Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Compositions to be polymerized by wave energy wherein said...
Reexamination Certificate
1998-08-10
2001-09-18
Seidleck, James J. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Compositions to be polymerized by wave energy wherein said...
C522S006000, C522S070000, C522S075000, C522S080000, C522S182000, C522S184000, C526S077000, C526S089000, C526S215000, C427S517000, C427S207100, C427S516000
Reexamination Certificate
active
06291544
ABSTRACT:
This invention relates to reactive esters of 2-cyanopenta-2,4-dienoic acid and the adhesives and polymers thereof.
Esters of the 2-cyanopenta-2,4-dienoic acid have been reported in the patent literature. The ethyl (U.S. Pat. No. 3,316,227), alkenyl and alkoxyalkyl (U.S. Pat. No. 3,554,990) esters have been particularly described. These monomers can polymerise under the influence of weak alkali and are suitable for adhesives. Their use as modifiers to cyanoacrylate adhesives (U.S. Pat. No. 4,425,471) and for the manufacture of photoresists (EP 0404 446 A2) has also been reported. All of the cyanopentadienoates reported in the literature were obtained and used in non-purified form, which renders them unstable for storage and does not reveal fully their inherent adhesive properties.
The present invention provides pure, storage stable, reactive esters of 2-cyanopenta-2,4-dienoic acid and the adhesives and polymers thereof. The monomers of the present invention have the formula:
where R is alkyl, alkenyl, alkynyl, alkoxyalkyl, alkenyloxyalkyl, alkynyloxyalkyl, poly(oxyalkyl), acryl, cycloalkyl or a heterocyclyc radical. R may also be one of the foregoing moieties substituted with one or more of the other moieties; this includes the case of a substituent itself being substituted. R may also contain halogens.
Specific examples of R are methyl, ethyl, allyl, methoxyethyl, ethoxyethyl.
The reactive monomers of this invention are obtained by reacting acrolein with
CHCH
2
COOR
where R is the same radical as described above. The reaction of acrolein with cyanoacetates is chemically consistent in nature to the reaction of acrolein with active methylene compound as described in U.S. Pat. No. 3,316,227. All of the considerations derived in this reference hold true for the present reaction between acrolein and cyanoacetates.
A distinctive feature of the reactive monomers of the present invention is that they are purified by one or more consecutive distillations under vacuum.
A distinctive feature of the reactive monomers of the present invention is that they posses improved shelf-life in monomeric form compared to non-purified monomers.
A distinctive feature of the reactive monomers of the present invention is that they have quicker setting time when used as adhesives, compared to non-purified monomers.
A distinctive feature of the reactive monomers of the present invention is that they can polymerise to high molecular weight polymers via anionic, cationic or radical mechanism (
FIG. 1
) as well as via a combination of any of them.
A distinctive feature of the reactive monomers of the present invention is their universal adhesion towards metals, plastics, rubbers, glass, wood, paper, live soft or bone tissue. Adhesive bond is formed within seconds to minutes at ambient temperature when the reactive monomers or their formulated adhesives are spread as a thin film between the substrates.
A distinctive feature of the reactive monomers of the present invention is that their adhesive bonds have higher bond strength, higher temperature and moisture resistance, compared to non-purified monomers.
A distinctive feature of the reactive monomers of the present invention is that the monomers and the adhesive bond and polymers thereof are free from impurities from the manufacturing process, compared to non-purified monomers.
A distinctive feature of the reactive monomers of the present invention is that their purity makes them especially suitable for bonding soft or bone tissue, as well as for embolic and occluding agent, in medicine and surgery. An added advantage is that the resultant polymeric adhesive jointing layer is rubbery at body temperature.
A distinctive feature of the reactive monomers of the present invention is that they are stabilised with anionic and free-radical polymerisation inhibitors. Anionic polymerisation inhibitors could be sulfur dioxide, hydrogen fluoride, phosphoric, phosphonic, sulfuric, sulphonic, carboxilic and organic sulfonic acids, sultones, boron trifluoride and its complexes, and phosphazenes for example. The free-radical polymerisation inhibitors are usually hydroquinone, p-methoxyphenol, t-butyl catehol, butylated hydroxytoluene or butylated hydroxyanisole, for example.
The inhibitors are normally used in small amounts of from 0.00001 to 1% by weight of the monomer. The preferred quantities for the above mentioned inhibitors are: acidic gasses—from 0.0001% to 0.06%; acids—from 0.0001% to 0.01%; sultones—from 0.001% to 0.1%; boron trifluoride—from 0.0001% to 0.01%; phosphazenes—from 0.00001% to 0.001%; free-radical inhibitors—from 0.001% to 1%. The foregoing percentages are percentages by weight of the reactive monomer. It should be noted that the quantity of inhibitor will influence the onset of polymerisation of the monomers of the present invention and could be used as a means to control the setting time of the adhesives.
The reactive monomers of the present invention may contain polymerisation initiators. They could be anionic polymerisation initiators like pyridine, aminopyridine, vinylpyridine, methoxyethylpyridine, piperidine, picoline, lutidine, N,N-dimethyl-p-toluidine, triphenylphosphine, triethylphosphine, tribenzylamine, triethylamine, benzyldimethylamine, diethylenetriamine, polyvinylpiridine, calixarenes, tertiary amine-SO
3
complexes, polyethylene glycol, phenolformaldehyde resins, vinylimidazole, triethanolaminatotitanium, aminosilanes, phosphites, metal acetylacetonates, N-(oxydiethylene)benzothiazole-2-sulfenamide, bismuth dimethyldithiocarbonate, as well as alcohols, bases and hydroxyl or amine group containing compounds. They could be cationic polymerisation initiators. They could be free-radical polymerisation initiators such as methylethylketone peroxide, cyclohexyl peroxide, cumene hydroperoxide, dibenzoyl peroxide or redoxy systems for generating free-radicals. Compounds which generate radicals or ions under visible, ultraviolet or electron-beam irradiation could also be used to initiate polymerisation of the reactive monomers of the present invention. The various initiators could be used alone or in conjunction with each other.
The reactive monomers of the present invention can be formulated into adhesives by incorporating certain modifiers and additives such as polymeric thickeners, viscosity regulators, plasticisers, thixotropic agents, compatibilisers, adhesion promoters, pigments and colourants, fillers, deodorants and perfums. They can also be used in composition with other monomers containing a reactive double bond, cyanoacrylates for example.
Application of the reactive monomers of the present invention is in structural and industrial, as well as in medical and surgical adhesives, sealants and coatings.
The above mentioned applications are only indicative and do not limit the scope of application of the reactive monomers of the present invention, as well as the applications of their adhesives and polymers.
The invention is illustrated by the following examples:
REFERENCES:
patent: 3554990 (1971-01-01), Quinn et al.
patent: 4313865 (1982-02-01), Teramoto et al.
patent: 4425471 (1984-01-01), Millet
patent: 4793886 (1988-12-01), Okamura et al.
patent: 4933234 (1990-06-01), Kobe et al.
patent: 5187048 (1993-02-01), Woods et al.
patent: 5340873 (1994-08-01), Mitry
patent: 5386047 (1995-01-01), Nakos et al.
Brobeck Phleger & Harrison LLP
Chemence, Inc.
McClendon Sanza
Seidleck James J.
LandOfFree
Reactive esters of 2-cyanopenta-2,4-dienoic acid and the... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Reactive esters of 2-cyanopenta-2,4-dienoic acid and the..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Reactive esters of 2-cyanopenta-2,4-dienoic acid and the... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2493893