US5554670A
Expired / Lapsed
US
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Method of preparing layered silicate-epoxy nanocomposites
Assignee: Cornell Research Foundation Inc
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Filing: 1994-09-12
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Granted: 1996-09-10
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Expires: 2014-09-12
Abstract
Abstract An epoxy-silicate nanocomposite is prepared by dispersing an organically modified smectite-type clay in an epoxy resin together with diglycidyl ether of bisphenol-A (DGEBA), and curing in the presence of either nadic methyl anhydride (NMA), and/or benzyldimethyl amine (BDMA), and/or boron trifluoride monoethylamine (BTFA) at 100°-200° C. Molecular dispersion of the layered silicate within the crosslinked epoxy matrix is obtained, with smectite layer spacings of 100 Å or more and good wetting of the silicate surface by the epoxy matrix. The curing reaction involves the functional groups of the alkylammonium ions located in the galleries of the organically modified clay, which participate in the crosslinking reaction and result in direct attachment of the polymer network to the molecularly dispersed silicate layers. The nanocomposite exhibits a broadened T s at slightly higher temperature than the unmodified epoxy. The dynamic storage modulus of the nanocomposite was considerably higher in the glassy region and very much higher in the rubbery plateau region when compared to such modulus in the unmodified epoxy.
Inventors
- 👤 Emmanuel P. Giannelis
- 👤 Phillip B. Messersmith
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 02:56
CPC Classifications
C; C08; C08G; C08G59/00; C08G59/18; C08G59/40; C08G59/14; C08G59/1405; B; B82; B82B; B82B3/00; B82Y; B82Y30/00; C08G59/4007; C08G65/00; C08K; C08K9/00; C08K9/04; C09; C09C; C09C1/00; C09C1/40; C09C1/42; C01; C01P; C01P2002/00; C01P2002/20; C01P2002/22; C01P2002/70; C01P2002/72; C01P2002/78; C01P2002/80; C01P2002/82; C01P2004/00; C01P2004/01; C01P2004/04; C01P2004/54; C01P2004/60; C01P2004/64; C01P2006/00; C01P2006/32; C01P2006/33; C01P2006/90
Claims Analysis
Total Claims: 11
Claim 1
Independent Claim
241 words
A method for preparing an epoxy-smectite clay nanocomposite, comprising dispersing a smectite clay in a dry state into a liquid diglycidyl ether of bisphenol A (DGEBA) said smectite-type clay having been modified to an organoclay by ion exchange with an alkyl ammonium salt; the positive ion of the salt being of the form + NH 3 R 1 , + NH 2 R 2 R 3 , + NHR 4 R 5 R 6 , or + NR 7 R 8 R 9 R 10 , wherein R 1 through R 10 are organic radicals; and wherein R 1 , at least one of R 2 and R 3 , at least one of R 4 , R 5 , and R 6 , and at least one of R 7 , R 8 , R 9 and R 10 , contain a functional group capable of reacting and bonding with the epoxy upon crosslinking of same; wherein said dispersing step is sufficient to transform the initial mixture from opaque to semi-transparent; and curing in the presence of a curing agent which both produces delamination of the organoclay and either cross-links the DGEBA in the presence of said organoclay, reacts directly with the organoclay, or catalyzes the crosslinking reaction between the organoclay and DGEBA, wherein said curing agent is selected from one or more members of the group consisting of nadic methyl anhydride (NDA), benzyldimethylamine (BDMA) and boron trifluoride monoethylamine (BTFA).
Claim 2
Independent Claim
241 words
A method for preparing an epoxy-smectite clay nanocomposite, comprising dispersing a smectite clay in a dry state into a liquid diglycidyl ether of bisphenol A (DGEBA) said smectite-type clay having been modified to an organoclay by ion exchange with an alkyl ammonium salt; the positive ion of the salt being of the form + NH 3 R 1 , + NH 2 R 2 R 3 , + NHR 4 R 5 R 6 , or + NR 7 R 8 R 9 R 10 , wherein R 1 through R 10 are organic radicals; and wherein R 1 , at least one of R 2 and R 3 , at least one of R 4 , R 5 , and R 6 , and at least one of R 7 , R 8 , R 9 and R 10 , contain a functional group capable of reacting and bonding with the epoxy upon crosslinking of same; wherein said dispersing step is sufficient to transform the initial mixture from opaque to semi-transparent; and curing in the presence of a curing agent which both produces delamination of the organoclay and either cross-links the DGEBA in the presence of said organoclay, reacts directly with the organoclay, or catalyzes the crosslinking reaction between the organoclay and DGEBA, wherein said curing agent is selected from one or more members of the group consisting of nadic methyl anhydride (NDA), benzyldimethylamine (BDMA) and boron trifluoride monoethylamine (BTFA).
Claim 3
Dependent Claim
28 words
A method in accordance with claim 1, wherein said functional group is selected from one or more members of the group consisting of hydroxyl, epoxy, and carboxylic groups.
Claim 4
Dependent Claim
23 words
A method in accordance with claim 1, wherein said ammonium salt has at least one alkyl ammonium chain having a terminal hydroxyl group.
Claim 5
Dependent Claim
20 words
A method in accordance with claim 1, wherein said ammonium salt comprises a bis (2-hydroxyethyl) methyl tallow alkyl ammonium salt.
Claim 6
Dependent Claim
14 words
A method in accordance with claim 1, wherein said smectite clay comprises a montmorillonite.
Claim 7
Dependent Claim
36 words
A method in accordance with claim 1, wherein said curing agent is capable of catalyzing the homopolymerization of DGEBA and catalyzing the reaction between said organoclay terminal hydroxyl group and the oxirane rings of said DGEBA.
Claim 8
Dependent Claim
13 words
A method in accordance with claim 6, wherein said curing agent comprises BDMA.
Claim 9
Dependent Claim
21 words
A method in accordance with claim 1, wherein said quaternary ammonium salt comprises a bis (2-hydroxyethyl) methyl tallow alkyl ammonium salt.
Claim 10
Dependent Claim
23 words
A method in accordance with claim 1, in which said curing is conducted at temperatures in the range of 100° to 200° C.
Claim 11
Dependent Claim
39 words
A method in accordance with claim 1, wherein dispersing of the dry smectite in the epoxy resin is carried out by mixing the smectite and DGEBA at temperatures in the range of 20° to 150° C., following by sonification.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1999-09-10 | 2000-03-11 | 2000-09-10 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2003-09-10 | 2004-03-11 | 2004-09-10 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2007-09-10 | 2008-03-11 | 2008-09-10 | $7700.00 | Window Closed / Lapsed |