. To a 50
ml flask was added 14.61 g of methylenebis(4-cyclohexyl isocyanate) and 5.75 g
of
latex of Example 43. A catalyst dibutyltindiacetate (O.lg) was added to the
mixture.
Within 1 hour, the reaction exothermed and formed a stiff polymer foam
containing the
latex.
02297987 2000-02-04
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1 xample 45
To a 1L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer; 395.93 g of a ethylene diol and 7.90 g of Hitenol HS-20 were added.
The
contents of the reactor were heated to 65 °C. In separate 500 ml flask,
a
monomer/surfactant mix of 180.62 g 2-ethylhexylacrylate, 22.58 g of styrene,
11.29 g
of allyl methacrylate, 11.29 g of methacrylic acid, 4.52 g of Hitenol HS-20
and 57.57 g
of ethylene diol was prepared. To the heated reactor, 28.79 g of the
monomer/surfactant mix was added. After allowing the contents of the reactor
to re-
equilibrate, 0.50 g of a 90 wt. % t-butyl hydroperoxide (t-BHP) dissolved in
11.2 g of
ethylene diol was added to the reactor followed by 0.23 g Sodium Formaldehyde
Sulfoxylate (SFS) dissolved in 11.2 g of Distilled water. After a few minutes,
the
reactor appearance from grayish white to white with a slight bluish tint
indicating the
formation of particles. The remaining monomer mix was fed into the rector over
a
period of 195 minutes. During the same time period, 0.65 g of SFS dissolved in
28 g of
distilled water was fed into the reactor. Also, 0.50 g of 90 wt. % t-BHP
dissolved in 56
g of EG was fed into the reactor. After all the monomer was added, the
reaction was
held at 65 °C for an additional one half hour at which point the
reactor was cooled to
room temperature.
The resulting emulsion was filtered through a 100 mesh screen. The particle
size of the emulsion was 100 nm as measured by dynamic light scattering.
ExamQle 46
'r A blend was prepared by the following procedure. Dimethyl terephthalate
(0.32
moles, 61.9 grams), 56.5 grams of the latex of Example 45 and catalyst metals
were
placed in a O.SL polymerization reactor under a 1 atmosphere nitrogen
atmosphere.
The mixture was heated with stirring under a slow nitrogen purge at 200
°C for 1 hour
and then 210 °C for two hours. At this point, the reaction mixture was
raised to 280 °C
and then vacuum was applied and the pressure was lowered from 1 atmosphere to
0.2-
__-- -__- -~A 02297987 2000-02-04
- 65 -
0.5 Torr over a period of 11 minutes. Pressure of 0.3-0.5 Torr was maintained
for 1
hour as the viscous melt stirred. Heat was removed and the polymer was allowed
to
cool and then ground. The Ih.V. of the polymer was 0.35 dL/g.
~ xam~le 47
To a 2L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer, 515.76 g of ethylene diol, 164.80 g of water and 12.28 g of 70 wt. %
Tergitol
15-S-40 (Non-ionic surfactant from Union Carbide) solution were added. The
contents
of the reactor were heated to 85 °C. In a separate 1500 ml flask, a
monomer/surfactant
mix of 325.65 g 2-ethylhexylacrylate, 17.19 g of trimethylopropane-
triacrylate, 7.37 g
of the 70% Tergitol 15-S-40 and 103.2 g of ethylene diol was prepared. To the
heated
reactor, 45.44 g of the monomer/surfactant mix was added. After allowing the
contents
of the reactor to re-equilibrate, 0.69 g of sodium persulfate dissolved in 17
g of water
was added to the reactor. After a few minutes, the reactor appearance changed
from
clear to a bluish white tint indicating the formation of small particles. The
remaining
monomer mix was fed into the reactor over a period of 90 minutes. At the same
time
the monomer was being added to the reactor, 1.72 g of sodium persulfate
dissolved in
34 g of water was fed into the reactor. After all the monomer was added, the
reaction
was held at 85 °C for an additional hour at which point the reactors
was cooled to room
temperature.
The resulting latex was filtered through a 100 mesh screen. The effective
diameter as measured by dynamic light scattering was 194 tort.
exam Ip a 48
The blend was prepared by the following procedure. Dimethyl terephthalate
(0.5 moles, 97.0 grams), ethylene glycol (1.0 moles, 62.0 grams), and catalyst
metals
were placed in a O.SL polymerization reactor under a 1 atmosphere nitrogen
atmosphere. The mixture was heated with stirring under a slow nitrogen purge
at
-.- - ----CA 02297987 2000-02-04
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200 °C for 1 hour and then 210 °C for two hours. The temperature
was increased to
280 °C and then nitrogen was shut off and vacuum applied. After 10
minutes of
vacuum (0.35 Torr achieved), the vacuum was removed, nitrogen was bled in to
increase the pressure to atmospheric pressure and 56.5 grams of the latex of
Example
47 was added with a 125 mL pressure-equalizing fimnel over a 20 minute period.
Again, nitrogen flow was shut off and-vacuum applied. Pressure of 0.3-0.5 Torr
was
maintained for 1 hour as the viscous melt was stirred. Heat was removed and
the
polymer was allowed to cool and then ground. A tough opaque white film was
melt-
pressed at 240 °C for 15 seconds. The Ih.V. was 0.80 dL/g, the Tg was
61.3 °C (2nd
cycle), the Tm was 212.3 °C (2nd cycle), TEM showed that the rubber
particles were
0.2-0.9 microns in size in the polyester matrix.
~xa~~~le 49
To a 2L jacketed reaction kettle equipped with a condenser, nitrogen purge,
and
stirrer, 656.7 g of ethylene diol and 26.86 g of Disponil FES 77 (anionic
surfactant
from Henkel) were added. The contents of the reactor were heated to 85
°C. In a
separate 1500 ml flask, a monomer/surfactant mix of 326.7 g 2-
ethylhexylacrylate,
17.19 g of trimethylopropane-triacrylate, 103.2 g of ethylene diol and 16.12 g
of
Disponil FES 77 was prepared. To the heated reactor, 46.3 g of the
monomer/surfactant mix was added. After allowing the contents of the reactor
to re-
equilibrate, 0.69 g of sodium persulfate dissolved in 16.8 g of water was
added to the
reactor. After a few minutes,.the reactor appearance changed from clear to a
bluish
white tint indicating the formation of small particles. The remaining monomer
mix was
fed into the reactor over a period of 90 minutes. At the same time the monomer
was
'r being added to the reactor, 1.72 g of sodium persulfate dissolved in 33.6 g
of water was
fed into the reactor. After all the monomer was added, the reaction was held
at 85 ° C
for an additional hour at which point the reactor was cooled to room
temperature.
The resulting latex was filtered through a 100 mesh screen. The effective
diameter as measured by dynamic light scattering was 155 nm.
_____.. _ . .. __ _ CA 02297987 2000-02-04 ___
-67-
Example 50
The blend was prepared by the following procedure. Dimethyl terephthalate
(0.5 moles, 97.0 grams), ethylene glycol ( 1.0 mole, 62.0 grams), and catalyst
metals
were placed in a O.SL polymerization reactor under a 1 atmosphere nitrogen
atmosphere. The mixture was heated with stirring under a slow nitrogen purge
at
200 °C for 1 hour and then 210 °C for two hours. The temperature
was increased to
280 °C and then nitrogen was shut off and vacuum applied. After 10
minutes of
vacuum (0.35 Torr achieved), the vacuum was removed, nitrogen was bled in to
increase the pressure to atmospheric pressure and 56.6 grams of the latex from
Example
49 was added with a 125 mL pressure-equalizing funnel over a 10 minute period.
Again, nitrogen flow was shut off and vacuum applied. Pressure of 0.3-0.5 Torr
was
maintained for 1 hour as the viscous melt was stirred. Heat was removed and
the
polymer was allowed to cool and then ground. A tough opaque white film was
melt-
pressed at 240 °C for 15 seconds. The Ih.V. was 0.82 dL/g, the Tg was
60.1 °C (2nd
cycle), the Tm was 212.2°C (2nd cycle). TEM showed that the rubber
particles were
0.2-0.9 microns in size in the polyester matrix.
--
