Cure accelerators for anaerobic adhesive compositions

Details Cure accelerators for anaerobic adhesive compositions Cure accelerators for anaerobic adhesive compositions

2002-03-15

2004-04-20

Zalukaeva, Tatyana (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Processes of preparing a desired or intentional composition...

C156S306900, C156S311000, C525S484000, C525S504000, C526S217000, C526S323100, C528S099000, C528S113000, C528S124000

Reexamination Certificate

active

06723763

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a novel class of cure accelerators for anaerobic adhesive compositions.
2. Brief Description of Related Technology
Anaerobic adhesive compositions generally are well-known. See e.g., R. D. Rich, “Anaerobic Adhesives” in
Handbook of Adhesive Technology,
29, 467-79, A. Pizzi and K. L. Mittal, eds., Marcel Dekker, Inc., New York (1994), and references cited therein. Their uses are legion and new applications continue to be developed.
Conventional anaerobic adhesives ordinarily include a free-radically polymerizable acrylate ester monomer, together with a peroxy initiator and an inhibitor component. Oftentimes, such anaerobic adhesive compositions also contain accelerator components to increase the speed with which the composition cures.
Desirable anaerobic cure-inducing compositions to induce and accelerate cure may include saccharin, toluidines, such as N,N-diethyl-p-toluidine and N,N-dimethyl-o-toluidine, acetyl phenylhydrazine (“APH”), maleic acid, and quinones, such as napthaquinone and anthraquinone. See e.g., Loctite U.S. Pat. Nos. 3,218,305 (Krieble), 4,180,640 (Melody), 4,287,330 (Rich) and 4,321,349 (Rich).
In addition, other curatives for anaerobic adhesives include thiocaprolactam (e.g., U.S. Pat. No. 5,411,988) and thioureas [e.g., U.S. Pat. No. 3,970,505 (Hauser) (tetra methyl thiourea), German Patent Document Nos. DE 1 817 989 (alkyl thioureas and N,N′-dicyclohexyl thiourea) and 2 806 701 (ethylene thiourea), and Japanese Patent Document No. JP 07-308,757 (acyl, alkyl, alkylidene, alkylene and alkyl thioureas)], certain of the latter of which had been used commercially up until about twenty years ago.
Recently, Loctite Corporation has discovered a new class of materials—trithiadiaza pentalenes—effective as curatives for anaerobic adhesive compositions. The addition of these materials into anaerobic adhesives as a replacement for conventional curatives (such as APH) surprisingly provides at least comparable cure speeds and physical properties for the reaction products formed therefrom. (See International Patent Publication No. WO 00/40664.)
In an unrelated field of technology, U.S. Pat. No. 5,503,936 (Blyakhman) describes and claims curable modified epoxy resin compositions having an epoxy resin, a hardener or curing agent and 2.5 to 12.5% by weight of a compound represented by
where E and T are C
5-12
alkyl, C
5-8
cycloalkyl, C
7-15
phenylalkyl, or C
6-10
aryl, with or without substitution by one or two C
1-4
groups. The hardeners or curing agents of the '936 patent are described as aliphatic, aromatic or cycloaliphatic di- or polyamines, such as diethylenetriamine, N-aminoethylpiperazine, 4,4′-diaminodicyclohexylmethane, 4,4′-diaminodiphenyl sulfone, diethyldiaminotoluene, dicyandiamide, or guanidine; polycarboxylic acid anhydrides, such as phthalic anhydride or trimellitic anhydride; catalytic curing agents such as tertiary amines, imidazoles or complexes of boron trifluoride; difunctional and multifunctional phenols; or phenol or cresol novolac resins.
In addition, a number of suppliers including Flexsys America, Akron, Ohio, Sumitomo Chemical, Osaka, Japan, and Crompton Corporation, Waterbury, Conn. sell phenylene diamine type anti-oxidants, which are promoted to retard oxidation, degradation, or pre-mature polymerization.
There is an on-going desire to find alternative technologies to differentiate existing products and provide supply assurances in the event of shortages or cessation of supply of raw materials. Accordingly, it would be desirable to identify new materials which function as accelerators in the cure of anaerobic adhesives.
SUMMARY OF THE INVENTION
The present invention provides a new class of materials—phenylene diamines—, which surprisingly are effective as cure accelerators for anaerobic adhesive compositions. Members of this class of materials are promoted to retard oxidation, degradation, or pre-mature polymerization, and nevertheless function to accelerate the cure of anaerobic adhesive compositions.
The addition of these materials into anaerobic adhesives as a replacement for some or all of the amount of conventional anaerobic cure accelerators (such as the toluidines noted above) surprisingly provides at least comparable cure speeds and physical properties for the reaction products formed therefrom.
In one aspect of the invention, this class of materials may be defined as those within the following structure I:
where R and R
1
may be the same or different and may be selected from C
1-12
alkyl, C
1-12
alkenyl, C
5-12
cyclo or bicycloalkyl, C
6-18
aryl, and derivatives thereof, R
2
and R
3
may be the same or different and may be selected from hydrogen, C
1-12
alkyl, C
1-12
alkenyl, C
5-12
cyclo or bicycloalkyl, C
6-18
aryl, and derivatives thereof and
is C
6-18
arylene, and derivatives thereof, and oxidized versions thereof.
This invention also provides anaerobic adhesives and anaerobic adhesive systems prepared with such cure accelerators, methods of preparing and using the inventive anaerobic adhesives as well as reaction products of the inventive anaerobic adhesives.
The present invention will be more fully appreciated by a reading of the “Detailed Description of the Invention”, and the illustrative examples which follow thereafter.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides phenylene diamine cure accelerators, for use in the cure of anaerobic adhesives and anaerobic adhesive systems. The addition of such compounds as cure accelerators into anaerobic adhesives as a replacement for some or all of the amount of conventional cure accelerators surprisingly provides at least comparable cure speeds and physical properties for the reaction products formed.
In one aspect of the invention, the cure accelerators should have at least two amines, desirably secondary amines, available for reaction. In some instances, one or more of the amines may be primary or tertiary amines. For instance, these cure accelerators may be represented as within the following structure I:
where R and R
1
may be the same or different and may be selected from C
1-12
alkyl, C
1-12
alkenyl, C
5-12
cyclo or bicycloalkyl, C
6-18
aryl, and derivatives thereof, R
2
and R
3
may be the same or different and may be selected from hydrogen, C
1-12
alkyl, C
1-12
alkenyl, C
5-12
cyclo or bicycloalkyl, C
6-18
aryl, and derivatives thereof and
is C
6-18
arylene, and derivatives thereof, and oxidized versions thereof.
Within structure I are a variety of materials that may be used herein, for instance, the aromatic diamines represented by structures II:
where X is NH, O or S, R, R
1
, R
2
, and R
3
are as described above.
With that structure are those compounds within structure III:
where R is as defined above. In addition, the oxidized version (shown below as structure IIIa) of structure III is also within the scope of the invention.
Within structure III is structure IIIb below, N-2-pentyl-N′-phenyl-p-phenylene diamine, which may also be used.
This phenylene diamine is believed to be available from Uniroyal Chemical Co., under the tradename FLEXZONE 7L.
Other specific examples within structure III include N-phenyl-N′-(1,3-dimethylbutyl)-p-phenylenediamine; N-phenyl-N-isopropyl-p-phenylenediamine; N-phenyl-N′-(1-methylheptyl)-p-phenylenediamine; N-phenyl-N′-cyclohexyl-p-phenylenediamine; mixed diaryl-p-phenylenediamines; N,N′-diphenyl-p-phenylenediamine; N,N′-di-beta-naphthyl-p-phenylenediamine; N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine; N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine; N,N′-bis(1-methylheptyl)-p-phenylenediamine; N-phenyl-N′-p-toluenesulfonyl-p-phenylenediamine; N-phenyl-N′-alkyl-p-phenylenediamines; dialkyl-p-phenylenediamines; N,N′-bis(1-cyclohexyl-1-ethyl)-p-phenylenediamine; N,N′-di(sec-hexyl)-p-phenylenediamine; N-(1,3-dimethylbutyl)-N′-(1,4-dimethylpentyl)-p-phenylenediamine; N-(sec-hexyl)-N

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