Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
1999-09-02
2001-09-18
Padmanabhan, Sreeni (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C568S628000, C568S630000, C568S632000, C568S732000, C568S733000, C568S806000, C528S205000, C528S171000
Reexamination Certificate
active
06291723
ABSTRACT:
FIELD OF INVENTION
This invention relates to condensation products of a hydroxyaryl and a diolefin, the method for preparation of such products as well as a catalyst system used for their preparation. More particularly, this invention relates to such condensation products and their method of manufacture in the presence of a catalyst composition containing trifluoromethanesulfonic acid (triflic acid) and a substance in an amount which decreases without eliminating the catalytic activity of the acid, said substance is also simply referred to as a retarder.
It has now been found that the reaction of a hydroxyaryl with a non-conjugated diene in the presence of both triflic acid and a retarder will produce products which are substantially different from such reaction without the use of the retarder. Broadly, the use of the retarder provides products which have lower molecular weights such as solids, crystalizable and non-crystalizable liquids having a wide range of viscosities. The retarder is a material which at certain concentrations in relation to the triflic acid decreases, without eliminating, the catalytic activity of the triflic acid. The retarders are generally about neutral to slightly basic in pH. The retarder acts as a base in relation to the triflic acid.
BACKGROUND OF THE INVENTION
The prior art shows the use of trifluoromethanesulfonic acid (triflic) acid as a catalyst for various hydrocarbon conversion processes but such prior art fails to suggest the instant invention. Some prior art patents involving the use of triflic acid as a catalyst or the preparation of condensation products from a diene and a hydroxyaryl are set forth below.
U.S. Pat. No. 4,973,764 of Nov. 27,1990 to A. Oswald et al discloses the use of triflic acid as an alkoxylation catalyst.
U.S. Pat. No. 5,521,260 of May 28, 1996 to N. Futaesaku et al discloses the use of triflic acid as a polymerization catalyst for thermosetting resins.
U.S. Pat. No. 5,607,890 of Mar. 4, 1997 to F. J. Chen et al discloses heterogeneous catalysts having certain insoluble triflic acid salts on an inorganic oxide support for catalyzing hydrocarbon conversion reactions including alkylation and polymerization. As suitable monomers for the conversion reactions a wide variety of olefins and carbocyclic aromatic compounds are mentioned. Monomer feed streams for polymerization are substantially free of impurities which may adversely affect polymerization such as basic and nitrogen materials. Lower alcohols along with organic acids are mentioned as catalyst promoters.
U.S. Pat. No. 5,663, 470 of Sep. 2, 1997 to F. Chen et al discloses a heterogeneous catalyst system comprising a solid state insoluble salt catalyst for polymerization and alkylation of olefinic monomers in the presence of a polar or non-polar reaction medium which comprises: (a) a solid state catalyst component of at least one salt of a strong acid and certain transition metals wherein the salt is insoluble in the reaction medium; and (b) a cocatalyst for promoting the polymerization. The salt of a strong acid includes that of triflic acid. Monomers include a wide variety of olefins and carbocyclic aromatic compounds. The enumeration of cocatalyst includes water, alcohols such as the lower alkanols, e.g., methanol, and Bronsted acids such as triflic acid or Lewis acids. This 470 patent of Chen et al describes triflic acid, water and methanol as catalyst reaction promoters. However, in, the catalyst system of the instant invention, water and alcohols, e.g., methanol are catalyst suppressors in that water and methanol both act as catalyst retarders instead of promoters. Although the applicant does not wish to be held to any theory, it is believed that water as well as methanol in contact with the insoluble catalyst salts of Chen et al cause dissociation of the salts which in turn promote the catalytic reaction.
3M Product Information Bulletin of 6-95 entitled “Fluorochem” discloses various properties and uses of triflic acid, e.g., the use of triflic acid as a catalyst in alkylation and polymerization reactions as well as some physical or chemical properties of mixtures of triflic acid with water or ethers.
Neftekhimiya, 1974, Volume XIV, No. 2, 280-283 (Russian) discloses the reaction of phenol with clicyclopentadiene in the presence of about 10% to 50% by weight, based on the weight of both monomers, of a cation exchange resin catalyst for the preparation of compounds, such as prepared in the instant invention, including some resin.
H. A. Bruson, et al., J. Amer. Chem. Soc. 68, 8 (1946), pp 8-10, shows the preparation of aryloxy-dicyclopentadiene compounds from hydroxyaryls and dicyclopentadiene in the presence of various acids.
SUMMARY OF THE INVENTION
In one aspect, this invention relates to a method for condensing a hydroxyaryl with a non-conjugated diene in the presence of a catalyst composition comprising trifluoromethanesulfonic acid (triflic acid) and a substance in a quantity which decreases without eliminating the catalytic activity of the acid .
In another aspect, this invention relates to a catalyst composition comprising triflic acid and a substance in a quantity which decreases without eliminating the catalytic activity of the acid and which does not react with a double bond of a non-conjugated diene.
In still a further aspect, this invention relates to a composition comprising a hydroxyaryl, a non-conjugated diene, trifloromethanesulfonic acid and a substance in a quantity which decreases without eliminating the catalytic activity of the acid and which does not react with a double bond of the diene.
In yet another aspect, this invention relates to a method for condensing a hydroxyaryl with a non-conjugated diene in the presence of a catalyst system comprising trifluoromethanesulfonic acid and a substance in a quantity which decreases without eliminating the catalytic activity of the acid and which does not react with a double bond of the diene to prepare condensates having one mole of diene bound with one mole of a hydroxyaryl, condensates having two moles of the hydroxyaryl bound with one mole of the diene, as well as higher molecular weight products, including resins.
In a further aspect, this invention relates to condensing a hydroxyaryl with a non-conjugated diene in the presence of a catalyst system comprising trifluoromethanesulfonic acid and a substance in a quantity which decreases without eliminating the catalytic activity of the acid while controlling the molecular weight, viscosity and other properties of the products produced over time and/or temperature variations.
In yet additional aspects, this invention relates to compositions of a hydroxyaryl and an non-conjugated diene, as well as their method of manufacture, for producing: (A) a condensation product of a hydroxyaryl and a non-conjugated diene wherein the ratio of aryloxy-non-conjugated-diene compound to hydroxyaryl-non-conjugated-diene compounds is about 0.5 to 1.5 and from about 40% to at least 90% of the product, preferably 40% to at least 95% of the product is that of both the aryloxy-diene compound and the hydroxyaryl-diene compound; (B) a condensation product of a hydroxyaryl and a non-conjugated diene wherein the product contains at least 90% of aryloxy-non-conjugated-diene compound and hydroxyaryl-non-conjugated-diene compound and less than about 5% of higher molecular weight products of the condensation; and (C) a condensation product having a maximum content of about 2% of aryloxy-non-conjugated-diene compound, from about 5% to 40% of hydroxyaryl-non-conjugated-diene compounds with the remainder being higher molecular weight products of the condensation reaction.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the broad method of this invention, the non-conjugated diene is typically contacted with a hydroxyaryl at an elevated temperature in the presence of the triflic acid and retarder for a time sufficient to react the hydroxyaryl with the diene. Completion of the reaction can be evidenced by gas chromatographic monitoring of the diene or consistency of refractive i
Borden Chemical, Inc.
Maskas George P.
Padmanabhan Sreeni
Van Wyck Kenneth P.
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