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Description  |
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FIELD OF INVENTION
This invention relates to the preparation of low density, porous,
crosslinked, polymeric materials. In one aspect, the invention relates to
reducing curing time in a high internal phase emulsion polymerization
process to manufacture low density porous crosslinked polymeric materials.
BACKGROUND OF THE INVENTION
Polymeric foams can be generally classified as either closed-cell foams or
as open-cell foams. Open-cell foams can be used as a matrix to contain
various liquids and gases. They are capable of various industrial
applications such as, for example, use in wipes and diapers, as carriers
and ion exchange resins For some of these applications, it is desirable to
have porous crosslinked polymer blocks which have a very low density and a
high capacity of absorbing and retaining liquids. Such high absorption
capacity, low density, porous polymer blocks can be prepared by
polymerizing a specific type of water-in-oil emulsion known as high
internal phase emulsion (HIPE) having relatively small amounts of a
continuous oil phase and relatively greater amounts of an internal water
phase. Further, other properties such as good wicking and good retention
of liquid under load (i.e., low compressive strain or resistance to
compression deflection) are also desirable for use as an absorbent.
Typically, these high absorption capacity, low density foams are prepared
by forming a high internal phase water-in-oil emulsion in the presence of
a surfactant and polymerizing the monomers in the oil phase of the
emulsion with a polymerization initiator at a temperature around
60.degree. C. for about 8 hours. However, it has been found that in order
to obtain foams with better properties, curing must be conducted for 16
hours or longer at a temperature of 60.degree. C. Further, to produce
these foams in a continuous process, it is desirable to heat the emulsion
rapidly and to reduce the curing time Therefore, it will be advantageous
to reduce the curing time and to heat the emulsion rapidly without
significantly affecting the resulting foam properties.
However, it has been found that by raising the temperature rapidly above
about 65.degree. C., the emulsion deteriorates thereby affecting the
resulting foam products Therefore, it will be desirable to be able to
rapidly heat the emulsions and/or reduce the curing time without degrading
the water-in-oil emulsion and adversely affecting the foam product
properties.
It is therefore an object of the present invention to provide a process to
prepare low density, porous crosslinked polymeric foams with improved
absorption properties. It is another object of the present invention to
provide a process to reduce curing time and/or to allow rapid heating
without substantially degrading the water-in-oil emulsion.
SUMMARY OF THE INVENTION
According to the invention, a process for the production of a porous
crosslinked polymeric material is provided, comprising the steps of:
(a) providing a water-in-oil high internal phase emulsion comprising i) a
mixture of polymerizable monomers comprising at least one vinyl monomer
and a difunctional unsaturated crosslinking monomer, ii) at least 90
weight percent, based on the emulsion, of water as the internal phase iii)
a surfactant, and iv) a polymerization catalyst;
(b) subjecting the water-in-oil high internal phase emulsion to a
temperature within the range of about room temperature to less than about
65.degree. C. for a time effective to form a gel having a rheometrics
dynamic shear modulus value of at least about 500 pascal; and
(c) heating the gel at a temperature of at least about 70.degree. C. for a
time effective to cure the monomers. The process provides low density,
open-cell foams having good absorption properties such as adsorption
capacity and/or resistance to compression deflection property in shorter
curing times.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graph of a Rheometrics dynamic modulus plot measured at
60.degree. C. against time of a water-in-oil high internal phase emulsion
having a water to oil ratio of 30:1 and monomer ratio of styrene to
divinyl benzene to 2-ethylhexyl acrylate of 1:1:3.
FIG. 2 is a graph of a Rheometrics dynamic modulus plot measured at
60.degree. C. against time of a wet foam having a water to oil ratio of
30:1 and monomer ratio of styrene to divinyl benzene to 2-ethylhexyl
acrylate of 1:1:3.
FIG. 3 is a graph of a Rheometrics dynamic modulus plot measured at
60.degree. C. against time of a dry foam having a water to oil ratio of
30:1 and monomer ratio of styrene to divinyl benzene to 2-ethylhexyl
acrylate of 1:1:3.
DETAILED DESCRIPTION OF THE INVENTION
According to the invention, a low density porous crosslinked polymeric
material (hereinafter "foam") having high absorption capacity and good
wicking and resistance to compression properties can be prepared without
substantially increasing curing time by curing the monomers in a
water-in-oil high internal phase emulsion in multiple-stages (i.e., at
least 2 stages). These foams generally have a dry density of less than
about 0.1 g/cc.
Various monomers may be used in the preparation of the foams, provided the
monomers can be dispersed in or form an oil phase of a water-in-oil high
internal phase emulsion and have a polymerizable vinyl group. Suitable
vinyl monomers include, for example, monoalkenyl arene monomers such as
styrene, .alpha.-methylstyrene, chloromethylstyrene, vinylethylbenzene and
vinyl toluene; acrylate or methacrylate esters such as 2-ethylhexyl
acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, hexyl
acrylate, n-butyl methacrylate, lauryl methacrylate, and isodecyl
methacrylate; and mixtures thereof.
Suitable crosslinking agents can be any difunctional unsaturated monomers
capable of reacting with the vinyl monomers Difunctional unsaturated
crosslinking monomers include, for example, divinyl benzene, diethylene
glycol dimethacrylate, 3-butylene dimethacrylate, and allyl methacrylate.
Crosslinking monomers are typically present in an amount of from about 2
weight percent to about 70 weight percent, preferably from about 5 weight
percent to about 40 weight percent based on the total monomer mixture.
Some of these crosslinking monomers can be incorporated as a
non-crosslinked monomer as long as at least about 2 weight percent of the
crosslinking monomers are crosslinked.
Suitable polymerization catalysts can be water-soluble or oil-soluble.
Water-soluble catalysts include, for example, potassium or sodium
persulfate and various redox systems such as ammonium persulfate together
with sodium metabisulfite. Oil soluble (monomer soluble) catalysts
include, for example, azodibisisobutyronitrile (AIBN), benzoyl peroxide
and di-2-ethyl-hexyl-peroxydicarbonate. The catalyst should be present in
an effective amount to cure the monomers Typically the catalyst can be
present from about 0.005 to about 15 weight percent based on the monomers.
The polymerization catalyst can be in the water phase and polymerization
occurring after transfer of the catalyst into the oil phase or an
activated monomer/catalyst reaction product can be added to the oil phase.
Alternatively, the polymerization catalyst may be introduced directly into
the oil phase. Preferably, the polymerization catalyst is added in the
water phase and polymerized after transfer of the catalyst into the oil
phase for ease of handling.
The surfactant used in making the high internal phase emulsion which is to
be polymerized is also important in forming a water-in-oil high internal
phase emulsion. Suitable surfactants include, for example, nonionic
surfactants such as sorbitan esters (e.g., sorbitan monooleate and
sorbitan monolaurate), glycerol esters (e.g. glycerol monooleate and
glycerol monoricinoleate), PEG 200 dioleate, partial fatty acid esters of
polyglycerol, and caster oil 5-10 EO; cationic surfactants such as
ammonium salts (e.g., distearyl dimethyl ammonium chloride and dioleyl
dimethyl ammonium chloride); and anionic surfactants such as bis-tridecyl
sulfosuccinic acid salt. Commercially available surfactants include, for
example, SPAN.RTM. emulsifying agents 20, 40, 60, 65, 80 and 85 (from
Fluka Chemical Corp.), and ALKAMULS.RTM.sorbitan esters SML, SMO, SMS, STO
and ALKAMULS.RTM. sorbitan ester ethoxylates PMSL-20 and PSMO-20 (from
Alkaril Chemicals Ltd.) among others. The amount of surfactant must be
such that a water-in-oil high internal phase emulsion will form.
Generally, the surfactant is present in an amount effective to form a
water-in-oil high internal phase emulsion. Preferably, the surfactant can
be present from about 2 to about 40% by weight, more preferably about 5 to
about 25% by weight based on the monomers.
The relative amounts of the water and oil phases used to form the high
internal phase emulsion are a factor in determining the structural,
mechanical and performance properties of the resulting polymeric foams.
The ratio of water and oil in the emulsion can influence the density, cell
size, and specific surface area of the foam products To form a polymeric
foam product with suitable density and high absorption capacity, the
water-in-oil high internal phase emulsion typically contains as the
internal phase, at least about 90 weight percent, based on the emulsion,
of water, corresponding to a water to oil weight ratio of at least about
9:1, more preferably at least about 95 weight percent of water, most
preferably at least about 97 weight percent of water, corresponding to a
water to oil weight ratio of at least about 33:1.
The internal water phase can preferably contain a water-soluble electrolyte
to stabilize the HIPE and to make the foam more water wettable Suitable
electrolyte includes inorganic salts (monovalent, divalent, trivalent or
mixtures thereof), for example, alkali metal salts, alkaline earth metal
salts and heavy metal salts such as halides, sulfates, carbonates,
phosphates and mixtures thereof. Such electrolyte includes, for example,
sodium chloride, sodium sulfate, potassium chloride, potassium sulfate,
lithium chloride, magnesium chloride, calcium chloride, magnesium sulfate,
aluminum chloride and mixtures thereof. Mono- or di-valent salts with
monovalent anions such as halides are preferred.
The formation of a water-in-oil high internal phase emulsion is dependent
on a number of factors such as the monomers used, water to oil ratio, type
and amount of surfactant used, mixing conditions, presence and the amount
of water-soluble electrolyte. Unless all of these factors are such that it
favors formation of a water-in-oil emulsion, the emulsion will form a
oil-in-water emulsion rather than water-in-oil high internal phase
emulsion. The formation of a water-in-oil emulsion is described in U.S.
Pat. No. 4,522,953, the disclosure of which is herein incorporated by
reference.
In general, to form the water-in-oil emulsion, the water can be mixed in
any way up to a water to oil ratio of about 4:1. An oil-in-water emulsion
becomes preferred if the water was added all at once beyond a water to oil
ratio of about 4:1. Typically, the water must be added gradually with a
moderate rate of shear. A small capacity mixer such as a paint mixer with
a shear rate of at least about 5 s.sup.-1, preferably at least about 10
s.sup.-1 can be used to mix the water-in-oil emulsion. A pin gap mixer
with a shear rate of at least about 50 s.sup.-1 preferably at least about
100 s.sup.-1 is preferred. If the shear rate is too low, the water-in-oil
emulsion will revert to a oil-in-water emulsion. It is desirable to at
least have a water to oil ratio of about 9:1, preferably at least about
19:1, more preferably at least about 30:1 for a high absorbency capacity
foam.
Stability of the high internal phase emulsion is important so the emulsion
will not degrade during the curing process. It has been found that when
some of the nonionic surfactants were used, the emulsion degraded, forming
bulk oil and water phases, when the curing temperature was raised above
about 65.degree. C. For example, more than approximately 75% of the
water-in-oil HIPE degraded when a HIPE containing styrene, 2-ethylhexyl
acrylate and divinyl benzene monomers was rapidly cured by placing in a
hot water bath at a temperature of 80.degree. C. using a sorbitan
monooleate (SPAN.RTM. 80 emulsifying agent) as a surfactant. Some of these
nonionic surfactants, for example, sorbitan fatty acid esters such as
sorbitan monolaurate, are desirable because of their low odor.
In order to cure the monomers faster and at higher temperature without
substantially degrading the water-in-oil HIPE, the emulsion is pre-cured
at a temperature of less than about 65.degree. C. until the emulsion has a
Rheometrics dynamic shear modulus of greater than about 500 pascal,
preferably greater than about 800 pascal, most preferably greater than
about 1000 pascal. Typically, the pre-cured emulsion will be lightly
gelled, having a consistency like a jelly or a gelatin referred to as
"gel".
In an alternative method, this consistency (gel) can also be tested
visually by a weight resistance test. In a weight resistance test, a probe
is placed on the surface of an emulsion or a gel, exerting a pressure of
0.3 psi accross a cross-sectional diameter of 6 mm, penetrates less than
about 6 mm, preferably less than about 3 mm in depth.
In the first curing stage the monomers are pre-cured at a temperature of
less than 65.degree. C. for a time sufficient to produce a rheometrics
dynamic mechanical shear modulus of greater than about 500 pascal,
generally, pre-cured for at least about 30 minutes. Subsequently, the
pre-cured materials are cured at a temperature of above about 70.degree.
C., preferably above about 75.degree. C., more preferably above about
85.degree. C. for a time effective to cure the monomers. The cure can be
as high as about 175.degree. C. under suitable pressure to prevent water
from boiling. The emulsions can be heated by hot water, hot air or steam.
Preferably, the HIPE should be pre-cured for at least about one hour at
60.degree. C. or at least about 2 hours at room temperature. Subsequently,
the monomers are cured at a temperature of greater than about 70.degree.
C. generally for at least about one hour. Generally, the extent of
reaction after curing is at least about 85% of the monomers, preferably at
least about 90%, more preferably at least about 95% (i.e., less than about
5% of free monomers), most preferably at least about 99% (i.e., less than
about 1% of free monomers) in order to obtain good properties.
Prior to the gel stage, the emulsions generally degrade with increasing
temperature thereby releasing water from the internal phase resulting in
unabsorbed water. Degradation of the emulsion, gel or foam can be seen by
free, unabsorbed water standing on the emulsion, gel, or foam surface (or
form a pool of water). Preferably, the emulsion should degrade less than 5
weight percent of water, more preferably less than 3 weight percent of
water, based on total water used to prepare the emulsion.
The pre-curing and curing can be done in multiple steps as long as the
temperature of the pre-curing stage is less than about 65.degree. C. until
the rheometrics dynamic shear modulus is at least about 500 pascal and
curing stage reaches a temperature greater than about 70.degree. C. for a
sufficient time to obtain good properties which is typically at least one
hour. For example, a ramping pre-curing/curing schedule can be preformed
starting at room temperature and raising the temperature gradually in a
number of steps up to about 60.degree. C., (i.e., the HIPE is heated below
about 65.degree. C. at least until the gel reaches a rheometrics dynamic
shear modulus of at least about 500 pascal) then further raising the
temperature to past 70.degree. C. until the monomers are cured.
Preferably, the temperature is raised past 75 .degree. C., more preferably
past 85 .degree. C.
The degree of necessary gelling (crosslinking) varies depending on the
severity of the curing temperature. For example, when the gel is cured at
a temperature of 75.degree. C., the emulsion will be stable as long as the
HIPE is pre-cured to a rheometrics dynamic shear modulus of at least 500
pascal. When the gel is cured at a temperature of 134.degree. C. at a
pressure of about 28 psi, a Rheometrics dynamic shear modulus of at least
800 pascal must be reached.
Alternatively, when the gel is cured at a temperature of 134.degree. C., an
emulsion must be pre-cured until the probe used in the weight resistance
test preferably penetrates the resulting gel less than about 3mm, which
requires pre-curing for at least about hour at 60.degree. C. For example,
a foam with a good absorbance capacity can be obtained by pre-curing at a
temperature of 60.degree. C. for 4 hours and then curing at a temperature
of 134.degree. C. and pressure of about 28 psi for 4 hours.
These foams can be post-cured to improve the foam properties. Better
properties such as, for example, thin thickness after drying (i.e.,
thickness of a foam after removing water), increased free swell (i.e.,
amount of liquid a foam can initially absorb), and/or good resistance to
compression deflection can be obtained depending on the monomer
formulation by post-curing the foam at a temperature of above about
75.degree. C., preferably greater than 90.degree. C., more preferably
above about 95.degree. C., most preferably at least about the boiling
point of water by steam, hot air or other heating source. Such heating may
be performed initially in a heat exchanger, oven, over heated rollers or
by other means.
When the temperature is near or above the boiling point of water, pressure
is preferably applied to keep the water in the liquid phase and to obtain
better properties. If desired, the pressure may be lowered to boil some of
the water, but in normal practice the water will be maintained in the
liquid state to stabilize the monomer :aqueous interface and retain the
foam structure, at least until the foam is gelled (i.e., pre-cured), and
preferably until it is cured. Once the curing and/or post-curing process
is completed, the water incorporated in the foam may be flashed by
lowering the pressure to a suitable level to evaporate the remaining
liquid to give the desired degree of dryness in the product foam. Such
vacuum drying will preferably be used after the desired state of cure is
developed in the foam material. The use of pressure to maintain the
aqueous phase in the liquid state allows very rapid curing of emulsions at
very high temperatures, provided the emulsions are stable at the high
temperatures used. The inventive process provides a way to stabilize the
emulsion so the foam can be processed at a higher temperature.
Pressure can be applied to the emulsion, if desired, at a pressure
generally from above atmospheric pressure, typically within the range of
about atmospheric pressure to about 150 psig. When the temperature is
about 100.degree. C., a pressure from about to about 10 psig is
sufficient; when the temperature is about 130.degree. C., a pressure from
about 30 psig to about 70 psig is preferred. The preferred pressures will
be from just above the autogenous steam pressure of the solution to about
twice that pressure on an absolute pressure basis, i.e., psia; higher or
lower pressures may be used as desired to achieve specific results. For
example, if the vapor pressure of the monomer mixture exceeds that of
water, a pressure sufficient to prevent volatilization of either water or
monomer will be used. The minimum preferred pressure will be that
sufficient to prevent volatilization. In general, pressures above such
value will be preferred to provide some margin of safety. Most preferred
will be pressures of from above the vapor pressure of the emulsion to
about twice the vapor pressure of the emulsion, although higher pressures
may be used if convenient. In general, the cost of pressure equipment will
be greater as the pressure is increased, resulting in the preferred range
having an upper limit of about twice the minimum necessary pressure for
economic reasons.
One method to cure an emulsion under pressure is to use an autoclave
operating under autogenous pressure of steam generated from pure water at
a given temperature. This method will prevent volatilization of the
aqueous salt solution in the emulsion. Another satisfactory method is to
use applied nitrogen or air pressure to prevent boiling of the emulsion.
In case a permanent gas is used, an inert gas such as nitrogen or argon
will be preferred over air or oxygen from a flammability point of view.
The pressure may also be maintained by mechanical means, such as rollers,
pistons, molds, or the like. This method will be particularly useful if
continuous processing is desired.
These foams prepared by the inventive process may be washed and dried to
yield an absorbent block which is especially useful for the absorption of
liquids. Typically, these foams are washed to reduce the electrolyte
content of the foam with a solvent such as, for example, an alcohol, a low
concentration electrolyte solution (lower concentration than the water
phase) such as 1% calcium chloride solution or deionized water. The washed
foams can generally be dried by squeezing the water and/or solvent out of
the foams and air or heat drying. The foams produced by the inventive
process possess high absorption capacities and good free swell values,
especially suitable for use in liquid absorbent articles such as wipes,
diapers and catamenial products for example.
Illustrative Embodiment
The following illustrative embodiments describe the process of the
invention and are provided for illustrative purposes and are not meant as
limiting the invention.
Washing and Drying Method
The following washing and drying method was used for all of the examples
below: After the foam blocks were cured, the blocks were sliced to 0.35
inches (0.89 cm) thickness. Then, each individual slice was placed on a
0.04 inch (0.1 cm) mesh screen between a 9".times.6.75" (22.9 cm .times.
17.1 cm) stainless steel plate that allowed the slice to be squeezed to a
0.045 inch (1.14 mm) thickness. The squeezed slices were placed in an
ARBOR-press made by DAKE and the calcium chloride solution was squeezed
out. The slices were then washed and squeezed twice by soaking the slices
in 2 gallons of 1% calcium chloride solution and placing in the
ANVIL-press. Then, after the slices were squeezed, a paper towel was
placed on both sides of the washed slices which were squeezed again to
remove excess water from the slices. The slices were then placed in an
oven at a temperature of 60.degree. C. for 4 hours to dry. The washed and
dried foam slices were analyzed for physical properties as discussed
below.
TESTING METHODS
Rheometrics Dynamic Modulus
The measurements on the emulsion were made on a Rheometrics RDS-7000 series
mechanical spectrometer (any oscilatory dynamic tester which is capable of
testing liquids in a couette fixture can be used) using a couette fixture,
consisting of a cylindrical bob which rotates centered in a concentric cup
(the bob has a conical end mating with a conical bottom on the cup). The
samples were put into the cup after oil-wetting and drying the cup and the
cup was placed so that the bob displaced the emulsion The clearance
between the bob and cup was about 2 mm and the total sample was less than
7 cc. A small amount of a low-volatility mineral oil TUFFLO.RTM. 6056 (a
hydrogenated mineral oil) was floated on top of the emulsion in the small
annulus formed surrounding the bob. The measurements were made at high
shear strain (typically 20%) at 4 discrete frequencies (0.1, 1, 10 and 100
radian/sec.) as a function of time after loading the cup. The sample was
vibrated rotationally (dynamic mode) and the torque, rpm and normal force
were recorded. The Rheometrics dynamic functions, G', shear modulus, G",
loss modulus and tangent delta and ratio of G" to G' were measured. These
data were plotted as a function of elapsed time.
Similar moduli were measured in the solid state between parallel plates
having a diameter of 1.3 inches (3.3 cm) using a sample thickness of about
0.2 inches (0.5 cm) instead of the cup for the wet final cured foam and
final cured foam which has been dried. Comparison of these similar moduli,
measured in the solid state for the wet final cured foam and final cured
foam gives a relative indication of the progress of the cure state to
completion based on the development of modulus. The technique of tracking
of the dynamic moduli as a function of time at a temperature can be found
in Encyclopedia of Polymer Science & Engineering, 1989, "Gel Point" by
Heening Winter; and H. H. Winter, Polymer Engineering and Science, V27
#22, P1698 (1987).
Data of a high internal phase water-in-oil emulsion having a water to oil
ratio of 30:1 and a monomer ratio of styrene to divinyl benzene to
2-ethylhexyl acrylate of 20:20:60 was measured at 60.degree. C. and
plotted in FIG. 1 (wet emulsion), FIG. 2 (wet foam) and FIG. 3 (dry foam).
The emulsion was formed in a similar manner to Example 2 below with 20%
surfactant (SPAN.RTM. 80 to SPAN.RTM. 85 ratio of 2:1) and 0.15% potassium
persulfate. Water phase was added at 0.4 lb/min. The emulsification
temperature was 40.degree. C. and the pin mill was spinning at 2400 RPM.
The foam was cured for 24 hours at 60.degree. C. prior to the wet foam and
dry foam measurement.
Weight Resistance Test
A flat-tipped probe of about 6 mm diameter was placed on top of an emulsion
or gel to create a pressure at the flat-tip of about 0.3 psi. The ease and
penetration of the object into the gel was measured. The emulsion is
gelled when the object no longer penetrates or penetrates less than about
3 mm.
Free Swell/Dry Thickness/Swollen Thickness/Foam Density/ Percent
Strain/Resistance to Compression Deflection/Swell Ratio
A 2".times.2" (5.08.times.5.08 cm) square is cut from a foam slice. The
thickness of the foam sample is measured while it is dry ("dry thickness")
using a dead weight thickness gage (a digital linear gage model EG-225
made by Ono Sokki) exerting 50 grams force applied to a 1.60" diameter
disk. This thickness is called the "caliper." The foam square is soaked in
warm 88.degree. F. (31.degree. C.) Syn-Urine from Jayco for 17 minutes.
From the 2".times.2" (5.08.times.5.08 cm) square, a circle of 1.129"
(2.868 cm) diameter is cut. This disk is re-equilibrated in the Syn-Urine
for 5 minutes. The wet disk is then weighed ("initial wet weight").
The thickness of the wet sample is measured using the same load gage
("initial wet caliper"). The disk is then placed under a 0.74 psi stress
where stress is the total dead weight applied to the gage divided by the
cross-sectional area. The thickness of the disk is measured under this
stress after 15 minutes ("wet caliper"). After 15 minutes, the specimen
disk is weighed to measure the retained fluid.
The excess urine is squeezed from the disk and the remainder of the square
from which it was cut. The foam is placed in boiling deionized water for
15 minutes. The foam is washed this way several times to remove
inorganics. The foam is then removed, blotted dry, then placed in a vacuum
oven at 60.degree.-70.degree. C. and dried until the foam has fully
expanded. The remnant from the square sample is used for TOLUENE-SWELL
test described below. The weight of the dry disk sample is then determined
in grams ("final dry weight").
The following values were calculated from the above measurements.
Free swell=initial wet weight/final dry weight
Resistance to Compression Deflection (RTCD)=wet weight after load at 15
minutes/final dry weight
Swell Ratio=RTCD/Free swell .times.100
##EQU1##
Foam Volume (cm.sup.3)=(diameter/2).sup.2 .times.3.142 .times. initial wet
caliper based on a 1.129" diameter circle cut (in cm)
Foam Density (mg/cm.sup.3)=final dry weight .times.1000/Foam Volume
Toluene Swell and Molecular Weight Between Crosslinks (MWBC)
The sample which was used for the Free-Swell procedure is used. The newly
cut sample, washed of inorganic impurities, is weighed to obtain the
initial sample weight. It is then placed on top of about 50 ml of methanol
in a glass jar. The sample is allowed to soak up methanol; if air pockets
are observed the sample is gently squeezed to expel air. After 24 hours at
room temperature the samples are removed, quickly blotted and immediately
weighed wet ("wet methanol weight"). The samples are gently squeezed to
expel the methanol and then dried in a vacuum oven for at least three
hours at 60.degree. C., then cooled, and weighed ("methanol dried
weight"). The samples are then placed on top of about 50 ml of toluene in
bottles and allowed to absorb and swell for 24 hours at room temperature.
The samples are then removed, quickly blotted and immediately weighed
("toluene swollen weight"). The samples are then gently squeezed to dispel
the toluene without breaking the foam and then dried in a vacuum oven at
60.degree. C. for 24 hours, and then weighed. This is a final "toluene
dried weight."
##EQU2##
Vertical Wicking Rats
From a foam slice, cut at 0.35 inches (0.89 cm) thickness, a 1 to 2 cm wide
strip is cut, greater than 5 cm in length. The strip of foam is clamped or
taped to a metal ruler, with the bottom of the foam strip flush with the 0
mark on the ruler. The ruler and foam are placed in a container of
approximately 100 ml Syn-Urine from Jayco, in an incubator at 99.degree.
F. (37.degree. C.) so the bottom of the strip (0 mark) is barely touching
the surface of the Syn-Urine (less than 1 mm). The Syn-Urine is dyed with
food coloring to more easily monitor its absorption and rise in the foam.
A stopwatch is used to measure the time required for the liquid level to
reach 5 cm vertical height in the foam sample.
Percent Free Liquid
The amount of unabsorbed water was measured by decanting fluid from the
foam in the container after pre-curing or curing stage and weighing the
decanted fluid.
EXAMPLE 1
This example demonstrates preparation of a low density crosslinked
polymeric material according to the invention under rapid heating
conditions. For comparison, this example also demonstrates that high
internal phase water-in-oil emulsions tend to break when rapidly heated.
In a 4 oz. glass jar, emulsions with aqueous phase to monomers ratio as
listed below were made with the monomers containing 20% styrene, 20% of a
commercial 55% divinyl benzene (from Aldrich Chemical Co.) and 60% of
2-ethyl hexyl acrylate with an addition of 12 parts of a sorbitan
monolaurate (SPAN.RTM. 20 emulsifying agent from Fluka Chemical Corp.
Aldrich Chemical Co.) for Series A and Series C or sorbitan monooleate
(SPAN.RTM. 80 emulsifying agent from Fluka Chemical Corp.) for Series B as
surfactants for every 100 parts of monomers. The combined monomers were
emulsified with 10% CaCl.sub.2 solution for Series A and Series B and with
1.1% CaCl.sub.2 solution for Series C in deionized water containing 0.15%
potassium persulfate as a curing agent. The following results were
obtained when the emulsion was formed at 40.degree. C. and the bottles
were then immediately placed into thermostatted water baths at
temperatures listed below. All runs were heated until a probe used in the
weight resistance test penetrated less than 3 mm unless otherwise
indicated in Table 1 as listed below. Percent Free liquid of the heat
treated emulsions (cured) is shown below.
TABLE 1
__________________________________________________________________________
Series A:
__________________________________________________________________________
Ratio 30:1
Pre-Curing
Temperature .degree.C.
60 60 60 60 -- -- -- --
Time hr 1 1 2 2 -- -- -- --
Curing
Temperature .degree.C.
80 100 80 100 60 60 100 100
Time hr 2 2 1 1 1 3 1 2
% Free Liquid
24 60 2.6
5.5
2 2 72 72
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Ratio 40:1
Pre-Curing
Temperature .degree.C.
60 60 60 60
Time hr 0.5
1 2 3
Curing
Temperature .degree.C.
100 100 100 100
Time hr 3 2.5
1 1
% Free Liquid
46 65 26 9
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Ratio 20:1 30:1 40:1
Curing 60 80 100 60 80 100 60 80 100
Temperature .degree.C.
% Free Liquid
1 2 3 1 5 10 15 65 90
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Series B:
__________________________________________________________________________
Ratio 20:1 30:1 40:1
Temperature
60 80 100 60 80 100 60 80 100
% Free Liquid
50 95 100 30 80 100 100 100 100
@60.degree. C. oven
48.4 64.5 100
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Series C:
__________________________________________________________________________
Ratio 30:1
Temperature 60 80 100
% Free Liquid 4 35 60
__________________________________________________________________________
The percent free liquid indicates the amount of emulsion breakage by the
time curing of the material was stoped. As can be seen from the results in
Series A, B and C, rapid warming to high temperature is responsible for
the loss emulsion. For example, 40:1 material of Series A may be cured in
a 32 oz. batch in an air oven set at 60.degree. C. with loss of less than
5% of the emulsion: in a 4 oz. batch in water bath set at 60 .degree. C.
or higher large amounts of emulsion is lost. This example demonstrates
that the stability of the emulsion is poor as the cure temperature is
increased. The instability of the emulsion is increased as the temperature
is raised to 80.degree. C., and further to 100.degree. C.
As can be seen from Table 1, Series A, a precure of at least about 2 hours
at 60.degree. C. may be necessary to give a low free liquid value when the
foam is rapidly heated to 100.degree. C. in a water bath at a 30:1 water
to oil ratio. At the higher 40:1 water to oil ratio, the emulsion is more
delicate, and a longer time of at least about 3 hours at 60.degree. C. may
be required to maintain full absorbancy in the cured material. As can be
seen from the differences in % Free Water at a given temperature depending
on the water to oil ratio, the surfactant used and concentration of the
electrolyte in Table 1, a particular time of precure must be optimized to
each system. As can be seen from Table 1, Series A, a suitable precure
time may be found to largely eliminate the emulsion instability observed
when the emulsion is heated rapidly to high temperatures.
EXAMPLE 2
This example demonstrates preparation of a low density crosslinked
polymeric material according to the invention. Table 2 below describes the
amount of the monomer components and surfactant used in the process. Runs
2a, 2c, 2e, 2g and 2i are comparative examples.
An Edge Sweets pin mill mixing machine incorporating a 1 hp motor belt
driving a 6" long 11/2" diameter pin mill with 12 layers of pins on the
central rotor, 0.02" clearance between rotor and barrel, and fitted with
flow meters and thermocouples for monitoring, was used to form the high
internal phase water-in-oil emulsions. Oil phase (monomers and
surfactants) were metered and controlled by a model 184-56C magnetic drive
pump made by Micropump Corporation. Water phase flow was controlled by a
similar pump of greater capacity (model 120-56C made by Micropump Corp.).
The maximum oil flow in the configuration is 0.04 lbs/min; the maximum
water phase (water, salt and potassium persulfate initiator) flow is 1.20
lbs/min. Control based on flow rates and/or pump RPM is provided by
software in an Eaton IDT FACTORY MATE control computer and an
Allen-Brodley PLC-5 programmable logic controller.
A 10 gallon tank fitted with an air motor stirrer was used to mix aqueous
internal phase. The oil phase was externally mixed by shaking or with a
stirrer bar. The water phase was fed directly from mixing tank by the
pump. The oil pump reservoir is a 1 liter steel tank.
In a typical run procedure, the pin mill is mounted and filled with oil
phase. The flow of water and oil is started with the pin mill spinning
typically at 2000 RPM. Typical conditions to establish emulsions are a
water to oil feed ratio of 2:1 to 10:1 (i.e., low water to oil ratio),
temperatures at mix heads of 25.degree. C. to 65.degree. C., feed rates of
oil and water of 0.05 to 0.50 lbs/min, pin mill rotation rates of 1500 to
3000 RpM, emulsion flow rates of 0.3 to 1.2 lb/min, pin mill len9th of 6"
to 18" and pin/barrel clearance of 0 05 to 0.02". Flow rate, pin mill
length, pin/barrel clearance, RPM and temperature are adjusted to give the
smoothest emulsions with most uniform back-pressure through the pin mill.
Following establishment of a smooth emulsion at low water to oil ratio, the
ratio was raised to the desired value as shown in Table 2 by increasing
the water flow and/or decreasing the oil flow. Changes are preferably made
smoothly, with adjustment of all the above factors to give optimum
emulsion quality.
The emulsion was let out of the pin mill mix-head through a static mixer to
complete emulsion homogenation. After the desired emulsion conditions are
reached, the emulsion was collected in 6 lb sample containers at a flow
rate of 0.3 to 1.20 lb/min and cured in an oven at a temperature and time
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