CA2148913A1 - Nanocomposites of gamma phase polymers - Google Patents

Abstract

2148913 9411430 PCTABScor01 This invention is directed to a composite formed from a gamma phase polyamide such as nylon (6) having dispersed therein a particulate material such as a phyllosilicate as for example montmorillonite.

Description

~i 21~8913 .

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BAC*~U~ OF IN~NTION

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Thi s inve~tion relat~s t~ a co3nposite ~a~e~c~ rising a polymer m.at~-ix having dispersed the~eln anlsotropic nanome-ter 5iZ2 particles sucr as Grgano~ilic :~?la~elet par~icles deriv~d ~r~m swel¦lab~ e 13 t n~erc~lated layered mate~ials and inc~rqanic fibr!illar ~,! ' r~ac~rials, and to artic' es of manu~acture ~rmed !f om t;~e cor~lposit~ rna~erial of this in-~enti3n. More . partic~alarly, ~h~ s invention ~elates ~o suc~ corQp~site !r~a e~ials and c~ os~ tes whar~ pol~er matrix ~ s E~r~ed 1~ o~ a pclymer in the ga;~ma pnase.
. 20 Prior Ar~
Polyamides rnay exist in v~rious c-ystall~ ne ~ orms .
Two ~r~ncipal crystalLirle fcrms o~ nylcn 6, aiF~ ~nc ~amma, have ~een c~a~ c_2rized st~-ucturally a~d .~, 20 ~`~er~nodynaznically ~see, ~,r exar~ple, Poly~e~
Colrununicati~ns, i951, 301 anc~ references citsd t'ner~in~ .
Various addl ~i~res have he~n us~d to rQGd~ ~ Ny lcn 6 ~nLch increasea t~e ra_~ o~ c~Ysta;liz~tl on to th~
25 alpha or garn~a ro~. See, ~c:r axa~p ~ e~ US Pate~t: ~o~ .
~,39,,~79 and 4,230,~35 and Japanesa ~a~er~t 55-14~346~. :
Polyami~es, such as nvlon ~,: co~.~pr sing a d~ spe~sion af particles, der~ ved ~'r~m organophili ~
~; 30 phyl~silicate3 arLd ha~ing a thickness or about 0. ~ 5 : ~) to a~out 1.2 n~ (12 ~) ! ha~re been re~orted ~n ,~:ne literature~ See ror exa~;pt~ U.S. Patent Nos. 4,73 3,0~7 and 4, 310, 754, and Ko~kai Publicatiorl ~o. lCag~8/ 1~.

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;J r . iJ ~ J L r~J~ ~ r t.~ .J.J r-r~J~ t ~) ~ ~'., , ' i ```.` ' 21~8~1 3 . - 2 -SV~Y OF T~; IN~NTION
. ~, Thls invention relates to a c~mposite corn~ri~ g a pol~mer mGtrix cGmprisinG at least one garun~ ~nas~
polyam~ de whe~ei~ at lea~- abcut one weight perceht or 5 said Folyarrude based on t;~e tot~l mcles o~ saLd pol~mide ~s ~n the gærruna phase, said po'ymer mat lix h~ring dis~ersed therein up to less than aDc~t O . 5~; by wt. cf the ~atr x ~f a namometer-s~ale p~rticulate ~a erial se1 ected r~o~.~ t'~e ~rc~p cGr.sist ng cf 1 i!yered 10 rr~a~rial :~a~ing a ~ickness eauai ~^ cr cS5 tha;ll, abou_ 20 nm ~200 A) and ri~rill~x :materi21s havin~ a diameter ~! equal to o- less than about 10 n~ (1'JO A). AnC-her aspect - f t~ls ir ver_ion rela.~s to an a~ticle of' .anufacture compr~sing a ~dy all c~ a portion o.~, wh-ch . 15 is formed of t~;e cor~posits or Ihis inve~Lt~cn, The com7~osite cf this inr~ntion exhibits s-~e~al ber.e~icial properties . Fcr 2xamp' e, in ~he ~or~l7~o~ite that portion c~ ~he po1~e~ in the g~La phc ~e crystall ne form is resis~ant to ccnvers_cr~ t~ the 20 a_pha crvs~alline form. Mcreo~rer, ~ n ~hcse i~.stanc~s ~r~ere the qa3m prase polymer ~ s a polya~de cuch~ as ~ly~epcllon-caprolactarn) (ny7On o) r the CC~pO;7 ti~r~ -exhi~its improved ri~idl t~i and ~r/ate~ reslst~c~
s~7rengt~ D63~ and ~S~M 37g0), while 25 _vbstanti lly retainin~ other propertie3 s~lc~h as toughness ~:ASTM D256), surfacf~ glos3 (ASIM ~523~ ¦and a~rasion resistar~c~ (AST~ ~1044).
DE:SC~IPTION OF T~ P~:FERRE;D ~I~E~T~ !
The cor~posi~e o~ this i~erLticn i ncludes t~c, 30 essential coD~ponents . One esse~tial compa~e7~t is ' a poLy~ner n~atrix comprisinc; a gzr~ p:~ase ~slyamide ~ her2 at lea t about 1 ~1~re ght ?e~cer~.~ or said polyamide ji5 ir.
the g~a cry~talli~le phase. As u~ed her~in a ~g l a AJ~E~lDED Sl I~ET

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phasa ~c' yaI~lide" is a se.rni-cr ,fst-lline po' ya~ni de ~3 , :!

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~ W094/11430 21 ~ 8 ~ 1 3 PCT/US93/10819 .~ . I

~ 3 -,~ capable of forming two or more crystalline phases, and ~ comprising at least one of the less stable crystalline ~-',,3j phases as determined by x-ray diffraction (XRD), i,~ infrared spectro~copy (IR), differential scanning calorimetry ~(DSC)~ and nucl~ar magnetic resonance (NM~), as described in N.5. Murthy and H. Minor, ~QlYmer ,pp. 996-1002 (l990). For example, nylon 6 is a gamma phase polyamide capable of forming two crystalline forms. The nylon S chain has a directionality so that adjacent chain segments in a crystalline phase can either be parallel or anti-par~lle}. In the more stab}e alpha pha~e, hydrogen bonds for~ between anti-parallel chanin segments, while in the les~ ~tabl~ gamma phase, hydrogen ~ond~ form between p~rall~l se~ments. ~y contrast, nylon 6,6 i8 not a ga~ma pha~ polymer and is capable of forming a ~ingle cystalline pha~e 3ince its chain has no directionality.
Polya~ides for use in th~ process of thia invention m~y vary wid~ly, the only raquirem~nt i~ tha~ they are capa~l~ of gamm~ phase crys~allinity and arQ preferably m~lt proc~sibl~. As used hersin, a "polya~iden is a ; subatanc~ composed of ten or more r~curring carbonamide ~onomeric un~t~ which may be th~ 9a~8 or diffQr~nto I:n ~ the pr~exr~d e~bodimentsi of the invention, the ! 2s polya~ide ~nclude~ at least thirty recurring ~ono~eric unit The upper limit to th~ nu~ker of recurring monomeric unit~ i8 not critical, provid@d that the ~elt index of ~he polymer under use conditionfi is such that Ir~;
th~ polymamide ~form~ a compo~ite ~aterial which can be 30 proce~ed into article~ of thi invention. ~or~ ~
preferab}y, th~ polya~ide include~ at least fro~ about ~--30 to ~bout lOO;recurring ~onomeri~ units. In the most preferred -~bodi~ents of thi~ invention, the number of r~curring units i~ such that the polya~ide h~ a ~elt indPx of from about O.Ol to about 12 grams per lO

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~, minutes, prererably Lrom about 0.01 tG about iO l ¦
grams~O ~inutes and more.prefera~ly rom about 0,.5 to about 10 ~ramsJ10 mir.utes as m~asured by .~M Teslt No.
"`' D-1238 2t ~ load o~ lOOQ grams at ~he px~-essi r c te~peratu-e.
~ llLustrative of usefuL ~olyamidec apa~le o~lgam~.a t, phast2 crystalli~ity ar2 those ,cr~ed fro~ he polvmer~zatior of ami~.o a~ds and cer~va_i~es t.he~eof as ~o~ example l~cta~s. Suc~ ~cl~a~. des include n~lo~
10 4, ~.ylon ~, nylcn 11, nylo~ o, nyl-n 17, nylo~ ryion 10, nylon 18 and the llke.: P~efe~_e~ g~a ph~se `~ po~yam des ar2 those ~or~ed Dy reac~i~n e,~ a~'no ac~
or de~i~ativ~s there~L such as lac~a~s. Mc~e ~Ferred ~;t ga~ma p:nase polyamides are nylo~ 11, Lnylcr 6 an~ ny~on 12, and ~ost pref~rred arè nY10LL 6 a~d r.ylor 12. INylsn is the ~ ~ a ~ha~e poly~er or choice, eapeciall~
where the nylon 6 has a ~elt incex Lrom about ~.Cl to a3c~t lC g~ams~iO m.in.utes, and pre~~r2~1y fr~-~ abou~
O.g t_ æoout 10 gra~s~LO mi."utes ~s m~aslred b~ AS~
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: ZO Test No. ~-1238 ~t a load of 1000 ~a~ a~ 23SC.' . The fraction OL ~he poiyam de ~.~'Ji-~ ~mma ~has2 ; crystallinity ~ay ~ary ~idelv. I~. ~ene~a_, ~h~ a~c_n~
~~ th~ ~olyamide _n the ga~ma phase _s at leas. a~au. 1 we~ht 3 based o~ the to~l we~ht of the pclyam~de.
~! 25 The amount of polyamiae h~vins ga~a pnase c~ystallini~y is pre~erably a~ 15~st about 1~ wei~ht ~ t 1, 1 : ; ~
mcsre, pre'er~ Ly ~ro~ ~bout 10 t3 abcSur 5C we ght.~ o~ :;
the ~oiyam~de and ~.ost pr~ferably ~rom a~ou~ 2~ t~
about 5~ weight ~ sn the ~f~re~e~tion~d basis. I~ the ~i 30 em~odiments cf choice, tne amaunt of pol~ami~es i~ the ' gam~a phase is ~rom a~out sO to about 50 weigL- ~rcent .1 bas~d on the total weight of ~he polya~ld~.

A~NOEOS~E~ I
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As a sec3~d essential L. g~ ecLi-nt, t~ C;:)rrpGs_t~ CI: ~`
this in~ren~i~n inc' ud~s dispersec p~rticles se' ec.tec frcm the grcl:~ consistin~ o lavered and fib_lilar ~.
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irorgar~i~ r~aterial~ . I,sefu~ ino~2r.~ c fibrillar ma~erials mai- va~y ~iAely. and are t~.ose havina av~ra~
'~ diameters eaual t~ or iess thar~ ~bou~ 10 mr.(' Q ~¦ ~ith a maxi~num dia~r.e~r CL~ 20 n~n~200 A), px~fer~bly fr~
:~ i abaut } 0 to ~out 10 nrr ~lOQ ~ h a m~ximum ~ te~
of 20 nm(2'00 A), r~ore pre.2rably rro~n about 1.0 ~(10~) ~ to abo~~ 5.0 7lm~0 Ai wl t~ a maxir.~.lLm ~iameter of io.o i:~, nm~ 0 Al, an~ :nost p~far, ly t rom 2bout ~ .0 ~io .
o about 2.C nr;l~ O ~ lt~ a ma.Yim~urn diaIr~et~r ^~ $ o 10 nm (50 ~! . T:~e ~ erage ler.g~h o~ us~ft~l brillar I
~na ~ria' s may ~lar~t~ ~idel~ a~d is usu~ ~ ly equal ~G I Cr less tha~. a~cut 200 nnL~2, ~0 .~) w~ t~ a maxi.~. let~gth OI abc~ut 1,00~ n(l^,030 A), pxaferaol~ ~om a^ou~¦20 il ~m(~OO ~ tG abou~ GOC nm~2, 000 A) wi~ a m.ax ~.u~ ¦
15 li~ngth ~f about 500 rm(i~ 000 .~) ~ ~ore preîe~ablv ~o.n .;~ about 30 nmt300 A! to a~u.t 200 rLrn~2,000 ~ i-h 1 ~axim~u~r. ler~gth o~ 20~ n(2000 A~ anc~ ~ost prafer~41y ~. fro~r~ æ~,o~t 40 r~m~ "GO A! .o a~u~ O, rlm(i, 000 A` ~ith a ;~ ma~'ml~ ngt~ OL ~bau_ 2Ca ~Lrn(2~ COC ~-! . I11ui~tra,.i~
'! 20 ~ useul fi~ri~ lar materlals a~ ogo:it~ and ~i~r.d ,~, cxi~
Useful 1 ayarcd r_terials are ~hcse ~ n whic~ iayers 3 }~a~e an aver~g2 t~ ~ ck~ess ~auai ~o o~ l~ss than ~aut .1 ~.5 nm~S A) w~h a max~mum thic~ness c~ 10 r~n(lûa A~, 2_ preferably f~om abo~l~ 0.5 ~m~5 ~) to ~out 2.5 ~25 A) '~ with a mLaximum th~ ck-ess ~r 7 . 5 r~n (75 A), more Fr_~~ra~ G~. ai~cu~ O.S nm~_ A) Lo _~c~ ~ 2. û .~( 2C ~) .
with a ~;Laximum thic.Ynes3 af 5. 0 ~(50 A), and mcre 3-f;~-prefer~bl~ rcm a~aut 0.7 nm~7 A1 ~o a~ou. ~,5 nm~ 25 A) 30 w~tr a ;r~aximllsr~ thil~kness of 2.5 r~(2_ A). .
Layered m2t~ials for use in this }~vention ~a ~ .
va~ wic~ely an~ includs p~rllo~l llca.es. Il~us ra~ e cf such mat~xials are smectite clay mire-als such ~s A~QF~ ET

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hectorit~, saponite, sausor~ite, A~n2gadii~ anc kenyaite; ~rmic~;liLe; and ~_~e li1.~e. ~the~ ~Asefu~
layerec~ Arnaterials incl~1de illite r~ neral~ such as j~ ledikite ar~.d ~dmixt:~res o-F 1.11.i._es with the c' ay S mAinerals named a~ove. Ctr er use~ul lay~red m,.-ter~ als, ' ~, :""
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` W094/l1430 ~1 ~ 8 9 1 3 PCT/US93/10819 ~:

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` particularly useful with anionic polymers, are the .
layered double hydroxid~s, such as Mg~13~(OH) la ~(C03) 1 7 H2Q (see ~. T~ Reich.le, J~ Catal., 9~ 985) 547), which have po3itively charged layers and exchangeable 5 anions in the interlayer spaces. Other layered materials having little or no charge on the layers may ~ be u~eful in this inve.ntion provided they can be t intercalated with swelling agent~ which expand their interlayer spacing. Such ~aterial~ include chlorides 10 such a~ ReCl3 and FeOCl, chalcogenides uch as TiS2, MoS2, and MoS3, cyanides such a~ Ni(CN) 2~ and oxides such a~ H25i2O~, Y6Ol3, HTiNbO" ~ro.sVosS2, W02V28~, cr303, ,, MoO3 (0~1) 2~ VOPO~-2H20, CaPO"C~I3-H20, PI~IA~O"-H20, ~ Ag~Mol0O33, and the lik~. Pr~ferred ~w~llabl~ layered 'i 15 mat~rial~ arQ phyllo~ilicat~ of the 2:1 type ha~ing a n~gativ~ charge on the layers ranging ~rom about 0.25 to about 0.9 charg~# per for~ula unit and a ~1~ comm~n~urate n ~ er of exchangeable cations in the '~ interlayer sp~ce~. Most pr~ferred layered materials are ~ectite clay minerals ~uch as ~ont~orillonite, nontrGnitet beid~llite, bvlkons~oite, hectorite, ~aponit~, 3auconite, magadiite; and k~nyait~.
Th~ ~ount o~ layered or ~irill~r m~terial included in th~ co~positQ ~aterial, that i~ ~ufficient to result in ~ ni~icant increa~e in the gam~a eontent of a ga~a pha~a poly~r, is a~ littl~ ~ about 5 pp~ by wQight- ,~
The ~ount of layered and ~ibrillar ~at~rial included in ~h~ ~o~po~it~ ~ateri~ y va~y widely 30 dapendiny on the intended u~e of th~ co~po~it@ ~ -provided tha~ th~ a~ount is les th~n ~bout 0.5~ by w~ight of th~ matrix. The low~r a~ount i8 not critical provided th~t the a~ount i~ suf~cient to provide the advantages o~ thi~ invention. For ~xample, the amount of such material~ may be as low a~ about 5 ppm.

F.P.~ MlE.~ 8 ~ o: "~ ~ ''t) ' l ~ t ~g 89 ~a5?9~ 6.~

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7: --:~ ~rereral~ly the alr.ou-t ~Jr layer2d ~r ibr llar ~c~erial - I
inc~ uded is eaual to or ~r~a~er th~. abou~. 1 0 ~m~ mo~e ~;
pref~ab' y equal to ~r greate~ than about 23 ppm and .. eclu~l to o~ ~e~s t:~an ab~ut O . ~ y w.ei~ht, anc n~st , ~ preferablv e~ual to cr ~e~ter tha~. ab~u_ ~ ~0 p~, ard ~`' equal to or 1 ess t~;an â~;Ol~t O . ~s by weig.~
;,i The la~ferea anc f i~ri ' lar materia;s a~3 su~stant~ all~ ~cmoger.e~o-~s- v dis~ers-d i~ he g~ tn~
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~ phase polym3r ma t-~ix. n the case o~ 1~yered .~ IO m~t~rial3, the layerSd ~at~ria` s c~s~erse~i as platelet ~a~~icles. .~s used `nerein telet .~ par~cl 3Sr~ ?a~ les ~avi~g t~o -ela l~el~ 'at ~p~osit~ f2ces w~.e~ein ;he thickness o~~N:r~^_h i~ ~h~
distance betwee~ .he races, ~hich is rel-_ voly ~all 15 ~cmpa-ed to the s'ze o~ t:n~ f2ce3. T:~e plate~t pa~tlcles dispersed in mat~ix ?cl~e~ ~ay '~v~ t:~e thichne~s o~ t~e ~n~ idual Laye-s, or small ~.u~ Les ` . less t'-.a.r. about lV,:p_ef~rably less t~ a~oat S and mor~ preferably less tha~ `a~c~lt 3 ~f ~:~e l~y~rs, ar.
20 s~ill more proferabl~J or 2 ~ye~s. ~'~e v~.~o_ di~enslcns ~r tke pl~tel~ pa~tic ~ mcy ~ra~y gre~ "
t ~n the case o_ ~rticle3 de~-v~d ~rcm clay ~ineralc, ~he particle ~ac~s zre ~o~g~ly rcund or oblonq h~v-ng a~erago d_~meters bet~2er a~o~t 1,Q~C
25 n~10,~00 ~) and aDou~ -~.C nm~0 ~i, such ~;~at th~
i aspect r2tio le~th~thickness ~a;ge~ ~om abou~ 5 t~
` ahout 1 ~cr the -~-~o~e`~ c~ '~e ~esent inven~~n, the averaqe diameter is de~ ned a~ t~.e di~ere- o~ z ~ c~rc~e having an area eqyal to t'~e surrace area ~ cn~ :
j 3a brcad surface ~ace o_ th~ p~ate~e~ s:~aped ~ticl~. i ~I The a~erag~ d~am~e~ i~ d~ter~.lned fr~m par~icl~ l `
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surface area as ~easured with. a Lei-z T~x-u~e ~r~aly-ze~
Sys~em in a fully computerized and 2ut~ma~ed ~o~e., 'n A~AEN~0 S~IEET

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E~A .~ CHI~ 0 1 : 8 ~ 94 ~ ~Z~ 5-~ `)CZ~7 1-- +q CZ ~39 '~:3~;Z944ZJ~ ZZ I O

! " 2 1 4 8 ~ ~ 3 the p~eferrecl er,oodiments o~ 'he irvent~on, the 2~,-efa~e ~, thir~ness o~ the plat~Zle_ particles is equal t~ oZr les~ Z
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,!,.( 8 than zbo~t 2 nrn ~20 A~ r~i-h -~ ma~i num thic~ ss cf ~ - I
~I' nm ( 50 ~ ) and the ~ ~er~ce di2.~ r is be~r,~fe~n 50C , ¦
`l nm(~,COG A) and 15 nrrl'100 A) with 2 r~aYi~nu~t. a~.. e~er ~f OCO nr~ l lO, OOC ~) . Mor~ pr- araDlt,r, the a~eras~
J 5 t}~ickness is e~ual t~ or i~ss ab~ut 1. 5 nm ( lS ~ J ;~it.~ 2 m2ximu~ ~hickness o~ 2~5 ~m~25 A) ~?~d th~ a~e~agei `~ diarneter is fr~m abou~_ 200 n~ 2, 0~ C A? te c.~out 2~
nrn~2ûO .~) w~th a ~xi~m diaxe~r ~ 500 rIrn(5,~,0'~).
~ost prefera~ ,h~ ~e-~ge hi~ r ess ~ :~; ro~ -~o~ t lC G . 5 nm ~ S ~) to ~bou. 1 . S ~ h ~ mt2~
~hick~ess of 2 . 5 n~;L '25 A? er~ t~.e ~ Qrac~ dia~r~e er ~ s ~, from about 2CO ~.m~2~0~ A) tv a~Gut 20 nm("OGA) ~ h maxi~um di~aete~ o~ _CO ~.n(S, ~OC ~ ! . I
The a~7eraqe interp2~-icle s~acir~.g ~et~2en 1 a~ers o lS the 1 a~erecl ~ateric ls and ~i~r_l= o~ _r.e fibri' lar .j ~a~eri~ls may v~ry widel~r depsn~ ~g on ~he conc~r.t~ation o~ ~a~erials . In g~n~r~l, t~ e h- ghe~ ~he con~ent~at ~r. a~ ~a_er 1 al ~ the ~o' v~ rnc tr~ x t~e ~mal l er ~he inter~a~ spacin~r, a~r~c~ con~erse 1~ e 20 lowe~ t~e concent~atio- ~ rna~ 9rial, tr~e la-~r t~e inte-par~ spacl~. Ir. g~n~ral, interpa~~ cl~
spacirg i~ equal to o~ ~r~at:~r t:ra.r a~out 1 . 5 n~ ( 15 A~
-O 3bout 40, 000 nm.~O ~ r~r~ a ~n,~r~a-t~c_~ ~
s~zcl~.g is p~efer3bly ecua1 to or g~cater than 2~ut ~ I
~5 rm~30 ~) to abou~ 20, ~00 rm~2~ rons), mor~ ~ ¦
3 pr~ferably eaual to cr-ate- ~ n --bout 5 nrn ~ 50 A) to u~ 5, C~0 ~L~5 ~aicr~n), ~nà ~.~st 7~-~ ~sr~D ~ e~ t~
or greater tha~ ab~ut 10 nm( 1~0 i) to about 1, ~05 i~
icrcn).
3~ ~.s used herein "urifoE~.ly c- spers~d" ~ s def~ r~ed as -~1 ~ a degree o~ dispers~ o~ c~ t~.e particles ;~a~ins a 1,~ starldard de~riation in -~a~tislQ d~rai~y, down t~ a . 3 J, sa~npling ~ Gf ~ l3 ~LS de!iaxm~.ed ~ ILss-or f~ S~IEET
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electron ~icroscopv.iLhe degree or dispersi~n 1 sl ~ ~
pre~era~ly less tha~ abou' 50~ G' ~ he mean, m~,re ' , .
pre,~era~ly less than al~out 30% or the mear., ar~d ~ost pre~er2~1y less t~n ahout 20~ o~ the mea~.
iThe composite ma~erial of this irlvention ~v, incl1~de ~arious optic~nal cornpo~.enrs which are adi ~ VeS
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, ~ ` WO 94/11430 2 1 ~ 8 ~ 1 3 PCI`/US93/10819 _ g _ _ ~
commonly employe~ with polyamides. Such optional omponent~: include nucleating agents, f illers, plasticizer~:, impact modif lers, chain extenders, plasticizers, colorant3, uv stabilizers, thermal 5 stabilizers, mold relea ie lubricant~, antista~ic agent~, pigment~3, f ire retardants, and the 1 ike . These c~ptional component~; and appropriate aD~ounts are well known to thos~ of skill in the art, accordingly, only the pref erred optional component~ will be described herein in detail.
The composite of this inventi~n carl be for~d by any suitable procei~ for forming the composite o~ this invention. For example, the composite of this inv~ntion can b~ conveniently prepared by in reactor blending proaei~ses 3~ t21e typ~ de~¢ribed in U. S.
Patent No~. 4, 739, 007 and 5, 810, 734 in which ~ ~onoDoer pr~scur~or o~ th~ polya~id~ ~uch a~ ~ lacta~ i~
polymerized using so~e suitabl~3 tQchniqueis a~ f or exampl~, condens~tion poly~erization, anionic poly3~leri2ation, hydrol~ic poly~erization and the li~ce, in the pr~anc~ o~ a ~wollen and compatibilized p~rticulat~ m~terial. For eacampl~, in on~ ~uch procedurQ ~ontmorillonite intercalated with protonate~
11~ ino~dscarloi:: ac:id i~ combine~ with caprolactam ~nd a~inoc2~proic acid, in a ratio of 4 ~ 9S l by w~ightO
Th~ D~ixtur~ tirr~d at 2S5 - C f~r tk~ree h Ur3 in an inert ~ao~pher~ ~ during whicbL ti~na th~ caprolact~ and a~aino aci~ rQa~:t ~ tantially to yi~ld ~ polyamide. ~ .
P}atQlet particle~ compri~ing on~ or a few l~yer~ of $.
l~ 30 ~sontmorillonit~ ara di ps~r~ed through th~ polya3~ide.
.i Th~ co~posi1:e of thi~ inv~ntiorl i~ pr~ferably prepzred via a ~elt blending proc~s~ in which one or laore ga~ma ~, phase polyaDIide~ ~nd one or mor~ compatibili2ed particulate ~aterials are sheared in th~ ~elt at a ~`.: 35 te~nperature 2qual to or greater than the D~elting point :
`
;

WO 94/11430 PCl`/US93/1081g; ~ ``
21~18913 ~`
` : ; !
c - lo`- L
~i !
of at least one polyamide in the mixture until th~ ', ~, particulate materials exfoliate and disperse to th~ ,~
j~ desired extent. For example, a suitable polyamide such ` a~ pellets of nylon 6 and the desired amount of a !; 5 particulate matexial such as montmorillionite is heated ~. to a temperature sufficient to form a polyamide melt ,;. which is then sheared by some suitable means. In the ', preferred embodiment~ of the invention, mechanical ~hearing methods are employed such as by extruders, injection moldinq machineq, Banbury~ type mixers, ~ 8rabender~ typa mixeri and the lik~. In the ~ore ,3 pref~rred embodi~ents of the inv~ntion, ~hearing is achieved by introducing the poly~er ~elt a~ one end of an extruder (3~ngle or dou~le screw) and rec~iving the . , ~- 15 sh~ared polymer at the other en~ of the extruder. The . te~perature o~ the po}ym~r melt, re~idence time of the ~elt in thR extrud~r an~ th~ de~ign of the extruder (singla ~cr~w, twin scr~w, nu~b~r o~ f}ight~ per unit length, chann~l ~epth, flight clearance, ~ixing zone 2~ etc.) ar~ s~ver~l variabl~ which control the amount of sh~ar to be applied~
The malt of the swellable int~rcal~ted material and th~ polya~id~ ubjected to ~h~ar mixing until the ~1~ d~s~ired a~ount of mat~rial exfoliates to the d~ssired ~ 25 ~xt~,nt. In g-n~r~l, at l~a8t a~o,ut 80~ by weight, j pr~@r~bly at 1~ about 85~ by weight, more pr~sf~r~bly a~ 1~a~t a~out 90~ by w~ig~t and ~ost ii pr~ferably a~ t abc,ut 95~ by weight o~ th~ ~aterial d~la~in~t~ to form f:ibrils or platel@t p~rticl~
30 ~u~tan~ially ho~cgensou~ly di~p~r~d in the polymer i-.
matrix.
In either the in-reactor blending proc~ or the ~ ,alt blending proce,ss, u~eful layered ~nd fibrill~r ;.~ înorganic material~ are preferably tho~e which hav~e, ~. 35 been: swollen~and intercalat~ed between l~yers or fibrils ~. .

~ WO94/]1430 2 1 ~ 8 ~ ~ 3 PCT/~S93/10819 with an organophilic intercalant which weaken the interlayer cohesive energy between layers and fibrils by sw~lling th2 int2rlayer or interfibril distanca~.
i In the preferred embo~iments of the invention, the ~ 5 intercalant or intercalants increas~ the compatibility j and bonding of the layers or fibrils with the polyamide ~ melt by having attractive interac~ions with both the J surfaces of the ~ibril~ or lay~rs and the polyamide.
¦ Intercalants which function to sw~ nterlayer or lO interfi~ril distances are hereinafter referred to as "~welling agents", intercalants which function to increase thQ co~patibility and ~onding of the layers or fibril~ with th~ polyamide melt ara hereinafter . re~erred to a~ ~co~patibilizir~ agent~ and 15 intercalant~ which function a~ ~welling ~gent~ a~d co~patibilizing ~gent~ are hereina~ter referred to as ~sw~lling/co~patibilizing agent~
Swellabl~ ~atsrials are material~ comprising planar lay~r~ arrayed in ~ coh~rent, coplanar structure or 20 fibril~, whera the bonding within th~ layers or ¦ fibril~ stronger than the bondin~ between the layers or P~bril~ ~uch that ~he ~r~teri~ xhibit incr~a~d int~rlay~r or interfibril ~p~cing in their i intQrcalation o~pounds. Th~ neutral or ionic 'I 25 ~O1QCU1~R~ called Nintercal~nt~ ay be introduc~d into th~ interlay~r or interfibril ~p~c~s by ~ither 1 in~ertion, in th~ ca~ o~ neutral ~olecules, or ion 11 ~xchang~, in th~ ca~e o~ ions~ The intercal~nts ~ay be introduced in thQ for~ o~ a solid, liquid, g~, or '-: 30 ~olute. Th~ intercalant~ ~ay b~ intr~duced into the ~pac~ b~tw~n ~vary layer or ~ibril, ~arly ~V~Ey layer or fibril, or a large fraction of the lay~r~ or fibril~ o~ thQ ~aterial uch that tho re~ulting pa~ticl~ co~pri less than about lO layer~ in 35 thic~ne~s or fibrils in dia~eter. The particle~ are Y U~ lk~ 4 _, 7 ~ 1 ~ +~9 8(~ 4~
~,""~
" - 21 ~ 8 ~
.

- 17 _ ___ i :-h~ pr~feri ~' y less ' han 2~:)0'~t ~3 lay~rs i n thickr~e~s or~ .
about 8 ~i~rils in di.~met~r, ~or~ _re ~rably less. th~
about 5 layers ir t~icl;ness or a~cl_t S ,-i~rils in.
i d' a.neter, and ~os~ pre~era~ly, abc~ 1 cr 2 layerls irl :
5 thickness or a}~cu_ ror or t~o ~i~ri~ s in diarr~2~er~.
S~e' lable layered or ~ l mte~ al i~, sucr ~s t~e pre~e~re~ smectite ~lay rn~teri.~ls, qer~.~ra~lv r_qu~e jJ$ t ~at~ent by ~r.e or r~.~r~ ercalcnts 'CG pr~-ide ~`n_ raqulred _nterlay~r G_ inrè~_lbri ' sWel 1 l nC ar.~o~
LO polymer compa~ ty. The r~s~:l ting i;~_~rla~e~ c_ ~, fibril spaclnc ~ s cri tlral to ~h~ parror;~ian-~ c~ t:re i~ ca~ted layer~d ~r~ate~iaL i- the practi~s~ ~~ th s invention. As used herei~} the "~ r-laver cr intarfi`D~il spaci~g" r2fars to t~e ci~tanc~ e_n ~a li faces o~ the layers or t~.e di~ a~ce betwe~n fibri~ as they are asse~ led in the i~t~-cal~t~d ~atar al ~r~r~
an~ dela~inati~n ~Gr exf~liarion) t~kes ~la~e. The preferr2d clay m~terials genera~ .clude i~_~rl~ r ~r exchan~eable c2t~cn~ such G~ ~at, C~", K-, M~ nd ~0 t~e like. In this st-~e, these ~at3r 1- c~ not del~mir~ate t n h~s ~ polymer ~elt3 ~2a_~1ess c~~ mixi~, ~1: because thei~ i~t~rla~e~ or in~arf ~r~' s~acir~s ~re `~ usu~llv equal .~ or 1~s3 thar abcut O . ~ n~
~ nsequen~ly the.i~terla~er or in~e~ibrll ~chesi~Je '~ 25 Pner~y is rela~i~ely.s~rong. Mo~o~ler, t;~e ~etal cations do not aid co~pati~ y '~et~ee~. la-~Jer3 a~d rils a~d the po ~ r ~elt. In h~ pr~ r embadiments~ the~e layered ~a~er~ ar~ lntercalate~
~i¦ by swelli~g agen~ts of suf~Icient si~e to L-C-e~S~
inte~layer or i~terri~ril distances to ~.e d~cir~
ex~ent. In generaL, ~h~ interla~e- or i-t~rt_kr~l .~ dlstance should be a~ least about ~.4 ~x~(4 A), asi determlned by x-~y di~ra-ti~n, in o~d3r tc f~ci~itat~

.
AMENDED SHE'T
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CIIt~ V I ~ J~I : 0: ~7 : 20 1 ~ V'~ 1- +~3 89 ~3~9'~

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2148~1~ 3 1 1 't ' _ 1 2~
de`~ 3~inatiorl CL th~ ia~e~d r:lat~rial or fibril m~er ~1 1 ;t at the nanoscale. In the: pre~erred em~odirQents o~f Lr.e ¦
in~erlticn, the: , ~y , :

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.. j '.~t ',` t .,,~ ' .,' r~ C.`HE\I ()l : 8~ - ''01 ~ii.............. -S ~o~ t lI.i-~ 1-;`: 21~8~13 i! _ } 3 _ , ., ) `,j interl~yer or interfibril dis~ance is ~t least aacu~
O . 8 nm ' 8 A) and ~r.ore pre 'e~ed int~rla~Jer ~e-~jl inte~_ik~il dis~a~ces are at l~s~ about .5 nm(l5 A) .
I~ these pre-erred e~n~bodimer~t3, t:~e swell i ~Lg agent ~ s ~' 5 a r~e~tral organic mo ~ ecul~ ~r ar ioni~ s~e-ies ~,~hic:~L s ,, c~p~bl e or~ excha~}ging wi~n t~.e ir~terla~er ~ :
interfibril cat~ons such as Li, I~Ta~, Y~ , a~d Ca-. anc1 is of suf~icien- siz~ t;) provi~e the re~rlir^d lr.terL~yer or int~rfib~il sp3cing. S~lch ionic ~i~e~l~s 10 include ~çtt Al-3, Cu~, Fe~, NH;~ RlR~ R3~, ~JRI~i.2i~i.3~, whe~ ~he Rl, R ,R3 and R~ ~re ~he s~..e ~r ~- f--e~e~-~t ancl are orgcn.~ c s~l~stitl.~nts, ~ he li~
In c~der to further tac~ litat3 de~ aticn c~
layeted or ~i~ri` materials is~to pla~ele~ ~a-t~ s or 1~ fibri!s, and pre~ent -eaggragation oL. the ?a~ t_cles, these layers and ri~rils ar~ ~r2 er~b7 y ~oi;,~Ler-,i co~n~atible. In ca~es where t~e po!~ner rnel- ' s r.c ;~ co.~npati~le with 'cha l~yers, tne s~e labl- l~ye~e~
matcrial or rir~ril m~terial is i~.~2rca' - ted ~y ~¦ , 20 compat ~ilizinq agen'~ which consist of a por~iorL ~ ich bonc:s to the sur 'ac~ cf t'r 2 la {ers and ~noth~r ?~r- o~
:! wh~ ch bcnds or intcracts f3vcra~ y with t'r.e ~cl~e~.
., In so~ne in.stanc2s, i ~ t~rcalants ~e used whi_h a re sw~ll in~;fcosLpatibili7 ng aq2~s w;~ ch --~'''Ji:~ bo~h t-.6 ~5 swellin~ ~unctlon and the c~mpatikili22tion fu~.~tLcn~
. . Su~h agents pref~ra~ly t ~cluce a ~o ~ty cr ;noie~ies ~! ' whic:rl in.~2~ac~ wi~h ~ s~_ac2 ~~ he layer~
~:~ displacing, tQtal ly or ir. parL, the or~g_n~' ~etal i^n~
~,'!; and which bonds to the surl'ace of the laye~s, 30 incl~des a m~iety or ~noieti es whose c~'~.e.ci~t~ t r~er~ es are suf~iclen~ly Ciml lar o ~ha~ cr the pol~,~cer t~at the ~ur~ace of the pLa~elets is m~de m~re ce~p~t ~ e ith ~h~ polymer, ~.ere~y e~har.cir.g the hcm~er~eity ~ f ', ^;~ N[~)ED SHEET

... .. , .. ... , .. ... . . . ~ .... ... . ... . ... ...

~?~'.L' ~ L~ +~9 ~J ";3g5~.. ,fi~i ~
"`.'``` 21~8913 1, ~'''' ''' i ~
~ 3 A - ~ I
the d~ sp~rsiori in th~ polyr~Ler~ c mat~ix. .~s us~c herei~ J
"~ompatible" rere~s to the extent -o which the ~dl~ner . ' '.
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~ AMENDED SHEET
.~

21~8~13 _ 14 _ I
, matrix and the su~ace c^atirg cr. the platelet particles (the com~a 1bilizi~g age-~t) hat7e a fa~orable i nter_c~ion which p~omotes t.~P ~ nterm~ngli~g of ~,he ~ :
rn~trix poly~Elq~. and ~he surr~ce 1 ai~-r ~ n the in~ce~2has2 5 regi^r. C~mpat~bilLty derlves fr3m cr.e or more af ~he follow~ng ~ ri~: si~ilar c~hesive e~ergy densi l es rGr ~he pol~ner a~r~d t~e ceriva_i~C~ ~latelets, si~t.i' ~r or _omplimen~a~y capaci~ es fe,~ dis~ersiv~, poL~ r hyd~oge~ ~ondin~ int~ract~ons, o~ c.:~e~ Sp2C f~-0 _nt2ractions, SUC~ 25 acl~2se ~r _ewis-3cid~L~w_s-ase lr~teractio~n~. Cor.~ati'3il iza~ion wiL1 lead ~ an i nF~o~red dispe~sicn o- the plat~ _ _ pcr i~les in th_ ma~~ix and ar~. ~p~o-~-~d percenta~e o_ delaminatqc~.
~latelet~ wlth a t~ict.~ness cf Less than 5 nrtL~SO A~ .
The na ur.~ o_ the swellir.gJc~lr.pati~ilizing ~e~t, 3~el l~ ng agenr/cornpatiki~ i7ing a~e~ Will ~ ry ~ el~i dependi~g o" the pa~,icu' ar polvmer and the p~rticul~
layered materi 1. Fcr ex2mple, ~.ere the swellai~lG
lay2rec ~at~riaL is ~ pryllosiii~a ~ ~s 'or ex~mp~e z 20 sme~tits clay a~d the pcl~ m de ls ^ ~ y ~ lacta~n) su~h as ~cl~r;ca~rolac~a~a?, ~well ing~c~ tihilizi-g ag~nts are pra~erably ~ ~e~lcnLc ard ~ ~nic sur~act~-L ~ype moL-c~l es, and mcst p~îer~bly n_utr~l c~~ar c mc~lecules cr zwitt~ioric and cati~nic suxfactant tyFe ~5 m~olecules. Use, ul neut~al. organic ~r.olecules include polar ~nolecule:s such as a~nid~s, ~ste~s, lact~ms, . '.
nit~il ' es ure~s, ca~bGna,2s, _hcs~h2~s, ~c _s~hor~a -s, sulfates, sulforLates, nitr~ compcunds, a~d t~e li)~
~ Preferred ;~eu~raLs ~r~an~ c~s a! 2 ~onolQ~s or oli~or~ers o 3~ t~.e na;rix l~olyme~. ~;seful ca,.ior.ic surf~crants ' incll:de cnium spec:ies such as zm~Lor.~ ri~y, secardary, tertiary, and quate~nar~ ), phcspr.an~ r ~uL~oniu~ d~rlvatit7es of aliphatic, a_omztt c or '.

Al`hE~!DED SHEET

21, _. . .

0~: El 'A ~ c~E~l l : 8 ~ a~ 3~9~ 6-~

-:.``. 21483.~ 3 ' .
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arylalip'~atic am nes phospni~es ar~d cul~ides. ~ ~

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~.~ ' `` 2148913 , ~

~, , s Illust~a_ive o~ suc~r. ~aterials a~e o~;oni~m c~mpouF,ld3 o ;; t!2e fcrm~la ~

X -- R~ '.
where X~ is ~n ammonium, sùlfcnium or p~osphonium 5 radical such ~s -NH3~, -N (~ ) 3l~ -N (CH~) ~ (CEI~CH3) ~, I
S (C~3) 2', -~P (C:~'3~ 1, pyridirium~ a~d t'~.e like and ?.~, s an crganic ~dlcal as far example s~b~ti.~_.ed or unsu~stit~1~ed all~.yl, cyclc:alk~nyl, cycloa' ~yl, ~r~l, or ;~ alkyl~ryl, e' ther ~s~ti~5ut~à c_ su~stituted w, '~h ^ G a~i~a~ al}cylamir.G, dial~VlaminG, nitrG~ a7 'do, al}~nyl, . .
alkoxy, cycloalk~, cycloalke~yl, ~ anoyl, alkyl~l~ o, ~iXyl, aryloxy, ar~-~lalkyla~- nc, ai'xy ~ ~Lir.o, a~yla~ ~o, d al :Yylamino~ diaryla}nLnc, a~y1t al~ylsul~ rl~
. aryloxy, all;vlsul~inyl, alkylsu~ onyl, aryl tl~lo, ' :
15 arylsulI'invl, alkox~carbon~l, a~yl~ulf~nyl, and alkyLsi~ ane.
Iliust_at~ ~e c: f useru~ a?s zre hyd~~gen, -l'cyl, such as ~.ethyl, et~yl, oc~yl, noryl, te~t~ uryl, N
~eopentyl, iscprcpyl, ~ec~ u~yl, doclecyl and the l,ike;
20 alkenyl s~ch cs 1-propenyl, 1-bu~ yl, 1-pe~t=~LyL, l-hexenyl, 1-heptany~ octan~1 and the l~ ke; al~ox~l~
such as pr~poxy, ~utoxy, me~hoxy, isopropcxv, p~n~oxy, nanoxy, e-hy~oxy, octoxy, and the ~ ike; cyclo~ cn~fii : such as cyclohexenyl, cyclopentenyl and the like;
5 alkanoyLaikyl ;,uch as 's~ut2r.c~1 octad~yl, pe-.~ar~o~1 -.cnac~cyl, cc~ncyl pent~decy~ hano~l ur.d ~ropanorl hexadecyl and the l~ ke; arnino;
a t kyl aminoal kyl, s uch a s i '-~`:

AI~ENO~D SHEET
;~ ~
~__.

~V~ rr:! ~t~ \,U~ J~ o--?~ ol '~5:~ "0`~1, +~'J ~;19 ');i39~1l4~5-t~''0 :.. , j 1 `` 2~48913 _16_ I !
methylatlino octader~yl, etnylamino p~ntadecyl, buty'~æ~no nona~ecyl and t:~e li~:~; dialkyla~inoal.kyl, suc~ ~s di~ethyla.~ino oct2decyl, ~.~thyle~hylamin~
r.cnadecyl ant~ th~ likei aryl~ alkyl su~ s 5 phenyl~ o octadec~l, ~ p-~ethYlphenylaminc n?ra~e~yl 5r~d the ii~e;
r,, d~Grylaminoalk~l, such a~ dipheny:~inQ p~ntadec~l, !' p-ni~rG~henyl-p'-methylphenyla~i-o c~tadecyl and t'~e like; alk~ylary`~ ~inoalkyl, suc:h as 10 2-henyl-4-methylæ~in~ pentadec~ Q the lik~, alkyls~_lr~nyi, alkyls~or~ll, alk~_rh~ arytthio~
arylsul~'i~yl, and ~r~lsul~onyl suc'~ as buty'~h~o , oct~decyl, necpentylthio pent~aec~,~l, methyls-~lrinyl nonadecyl, ~enzyls~lf~ny~ pentadecyl, ~henylsulri~y' 15 octadecyl, propyl~:~ ooctaaecyl, octylthi~ pe~_a~e:cyl, ~onylsul~cnt!l nonadecyl, octylsu`~r~nyl hexadec~
~thvL~hio ncncaecyl, isopropylthi~ ~ctadecyl, pher.ylsu~fonyl ~entadecyl" ~ethy'suL~yl nonadecy , nonylthiG p~n~a~ecyl, phenyl~ c o~t~decyl, ethyltnio 2G ncnadec~Il, ben~ylthio ~n~ecyl, ph~e~hylthio p~e-,nt~decyl, sec-kutyl~hio;octadecvl, na~h~hylt:~.io undecyl ar.d ~he li~2; ~lkox~ca~~ylal~rl s_ch as me~hoxyca~bonyl, etho~ycarbanvl, h~toY.yca-bonyl and ~.a like, cyclaalkyl sucn as cyclohexyl, cyclopentvl,~
25 cyclo-oc~yl, cycToheFty~ and t'~.e like, al~oxy~lkyh su-h as ~ethcxy-methyL, ~t~.~xy~e~h~fl, ~utoxymethy~
prc~axy~ hy!, per.to~ybut~l and ~he ~ ; 2~yl ~xi'2ix~l and a~yloxyaryl suc~ as phenox~,~kenyl, p~enoxy~6t~yl ~-anà the like; aryl~rya~ky~ such 2S phenox~decyl, 30 phe~oxy~ctyl and th~ l~ke, arylal'<yl s-~ch as ~enz~
pr.~nethyl, 8-phe~yloc~yl, 13-phen.~ldecyl ard th~ ~ ke;
alkylaryl such as 3-dec~ henyl, 4-cctylphen~ , 4, nonylphenyl and the ltke; and poly~ropylene gly~oL anc "i ' AME~'~E~ SHEET

~t~ '3 ~ G.~ )() > 1 - ~ J );39'~ . h ) 1 ~
s ~; 2 1 ~ 8 ~ 1 3 : ; i !
_ 16A
polyet~.y~le~e glycol ~erminated witn substl tusnls ~sucn a~ e~h-~yl, propyl, `c:utyl, phenyl, b~n~;l, to ~ styryl, p-phenylmethyl c~'' oride~ c~tyl, dodecyl, " ~ct~de~:yl , ~eth~xy-~thy ~, ,~

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AMEN~ SHEEl ~ ,.
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~J.`. L~ U~ : U:"'J: "()~ 9 a~ 99q1~ "'' .-.
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`` 2148913 l ~1 - !
~r.oieries o~ ths ~or~La -C3~ococH~ H oCOOh.~ -C7H~CaO~, ~J -C.~ CCOU., -^gH~gC30~ -C iH22COGH, -CI~H26rOCH, -Clj.',cCOO~
;i a~.d -'-~7H~COCH arld -C~=C (C~;3) COOC~ C~ nd th~ i}ce.
,j '~ Such ~noni~, sulforiium 2~d phc~hon~ um L-ad_-2l s are wel 1 kr.own in th~ art and ca~ be derived from h~
-or-es-oGnding 2m` n~s, phocphines, and sul fides .
U~ef~ll s~el}ing~c3rQpa~ibil ~ ~g 5sents also lnc~. ud~
3 neutr_l compoun.ds. r~or e~-m~le use~ul swel~l ing~ccrn~2tib~ a~ents _~.~lude n~u~ral ami~e, 10 pn~sph ne, and su' ~ide ror~Ls cf t:te a~o~ re~^r~r.cec OXOIl~ ur.r. c~Jn-.pou~.As whic:rl hydr~gen r~nd t~ ~he ` ~e~s.
In this c~se, the origina metal c2t_0ns are not r~laced .
ar~ot;~ar c ~ss or s~le li~g/cor~2tib 1~zin~ ~g~nts 15 ra ~hos~ whic:~ or~ co~a'en.; boncs ~o the l~y2rs.
IllustrGt~e cf such asents use ~l in thP p~^c~ice of t.~is i~vention ar~ sil~ne coupling a~e~ ~ of the . fo.~ula:
~ 9)3R
: 2!~ ~n2re ~ is th_ s~me o- difre~ at ea_h occurr~.~ce and _s ~ yi, ~!koxy c~ ~x~-3ilan~ ~rov~ded at le~s~ one i3 al~ox~, and ~a is s~ ct~d _rc~ the ~3U~ c3.sis_i~g cf organic ~._dicals ~hich.ara cs~p~tib 2 ~ _h~
Fol~er f~.in~ the ~omFosite; ex-~ 2S 0~ SUC~ agen~s 25 i~clude alkoxysiLane compounds a~ ror exa,~ple cctadecyltr~e~hoxysiLane:, gamma-~minopropyl-` 1 , : , t~i~.hoxysi i~-L~ g~mz- ~i~oF~cpy7tri~ Gx~siian~, ga~-a~nopropylphen~ldimethoxysil~ne, g~mma-glyciaoxyp~p~l tripropox.ysilane, 3,3-~C epcx-lcyclohexyl6thyl trime~hoxysila~e, ga~a-p~o~iora~ida trethoxysilane, N-trime~hoxysilylp~cpyl-N~beta-a~i~ethyL; am~ne, t~imet:~oxysilylundec~ he, ;:'1 ! :
' trimethoxy silyl-2-chlor~methylp~.enylethane, . .
~f~A I~lnsD SHEET
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~'?~ c~ 8~ 5.~ +~13 8~ ~a~J9~f~;> ~ a 1 `
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~ `` ^` 21~8~1 ~ r~ ~
, i ," . . I
t 7 ~ -tri~.e~hoxysil yl-ethyl~henyls~lforL~ri-2ide, N-tri~nethoxysilyl?ropyl-~,~,N-t~ im~thyla~monium chl~ri~e, - t '~iner~ox~s~ lylpropyll -N-meth~ J, N-ciallylam~oni~m -~ chl~e, ~rlL~e,~hoxysylilprcpylci;lr.~ ate, 3-~3 .
'' 1.

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A vlENDED SH~ET

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o~; El','~ iC~ 01 : 8~ '3~ '9 : ~()1 4 .~ u ~ 3 8~ 3'S') ~ 4 2:1~8~13 , ~``

1 ~erca~cpro~yL tri~erhoxys~ane, 3-isocyanatcpropy'- 1 triethoxysila3e, ~n~ t~ liX~. ~ r ~ In o~her ins,ances, _t is c~r.ven-ent to use a ~.
!,j, co~patib~l~ 77n~ ase~ tha~ 's dirf~r~rlt ~r~ tr.e, S swelling '7gent. '~ exam~le, ai`.~ la~.onium ca~ions ~.ay be used to replacQ the ~.e~a~ cat_o~J of a s~e~- t2 m~neral, and be p3rtlally repiac_d, i~ ~urn, 7y silane coupling a~e~t. I~ rhis -ase, ~he alkvla!~moni~
catio~ func~ions a~ a ~e-.e~al clr~3~ swel~ir~ a7e~7 ~C ~hile t:^e silan~i can .un~t_cr ~-, a c-~a~îbili7 ~g a~e~.t t:!at is hi5hl~y s~eciric to a selec_ed pcl~er , sy~tem.
1~ ~hs pre~r~d e.~b~_~en~s 5- ~hs i~var.ti^~., the swellins a~e~t, c~mpati~ ing agen~ a~dlor 1~ swellinq~co~c~tl~iliz~n~ agen.t wll irc~ude 2 mci~ry wh~c~ bonds to the s~r~ac~ c, t~.e ' _~rcd ~a~2~i~1 a~
will not be react~-e w-th ~~e p~ J~er. P-ef~r_b~y the.
agent wili ~lso i~lude a ~.oiety which dees n~ ~cnc ~ith t:e layered mat ri-~l and ~ni~h is _ompa i~le ~i,h t:~,e cly~er. -n tke pref~r_ed e~ ~C~7~rlts oC ~ S
. i~ e~ n, ~weili~glc~m~â'_ i~iz~ ag6nts are empl~ye~, espe~i~lly cni~1~ age. s and .i' an~ a~en;s.
In ~he pre~er~e~ em~c~i~ents o the in~ rtion lipop~ c sweLl'n~ ~-nd ~ompatik li~ing ~ents are ~5 ~lse~. Such agents will ~erer~bl~J incl~de a li~op~ilic S
~o~ticn as for exa~pl~ a long c:~ai- a~ y', a'.~enyi o~
.i clky'aryl grcup (~r~2~ y 0~ ~r_ t-ar a~c~_~ 9 aliphatic carbor~at~ms!. aUCn ~se~s a~e w~ wn i.
`.! ~he art and incLude silan~i compo~nds and the arlm~.GniurQ, . -.. . ~0 ~ul for~ um and phcs~honiu~n :der~ Jes ~f oc~adecylami~e~ ~ic~a~ecylphosphire, ~r~6;hyl dodecyl sulfid~, octadecylsul-ide, cimathtilc~dodec~-l a~ire, ':^ ' ' ', .!
Ar~ E~) SHEET

;:^ W094/11430 PCT/US93110819 i~`-2148~13 .

I octadecylamine, dioctylphosphine, methylocladecylamine, dioclysulfide, decylsulfide and the like.
The amount of swelling age~t/compatibilizing agent ~ and swelling~compatibilizing agents intercalated into 3 ~ swellable material5 ugeful in thi~ inYention may vary substantially provided that the ~mount i8 ~ffective to swell and, preferably to compatibilize ~he layers or fibrils of the intercalated material to th~ extent required ~o provide the decired ~ub~antially uniform 10 dispersion. In the preferred embodiments of the invention where ~welling/co~patibilizing ~gent~ are employed~ a~ounts o~ agents employed will preferably range from about lO mmol~/lOO g of material to about lOOO ~o}e/lOO g of ~aterial. More preferred amounts ar~ fro~ about 20 m~ole/lOO g to about 200 mmole/lOO g.
In the casa o~ th~ preferred ~ectits lay ~inerals, the more pref~rred amounts ara fro~ a~out 80 ~mole/lOO
g to about 120 m~ole/lOO g o~ layered ~ateria~.
Swell~bl~ and poly~er;-compatible intercalated . 20 msterial can ~8 ~or~ed by any ~Qth ~. Preferably ~uch m~terial~ ar~ foroed by int~rcalation o~ ~uitable agent or ~g~nts ir~ in~erl~yer or int~rf ibril 3pace~ of . t:h~ swellabl~ ~aterial by zlny ~ui~abl~ laethod. The ~w~lling/co~patibilizing agent~ are introduced into the int~rl~yer or int~rfib~il spac~ of ths swellable t~rial b~ any ~uitabl~ ~th~d a~, for ex~mpl~, by either in~ertion of neutral ~ol~cul~ or by ion exchangQ with ionic fflol~cul~ u9ing conventional proc~dur~8. In ~r~io~ of neutral ~ol~cul~s ~ay be .-i 30 performed by ~Xpo8~g fin@ly divid~d ~aterial to .:! : int realant~ in ~he form of a g~, neat liquid, finely ;~1 di~ided ~olid, or~s~te in a solvent which, preerably sw~ the material. Insertion is g~rally aided by - exposure of the ~ixture of intexcalant and layere~
;~ 35 materia~ t~ sh~ar, heat, ultra~onic eavi ation, or ~,~
.;.

WO94/11430 PCT/US93/1081~
21~8~13 microwaves. Ion exchange by ionic molecules may be performed by suspendlng the material in a relati~ely volatile liquid which is capable of both exfoliating and dispersinq the layers or fibril~ and dissol~ing a -salt of the ionic intercalant as well a the resultingsalt of the ion displaced from the material (e~g., Na , Mg2, Ca 2~, adding the alt of the ionic intercalant, and r~moving the material (now complexed with the new intercalant) fro~ the liquid (now containing the dissolved salt of the displaced ion). For example !
swellable layered mineral~ such ~s montmorillonite and hectorite (having primarily Na cations in the interlayer space~ intercalate water to ths point that the layer~ ars exfoliated and disper~ed uniformly in l water~ Di~persion in water i~ generally aided by mixing with rslativaly high ~hear. A ~1itable ~walling/compatibilization agent such a~ the hydrochlorid~ salt of di~ethyld~d~cylamin~ i~ then added in the d~ired amount after which the layers complexed with th~ am~onium catîon are separated from the d~p~r~ion, wa~hed og residu~} NaCl, and dried. In the preferred ~mb~diment. of the invention, the swella~l~ lay~red ma~erial is intercalated by ion exchangaO For ~x~mple, a su~pen~ion o~ a montorillonit~ or ~ saponite in water, ~ay be heat~d to about B0-C and ~tirred using a high ~peed ho~og~nizer ~ix~r, in a conc~ntration low enough to yield a 1sw ~i~co~ty di~p~r~ion fro~ which non-di~p~r~iblg particle~ can b~ ~eparated by sedi~ent~tion (~ineral ~f concentr~tion of about 2~ by w~ight, OE 5~ to 15% with addition of a peptizing agent such ~ sodi~
~exa~etaphosphate)O The dispersion i~ com~ined wit~ a soluti~n of a suitable swelling/co~patibilizing agent ~uch a~ an a~moniu~ salt (a3, for ex~ple the hydrochlorides of -octad~cylamine, ll a~inound~canoic ~ WO94/11430 PCT/US93/10819 `
21~8~13 acid, dioctylamine, dimethyldodecylamine, mekhyloctadecylamine, dimethyldidodecylamine, and the like) such that the mole ratio of ammonium salt to exchangeable ions in:the mineral is between 0.5 and 5 The amine-complexed layer5 may be separated from the solution by ~ome suitable method such as filtration or centrifugation, followed by rinsinq in fresh water, rough drying, and ball milling to about l00 mesh powder. The powder may be rigorously dried a l00-C to 160-C in vacuu~ ~or 8 to 24 h in the presence o~ a drying agent such a5 phosphorous pentoxide, to provide the desired swellable/poly~er compatible intercalated layered ma~erial. -Intercalated layered materials int~rcalated with 15 ~ilane~ may b~ ~orm~d by treating a ~wellable and poly~er co~patibl~ intercalated layered material I alr~dy int~rcalat~d with an onium cation with a silane coupling ag~nt in a swellin~ liquid, ~uch as dioxane, I' glyme, digly~e, dimethyl3ulfoxide, m~thylethylketone, ¦ 20 and the lik~, or by treating an aqueou~ suspen~ion of a ¦ layQred ~terial with wat~r-soluble ~ilane coupling ag~nts 3uch a~ trialko~y~ilan~. In th~ pref~rred ~mbodi~ents, ~ n~ intercalated swellable/polymer co~patibl~ intercalated layered material is ~orm~d a 25 ~ollowg~: Onium-int~rc~lated layered m~terial~, prs~rably prep~r~d a~ de~crib~d above are ~uspended and swollen in a swelling orga~ liquid and ~reated with a tria}koxysilane. For ex~mpl@, ~ont~orillonit~ p intercal~t~d with octadecyl~mmoniuD~ cation, at a~out ~0 3 0 mIaole o~ a~oniu~a eation/ lû0 g ~ineral, i~ co~bin~d ~j~
with dioxane~ to ~or~ a 5~ by wei~ht ~u~pension which is h~at~d to 60 - C and co~in~d with a dioxana solu~ion of aminoethyla~inopropyl trimethQxy~ n~, su ::h tha~ the ratio o silan~ ~o min~ral i about 20 ~mole/100 g.
The silan~ displaces the ammonium cation quantitatively L'.!'-~ ,`tl(,i~,CI7!E.~ 0 1 : 8 ~ 0: ;30 : ~ ) ' L-- + ~ '';3'J9~ ;5 ~

2 1 4 ~ r9 ~ 3 1 1 t~ fo~m a mixes 7 ntercalct2c I ~ered matarial ha~ g a~out 60 mm~ole c~ a;~umcni~lm cation ar~d 2~ lnmo' e o~
silane ~e~ laO g cf ~.ineral 7 ayers . ¦
~ ;n t;~e prefer~ ~d c~bodime~.tâ of ~ inve~ ?.., swel la~le and pol~cr-com?at~le inte~calared la~ered c;~m~aunds i:~cl~lde m~n~mor~ llo~!ite ~Gel~hit~ Hh~
Southern Cla~I Prod~t- ! co~r~pl~xc~ ~ith cctdecyl~ on~
cat cn ~lao rnrco~eJiO0 ~ r~l), mont;~c-lllo~it~
compiexed ~olcla~ T~.er- _an C-llo~ d~ Com~y) ~It:r 10 ~,~ ;d ~thyioct~decylacrmc~ m cc tior. ( 00 ~L012~ 50 ~), synthetic hectorite (T al:)orlite S, Lapar~e lràu~tr~es j coclplexed w~ th d ;~eth~,~ld_oct~ ~rLcnium catior. ' 8~
~nmole/100 g), comme-c_al y av~ organoclav ¦ -(Clay~one APA', South~n Cl~y ~roductsl, 15 ~nont~orillonite compl~xed w- th octadec~Jla.~l~.orlt ~ C5t~
~about 80 mmoleig~ and deri~r~.t~ zed w~ ~h ~inoethylar~ opr~ylr-~:~ethaxysilane (20 ~c~ 00 ~), ard t}~.e 1i!c~, ~ pre~erred use in :for~r~ r~g na~oc~mposlt~s, I t:~
20 swel~ in~co~pa~ibil ~i~g ager~.~ ls selectG~Y 50 hlt ~,~rhe~
sub~ ac ~d t3: the ~rc ess n~ ~ærn~erat~r~ c . t'n~ t- x poiymer (s~, it dces r.-t ~Jol~e decc~L3031tion~ ~rl ducts which c~n c~use chair. sci ~si~n o'r cthe~ cecrad~tic~
the ma~rix polymers . Special ca~e mus~ ~;e ta~:en! ~he~
75 polyrr.ers which ~ecuir,t high p~cess' ng empe~a~ es ara used. For exa~r.?' e, qua.ernary aK~cniurt~ cations ctart ~o thermall~ ciec~pos~ ~t a~cut 52~ ?~O~C ~ ~.t I .
al3carles and ami~es. ~n t~e Dasis o$ t~te~mal stait~il i ty, ~ :
silanes and onil:~ ca~icn3, that carnot IL1-dergc b~ta- ~-30 eliminatic~ are pre~e-r~d, e.g., a~r.onium ~ation or ~.the ~or~ula: ¦ .
[ ~ C (R') ~ C ~' L ) ] -I
AMENn~D SHEET
~` . I
!

. ... . . . ~ ... . _ _ /~ ~r ~ k;\i u I u l ~ - J l ' U ~0 ` ~i L } ~ T ~ ,_t, ~, 216~8913 ll f``- ;`

-''2,~
~here Rl~ is ~ryroger. or cn o~gani~ .~Loiet~, R is' ~n orqa~.ic ~oiety a,~d R - ~ s the sam~ or difre~er.~ at ~ach , .
occurrence and LS ar. organlc radic21. :

. ~,' 'r ~

` ' A~E~ EI~ S~'EEI

`~`W094/11430 2148~13 PCT/US93/10819 1~
Il .

: - I

~ The nanocomposite compositions according to the 1~
i - invention are thermoplastic materials from which molded r . article~ of manufacture hav.ing valuable properties can , ~ be produced by conventional shaping processes, such ~s ¦ 5 melt spinning, casting, vacuum molding, sheet molding, ~ injection molding and extruding. Example~ of s3uch 3 molded articles are com~onent8 for techni~al equipment, apparatus ~astings, household equipment, sport~
~quipment, bottles, containQr~, co~ponents for the 10 electrical and electronic5 ind~stries, car components, Ci~CUit8, fi~ers, se~i-fini3h~d prod~cts which can be shaped by ~achining and the like~ The u3e of the ~materia}~ for coating article~ by mean~ of powder coating proc~se~ is~ al~o po~ssible, as i~ their use as lS hot-melt adh~siv~. Th~ ~old~ng co~position~ according to the inv~nt~on ~r~ out~t~ndingly suitable for pecific applic~tions af all type~ ~ince th~ir s~pectrum o~ propertie~ can be m~dified in th~ de ired direction ~.1 in manifo}d way ;1~ 20 Th~ co~po~it~ons o~ thi~ invention which include di persed pl~telet particle5 are ~pecially useful for f abrication og ~xtruded f il~ and f il~ laminate~, as or exampl~, film~ for use in food p~c~;aging. Such film~ can b~ f~bricated using conventional film ~xtrusion t~chniqu~. The ~ilms ~re pr~erably from a~ut 10 to zlbout 10~ ~icrorls, more prefsrably from about 20 to ~bout 100 DliC~ron~ and ~ao~t prefera~ly fro~a 3 ~bout 2 5 to ~out 7 5 ~icron~ in th~ ckne~s . In ~he f i}EI~ the ~ajor plan~ o~ the platel~t ~ r~ is sub~t~ntially par~llel to th~ mz~or pl~n~ of the ~ilm.
The eXtQnt e~f p~rallelis~ of particle~ and f il~ can be d~ermined by X-ray analysis. X-ray analysis is a useful way to de~cribed the cry~t~}linity and orientation of polymer crystals and th~ orientation of platelet particles. A convenient method of X-ray ? ~ ~

W094/11430 PCT/US93/10819'~............................................ f ~ ~:
2-:14X~l~

analysis is that described in X-ray Diffraction Methods ;~
in Polymer Science, L.E. Alexander, Wiley, NY, pp. 137- '-229 (1969), hereby incorporated by reference.
For the purpose of the present invention Op, the platelet orientation factor, i~ an indication of the platelet particle orientation in the film. The Op was d~termined by m~king azimuthal scan~ from densitometer tracings of the X-ray photogràph~ which were obtained by ~xposing the edge of the film to the incident X-ray The angle is the angle between the re~erencedirection, the normal to the film, and the normal to the plane of int~rest, th~ major plane of the platelet.
Th~ Op values were calculated as the aYerage cosine square (<co~2t~ ~ where ~ is the angle between platelet nor~al and th~ ~ilm normal) for th~ nor~al to the flat face~ o~ th~ platelet particle~. An Op of l.0 indicate~ that th~ face~ of the platelQts are complets}y paralleI to the plane of the ~ilm. An Op of O.O indicates that ~hQ ~aces of the platelets are perpendicular to th~ plane of th~ film. The Op of the platelets in th~ fil~ o~ t~e pre~ent in~ention i~
pro~@rably frQm about 0.70 to about l.0, ~ore pr~rably ~rom about 0.90 to about l.0 and most pra~r~bly fro~ a~out 0.95 to about lØ Such pr~rr~d orisntation of pl~let partic~e~ resul~ in ~hanced barri~r propertie and increa~ed tare ~tr~n~th.
Th~ ho~ogen~ou~ly distributed platelat particl~s and poly~er ar~ f or~ed into a ~il~ by ~uitable ~ilm . ~-~0 for~in~ mQthods. Typically, th~ co~po~ition i~ ~elt~d i and forced through a film for~ing di~. The die can be a flat di~ or ~ circular di~. A typic.l ~lat di is a -h~nger sh~ped die, and a typica} eircular die is a tubular ~ die.

.

~ ` WO94/11430 214~13 PCT/US93/]0819 :~

.

.

- 25 - ;
The film of the nanocomposi~e of the present invention may go through steps to cause the platelets 1-to ~e further oriented so th~.major planes through the platelets are substantia}ly parallel to the major plane through the film. A method to do thi5 i5 to biaxially stretch the ~ilm. ~or example, the film i~ stretched in the axial or machine direction by ten~ion rollers pulling the ~ilm as it is extruded fro~ the die. The film i~ simultaneously stretched in the transverse direction by clamping the edge5 of the fil~ and drawing the~ apart. Alternativ~ly, the film i~ ~tretched in.
the transverse direction by using a tu~ular film die and blowing the fi1m up a~ it passe~ ~rom the tubular film die. The films of thi~ invention may exhib~t one or more o~ the following benefit~: increa d ~odulus, wet ~tr~ngth, and dimensional stability, and decreased moi5ture abaorption and permesbility to ga~e~ such as oxygen and liquid~ such a~ water, alcohols and other 501v~nt~
The following exa~ples are presented to ~ore particular illu~trate the invention and should not be con~trued~a~ li~itation thereon.

Dilut~ nanoco~poYites a~ organoclay in nylon 6 we~e pr~p~r~d by e ~ ruder eompounding, and characterized by ~ :
xr~y di~fraction, ~ , og th~ exkrud~te and ~echanical properti@~ of their ~njection mold~d t~t ~a~ples.
Th~ dilut~ nanoco~pa~ite~ w~re prep~red ~ro~ a dry 30 ~iXtUrQ 0~ (1) Bentone 34~ ~owd~r (a ~ont~orillonite who~ native int~rlayer cation~ w~xe ion exch~n~ed ~or . :
dimethyldio~tadecyla~onium cation, obt~ined from Rh~ox~ IncO ) and (2) unfill~d nylon ~ pellets (capron 8209F, obtained fro~ Allied-Sig~al); by co~pounding the ~:~ 35 mixture using~a twinser~w extruder equippad with WO94/11430 PCT/US93/1081``~ ~
2 1 4 8 ~ 3 3 r i g~ner 1 purpose mixing screws. Prior to compoundiny, the Bentone 34 powder was vacuum dried at 60~C to a detectable moisture level o~ le,ss than about 0.2%, and the nylon pallets were vacuu~ oven dried at 80C to a 5 moisture level Qf less than about 0.1%. The mixture of ~:
Bentone 34 powder and nylon pellets was firs~
compounded into a masterbatch which wa~ determined by its ash content to be about 0.2% by weight inorganic, presumed to ~e aluminosilicat~ from the Bentone 34.
10 Portions of this masterbatch were compounded with additional nylon 6 p~llet~ to yield extrudate having ealculated miner~l concentrat1ons of about 0.1, 0~05, and 0.01~ by wei~ht.
After vacuum drying, the final extrudate~ were 15 analyzed by XRD and found to be, in general, about 65%
amorphou8, 30% in a~ga~a cry~talline pha~e, and 5~ in an alpha crystallin~ phase. The variou~ nanocomposites plu~ an unfilled nylon 6 control were injectinn molded into te~t 3a~ple~ using and Arburgh in~Qction molder, 2 0 and a portion of set o~ samples wa~ immer~ed in water f or 21 day~ at a te~peratur~ of about 2 0 c . The f l~xural al~d t~n~ile propertie~ of th~se ~amples, both dry ~nd w~t, wQr~ dete~ined according to the procedur~s o~ ASM D790 and AS$~ D638, r~pectively.
25 Th~ notc:h~d ~mpact: strength~ of th~ dry sample~ were d~e~r~ined a~cording to th~ pr~c~dur~ o~ ASTPS D2 5 6, and th~ir a~r~rAg~a v~lues ~re ~e'c f o~th in T~ble 3 . The flQxur~l ~nd tQnsile propertie~ are . ~t ~orth in Tables 1 through 4., ~ W O 94/11430 21~8~13 PC~/~S93/10819 T~la l. DRY lUB ~O~DED FLB~nU~ PROP ~ TI~ ~lL3T~ D79 (Inj~c~on rnold~d sampi~) _= ~_ ~-- - ~ _ nylon a~Lllinrty n~xural rno4ulu~, ~ changn in ~xur~ tron~ ~ chan~ootganoday^ ~ alph~ / p~ MP~ flsxur~l to S~ ~ in, p~ in fl-xur~
% ~mrn- rnodulu~ in (MP~) ~r-n~
n ~ to r~l~ to unflii~ nyton I-nfili-d _ ~ _~ ~ _ ~ _ ny~n W: 20 / ~ 401.000 t2,T70) O 15,700 (108) O
unfil~ ___ ~ _ _ ¦ _ _ .
: 0.01% ~5 1 30 ~,000 (3.070) 111~ ¦ 17,300 (120) 10~ ¦
L~ ~5 ! 3o 453000 (3~130) 13~ 118,000 (124) ~5% I
0.1~% ~s / 30 ~58.0~0 ~3.1~01 1~ 18,0Q0 ~124) 15~ .
~--- - - - - - - =, :
~: 20 U~ 0 (3.~0) O 17,~00 (t18) . O
Iur~ d_ _ . ... __ ... - . :_ . . , _ . .
¦ : 0.01% 20 __ ~,OOD 13.~X) 1% _ ¦ 17,~00 (1~0) _ 2% :.
L: : 0.015% 20 _ ~51.040 (3,120) 1% ¦ 17,~ t120) _ 2% -.
o lo~20 ~ 0 (3 1~) 3~ 17,4~ ) L~;~ t p~3rco ;~;3~ ed from 3en one 34 (~ontmorillonite co~plexed with quat~rn~ry ammonium : cation) . .
2 0 ~ 2 . llA~ TIIIIAT~D: IL----DV~ RROPg~ 8 ~npe~on mo~d sami~ bnm~d 3 w~ in wsb~s _ ~ ~
nybn: c~lty lbxùr~l % elw~ in fl-x~ 2ro~ to # ch~
2 5 ~ ~ ~ / modu!u~, isd fll~xw~l ~ ~n, psi in fl~xu~a~l ~ U pAP-) rno~ ~8) r~ O
~bd ~ nylon , .-_ __ _ __ , ...
N~: 3~`t ~ ~ 1t) 2~ ~ , L~ .~,, _ __ ~ ............. -:
L~ ~ 30 .~oo s~7) . ~ 22~ 310D 122) 24%
L~ 1~/ 30 79,~X ~5~0) 32~ _ 3.~ 33S
3 0~ 17 / 3S n.o~o~so ~1~ 3,~X ~O 3J~
: ~: 100;~DO (ISI~O) 4,0tlO ~8~ . t `
~d ~ _ . ~--. :oo1~ ;Iw~O ~ o~ 3.9X ~7) 01 0 03~ 101.~0 ~7a3) 2% _ 4,030 ~ 1 _ ___ _ .
3S :o10~ ~ ........ 1~XO ~ 2~ ~,030 P~) 1~ ^.

:

W094/~1430 PCT/US93/1081~
21~8913 aO weight percent clay mineral derived from Bent~ne 34 (montmorillonite complexed with quaternary ammonium cation).

T~bl- 3. DRY AB ~O~D~D ~ D P~OPER~8 (A8T~ D638) ~ml~ m~d S~TIph~) _ e ~ c n~n: t-n~ib ybld % d~ in n~ch-d ~hn~t~on to org~ y str~ t~n~ib y~ld imp~ br~
(MP~) ~r~ ro~a~ to tt.lb~/lnch un~ d nylon (J/m) _ , ~ ~__ ~ ~.,. ~-10~ unfllld 11,200 ~ - . 1.~ (~) 2~0%
: 0.01~ 12,000 (83) 7 '$ _ 1.2 (6~) 1S0 :O.OS% 12,~ ) 11~ 1.2 (6~) 90 .
_ - _ _ _ _ _ ~ - . _ I
L~ ~2.3Q0~ # ~ 5) 100 12,2~0 (~) ._ 1.1 (S8) _ 20 I5I :o.o1~ 12d~ ~) o%_ 1.0 (~)_ 20 . I :_o.~_ 12.~ o~ o.~ o .
~; ~ !: ~%- .~ , ,.~ o~,~, ~o : ~ ' ~5LL~L~ T~ 8AT~aAr~D ~8S~ PROP~RTIE8 ~A8TX D63~'3 ~In,o~on rndd d wnpb~ imrn~ in ~r 3 ~) :
_ ~ _1 : nybn: t~db yldd ~ ~ ~n ib; _ 2 5 o~ P~l (~) yb~ ~ to b~.
: unfil~i ny~on %
. I _,_ _ _l " ~
_: untill d_ 3,tC~ ~1? _ 300% _ : ~:QOt~ 3.900 ~ 2~ 260 ; ~ ` : 0.05S ~ 1~ ~ Z~
0~01~ 4,~ 270 ~` ' 30 N~:un~ i ~ _ 300 _ : O.O~S ~,11110 ~ 0 ~ _ . 2~0 _ ! ~ o~ 5.~ (~!: _ . _~ x4 : ~.10% 5.~ 1) 2 % 2~0 ~: _ ~__ , ...
;'~ 35 T~e ~trength and stiffnes~ of dry nylon 6 are increa~edby at least l0 ~ by the addition of dispersed ~ organoclay~at concen~ration~ a low a~ 0.0l % ~y c,~ weight(or about 0.005 % by volume). At the same time, ., ~::
:~ :

~, WO94/11430 2 1 4 8 ~ 1 ~ PCT/U593/10819 : - 29 - :
the toughness of dry nylon 6 (as suggested by the ultimate elongation and notched impact strength) is o~ly sligh~ly reduced by the addition of low -concentra~ion~ of dispersed organoclay. At high moisture content; the strength and stiffness of nylon 6 are increased by at least 22 S by the addition of dispersed orgaDoclay.

o~D~
Dilute nanoc~mposites of organoclay ~Bentone 34, ,-.
obtained from Rheox, Inc~) in nylon 66 (~ytel lOl, obtained from DuPont) w2re prepared, injeotion molded, and characterized according to th~ proc~dures described in Example l t and the re~ult~ ~re et forth in Tables l 1~ ; 15~ through 4. According to th~ir XRD patt~rn~, the~e ¦~ nylon 66 nanoco~posite~ ~xhibited cry~tallinity that wa~ substantially tha sa~e as unfilled nylon 66 which I~ wa~ about 20% in its alpha crystallin~ ph~e and which doe~ not form a gamma cry~tallin- phasQ.
Unlik~ tho~ of nylon 6, the ~trength and stiffness of nylon 66 (both dry and water~o~ked) were in~reas~d by only about 1% to~ 3% by the addition of di~persed ~; : org~nocl~y ~t concentr~tion3 of 00 05% by w~ight or . Tha ~:oug~ne~s of dry nylon: 66 (a~ indicat~d by 2 5 ulti~t~ elo3~gatio~ and notched i~pact stre~sgth) , r~in~d l:ow compared to nylon 6.
: 1 : A ~lxtur~ of organoc~y ~l2ytone APA , a -montmorillonite compl~xed with a tetra~lkyla~onium catlo~, obt~ined from 50uthern Clay Product~, Inc.) and A~
; nylon 6 tCapron 8209F, o~tained~from Allied-Signal, Inc.~ wa ~t N ded and injection molded into tsst `~ ~asple~ who~ Drop W~ight I~pact Strength w~.
detenmined~8cco~dlng to the p~oeedure3 of ASTM D30Z9.

" :

U ~ ", I.~V _"~ ~ r ~-_J_~~J ' )'J.J r tr~.> . ;t ~ I

;``` 2148~t3 ,o i :.
The T~.,neral c~ten~ cr the e;~trucat-, e~t~ .atec ~ its ash co~tent, was ~Gu~ ~. 0 ' ~ ~ b~ eiG~t `~he o~g~ncclay and ny' ~n ~ we~ epa~ed and extr~lceG
accordirlg t~ the ?rGce~r~s -~sG~i~ed 1~ E.ca~.plel 1.
The r2sults of t:~e r)r~p Welg,`~ act te-~ ~ a'l cr.7 w~
th~s~ or flaxural ar.d te~s~ a ~es~s, ~re S5_ fcrth ' n Tabl~ 5.
A~ ding ro ~~s .C~J ~a-te~, th~ 1G~ crsanocl~ -compos ` te ex_ru~a~e w~s 4()~ c~ ~s -1~ n_ a-. r~ cn O ~ammc-Dhas~ c. ys~al " t~s .

T~lo 5. 5~-RICH vs ALPE~-RIC~ ~YL-ON 6~:
F!sxu~, Tensll~, and Drop W~ignt !mpsct P~petti~s ~drv ~s ~ntJldt~
. . . _ _= `~ ~--~ _ t711er cys~lru~i~ f~l n~u~u~" ~un~ 5t~S to I u~ dr~p ffl~gnt alphal* ,~d (MPa) 5~, a~in' K&sl I ~atit~n. impscl ~arnma (MPa~ ~ ~, stren~h, N rn . _ . ~ ~- ,~ 'i1 _ ~2/2~ ~t3,0~ 1 18 ~1~,4) L i 1s7~ll6) 020%~ 22~ 3 ~a40) 17 (11l) ~ 87~64?
I Mio~onnt~ ~ . ~:
--~ - ~
a. C rystalll'nity t~f ext~uda~ e dPterm~he~ x-~a~
dif~r_ct~ ~n.
'2 0'~ ,t~ tup .

0 COMPAR~TIv~ EXA~P~
, ~ mixture or^ ~r.iorcfin~ t~lc ~3~T-2 CO, s`r~~i~ed fr~m P, i~r~ 2nd nyi~n 6 ~ Pr_n ~O~F~ wa;, ex ~_d~d ar~d in~ec~ion moL~ed into t-st s,~ pl~ hose ~
We~ght Impact i,tre~gt:e w.~s cet~ r~.~ ne~ acc::r~ .g t~ ~e 5 p r ~ c 2 aur ~ s ~ T 2 ~ r t ~ e ~, ex~udat2r esti~atPd b~ its ash c3nt~nt, wc s a~o~ ~J .18 by we~ ght .
EXP~E 3 A Se-ies of ~ery dih.~e ryLon v~o~g2r.c;:La~ ' 30 nanocompositeS was ~repa~e~ ~y ri~st co~cunc~ s, Clayton A~?A with nylor, 6 (C~p~ on ~2C~-) --~.1' GwLn~, -h~
.
: AM~N~ S~EtT

,:

'r~C~ . VO~ 'A ~ c~lE\I 01 ~-1 1-94 : ~ : "() I 4~ ' 1 ; +~ 89 '>3~;1'y4~

,, .
li~` 21~18~

., , _ 3 1 _ ' ~r~cedures d~scrlbed in r.xample 1 to proa~lce a ~ i masterbatch, and then re-ext-uding po~'ion;, of ~e masterba ~ch ~ith unf illed a20~F nylon 5 . The ~.iner21 content o~ the ~esL~ltirl~ na-noc~mpcsit~s, as caLcu7ât ~`1; . S based on the ash conterlt -of t:r~e mas~e-~atr~ (0 . oi~ ~y `~ ~eight), were ~.00~, 0.0~36~, ana 0.0~ by we~aht.
~nJ ~ction molded sæ~pl~s ~ ~he dilu~e com~osite~, unfilled 8~0~F nylon 6, 3~d ~ke talc-nucle~ted n~lon r ol CorrLparative Exam~le 2 were chara~~rlzed ~y ~RD and 10 tested ~'or the~ ~ rnech~nical pro~er i~s i~ccord~.~g to rhe procedure~ of ~ST~ D ,go ~n~d ~or t:~lei~ ater u~ta~2 .!j dllring prolonged i~nmersion. T`~e res_lts o- the~e .-sts a~e set forth in Tab' e 6 .i 15 TABLE 6, DILUTE N6~0RGP~NOCL~Y COMPOSITES (AST~,~790~3 r--__ ~ __ ~
clayc~rt~, cy~ii~ ~exuralmodulu;, I ~ai~5to5~ wa~up~ by I
pp~n b~ j ~6 alph~ ~amma K~ UPa) I nra~, ~psi SMPa) wo~hPI I
~ (~,~ ) _____. _ _ O~111 ~0.4nm) (64A) ~ ,770) 15.7 (108) ~.t ; . _ _ ~ __ ._ ' 18O I ~g t~,5n~ 438 ~3,030) 17.9 (lZ4) 5.~ 1 __ . ~ -- _ . -~, 360138 (i 1nm~ OA) 439 (3,t~0~ 17 ~ ~123) 5.~ i .~ _ __ so O ~ lOn~) tl o~A) 439 ~3~30) l, .~ (123) 5.
I _ . _ . _ ~ .--I
',~ 180 014;~ m) (12QA) 43g (3,030) 17.7 ~? 4.3 ¦
"~ . ~ ... ~ _ . ~_=
-1 2,000 tak _ 440 (3,040) ¦ l 7.0 ~117) ¦ 6.;
~1 ~ . . ~.

f a. Mineral cc)ntent deri~e~ from Clavtc:ne ~A~
`~ b. Crystallini~y of 1~4 inch molded sar~p~ es, ~ased on , i 20 X~D analysis c. Iqe~sured aft-~ t~o we~ks 5f~ mersion i r wzt~r 2~ C.

All o~ the dilute n~:~n ~/~_ganocl ay compos1lt2s 25 exhiblted greater stif~nes3 and s;rength t'nan unl~illed nylon 6 and grea~er re~1stance to water absc~pti~n thcn the talc-contain~ rg nylor~ 6 of Comparati~e Ex~ple 2 .
The ~nolded sa~ples chara.ct~ri~ed by XRI: were founa to i i A~AE~E~ S~.EET

.` 1 .
... .

~C\/ ~o,\~ C~ 8~ 9~ 0~ '701 ~ 0'~ +'1`9 8';3 ')~994~6.~ >~ ~

.~. :`.. ~ .
`~` ` ` 21~8~13 'I
.` I .
.
. ~ !
_ 3 ~ _ .
consist c_ a~out ~S to 42~ camma c~stalline ~.ylon 6 and 1~ th~ about 2 ~ ~f t~e al ~ha fv~n . ;n cor~tr s a s~ple cf urLfilled ~20~ nylon 6, ~Lolc~ed under' t:ra same condi~ions, wa.s fcu~;d to ha~2 com~arable t~tal S crystalli~ity (~0~ but wit:~ ~n alpha to gar;una ratio of 72 to 28. The ai'~' ard perIecticn cf the il crystallites ircreas~c. wlt~. ~ ncr~asir~s cla~ cor.t6~t .

,.
~X~iP~: 4 A nylon 6~org~no~:' ay c~poslte hav_ng a~:cut '0 ~27Ss clay ~ine~al was pr~parec: ky compou~ding ~ mi~c~ur~ o~
pow~ered montmo~illonite, comp ~ exed with ~rotona,~ed 11~
ami~au~decano~-acil, wi~h nylGn 6 ,,elle~3 ;Ca~ron 8207F) accor~ing t~ the prcc2dures descrir~d ~ n E~ample 15 ~
The orga~oc' ay powc~r w~s prapared b~l C~ N-r~ a 4~ ~isperslcn c~ ~ontmo_llior.~ te (Gelwhi~e ~F, obtained frorn Southexn Cl ~.y Pr~ducts) w~ ~h ~n aqueous solutio~. o~ æ~.inounceca~cicaci~-HCl ~100 nL~o1:~/ 100 c 20 cl y) at about 80 C und~r h~ ~;h-shear mi~
1Oc_ul~tad produc~ ra~ f~ red, ~ashiad 4; i:nes. wi.h hot wa~er, dri2d at 60C in v;~cuum, tu~bled ln baL' mill, and p~ssed ~hrou~h a 200 mesh scree~.
Pellets o~ nyl^n 6l0rg3noclay compo~ite a~d als~l 25 pellets o~ ~ co~nmercial ~a~rna-rich nyl cn ~ ~ iO17~, obtained from Toray) wer~ anneal ed ~or 2 hou~s ~t various tempe~^aturas, a~d wer- c.~ar~c~rize-~ ~y ~;~^ r X~D patterns. ~rh~ c-ysta~ .ities cf the s~pl~s a~-ex `, anneaLi ng are set fort~ in ~a~le I .
.~ ' i.

, ~ .
.1, !
.~ I
`1 AMENDE3 S~!EET
i ... .... .. . _ I~C~ . ~'O~ El~ ;CHEI~l O I ~ 9~ 0: 31 : 2~1 465 :20'>1~ +4 ~3 8~ 239~ 8 l .-~., ' ' ``- 2148~13 3 ~
.
TA~ 7 . GAM~ CRYS~INI TY OF A ~ 6/OR~O~:L~Y
~ANOCO~IPOSIT~ 3R A~ G E~R IrWO HO~ et~x;n~ ne~
by X-~ay l:)if fraction) ~.- ,_ ~ _ i F~ '-NT OF TOTAL (~RYSTALLIN~Y I N GAMMA F! IAS~' ¦
'i ~Tlph - ~ ~ __ ~ , ' . ~
b~t~e anne;~ 195 C 2~0 C ~05 C ¦
' ~ . . __ , 0.27%c~ 88% 42q~ 4C~ 33~ , ~ Tor~y 1017K ' ~5% ~4~ _ 1 131~ ¦
3 l . __ ~_ _~ . _ _ _ _ 5 a 'rc~21 -rystallin t~ cr e~ CiarQ~le ~a i a~ou- 5~ t-~
3 ~iC~

1 0 ~LE S
A~. immiscible blend o_ nyl^r 6, ct nta_-i..g 1~
~, dispersed organoclay, and a r~er racdifie~ exhi~i~s ~ ncreased flexural strength and ~nodulus, rel2ti~e -G
si~niiar blend contain~ na r.c organoclay, w~ile r~,tainin~
1~ its im~act strerlgth . Th:e blend i s p~par~d l~y ~11 J
compoundin~ nylon 6 with ~r,ontmorill~ni e c~mp e~ed protar.ated di?entyla a~m~nium ~ati~n in a t.,finsdr2w extnld~ r such that the ~;om~c s i t e comp r l 3 e s abcu _ C 2 `3 mineral by we1 g:rLt, ard t2) co~-oaundlna the nylol:~
~, ~0 6/ara~clay c~m~?osite wit~:~ a Z~ iono~er c~ i poly (ethyle~e-~o-methacry~ acid~ (Su~l yn ~slo,~
obtained ~rom ~uPont ) such ~hat tne blend c~r.r.or~ses a~out 20~ by weight Surl~ The re:;ul~ing '~lend exhibits predtaminGntly gamma c2:ystallini~y ir i~s ~y~o.
25 6 ~raction, while the b~ e~d a_ Su~lyn ar. ~ylc-~ ' o ~; ho~polymer t_xhi}:)its predo~sLinantly al::~ha crystalLlirllty ~! ir its nylon fraction.

:!1, 30 P~ dilute com~:osit6 o~ ny'~go~ 6 and part~ c1 es, o~
~i _ dispersed clt plateletst c~rising no or.ium o~
.: j , . ¦
AMEN~ED Si lEET
.
''I . .

~C~ C`HE~I 01 : 8-11-94 : 0: 31 : '7~ 1)'71- +~9 L7~ ~.39~
~; 21~8~13 1 :~

.
-- 4~
orga~rlic grou~s covalently Dcnded to tAe cl~y, exhi~its lncrezsed strength ar~d ri~ ty, and p~edo.~_nar,t~ y gamma crystallinity. Th.~ _omposite is ~re~ared ~y (1) ~ix~ ng, at ~.igh shear, m~nt~.or~ llonit~ e~ala ed 5 ~ith Na~ ca' ions with mcl t2r. caprolactam a~d wat~r ' n a ratio o ~ a~out 1: 3 ~ 2 3 r~mo~in~ WZ.ter ~-om a I
powdered t~r~ of the ~ixtu~ y v~ cuum. d~y_n.$, ~) compourldin~ the mixtu~e with n~lon 6, in an extrt~d~, an~ ~ 4 ) 1 eaching the caoxolzc ~ rom th~ extrudate O with '~c)iling ~ater.

' A composite o~ nylon 6, or~anoclay, an~_ ~ cs's _ib~r ~nd ali other non-nucleat' n~ ers ~no~ r~all y lJ8 15 in-h in lenslth), ir} a ra~i~, of ~k~ut 8~ O . 2 ; 15 by ~eishtr eixhi~i~s high~r s~reng~h and stifr.ess rrlati-~Je to a si~.ilar cc}nposi ~e cor~t ~ ir~ing nG organccl~y . I Tne co~pcsi~a also exhi~its ~ir~dor~inant1~ ~a~
crysta1 inity in its n ~rlcn ~iract~ on. The ccm~oslLte ~ s 20 pre~are~ ~y com~ound_r.~; nv'' C.L ~ ~ectcrit~ ccm~lex2d ith protohated ocwac2cv1ar~.onium _~tl ~L;~ ænd t~
, ci~imp~unding this ~anocc~Lpos ~ it~. ~laas ~ik~r .

.

~, .

i ' ~,~

~~ AMÉ~I~E~ SHE~
J

Claims (11)

WHAT IS CLAIMED IS:

1. A composite material comprising a polymer matrix comprising a gamma phase polyamide, wherein at least about 1 weight percent of said polyamide based on the total weight of said polyamide is in the gamma phase, having dispersed therein less than about 0.5% by wgt. of the matrix of an organophilic particulate material selected from the group consisting of layered materials having a thickness equal to or less than about 20 nm(200 .ANG.) and fibrillar materials having an average diameter equal to or less than about 10 nm(100 .ANG.).

2. A composite according to claim 1 wherein the amount of dispersed particulate material is equal to or greater than 5 parts of material per million of matrix (ppr.).

3. A composite according to claim 2 wherein said amount is equal to or greater to or greater than about 10 ppm.

4. A composite according to claim 3 wherein said amount is equal to or greater than about 20 ppm.

5. A composite according to claim 4 wherein said amount is equal to or greater than about 100 ppm.

6. A composite according to claim 2 wherein said particulate material is a layered material.

7. A composite according to claim 6 wherein said layered material is a phyllosilicate.

8. A composite according to claim 7 wherein said polymer is selected from the group consisting of polyamides formed by the polymerization of an amino acid or a derivative thereof.

9. A composite according to claim 8 wherein said polyamide is nylon 6 or nylon 12.

10. A composite according to claim 9 wherein said polyamide is nylon 6.

11. Articles of manufacture formed from said composite material of claim 1.