CA2223824C - Use of foam materials derived from high internal phase emulsions for insulation - Google Patents

Abstract

The invention relates to the use of polymeric foam materials for insulation. These polymeric foams are prepared by polymerization of certain water-in-oil emulsions having a relatively high ratio of water phase to oil phase, common ly known in the art as high internal phase emulsions, or "HIPEs". The HIPE- derived foam materials used in the present invention comprise a generally hydrophobic, flexible, semi-flexible, or rigid nonionic polymeric foam structure of interconnected open-cells. These foam structures have: A) a specific surface area per foam volume of at least about 0.01 m2/cc; B) a density of less than about 0.05 g/cc; and C) a glass transition temperature (Tg) of between about -20~ and 90 ~C. The foams can be used as thermal, acoustic, and/or mechanical insulation materials. In a preferred embodiment, the foams used can be prepared, packaged, and shipped in a compressed, high density state and will "spring back" upon activation (e.g. heat) to the original density of the foam.

Description

W O 96140824 PCTlUS96/IOI69 USE OF FOAM MATERIALS DERIVED FROM
HIGH INTERNAL PHASE EMULSIONS FOR INSULATION

io This application relates to the use of microporous, open-celled polymeric foam materials as insulation materials. The application particulariy relates to the use of foam materials made from high internal phase emulsions.
BACKGROUND OF THE INVENTION
is The development of efficient and effective insulating materials has been the subject of substantial commercial interest. This is particularly true for materials which are thermal insulators, e.g. which reduce the rate of heat loss (or gain) of any device, construct, or container. Foams are broadly used as insulators. References describing such uses and properties of foams include zo Oertel, G. "Polyurethane Handbook" Hanser Publishers, Munich, 1985, and Gibson, L. 1.; Ashby, M. F. "Cellular Solids. Structure and Properties"
Pergamon Press, Oxford, 1988. The term "insulator" refers to any material which reduces the transfer of energy from one location to another. Such energy may be include heat, acoustic, and/or mechanical types. Heat is insulation is of particular importance and relates to the thermal conducl:iviry of the insulating medium.
The "perfect" insulator is a vacuum. Developing and maintaining an evacuated space around the area to be insulated can, however, be impractical, particularly for larger volumes. The structural integrity required to withstand 3o atmospheric pressure acting upon a vacuum vessel can be an issue.
A common insulating medium is a foam or cellular material having porous regions surrounded by a solid that provides integrity. The function of the foam as an insulator is to trap air and reduce thermal conductivity of the ' types described above. Foams are generally characterized by the size of the ss pores or cells within the structure as well as their density, which approximates the ratio of open-to-solid structure within the foam a The thermal conductivity of any foam depends on four characteristics:
1. convection through the pores;

2. conduction through the gas;

3. conduction through the poiymer; and s 4. thermal radiation through the cell walls and across the cell voids.
Convection via movement of a gas through pores of an insulating medium diminishes with cell sizes down to about 4 mm, below which it becomes negligible. Convection through pores is suppressed in cells smaller ~o than 10 mm. Most foams have cells much smaller than mm scale dimensions.
Conduction through the gas typically can account for as much as two-thirds of the system's thermal conduction. For this reason, foams filled with low conductivity gases can be preferred, although the gas will typically exchange with the atmosphere over time. Conduction through the solid is polymer is negligible with low density foams.
Thermal radiation can account for one-quarter to one-third of the thermal conductivity in a foam. (See Glicksman, L. R.; Torpey, M.; Marge, A. J. Cell. Plastics 1992, 28, 571 and DeVos, R.; Rosbotham, D.; Deschaght, J. ibid 1994, 30, 302.) Radiative heat transfer is highly dependent on the cell zo size of the foam and decreases with cell size (which preferably would be <_100 pm). Kodama et al. (ibid, 1995, 31, 24) report on improvements in the k factor (a measure of thermal insulation ability) of a series of polyurethane foams ("PUFs") as average cell sizes decreased from 350 ~m to 200 p,m at a density of 0.052 g/cc. Doerge reports that foams with densities lower than zs about 0.037 g/cc showed increases in thermal conductivity attributable to the increase in cell sizes that typically occurs at these lower densities (Doerge, H.
P. ibid, 1992, 28, 115), in part due to the increasing transparency of the cell walls and cell wall rupture (allowing rapid diffusion of the low conductivity gas filler). The best insulating rigid foams are low density foams (ca. 0.03 -so 0.07 g/cc for closed cell PLTFs) having the smallest cells possible filled with a gas having a low coefficient of thermal conductivity (or no gas at all). Thus, it would be desirable to produce foams having both low density and very small cells, e.g. 5100 Vim. Such foams apparently cannot be produced by state-of the-art blown foam processes.
as The historical approach to making insulating foams for the appliance industry (e.g. refrigerators, water heaters, etc.) has been to use chlorofluorocarbons (CFCs) as physical inflating agents, especially for foams based on polyurethane and polyisocyanate starting materials. The reported association between ~CFCs and ozone layer depletion has sharply curtailed their production and increased the need for alternate materials and/or methods for making foams. Alternate blowing agents such as carbon dioxide or pentane s however develop less efficient insulating foams relative to those made with CFCs. This results from the di~culty in achieving the same fineness of microstructure and densities possible with CFC blown foams. See for examples Moore, S. E. J. Cell. Plastics 1994, 30, 494 and U.S. Patent 5,034,424 (Weaning et al.) July 23, 1991. See also Oertel, p 273; Gibson and ~o Ashby, Chapter 7, p :!01.
Polyurethane foams are perhaps the most broadly used type in such applications. T'he chemistry used in processing presents certain disadvantages including poor photostability (see Valentine, C.; Craig, T. A.; I3ager, S. L.
J.
Cell. Plastics 1993, s!9, 569), the inevitable existence of undesdrable chemical ~s residues in the foams (see U.S. 4,211,847 to Kehr et al., issued July 8, 1980, and U.S. 4,439,553 to Guthrie et al., issued March 27, 1984, describing efforts to minimize these residues), and the production of noxious gases developed during burning due to the presence of nitrogen atoms within the composition (see Hartzell, G. E. J. CeIL Plastdcs" 1992, 18, 330). This can be particutarty zo problematic in accidents involving public conveyances such as boats, automobiles, trains or airplanes which may catch fire. Injuries and fatalities may result solely from inhalation of these noxious gases. See Gibson and Ashby Chapter 8, p 2112. This can also be an issue when the foam is discarded into a waste stream that is to be incinerated.
=s The building insulation industry has widely used foamed polystyrene rigid pangs ('m addityon to glass batting and blown cellulose insulation).
Styrene foam panels are useful in that they are rigid and may be nailed during cor~uction, are hydrophobic to provide moisture resistance (which otherwise diminishes ins~on value), and are relatively inexpensive. See Oertel p 277.
>o This material is also vridely used in beverage cups and food containers.
The cell sizes of these materials are typically in the 300-500 Eun range. Smaller celled polystyrene foams have been prepared using the Thermally Induced Phase Separation Proc:esa (TES) described in Chemtech 1991, 290 and U S.
5.128.382 (EUiott, et al.) issued July 7, 1992.
ss An important issue in making polymeric insulating foams commercially attractive for use a insulators is economics The economics of foams depend on the amouru and cost of the monomer: used, as well as the cost of converting the monomers to a usable polymeric foam. The effort to reduce the cost of such insulating foams, especially in terms of reducing the total amount of monomer used, can make it very difficult to achieve the desired insulation and mechanical properties.
s Accordingly, it would be desirable to be able to make an open-celled insulating polymeric foam material that: ( 1 ) has adequate rigidity or flexibility according to the requirements of use; (2) can be made with relatively small cell sizes to limit thermal conductivity contributed by radiation; (3) can be made without chlorofluorocarbons or other gases which may induce undesired io environmental problems; (4) contains no nitrogen chemically bound in the structure that, upon combustion, may release toxic gases; and (5) can be manufactured economically without sacrificing desired insulating and mechanical properties to an unacceptable degree.
~s ~LTMMARY OF THE INVENTION
The present invention relates to the use of polymeric foam materials for insulation. These polymeric foams are prepared by polymerization of certain water-in-oil emulsions having a relatively high ratio of water phase to oil phase, commonly known in the art as "HIPEs." As used herein, polymeric io foam materials which result from the polymerization of such emulsions are referred to hereafter as "HIPS foams." The HIDE foam materials used in the present invention comprise a generally hydrophobic, flexible, semi-flexible, or rigid nonionic polymeric foam structure of interconnected open-cells. These foam structures have:
zs A) a specific surface area per foam volume of at least about 0.01 m2/cc;
B) a density of less than about 0.05 g/cc; and C) a glass transition temperature (Tg) of between about -20° and 90°C.
so The present invention provides the use of low density insulating foams prepared via polymerization of a HIDE comprising a discontinuous water phase and a continuous oil phase wherein the ratio of water to oil is at least about 12:1. The water phase generally contains an electrolyte and a water soluble initiator. The oil phase generally consists of substantially water-ss insoluble monomers polymerizeable by free radicals, an emulsifier, and other optional ingredients defined below. The monomers are selected so as to confer the properties desired in the resulting polymeric foam, e.g. the glass transition (Tg) between about -20° and 90°C, mechanical integrity sufficient for the end use, and economy.
In a preferred embodiment of the present invention, the foams used can be prepared, packaged, and shipped in a compressed, high density state and will "spring back" upon activation (e.g. heat) to the original density and dimensions of the foam.
These foams are referred to herein as "compressible foams". These compressible foams are particularly useful in building insulation wherein rolled bans of insulation are shipped to widely dispersed locations and the full volume of the transporting vehicle may be filled well before the weight limit of the vehicle is approached.
In accordance with one embodiment of the present invention is the use of a polymeric open-celled foam material as an insulator, wherein the polymeric foam material has:
A) a specific surface area per foam volume of at least 0.01 m2/cc;
B) a dry density of less than 0.05 g/cc; and C) a glass transition temperature (Tg) of between -20° and 90°C.
In accordance with another embodiment of the present invention is the use of a polymeric open-celled foam material as an insulator, wherein the polymeric foam material has:
A) a specific surface area per foam volume of at least O.Olm2/cc;
B) a dry density of less tlhan 0.05 g/cc; and C) a glass transition temperature (Tg) of between -20° and 90°C;
and wherein the polymeric open-celled foam material is prepared by a process comprising the steps of (A) forming a water-in-oil emulsion at a temperature of 30°C or higher and under low shear mixing from:
(1) an oil phase comprising:
(a) from 80°/> to 98% by weight of a monomer component capable of forming a copolymer having a Tg value of from -20°C to 90°C, said monomer component comprising:
(i) from 10'% to 70% by weight of a substantially water-insoluble, monofunctional monomer capable of forming a homopolymer having a Tg of 35°C or less;
(ii) from 10% to 70% by weight of a substantially water-insoluble, monofunctional comonomer capable of imparting toughness equivalent to 5a that provided by styrene;
(iii) from 2% to 50% of a first substantially water-insoluble, polyfunctional crosslinking agent selected from the group consisting of divinyl benzene and analogs thereof; and (iv) from 0% to 15% of a second substantially water-insoluble, polyfunctional crosslinking agent selected from the group consisting of diacrylates of diols and analogs thereof; and (b) from 2% to 20% by weight of an emulsifier component which is soluble in the oil phase and which is suitable for forming a stable water-in-oil emulsion;
(2) a water phase comprising from 0.1 % to 20% by weight of a water-soluble electrolyte; and (3) a volume to weight ratio of water phase to oil phase in the range of from 12:1 to 250:1; and (B) polymerizing the monomer component in the oil phase of the water-in-oil emulsion to form the polymeo-ic foam material.
In accordance with another embodiment of the present invention is the use of a hydrophobic polymeric open-celled foam material as an insulator, wherein the polymeric foam material has:
A) a specific surface area per foam volume of at least 0.025 m2/cc;
B) a dry density of from 0.08 g/cc to 0.004 g/cc;
C) a glass transition temperature (Tg) of between 0° and 50°C;and D) a number average cell size of from 10 pm to 50 Vim.
BRIEF DESC.R_IPTION OF THE DRAWINGS
Figure 1 of the drawings is a photomicrograph (250 X magnification) of a cut section of a representative polymeric foam useful in the present invention made from HIPE having a 48:1 water-to-oil weight ratio and poured at 57°C, and where the monomer component consisted of' a 12:14:62:12 weight ratio of styreneaechnical grade divinyl benzene (about 55% DVB and about 45% ethyl styrene):2-ethylhexyl acrylate:
1,4-butanediol dimethacrylate, and where 5% (by weight of the oil phase) of diglycerol monooleate (DGMO) and 1%, commercial Span 85 emulsifiers were used.

$b Figure 2 of the drawings is a photomicrograph (1000 X magnification) of the foam of Figure 1.
Figure 3 of the drawings is a photomicrograph (2$0 X magnification) of a cut section of a representative polymeric; foam useful in the present invention made from RIPE having a 140:1 water-to-oil weight ratio and poured at 37°C, and where the monomer component consisted of a 20:20:60 weight ratio of styreneaechnical grade divinyl benzene (about $$% DVB and about 4$% ethyl styrene):2-ethylhexyl acrylate, and where 6% (by weight of the oil lrhase) of diglycerol monooleate (DGMO) Figure 4 of the drawings is a photomicrograph (1000 X magnification) of the foam of Figure 3.

DETAILED DESCRIPTION OF THE INVENTION
I. Uses of Polymeric Foams A. In General s Polymeric foams for the uses of the present invention are broadly useful as thermal insulating materials. In thermal insulation applications, these polymeric foams can be provided as relatively rigid slabs of foam for use where some rigidity is desired, as with vacuum insulation panels or with building construction insulation panels that are nailed to a support structure.
io For these uses, the foams would generally be provided in a fully expanded state and would comprise those formulations which yield a relatively high Tg, from about SO° to about 80°C. The formulation would also contain relatively higher levels of toughening monomers as described below. As rigid slabs, the foams of this invention may be laminated. or bonded to other support media to is provide stiffness, strength, or better insulating properties. For example, a thin sheet of reflective foil can be laminated on one or both sides of the foam slab so as to reduce further radiative heat transfer through the structure.
These polymeric foams may also be provided in virtually any shape desired. Preferably, such shapes will allow compressive dewatering of the zo polymerized emulsion so as to limit the expense and effort associated with water removal.
B. Insulating Articles Polymeric foams derived from FiIPEs are particularly useful in a variety of thermal applications including appliances (refrigerators, ovens, ranges, is toasters, freezers), transportation equipment (cars, trains, planes, boats), buildings (wall insulation, attic insulation), and for many other uses. One preferred embodiment comprises the use of a continuous slice of said foam compressed to at least about one-third of its thinnest dimension, stored, shipped, and applied as a roll stock item, and expanded after application by 3o either time and/or heat to restore the original dimensions and insulating properties.
Foams for the uses of the present invention may also be used inside vacuum insulation panels to provide strength and stiffness to the panel without adding much mass which would provide a pathway for convection of heat as through the polymer structure. For such uses, it would generally be desirable to use high Tg versions of foams of the present invention, for example, WO 96/40824 PCTlL1S96/~0169 between about 50° and 80°C. Such foams may still be effectively dewatered by squeezing if the water is heated to near the Tg during the squeeze-out process. The ability to remove the water from the foams of the present invention by squeezing is highly preferred so as to limit cost and process s complexity. Since the foams of the present invention can be manufactured with very low densities (e.g. < 0.020 glee), they are particularly us,;iul as vacuum insulation structural filler. The small cell sizes feasible with these foams reduce radiative heat transfer through the vacuum panel. The low density provides relatively little solid polymer through which thermal energy io may be conducted. These two attributes are of particular significance herein where conduction through the gas of a foam is negligible.
C. Other Uses These foams can also be employed as insulators against acoustic or mechanical forces. When intended for use as insulators against transnvssion of is acoustic and/or mechanical vibrations, these foams are particularly useful in that both the Tg of the material and the width of the transition can be optimized for the specific application. It is generally desirable that the Tg of the foam be closely aligned with the temperature and frequency of the midpoint of the acoustic or vibration energy to be damped. The foams of the zo present invention are easily "tuned" to this end, as described below. For example, if a continuous noise of 1000 Hz at 25°C is to be damped, the Tg of the foam measured at 1000 Hz should be 25°C. If the noise or vibration is of a combination of frequencies (as is usually the case), or if the damping is desired over a wider temperature range, then the glass-to-rubber transition region of zs the foam should be as broad as possible. Alternately, the foam can be post-treated with a second polymeric material to make a macroscopic interpenetrating network wherein both polymers will contribute to sound/vibration damping at different regions of temperature and frequency.
Further descriptions of generic uses of foams as acoustic or mechnical shock so insulators are given in Brandup, J.; Immergut, E.H. "Polymer Handbook", 2nd Ed., Wiley-Interscience, New York, NY, 1975, pp 240-242 and pp 210-216 and pp 286-325.
II. Insulating Polymeric Foam A. Generai_ Foam Cha_racteristic~
3s The polymeric foams used in accordance with the present invention are relatively open-celled This means the individual cells of the foam are in complete, unobstructed communication with adjoining cells. The cells in such substantially open-celled foam structures have intercellular openings or "windows" connecting one cell to the other within the foam structure.
These substantially open-celled foam structures will generally have a s reticulated character with the individual cells being defined by a plurality of mutually connected, three dimensionally branched webs. The strands of polymeric material making up these branched webs can be referred to as "struts." Open-celled foams having a typical strut-type structure are shown by way of example in the photomicrographs of Figures l and 2. As used herein, a io foam material is "open-celled" if at least 80% of the cells in the foam structure that are at least 1 p,m in size are in open communication with at least one adjacent cell.
In addition to being open-celled, these polymeric foams are generally hydrophobic to inhibit the passage of aqueous fluids through the foam The ~s internal surfaces of the foam structures are rendered hydrophobic by removal of hydrophilizing surfactants and salts left in the foam structure after polymerization, or by selected post-polymerization foam treatment procedures, as described hereafter.
The foams used according to the present invention are readily Zo optimized so as to confer the properties desired in each specific application.
The ease of control over a wide range of properties of these foams is unprecedented. As examples, these foams may be hydrophilic or hydrophobic (preferably hydrophobic); microcellular (< 10 p,m) up through moderate cell diameters (ca. 100 p,m); low density (0.05 g/cc) to very low density (0.005 zs g/cc); rigid to flexible (corresponding, high Tg to low (subambient) Tg);
and strong to weak. The foams may be provided as continuous sheets, rigid thick boards, particulates of various sizes, specific shapes, etc., as required by their end use. However optimized, these foams avoid some of the deficiencies associated with the foam methods described hereinabove. That is, they so preferably contain no nitrogen so that burning produces no unusually noxious gases, require no CFC or volatile organic compound ("VOC") materials during , manufacture, are producible readily in large quantities with reasonable economics as either slabstock, roll stock, particulate foam, and the like.
Further, the foams used in the present invention are inherently photostable.
3s In a preferred embodiment, the polymeric foams can be prepared in the form of compressed, polymeric foams that, upon heating or the passage of time, expand and reach their full insulating capability (herein referred to as "compressible foams") These collapsed polymeric foams are usually obtained by expressing the water phase from the polymerized HIDE foam through compressive forces, and/or thermal drying and/or vacuum dewatering. After compression, and/or thermal drying/vacuum dewatering followed by rapid chilling, the polymeric foam is in a compressed, or unexpended state.
A key parameter of these compressible foams is their glass transition temperature (Tg). The Tg represents the midpoint of the transition between the glassy and rubbery states of the polymer. Foams that have a Tg higher than the temperature o~f use can be very strong but will also be very rigid and ~o potentially prone to fracture. Such foams also typically take a long time to recover to the expanded state after having been stored in the compressed state for prolonged periods. Though the end use of a particular foam is an important factor when determining the desired Tg of the foam, preferred are foams having a Tg of from about 0 to about 50°C. More preferred are foams is having a Tg of from about 10 to about 40°C.
B. Foam D~
Another important property of the insulating foams used in the present invention is their density. "Foam density" (i.e., in grams of foam per cubic centimeter of foam volume in air) is specified herein on a dry basis, io unless otherwise indicated. Any suitable gravimetric procedure that will provide a determination of mass of solid foam material per unit volume of foam structure can be used to measure foam density. For example, an ASTM
gravimetric procedure described more fully in the TEST METHODS section of U.S. 5,387,207 (Dryer et al), issued February 7, 1995 zs is one method that can be employed for density deLQmination While foams can be made with virtually arty density ranging from below that of air to just less than the bulk density of the polymer from which it is made, the foams of the present invention are most useful when thry have a dry density in the expanded state of less than about 0.05 g/cc, ~o preferably between about 0.08 and about 0.004 g/cc, more preferably betvveat about 0.038 and 0.013 g/cc, and most preferably about 0.03 g/cc.
C. ~rooerties of Polymeric Foam Foam cells, and especially cells thu are formed by polymerizing a monomer.corttaining of phase that surrounds reluively monomer-free water ~~ phase droplets, will frequently be substantially spherical in shape The size or 'diameta~ of such :spherical cells is a commonly used parameter for l0 characterizing foams in general. Since cells in a given sample of polymeric foam will not necessarily be of approximately the same size, an average cell size, i.e., average cell diameter, will often be specified.
A number of techniques are available for determining the average cell s size of foams. The most useful technique, however, for determining cell size in foams involves a simple measurement based on the scanning electron photomicrograph of a foam sample. Figure 1, for example, shows a typical HIDE foam structure according to the present invemion in its expanded state.
Superimposed on the photomicrograph is a scale representing a dimension of ~0 20 Vim. Such a scale can be used to determine average cell size via an image analysis procedure.
The cell size measurements given herein are based on the number average cell size of the foam in its expanded state, e.g., as shown in Figure I.
The foams useful as insulation materials in accordance with the present ~ s invention will preferably have a number average cell size of less than about 100 Vim, more preferably from about 10 to 50 Vim, and most preferably from about 15 ~m to 3 5 pm~.
D. c Surface Area Another key parameter of the foams is their specific surface area, zo which is determined b~y both the dimensions of the cellular units in the foam and by the density of the polymer, and is thus a way of quantifying the total amount of solid surface provided by the foam.
Specific surface area is determined by measuring the amount of capillary uptake of a low surface tension liquid (e.g., ethanol) which occurs is within a foam sample of known mass and dimensions. A detailed description of such a procedure fair determining foam specisc surface area via the capillary suction method is set forth in the TEST METHODS section of U.S. Patent 5,38?,20? (Dyer et al.), issued Feb. 7, 1995.
Other similar tests for determining specific surface area can be used so with the present insWation foams.
' The foams of the present invention have a specific surface arcs of at least about 0.01 m2/cc, preferably at least about 0.025 m2lcc.
E. Somoressible Foams With regard ta~ foams that can b~e maintained in a compressed state, this ~s state is maintained by ketping the polymeric foam substantially below the Tg of the polymer. In this state, the flow of the individual polymer chains is WO 96/40824 I'CTlilS96/I0169 a relatively slow. However, the thermoset characteristic of these foams (deriving from a relatively high level of crosslinker incorporated therein) provides memory of the prexisting expanded state. Thus, when warmed or allowed to stand unrestrained, the foams will recover their original dimensions.
s These dimensions provide for the low density inherent in providing a useful insulating material. This attribute is particularly useful wherein the foam is to be shipped, stored, and applied in roll form to cover a comparatively large area such as an attic of a dwelling. During these steps it occupies considerably less bulk than is characteristic of fiberglass batting, for example. During or after o application, either heat and/or the passage of time will restore its original dimensions and insulating ability. The Tg of the polymeric foam is obviously important to maintaining stability in the compressed state and still provide for reepansion within a reasonable period or at achievable temperatures.
Upon exposure to heat or the passage of time, the compressed foams is used in a preferred embodiment regain their original dimensions and shape.
This is attributable to the thermoset nature of the polymer used to make the foam. Generally, the foams are compressed in one dimension, called the "z direction", which is the thinnest dimension of a sliced sheet of foam. Upon recovery of the original expanded dimensions of the foam, an "expansion 2o factor" can be defined which relates the ratio of the thinnest dimension in the expanded versus the compressed state. For these compressible foams, the expansion factor is at least about 3X, i.e. the thickness of the foam in its expanded state is at least about 3 times the thickness of the foam in its compressed state. The compressible foams typically have an expansion factor zs in the range of from about 3X to about IOX. By comparison, compressed fiberglass batting foams typically have a recoverable expansion factor of only about 2X.
As an example, a foam made by polymerizing a HIDE comprising 35%
styrene, 20% divinyl benzene, and 45% 2-ethylhexyl acrylate with a density of so 0.020 and Tg of 40°C can be compressed when filled with water at 40°C and chilled immediately after release from compression. The degree of compression is governed by the geometry of the nip rolls though which it is passed, the density of the foam, and. to a lesser extent, the rate and temperature at which it is compressed. In this instant, the foam can be as compressed about 5x to about 20% of its original thickness. The compressed foam will retain that set almost indefinitely when stored at a temperature of about 8°C or more below the Tg of the foam (in this case. less than about a 32°C). That is, the compressed foam will regain no more than about 10%
of its original thickness over a period of at least about a week unrestrained at ambient temperature (22°C). In other words, it will expand to no more than about 30% of its original thickness. In practice, the foams will grow much less s over even longer periods of time, particularly if restrained by appropriate packaging in, for example, shrink-wrapped roll form. When the foam is heated to at least about its Tg (in this case, 40°C), it will regain virtually all of its original thickness, or at least about 80% of its original thickness, in a period of about an hour, preferably less. In practice, such a foam would regain more io than 90% of its original thickness when heated to at least about 40°C in less than an hour. These conditions approximate what might be encountered, for example, in an attic in summer time after the compressed foam had been released from shrink-wrapping and applied as desired.
III. Preparation of Polymeric Foams From HIDE Having Relatively I~sth is Water-to-Oil Ratios A. In General Polymeric foams useful in the present invention are prepared by polymerization of HIPEs. The relative amounts of the water and oil phases used to form the HIPEs are, among many other parameters, important in zo determining the structural, mechanical and performance properties of the resulting polymeric foams. In particular, the ratio of water to oil in the emulsion can influence the density, cell size, and specific surface area of the foam and dimensions of the struts that form the foam. The emulsions used to prepare the HIDE foams will generally have a volume to weight ratio of water zs phase to oil phase in the range of from about 12:1 to about 250:1, more preferably from about 25:1 to about 125:1, most preferably about 30:1.
The process for obtaining these foams comprises the steps of (A) forniing a water-in-oil emulsion at a temperature of about 30°C or higher and under low shear mixing from:
so (1) an oil phase comprising:
(a) from about 80% to about 98% by weight of a monomer component capable of forming a copolymer having a Tg value of from about -20°C to about 90°C, said monomer ' component comprising:
as (i) from about 10% to about 70% by weight of a substantially water-insoluble. monofunctional WO 96l4Q824 PCTlUS961101G9 monomer capable of forming a homopolymer having a Tg of about 35°C or less;
(ii) from about 10% to about 70% by weight of a substantially water-insoluble, monofunctional ' s comonomer capable of imparting toughness about equivalent to that provided by styrene;
(iii) from about 2% to about 50% of a first substantially water-insoluble, polyfunctional crosslinking agent selected from the group io consisting of divinyl benzene and analogs thereof;
and (iv) from about 0% to about 15% of a second substantially water-insoluble, polyfunctional crosslinking agent selected from the group is consisting of diacrylates of diols and analogs thereof; and (b) from about 2% to about 20% by weight of an emulsifier component which is soluble in the oil phase and which is sutable for forming a stable water-in-oil emulsion;
20 (2) a water phase comprising from about 0.1% to about 20% by weight of a water-soluble electrolyte; and (3) a volume to weight ratio of water phase to oil phase in the range of from about 12:1 to about 250:1; and (B) polymerizing the monomer component in the oil phase of the water-in-oil is emulsion to form the polymeric foam material.
The polymeric foam material can be subsequently iteratively washed and dewatered to provide a dry, hydrophobic foam that may be shaped as desired. Typically, this shaping will comprise slicing into relatively thin sheets.
These sheets may optionally be compressed, e.g. continuously through 3o pressure nips, into a thin state and wound into rolls. Preferred compressible sheets will retain their relatively thin compressed state until unwound, applied as desired, and either heated above their activation temperature (usually about the Tg of the polymer) or allowed to stand for a relatively long period of time, e.g. several weeks or months, depending on the ambient temperature.
ss 1. Qil Phase Components The continuous oil phase of the E~PE comprises monomers that are polymerized to form the solid foam structure This monomer component is formulated to be capable of forming a copolymer having a Tg of from about -20° to about 90°C, and preferably from about 15° to about 50°C, more preferably from about 20° to about 40°C. (The method for determining Tg by Dynamic Mechanical Analysis (DMA) is described in the TEST METHODS
s section i~~a. This monomer component includes: (a) at least one monofunctional monomer whose atactic amorphous polymer has a Tg of about 25°C or lower (see Brandup, J.; Immergut, E.H. "Polymer Handbook", 2nd Ed., Wiley-Interscience, New York, NY, 1975, III-139.); (b) at least one monofunctional comonomer to improve the toughness or tear resistance of the io foam; (c) a first polyfunctional crosslinking agent; and (d) optionally a second polyfunctional crosslinking agent. Selection of particular types and amounts of monofunctional monomers) and comonomer(s) and polyfunctional cross-linking agents) can be important to the realization of absorbent HIPS foams having the desired combination of structure, and mechanical properties which is render such materials suitable for use in the invention herein.
The monomer component comprises one or more monomers that tend to impart rubber-like properties to the resulting polymeric foam structure.
Such monomers can produce high molecular weight (greater than 10,000) atactic amorphous polymers having Tgs of about 25°C or lower. Monomers zo of this type include, for example, the C4-C 14 alkyl acrylates such as butyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl (lauryl) acrylate, isodecyl acrylate, tetradecyl acrylate;
aryl and alkaryl acrylates such as benzyl acrylate and nonylphenyl acrylate;
the C6-C 16 alkyl methacrylates such as hexyl methacrylate, octyl methacrylate, is nonyl methacrylate, decyl methacrylate, isodecyl methacrylate, dodecyl (lauryl) methacrylate, and tetradecyl methacrylate; acrylamides such as N-octadecyI
acrylamide; C4-C 12 alkyl styrenes such as p-n-octylstyrene; and combinations of such monomers. Of these monomers, isodecyl acrylate, dodecyl acrylate and 2-ethylhexyl acrylate are the most preferred. The monofunctional 3o monomers) will generally comprise 10 to about 70%, more preferably from about 20 to about 50%, by weight of the monomer component.
The monomer component utilized in the oil phase of the HIPEs also comprises one or more monofunctional comonomers capable of imparting toughness about equivalent to that provided by styrene to the resulting as polymeric foam structure. Tougher foams exhibit the ability to deform substantially without failure. These monofunctional comonomer types can include styrene-based comonomers (e.g., styrene and ethyl styrene) or other WO 96/4084 PCT/IJS96/102b9 monomer types such as methyl methacrylate where the related homopolymer is well known as exemplifying toughness. The preferred monofunctional comonomer of this type is a styrene-based monomer with styrene and ethyl styrene being the most preferred monomers of this kind. The monofunctional s "toughening" comonomer will normally comprise from about 10 to about 70%, preferably from about 20% to about 50%, most preferably from about 30% to about 50%, by weight of the monomer component.
In certain cases, the "toughening" comonomer can also impart the desired rubber-like properties to the resultant polymer. The C4-C 12 alkyl io styrenes, and in particularp-n-octylstyrene, are examples of such comonomers.
For such comonomers, the amount that can be included in the monomer component will be that of the typical monomer and comonomer combined.
The monomer component also contains a first (and optionally a second) polyfunctional crosslinking agent. As with the monofunctional is monomers and comonomers, selection of the particular type and amount of crosslinking agents) is important to the eventual realization of preferred polymeric foams having the desired combination of structural and mechanical properties.
The first polyfunctional crosslinking agent can be selected from a wide Zo variety of monomers containing two or more activated vinyl groups, such as divinylbenzenes and analogs thereof. Analogs of divinylbenzenes useful herein include, but are not limited to, trivinyl benzenes, divinyltoluenes, divinylxylenes, divinylnaphthalenes divinylalkylbenzenes, divinylphenanthrenes, divinylbiphenyls, divinyldiphenylmethanes, divinylbenzyls, divinylphenylethers, as divinyldiphenylsulfides, divinylfurans, divinylsulfide, divinylsulfone, and mixtures thereof. Divinylbenzene is typically available as a mixture with ethyl styrene in proportions of about 55:45. These proportions can be modified so as tai enrich the oil phase with one or the other component. Generally, it is advantageous to enrich the mixture with the ethyl styrene component while so simultaneously reducing the amount of styrene in the monomer blend. The preferred ratio of divinylbenzene to ethyl styrene is from about 30:70 to 55:45, most preferably from about 35:65 to about 45:55. The inclusion of higher levels of ethyl styrene imparts the required toughness without increasing the Tg of the resulting copolymer to the degree that styrene does. This first cross-as linking agent can generally be included in the oil phase of the RIPE in an amount of from about 2 to about 50%, more preferably from about 10 to about 35%. most preferably from about 15% to about 25%, by weight of the r monomer component ( 100% basis).
The optional second crosslinking agent can be selected from polyfunctional acrylates selected from the group consisting of diacrylates of diols and analogs thereof. Such crosslinking agents include methacrylates, s acrylamides, methacrylamides, and mixtures thereof. These include di-, tri-, and tetra-acrylates, as well as di-, tri-, and tetra-methacrylates, di-, tri-, and tetra-acrylamides, as well as di-, tri-, and tetra-methacrylamides; and mixtures of these crosslinking agents. Suitable acrylate and methacrylate crosslinking agents can be derived from diols, triols and tetraols that include 1,10-io decanediol, 1,8-octanediol, 1,6-hexanediol, 1,4-butanediol, 1,3-butanediol, 1,4-but-2-enediol, ethylene glycol, diethylene glycol, trimethylolpropane, pentaerythritol, hydroquinone, catechol, resorcinol, triethylene glycol, polyethylene glycol, sorbitol and the like. (The acrylamide and methacrylamide crosslinking agents can be derived from the equivalent is diamines, triamines and tetramines). The preferred diols have at least 2, more preferably at least 4, most preferably 6, carbon atoms. This second cross-linking agent can generally be included in the oil phase of the RIPE in an amount of from 0 to about 15% by weight of the monomer component.
The major portion of the oil phase of the HIPEs will comprise the zo aforementioned monomers, comonomers and crosslinking agents. It is essential that these monomers, comonomers and crosslinking agents be substantially water-insoluble so that they are primarily soluble in the oiI
phase and not the water phase. Use of such substantially water-insoluble monomers ensures that HIPEs of appropriate characteristics and stability will be realized.
zs It is, of course, highly preferred that the monomers, comonomers and crosslinking agents used herein be of the type such that the resulting polymeric foam is suitably non-toxic and appropriately chemically stable. These monomers, comonomers and cross-linking agents should preferably have little or no toxicity if present at very low residual concentrations during post-so polymerization foam processing and/or use.
Another essential component of the oil phase of the HIDE is an _ emulsifier component that comprises at least a primary emulsifier. Suitable primary emulsifiers are well known to those skilled in the art. Particularly preferred emulsifiers include Span 20TM, Span 40TH, Span 60TM, and Span 3s 8f"''. These are nominally esters of sorbitan derived from lauric, myristic, stearic, and oleic acids, respectively. Other preferred emulsifiers include the diglycerol esters derived from monooleate, monomyristatt, monopalmitate, and monoisostearate acids. A preferred coemulsifier is ditallowdimethyl ammonium methyl sulfate. Mixtures of these emulsifiers are also particularly useful, as are purified versions of each, specifically sorbitan esters containing minimal levels of isosorbide and poiyol s impurities.
In addition to these primary emulsifiers, secondary emulsifiers can be optionally included in the emulsifier component. Again, those skilled in the art well recognize that any of a variety of known emulsifiers may be usai. These secondary emulsifiers are at least cosoluble with the primary emulsifier in the oil phase. Secondary emulsifiers can be obtained commercially or prepared using methods known in the art. The preferred secondary emulsifiers are ditallow dimethyl atrumonium methyl sulfate and ditallow dimethyl ammonium methyl chloride. When these optional secondary emulsifiers are included in the emulsifier component, it is typically at a weight ratio of primacy to secondary is emulsifier of from about 50:1 to about 1:4, preferably from about 30:1 to about 2:1.
As is indicated, those skilled in the art will recognize that any suitable emulsifiers) can be used in the processes for making the foams of the present invention. For exatnple, See U.S. Patent 5,387,207 and copending U.S.
io Patent No. 5,563,175 by stone et al.
The oil phase: used to form the HIPEs comprises from about 85 to about 98% by weight monomer component and from about 2 to about 15% by weight emuisifie;r component. Preferably, the oil phase will comprise from about 90 to about 9 ~ro/o by weight monomer component and from about 3 to ' a about 10% by weight emulsifier component. The oil phase also can contain other optional components. One such optional component is an oil soluble polymerization initiator of the gexteral type well known to those skilled in the art, such as describai in U.S. Patent 5,290,820 (Bass et al), issued March 1, 1994.
so A~ preferrai optional componertt is an antioxidant such as a F~utdaed Amine Light Stabili~r (HALS) such as bis-( 1,2,2,5,5-pexttamethylpiperidinyi) sebacate (Tinuvin-7Ei5~ or a I-Lndered Phenolic Stabilizer (1-1pS) such as Iraanox-1076~ and t-butylhydroxy-quinone. Another preferred optional component is a plasticizer such as dioctyl azelate, dioctyl se~bacate or diocy I
ss adipate. YeK another optional ingredient is filler particles which may toughen the polymer andlor i.naease its thermal insulating propextie~s. Example fiber particulea include aluuninum, titanium dioxide, carbon black graphite. calcium carbonate, talc, and the like. Generally, particles which help make the polymer opaque in the infrared region are preferred, such as carbon black and graphite.
Other optional components include colorants (dyes or pigments), fluorescent agents, opacifying agents, chain transfer agents, and the like.
s 2. Water Phase Components The discontinuous water internal phase of the HIDE is generally an aqueous solution containing one or more dissolved components. One essential dissolved component of the water phase is a water-soluble electrolyte. The dissolved electrolyte minimizes the tendency of monomers, comonomers, and iu crosslinkers that are primarily oil soluble to also dissolve in the water phase.
This, in turn, is believed to minimize the extent to which polymeric material fills the cell windows at the oil/water interfaces formed by the water phase droplets during polymerization. Thus, the presence of electrolyte and the resulting ionic strength of the water phase is believed to determine whether is and to what degree the resulting preferred polymeric foams can be open-celled.
Any electrolyte capable of imparting ionic strength to the water phase can be used. Preferred electrolytes are mono-, di-, or trivalent inorganic salts such as the water-soluble halides, e.g., chlorides, nitrates and sulfates of alkali zo metals and alkaline earth metals. Examples include sodium chloride, calcium chloride, sodium sulfate and magnesium sulfate. Calcium chloride is the most preferred for use in preparing the HIPEs. Generally the electrolyte will be utilized in the water phase of the HIPEs in a concentration in the range of from about 0.2 to about 20% by weight of the water phase. More preferably, the zs electrolyte will comprise from about 1 to about 10% by weight of the water phase.
The HIPEs will also typically contain an effective amount of a polymerization initiator. Such an initiator component is generally added to the water phase of the HIPEs and can be any conventional water-soluble free 3o radical initiator. These include peroxygen compounds such as sodium, potassium and ammonium persulfates, hydrogen peroxide, sodium peracetate, sodium percarbonate and the like. Conventional redox initiator systems can also be used. Such systems are formed by combining the foregoing peroxygen compounds with reducing agents such as sodium bisulfite, L-ascorbic acid or as ferrous salts.
The initiator can be present at up to about 20 mole percent based on the total moles of polymerizable monomers present in the oil phase. More WO 9614Q8~4 ~CTlilS96110169 preferably, the initiator is present in an amount of from about 0.001 to about mole percent based on the total moles of polymerizable monomers in the oil phase.
3. F-Ivdrophilizin~ Surfactants and Hvdratable Salts s The polymer forming the HIDE foam structure will preferably be substantially free of polar functional groups. This means the polymeric foam will be relatively hydrophobic in character. When these foams are to be used as insulating materials, resistance to water is generally a desired feature.
Removal of the residual emulsifier and/or salt following polymerization is io generally desired in a manner described more fully hereafter.
B. Processing Conditions for Obtainin~RIPE Foams Foam preparation typically involves the steps of 1) forming a stable high internal phase emulsion (HIDE); 2) polymerizing/curing this stable emulsion under conditions suitable for forming a solid polymeric foam is structure; 3) optionally washing the solid polymeric foam structure to remove the original residual water phase, emulsifier, and salts from the polymeric foam structure, and 4) thereafter dewatering this polymeric foam structure.
1. Formation of HIDE
The HIDE is formed by combining the oil and water phase components zo in the previously specified ratios. The oil phase will typically contain the requisite monomers, comonomers, crosslirdCers, and emulsifiers, as well as optional components such as plasticizers, antioxidants, flame retardants, and chain transfer agents. The water phase will typically contain electrolytes and polymerization initiators.
Zs The HIDE can be formed from the combined oil and water phases by subjecting these combined phases to shear agitation. Shear agitation is generally applied to the extent and for a time period necessary to form a stable emulsion. Such a process can be conducted in either batchwise or continuous fashion and is generally carried out under conditions suitable for forming an so emulsion where the water phase droplets are dispersed to such an extent that the resulting polymeric foam will have the requisite structunai characteristics.
Emulsification of the oil and water phase combination will frequently involve the use of a mixing or agitation device such as a pin impeller.
One preferred method of forming RIPE involves a continuous process ss that combines and emulsifies the requisite oil and water phases. In such a process, a liquid sueam comprising the oil phase is formed. Concurrently, a separate liquid stream comprising the water phase is also formed. The two separate streams are then combined in a suitable mixing chamber or zone such that the requisite water to oil phase weight ratios previously specified are achieved.
In the mixing chamber or zone, the combined streams are generally subjected to shear agitation provided, for example, by a pin impeller of suitable configuration and dimensions. Shear will typically be applied to the combined oil/water phase stream at an appropriate rate. Once formed, the stable liquid HiPE can then be withdlrawn from the mixing chamber or zone. 'This preferred ~o method for forming Hl~'Es via a continuous process is described in greater detail in U.S. Patent 5,:149,720 (DesMarais et al), issued September 22, 1992.
See also copending Canadian. Patent Application No. 2,208,419, filed January 11, 1996 by 'T. DesMarais, which describes an improved continuous process having a recirulation loop for the HIPS.
~s Z. ~'olvmerization/Curin~ of the HIDE
The HIDE formed will generally be collected or poured in a suitable reaction vessel, container or region to be polymerized or cured. In one embodiment , the reaction vessel comprises a tub constructed of polyethylene Zo from which the eventually polymerized/cured solid foam material can be easily removed for further processing after polymerization/curing has been carried out to the extent desired. The temperature at which the HIDE is poured into the vessel is preferably approximately the same as the polymerizationlcuring temperature.
is Suitable polymerizarion/curing conditions will vary depending upon the monomer and other makeup of the oil and water phases of the emulsion (espeaaUy the emulsifier systems used), and the type and amounu of polymerization initiators used. Frequently, howrva, suitable polym~ization/curing conditions will involve maintaining the HIPS at elevated so tempuatures above about 30°C, more preferably above about 35°C, for a time period ranging from about 2 to about 64 hours, mote preferably from about 4 to about 48 hours. The HIDE can also be cured in stages such as described in U.S. .patent 5.189,070 (Brownscombe et al), issued February 23, 1993, a One particular advantage of the more robust emulsifier systems used in these HIpEs is that the polvmerizatiorvcunng conditions can be carried out at more elevated temperatures of about 50°C or higher, more preferably about WO 96/40824 PCTlFlS96/20169 60°C or higher. Typically, the HIDE can be polymerizedlcured at a temperature of from about 60° to about 99°C, more typically from about 65°
to about 95°C.
A porous water-filled open-celled HIDE foam is typically obtained after s polymerization/curing in a reaction vessel, such as a tub. This polymerized HIDE foam is typically cut or sliced into a sheet-like form. Sheets of polymerized HIDE foam are easier to process during subsequent treating/washing and dewatering steps, as well as to prepare the H1PE foam for use in insulation materials. The polymerized HIPS foam is typically io cut/sliced to provide a cut thickness in the range of from about 0.08 in.
to about 3.5 in. Subsequent dewatering by compressing the foam in the z-direction typically leads to HIDE foams having a thickness in the range of from about 10 to about 17% of its cut thickness.
3. Treating/WashinQ HIDE Foam is The polymerized HIDE foam formed will generally be filled with residual water phase material used to prepare the HIDE. This residual water phase material (generally an aqueous solution of electrolyte, residual emulsifier, and polymerization initiator) should be removed prior to further processing and use of the foam. Removal of this original water phase material zo will usually be carried out by compressing the foam structure to squeeze out residual liquid and/or by washing the foam structure with water or other aqueous washing solutions. Frequently several compressing and washing steps, e.g., from 2 to 4 cycles, can be used. It is preferable that the water used in these washing be heated to at least about the Tg of the polymer so as to is maimtain its flexibility and compliance during compressive dewatering and reduce and prevent damage to the foam structure.
4. Foam Dewatering After the HIPS foam has been treated/washed, it will be dewatered.
Dewatering can be achieved by compressing the foam to squeeze out residual so water, by subjecting the foam, or the water therein to temperatures of from ' about 60° to about 200°C or to microwave treatment, by vacuum dewatering or by a combination of compression and thermal dryingimicrowave/vacuum dewatering techniques. These HIDE foams are typically compressiveiy dewatered to a thickness of about 1/3 (33%) or less of their fully expanded 33 thickness. The dewaterang step will generally be carried out until the HIPS
foam is ready for use and is a5 dry as practicable Frequently such a compression dewatered foams will have a water (moisture) content as low as possible, from about 1 % to about 15%, more preferably from about 5% to about 10%, by weight on a dry weight basis.
IV. Test Methods s A. Dynamic Mechanical Analysis DMA) DMA is used to determine the Tgs of polymers including polymeric foams. Samples of the foams are sliced into blocks 3-5 mm in thickness and washed 3-4 times in distilled water, expressing the fluid through roller nips between each washing. The resulting foam blocks are allowed to dry in air.
io The dried foam slices are cored to yield a cylinders 25 mm in diameter.
These cylinders are analyzed using a Rheometrics RSA II dynamic mechanical analyzer set in compression mode using parallel plates 25 mm in diameter.
Instrument parameters used are as follows:
~ Temperature step from ca. 85°C to -40°C in steps of 2.5°C
~s ~ Soak intervals between temperature changes of 125-160 seconds ~ Dynamic strain set at 0.1% to 1.0% (usually 0.7%) ~ Frequency set at 1.0 radians/second ~ Autotension set in static force tracking dynamic force mode with initial static force set at 5 g.
zo The glass transition temperature is taken as the maximum point of the loss tangent versus temperature curve.
B. Expansion Factor Expansion factor can be quantified by measuring the thickness of a foam sample in the collapsed (compressed) state and in the expanded state.
zs The ratio of the expanded thickness to the initial collapsed thickness is the expansion factor. ' The foam sample in its compressed state is placed on a flat granite base under a gauge suitable for measuring the sample thickness. The gauge is set up to exert a pressure of 0.08 psi on the sample. Any gauge fitted with a foot ~o having a circular surface area of at least 1 in2 (6.5 cm2) and capable of measuring thickness to 0.0010 in (0.025 mm) can be employed. Examples of such gauges are an Ames model 482 (Ames Co.; Waltham, MA) or an Ono-Sokki model EG-225 (Ono-Sokki Co., Ltd.; Japan). The initial thickness is recorded (XO).
ss The assembly including the foam is then placed in an oven set at T = Tg + 20°C. After 60 minutes, the expanded thickness (X1) is recorded.

The expansion factor (EF) is calculated as EF = X1/Xo. The expansion factor may be recorded after storage at T = Tg + 20°C for 1 day or longer to ensure ' that complete recovery to the dimensions of the unexpanded sample are obtained. Generally, the sample is left at the higher temperature until no s further reexpansion is recorded.
C. Specific Surface Area As discussed supra, a detailed description of a procedure for determining foam specific surface area via the capillary suction method is set forth in the TEST METHODS section of U.S. Patent 5,387,207.
~o V. specific Examples The following examples illustrate the preparation of HIDE foams useful in the present invention.
xam le 1 Preparation of Foam from a HIDE
is A) I~PE Preparation Anhydrous calcium chloride (36.32 kg) and potassium perstalfate (189 g) are dissolved in 378 liters of water. This provides the water phase stream to be used in a continuous process for forming the HIDE.
To a monomer combination comprising styrene (2400 g), zo divinylbenzene 55% technical grade (1200 g), 2-ethylhexylacrylate (2400 g), is added Span 40TM (480 g). After mixing, the solution is allowed to settle overnight. The supernatant is withdrawn and used in the oil phase as the emulsifier in forming the HIPE. (Any resulting sticky residue is discarded.) Separate streams of the oil phase (25°C) and water phase (42°-44°C) is are fed to a dynamic mixing apparatus. Thorough mixing of the combined streams in the dynamic mixing apparatus is achieved by means of a pin ' impeller. At this scale of operation, an appropriate pin impeller comprises a cylindrical shaft of about 21.6 cm in Length with a diameter of about 1.9 cm.
The shaft holds 4 rows of pins, 2 rows having 17 pins and 2 rows having 16 so pins, each leaving a diameter of 0.5 cm extending outwardly from the central axis of the shaft to a lengeh of 1.6 cm. The pin impeller is mounted in a cylindrical sleeve which forms the dynamic mixing apparatus, and the pins have a clearance of 0.8 mm from the walls of the cviindrical sleeve.
A spiral static mixer is mounted downstream from the dynamic mixing 3s apparatus to provide back pressure in the dynamic mixer and to provide improved incorporation of components into the emulsion that is eventually formed. Such a static mixer is 14 inches (35.6 cm) long with a 0.5 inch (1.3 cm) outside diameter. The static mixer is a TAH Industries Model 070-821, modified by cutting off 2.4 inches (6.1 cm).
The combined mixing apparatus set-up is filled with oil phase and s water phase at a ratio of 3 parts water to 1 part oil. The dynamic mixing apparatus is vented to allow air to escape while filling the apparatus completely. The flow rates during filling are 1.89 g/sec oil phase and 5.68 cc/sec water phase.
Once the apparatus set-up is filled, agitation is begun in the dynamic m mixer, with the impeller turning at 1800 RPM. The flow rate of the water phase is then steadily increased to a rate of 45.4 cc/sec and the oil phase flow rate is reduced to 0.82 g/sec over a time period of about 2 min. The back pressure created by the dynamic and static mixers at this point is 13.4 PSI
(92 kPa). The impeller speed is then steadily decreased to a speed of 1200 RPM
is over a period of 120 sec. The back pressure drops to 5.4 PSI (37 kPa). At this point, the impeller speed is instantly increased to 1800 RPM. The system back pressure increases to 6.5 PSI (44 kPa) and remains constant thereafter.
The resultant HIDE has a water-to-oil ratio of about S5:1.
B) Polvmerization/CurinQ of HIDE
zo The HIDE from the static mixer is collected in a round polypropylene tub, 17 in. (43 cm) in diameter and 7.5 in. ( 10 cm) high, with a concentric insert made of Celcon plastic. The insert is 5 in. (12.7 cm) in diameter at its base and 4.75 in ( 12 cm) in diameter at its top and is 6.75 in. ( 17.14 cm) high.
The HIDE-containing tubs are kept in a room maintained at 65°C for 18 hours zs to cure and provide a polymeric HIDE foam.
C) Foam Washing and Dewatering The cured HIDE foam is removed from the tubs. The foam at this point has residual water phase (containing dissolved emulsifiers, electrolyte, initiator residues, and initiator) about SO-60 times (50-603 the weight of 3o polymerized monomers. The foam is sliced with a sharp reciprocating saw blade into sheets which are 0.2 inches (0.5 cm) in thickness. These sheets are then subjected to compression in a series of 2 porous nip rolls equipped with vacuum which gradually reduces the residual water phase content of the foam to about 6 times (67~ the weight of the polymerized monomers. At this point, ~s the sheets are then resaturated with a water at 60°C, are squeezed in a series of 3 porous nip rolls equipped with vacuum to a water phase content of about 4X. Optionally, the water used to resaturate the foam contains about 1 sodium bicarbonate. This serves to react with any residual calcium chloride that would tend to render the washed foams hydrophilic and form insoluble, non-hygroscopic calcium carbonate. The CaCl2 content of the foam is less s than about 1 %.
The HIDE foam remains compressed after the final nip at a thickness of about 0.019 in. (0.048 cm). The foam is then dried in air for about 16 hours.
Such drying' reduces the moisture content to about 1-8 % by weight of polymerized material. In the compressed state, the density of the foam is ~o about 0:14 g/cc. When expanded, the foam has a dry density of about 0.018 g/cc and has a glass transition temperature of 50°C.
Ex i pie.
~aration of Foam from a HIDE
A) HIDE Preparation is Anhydrous calcium chloride (36.32 kg) and potassium persulfate (189 g) are dissolved in 37F1 L of water. This provides the water phase stream to be used in a continuous process for forming the HIDE.
To a monomer combination comprising distilled divinylbenzene (40'/°
divinyibenzene and 6(~/o ethyl styrene) (2100 g), 2-tthylhexylacryiate (3300 m g), and hexanediol diacryiate (600 g) is added a very high purity diglycerol monooleate (360 g), and Tinuvin 765 (30 g). The diglycerol monooleate emulsi5er (Grindsted .Products; Brabrand, Denmark) comprises approximately 81% diglycerol rttimooleate, 1% other diglycerol monoesters, 3°/.
poiyglycerots, and l:i% other polyglycerol esters, imparts a minimum oil xs phsse/wster phase intadfacial tension value of approximately 2.5 dyneJcm and has a Qitical aggregation concentration of approximately 2.9 wt%. After m>s~g, this emulsifier mixture is allowed to settle overnight. No visible residue is formed and all of the mix is withdrawn and used in the oil phase as the emulsifier in fornung the HIPS.
>o Separate streams of the oil phase (25°C) and water phase (53°-55°C) are fed to a dynamic mixing apparatus as in Example ~ 1. A portion of the marital airing the dynamic mixing apparatus is withdrawn and recirculated by a recirulation loop as shown and described in the Figure of copending Canadian Patent Application No. 2,208,419, filed January 11, 1996 by ~s DesMarais et al., to the entry point of the oil and water phase flow streams to the dynamic mixing zone.

The combined mixing and recirculation apparatus is filled with oil phase and water phase at a ratio of 3 parts water to 1 part oil. The dynamic mixing apparatus is vented to allow air to escape while filling the apparatus completely. The flow rates during filling are 3.78 g/sec oil phase and 11.35 cc/sec water phase with about 15 ce/sec in the recirculation loop.
Once the apparatus set-up is filled, the water phase flow rate is cut in half to reduce the pressure build up while the vent is closed. Agitation is then begun in the dynamic mixer, with the impeller turning at 1800 RPM. The flow rate of the water phase is then steadily increased to a rate of 45.4 cc/sec over a io time period of about 1 min., and the oil phase flow rate is reduced to 0.757 g/sec over a time period of about 2 min. The recirculation rate is steadily increased to about 45 cc/sec during the latter time period. The back pressure created by the dynamic and static mixers at this point is about 10 PSI (69 kPa).
The Waukesha pump speed is then steadily decreased to a yield a recirculation is rate of about 11 cc/sec.
B) Polvmerization/Curing of HIDE
The formed emulsion flowing from the static mixer at this point is collected in a round polypropylene tub, 17 in. (43 cm) in diameter and 7.5 in (10 cm) high, with a concentric insert made of Celcon plastic. The insert is S
Zo in ( 12.7 cm) in diameter at its base and 4.75 in ( 12 cm) in diameter at its top and is 6.75 in ( 17.14 cm) high. The emulsion-containing tubs are kept in a room maintained at 65°C for 18 hours to bring about polymerization of the emulsion in the containers to thereby form polymeric foam.
C) Foam Washing and Dewaterinst is The cured HIDE foam is removed from the tubs. The foam at this point has residual water phase (containing dissolved emulsifiers, electrolyte, initiator residues, and initiator) about 50-60 times (50-60X) the weight of polymerized monomers. The foam is sliced with a sharp reciprocating saw blade into sheets which are 0.160 inches (0.406 cm) in thickness. These sheets so are then subjected to compression in a series of 2 porous nip rolls equipped with vacuum which gradually reduce the residual water phase content of the foam to about 6 times (6X) the weight of the polymerized material. At this point, the sheets are then resaturated with 60°C., are squeezed in a series of 3 porous nip rolls equipped with vacuum to a water phase content of about 4X.
ss The CaCl2 content of the foam is less than 1%.
The foam remains compressed after the final nip at a thickness of about WO 96/4084 PCTlUS96/10169 a 0.021 in. (0.053 cm). The foam is then dried in air for about 16 hours. Such drying reduces the moisture content to about 9-17 % by weight of ' polymerized material. At this point, the foam sheets are very drapeable. The foam also contains about 5% by weight of residual diglycerol monooleate ' s emulsifier. In the collapsed state, the density of the foam is about 0.14 g/cc.
When expanded this foam has a dry density of about 0.018 g/cc and has a glass transition temperature of about 23°C.
Examples 3-11 Preparation of HIDE Foams From Different Monomers ]o Absorbent foams are prepared from HIPEs having varying monomer components using procedures similar to those described in Examples 1 and 2 above. The monomer formulations, water-to-oil (W:O) ratios, and resulting Tg are shown in Table 1.
Table 1 Fnam ~'nmnncitinn ~n~i Tn Exam le STY % DVB % EHA % T C)*
#

3 40% 22% 38% 52 4 34% 22% 44% 44 32% 24% 44% 50 6 31% 22% 47% 38 7 29% 24% 47% 41 8 25% 22% 53% 32 9 38% 22% 40% 54 36% 22% 42% 49 11 28% 22% 50% 30 ]$
STY ~ styrene; available from Aldrich Chemical Corp.
DVB = divinyl benzene, based on 55% purity with 45% ethyl styrene impurity;
available from Dow Chemical Corp.
EHA = 2-ethylhexyl acrylate:available from Aldrich Chemical Corp.
Zo *Detersnined via Dynamic Mechanical Analysis at 1.0 radaans/second.
Examples 12-16 1?revaration of HIDE Foams From Different Monomers Additional foams of the present invention were prepared essentially as described in Example 1. The insulating properties of these foams were a measured via ASTM C 177-85. The results are shown in Table 2.
Table 2. Insulating Values for Foams -~_ , Example Densit~~STY DVB EHA Tg(C) Thermal , # cc % io % Conductivitv*

12 0.011 20% 40%a 40% 60 38 13 0.012 20% 40% 40% 60 34 14 0.008 0% 40%b 60% --18 37 ISc 0.015 0% 33% 55% --23 34 l6c 0.012 0% 33% ~5% -23 35 (**Calculated using DMA) s (**Units are mW/(m . K). Calculated using ASTM C 177-85) a: 55% pure DVB was used b: 50% pure DVB was used c: 12% 1,6-hexanedioldiacrvlate was used The data show excellent thermal insulating properties for the foams of io the current invention.
Example 17 A continuous sheet of foam 12" wide and 3" thick is prepared from a HIDE comprising' 40% styrene, 20% DVB, and 40% EHA at a water-to-oil ratio of 50:1 by the process described in Example 1. This foam is dewatered is while warm (ca. 40°C) by passing through compressive dewatering nip rolls with successive gaps of 2", I ", 0.5", and 0.3". The foam slice retains a thickness at that stage of about 0.5". The continuous foam slice is then laminated to a 0.01" thick aluminum foil and rolled into a bail about 2.5' in diameter. This is then packaged in shrink wrap plastic. The foam remains zo stable in this configuration through warehousing, shipping, retail display, and application. Application takes the form of unrolling the product and inserting it between ceiling joists in a residential attic to the desired cut lengths.
The product at that point is still about 0.5" in thickness. The elevated temperature , in the attic causes a fairly rapid reexpansion to the original thickness and a density, 3" and 0.020 g/cc respectively, of the foam This serves as an .
excellent insulating material, conveniently managed from manufacturer to final use.

Claims (12)

What is Claimed is:

1. The use of a polymeric open-celled foam material as an insulator, wherein the polymeric foam material has:
A) a specific surface area per foam volume of at least 0.01 m2/cc;
B) a dry density of less than 0.05 g/cc; and C) a glass transition temperature (Tg) of between -20° and 90°C.

2. The use of a polymeric open-celled foam material as an insulator, wherein the polymeric foam material has:
A) a specific surface area per foam volume of at least 0.01 m2/cc;
B) a dry density of less than 0.05 g/cc; and C) a glass transition temperature (Tg) of between -20° and 90°C;
and wherein the polymeric open-celled foam material is prepared by a process comprising the steps of (A) forming a water-in-oil emulsion at a temperature of 30°C or higher and under low shear mixing from:
(1) an oil phase comprising:
(a) from, 80% to 98% by weight of a monomer component capable of forming a copolymer having a Tg value of from -20°C to 90°C, said monomer component comprising:
(i) from 10% to 70% by weight of a substantially water-insoluble, monofunctional monomer capable of forming a homopolymer having a Tg of 35°C or less;
(ii) from 10% to 70% by weight of a substantially water-insoluble, monofunctional comonomer capable of imparting toughness equivalent to that provided by styrene;
(iii) from 2% to 50% of a first substantially water-insoluble, polyfunctional crosslinking agent selected from the group consisting of divinyl benzene and analogs thereof; and (iv) from 0% to l5% of a second substantially water-insoluble, polyfunctional crosslinking agent selected from the group consisting of diacrylates of diols and analogs thereof; and (b) from 2% to 20% by weight of an emulsifier component which is soluble in the oil phase and which is sutable for forming a stable water-in-oil emulsion;
(2) a water phase comprising from 0.1% to 20% by weight of a water-soluble electrolyte; and (3) a volume to weight ratio of water phase to oil phase in the range of from 12:1 to 250:1; and (B) polymerizing the monomer component in the oil phase of the water-in-oil emulsion to form the polymeric foam material.

3. The use according to Claim 1, wherein the polymeric foam material has a glass transition temperature (Tg) of from 0° to 50°C.

4. The use according to Claim 1, wherein the polymeric foam material has a number average cell size of less than 100µm.

5. The use according to Claim 4, wherein the polymeric foam material has a number average cell size of from 10 µm to 50 µm preferably of from 15 µm to 35 µm.

6. The use according to Claim 5, wherein the polymeric foam material has a glass transition temperature of from 10° to 40 °C.

7. The use of a hydrophobic polymeric open-celled foam material as an insulator, wherein the polymeric foam material has:
A) a specific surface area per foam volume of at least 0.025 m2/cc;
B) a dry density of from 0.08 g/cc to 0.004 g/cc;
C) a glass transition temperature (Tg) of between 0° and 50°C;
and D) a number average cell size of from 10 µm to 50 µm.

8. The use according to Claim 2, wherein the monomer component used in step (A) comprises from 10% to 70% monofunctional comonomer (ii), preferably from 20% to 50% monofunctional comonomer (ii).

9 The use according to Claim 8, wherein the monomer component used in step (A) comprises from 20% to 50% monofunctional monomer (i).

10. The use according to Claim 9, wherein the monomer component used in step (A) comprises from 10% to 30% crosslinking agent (iii).

11. The use according to Claim 2, wherein monofunctional monomer (i) of the monomoer component is selected from the group consisting of 2-ethylhexyl acrylate, isodecyl acrylate, lauryl acrylate, and lauryl methacrylate;
monofunctional comonomer (ii) of the monomoer component is selected from the group consisting of styrene,. ethyl styrene, and p-n-octylstyrene; and the first crosslinking agent (iii) of the monomoer component is selected from the group consisting of divinylbenzene, trivinylbenzene, divinyltoluene, and divinylxylene.

12. The use according to Claim 2, wherein the volume to weight ratio of water phase to oil phase is in the range of from 25:1 to 125:1.