Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1998-10-07
2001-07-10
Lipman, Bernard (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S320000, C526S286000, C568S814000
Reexamination Certificate
active
06258909
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to novel polymerizable compositions, novel resins, novel crosslinked polymers, novel polyester polymers, novel polyester polymers that display improvement over Rolivsan Resins, and to novel methods for obtaining resins, and polymers.
2. Background of the Art
Polymers have been able to provide a wide range of properties and capabilities which have found tremendous outlet in the commercial markets. Polymers are used in all forms of technology from medicine, commercial and residential construction, vehicular construction, optics, imaging, protective coatings, film supports and sheeting, data storage and magnetic recording, toys, inks, adhesives, binders, structural housing for appliances and conveniences, and many other commercial areas. Each of these different fields has its own unique requirements for the performance of the polymeric materials. No one polymer can meet all of the requirements for all of the fields of potential use. For this reason, certain polymers have been developed to provide better performance within certain areas of technology. For example, polyesters (such as polyethyleneterephthalate and polyethylenenaphthalate) are preferred films supports for imaging technology, as are certain cellulose acetates. Polycarbonates are preferred polymeric materials for use with window construction and lens construction. Polyacrylates have found general utility for protective coatings, particularly weatherable and UV exposed protective coatings. Epoxy resins and acrylates have found wide acceptance as adhesive materials; silicone resins have found utility as caulking, release compositions, and moisture protective coatings and compositions. Polyamides have found utility as fabric materials, thermal adhesive and biocompatible polymers in the medical field, etc.
Even within these classes of polymers and these fields, variations in the properties of the polymer are important. Failure to understand the nature of the polymer, the actual reaction mechanisms in its polymerization, impurities and additives, reaction conditions and catalysis has led to the underutilization, underachievement or at least underappreciation of some polymer compositions.
In the 1970's and 1980's, a new class of polymer was introduced by research done in the Union of Soviet Socialist Republics by Dr. Boris A. Zaitsev at the Russian Academy of Sciences. This new class of resins was referred to in the literature as Rolivsan Resins. The resins originally were known to comprise at least about three ingredients comprising three monomers. Further advances in the resins provided for the inclusion of oligomers with the monomers. The resins were initially described as derived from compositions of monomers (M) comprising from about
1-45% by weight of:
p-(CH
2
═CH—C
6
H
4
)
2
O, bis-(4-vinylphenyl)ether (M1 type)
2-35% by weight of:
CH
2
═CH—C
6
H
4
—O—C
6
H
4
—CH(CH
3
)OCOC(CH
3
)═CH
2
(M2 type) methacrylic ester of 4-vinyl-4′-(1-hydroxyethyl)-diphenyl-oxide or methacrylic ester of 4-vinyl-4′-(sec-ethylol)-diphenyloxide, and
5-30% by weight of:
(p-CH
2
═C(CH
3
)—COOCH(CH
3
)C
6
H
4
)
2
O (M3 type) dimethacrylic ester of bis-[4-(1-hydroxyethylphenyl]ether, and
5-88% by weight of:
oligomers.
The oligomers which were also described in the literature as possibly being present within the compositions (resulted from acid-catalyzed repeated dimerization and co-dimerization reactions of M1 with itself and M2) were described as having different formulae, e.g.:
Y═CR═CH
2
, or —CH(CH
3
)OCOC(CH
3
)═CH
2
,
and
Ar═C
6
H
4
—O—C
6
H
4
,
and
n=0-3
The objective of this class of resins was to provide easy processing for high temperature resistant thermosetting resins and advanced composites. The resin reaction mixtures were provided as solvent-free compositions having viscosity ranges of from 600 up to 5,000 cps at room temperature, with melting points between 5 and 50° C. for the uncured resins. The resins were to provide excellent chemical resistance to the most aggressive chemical materials (e.g., organic solvents, strong acids, alkalis, hydrazine and solutions of hydrofluoric acid). The resins were also to provide high-temperature (300±50° C.) performance properties and advanced composite reinforced plastics (e.g., fiberglass, polyamide and polyimide fiber, graphite, and tungsten-reinforced plastics). The resins were also to have mixing compatibility with conventional reactive resins and oligomers such as epoxy resins, unsaturated polyester resins, vinylester resins, and bis-maleimide resins. The Rolivsan Resins were also expected to exotherm in the presence of phenols, condensing with them quite readily (alkylating phenols by ethylenically unsaturated ingredients of Rolivsan Resins) at room temperature in the presence of acidic catalysts (strong acids).
An essential precursor for obtaining Rolivsan resins was bis-[4-(1-hydroxyethyl)phenyl]ether (referred to as BHEPE). The BHEPE had been obtained by the catalytic hydrogenation of bis-(4-acetyl)phenyl ether (BAPE), for example on a Raney-Nickel catalyst at conditions varying from room temperature (at high pressure) to 40 to 50° C. with a hydrogen pressure of 100 atmospheres for 0.5 to 1 hour in ethyl alcohol followed by recrystallization from toluene or benzene (mp 86° C.).
The Rolivsan Resins were formed by heating the BHEPE (which have been found by the present inventors to have comprised uncontrollable amounts (~5±3%) of a phenolic impurity) with unsaturated carboxylic acids (e.g., methacrylic acid) in the presence of the considerable amounts (2.5% of BHEPE weight) of acid catalysts (such as p-toluenesulfonic acid monohydrate) in an aromatic solvent at its boiling temperature in the presence of considerable amounts (>1% of BHEPE weight) of hydroquinone. It has been found by Applicant in the background of the present invention that the synthetic procedure for the production of intermediates (precursors) for the resins, especially in the synthesis of the diols which are then converted to the ethylenically unsaturated monomeric and oligomeric components of the resin, formed by-product impurities. These impurities have been found by the present inventors to produce heretofore unknown active effects on the properties and performance of the resulting resin and prevent the diols and their polymerizably active products of their transformations from use in other fields where purity might be even more critical. Some of these impurities were carried through to the final resin composition, even where standard purification techniques were used, because the physical properties of the impurities did not substantially differentiate the properties of the objective compounds.
According to the method for the manufacture of BHEPE, the basis of the pilot scale production of bis-[4-(1-hydroxyethyl)phenyl]ether (BHEPE) was by hydrogenation of bis-(4-acetyl)phenyl ether (BAPE) in the presence of Raney-nickel catalyst in processes exemplified by the following description (with variations in temperatures and pressures and time as noted herein): in Examples 1-6, in the section of EXAMPLES below.
These examples illustrate that the previously published and commercially used procedures had operated with quite high concentrations of acidic catalyst (p-toluenesulfonic acid) (2.5 to 28% of BHEPE weight) and hydroquinone (1 to 2% of BHEPE weight), and the products retained an extra-amount of the phenolic compounds as unremoved impurities in the BHEPE.
As a result, according to the Soviet Union technical (standard) specifications for the Rolivsan MV-1 resin manufacture (TU-6-14-24-62-79, valid from Jul. 20, 1979 for one ton production, and, more recently, TU 6-36-57-0-91 (instead of the previous TU-6-14-24-143-85) from Feb. 15, 1991 to Feb. 15, 1994) (Zaitsev, B. A. et al., Rolivsans—New Binders for Heat-Resistant and Strong Reinforced Plastics,
Mechanics of Composite Materials,
18(5):512-515 (1982); Z
Lipman Bernard
Mark A. Litman & Associates P.A.
Zalukaeva Tanya
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