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INTERNAL CORRESPONDENCE
CHEiVsS
AND PLASTICS
To (Nant) Dimion locslion
Mr. J. L. Myers Niagara Falls
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F. H. Ancker S. E. Berger R. E. 3yrne F. E. Critchfield L. G. Krauskopf R. W. Lind berg J. E. McKeon M. W. Ranney W. C. Thurber J
tarrytown technical center.
tarrytown. new york 10591
0a,# August 16, 1974
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Organic Elastomers
Amworing Itl'tr dal*
scbj.rt Coupling Agents - CALIDRIA Asbestos
Ref.:
Letters DDB to JLM dated 8/14/72 and 8/1/73
PLAINTIFF'S EXHIBIT
UC-379
The program to investigate the potential of utilizing phenolic inter facial coupling agents as a means of upgrading heat distortion resistance, compression set, permanent set and modulus when asbestos is used as a filler in rubber was augmented by the inclusion of a silane treated asbestos. The results to date in both respects are encouraging in that a positive coupling of the asbestos to the rubber backbone has been achieved. This letter will update you on our findings and serve to advise you that we recommend a con tinuance of these investigations. A Project Report will be issued shortly delineating the technology and tabulating the data with recommendations for further investigation.
Phenolic Interfacial Acents
The initial work involved the use of RG-600 (dimethylol tertiary-butyl
phenol treated asbestos) as well as an "in-situ" treat:
HFDO both
EPDM and NR using peroxide free radical and ionic sulfur and free radical
sulfur mechanisms. The results showed a blocking effect due to the t-butyl
tails with a drastic reduction in physical properties when compared to a
control of straight HPO.
A review of the chemistry indicated the need of an active site to
effect a coupling of the pre-reacted phenolic/asbestos specie with a rubber
polymer backbone. Dr. M. Bertolucci provided us with a sample of HPO
reacted with dimethylol isopropyl phenol and the results verify a coupling
effect. The negative results of the RG-600 (DMTBP) were rectified via
utilization of the active hydrogen available on the DM1PP submittal. It
is apparent that the logic that led to this coupling should be extended to
the use of a sulfur activated tail, most probably an ^-SH or, if practical
synthesis permits, a disulfide such as
- S-~- . In any event, reso
lution of this technology should be programmed via environmental testing
to determine the utility of phenolic interfacial agents on asbestos from akv^.u-c_j
cost-performance viewpoint in rubber.
i
1974
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Mr. J. L. Myers
August 16, 1974
Silane Coupling Agents
The letter of MWR to JHL (attached) indicates that the Acid Leached HPO (ALX) that was treated by S. E. Berger at Tarrytown with A-189 silane coupling agent gave positive filler-polymer coupling with a sulfur mechanism in EPDM and NR. The treatment of HPO with A-189 was tried a few years ago with no success. It was theorized that the resulting filler-coupling agent reaction of -~*Mg-0-Si-*^ was the weak link in the filler-polymer bonding. Mr. Berger's treatment to remove the brucite surface of the HPO with sub sequent treatment with A-189 has produced an a--Si-O-Si bond, the results of which are very encouraging. In strictly preliminary screening, we have seen the heretofore very high "set at break" (over 100%) reduced by factors of 4 to 5. This, along with over 50% increase in modulus, is proof that an effective coupling has occurred. We have asked Mr. Berger to prepare 10 lbs. of this material for further investigations. It is recommen ded that an acceleration study followed by environmental tests be set up to determine the cost-performance parameters of this specie.
In closing, it is apparent that an effective chemical bond is possible (with both of the above methods) between asbestos and a rubber backbone. As far as we know, this is the first time this has been done using these technologies. While considerable work is ahead to determine the feasibility of market penetration, the positive results to date encourage us to make the recommendation of extension of the concept of coupling agents for asbestos.
D. D. Berry/et Enc. .
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J. H. Lorenz Chemicals and Plastics New York - 32nd Floor
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S. E. Berger C. A. Bergeson ^ D. D. Berry L. G. Krausk G. A. Skoler K. J. Sollman S. Sterman W. C. Thurber
TARRYTC'.VN UCKNICAL CENTER.
TARRYTCTVN. NEW YORK 1053:
but* August 13, 1974
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Answering teller dolt
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Silane-treated Asbestos
As an extension of our recent work relating to the activation of asbestos for subsequent use as interfacial bonding agents, we have prepared a mercapto- and methacrylato-silane treated asbestos. Mr. Berger and I believe that these should respond in elastomers, epoxy, thermoset polyesters, etc., to give the typical rein forcing action noted with many other fillers and silanes.
A sample of A-189 treated asbestos (activated) was provided to Mr. D. Berry on May 8, 1974 with a request to run a few screening studies. The initial results look pretty encouraging and the physical properties clearly indicate that we are seeing effective coupling of the asbestos and the elastomers.
We believe that these observations, the first truly effective coupling of asbestos in rubber, can be translated to many similar polymer systems. This effect appears patentable and Mr. Berger is proceeding along these lines. As this is largely a non-programmed area, progress will be limited this year, but we do plan a continuing program and we will obtain sufficient data for a patent application by December 1, 1974.
findings.
In the meantime, we plan no outside disclosure of these very significant
M. W. Ranney/ok