Polymer nanocomposites comprising a polymer and an exfoliated particulate material derivatized with organo silanes, organo titanates, and organo zirconates dispersed therein and process of preparing same

Claim 2

A composite material comprising a polymer matrix comprising a polymer, said matrix having layered or fibrillar particles uniformly dispersed therein, wherein the interlayer or interfibril distances is equal to or greater than about 50 A, the average thickness of said platelet particles is equal to or less than about 50 A where the maximum thickness is equal to or less than about 100 A and the average diameter of said fibrils is equal to or less than about 100 A where the maximum diameter is equal to or less than about 200 A, wherein the length to diameter ratio of said fibril is equal to or greater than about 10 to about 1, said particles having organo metallic species bonded thereto, said bonded species selected from the group consisting of organo silanes, organo titanates, and organo zirconates and having one or more moieties bonded to at least one polymer in said polymer matrix, or said bonded species having one or more moieties which promote intermingling with at least one polymer in said polymer matrix or a combination of said species.

Claim 3

Composite material of claim 1 wherein said particles are layered particles.

Claim 4

Composite material of claim 2 wherein said layered particles are derived from phyllosilicates.

Claim 5

Composite material of claim 3 wherein said phyllosilicates have from about 0.2 to about 0.9 basic charges per formula unit.

Claim 6

Composite material of claim 4 wherein said phyllosilicates are smectites clay minerals.

Claim 7

Composite material of claim 5 wherein said smectites are selected from the group consisting of montmorilonite, nontronite, beidellite, volkonskoite, hectorite, saponite, sauconite, magadiite and kenyaite.

Claim 8

Composite material of claim 6 wherein said smectites are montmorillonite or hectorite.

Claim 9

Composite of claim 3 wherein said organo metallic species is selected from the group consisting of species of the formula: (--).sub.n N (Z.sup.2).sub.y (R.sup.1).sub.o !.sub.m (Z.sup.1).sub.x (R).sub.l)!.sub.4-n-m wherein: (--) is a covalent bond to the surface of the layer or fibril; N is Si, Zr or Ti; Z 1 and Z 2 are the same or different and are --O--, --OC(O)--, --OC(O)O--, --OP(O)(O--) 2 ,, --OP(O)(OH)P(O)(O--) 2 or, --OS(O) 2 --, or any two Z 1 or Z 2 or any Z 1 and Z 2 together form a divalent chain forming cyclic structure; l and o are the same or different and are 1 or 2; x and y are the same or different and are 0 or 1 with the proviso that when N is Si, x and y are 0 and when N is Ti or Zr, x and y are 1; m and n are the same or different and are 0, 1, 2 or 3, with the proviso that the sum of m and n is equal to 4 or less; R 1 is the same or different at each occurrence and is a nonhydrolyzable organic radicals which are bonded to the N atom and not displaceable during the formation of the composite and is compatible with said polymer; and R are the same or different at each occurrence and are organic radicals which are bonded to the N atom, and which are not hydrolyzable and displaceable during the formation of the composite, and which is reactive with the polymer matrix or said polymer of the polymer matrix or with the polymer precursor to form covalent bonds between the reaction residue of R and the polymer or polymer precursor.

Claim 10

Composite material of claim 8 wherein: R 1 is alkyl, cycloalkyl, alkoxyalkyl, phenyl, phenylalkyl, alkoxyphenyl or alkylphenyl; N is Si; y and x are 0; o and l are 1; m is 0, 1, 2, or 3; n is 1; and R is an organic radical having at least one functional group which is capable of reacting with one or more polymeric components of the polymeric matrix to form covalent bonds, which radical may optionally include one or more heteroatoms or carbonyl atoms.

Claim 11

Composite material of claim 8 wherein: N is Si; y and x are 0; o and l are 1; m is 0, 1, 2 or 3; n is 1; --R 1 is alkyl, with the proviso that when m is 3 at least one --R 1 is alkyl having at least about 8 carbon atoms; and --R is an aromatic or a aliphatic radical of the formula: --R.sup.2 --Z.sup.3 wherein: --R 2 -- is a divalent aliphatic chain or aromatic chain which optionally includes one or more divalent heteroatoms or carbonyl groups in the chain; and Z 3 is a moiety of the formula: --N(R.sup.3)C(O)N(R.sup.3).sub.2, --C(R.sup.3).sub.2 --CR.sup.3 ═C(R.sup.3).sub.2, --C(R.sup.3)--Ar--C(R.sup.3)═C(R.sup.3) (where Ar is aromatic) or NHR 3 , --S - M + , --O - M + , --OH, --(cyclo-OCR 3 --C(R 3 ) 2 ), --C(O)X 2 , --SH, --S(O) 2 --X 2 , --NR 3 C(O) C(R 3 ) 2 ! p , --S 4 H, --S 2 H, --S(O)X 2 --C(O)--N(R 3 ) 2 , --N═C═O, --C(O)OR 3 , or C(O)OC(O)R 3 ; p is an integer of from about 3 to about 2l; X 2 is Cl, Br, OH or OM; M is a metal cation; and R 3 is the same or different at each occurrence and is the hydrogen or alkyl.

Claim 12

Composite material of claim 10 wherein: N is Si; y and x are 0; o and l are 1; m is 0, 1, 2 or 3; n is 1; --R 1 is alkyl of from 1 to about 4 carbon atoms, with the proviso that when m is 3 at least one --R 1 is alkyl having at least about 8 carbon atoms; and --R is an aromatic or a aliphatic radical of the formula: --R.sup.2 --Z.sup.3 wherein: --R 2 -- is a divalent aliphatic chain or aromatic chain which optionally includes one or more divalent heteroatoms or carbonyl groups in the chain; and Z 3 is a moiety of the formula: --CH.sub.2 --CH═CH.sub.2, --NH.sub.2, --(cyclo-O-HC-CH.sub.2 --), --N(R 3 )C(O)N(R 3 ) 2 , --C(R 3 ) 2 --CR 3 ═C(R 3 ) 2 , --C(R 3 )--Ar--C(R 3 )═C(R 3 ) (where Ar is aromatic or NHR 3 , --S - M + , --O - M + , --OH, (cyclo-O-CR 3 C(R 3 ) 2 , --C(O)X 2 , --SH, --S(O) 2 --X 2 , --NC(O) C(R 3 ) 3 ! p , --S 4 H, --S 2 H, --S(O)X 2 --C(O)--N(R 3 ) 2 , --N═C═O, --C(O)OR 3 , or C(O)C(O)R 3 ; p is an integer of from about 3 to about 2l; X 2 is Cl, Br, OH or OM; M is a metal cation; and R 3 is the same or different at each occurrence and is the hydrogen or alkyl.

Claim 13

Composite material of claim 11 wherein: N is Si; y and x are 0; o and l are 1; m is 0, 1,2 or 3; n is 1; --R 1 is alkyl, with the proviso that when m is 3 at least one --R 1 is alkyl having at least about 10 carbon atoms; R is a moiety of the formula: --R.sup.2 --Z.sup.3 wherein: --R 2 -- is divalent substituted or unsubstituted alkylene or a divalent moiety selected from the group consisting of: --(R.sup.4 --Z.sup.4).sub.r -- and --(R.sup.4 --Z.sup.4).sub.r --R.sup.5 --).sub.r wherein: R 4 is the same or different at each occurrence and is substituted or unsubstituted divalent alkylene having from 1 to about 4 carbon atoms or phenylenewherein permissible substituents are one or more hydroxy, cyano, or alkoxy or alkyl having from 1 to about 4 carbon atoms; and r is an integer equal to or greater than 1; --Z 4 -- is the same or different at each occurrence and is --O--, --NH--, --C(O)--,--OC(O)--,--N(H)C(O)-- or --N(H)C(O)N(H)--; Z 3 is a moiety selected from the group consisting of --CH 2 X 2 , --CH═CH 2 , --NH 2 , --OH, --O--M + , HC--CH 2 , --C(O)X 2 , --SH, --S - M + , --S 2 H, --S 4 H, --C(O)NH 2 , --NHC(O)-- --CH 2 !-- p , --N═C═O, --NHC(O)-(N-lactam, --NHC(O)-(O-ketoxime) and --NHC(O)-(O-phenol); X 2 is Cl, Br, I, OH or --OM; M + is a metal cation comprising; and p is an integer from about 3 to about 20.

Claim 14

Composite material of claim 12 wherein: N is Si; y and x are 0; o and l are 1; m is 0,1,2 or 3; n is 1; --R 1 methyl or ethyl, with the proviso that when m is 3 at least one --R 1 is alkyl having at least about 12 carbon atoms; R is a moiety of the formula: --R.sup.2 --Z.sup.3 wherein: --R 2 -- is divalent alkylene; and Z 3 is a moiety selected from the group consisting --NH 2 , --OH, --(cyclo-O-HC-CH 2 ), --N═C═O, --NHC(O)-(N-lactam, --NHC(O)-(O-ketoxime) and --NHC(O)-(O-phenol).

Claim 15

Composite material of claim 1 wherein said polymeric matrix comprises a polyamide, a polyester, a halogenated polyolefin, a polycarbonate, a polyurethane, a polyether, a polyolefin, a polyvinyl, a polyamide or a combination thereof.

Claim 16

Composite of claim 14 wherein said polyester is poly (ethylene terephthalate), poly(butylene terephthalate) or poly(ethylene naphthalate).

Claim 17

Composite material of claim 14 wherein said polyolefin and halogenated polyolefin are selected from the group consisting of polyethylene, polypropylene, poly(methyl pentene), a polyolefin elastomer and poly(chlorotrifluoroethylene).

Claim 18

Composite material of claim 14 wherein said polyvinyl is poly(co-ethylene-vinylalcohol), or polyvinyl chloride.

Claim 19

Composite material of claim 14 wherein said polyamide is nylon-6, nylon 6,6 or nylon -12.

Claim 20

Composite material of claim 1 wherein said particles is less than about 50 A thick.

Claim 21

Composite material of claim 19 wherein said particles is less than about 20 A in thickness.

Claim 22

Composite material of claim 20, wherein the thickness of said particles is about 5 to about 20 A thick.

Claim 23

Composite material of claim 19 wherein the average interparticle spacing between particles is greater than about 15 A.

Claim 24

Composite material of claim 22, wherein the average interparticle spacing between particles is greater than about 200 A.

Claim 25

Composite material of claim 1 wherein the amount of said particles in said material is equal to or greater than about 0.001% by weight of the material.

Claim 26

Composite material of claim 24 wherein said amount is from 0.001 to about 60% by weight of the material.

Claim 27

Composite material of claim 25 wherein said amount is from about 0.01 to about 20% by weight of the material.

Claim 28

Composite material of claim 26 wherein said amount is from about 0.1 to about 10% by weight of the material.

Claim 29

An article of manufacture comprising a body, said body fabricated, totally or in part, from a composite material comprising a polymer matrix comprising a polymer, said matrix having layered or fibrillar particles uniformly dispersed therein, wherein the interlayer or interfibril distances is equal to or greater than about 50 A, the average thickness of said platelet particles is equal to or less than about 50 A where the maximum thickness is equal to or less than about 100 A and the average diameter of said fibrils is equal to or less than about 100 A where the maximum diameter is equal to or less than about 200 A, wheren the length to diameter ratio of said fibril is equal to or greater than about 10 to about 1, said particles having organo metallic species bonded thereto, said bonded species selected from the group consisting of organo silanes, organo titanates, and organo zirconates and having one or more moieties bonded to at least one polymer in said polymer matrix, or said species having one or more moieties which promote intermingling with at least one polymer in said polymer matrix or a combination of said species.

Claim 30

An article of manufacture comprising a body, said body fabricated, totally or in part, from a composite material comprising a polymer matrix comprising a polymer, said matrix having layered or fibrillar particles uniformly dispersed therein, wherein the interlayer or interfibril distances is equal to or greater than about 50 A, the average thickness of said platelet particles is equal to or less than about 50 A where the maximum thickness is equal to or less than about 100 A and the average diameter of said fibrils is equal to or less than about 100 A where the maximum diameter is equal to or less than about 200 A, wheren the length to diameter ratio of said fibril is equal to or greater than about 10 to about 1, said particles having organo metallic species bonded thereto, said bonded species selected from the group consisting of organo silanes, organo titanates, and organo zirconates and having one or more moieties bonded to at least one polymer in said polymer matrix, or said species having one or more moieties which promote intermingling with at least one polymer in said polymer matrix or a combination of said species.

Claim 31

A process for forming a polymeric composite which comprises layered or fibrillar particles dispersed in a polymeric matrix which comprises: forming a reaction mixture of an inorganic meterial comprising layered or fibrillar particles and an organo metallic species selected from the group consisting of organo silanes, organo titanates and organo zirconates, said species having one or more moieties which are capable of forming covalent bonds with said particles and said species having one or more moieties which are reactive with a polymer precursor or said species having one or more moieties which promote intermingling with a polymer formed by polymerization of said polymer precursor or a combination of said species to form a swellable and polymer compatible intercalated material comprising said species arrayed between said layers or fibrils with increased interlayer or interfibril spacing having a first residue of said organo metallic species covalently bonded to a surface of all or a portion of said particles; and polymerizing said polymer precursor in the presence of said swellable and polymer compatible intercalated material to form a composite having said particles uniformly dispersed in a polymeric matrix comprising said polymer, wherein the interlayer or interfibril distances is equal to or greater than about 50 A, the average thickness of said platelet particles is equal to or less than about 50 A where the maximum thickness is equal to or less than about 100 A and the average diameter of said fibrils is equal to or less than about 100 A where the maximum diameter is equal to or less than about 200 A, wheren the length to diameter ratio of said fibril is equal to or greater than about 10 to about 1, said particles having organo metallic species bonded thereto said bonded species having one or more moieties bonded to at least one polymer in said polymer matrix, or said species having one or more moieties which are comparable with at least one polymer in said polymer matrix which project away from the particle surface and which are not bonded to said polymer or a combination of said species.

Claim 32

A process for forming a polymeric composite which comprises layered or fibrillar particles dispersed in a polymeric matrix which comprises: forming a reaction mixture of an inorganic meterial comprising layered or fibrillar particles and an organo metallic species selected from the group consisting of organo silanes, organo titanates and organo zirconates, said species having one or more moieties which are capable of forming covalent bonds with said particles and said species having one or more moieties which are reactive with a polymer precursor or said species having one or more moieties which promote intermingling with a polymer formed by polymerization of said polymer precursor or a combination of said species to form a swellable and polymer compatible intercalated material comprising said species arrayed between said layers or fibrils with increased interlayer or interfibril spacing having a first residue of said organo metallic species covalently bonded to a surface of all or a portion of said particles; and polymerizing said polymer precursor in the presence of said swellable and polymer compatible intercalated material to form a composite having said particles uniformly dispersed in a polymeric matrix comprising said polymer, wherein the interlayer or interfibril distances is equal to or greater than about 50 A, the average thickness of said platelet particles is equal to or less than about 50 A where the maximum thickness is equal to or less than about 100 A and the average diameter of said fibrils is equal to or less than about 100 A where the maximum diameter is equal to or less than about 200 A, wheren the length to diameter ratio of said fibril is equal to or greater than about 10 to about 1, said particles having organo metallic species bonded thereto said bonded species having one or more moieties bonded to at least one polymer in said polymer matrix, or said species having one or more moieties which are comparable with at least one polymer in said polymer matrix which project away from the particle surface and which are not bonded to said polymer or a combination of said species.

Claim 33

A process according to claim 29 which comprises the steps of: (a) forming a reaction mixture comprising a polymer precursor and a swellable and polymer compatible intercalated material comprising layered or fibrillar particles having an organo metallic species selected from the group consisting of organo silanes, organo titanates and organo zirconates covalently bonded to their surfaces, said species having one or more moieties which are reactive with said polymer precursor or said species having one or more moieties which promote intermingling with a polymer formed by polymerization of said polymer precursor or a combination of said species said species being reactive with said polymer precursorf; and (b) polymerizing said polymer precursor in the presence of said swellable and polymer compatible interelated material to form a composite having said particles uniformly dispersed in a polymeric matrix comprising said polymer, wherein the interlayer or interfibril distances is equal to or greater than about 50 A, the average thickness of said platelet particles is equal to or less than about 50 A where the maximum thickness is equal to or less than about 100 A and the average diameter of said fibrils is equal to or less than about 100 A where the maximum diameter is equal to or less than about 200 A, wherein the length to diameter ratio of said fibril is equal to or greater than about 10 to about 1, said particles having organo metallic species bonded thereto said bonded species having one or more moieties bonded to at least one polymer in said polymer matrix, or said species having one or more moieties which are compatible with at least one polymer in said polymer matrix which project away from the particle surface and which are not bonded to said polymer or a combination of said species.

Claim 34

A process according to claim 30 which comprises the steps of: (a) forming a reaction mixture comprising a polymer precursor, a swellable comprising layered or fibrillar particles and an organo metallic species selected from the group consisting of organo silanes, organo titanates and organo zirconates, said species having one or more moieties which are capable of forming covalent bonds with said particles and said species having one or more moieties which are reactive with a polymer precursor or said species having one or more moieties which promote intermingling with a polymer formed by polymerization of said polymer precursor or a combination of said species to form a swellable and polymer compatible intercalated material having a first residue of said organo metallic species covalently bonded to a surface of all or a portion of said particles; and (b) polymerizing said polymer precursor in said mixture to form a composite having said particles uniformly dispersed in a polymeric matrix comprising said polymer, wherein the interlayer or interfibril distances is equal to or greater than about 50 A, the average thickness of said platelet particles is equal to or less than about 50 A where the maximum thickness is equal to or less than about 100 A and the average diameter of said fibrils is equal to or less than about 100 A where the maximum diameter is equal to or less than about 200 A, wheren the length to diameter ratio of said fibril is equal to or greater than about 10 to about 1, said particles having organo metallic species bonded thereto said bonded species having one or more moieties bonded to at least one polymer in said polymer matrix, or said species having one or more moieties which are compatible with at least one polymer in said polymer matrix which project away from the particle surface and which are not bonded to said polymer or a combination of said species.