Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From heterocyclic reactant containing as ring atoms oxygen,...
Patent
1998-07-20
2000-03-21
Marquis, Melvyn I.
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From heterocyclic reactant containing as ring atoms oxygen,...
528417, 528421, C08G 5968
Patent
active
060404191
DESCRIPTION:
BRIEF SUMMARY
FIELD OF THE INVENTION
This invention generally relates to an improved polymerization process for cyclic ethers using as a catalyst a polymer which contains a large amount of hydrocarbon, and also contains sulfonic acid groups which are fluorinated in at least the alpha and beta positions.
BACKGROUND OF THE INVENTION
Polyethers are important items of commerce, being useful as monomers in polyurethane polymers which are useful as molding resins and spandex fibers, in adhesives, and for many other uses. One common method of making polyethers is the ring opening polymerization of cyclic ethers, such as oxiranes (epoxides), oxetanes, tetrahydrofurans, etc. It is known that oxiranes are particularly susceptible to such ring opening reactions such as polymerization, but other cyclic ethers typically require strong cationic (or other type) of catalysts.
One such type of catalyst include strong Bronsted acids, for example fuming sulfuric or fluorosulfonic acid. It is also known that highly fluorinated organic sulfonic acids are effective catalysts. These sulfonic acids may be low molecular weight compounds or may be part of polymers, particularly perfluorinated polymers; see for instance B. Elvers, et al., Ed., Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A21, VCH Verlagsgesellschaft mbH, Weinheim, 1992, p. 583-584; H. Mark, et al., Ed., Encyclopedia of Polymer Science and Engineering, 2nd Ed., Vol. 16, John Wiley & Sons, New York, 1989, p. 658-668; and U.S. Pat. Nos. 4,120,903; 4,139,567; 4,153,786; 4,163,115; 5,118,869; and 5,130,470. However, with such perfluorinated polymers polymerization, rates often tend to be relatively slow. One advantage of using such polymeric sulfonic acids is that if the sulfonic acid containing polymer is insoluble in the polymerization medium, the acid catalyst is easily separated from the polyether product.
SUMMARY OF THE INVENTION
This invention concerns a process for the polymerization of cyclic ethers using a strong Bronsted acid catalyst, wherein the improvement comprises, using as said strong Bronsted acid catalyst a fluorinated sulfonic acid containing polymer, provided that said fluorinated sulfonic acid containing polymer: per kg of said sulfonic acid containing polymer; carbon; and R.sup.2 CR.sup.3 R.sup.4 SO.sub.3 H wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are each independently fluorine or perfluoroalkyl.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the process described herein, cyclic ethers are polymerized to usually linear polyethers using as a catalyst a fluorinated sulfonic acid containing polymer (FSAP). The polymerization of cyclic ethers using strong Bronsted acids is known, see for instance B. Elvers, et al., Ed., Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A21, VCH Verlagsgesellschaft mbH, Weinheim, 1992, p. 583-584; H. Mark, et al., Ed., Encyclopedia of Polymer Science and Engineering, 2nd Ed., Vol. 16, John Wiley & Sons, New York, 1989, p. 658-668; and U.S. Pat. Nos. 5,118,869 and 5,130,470. Typically, the cyclic ether is contacted with the strong Bronsted acid to form the polymer. Often a "co-catalyst" is also present. Such co-catalyst compounds are typically carboxylic acids, carboxylic acid anhydrides, or acyl halides. Portions of these co-catalysts often become part of some or all of the end groups of the resulting polyethers. For instance, if a carboxylic acid anhydride is present, some or all of the polyether end groups are usually esters. If hydroxyl end groups are desired, these esters may be subsequently hydrolyzed.
As used herein, "strong Bronsted acid" means a Bronsted acid whose pKa in water at 25.degree. C. is less than 0, preferably less than -1.
It is preferred that the FSAP have a number average molecular weight of about 2,000 or more, preferably about 5,000 or more, or is crosslinked, which herein is considered to be an infinite molecular weight. The polymer may be crosslinked by methods known to the artisan, such as by using peroxides, optionally with coagents. Alternatively, the FSA
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Drysdale Neville Everton
Wang Lin
Yang Zhen-Yu
E. I. Du Pont de Nemours and Company
Marquis Melvyn I.
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