Melt process formation of polymer nanocomposite of exfoliated layered material

Claim 2

A composite material comprising: a) a polymer matrix which comprises a melt processible polymer having a melt processing temperature equal to or greater than about 220° C., and b) dispersed platelet particles having average thickness less than 50 Å and a maximum thickness of about 100 Å, and having an onium chemical species bonded to them, said chemical species selected from the group consisting of onium compounds of the formula +NH.sub.3 R.sub.1 and +NH.sub.2 R.sub.2 R.sub.3 wherein: R 1 has the formula --(CHR 9 Z) q --R 8 and R 2 and R 3 are the same or different and are organic radicals having at least about 4 carbon atoms; and R 2 , and R 3 are alkyl, alkenyl, alkynyl, aryl, alkoxy, alkoxyalkyl, aryloxyalkyl, aryloxyaryl, cycloalkyl. cycloalkenyl, cycloalkynyl, alkanoylalkyl, alkylaryl, arylalkyl, amino, alkylaminoalkyl, dialkylaminoalkyl, arylaminoalkyl, diarylaminoalkyl, alkylarylaminoalkyl, alkylsulfinyl, alkylsulfonyl, alkylthio, arylsulfinyl, arylsulfonyl, arylthio, alkoxycarbonylalkyl, a moiety of the formula: --(CHR.sub.9 Z).sub.q --R.sub.8 wherein R 8 is alkyl, cycloalkyl, or aryl, R 9 is hydrogen, alkyl, or aryl, q is an integer equal to or greater than 1, and Z is --O-- or --NR 10 -- where R 10 is hydrogen, alkyl, aryl, or alkylsilane, or a moiety of the formula --R.sub.11 --Z.sub.1 --R.sub.12 or R 2 and R 3 together form a divalent moiety of the formula: --R.sub.11 --,--R.sub.11 --Z.sub.1 --R.sub.11, or --R.sub.11 Z.sub.1 completing an alicyclic ring, wherein --R 11 is alkylene,, alkenylene, alkynylene, and --Z 1 -- is --O--, --NR 13 --,--+N(R 13 ) 2 --, --S--, --S(O) 2 --, --OC(O)--, or--N(R 13 )C(O)--; wherein R 12 is alkyl, alkylaryl, alkoxyalkyl, alkenyl, alkynyl, aryl, cycloalkyl, or cycloalkenyl and R 13 is hydrogen or alkyl having from 1 to 4 carbon atoms; wherein the onium compounds are either unsubstituted or have as substituents amino, alkenyl, oxide, acyloxy, hydroxy, isocyanato, ureido, halo, epoxy, epichlorohydrin, sulfuryl halide, mercapto, ester, --NH 2 , CONH 2 , CH 2 --X (where X is Cl, Br, or I), --CH═CH 2 , --SH, S--M+, or O--M+ (where M+ is Na+, Li+, and K+) moieties, said platelet particles being present in an amount of from about 0.001 to about 60% by weight of the composite material.

Claim 3

Composite material of claim 1 wherein said platelet particles are derived from phyllosilicates.

Claim 4

Composite material of claim 2 wherein said phyllosilicates have from about 0.2 to about 0.9 basic charges per formula unit.

Claim 5

Composite material of claim 3 wherein said phyllosilicates are smectites clay minerals.

Claim 6

Composite material of claim 4 wherein said smectites are selected from the group consisting of montmorillonite, nontronite, beidellite, volkonskoite, hectorite, saponite, sauconite, magadiite and kenyaite.

Claim 7

Composite material of claim 5 wherein said smectites are montmorrillonite or hectorite.

Claim 8

Composite material of claim 3 wherein said swelling/compatibilizing agent is selected from the group consisting of primary ammonium cationic complexes of the formula: .sup.+ NH.sub.3 R.sub.1 or .sup.+ NH.sub.2 R.sub.2 R.sub.3 wherein: R 1 is an aliphatic radical having at least about 15 aliphatic carbon atoms, said radical including one or more heteroatoms, carbonyl functions or a combination thereof; and R 2 and R 3 are the same or different and are aliphatic radicals having at least about four aliphatic carbon atoms, or R 2 and R 3 together may form a divalent aliphatic chain having at least about four aliphatic carbon atoms forming an alicyclic structure, said radical or chain optionally including one or more heteroatoms, carbonyl function or a combination thereof.

Claim 9

Composite material of claim 7 wherein: R 1 is an aliphatic radical having at least about 18 carbon atoms, said aliphatic radical includes one or heteroatoms, carbonyl functions or a combination thereof; and R 2 and R 3 are the same or different and are aliphatic radicals having at least about five aliphatic carbon atoms or R 2 and R 3 together may form a divalent aliphatic chain having at least about five aliphatic carbon atoms, said aliphatic radicals and chain may optional include one or more heteroatoms, carbonyl functions or a combination thereof.

Claim 10

Composite material of chain 8 wherein: R 2 and R 3 are the same or different and are cycloalkyl, cycloalkenyl, cycloalkynyl, alkyl, alkenyl or alkynyl or a moiety of the formula: --R.sup.17 --Z.sub.1 --R.sup.18 or R 2 and R 3 together may form a divalent moiety of the formula: --R.sup.17 --, --R.sup.17 --Z.sub.1 --R.sup.17 -- or --R.sup.17 --Z.sub.1 -- completing an alicyclic ring, wherein: --R 17 -- is the same or different at each occurrence and is divalent, alkylene, cycloalkylene, cycloalkenylene, alkenylene or alkynylene; --R 18 is alkyl, alkylaryl, alkoxyaryl, alkenyl, alkynyl, aryl, cycloalkyl, or cycloalkenyl; --Z 1 -- is --O--, --NR 19 --, -- + N(R 19 ) 2 --, --S--, --S(O) 2 , --OC(O)-- or --N(R 19 )C(O)-- and R 19 is hydrogen or alkyl having from 1 to abot 4 carbon atoms.

Claim 11

Composite material of chain 8 wherein: R 2 and R 3 are the same or different and are cycloalkyl, cycloalkenyl, cycloalkynyl, alkyl, alkenyl or alkynyl or a moiety of the formula: --R.sup.17 --Z.sub.1 --R.sup.18 or R 2 and R 3 together may form a divalent moiety of the formula: --R.sup.17 --, --R.sup.17 --Z.sub.1 --R.sup.17 -- or --R.sup.17 --Z.sub.1 -- completing an alicyclic ring, wherein: --R 17 -- is the same or different at each occurrence and is divalent, alkylene, cycloalkylene, cycloalkenylene, alkenylene or alkynylene; --R 18 is alkyl, alkylaryl, alkoxyaryl, alkenyl, alkynyl, aryl, cycloalkyl, or cycloalkenyl; --Z 1 -- is --O--, --NR 19 --, -- + N(R 19 ) 2 --, --S--, --S(O) 2 , --OC(O)-- or --N(R 19 )C(O)-- and R 19 is hydrogen or alkyl having from 1 to abot 4 carbon atoms.

Claim 12

Composite material of claim 9 wherein: R 2 and R 3 are the same or different and are alkyl; or R 2 and R 3 together may form a divalent moiety of the formula: -R.sup.17 -- or --R.sup.17 --Z.sub.1 --R.sup.17 -- --R.sup.17 -- is alkylene; Z.sub.1 is --O--, --NH--or --.sup.+ N(R.sup.19).sub.2 --; R 19 is hydrogen or alkyl of from 1 to about 4 carbon atoms.

Claim 13

Composite material of 1 wherein said polymeric matrix comprises a polyamide selected from the group consisting of nylon-6, nylon 6,6 or nylon -12.

Claim 14

Composite material of 1 wherein said polymeric matrix comprises a polyamide selected from the group consisting of nylon-6, nylon 6,6 or nylon -12.

Claim 15

Composite material of claim 1 wherein said platelet particle is less than about 50 Å thick.

Claim 16

Composite material of claim 12 wherein said platelet particle is less than about 20 Å in thickness.

Claim 17

Composite material of claim 13 wherein the thickness of said platelet particle is about 5 to about 20 Å thick.

Claim 18

Composite material of claim 14 wherein the average interparticle spacing between platelet particles is greater than about 15 Å.

Claim 19

Composite material of claim 15 wherein the average interparticle spacing between platelet particles is greater than about 200 Å.

Claim 20

Composite material of claim 16 wherein the average interparticle spacing between platelet particles is greater than about 2,000 Å.

Claim 21

Composite material of claim 16 wherein the amount of platelet particles in said material is equal to or greater than about 0.01% by weight of the material.

Claim 22

Composite material of claim 18 wherein said amount is from 0.01 to about 60% by weight of the material.

Claim 23

Composite material of claim 19 wherein said amount is from about 0.01 to about 40 by weight of the material.

Claim 24

Composite material of claim 20 wherein said amount is from about 0.1 to about 30 by weight of the material.

Claim 25

An article of manufacture comprising a body, said body fabricated, totally or in part, from a composite material comprising a polymer matrix comprising a melt processible polyamide polymer having a melt processing temperature equal to or greater than about 220° C. and dispersed platelet particles having average thickness less than 50 Å, said particles having an onium chemical species bonded to the surface thereof, said onium species of the formula: +NH.sub.3 R.sub.1 and +NH.sub.2 R.sub.2 R.sub.3 wherein: R 1 has the formula --CHR 9 Z) q--R 8 and R 2 and R 3 are the same or different and are organic radicals having at least about 4 carbon atoms; and R 2 , and R 3 are alkyl, alkenyl, alkynyl, aryl, alkoxy, alkoxyalkyl, aryloxyalkyl, aryloxyaryl, cycloalkyl, cycloalkenyl, cycloalkynyl, alkanoylalkyl, alkylaryl, arylalkyl, amino, alkylaminoalkyl, dialkylaminoalkyl, arylaminoalkyl, diarylaminoalkyl, alkylarylaminoalkyl, alkylsulfinyl, alkylsulfonyl, alkylthio, arylsulfinyl, arylsulfonyl, arylthio, alkoxycarbonylalkyl, a moiety of the formula: --(CHR.sub.9 Z).sub.q --R.sub.8 wherein R 8 is alkyl, cycloalkyl, or aryl, R 9 is hydrogen, alkyl, or aryl, q is an integer equal to or greater than 1, and Z is --O-- or --NR 10 -- where R 10 is hydrogen, alkyl, aryl, or alkylsilane, or a moiety of the formula --R.sub.11 --Z.sub.1 --R.sub.12 or R 2 and R 3 together form a divalent moiety of the formula: --R.sub.11, --R.sub.11 --Z.sub.1 --R.sub.11 or --R.sub.11 Z.sub.1 completing an alicyclic ring, wherein --R 11 -- is alkylene, alkenylene, alkynylene, and --Z 1 -- is --O--, --NR 13 --, --+N(R 13 ) 2 , --S--, --S(O) 2 --, --OC(O)--, or--N(R 13 )C(O)--; wherein R 12 is alkyl, alkylaryl, alkoxyalkyl, alkenyl, alkynyl, aryl, cycloalkyl, or cycloalkenyl and R 13 is hydrogen or alkyl having from 1 to 4 carbon atoms; wherein the onium compounds are either unsubstituted or have as substituents amino, alkenyl, oxide, acyloxy, hydroxy, isocyanato, ureido, halo, epoxy, epichlorohydrin, sulfuryl halide, mercapto, ester, --NH 2 , CONH 2 , CH 2 --X (where X is Cl, Br, or I), --CH═CH 2 , --SH, S--M+, or O--M+ (where M+ is Na+, Li+, and K+) moieties, said platelet particles being present in an amount of from about 0.001% to about 60% by weight of the composite material.

Claim 26

An article of manufacture comprising a body, said body fabricated, totally or in part, from a composite material comprising a polymer matrix comprising a melt processible polyamide polymer having a melt processing temperature equal to or greater than about 220° C. and dispersed platelet particles having average thickness less than 50 Å, said particles having an onium chemical species bonded to the surface thereof, said onium species of the formula: +NH.sub.3 R.sub.1 and +NH.sub.2 R.sub.2 R.sub.3 wherein: R 1 has the formula --CHR 9 Z) q--R 8 and R 2 and R 3 are the same or different and are organic radicals having at least about 4 carbon atoms; and R 2 , and R 3 are alkyl, alkenyl, alkynyl, aryl, alkoxy, alkoxyalkyl, aryloxyalkyl, aryloxyaryl, cycloalkyl, cycloalkenyl, cycloalkynyl, alkanoylalkyl, alkylaryl, arylalkyl, amino, alkylaminoalkyl, dialkylaminoalkyl, arylaminoalkyl, diarylaminoalkyl, alkylarylaminoalkyl, alkylsulfinyl, alkylsulfonyl, alkylthio, arylsulfinyl, arylsulfonyl, arylthio, alkoxycarbonylalkyl, a moiety of the formula: --(CHR.sub.9 Z).sub.q --R.sub.8 wherein R 8 is alkyl, cycloalkyl, or aryl, R 9 is hydrogen, alkyl, or aryl, q is an integer equal to or greater than 1, and Z is --O-- or --NR 10 -- where R 10 is hydrogen, alkyl, aryl, or alkylsilane, or a moiety of the formula --R.sub.11 --Z.sub.1 --R.sub.12 or R 2 and R 3 together form a divalent moiety of the formula: --R.sub.11, --R.sub.11 --Z.sub.1 --R.sub.11 or --R.sub.11 Z.sub.1 completing an alicyclic ring, wherein --R 11 -- is alkylene, alkenylene, alkynylene, and --Z 1 -- is --O--, --NR 13 --, --+N(R 13 ) 2 , --S--, --S(O) 2 --, --OC(O)--, or--N(R 13 )C(O)--; wherein R 12 is alkyl, alkylaryl, alkoxyalkyl, alkenyl, alkynyl, aryl, cycloalkyl, or cycloalkenyl and R 13 is hydrogen or alkyl having from 1 to 4 carbon atoms; wherein the onium compounds are either unsubstituted or have as substituents amino, alkenyl, oxide, acyloxy, hydroxy, isocyanato, ureido, halo, epoxy, epichlorohydrin, sulfuryl halide, mercapto, ester, --NH 2 , CONH 2 , CH 2 --X (where X is Cl, Br, or I), --CH═CH 2 , --SH, S--M+, or O--M+ (where M+ is Na+, Li+, and K+) moieties, said platelet particles being present in an amount of from about 0.001% to about 60% by weight of the composite material.

Claim 27

A process for forming a polymeric composite which comprises platelet particles dispersed in a polymeric matrix, said process comprising: (a) forming a flowable mixture comprising a polyamide polymer melt at a temperature equal to or greater than about 220° C. and a swellable and polymer-compatible intercalated layered material having an onium species is bonded to the surface of the layers of said material, said onium species of the formula: +NH.sub.3 R.sub.1 and +NH.sub.2 R.sub.2 R.sub.3 wherein: R 1 has the formula --(CHR 9 Z) q --R 8 and R 2 and R 3 are the same or different and are organic radicals having at least about 4 carbon atoms; and R 2 , and R 3 are alkyl, alkenyl, alkynyl, aryl, alkoxy, alkoxyalkyl, aryloxyalkyl, aryloxyaryl, cycloalkyl, cycloalkenyl, cycloalkynyl, alkanoylalkyl, alkylaryl, arylalkyl, amino, alkylaminoalkyl, dialkylaminoalkyl, arylaminoalkyl, diarylaminoalkyl, alkylarylaminoalkyl, alkylsulfinyl, alkylsulfonyl, alkylthio, arylsulfinyl, arylsulfonyl, arylthio, alkoxycarbonylalkyl, a moiety of the formula: --(CHR.sub.9 Z).sub.q --R.sub.8 wherein R 8 is alkyl, cycloalkyl, or aryl, R 9 is hydrogen, alkyl, or aryl, q is an integer equal to or greater than 1, and Z is --O-- or --NR 10 where R 10 is hydrogen, alkyl, aryl, or alkylsilane, or a moiety of the formula --R.sub.11 --Z.sub.1 --R.sub.12 or R 2 and R 3 together form a divalent moiety of the formula: --R.sub.11 --, --R.sub.11 --Z.sub.1 --R.sub.11, or --R.sub.11 Z.sub.1 completing an alicyclic ring, wherein --R 11 -- is alkylene, alkenylene, alkynylene, and --Z 1 is --O--, --NR 13 --, --+N(R 13 ) 2 --, --S--, --S(O) 2 , --OC(O) or --N(R 13 )C(O)--; wherein R 12 is alkyl, alkylaryl, alkoxyalkyl, alkenyl, alkynyl, aryl, cycloalkyl, or cycloalkenyl and R 13 is hydrogen or alkyl having from 1 to 4 carbon atoms; wherein the onium compounds are either unsubstituted or have as substituents amino, alkenyl, oxide, acyloxy, hydroxy, isocyanato, ureido, halo, epoxy, epichlorohydrin, sulfuryl halide, mercapto, ester, --NH 2 , CONH 2 , CH 2 --X (where X is Cl, Br, or I), --CH═CH 2 , --SH, S--M+, or O--M+ (where M+ is Na+, Li+, and K+) moieties, said platelet particles being present in an amount of from about 0.001% to about 60% by weight of the composite material; and (b) subjecting said mixture to a shear having a shear rate which is sufficient to dissociate all or a portion of said layers to form platelet particles having an average thickness of less than about 50 Å and to uniformly disperse said platelet particles in said polymer to form said polymer composite wherein said platelet particles are uniformly dispersed in said matrix.

Claim 28

A process for forming a polymeric composite which comprises platelet particles dispersed in a polymeric matrix, said process comprising: (a) forming a flowable mixture comprising a polyamide polymer melt at a temperature equal to or greater than about 220° C. and a swellable and polymer-compatible intercalated layered material having an onium species is bonded to the surface of the layers of said material, said onium species of the formula: +NH.sub.3 R.sub.1 and +NH.sub.2 R.sub.2 R.sub.3 wherein: R 1 has the formula --(CHR 9 Z) q --R 8 and R 2 and R 3 are the same or different and are organic radicals having at least about 4 carbon atoms; and R 2 , and R 3 are alkyl, alkenyl, alkynyl, aryl, alkoxy, alkoxyalkyl, aryloxyalkyl, aryloxyaryl, cycloalkyl, cycloalkenyl, cycloalkynyl, alkanoylalkyl, alkylaryl, arylalkyl, amino, alkylaminoalkyl, dialkylaminoalkyl, arylaminoalkyl, diarylaminoalkyl, alkylarylaminoalkyl, alkylsulfinyl, alkylsulfonyl, alkylthio, arylsulfinyl, arylsulfonyl, arylthio, alkoxycarbonylalkyl, a moiety of the formula: --(CHR.sub.9 Z).sub.q --R.sub.8 wherein R 8 is alkyl, cycloalkyl, or aryl, R 9 is hydrogen, alkyl, or aryl, q is an integer equal to or greater than 1, and Z is --O-- or --NR 10 where R 10 is hydrogen, alkyl, aryl, or alkylsilane, or a moiety of the formula --R.sub.11 --Z.sub.1 --R.sub.12 or R 2 and R 3 together form a divalent moiety of the formula: --R.sub.11 --, --R.sub.11 --Z.sub.1 --R.sub.11, or --R.sub.11 Z.sub.1 completing an alicyclic ring, wherein --R 11 -- is alkylene, alkenylene, alkynylene, and --Z 1 is --O--, --NR 13 --, --+N(R 13 ) 2 --, --S--, --S(O) 2 , --OC(O) or --N(R 13 )C(O)--; wherein R 12 is alkyl, alkylaryl, alkoxyalkyl, alkenyl, alkynyl, aryl, cycloalkyl, or cycloalkenyl and R 13 is hydrogen or alkyl having from 1 to 4 carbon atoms; wherein the onium compounds are either unsubstituted or have as substituents amino, alkenyl, oxide, acyloxy, hydroxy, isocyanato, ureido, halo, epoxy, epichlorohydrin, sulfuryl halide, mercapto, ester, --NH 2 , CONH 2 , CH 2 --X (where X is Cl, Br, or I), --CH═CH 2 , --SH, S--M+, or O--M+ (where M+ is Na+, Li+, and K+) moieties, said platelet particles being present in an amount of from about 0.001% to about 60% by weight of the composite material; and (b) subjecting said mixture to a shear having a shear rate which is sufficient to dissociate all or a portion of said layers to form platelet particles having an average thickness of less than about 50 Å and to uniformly disperse said platelet particles in said polymer to form said polymer composite wherein said platelet particles are uniformly dispersed in said matrix.

Claim 29

A composite material of claim 1 having an ultimate elongation, tensile modulus, tensile yield strength and heat distortion under load which is greater than that of said polymer.

Claim 30

A composite material of claim 24 wherein said ultimate elongation is at least about two times the ultimate elongation of said polymer.

Claim 31

A composite material of claim 25 wherein said ultimate elongation is at least about three times the ultimate elongation of said polymer.