Valves used in industrial environments often have rigorous performance standards. In the past, packings of polytetrafluoroethylene and other fluoropolymers have been used which were considered to seal valves satisfactorily. While packings were previously considered satisfactory with leakages of 10,000 ppm, such levels have now been found to be unacceptable for many applications. Desired emission levels for many industrial applications are below 500 ppm, and levels of less than 10 ppm for particularly toxic and carcinogenic materials would be desirable, particularly for those materials for which emission or handling standards have been established by various governmental agencies. Current requirements for valve sealing have created a need for packing systems that exceed earlier performance requirements in a cost-effective manner.

Summary of the Invention The present invention provides a valve packing which can reduce valve emissions to levels previously unattainable without precision metal bellows components.

Specifically, the present invention provides a valve packing comprising at least thre^. rings, including

(a) a male adapter,

(b) a female adapter, and

(c) at least one perfluoroelastomer chevron seal ring positioned between the male adapter and the female adapter, the male and female adapters being formed from a substantially non-elastomeric high

temperature polymer having about from 1 to 50 weight % of a fibrous filler intimately admixed therewith.

Brief Description of the Drawings

Figure 1 is a cross-sectional view of a valve packing of the present invention.

Figure 2 is a perspective view of a preferred valve packing of the present invention. Detailed Description of the Invention

The valve packings of the present invention are composed of a plurality of individual rings, as can be seen in cross-sectional illustration in Figures 1 and 2. There, male adapter 1 is at the upstream end of the packing, and female adapter 2 is at the atmospheric, or downstream end of the packing. Perfluoroelastomeric seal rings 3 are in a chevron or "V configuration, fitting with ridge 4 of the male adapter and groove 5 of the female adapter.

When two or more seal rings are used in the packings of the present invention, the seal rings are separated by spacer rings 6. These spacer or backup rings can be prepared from the same or different materials as the male and female adapters.

In accordance with the present invention,the male and female adapters and the spacer rings, if present, are prepared from fiber-filled non-elastomeric fluoropolymer. Fluoropolymers are preferably used for this component, and can include polytetrafluoroethylenes, such as those commercially available from the Du Pont Company as Teflon ^® PTFE fluoropolymer resins; melt-processable copolymers of tetrafluoroethylene and hexafluoropropylene such as those commercially available from the Du Pont Company as Teflon* FEP fluoropolymer; and clear, thermoplastic fluoropolymers such as those tetrafluoroethylene/fluorovinylether copolymers

commercially available from the Du Pont Company as Teflon* PFA. Still other fluoropolymers which can be used effectively in the present invention are those modified copolymers of ethylene and tetrafluoroethylene commercially available from the Du Pont Company as Tefzel ^® fluoropolymers.

The fluoropolymer used for the spacers, if present, and the adapters, is intimately admixed with about from 1 to 50 weight % fibrous filler, and preferably at least about 10 weight % fibrous filler, and especially at least about 20 weight % of the fibrous filler. The weight % is based-on the total weight of fluoropolymer and filler.

Fillers which can be beneficially used include glass, graphite and carbon fiber, of which carbon fiber is preferred. Such materials, with about 20 weight % of admixed carbon fiber filler, are commercially available from the Du Pont Company as Corrosion Resistant Composite Systems. Representative of such materials and their preparation are those described in Mansure, U.S. Patent 4,163,742 and Michel, U.S Patent 4,414,356, both of which are hereby incorporated by reference. These materials can be prepared by the process described in Michel, U.S Patent 4,422,992, which is also hereby incorporated by reference.

The filled fluoropolymer resins exhibit a particularly desirable combination of physical and mechanical properties. The combination of fluoropolymer resin and fiber filler, and especially carbon fiber filler, not only resists particularly high temperatures in normal operating environments, but, in the event of fire, the fiber filler and the resin matrix provide a sealing function that exceeds the capability of the resin alone.

In a preferred embodiment of the valve packings of the present invention, a ring of flexible graphite is included on the atmospheric side of the female adapter, shown as element 7 in Figures 1 and 2. Flexible graphites which can be used include that commercially available from Union Carbide Corporation as Graphoil ^® . This flexible graphite provides the further improvement of a sealing effect when the packings are exposed to exceptionally high temperatures, as in the case of fire. The flexible graphite, in conjuσtion with the fibers from the composite, forms a seal between the stem and the valve body, even above temperatures at which the seal element itself is subsequently destroyed.

Perfluoroelastomers which can be used in the preparation of the seal rings of the present invention include, for example, those perfluoroelastomers described in Breazeale, U.S. Patent 4,281,092. Perfluoroelastomers of tetrafluoroethylene and perfluoro (methyl vinyl ether) are commercially available from the Du Pont Company as Kalrez* perfluoroelastomers. These perfluoroelastomers generally have a termonomer to facilitate curing, such as CF ₂ =CF-0-CF ₂ -CF(CF ₃ )-0-C ₈ F ₅ , CH ₂ =CH-CF ₂ -CF ₂ Br, CF ₂ =CF-0-CF ₂ CF(CF ₃ )OCF ₂ CF ₂ CN, and CF ₂ =CH ₂ .

Other perfluoroelastomers which can be used are those copolymers of tetrafluoroethylene and a mixture of perfluoromethylvinyl ether and higher molecular vinyl ether, and having a cure site monomer derived from perfluoro alkyl diiodide. Those copolymers are commercially available from Daikin Kogyo Co., Ltd. as Perfluor ^® . perfluoroelastomer, and marketed by Green, Tweed as Chemraz ^® perfluoroelastomer. Still another perfluoroelastomer which can be used in the present invention is that

commercially available from NOK-Freudenberg as Simraz perfluoroelastomer.

For those applications in which temperatures greater than about 400 ^* F will be encountered, Kalrez ^® perfluoroelastomers exhibit exceptional stability, and better long term performance than other commercial perfluoroelastomers. These materials are accordingly preferred.

The configuration of the present packings will, of course, vary with the particular stem which is to be sealed and the associated cavity. Typically, the valve stems to be sealed have an outer diameter of 1/4 to 1 1/2 inch, which corresponds to the inner diameter of the packing. The diameter of the cavity in which the stem is located, corresponding to the outer diameter of the packing, is generally about from 1 1/2 to 2 times the diameter of the stem.

The packings of the present invention provide a marked improvement in sealing performance over standard fluoropolymer or flexible graphite packings that have heretofore been used. This is particularly advantageous in industrial chemical equipment, where the emissions of toxic or corrosive fluids such as benzene, butadiene and other carcinogenic or toxic substances can be reduced to less than 500 ppm. In many cases, emissions can be reduced to less than 10 ppm or substantially eliminated.

The present invention is further illustrated by the following specific examples, in which parts and percentages are by weight unless otherwise indicated. Example 1

Valve packings were assembled substantially as illustrated in Figure 1, to fit valves having a 3/8-inch stem. In each packing, the male and female

adapters, as well as the spacer, were prepared from Teflon ^® fluoropolymer admixed with 20 weight % carbon-fiber, and available from the Du Pont Company as CRCC components. Teflon ^® PFA fluoropolymer. The two chevron seal rings were prepared from Kalrez ^® 3018 perfluoroelastomer compound. The outer diameter of the packing components was 0.873 inch. The spacer and the perfluoroelastomer seals were each 0.274 inch thick, the male adapter was 0.184 inch thick, and the female adapter was 0.242 inch thick.

If the packings were assembled in valves controlling benzene and butadiene in systems in which the pressures are up to about 200 psi and the temperatures are up to 500 ^β F, emission levels over an 8 week period would average less than 20 parts per million for either benzene or butadiene. In addition, the packings will exhibit low creep and cold flow, and low compressibility. Example 2

A valve packing was assembled substantially as in Example 1, except that a further ring of Graphoil ^® flexible graphite, having a hickness of 0.250 inch, was included on top of the female adapter. The valve packing was assembled in a valve, and tested in a fire certification test.

The pressure of the line controlled by the valve during the test averaged 200 psi, with a minimum pressure of 195 psi and a maximum pressure of 222 psi. The fluid in the line was hot water and steam.

The valve was exposed to three natural gas burner flames in a test chamber for a total test period of 30 minutes. The test elevated the temperature of the valve body to 1245"F within 12 minutes, 50 seconds, and to 1430 ^β F at the end of the test. The test elevated the temperature of the

packing to 1200"F within 12 minutes, 50 seconds, and to 1383 ^β F at the end of the test.

The valve was tested for leaks after the flame test, at a low pressure of about 30 psig. The valve exhibited a leakage of 3.4 ml/min. American Petroleum Institute (API) #607 Fire Test permits 20 ml/min.

The valve was tested for leaks after the flame test, at a high pressure of about 200 psig. The valve exhibited a leakage of 8.7 ml/min. API standards permit 200 ml/min.

No external leakage was noted during either the course of the test or cool down after the test. API standards permit 100 ml/min.