US2898999A - Disposable rubber products - Google Patents
Disposable rubber products Download PDFInfo
- Publication number
- US2898999A US2898999A US550247A US55024755A US2898999A US 2898999 A US2898999 A US 2898999A US 550247 A US550247 A US 550247A US 55024755 A US55024755 A US 55024755A US 2898999 A US2898999 A US 2898999A
- Authority
- US
- United States
- Prior art keywords
- rubber
- spacer
- packer
- oxidant
- rubbery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920001971 elastomer Polymers 0.000 title description 33
- 239000005060 rubber Substances 0.000 title description 33
- 239000000203 mixture Substances 0.000 claims description 27
- 239000007800 oxidant agent Substances 0.000 claims description 19
- 230000001590 oxidative effect Effects 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 238000002485 combustion reaction Methods 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 150000001993 dienes Chemical class 0.000 claims description 8
- 229920003052 natural elastomer Polymers 0.000 claims description 8
- 229920001194 natural rubber Polymers 0.000 claims description 8
- 244000043261 Hevea brasiliensis Species 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 238000009877 rendering Methods 0.000 claims description 6
- 125000006850 spacer group Chemical group 0.000 description 27
- 239000000463 material Substances 0.000 description 12
- 239000003129 oil well Substances 0.000 description 12
- 238000012856 packing Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 9
- 241001441571 Hiodontidae Species 0.000 description 7
- 238000011065 in-situ storage Methods 0.000 description 7
- 229920003051 synthetic elastomer Polymers 0.000 description 7
- 239000005061 synthetic rubber Substances 0.000 description 7
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- 239000012530 fluid Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- XQCFHQBGMWUEMY-ZPUQHVIOSA-N Nitrovin Chemical compound C=1C=C([N+]([O-])=O)OC=1\C=C\C(=NNC(=N)N)\C=C\C1=CC=C([N+]([O-])=O)O1 XQCFHQBGMWUEMY-ZPUQHVIOSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- -1 bulk Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- SXLIFQSDMYZOBA-UHFFFAOYSA-N 2,5-bis(ethenyl)pyridine Chemical compound C=CC1=CC=C(C=C)N=C1 SXLIFQSDMYZOBA-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical class C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- CJSBUWDGPXGFGA-UHFFFAOYSA-N 4-methylpenta-1,3-diene Chemical compound CC(C)=CC=C CJSBUWDGPXGFGA-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VYZAHLCBVHPDDF-UHFFFAOYSA-N Dinitrochlorobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 VYZAHLCBVHPDDF-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- PDIOKWSXIIMYCJ-UHFFFAOYSA-I [O-]O.[O-]P([O-])(=O)OP(=O)([O-])[O-].[Fe+5] Chemical compound [O-]O.[O-]P([O-])(=O)OP(=O)([O-])[O-].[Fe+5] PDIOKWSXIIMYCJ-UHFFFAOYSA-I 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-L dioxidosulfate(2-) Chemical compound [O-]S[O-] HRKQOINLCJTGBK-UHFFFAOYSA-L 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/12—Packers; Plugs
- E21B33/1208—Packers; Plugs characterised by the construction of the sealing or packing means
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S277/00—Seal for a joint or juncture
- Y10S277/935—Seal made of a particular material
- Y10S277/944—Elastomer or plastic
Definitions
- This invention relates to disposable rubbery products of manufacture. In one aspect, the invention relates -to the method of disposing of, in situ, disposable rubbery products.
- a further example is the use of rubber packers in oil wells.
- the packer is positioned in the lower portion .of the well in the annular space between the casing and the tubing thus sealing the annulus.
- an oil-well pump such as a reciprocating pump, is lowered through the tubing to the desired depth; the oil-Well pump being connected to a pumping unit at the surface by means of sucker rods.
- the oil-well pump literally lifts the uid from the oil formation up the tubing to the surface for storage in tanks.
- a still further example is where a mass, such as machinery, is to be lowered or raised to dicultly accessible places by means of a hoist, crane and the like.
- a temporary rubbery spacer molded to the desired shape such as dove-tail, barbell, etc., is the connecting link between the mass to be transported and the hoisting means.
- the temporary rubber spacer undergoes extensive stress as there is a force continually tending to rupture the spacer.
- An object of this invention is to provide an improved rubbery spacer.
- Another object is to provide an improved rubbery spacer which may be chemically disposed of in situ.
- Another object is to provide a novel rubbery spacer which serves as a seal in oil wells.
- a still further object is the manufacture of a novel rubbery spacer to serve as a temporary member in a system or machine wherein its removal when the situa ⁇ tion arises may be effected by ignition or burning of the' spacer in situ.
- a further object is to provide a disposable article of manufacture undergoing continual compressive stress or extensive stress during its use as a temporary member in a system.
- a yet further object is to provide a disposable rubber spacer which functions as a temporary service barrier in a system.
- novel rubbery spacer of this invention is composited with components hereinafter described so that the removal or disposal of the spacer is accomplished merely by raising its temperature to the combustion temperature,'such as ignition by an electrical squib, a torch, a fuse, or the' like, and thus, burning the spacer in situ.
- spacer in this invention designates a seal, packer, support, washer, ball'valve, connecting link, and the like. Artisans skilled in the art are familiar with such terminology and with their application and use in the various fields. i
- the spacer of my invention comprises predominantly a mixture of rubber and an voxidant wherein the rubber is in the continuous phase.
- the rubber component may be natural or synthetic together with its appropriate compounding ingredients. It is only necessary that the rubber have such a Mooney value that it can be worked so that an oxidant can be blended therewith. Rubbers with Mooney (ML-4) values upto '100 are applicable although it is preferable to have a Mooney value in the range of from about l0 to about 40.
- the synthetic rubbers can be prepared in any suitable polymerization system, such as emulsion, bulk, or suspension systems.
- an emulsion polymerization .system aan. be used te prepare homopolymers or copolymersgf .conjugated f olsns or copolymers of coniugated ,diQlenS with other monomeric Compounds.
- the conjugated d iolens which are applicable include 1,3- butadiene, isoprene, Vchlortylgnrene, 2,3-dimethyl-l,3buta diene, methylpentadiene, piperylene, and others.
- the conjugated vdienes of 4 to 6 carbon atoms are preferred, althoughdienes -o f more than 6 carbon atoms can be used as well as the various alkoxy, such as methoxy and ethoxy, and cyano derivatives.
- Monomeric substances capable of copolymeriyzng with the conjugated dienes are styrene, a-methylstyrene, acrylonitri1e,vand the vinylpyridines, i.e., v ⁇ 2-vinylpyridine, 2,5-divinylpyridine, 2- methyl-S-Vinylpyridine, B-ethyl-S-vinylpyridine, and others.
- Any initiatorl system can be used, such as the iron pyrophosphate-hydroperoxide, either sugar-free or containing sugar; the sulfoxylate recipe; the persulfate recipe,l and the like.
- Any suitable emulsifier such as fatty orV iosin acid-soaps can be used.
- Conventional short stops i.e., t-butylhydroquinone, 2,4-dinitrochlorobenzene, water-"solubledithiocarbarriates, may be employed as well as otheringrefdients ,such as antioxidants.
- the emulsion polymerization temperature is generally in the range of -40 lto 140 F. The treatment of crude natural rubber is too well-known to the art to warrant further discussion thereof.
- any suitable oxidant such as ammonium nitrate, ammonium perchlorate, Ypotassium perchlorate, potassium nitrate, or mixtures thereof, and the like may be employed.
- the oxidant and rubber can be mixed in any manner known in the art, such as by a dispersion blade mixer.
- the composition of the rubber spacer of my invention consists essentially of 50-85 or more parts of oxidant per 100 parts by weight of rubber binder-oxidant blend.
- the rubber binder comprises raw rubber, carbon black, plasticizer, antioxidant, vulcanizing agent and other compounding ingredients as desired,
- the rubber binder is subsequently mixed or blended with the oxidant; the blend possessing a. consistency which can be molded to the desired shape by injection molding, extrusion molding, or other molding processes known to the art.
- Heat treating the molded article, i.e., spacer, at a temperature in the range from about 70 to aboutf250 F., preferably from about 140 to about .180? F., and for a period of time between about 3 hours to about 7 days follows, thus permanently setting or freezing the shape of the spacer.
- An oil resistant rubber can be made from Ythe following emulsion polymerization recipe. i
- the emulsion polymerization is carried at a temperature of approximately 25 C. for a period of about 15 hours. After shortstopping and removal of unreacted monomers the polymer is recovered from the latex in a conventional manner.
- the synthetic rubberv and carbon black are masterbatched and subsequently there is added to the masterbatch the remaining ingredients listed above.
- To this mixture (the components of which now form the rubber binder) is added 75 parts of ammonium nitrate per 25 parts by weight of the rubber binder. Substantial uniform distribution of the entire mix can be obtained in a Baker- Perkins dispersion mixer.
- the rubber binder-oxidant blend is molded to the desired shape and cured 48 hours at 170 F.
- a molded and cured rubber binder-ammonium nitrate blend consisting vof 50 parts by weight of binder per 50 parts by weight-of ammonium nitrate will vignite when it oxidant incorporated into the blend.
- the ultimate use of the shaped and cured rubber binder-oxidant blend will, in a number of instances, govern the choice of the synthetic rubber component in the blend. For example, in a situation where my novel packer is exposed to hydrocarbons, the synthetic rubber component must be oil resistant, and thus, the use of, for example, the acryloniytrile copolymers is desired.
- the drawing is a schematic View of a typical oil-well.
- the numeral 1 indicates the surface casing set and cemented. This casing is to protect fresh water supplies near the surface, prevent vthe unconsolidated formations from caving and provide a means of controlling the flow of drilling Huid.
- oil-string casing 2 also set and cemented.
- the oil-string casing is not ordinarily set in a well until it has demonstrated that it is likely to be a producer.
- the nal step in preparing the piping for a producing well is running in the tubing 3 to the bottom of the well or pay zone 4 so that an annular chamber is formed between the tubing 3 and the oil-string casing 2.
- Packer 5 comprising 75 parts by weight of ammonium nitrate and 25 parts by weight of acrylonitrile-butadiene blend prepared in the manner explained above, is fitted in the annulus at the desired depth, and is connected to electric source 6.
- An electric squib may either be incorporated into the packer or be adjacent thereto.
- reciprocating pump 7 connected by means of sucker rods 8 Ito the pump unit 9 on the surface. The pump technique is ernployed when the oil formation lacks the necessary pressure to ow naturally. As the piston within reciprocating pump 7 is moved upward, ball valve 11 is opened and fluid from pay zone 4 is admitted while ball valve 12 remains in a closed position.
- the packer is merely burned or ignited 'm situ by setting off the electrical squib by turning on electric source 6.
- the packer can be also ignited by other means, such as lowering a torch through the tubing to a point adjacent to the packer.
- the metal tubing is heated at that point whereby the packer will ignite and burn when the ignition temperature is reached.
- the gas can escape upward through the unimpeded annulus to the surface to be utilized or discarded, as desired.
- the gas can eventually be worked out of the reciprocating pump.
- an oil well packer having an annular resilient seal member consisting essentially of a composition comprising a rubbery binder selected from the group consisting of natural rubber and synthetic, conjugated diene polymer :and sufficient oxidant in admixture therewith to supply the oxygen necessary for combustion with substantial decomposition of said packer, thereby rendering said packer both ignitible and self-sustaining in combustion even in the absence of any external source of oxygen.
- an oil well packer having an annular resilient seal member consisting essentially of a composition comprising a mixture of rubbery binder selected from the group consisting of natural rubber and synthetic, conjugated diene polymer and from 50 to 85 parts by weight per 100 parts olf mixture of oxidant selected from the group consisting of ammonium nitrate, ammonium perchlorate, potassium nitrate, potassium perchlorate, and mixtures thereof, thereby rendering said packer both ignitible and self-sustaining in combustion to substantial decomposition thereof even in the absence of any external source of oxygen.
- the improved method which comprises positioning in the path of said force a body consisting essentially of a composition comprising a rubbery binder selected from the group consisting of natural rubber and synthetic, conjugated diene polymer and sufiicient oxidant in admixture therewith to supply the oxygen necessary for combustion with substantial decomposition of said body, thereby rendering said composition both ignitible and self-sustaining in combustion even in the absence of any external source of oxygen, and igniting said body in situ so that said body substantially decomposes.
- a body consisting essentially of a composition comprising a rubbery binder selected from the group consisting of natural rubber and synthetic, conjugated diene polymer and sufiicient oxidant in admixture therewith to supply the oxygen necessary for combustion with substantial decomposition of said body, thereby rendering said composition both ignitible and self-sustaining in combustion even in the absence of any external source of oxygen, and igniting said body in situ so that said body substantially decomposes.
- a method of packing oit and subsequently removing the packing material from an oil well which comprises positioning in said Well packing material comprising a rubbery binder selected from the group consisting of natural rubber and synthetic, conjugated diene polymer and sufficient oxidant in admixture therewith to supply the oxygen necessary for combustion with substantial decomposition of said packing material, thereby rendering said material both ignitible and self-sustaining in combustion even in the absence of any external source of oxygen, and igniting said packing material in situ so that said packing material substantially decomposes.
- a rubbery binder selected from the group consisting of natural rubber and synthetic, conjugated diene polymer and sufficient oxidant in admixture therewith to supply the oxygen necessary for combustion with substantial decomposition of said packing material, thereby rendering said material both ignitible and self-sustaining in combustion even in the absence of any external source of oxygen, and igniting said packing material in situ so that said packing material substantially decomposes.
- a method of packing oi and subsequently removing the packing material from an oil well which comprises positioning in said well packing material comprising a mixture of rubbery binder selected from the ⁇ group consistinlg of natural rubber and synthetic, conjugated diene polymer and from to 85 parts by weight per 100 parts of mixture of oxidant selected from the group consisting of ammonium nitrate, ammonium perchlorate, potassium perchlorate, potassium nitrate, and mixtures thereof, thereby rendering said packing material both ignitible and self-sustaining in combustion to the substantial decomposition thereof even in the absence of any external source of oxygen, and igniting said packing material in situ so that said packing material substantially decomposes.
- said rubbery binder is a rubber having a Mooney (ML-4) value in the range of about 10 to 40.
- the body comprises from about 50 to about 15 parts of a rubbery binder possessing a Mooney value not greater than and from about 50 to about 85 parts of an oxidant.
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- Mining & Mineral Resources (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Sealing Material Composition (AREA)
Description
Aug. l1, 1959 P. G. CARPENTER DISPOSABLE RUBBER PRODUCTS Filed Deo IN VEN TOR. P G. :ARPENTER #miam M4 LA T TOR/v5 V5 United States Patent msPosABLE RUBBER PRODUCTS Paul G. Carpenter, Bartlesville, Okla., assignor to Phillips Petroleum Company, a corporation of Delaware Application December 1, 1955, Serial No. 550,247 8 Claims. (Cl. `166-46) This invention relates to disposable rubbery products of manufacture. In one aspect, the invention relates -to the method of disposing of, in situ, disposable rubbery products.
In various instances it is necessary to use a temporary member in the set-up of a system or machine, and thereafter, to remove the temporary member when its usefulness or function has been served. For example, it is sometimes desired to utilize a temporary rubber spacer to hold the valve stem of a remote valve in the open or closed position, and subsequently, to remove the spacer when the position of the valve is to be altered, i. e., closed from an open position or vice versa. Another example is when 'the corners of heavy machinery are mounted on temporary rubber spacers, and the removal of the spacers is deemed necessary to set the machinery in its proper foundation. The foregoing examples illustrate situations wherein the temporary rubbery spacer undergoes compressive stress inasmuch as a weight or force is continually maintained on the spacer. A further example is the use of rubber packers in oil wells. The packer is positioned in the lower portion .of the well in the annular space between the casing and the tubing thus sealing the annulus. However, when pressures in the oil reservoir have fallen to the point where a well will not produce by natural energy, some method of artificial lift must be used. For this purpose an oil-well pump, such as a reciprocating pump, is lowered through the tubing to the desired depth; the oil-Well pump being connected to a pumping unit at the surface by means of sucker rods. In actual operation, the oil-well pump literally lifts the uid from the oil formation up the tubing to the surface for storage in tanks. To secure eicient pump operation it is important to maintain gas control in the vicinityl of the pump at the producing formation. Gas entering the pump with the oil can cause serious loss of etliciency and, at times, may even prevent operation of the valves within the pump. This diculty, due to the presence of free gas between the valves of the pump, may be prevented or alleviated by removing lthe rubber packer in the annulus to permit an escape passage for the troublesome gas. The gas is then tapped Vfrom the annulus at the surface to be disposed of as desired. Thus, the oil well illustration represents a situation wherein the temporary rubber spacer functions as a service barrier or seal. A still further example is where a mass, such as machinery, is to be lowered or raised to dicultly accessible places by means of a hoist, crane and the like. A temporary rubbery spacer, molded to the desired shape such as dove-tail, barbell, etc., is the connecting link between the mass to be transported and the hoisting means. In this particular situation, the temporary rubber spacer undergoes extensive stress as there is a force continually tending to rupture the spacer. =In the preceding illustrations it is readily apparent that the manual or physical removal of the rubber spacer may become a tedious and time-consuming and expensive manipulation.l 'The novel rubber spacer of my invention overcomes, in the main, these diiculties.
Patented Aug. 11, 1959 ICC The following therefore, are objects of the invention:
An object of this invention is to provide an improved rubbery spacer.
Another object is to provide an improved rubbery spacer which may be chemically disposed of in situ.
Another object is to provide a novel rubbery spacer which serves as a seal in oil wells.
A still further object is the manufacture of a novel rubbery spacer to serve as a temporary member in a system or machine wherein its removal when the situa` tion arises may be effected by ignition or burning of the' spacer in situ.
A further object is to provide a disposable article of manufacture undergoing continual compressive stress or extensive stress during its use as a temporary member in a system.
A yet further object is to provide a disposable rubber spacer which functions as a temporary service barrier in a system.
Other and further objects of this invention will be apparent to those skilled in the art upon study of the accompanying disclosure.
The novel rubbery spacer of this invention is composited with components hereinafter described so that the removal or disposal of the spacer is accomplished merely by raising its temperature to the combustion temperature,'such as ignition by an electrical squib, a torch, a fuse, or the' like, and thus, burning the spacer in situ.
The term spacer in this invention designates a seal, packer, support, washer, ball'valve, connecting link, and the like. Artisans skilled in the art are familiar with such terminology and with their application and use in the various fields. i
The spacer of my invention comprises predominantly a mixture of rubber and an voxidant wherein the rubber is in the continuous phase. The rubber component may be natural or synthetic together with its appropriate compounding ingredients. It is only necessary that the rubber have such a Mooney value that it can be worked so that an oxidant can be blended therewith. Rubbers with Mooney (ML-4) values upto '100 are applicable although it is preferable to have a Mooney value in the range of from about l0 to about 40.
The synthetic rubbers can be prepared in any suitable polymerization system, such as emulsion, bulk, or suspension systems. To illustrate, an emulsion polymerization .system aan. be used te prepare homopolymers or copolymersgf .conjugated f olsns or copolymers of coniugated ,diQlenS with other monomeric Compounds. The conjugated d iolens which are applicable include 1,3- butadiene, isoprene, Vchlortylgnrene, 2,3-dimethyl-l,3buta diene, methylpentadiene, piperylene, and others. The conjugated vdienes of 4 to 6 carbon atoms are preferred, althoughdienes -o f more than 6 carbon atoms can be used as well as the various alkoxy, such as methoxy and ethoxy, and cyano derivatives. Monomeric substances capable of copolymeriyzng with the conjugated dienes are styrene, a-methylstyrene, acrylonitri1e,vand the vinylpyridines, i.e., v`2-vinylpyridine, 2,5-divinylpyridine, 2- methyl-S-Vinylpyridine, B-ethyl-S-vinylpyridine, and others. Any initiatorl system can be used, such as the iron pyrophosphate-hydroperoxide, either sugar-free or containing sugar; the sulfoxylate recipe; the persulfate recipe,l and the like. Any suitable emulsifier such as fatty orV iosin acid-soaps can be used. Conventional short stops, i.e., t-butylhydroquinone, 2,4-dinitrochlorobenzene, water-"solubledithiocarbarriates, may be employed as well as otheringrefdients ,such as antioxidants. The emulsion polymerization temperature is generally in the range of -40 lto 140 F. The treatment of crude natural rubber is too well-known to the art to warrant further discussion thereof.
Regardless of the source of the rubber, as stated previously, it is only necessary that the rubber have such a Mooney value that it can be worked so that the oxidant can be blanded therewith. Any suitable oxidant, such as ammonium nitrate, ammonium perchlorate, Ypotassium perchlorate, potassium nitrate, or mixtures thereof, and the like may be employed. The oxidant and rubber can be mixed in any manner known in the art, such as by a dispersion blade mixer.
The composition of the rubber spacer of my invention consists essentially of 50-85 or more parts of oxidant per 100 parts by weight of rubber binder-oxidant blend. The rubber binder comprises raw rubber, carbon black, plasticizer, antioxidant, vulcanizing agent and other compounding ingredients as desired, The rubber binder is subsequently mixed or blended with the oxidant; the blend possessing a. consistency which can be molded to the desired shape by injection molding, extrusion molding, or other molding processes known to the art. Heat treating the molded article, i.e., spacer, at a temperature in the range from about 70 to aboutf250 F., preferably from about 140 to about .180? F., and for a period of time between about 3 hours to about 7 days follows, thus permanently setting or freezing the shape of the spacer.
An oil resistant rubber can be made from Ythe following emulsion polymerization recipe. i
The emulsion polymerization is carried at a temperature of approximately 25 C. for a period of about 15 hours. After shortstopping and removal of unreacted monomers the polymer is recovered from the latex in a conventional manner.
To 100 parts by weight of the synthetic rubber produced above are added the following materials to produce the rubber binder.
Ingredient: Parts by weight Synthetic rubber 100 Carbon black 65 Zinc oxide 5 Dibutyl phthalate 10 Philcure-l13 1 1.5 Sulfur 2 Stearic acid l Phenyl--naphthylamine 3 1 N,N-dimethyl-S-tert-butylsulfenyl dithocarbamate.
The synthetic rubberv and carbon black are masterbatched and subsequently there is added to the masterbatch the remaining ingredients listed above. To this mixture (the components of which now form the rubber binder) is added 75 parts of ammonium nitrate per 25 parts by weight of the rubber binder. Substantial uniform distribution of the entire mix can be obtained in a Baker- Perkins dispersion mixer. The rubber binder-oxidant blend is molded to the desired shape and cured 48 hours at 170 F.
A molded and cured rubber binder-ammonium nitrate blend consisting vof 50 parts by weight of binder per 50 parts by weight-of ammonium nitrate will vignite when it oxidant incorporated into the blend. The ultimate use of the shaped and cured rubber binder-oxidant blend will, in a number of instances, govern the choice of the synthetic rubber component in the blend. For example, in a situation where my novel packer is exposed to hydrocarbons, the synthetic rubber component must be oil resistant, and thus, the use of, for example, the acryloniytrile copolymers is desired.
The specification is accompanied by a drawing disclosing a specific embodiment of the application of my novel rubbery spacer. The drawing is merely illustrative and is not to be construed as limiting the scope of the invention.
The drawing is a schematic View of a typical oil-well.
In the drawing, the numeral 1 indicates the surface casing set and cemented. This casing is to protect fresh water supplies near the surface, prevent vthe unconsolidated formations from caving and provide a means of controlling the flow of drilling Huid. Within the surface casing is oil-string casing 2 also set and cemented. The oil-string casing is not ordinarily set in a well until it has demonstrated that it is likely to be a producer. There are generally other casings, such as the intermediate casing, which are not shown in the simplified drawing. The nal step in preparing the piping for a producing well is running in the tubing 3 to the bottom of the well or pay zone 4 so that an annular chamber is formed between the tubing 3 and the oil-string casing 2. Packer 5 comprising 75 parts by weight of ammonium nitrate and 25 parts by weight of acrylonitrile-butadiene blend prepared in the manner explained above, is fitted in the annulus at the desired depth, and is connected to electric source 6. An electric squib may either be incorporated into the packer or be adjacent thereto. Within the tubing is reciprocating pump 7, connected by means of sucker rods 8 Ito the pump unit 9 on the surface. The pump technique is ernployed when the oil formation lacks the necessary pressure to ow naturally. As the piston within reciprocating pump 7 is moved upward, ball valve 11 is opened and fluid from pay zone 4 is admitted while ball valve 12 remains in a closed position. The downward stroke of the piston, closes ball valve 11 and opens ball valve 12 wherein the fluid enters the cavityv above the reciprocating pump. In this continuous fashion, the fluid is lifted to the surface. However, gas entering the reciprocating pump along with the fluid may lodge between the ball valves, thus decreasing the efficiency of the pump. The gas within the pump is merely compressed and expanded by the action of the pump, and little fluid is thereby lifted through the tubing to the surface. When such a situation arises it may be necessary to remove the packer to permit the gaseous buildup at the well bottom to escape through the annular chamber. The pulling of the packer is a tedious, expensive, time-consuming procedure. With the novel packer of my invention, the packer is merely burned or ignited 'm situ by setting off the electrical squib by turning on electric source 6. The packer can be also ignited by other means, such as lowering a torch through the tubing to a point adjacent to the packer. The metal tubing is heated at that point whereby the packer will ignite and burn when the ignition temperature is reached. Thus, the gas can escape upward through the unimpeded annulus to the surface to be utilized or discarded, as desired. By the above expedient'the gas can eventually be worked out of the reciprocating pump.
The preparation of a typical synthetic rubber, the cornpounding thereof, followed by blending with an oxidant,
is heated to a temperature of approximately '450 F.
prior to molding and curing the blend, has been set out in particular detail. The application of the molded and cured blend as a packer in an oil well operation has also been set forth. It is not my intent to be limited to this speciiic embodiment. It is desirable that the invention be practiced with a natural or synthetic rubber which has 'such a Mooney value, i.e., up to 100, that it can be'worked so that an oxidant can be blended therewith. It will be apparent to those skilled in the art that various modifications and applications of this invention can be made upon study of the accompanying disclosure without departing from the spirit and scope of the said disclosure.
I claim:
1. As an article of manufacture an oil well packer having an annular resilient seal member consisting essentially of a composition comprising a rubbery binder selected from the group consisting of natural rubber and synthetic, conjugated diene polymer :and sufficient oxidant in admixture therewith to supply the oxygen necessary for combustion with substantial decomposition of said packer, thereby rendering said packer both ignitible and self-sustaining in combustion even in the absence of any external source of oxygen.
2. As an article of manufacture an oil well packer having an annular resilient seal member consisting essentially of a composition comprising a mixture of rubbery binder selected from the group consisting of natural rubber and synthetic, conjugated diene polymer and from 50 to 85 parts by weight per 100 parts olf mixture of oxidant selected from the group consisting of ammonium nitrate, ammonium perchlorate, potassium nitrate, potassium perchlorate, and mixtures thereof, thereby rendering said packer both ignitible and self-sustaining in combustion to substantial decomposition thereof even in the absence of any external source of oxygen.
3. An article of manufacture according to claim 2 wherein said rubbery binder is a copolymer of butadiene and acrylonitrile.
4. In an operation wherein the application of a force is adapted to be temporarily restrained and subsequently released, the improved method which comprises positioning in the path of said force a body consisting essentially of a composition comprising a rubbery binder selected from the group consisting of natural rubber and synthetic, conjugated diene polymer and sufiicient oxidant in admixture therewith to supply the oxygen necessary for combustion with substantial decomposition of said body, thereby rendering said composition both ignitible and self-sustaining in combustion even in the absence of any external source of oxygen, and igniting said body in situ so that said body substantially decomposes.
5. A method of packing oit and subsequently removing the packing material from an oil well which comprises positioning in said Well packing material comprising a rubbery binder selected from the group consisting of natural rubber and synthetic, conjugated diene polymer and sufficient oxidant in admixture therewith to supply the oxygen necessary for combustion with substantial decomposition of said packing material, thereby rendering said material both ignitible and self-sustaining in combustion even in the absence of any external source of oxygen, and igniting said packing material in situ so that said packing material substantially decomposes.
6. A method of packing oi and subsequently removing the packing material from an oil well which comprises positioning in said well packing material comprising a mixture of rubbery binder selected from the `group consistinlg of natural rubber and synthetic, conjugated diene polymer and from to 85 parts by weight per 100 parts of mixture of oxidant selected from the group consisting of ammonium nitrate, ammonium perchlorate, potassium perchlorate, potassium nitrate, and mixtures thereof, thereby rendering said packing material both ignitible and self-sustaining in combustion to the substantial decomposition thereof even in the absence of any external source of oxygen, and igniting said packing material in situ so that said packing material substantially decomposes.
7. A method according to claim 6 wherein said rubbery binder is a rubber having a Mooney (ML-4) value in the range of about 10 to 40.
8. The method of claim 4 wherein the body comprises from about 50 to about 15 parts of a rubbery binder possessing a Mooney value not greater than and from about 50 to about 85 parts of an oxidant.
References Cited in the file of this patent UNITED STATES PATENTS 1,249,180 Ostromislensky Dec. 4, 1917 2,138,156 Halliburton NOV. 29, 1938 2,291,862 Bailey Aug. 4, 1942 2,624,603 Sweet Ian. 6, 1953
Claims (1)
- 4. IN AN OPERATION WHEREIN THE APPLICATION OF A FORCE IS ADPATED TO BE TEMPORARILY RESTRAINED AND SUBSEQUENTLY RELEASED, THE IMPROVED METHOD WHICH COMPRISES POSITIONING IN THE PATH OF SAID FORCE A BODY CONSISTING ESSENTIALLY OF A COMPOSITION COMPRISING A RUBBERY BINDER SELECTED FROM THE GROUP CONSISTING OF NATURAL RUBBER AND SYNTHETIC, CONJUGATED DIENE POLYMER AND SUFFICIENT OXIDANT IN ADMIXTURE THEREWITH TO SUPPLY THE OXYGEN NECESSARY FOR CUMBUSTION WITH SUBSTANTIAL DECOMPOSITION OF SAID BODY, THEREBY RENDERING SAID COMPOSITION BOTH IGNITIBLE AND SELF-SUSTAINING IN COMBUSTION EVEN IN THE ABSENCE OF ANY EXTERNAL SOURCE OF OXYGEN, AND IGNITING SAID BODY IN SITU SO THAT SAID BODY SUBSTANTIALLY DECOMPOSES.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US550247A US2898999A (en) | 1955-12-01 | 1955-12-01 | Disposable rubber products |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US550247A US2898999A (en) | 1955-12-01 | 1955-12-01 | Disposable rubber products |
Publications (1)
Publication Number | Publication Date |
---|---|
US2898999A true US2898999A (en) | 1959-08-11 |
Family
ID=24196328
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US550247A Expired - Lifetime US2898999A (en) | 1955-12-01 | 1955-12-01 | Disposable rubber products |
Country Status (1)
Country | Link |
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US (1) | US2898999A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US3013608A (en) * | 1960-03-22 | 1961-12-19 | Church Melvin | Cement jacketed well and method of drilling same |
US3048224A (en) * | 1959-07-10 | 1962-08-07 | Phillips Petroleum Co | Apparatus and process for igniting a stratum around a well |
US20080017379A1 (en) * | 2006-07-20 | 2008-01-24 | Halliburton Energy Services, Inc. | Method for removing a sealing plug from a well |
US20100089566A1 (en) * | 2006-06-08 | 2010-04-15 | Halliburton Energy Services, Inc. | Consumable downhole tools |
US20100108327A1 (en) * | 2006-06-08 | 2010-05-06 | Halliburton Energy Services, Inc. | Consumable Downhole Tools |
US8056638B2 (en) | 2007-02-22 | 2011-11-15 | Halliburton Energy Services Inc. | Consumable downhole tools |
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US1249180A (en) * | 1916-07-28 | 1917-12-04 | New York Belting And Packing Company | Process for vulcanizing rubber and products obtained thereby. |
US2138156A (en) * | 1936-11-16 | 1938-11-29 | Halliburton Oil Well Cementing | Packer |
US2291862A (en) * | 1942-04-24 | 1942-08-04 | Chrysler Corp | Removal of bonded rubber |
US2624603A (en) * | 1949-09-13 | 1953-01-06 | Sweet Oil Well Equipment Inc | Well packer rubber |
-
1955
- 1955-12-01 US US550247A patent/US2898999A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US1249180A (en) * | 1916-07-28 | 1917-12-04 | New York Belting And Packing Company | Process for vulcanizing rubber and products obtained thereby. |
US2138156A (en) * | 1936-11-16 | 1938-11-29 | Halliburton Oil Well Cementing | Packer |
US2291862A (en) * | 1942-04-24 | 1942-08-04 | Chrysler Corp | Removal of bonded rubber |
US2624603A (en) * | 1949-09-13 | 1953-01-06 | Sweet Oil Well Equipment Inc | Well packer rubber |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3048224A (en) * | 1959-07-10 | 1962-08-07 | Phillips Petroleum Co | Apparatus and process for igniting a stratum around a well |
US3013608A (en) * | 1960-03-22 | 1961-12-19 | Church Melvin | Cement jacketed well and method of drilling same |
US8256521B2 (en) | 2006-06-08 | 2012-09-04 | Halliburton Energy Services Inc. | Consumable downhole tools |
US8291969B2 (en) | 2006-06-08 | 2012-10-23 | Halliburton Energy Services Inc. | Consumable downhole tools |
US8291970B2 (en) | 2006-06-08 | 2012-10-23 | Halliburton Energy Services Inc. | Consumable downhole tools |
US20100089566A1 (en) * | 2006-06-08 | 2010-04-15 | Halliburton Energy Services, Inc. | Consumable downhole tools |
US20100108327A1 (en) * | 2006-06-08 | 2010-05-06 | Halliburton Energy Services, Inc. | Consumable Downhole Tools |
US20100108328A1 (en) * | 2006-06-08 | 2010-05-06 | Halliburton Energy Services, Inc. | Method for Removing a Consumable Downhole Tool |
US20100314127A1 (en) * | 2006-06-08 | 2010-12-16 | Halliburton Energy Services, Inc. | Consumable downhole tools |
US8272446B2 (en) | 2006-06-08 | 2012-09-25 | Halliburton Energy Services Inc. | Method for removing a consumable downhole tool |
US7591318B2 (en) | 2006-07-20 | 2009-09-22 | Halliburton Energy Services, Inc. | Method for removing a sealing plug from a well |
US20090308620A1 (en) * | 2006-07-20 | 2009-12-17 | Halliburton Energy Services, Inc. | Method for Removing a Sealing Plug from a Well |
US20080017379A1 (en) * | 2006-07-20 | 2008-01-24 | Halliburton Energy Services, Inc. | Method for removing a sealing plug from a well |
US8056638B2 (en) | 2007-02-22 | 2011-11-15 | Halliburton Energy Services Inc. | Consumable downhole tools |
US8322449B2 (en) * | 2007-02-22 | 2012-12-04 | Halliburton Energy Services, Inc. | Consumable downhole tools |
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