CA1201256A

CA1201256A - Organic-inorganic composites of neutralized polyelectrolyte complexes

Info

Publication number: CA1201256A
Application number: CA000441611A
Authority: CA
Inventors: Shy-Hsien Wu
Original assignee: Corning Glass Works
Current assignee: Corning Glass Works
Priority date: 1983-01-27
Filing date: 1983-11-21
Publication date: 1986-03-04
Also published as: EP0115398A3; US4455382A; JPS59155482A; EP0115398A2

Abstract

Abstract of the Disclosure This invention is directed to the preparation of neutralized polyelectrolyte complexes exhibiting hydrophobic behavior containing crystals of an organic polycation exchanged lithium and/or sodium water swelling mica. The process for making such products comprises:
(1) forming a glass-ceramic body containing crystals selected from the group of fluorhectorite, hydroxyl hectorite, boron fluorphlogopite, hydroxyl boron phlogopite, and solid solutions among those and between those and other structurally-compatible species selected from the group of talc, fluortalc, polylithionite, fluorpolylithionite, phlogopite, and fluor-phlogopite, (2) contacting that body with a polar liquid to cause swelling and disintegration of the body accompanied with the formation of a gel; and (3) contacting said gel with a source of organic poly-cations to cause a reaction between the Li+ and/or Na+ ions from the interlayer of the crystals and to neutralize the charge density of the crystals, thereby forming neutralized polyelectrolyte complex, said organic polycations being selected from the group of (a) a primary amine solubilized with acid, (b) a secondary amine solubilized with acid, (c) a tertiary amine solubilized with acid, (d) a quaternary ammonium acid salt, (e) a quaternary phosphonium acid salt, and (f) a ternary solfonium acid salt.

Description

Background of the Invention United States Patent No. 4,239,519 is directed to the preparation of inorganic, crystal-containing gels and papers, fibers, films, boards, and coatings roduced wherefrom.
U.S. Patent 4,239,519 issued on December 16, 1980, to Corning Glass Works. The inYentOrs are G.H. Beall, D.G.
Grossmanl and S.N. Hoda.
Long term testing ox products made in accordance with the disclosure of that patent has indicated that the values of such physical properties as mechanical strength, flexibility, dielectric strength, 105s tangent, and ionic conductivity are influenced by the relative humidîty of the surrounding environment. Stated differently, the properties displayed by the products ore not stable. In the main, there is an overall deterioration in toe mechanical and electrical properties as the relative humidity of the atmosphere is increased.
Consequently, the primary objective of the instant invention is to devise means for rendering papers, films, boards, fibers, and coatings prepared in accordance with the disclosure of Patent No. 4,239,519, supra, relatively insensitive to the relative humidity of the environment in which the product will be used.
Summary of the Invention It is well recognized in the orsanic polymer field what neutralized polyelectrolyte complexes rormed through the reaction of polycations with polyanions exhibiting equiva-lent charges will resist water swelling, i.e., w;ll demon-strate little water sorption. That phenomenon is postulated

-2~ r Z~i3 l to be due ta a tight, neutraLized, polylonic interac~i~n.
The resent i~ention is founded it the discovery of a new composite matexial, ~iz~, a neutralized polyelectxolyte complex, which, when abr~cated in the form of paper, film, fiber, board, ox coating, possesses such 2esirable physical characteristics 25 excellent hydrophobicity, remarkable toughness, high dielectric constant, high electrical resis-tivity, and high mechanical ~rength, can ye prepared by reacting zn e~uivalen~ amaunt of an organïc polycat~on with an anionic gel produced it the ~an~ex disclosed in Patent No. 4,239,519, sure Por example, paper made from a neutralized polyelectro-lyte complex via a Fourdrinier-type process can demonstrate good dry strength, substantial wet strength, and excellent water repellency. Howe~e~, the most exceptiGna:L property manifested bv the paper way the substantial insensitiveness of the loss tangent thereof to exposure to different sir-rounding relative humidity ca~ditions~ the paper can al 50 exhibit very high dielectric strengths and dielectxic ZO constants which are stable in atmospheres of varying relative humidities.
Board prepared in accordance with the in~entîve process can display high strength coupled with remarkable toughness.
Examples there~r czn be nailed wlthqut showing cracking and evidence Good dry and wet strength, water repellency, high surface rQ~isti~ity, and are essentially non-flammable, i.e., they will not flare, jut merely char, wren contacted with a flame.
Finally, densQ, non-porous coatings which aisplay ex-3G cellent water repellency can be formul ted which, VDecause oftheir inherent high mechanical strength and surface Ward-ness, cay be useful in protecting weak andior table ~2~3~6 substrate materials Whereas ion exchange of zn organic polycatlon wit an anionic gel wzs briefly mentioned in Pate No. 4,23~,51~, no indic:ation was made therein to achieving charge neu~rallty in the exchanged system. Ye, charge neu~ral~ty compri3es the cornerstorle of the inventit~e composite maternal.
pence, each of the exceptional and desirable properties demonstrated my the i~venti~e materials it a dlrect conse-quench of organic polycations reacting strongly with an e~uivale~t amount of inorganic p~lyan:ians gels Jo form a neutralized polyelectrolyte complex. Any substantial deviation from charge neutrality renders the resulting polyelectroly~e complex systems, i.e., thy composit:e materials, essentiallx useless because af their sigh susceptihility to a swelling action in the presence af moisture water In the last gen2ral tents, the p~eparatlon of khe inventive materials contemplates three fundamental steps:
~11 a glass-eeramic body is produced according Jo the method and having an overall composition and mlcrostruc~ure disclosed in Patent No. 4,239,519;
~2) said glas -cer mic body i5 cantacted with a polar l~guid, commonly water, fcr a time sufficient to cause swelling and disintegration thereor accompanied with the formatLon of a gel contal~ing crystal; and . ~3~ said gel is contacted with a source of organic polycations in an amount and for a time sufficient to cause an ion exchange reaction to occur between the organio poly-cations ala he Li and/or Na ions from ths nterlayer of - said crystals and to neutralize the charge density of said crystals, whereby effecting the fa~mation ox neutr31ized polyelectrolyte complex.
Where pape:r, film, giber, board, or coating i3 desired, _~ _ the neutralized polyeleotralyte complex will by dispersed into a liquid vehicle; the solid:liguid ratio of the complex and vehicle will ye adjusted to a pxoper value for toe formation of a paper, board, film, fiber, or coating, and then paper, board, film, iber, or coating will pa made th~refromO
Because the neutralized polyelectrolyte complex exh~blts hydrophobic ~ehavaor, water alane is ~,ot suitable as a dispersing solution. laboratory investigations indicated that polar organic liquids such as short chain aliphatic acids, alcohols, aldehyde~, and amides could be us zed for that function. It was also found what aqueous Walt salutions of such large aations as K , R~ , Cs , N~4 , Ca , Sr Cu , Ag , Ba , and Pb were aLsa suitable as were aqueous NH40H solutions. Fo~mamide has been deemed to ye the preferred liquld organic dispersing solution and aqueous solutions of KCl and NH40~ as the preferred inorgansc dispersants.
Generally, there are thxee categories of organic cations, Liz., N+, P+, and S , each of which is operable in the inventive process. The most commcn af those is N , of which there are fcur types:
a a primary amine salubilized with acid, exemplified by R-N~3~X
b) a secondary amine salubilized with acid, exemplified (c) a tertiary amine s~l~bllized with acid, exemplified by l3 Rl-NEI X

~d~ a ~uaternary ammonium acid salt, exemplf7ed my -N+ R K
l2 The cationic characteristic increa-es from the primary amlne up the ~uaternary cation.
The Pi cation is illustrated by the ~ua~ernar~ phos-phonium acid salt R -D+-R K

The S cation is exemplified by the ternary sulfonium acid salt Rl-S+X

The abo~e-recited nonpoly~eric cations are kr.own to react, i.e., ion exchange, with anionic clay ma~erial~.
Because of the strong anionic character ox the yels derived from Patent No. 4,239,519, the amount of arganic polyca~on requir0d as an e~ecti~e and camplet~ counterbalance 50 as to yield style flocs is dependent upon the charge strength thereof. pence, a larger quantity of a primary amine solubilized with an acid will be necessary to balance the anionic charge of the gels than of a quatQrnary ammonium Walt.
In sum~a~y, the preset in~en~ion provides a method for preparing a neutralized polyelectrolyte complex con~alnlng relatively uniforTnly-sized c~f3tals consistirg e~;~entially of an organic polycation-exch~nged lithium and/or sodlum water-swelling mica selected from the group of fluorhec~ori~e, hydroxyl hectorite, boron fluorphlogop.~te, hydroxyl boron phlogopite, and solid solutions among those and between those and other structurally-compatible species selected from the group of talc, fluortalc, polyl~thionite, fluor polyli~hionite, phlogopite, and fluorphlogopite, at least a substantial proportion of said crys~ ls; exhibiting a mor-phology of a continuum of flakes, rectzmgular like strips, and interwoven ribbons in pa~all~l or sub-parallel 30nes or sheaths. Commonly, the strips and ribbon will be about 0.5-10 micros in length, about 5~0A 500~A wide, and less than about 100~ thick, and the flee will ye irregularly shaped with diameters between about ~.5-10 microns and cross sections of less than about lOOA.
In specific terms, the inventive method involves three basic steps:
(.1) a glass-ceramic body is formed containing relatively uniformly-sized crystals consisting essentially of a lithium and/or sodium water-swelling mica selected from the group of fluorhectorite, hydroxyl\hectorite, moron fluorphlogopite, hydroxyl boron phlogopite, and sslid solutions among those and between whose and other structurally-compatible species selected prom the group of talc, fluortalc, polylithionite, fluorpolylithionite, phlogopi~e, and fluorphlogopite;
2~ said body is contacted with a polar liquid for a time ~uf~icient to cause swelling and disintegr2tion thereof accompanied with the formation of a gel, at least a su~stan-tial portion of the crystals in the gel exhibiting the above~described morphology ox a continuum of flakes, rectangu-lar-like strips, and interwoven ribbons in parallel or sib parallel zones or sheaths; and

3~ said Mel is contacked with a source ox organic polycations ~o~ a time suficisnt to cause an ion exchange reaction to occur between thy organic polycations and the Li and/or Na ions from the interlayer a said crystals and to neutralize the ch2rge density of said crystals, thereby effecting the formation o neutralized polyelec~rolyte csmplex .
Paperg bad fixer, film, or coating i5 produced via three additional steps:
i said complex is dispersed into a li~u~d selected prom the group of polar organic liquids, aqueous N~40 solutions, and aqueous szlt solutions of large cations selected prom the group of R+t R~ , Cs , ~4 , Ca , Sr Cu , Ag , Ba , and Pb 2) the solid:liq~id ratio ox the complex and liquid ls adjusted to a desired 1uidity; and 3) a paper, board, fiber film, or coatlng Lo prepared therefrom.
The paper, ~oa~d, fixer, film, and coating wafter application to a s~bstrate~ aye dried and cured by heating to slightly elevated temperatures, i.e., temperatures above room temperature, but normally not in excess oE 2~~, znd, most commonly, at temperatures below 150 C.
Glass-ceramic bodies consisting essentially, crossed in weight percent on the oxide basis, ox Li200-12 ~a2o a-Limo + Na20~.5-14 go la-3 B203~~3 Al203 a -~2~

SiO2 35-7 F 0~15 F + ox 4-15 are operable in the inventive method with the preferxed compositions consisting essentially, expressed on weight percent on the oxide basis, of Li2o . 0.5-12 Na20 0-10 Li2O + Na2O 0.5-14 MgO 14-38 Sio2 3~_ Customarily, water will constitute the polar liquid utilized to cause gel formation, although polar organic liquids can be operable. In general, the time required to effect swelling, disintegration, and gelation ranges between Z0 about 1-48 hours.

Description of Preferred Embodiments In the following illustrative examples, gel prepared from Example 14 of Patent No. 4,239,519 (the preferred com-position of that patent), and in accordance with the method described in that patent, constituted the precursor material.
Thus, a glass body having the following approximate compo-sition, expressed in terms of weight percent on the oxide basis as calculated from the batch, of SiO2 64.5 MgO 10.8 Li2O 8.0 MgF2 16.7 was heat treated at about 700°C for about four hours to form a highly crystalline body containing fluorhectorite as the predominant crystal phase. The body was immersed into deionized water whereupon it swelled, disintegrated, and formed a gel. After occasional stirring, the material was permitted to settle and the gel decanted, leaving any residual glass and non-micaceous phases, if present. The viscosity of the decanted portion was then adjusted to a predetermined viscosity in preparation for further use.
In carrying out the present invention, preparation of neutralized polyelectrolyte complex from the above gel was undertaken in the following manner. 600 grams of gel (8.42%
solids content) were added slowly into 1000 grams of KYMENE*
557H solution (6.25% solids content) accompanied with vigorous stirring. KYMENE*557H, marketed by Hercules, Incorporated, Wilmington, Delaware, comes within the cate-gory of a quaternary ammonium acid salt and can be described * trade mark.

as a cationic, waxer soluble condensate of a ~as~c polyamide and epichlorohydrin which has assumed a polyamide-polyam~ne eplchlorohydrin resin formO Flocs of neutralized poly-electrolyte complex are developed essentially instantaneously.
The coarse flocs were sheared further via a t~.~o-mlllute residence in a Waring blender operating at high speed. Toe flocs were thereafter subjected to mollera~e stirring for six hours and when allowed to separate overnightO the xesultant slurry consisted of ine flocs settled at the bottom o'er-laid with a cloudy supernata~t solution. The supernatantsolution was decantad off and discarded. The separated fine 10cs were washed my running into distilled water, stirring fox 10 minutes, and then filtering. This washing was repeated several times to insure complete remaval of ex¢ess KYMENE~ The yleld ox the final wet floc was about 120 grams hiving a solids content af a~aut 33% my welg~t.
The amount of organic polycations present in the final product is governed by the re~uire~ent of charge neutrality in the neutralized polyelectrolyte complex system. Y.ence, where the preoursor gel is insu~iciently separated, the result is a re}a~ively low charge de~s~ty. Fur example, where the gel is ~ubjec~ed Jo can~entional ball fling techniques, the fluorhectorite flakes are not sufficiently separated and the isoelectric point ox the system can be reached at a KY.~ENE 557~ addition level of about lS~ by weight, pa ed upon the amount of flusrhac~orite sollds.
However, in a highly sheared gel the isaelectr~c point will be at a much higher KY~ENE level. Thus, the flees of fluorhectorite in highly sheared gel are so well separated as to assume a rela~i~ely high charge density, thereby dema~din~ a large auantity o f polyca~ions to clan the isoelec tric point . To illustrate, a nitrogen a:na].ysis of 2~6 the flo ::s described above indicated a KY~lENE content oE
about 3~96 by weight, based upon total colids, or about 56~4 by weight, based upon the ~luorhectorite solids. E~ldently, the flakes of 1uorhectorita in a highly sheared gel are very well separated and, thus, assume-a relativelv high charge density. That condition requires a large leva} of polycations to achieve the isoelectric point.
Laboratory experience has indicated a the raze o ion exchange between an org nic polycation and the gel $S
considerably slower than that a urring between a catlon such as and the gel. Consequently, to insuxe the greate-t extent of exchange, an excess of ~MENE 557~ is used for neutralization and a relatively long time for the reactîon to take place i5 utilized. the excess ~YMENE us removed by subsequent successive waYh~ngs and ilterings of the slurry.
The lnitiaL filtering step may require as long as two hours to complete; whereas after several washings and ~llteri~gs, the time there-Eor can be measured in seconds. the rapid filter rate indicates the essentially total removal of excess KY~ENE and illustrates the substantial hydropho~lc character of the complex. It is this hydr~pho~ic behavior which imparts the exceptionally good stability oE mechanical and electrical properties to the inventivq products when ln contact with environments of varying relative humidities.
The neutralized polyelectrolyte complexes exhlbit two distinct properties, Liz., they rele?sa water easily and they demonstrate a combination of toughness and hardness.
For example, relatively light pressure with a finger can cause wet flocs thereof to 1052 water and to assume a verv compact form which is tough and hard, but not brittle. It is believed thaw the strong and co~ple~e ~olycation-polyanion interactian ¢KY~ENE-gel~ replaces the original afinity ox the KY~EWE or the gel taward water Therefore, toe resultiny flocs do not readily adsorb or absorb water. Furthermore, the polymeric characteristics o ~Y.~ENE impart toughness to the product.
. The hydrolytic stability of the complexes was ~nve~-tigated by immersion into water at a~ient temperature for seYen days. A comparisan or con~.rol floe prepared utilizir.g K ions 2S the flocculating agent wa3 also immersed into water for the same period of time. The latter rapidly disintegratea~ whereas the inventive complex xhibited little attack.
The inventive materials were also cast as films onto glass slides to evaluate the water repeLlency ~ual:ity thereo, this characteristic being a function not only ox khe intrinsic hydrQphobic nature o the complexes, but alga the smoothness and tightness of the cast films. The films demonstrated exceptional watar repellency as evidenced by water reading ror one hour. Such excellent ilm ormation is a result of the poLycations manifesting high inter10c affinity or cohesive strength.
The water repellency exhibited by the inventive films can be urther improved via a pout treatment with a silane salution. For example, methanol solutions were prepared containing 0.1~, 0.5~ 1.0%, and 5% by weight, respectively, o~.Z~6032 silaner marketed by Dow Corning Corporation, midland, Michigan, and desi~n~ed as N-~-SN-vinylbenzy-laminoethyll-y-ami~opropyltrimethoxysilane Eydrogenchloride.
films of the inventive flocs wexe prepared on glass sl}des, the coated slides contacted with the s~lane sol~tons, and thereafter the silane was cured by sequentially heating or ?.J~
owe hour at 100 C follQwed my ye hour at 12~ O Even at only the 0.1% solution concentration, the silane coated films displayed water beading after soaking overnight in waxer at ambient temperature. ~owe~er, to insure even greater resistance to attack by moisture, a ~.5~ silane solution concentration has been deemed preferred. Whereas some further improvement may be evidenced at h~g~er solution concentrations, So has been teemed a practiGal maximum. the curing temperatures will be maintained below about 2~0 C.
Post treatment of films in like wanner with methanol solutions containing 0.5% by weight, respectively, of ~-174 and A-187 silanes marketed by Unian Carbide, Jew York, New York, again evidenced exceptional resistance to moisture attack after an overnight immerYiOn in water a amb~en-t temperatu~e~ A-174 is designated as y-MethacryloxyproQyl-trimethoxysilane and ~-187 is designated as y-Glycidoxy-propyltrimethoxysilane.
The oohesive strength of the inventive mater$als is dependent upon the charge nature of both the poly~alent 2~ cations and anions, i.e., the density and strength of the charge exhibited thereby, and the molecular c~aracteris~ics thereof, to such pxcperties as steric hindrance and molecular weight. The quater~ary ammonium IcTd salts appear to yield products displaying the greatest cohesive strensth.
As h s been observed above, three types of li~u~d media have been found operable to uniormly red~Rperse the neutral-iced polyelectrolyte complex preparatory to making paper, board, giber, film, ox coating; viz., certain polar organic liquids such as short chain aliphatic acids, alcohols, aldehydes, and amides, aqueous N~40H solutions, and aaueou~
salt solutions o a larse cation. A particularly useful solution of the latter contains K Ians. Laboratory in~es-tigations utilizing aqueous solutions of KCl ~0~0~5-2N) have pointed to two significant features arisïng Erom the use thereof- ~11 KCl solutions can depress double layers of polyionic interaction thereby weakening it to permit water to diffuse and penetrate between polyions for wetter disper-sion; znd ~2) R+ ions can be utilized as a scavenger to ion exchange with any residual fluorhectorite sites which were inaccessible to the organic polycation~ because of sterlc hindrance, thereby completing ully the exchange process.
Contact with an aqueous NH40X solution cauqes a XYMEN~
treated product Jo swell. This phenomenon i5 or very practical significance since the observed aefinity of NH~OH toward KY~E~E causes 10cs of the in~enti~e complexes to swell which, in turn, renders them more easily broken down into very finely-divided paxticles under a dispersing condition of high shear.
ACCOSTRENGTH 711, marketed by American Cyanamid Company, Wayne, New Jersey, and NALCOLYTE 7134, marketed by Nalco Chemical Company, Chicago, Illinois, are otter poly~uaternary ammonium salts which, when utilized in the manner described above with respect to KY~ENE,* also yield products exhibiting like characteristics.
Preparation of Paper About 1.3 srams of the neutralized polyelectrolyte KYM~NE complex were dispersed into 50 grams of formamide utilizing a 10-minute residence in a Waring blender opera-ting at high speed. The resultant slurry was diluted through the addition of 50 grams of distilled water accompanied with moderate stirring and then poured into a Britt jar pa Eli laboratory scale papermaking device utîlizing a Fourdrlnier-* trade mark. -15--type processl. A uniform we we was formed o'er a piece of stainless steel screen ~200 mesh -74 micrans) inside the Sax after applying a vacuum suction far jive minutes. The web and the screen were dried for about 15 minutes at 80 C to facili~a e separation of the partially dried web from ye screen.
The web was there fter immersed for two hours into an aqueous 2N Of solution to effect ~urt~er ion exchange, if necessary, to insure the essential absence of I ions in the product. The web was washed twice it d}stilled water and then dried cured for 3Q minutes each at 8~ C, 10~ C, and 120 C. The dried paper sheet, circular with a diameter of about 4" and a thickness of about 5", demon trated a smooth ~u~ace and appeared to be free prom pin Poles.
In another method o~ preparing paper, 1.3 grams o the neutralized polyelectrolyte KYMENE complex were dispersed into 200 grams of an aqueous 0.05N Of 501ution employing a 15-minute residence in a Waring blender operatîng at high speed. The slurry produced whereby was passed through a stainless steel screen -U00 mesh-~149 micronsJ to remove any o~er~ize flocs and then 400 grams of distilled water were admixed therewith. The diluted slurry wa6 poured into a Britt jar and subjected to a brief mild stirring, the slurry was allowed to stand for one hour in the Britt jar to insure the formation ox a uniform we over the 20~ mesh tainless creel screen before ~ac~um suction was applied to remove the liquid therefrom. Drying l LS minutes at 80C
permitted ready separation ox the web from the screen. The web was subsequently washed twice in distilled water and dried (cured for 30 minutes each at 80C, 100C, and 120C. The resultant dried paper disc had a thickness o l . .

:~2~ So about 0.0012", exhibited a smooth surface, had a un;~orm appearance, and seemed to be free frQm pîn holes.
Variations on the above method were conducted utiliz7ng aqueous XCl solutions having concentrations o ~.5~, O.lN, O~OlN, and 0.005~ where solutions of lo KCl concentra-tions were employed, Liz., O.OlN and ().~5~, the neutraliged polyelectrolyte complex slurry was quite coarse, thereby leading to poor paper quality. It was found, however, that the addition of a small amount of aqueous N~40E, e.g., 0.05 cc of 2~ by weigh ~H40~, to the coarse slurries with low XCl concentrations would result in the pxoduction of good union paper. moreover, the neutralized polyel~ctrolyte complex in the WX40H-containing soLution displayed a slight amount of elasticity, posited to be due to some swelling, and the paper derived therefrom appeared to be muck smother than that prepared from N~0~-ree salut.ion.
The above papers preparea with or without N~40E additions displayed a dry strength comparable to paper made via the same process, but utilizing ions fur dispersion. moreover, the papers exhibited excellent water repellency and su~stan-tial wet strength after an overnight immersion in waxer, whereas the X ion paper absorbed water very read.~ly and manifested essentillly no wet strength.
Typical electrical propertiec o papers prepared in accordance with toe above descriptioh wherein I+ ions constitute the dispersing agent are xecorded below in Table I.

-.17-~2i~
TALE I

~lelec~Con~eant 120 ~z1 K~z 10 X
25C 16.631~.12 1~.36 52C 18.1817.3~ 1~.61 79C 22.27lg.99 18.53 12~C 34.6527~6~ ~2~72 161C 42.442~.S5 31~8 206 i7.423~.~0 26.43 Loss Tangent 120 ~z1 ~z l K~z ~5C 0.0210o.n270 a. ~4ao 52C 0.04000.0320 0.~4 79C 0.1100~.~700 ~.~52 128C 0.43~00.23~0 0.13 ~61C 0.~500~.31~a 0.1 ~0 206C 0.7500~.470a 0.28 Electrical Resisti~it~
Log p 25 C
~0 Log p 52C
Log p 79C 13.16 Log p 128 C 11.91 Log p 161 C 10.91 jog p 206C 8.37 Those data clearly indicate that the paper would be su~tabls for low..tempexature electrical applications only ~15gC).
The loss tangent of 0.02 at roam temper ore and 120 is relatively low, but till not sufficiantly low to be operable : in capacitor applications. ~e~ert~elP~s, both the electrical resisti~ity and the dielectrïc constant are desirably high.

f It i.s postulated that a very limited number of water mole-oul2s are essentially fixed within ths matxix structure, c presence ox 5uch molecules and the extremely tight bonding thereor within the matrix giving rise to the hlg~ dielectric constant and high dielectric strength displayed my the inventive papers.
The most interesting characteristic of the inventive papers i5 the relative insensitivity of toe electrical properties thereof Jo ambient moiskure. That feature is illustrated in Table II below, which reports loss tangsnt measurements conducted at room temperature (25 O at 0~
relative humidity and at 46~ relative humidity. As can be seen therein, the loss tangent is substantially unaffected by change in relative humidity.

TABLE II
, 0~ Relative tumidity 46~ Relative ~umidi~
120 ~z 0.017 a.~lg5 1 KHz 0.021 ~.021 10 RHz 0.026 9.G2~

Finally, high values haze been determined for the dielectric strength demonstrated by the inventive papers, e.g., 1000 volt/mil for A.C. at 60 Ho and 1600 volt~mil for D.C. at 70% relative humidity.

Preparation ox Board About 13 grams of the neutralized polyelectrolyte XY~NE oomplex were dispersed into 117 gram of on aqueous O.lN KCl solution utilizing a 10-minute residence in a Waxing blender operating at high ~peQd. The resultant slurry was vacuum filtered o'er a period of tree hours lnto 2`~
a plastic mold having base dimensions of ~5~8" x 3/." to form a bar-shaped wet cake. The cake was wash*d Ln digtill~d water ovaxnight Jo extract excess Of and then plaeed undar weight for 40.hours in a vacuum to remove waxer. Thereafter, the cake was pressed for one minute in a metal die under a pressure of 250Q psi and subse~uer.tly cured by exposure for two hours each at 80C, 100C, and 120 C. the pressed board (b?r) was smooth ana flat with dimensions of 2-~16" x 3~8"
x 5/32" and a weight of about four grays. Aqueous solu~lons of O.O5N, lN, and 2~ KCl were also found to be e~ect~ve in producing such boards.
The bar-shaped boards displayed smooth surfaces and were hard but not brittle. The boards could be nailed without cracking and wauld not burn, but only char, when contacted with the flame of a match 600 O furthermore, the boards exhibited excellent water repellency and good wet strength, the latter property beinq essentially unaffected after overnight immersion in water.
The combination ok toughness and hardness characterlstic of the inventive materials is evidenced by an elastic modulus measurement of L.6 x 10 psi and a modulu3 ox rupture measurement of 6000 pi. Also, a fracture strain o about 2.1~ was determined which is siyniicantly gxeater than that displayed by pine wood.

Preparation of Coatings Two portions of gel prepaxed from Example 14 of Potent No. 4,239,519 were neutralized wïth ~YL~ENE 557EE solution in the manner described above, but wher3in the first portian was centrifuged continuously at 1200 rpm Ed the second 30 portion was centrifuged continuously at 9~0 rpm. There-after, 18.7 grams of the fixst portion ox the neutralized 5~ `
complex and 6.3 gram of the second portion were redispersed in 475 grams of an aqueous O.OlN KCl solution via a five-minute residençe in a Warins blender operating a high speed. The resulting sluxry was then utilized for coa~lng foamed glass blocks having surace dirnensions of 6." x 6".
The coating procedure comprisea two steps: a fulling the cell voids gradually; arld ~b) building up the o~terlaylng coal:ing guic:kly. pence, initially, the foam cells were slowly filled through five successive applications of slurry, about 30 grams of slurry in each application wit 1.5 hour ambient air drying period intermediate the appl~ca-tions. After the cells were deemed full, a surrounding coating was relatively quickly quilt up via our aE~plica-tions of larger amounts of slurry, viz., about 90 grams of slurry in each case, with a 2-hour ambient air drying period ~e~ween ~ucce~slve applicationq. The coated big were allowed to dry overnight in the ambient environment and then cured for two hours each at 80C, 1~0 C, and 12~C. The final coating was relatively smooth and hard with a thicXness of about 0.001" and a coating weight of about ~.22 grams/
in.
In a modification of the ab~ve-described practice, a layered coating was prepared on the foamed glass blocs.
Instead of utilizing the mixed slurry described above, the cells were filled through successive applications or the first portion slurry prepared via centriuging at l2ao rpm~
and an en~el~pin~ coating prepared therefrom through two applications o larger amounts of that slurry. Thereafter, two applications of the second portion ~sl~rr~ prepared lie centrlfuging at 9000 rpm~ were made superjacent Jo the enveloping coating and the blocks then aried and cured.

~21-Thy inventive coatings are exceptionally useful in that they have the capability of coalescing and being cured to form a twin, hard, tough, water-repellen~, smooth, es~énti211y pin hole-free film without pressing. Consequently, the coatings can provide physical protectiorL for the fragile cell structure of foamed glass blocs. If de ired, conven-tional paint 6pref~rably ~iL-ba~ed~ carL ye applied o'er th2 coatings since. the coating are very compatible therewith.
Neutralization of the above gel way also tarried out utillzing a ~uaternary phospho~ium acid salt, viz., te~ra-N-butyl phosphonium chloride. The process in~o~ved slowly adding 60 grams of gel ~8 . 42% solids contentl into l grams of the chloride ~12.5~ solid contentl with constant siring Very fine, fluy 10cs of ne~traliz.e~ polyelectrolyte complex formed virtually instantaneously. The flocs were consolidated by precipitatLng in acetone (four volumes, iltered, and red ~curedl at 12QC ox two hours.
The water repellency o the product in film form was inferior to what prepared rom KY~ENE 557~. This decrease in cohesive strength exhibited in the floc i5 ccnsldered ta be due to the intrinsic differences in molecular character-istics and in charge density and strength existing between quaternary phosphonium acid salts and ~uaternary ammonium acid salts.
Two gels were prepared ha~in~ lower charge densities than what f the abo~e-de3cribed Example 14 of Patent No.

4,239,519 to study the effect ox anionic charge density upon the properties of neutralize polyelec~rolyte complexes resulting from reacting such gels with the organic poly-cation R~E~E 557~. The precut or glass bodies had t~efollowing approximate compositions, expressed it terms of weight percent on the oxide basis a calculate from the ~5~,0 6 batch, of A B
lo 3.~ 298 Na20 2.6 2~1 MgO 13.0 15.2 F2 17.8 22.1 SiO2 62.7 57.8 Example A was calculated Jo haze ah~ut 2~3 and Example B
about l/3, respectively, the charge deity of example 14 rP~erred to above The glass bodies were heat treated to covert them into glass-ceramic bodies containLng fluorhectorite as the predom inant crystal phase and tho e bodies L~mersed into deionized water to for a geL in live manner to the description above with re~pec~ ko Example 14.
Neutralizatior. of gel in Example A was unde~taXen in the following manner. 722 grams of gel (7~ solids content]
were added slowly into lOOO grams of KY~ENE 557X solution t6.25% solids contentl with vigorous s~lrring. Flocs of neutxalized polyelectrolyte complex formed substantially ins~an~ane~usly which were sub~eq~entl~ sheared, washed, and filtered $imilarly to thy treatment discussed above with regard to gel of Example 14. Neutralizatian of Example B
was carried out in a similar manner to Example A with 574 grams of gel ~8.8% solids content being combined wit laaO
grams of KY~EN~ 557~ solution ~6.25% solids content.
The amount of KY~E~E present in tha flocs, as determined via nitrogen analysis in terms of weight percent, were:
Example 14 35.6 Example A 35.2 Example B 31.1 ~.j4`~
It it evident from those values that, although the charge density of Example B is calculated to be but about 1~3 ha of Example 14, there was only a small difference observed on the amount of gYME~E picked up. The waxer repellenGies of Examples A and B in film form were very good, Example B
being slightly lets a~orable than Example A.
Examp}es A and could be readily processed in the form of boards or bars. ~ec~anical propertLes measured on bar shaped samples of Example hazing the approximate dimensions 2 15/32" x 3/8" x 5/32" are reported ~210w in comparison with KY~ENE-treated gel of Example 14 C = ~o~u~us of Rupture in psi, MOE - Modulus ox Ela3ticity in 10~ pi and F.S. = Fracture 5train in %1: .

OR MOE S.
_ _ Example B 2880 1.02 1.
Example 14 ~1~0 1.91 2.8~

The above data reinforced the above observation that the Example 14 - ~YMENE 557~ neutralized polyelectrolyte com-plexes provide hard, strong OR 8~0~ p5i~, yet very tough fracture strain 3%~ materials. However when toe anîonic charge of the fluormica-containing starting material is reduced, the inal product is weaker and lest taugh. This circumstance is believed to ye the r2sult of a loss of cohesive strength among the flocs.
In summary, whereat a lesser amount o ye organic ~olyca~icns can be utilized by decxeasing the charge density of the gel, that action results in a substantial depreciation in the mechanical properties ox the final product. Further-more properties such as water repellency and bulk mechanical strength are closely related to the in~exent cohesîve -:~.?~ 6 .!
strengths o the 1acs which, in tur~L, is g~v2rned my the charge nature ~den~ity and skreng~h~ and mc~lec~llar c:haracterist~cs, such as molecular weight arid steric his~drance, of bath the polyanion gel) and the organic polycat:Lon.

Claims

1. Flocs of a neutralized polyelectrolyte complex exhibiting hydrophobic behavior containing relatively uniformly-sized crystals and consisting essentially of an organic polycation-exchanged lithium and/or sodium water-swelling mica selected from the group of fluorhectorite, hydroxyl hectorite, boron fluorphlogopite, hydroxyl boron phlogopite, and solid solutions among those and between those and other structurally-compatible species selected from the group of talc, fluortalc, polylithionite, fluorpolylithionite, phlogopite, and fluorphlogopite, at least a substantial portion of said crystals exhibiting a morphology of a continuum of flakes, rectangular-like strips, and interwoven ribbons in parallel or subparallel zones or sheaths, wherein said strips and ribbons are about 0.5-10 microns in length, about 500.ANG.-5000.ANG. in width, and less than about 100.ANG. in thickness, and said flakes are irregularly shaped with diameters between about 0.5-10 microns and cross sections of less than about 100.ANG..

2. A complex according to claim 1 wherein said organic polycation is selected from the group of (a) a primary amine solubilized with acid, (b) a secondary amine solubilized with acid, (c) a tertiary amine solubilized with acid, (d) a quaternary ammonium acid salt, (e) a quaternary phosphonium acid salt, and (f) a ternary sulfonium acid salt.

3. Flocs according to claim 1, wherein said organic polycation is a water soluble condensate of a basic poly-amide and epichlorhydrin which has assumed a polyamide-polyamine-epichlorhydrin resin form.

2. A complex according to claim 1 in the form of paper, board, film, fiber, or coating exhibiting high strength, good toughness, essential non-flammability, excellent water repellency, high electrical resistivity, and high dielectric constant, the electrical properties thereof being substantially insensitive to changes in relative humidity.

5. Paper, board, film, fiber, or coating according to claim 4 having a silane coating thereon for improved water repellency.

6. A method for preparing the neutralized polyelectrolyte complex of claim 4, which comprises the steps of:
(a) forming a glass-ceramic body containing relatively uniformly-sized crystals consisting essentially of a lithium and/or sodium water-swelling mica selected from the group of fluorhectorite, hydroxyl hectorite, boron fluorphlogopite, hydroxyl boron phlogopite, and solid solutions among those and between those and other structurally-compatible species selected from the group of talc, fluortalc, polylithionite, fluorpolylithionite, phlogopite, and fluorphlogopite;
(b) contacting said body with a polar liquid for a time sufficient to cause swelling and disintegration thereof accompanied with the formation of a gel, at least a sub-stantial portion of the crystals in said gel exhibiting a morphology of a continuum of flakes, rectangular-like strips, and interwaven ribbons in parallel or sub-parallel zones or sheaths; and (c) contacting said gel with a source of organic poly-cations for a time sufficient to cause an ion exchange reaction to occur between the organic polycations and the Li+ and/or Na+ ions from the interlayer of said crystals and to neutralize the charge density of said crystals, thereby effecting the formation of neutralized polyelectrolyte complex.

7. A method according to claim 6 wherein said lithium and/
or sodium water-swelling mica consists essentially, expressed in weight percent on the oxice basis, of Li2O 0-12 Na2O 0-10 Li20 + Na2O 0.5-14 MgO 10-38 Al2O3 0-10 SiO2 35-70 F + OH 4-15

8. A method according to claim 6 wherein said time to cause an ion exchange reaction and to neutralize the charge density of said crystals ranges about 1-48 hours,

9. A method according to claim 6 wherein said polar liquid is water, or an organic liquid selected from the group of short chain aliphatic acids, alcohols, aldehydes, and amides.

10. A method according to claim 6 wherein said neutralized polyelectrolyte complex is formed into paper, board, film, fiber, or coating comprising the steps of:
(a) dispersing said complex into a liquid selected from the group of polar organic liquids, aqueous NH4OH
solutions, and aqueous salt solutions of large cations selected from the group of K+, Rb+, Cs+, NH4+, Ca+2, Sr+2, Ag+, Cu+, Ba+, and Pb+2;
(b) adjusting the solid:liquid ratio of the complex and liquid to a desired fluidity;
(c) preparing paper, board, film, or coating therefrom;
and then (d) drying and curing said paper, board, film, fiber, or coating (after application of the latter to a substrate) by heating to a temperature not in excess of about 200°C.

11. A method according to claim 10 wherein, after drying and curing, said paper, board, film, fiber, or coating is contacted with a silane solution and the resulting silane coating is cured by heating to a temperature not in excess of about 200°C, thereby improving the water repellency of said paper, board, film, fiber, or coating.