US3127135A - Polyurethane - Google Patents
Polyurethane Download PDFInfo
- Publication number
- US3127135A US3127135A US3127135DA US3127135A US 3127135 A US3127135 A US 3127135A US 3127135D A US3127135D A US 3127135DA US 3127135 A US3127135 A US 3127135A
- Authority
- US
- United States
- Prior art keywords
- envelope
- airship
- polymer
- mercaptan
- product
- 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
- 229920002635 polyurethane Polymers 0.000 title 2
- 239000004814 polyurethane Substances 0.000 title 2
- 229920000728 polyester Polymers 0.000 claims description 36
- 229920001228 Polyisocyanate Polymers 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 32
- 239000005056 polyisocyanate Substances 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 30
- 229920000642 polymer Polymers 0.000 claims description 28
- 229920000570 polyether Polymers 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 16
- 150000001993 dienes Chemical class 0.000 claims description 14
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 238000007792 addition Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229920003051 synthetic elastomer Polymers 0.000 claims description 8
- 239000005061 synthetic rubber Substances 0.000 claims description 8
- 239000004636 vulcanized rubber Substances 0.000 claims description 8
- 239000004816 latex Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 4
- JJCFRYNCJDLXIK-UHFFFAOYSA-N Cyproheptadine Chemical compound C1CN(C)CCC1=C1C2=CC=CC=C2C=CC2=CC=CC=C21 JJCFRYNCJDLXIK-UHFFFAOYSA-N 0.000 claims 2
- ORGHESHFQPYLAO-UHFFFAOYSA-N Vinyl radical Chemical class C=[CH] ORGHESHFQPYLAO-UHFFFAOYSA-N 0.000 claims 2
- 239000004744 fabric Substances 0.000 description 40
- 229920001971 elastomer Polymers 0.000 description 34
- 239000001307 helium Substances 0.000 description 26
- 229910052734 helium Inorganic materials 0.000 description 26
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium(0) Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 26
- 239000005060 rubber Substances 0.000 description 24
- 239000011248 coating agent Substances 0.000 description 22
- 238000000576 coating method Methods 0.000 description 22
- 238000009792 diffusion process Methods 0.000 description 20
- 239000001257 hydrogen Substances 0.000 description 20
- 229910052739 hydrogen Inorganic materials 0.000 description 20
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 18
- 239000008199 coating composition Substances 0.000 description 18
- 125000005442 diisocyanate group Chemical group 0.000 description 16
- 239000002904 solvent Substances 0.000 description 14
- 239000004721 Polyphenylene oxide Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 239000004615 ingredient Substances 0.000 description 12
- 125000004432 carbon atoms Chemical group C* 0.000 description 10
- 239000000806 elastomer Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000004568 cement Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- LSDPWZHWYPCBBB-UHFFFAOYSA-N methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 8
- -1 polyesteramides Polymers 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 1-butanal Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 6
- YACLQRRMGMJLJV-UHFFFAOYSA-N Chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- 238000010276 construction Methods 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229920001194 natural rubber Polymers 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 238000010422 painting Methods 0.000 description 6
- 229920001281 polyalkylene Polymers 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-Butanediol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N Adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N Diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 240000008528 Hevea brasiliensis Species 0.000 description 4
- 241001441571 Hiodontidae Species 0.000 description 4
- 229920000126 Latex Polymers 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 125000006267 biphenyl group Chemical group 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000007859 condensation product Substances 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 150000002334 glycols Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- SJRJJKPEHAURKC-UHFFFAOYSA-N n-methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000003892 spreading Methods 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- VHOQXEIFYTTXJU-UHFFFAOYSA-N 2-methylbuta-1,3-diene;2-methylprop-1-ene Chemical compound CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 2
- DXGJPCOIHCEGFD-UHFFFAOYSA-N 5-isocyanato-2-(isocyanatomethyl)-5-phenylcyclohexa-1,3-diene Chemical compound C1=CC(CN=C=O)=CCC1(N=C=O)C1=CC=CC=C1 DXGJPCOIHCEGFD-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 229920004934 Dacron® Polymers 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N Diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 241001164416 Sclerolaena birchii Species 0.000 description 2
- 241000738583 Senna artemisioides Species 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N Toluene diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001414 amino alcohols Chemical class 0.000 description 2
- 230000001588 bifunctional Effects 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbamate Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010073 coating (rubber) Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- SNQXJPARXFUULZ-UHFFFAOYSA-N dioxolane Chemical compound C1COOC1 SNQXJPARXFUULZ-UHFFFAOYSA-N 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 238000009958 sewing Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B64—AIRCRAFT; AVIATION; COSMONAUTICS
- B64B—LIGHTER-THAN AIR AIRCRAFT
- B64B1/00—Lighter-than-air aircraft
- B64B1/58—Arrangements or construction of gas-bags; Filling arrangements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1362—Textile, fabric, cloth, or pile containing [e.g., web, net, woven, knitted, mesh, nonwoven, matted, etc.]
- Y10T428/1366—Textile, fabric, cloth, or pile is sandwiched between two distinct layers of material unlike the textile, fabric, cloth, or pile layer
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
- Y10T428/31587—Hydrocarbon polymer [polyethylene, polybutadiene, etc.]
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31826—Of natural rubber
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/30—Woven fabric [i.e., woven strand or strip material]
- Y10T442/3472—Woven fabric including an additional woven fabric layer
- Y10T442/3528—Three or more fabric layers
- Y10T442/3561—Woven fabric layers impregnated with a natural or synthetic rubber
Definitions
- This invention relates to airships of the lighterathanair type. More particularly, it relates to improved outer covers or envelopes for airships, to methods for preparing these improved covers and to methods for repairing the outer covers of airships while in service.
- the outer cover or envelopes "for airships are prepared by coating a cloth or fabric, such as rayon, cotton, nylon or ⁇ dacron, on both sides with a rubber composition, plyingup two such coated fabric layers so that the warp of one layer is at an approximate 45 angle to the warp of the other layer to aid in providing dimensional stability in the envelope, curing the plied-up assembly, cutting patterns from the cured laminate, bufiing the rubber from the edges of the cut patterns, cementing the buffed edges, sewing the cut patterns to form the desired envelope shape, taping the sewn seams and applying an exterior paint to the finished envelope.
- a cloth or fabric such as rayon, cotton, nylon or ⁇ dacron
- the envelope is the container for the helium gas conventionally employed to provide the lift to the airship, it is necessary that the envelope be as nearly gastight and difiusion-resistant as possible. It has been observed that even when the airship envelopes are coated with rubber having outstanding resistance to diffusion, the airships after being in service for some time lose helium through leakage or diffusion at such a rate that the effective lift of the aircnaf-t is seriously reduced. Also, the air dilfusing into the envelope increases the density of the gas. This air can be removed only by an expensive and time-consuming purification operation or by removing the impure helium gas and re-inflating with purer helium.
- One solution to this leakage and diffusion problem is to increase the thickness of rubber coating employed on the envelope fabric. This, however, increases the dead weight in the airship and reduces its effective lift.
- an object of this invention to provide coatings for airship envelopes. Another object is to prepare airship envelopes from these improved coatings without increasing the dead weight of the airship. Another object is to provide envelopes for airships which have a minimum weight amount of coating composition consistent with maximum resistance to leakage and diffusion. Still anothetr object is to repair the envelopes of airships in service without the removal of the envelope from the airship. Another object is to reduce the amount of diffusion and leakage of helium gas in airship envelopes so that the requirement for purifying the contained helium gas will be minimized. Other objects will appear as the description proceeds.
- the objects of this invention are accomplished by employing as the coating for airship envelope fabric, either in the manufacture of new envelopes or the repair of existing envelopes, a reaction product of a poly-isocyanate and an active-hydrogen containing polymeric material such as a polyester, polyether or polyeste-rannde.
- FIG. 1 and FIG. 2 are sectons of airship envelope constructions.
- FIG. 1 shows two plies 1 and 2 of cloth coated with layers 3, 4 and 5 of rubber composition.
- a layer 6 of the reaction product of a polyisocyanate and an active-hydrogen containing polymeric material is applied over the outer layer 3 of ice rubber.
- This outermost layer 6 may be applied .to the envelope as originally fabricated or it may be applied at any time the gas-retaining properties of the envelope fall below the degree required for satisfactory service of the airship.
- FIG. 2 shows an airship envelope comprising two plies 7 and -8 of cloth coated with layers.
- Examples of the active-hydrogen-containing polymeric materials useful in preparing the reaction product used to coat the airship envelopes are polyesters, polyesteramides, polyalkylene ether glycols .and mixtures of two or more of these.
- active-hydrogen used to describe these polymeric materials is meant those hydrogen atoms which are reactive as measured and determined by the Zerewitinofi method.
- the polyesters are prepared by the condensation reaction between one or more glycols and one or more dibasic carboxy-li-c acids.
- the polyesteramides are prepared from one or more glycols, one or more dib-asic carboxylic acids and relatively small amounts of one or more bifunctional amino beaning compounds such as amino carboxylic acids, amino alcohols, or diamines.
- the polyalkylene ether glycols are hydroxyl-terminated polyethers derived from gylcols or alkylene oxides or from other heterocyclic others such as dioxolane. Further examples of these 'active-hydrogen-containing polymeric materials and methods for their preparation are described in United States Patents 2,6255 31 2,625,532; 2,625,5 35 which show polyesters and polyesteramides and United States Patents 2,692,873 and 2,702,797 which show the polyalkylene ether glycols.
- Preferred vactive-hydrogen-containing polymeric materials are the polyethers having an average molecular weight of from approximately 1,000 to 5,000, and polyesters of similar molecular weight having an acid number not greater than 5. Best results are obtained with the hydroXyl-terminated polyethers having an average molecular weight of approximately 2,000.
- the polyesters, polyethers and polyesteramides of average molecular weight between 1,000 and 5,000 are either liquid at room temperature or capable of being melted at relatively low temperatures. They are transformed by reaction with polyisocyanate into sol-id cured materials. In such liquid form they can be applied in admixture with polyisocyanates and other compounding ingredients, directly to the outer surface of an already-formed airship envelope by painting or spraying, for instance. Also such liquid mixtures may be painted or spread upon the plies of fabric employed to fabricate the airship envelope. It is desirable to add a solvent such as methyl isobutyl ketone to the polymer/poylisocyanate reaction mixture to provide the consistency desired for most efiicient application to the fabric or airship envelope.
- a solvent such as methyl isobutyl ketone
- a liquid prepolymer of the polyester or polyether and polyisocyanate before applying it to the fabric.
- These prepolymers are conveniently prepared by adding approximately two mols of diisocyanate to one mol of polyester or polyether and heating the mixture, in the presence or absence of solvents, for approximately ten hours at F.
- this solid uncured elastomer is described in the patents referred to above. These solid uncured elastomers are also useful in the practice of this invention by mixing them with the curing agent, such as additional polyisocyan-ate, and other conventional compounding ingredients, and spreading the compounded uncured elastomer onto the fabric in cement form or calendering such compounded elastomers onto the layer of fabric.
- This solid form of the reaction product may also be used in the outer cover coating of new airships or for repairing the envelopes of airships already in service by making a paint or cement of the elastomer and a solvent.
- a particularly effective coating composition is one prepared in the form of a cement or paint containing approximately 35% by weight of a prepolymer of polyether/polyisocyanate, for instance, and approximately 65% by weight of solvent. This weight ratio of solids to solvent provides a solution which is readily flowable and easily applied to the fabric by painting.
- any polyisocyanate, and preferably a diisocy-anate may be employed in these coating compositions.
- Representative examples of such polyisocyanates are the meta-tolylene diisocyanates such as 2,4 and 2,6-tolylene diisocyanate or mixtures of these; 4,4-diphenyl methane diisocyanate; 4,4'-dipheny1diisocyanate; 1,5-naphtha1ene diisocyanate; 3,3'-dimethyl 4,4'-diisocyanato diphenyl; 3,3'-dimethoxy 4,4-diisocy-anato diphenyl; 3,3'-dimethyl 4,4- diisocyanato diphenyl methane and mixtures of diisocyanates and higher functional polyisocyanates such as those described in United States Patent 2,683,730.
- compounding ingredients useful in the preparation of the fabric coating composition may be added compounding ingredients useful in the preparation of the fabric coating composition.
- These useful ingredients include catalysts, and a metallic powder or flake, such as aluminum flake, for coatings which are to be applied to the outer surface of the airship envelopes.
- catalysts which are useful in accelerating cure of the coating composition are the tertiary amines, such as N- methyl morpholine and the condensation products of aldehydes and amines, such as the condensation product of approximately 4 mols of butyraldehyde and one mol of aniline similar to those described in The Journal of American Chemical Society, vol. 70, page 1624 for April 1948.
- the metallic powders employed in outer surface coating aid in the weathering resistance of the coating itself and provide a reflective surface which maintains the helium gas enclosed in the envelopes at a lower temperature.
- a suitable metallic powder for the purpose is Alcoa aluminum powder #422.
- any of the natural or synthetic rubbers may be employed in coating the fabric layers of the airship envelope which is subsequently to be coated on its outer surface with the polymer/polyisocyanate coating.
- these rubbers are natural rubber, the rubberlike copolymers of butadine and styrene, the copolymers of a major proportion of an iso-olefin and a minor proportion of a di-olefin, known as butyl rubber, and the polymers of 2- chlorobutadiene-l,3, known as polychloroprene or neoprene.
- neoprene is preferred because of its resistance to weathering and its high resistance to diffusion.
- rubbers which can be advantageously employed in coating fabric for airship envelopes are the mercaptanmodified polymers described in copending application Serial No. 543,360 filed October 28, 1955, now abandoned. As described therein, these rubbers are prepared by reacting at least one aliphatic mono-mercaptan containing from 1 to 6 carbon atoms, such as methyl mercaptan, with at least one synthetic rubber latex containing a polymer selected from the group consisting of emulsion-polymerized conjugated diolefins containing from 4 to 6 carbon atoms, such as polybut-adiene, and emulsion-polymerized copolymers of at least one conjugated diolefin containing from 4 to 6 carbon atoms with up to an equal amount by weight of at least one monomer containing a reactive component selected from the group consisting of vinyl and vinylidene radicals polymerizable with said diolefin, the double bonds present in said polymer being saturated by reaction with the mercaptan to
- a methyl mercaptan modified polybutadiene saturated to the extent of from to of the double bonds is particularly useful.
- This type of rubber is lower in specific gravity than neoprene and has outstanding resistance to diffusion as well as excellent resistance to oxidation, sunlight, and ozone, which properties make it particularly attractive for airship envelope construction.
- a prepolymer was prepared by reacting, in 34 parts of ethyl acetate solvent, 16.4 parts of tolylene diisocyanate with 85 parts of a polyester prepared from the condensation reaction between adipic acid and 33.3 mol percent of ethylene glycol and 33.3 mol percent of diethylene glycol and 33.3 mol percent of 1,4-butane diol. This polyester had a hydroxyl number of approximately 60, an acid number of about 1.0 and an average molecular weight of approximately 1850.
- the prepolymer was prepared by reacting the polyester/diisocyanate mixture for approximately 10 hours at 175 degrees F. This prepolymer was then dissolved in methyl isobutyl ketone to a solids content of about 35%. Based upon parts of prepolymer in solution the following ingredients were added to the prepolymer solution just before it was to be applied to the outer surface of an airship envelope.
- EXAMPLE II 10% solution in toluene of an accelerator prepared by condensing butyraldehyde with aniline, 2.0 parts of metatolylene diisocyanate and 6.4 parts of aluminum flake were added to the prepolymer solution.
- coating compositions prepared according to Examples I and II have outstanding resistance to difiusion and excellent resistance to weathering. As coatings for airship envelope construction or repair they provide for relatively trouble-free service and maximum protection against loss of lift in the airships consistent with minimum added dead Weight.
- Other coating compositions may be prepared as described in Examples I and 11 employing other diisocyanates, other polyester, polyethers, or polyesteramides, other accelerators and other compounding ingredients as disclosed above. Such coating compositions may be employed either to fabricate an 15 entire airship envelope, to coat the outer surface of a new airship envelope, or to repair air-ship envelopes after.
- An airship envelope comprising a plurality of layers of fabric coated with a vulcanized rubber composition which is covered c-ontiguously on its outermost surface with a reaction product of a polyisocyanate and an activehydrogen-containing polymeric material selected from the group consisting of polyesters, polyethens and polyesteramides having an average molecular weight of from 1,000 to 5,000 and an acid number not greater than 5, said re- 6 action product being in direct contact with said envelope, said vulcanized rubber composition comprises the elastomeric addition product of (A) at least one aliphatic mono-mercaptan having from 1 to 6 carbon atoms and (B) at least one synthetic rubber latex containing an emulsion polymerized polymer of at least one conjugated diolefin having from 4 to 6 carbon atoms with from none to an equal amount by weight of at least one monomer containing a reactive component selected from the group consisting of vinyl and vinylidene radicals which are polymerizable with said diolefin, in which
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Aviation & Aerospace Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
March 1964 w. w. BURR ETAL AIRSHIP ENVELOPES Filed April 27, 1956 m V Z/ /V/lf/l /l/ LAYERS OF CLOTH 7 A I 9 I F. E H z W m e H F m .H m L Y 5 m RUBBER COMPOSITION United States Patent l 3,127,135 AIRSHIP ENVELOPES Warren W. Burr, West Richfield, William F. Durbin, Akron, Vito F. Giulitto, Ravenna, Nelson V. Seeger, Cuyahoga Falls, and Carl E. Snyder, Silver Lake, Ohio, assignors to The Goodyear Tire & Rubber Company, Akron, Ohio, a corporation of Ohio Filed Apr. 27, 1956, Ser. No. 581,025 2 Claims. (Cl. 244-126) This invention relates to airships of the lighterathanair type. More particularly, it relates to improved outer covers or envelopes for airships, to methods for preparing these improved covers and to methods for repairing the outer covers of airships while in service.
The outer cover or envelopes "for airships are prepared by coating a cloth or fabric, such as rayon, cotton, nylon or \dacron, on both sides with a rubber composition, plyingup two such coated fabric layers so that the warp of one layer is at an approximate 45 angle to the warp of the other layer to aid in providing dimensional stability in the envelope, curing the plied-up assembly, cutting patterns from the cured laminate, bufiing the rubber from the edges of the cut patterns, cementing the buffed edges, sewing the cut patterns to form the desired envelope shape, taping the sewn seams and applying an exterior paint to the finished envelope.
Since the envelope is the container for the helium gas conventionally employed to provide the lift to the airship, it is necessary that the envelope be as nearly gastight and difiusion-resistant as possible. It has been observed that even when the airship envelopes are coated with rubber having outstanding resistance to diffusion, the airships after being in service for some time lose helium through leakage or diffusion at such a rate that the effective lift of the aircnaf-t is seriously reduced. Also, the air dilfusing into the envelope increases the density of the gas. This air can be removed only by an expensive and time-consuming purification operation or by removing the impure helium gas and re-inflating with purer helium. One solution to this leakage and diffusion problem is to increase the thickness of rubber coating employed on the envelope fabric. This, however, increases the dead weight in the airship and reduces its effective lift.
It is, therefore, an object of this invention to provide coatings for airship envelopes. Another object is to prepare airship envelopes from these improved coatings without increasing the dead weight of the airship. Another object is to provide envelopes for airships which have a minimum weight amount of coating composition consistent with maximum resistance to leakage and diffusion. Still anothetr object is to repair the envelopes of airships in service without the removal of the envelope from the airship. Another object is to reduce the amount of diffusion and leakage of helium gas in airship envelopes so that the requirement for purifying the contained helium gas will be minimized. Other objects will appear as the description proceeds.
The objects of this invention are accomplished by employing as the coating for airship envelope fabric, either in the manufacture of new envelopes or the repair of existing envelopes, a reaction product of a poly-isocyanate and an active-hydrogen containing polymeric material such as a polyester, polyether or polyeste-rannde.
The practice of this invention is illustrated with respect to the accompanying drawings in which FIG. 1 and FIG. 2 are sectons of airship envelope constructions. FIG. 1 shows two plies 1 and 2 of cloth coated with layers 3, 4 and 5 of rubber composition. In this particular embodiment of this invention a layer 6 of the reaction product of a polyisocyanate and an active-hydrogen containing polymeric material is applied over the outer layer 3 of ice rubber. This outermost layer 6 may be applied .to the envelope as originally fabricated or it may be applied at any time the gas-retaining properties of the envelope fall below the degree required for satisfactory service of the airship. FIG. 2 shows an airship envelope comprising two plies 7 and -8 of cloth coated with layers. 9, 10, and 111 of a composition containing a polyisocyanate and an active-hydrogen-containing polymeric material. In this embodiment of the invention the excellent diffusion and weathering properties of the reaction mixture are taken full advantage of, since type of material represents the only rubber-dike material present in the airship envelope.
Examples of the active-hydrogen-containing polymeric materials useful in preparing the reaction product used to coat the airship envelopes are polyesters, polyesteramides, polyalkylene ether glycols .and mixtures of two or more of these. By the term active-hydrogen used to describe these polymeric materials is meant those hydrogen atoms which are reactive as measured and determined by the Zerewitinofi method. The polyesters are prepared by the condensation reaction between one or more glycols and one or more dibasic carboxy-li-c acids. The polyesteramides are prepared from one or more glycols, one or more dib-asic carboxylic acids and relatively small amounts of one or more bifunctional amino beaning compounds such as amino carboxylic acids, amino alcohols, or diamines. Small amounts of trifunctional materials may optionally be employed in preparing the active-hydrogen-containing polyesters and polyesteramides. The polyalkylene ether glycols are hydroxyl-terminated polyethers derived from gylcols or alkylene oxides or from other heterocyclic others such as dioxolane. Further examples of these 'active-hydrogen-containing polymeric materials and methods for their preparation are described in United States Patents 2,6255 31 2,625,532; 2,625,5 35 which show polyesters and polyesteramides and United States Patents 2,692,873 and 2,702,797 which show the polyalkylene ether glycols. Preferred vactive-hydrogen-containing polymeric materials are the polyethers having an average molecular weight of from approximately 1,000 to 5,000, and polyesters of similar molecular weight having an acid number not greater than 5. Best results are obtained with the hydroXyl-terminated polyethers having an average molecular weight of approximately 2,000.
The polyesters, polyethers and polyesteramides of average molecular weight between 1,000 and 5,000 are either liquid at room temperature or capable of being melted at relatively low temperatures. They are transformed by reaction with polyisocyanate into sol-id cured materials. In such liquid form they can be applied in admixture with polyisocyanates and other compounding ingredients, directly to the outer surface of an already-formed airship envelope by painting or spraying, for instance. Also such liquid mixtures may be painted or spread upon the plies of fabric employed to fabricate the airship envelope. It is desirable to add a solvent such as methyl isobutyl ketone to the polymer/poylisocyanate reaction mixture to provide the consistency desired for most efiicient application to the fabric or airship envelope. To save time in the curing of the coating after it is applied, it it preferred to form a liquid prepolymer of the polyester or polyether and polyisocyanate before applying it to the fabric. These prepolymers are conveniently prepared by adding approximately two mols of diisocyanate to one mol of polyester or polyether and heating the mixture, in the presence or absence of solvents, for approximately ten hours at F.
It is possible to produce from polyethers, as well as from polyesters and polyestenamides, uncured elastomeric products similar in physical state to unvulcanized natural rubber by controlling the extent of reaction between the polyether and the polyisocyanate.
Methods for preparing this solid uncured elastomer are described in the patents referred to above. These solid uncured elastomers are also useful in the practice of this invention by mixing them with the curing agent, such as additional polyisocyan-ate, and other conventional compounding ingredients, and spreading the compounded uncured elastomer onto the fabric in cement form or calendering such compounded elastomers onto the layer of fabric. This solid form of the reaction product may also be used in the outer cover coating of new airships or for repairing the envelopes of airships already in service by making a paint or cement of the elastomer and a solvent. Conventional solvents such as methyl ethyl ketone or dimethyl formamide may be employed to make the cement for spreading or painting purposes. It is also possible to apply the uncured elastomeric material to the fabric in the form of a melt formed by heating the material sufiiciently to reduce it to a flowable consistency.
Of the various physical forms in which the coating can be applied to the fabric or envelope and the various methods of preparing the coating composition, a particularly effective coating composition is one prepared in the form of a cement or paint containing approximately 35% by weight of a prepolymer of polyether/polyisocyanate, for instance, and approximately 65% by weight of solvent. This weight ratio of solids to solvent provides a solution which is readily flowable and easily applied to the fabric by painting.
Any polyisocyanate, and preferably a diisocy-anate may be employed in these coating compositions. Representative examples of such polyisocyanates are the meta-tolylene diisocyanates such as 2,4 and 2,6-tolylene diisocyanate or mixtures of these; 4,4-diphenyl methane diisocyanate; 4,4'-dipheny1diisocyanate; 1,5-naphtha1ene diisocyanate; 3,3'-dimethyl 4,4'-diisocyanato diphenyl; 3,3'-dimethoxy 4,4-diisocy-anato diphenyl; 3,3'-dimethyl 4,4- diisocyanato diphenyl methane and mixtures of diisocyanates and higher functional polyisocyanates such as those described in United States Patent 2,683,730.
To the reaction mixture of polyisocyanate and the active-hydrogen-containing polymeric material, may be added compounding ingredients useful in the preparation of the fabric coating composition. These useful ingredients include catalysts, and a metallic powder or flake, such as aluminum flake, for coatings which are to be applied to the outer surface of the airship envelopes. Specific catalysts which are useful in accelerating cure of the coating composition are the tertiary amines, such as N- methyl morpholine and the condensation products of aldehydes and amines, such as the condensation product of approximately 4 mols of butyraldehyde and one mol of aniline similar to those described in The Journal of American Chemical Society, vol. 70, page 1624 for April 1948. The metallic powders employed in outer surface coating aid in the weathering resistance of the coating itself and provide a reflective surface which maintains the helium gas enclosed in the envelopes at a lower temperature. A suitable metallic powder for the purpose is Alcoa aluminum powder #422.
Any of the natural or synthetic rubbers may be employed in coating the fabric layers of the airship envelope which is subsequently to be coated on its outer surface with the polymer/polyisocyanate coating. Examples of these rubbers are natural rubber, the rubberlike copolymers of butadine and styrene, the copolymers of a major proportion of an iso-olefin and a minor proportion of a di-olefin, known as butyl rubber, and the polymers of 2- chlorobutadiene-l,3, known as polychloroprene or neoprene. Of these rubbers, neoprene is preferred because of its resistance to weathering and its high resistance to diffusion.
Other rubbers which can be advantageously employed in coating fabric for airship envelopes are the mercaptanmodified polymers described in copending application Serial No. 543,360 filed October 28, 1955, now abandoned. As described therein, these rubbers are prepared by reacting at least one aliphatic mono-mercaptan containing from 1 to 6 carbon atoms, such as methyl mercaptan, with at least one synthetic rubber latex containing a polymer selected from the group consisting of emulsion-polymerized conjugated diolefins containing from 4 to 6 carbon atoms, such as polybut-adiene, and emulsion-polymerized copolymers of at least one conjugated diolefin containing from 4 to 6 carbon atoms with up to an equal amount by weight of at least one monomer containing a reactive component selected from the group consisting of vinyl and vinylidene radicals polymerizable with said diolefin, the double bonds present in said polymer being saturated by reaction with the mercaptan to the extent of at least 30% of the total double bonds present in said polymer, the mercaptan/polymer addition product having a Mooney plasticity, as measured by the large rotor at 212 F. of not less than 35. For airship envelope construction a methyl mercaptan modified polybutadiene saturated to the extent of from to of the double bonds is particularly useful. This type of rubber is lower in specific gravity than neoprene and has outstanding resistance to diffusion as well as excellent resistance to oxidation, sunlight, and ozone, which properties make it particularly attractive for airship envelope construction.
The practice of this invention is further illustrated with respect to the following examples which are representative rather than restrictive of the scope of this invention. Parts are shown by weight unless otherwise specified.
EXAMPLE I A prepolymer was prepared by reacting, in 34 parts of ethyl acetate solvent, 16.4 parts of tolylene diisocyanate with 85 parts of a polyester prepared from the condensation reaction between adipic acid and 33.3 mol percent of ethylene glycol and 33.3 mol percent of diethylene glycol and 33.3 mol percent of 1,4-butane diol. This polyester had a hydroxyl number of approximately 60, an acid number of about 1.0 and an average molecular weight of approximately 1850. The prepolymer was prepared by reacting the polyester/diisocyanate mixture for approximately 10 hours at 175 degrees F. This prepolymer was then dissolved in methyl isobutyl ketone to a solids content of about 35%. Based upon parts of prepolymer in solution the following ingredients were added to the prepolymer solution just before it was to be applied to the outer surface of an airship envelope.
8.8 parts of meta tolylene diisocyanate 22.7 parts of aluminum powder (Alcoa #422) 2.0 parts of a 10% solution in toluene of an accelerator prepared by condensing butyraldehyde with aniline.
An airship, origin-ally charged with 99.5% pure helium, had after one year of service lost helium through leakage and diffusion to such an extent that the percentage of helium purity in the airship had been reduced to 87.2%. The polyester/diisocyanate mixture prepared according to Example I was applied to the envelope of this airship, and the helium content of the airship was purged to provide a new helium purity of 96.2%. After seven months of service with the polyester/diisocyanate coating functioning as a diffusion-resistant barrier, further determinations showed that there was no measurable loss in helium punty.
he coating compositions prepared according to Examples I and II have outstanding resistance to difiusion and excellent resistance to weathering. As coatings for airship envelope construction or repair they provide for relatively trouble-free service and maximum protection against loss of lift in the airships consistent with minimum added dead Weight. Other coating compositions may be prepared as described in Examples I and 11 employing other diisocyanates, other polyester, polyethers, or polyesteramides, other accelerators and other compounding ingredients as disclosed above. Such coating compositions may be employed either to fabricate an 15 entire airship envelope, to coat the outer surface of a new airship envelope, or to repair air-ship envelopes after.
they have been in service.
While certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in this art that various changes and modifications may be made therein Without departing from the spirit or scope of the invention.
We claim:
1. An airship envelope comprising a plurality of layers of fabric coated with a vulcanized rubber composition which is covered c-ontiguously on its outermost surface with a reaction product of a polyisocyanate and an activehydrogen-containing polymeric material selected from the group consisting of polyesters, polyethens and polyesteramides having an average molecular weight of from 1,000 to 5,000 and an acid number not greater than 5, said re- 6 action product being in direct contact with said envelope, said vulcanized rubber composition comprises the elastomeric addition product of (A) at least one aliphatic mono-mercaptan having from 1 to 6 carbon atoms and (B) at least one synthetic rubber latex containing an emulsion polymerized polymer of at least one conjugated diolefin having from 4 to 6 carbon atoms with from none to an equal amount by weight of at least one monomer containing a reactive component selected from the group consisting of vinyl and vinylidene radicals which are polymerizable with said diolefin, in which the double bonds present in the polymer are saturated by reaction with the mercaptan to the extent of at least 30% of the total double bonds present in said polymer, said addition product having a Mooney plasticity (large rotor) or not less than 35.
2. An airship envelope defined by claim 1 in which the active-hydrogen-containing polymeric matenial is a polyether.
References Cited in the file of this patent UNITED STATES PATENTS 1,749,474 Edwards Mar. 4, 1930 2,126,818 Sager et a1 Aug. 16, 1938 2,282,827 Rothrock May 12, 1942 2,424,883 Habgood et al July 29, 1947 2,523,312 Leboime et al Sept. 26, 1950 2,729,618 Muller et a1. Jan. 3, 1956 2,749,960 Schwartz June 12, 1956 2,751,363 Martin June 19, 1956 2,805,182 Hallenbeck Sept. 3, 1957
Claims (1)
1. AN AIRSHIP ENVELOPE COMPRISING A PLURALITY OF LAYERS OF FABRIC COATED WITH A VULCANIZED RUBBER COMPOSITION WHICH IS COVERED CONTIGUOUSLY ON ITS OUTERMOST SURFACE WITH A REACTIN PRODUCT OF A POLYISOCYANATE AN AN ACTIVEHYDROGEN-CONTAINING POLYMERIC MATERIAL, SELECTED FROM THE GROUP CONSISTING OF POLYESTERS, POLYETHERS AND POLYESTERAMIDES HAVING AN AVERAGE MOLECULAR WEIGHT OF FROM 1,000 TO 5,000 AND AN ACID NUMBER NOT GREATER THAN 5, SAID REACTION PRODUCT BEING IN DIRECT CONTACT WITH SAID ENVELOPE, SAID VULCANIZED RUBBER COMPOSITION COMPRISES THE ELASTOMERIC ADDITION PRODUCT OF (A) AT LEAST ONE ALIPHATIC MONO-MERCAPTAN HAVING FROM 1 TO 6 CARBON ATOMS AND (B) AT LEAST ONE SYNTHETIC RUBBER LATEX CONTAINING AN EMULSION POLYMERIZED POLYMER OF AT LEAST ONE CONJUGATED DIOLEFIN HAVING FROM 4 TO 6 CARBON ATOMS WITH FROM NONE TO AN EQUAL AMOUNT BY WEIGHT OF AT LEAST ONE MONOMER CONTAINING A REACTIVE COMPONENT SELECTED FROM THE GROUP CONSITING OF VINYL AND VINYLIDENE RADICALS WHICH ARE POLYMERIAZBLE WITH SAID DIOLEFIN, IN WHICH THE DOUBLE BONDS PRESENT IN THE POLYMER ARE SATURATED BY REACTION WITH THE MERCAPTAN TO THE EXTENT OF AT LEAST 30% OF THE TOTAL DOUBLE BONDS PRESENT IN SAID POLYMER, SAID ADDITION PRODUCT HAVING A MOONEY PLASTICITY (LARGE ROTOR) OR NOT LESS THAN 35.
Publications (1)
Publication Number | Publication Date |
---|---|
US3127135A true US3127135A (en) | 1964-03-31 |
Family
ID=3456157
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US3127135D Expired - Lifetime US3127135A (en) | Polyurethane |
Country Status (1)
Country | Link |
---|---|
US (1) | US3127135A (en) |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3178560A (en) * | 1960-11-18 | 1965-04-13 | Dowty Rotol Ltd | Electrical de-icing devices |
US3486966A (en) * | 1965-07-06 | 1969-12-30 | Chem Seal Corp Of America | Cloth ballistic penetrating resistance laminate |
US3509016A (en) * | 1966-02-16 | 1970-04-28 | Goodyear Tire & Rubber | Self-sealing fuel cell wall |
US3974989A (en) * | 1975-04-10 | 1976-08-17 | E. I. Du Pont De Nemours And Company | Inflatable lighter-than-air article composed of a coated triaxial weave construction |
US4125233A (en) * | 1977-05-04 | 1978-11-14 | Raven Industries, Inc. | Tethered aerodynamic balloon with integral fins |
US4149921A (en) * | 1976-01-26 | 1979-04-17 | Stannard Donald H | Elastomer coated fabric provided by a casting process |
US4235444A (en) * | 1978-09-11 | 1980-11-25 | Meyer Leonard S | Target particularly for archery |
US4282283A (en) * | 1979-10-29 | 1981-08-04 | Textured Products, Inc. | Laminated fiberglass fabric |
US4463465A (en) * | 1982-12-23 | 1984-08-07 | The United States Of America As Represented By The Administrator Of National Aeronautics And Space Administration | Fire blocking systems for aircraft seat cushions |
US6074722A (en) * | 1994-09-30 | 2000-06-13 | Lockheed Martin Corporation | Flexible material for use in an inflatable structure |
US6474595B1 (en) * | 2000-02-01 | 2002-11-05 | Harnessing Energy/Storm Reduction, Inc. | Electrical energy depletion/collection system |
US20040180161A1 (en) * | 2003-03-14 | 2004-09-16 | Lavan Charles K. | Flexible material for lighter-than-air vehicles |
US20060084336A1 (en) * | 1999-08-10 | 2006-04-20 | Warwick Mills, Inc. | High strength lightweight composite fabric with low gas permeability |
US20070128963A1 (en) * | 2005-08-23 | 2007-06-07 | Vogt Kirkland W | Flexible sheet-like composites |
US20070281570A1 (en) * | 2006-05-30 | 2007-12-06 | Liggett Paul E | Reduced weight flexible laminate material for lighter-than-air vehicles |
US20090042037A1 (en) * | 2005-09-21 | 2009-02-12 | Liggett Paul E | Metallized Flexible Laminate Material for Lighter-Than-Air Vehicles |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1749474A (en) * | 1927-09-06 | 1930-03-04 | Aluminum Co Of America | Balloon envelope |
US2126818A (en) * | 1936-08-22 | 1938-08-16 | Theron P Sager | Gas-retaining fabric |
US2282827A (en) * | 1939-11-13 | 1942-05-12 | Du Pont | Resinous product and method of making |
US2424883A (en) * | 1941-10-14 | 1947-07-29 | Ici Ltd | Paraformaldehyde modified reaction products of diisocyanates with linear polyester polyamide |
US2523312A (en) * | 1940-05-28 | 1950-09-26 | Leboime Rene | Balloon envelope fabric |
US2729618A (en) * | 1952-11-18 | 1956-01-03 | Bayer Ag | Isocyanate-modified polyesters reacted with glycols |
US2749960A (en) * | 1953-09-18 | 1956-06-12 | Du Pont | Composite structures |
US2751363A (en) * | 1953-04-02 | 1956-06-19 | Us Rubber Co | Flock-filled isocyanate-containing elastomer |
US2805182A (en) * | 1955-12-22 | 1957-09-03 | Goodrich Co B F | Elastic polyurethane elastomer composites |
-
0
- US US3127135D patent/US3127135A/en not_active Expired - Lifetime
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1749474A (en) * | 1927-09-06 | 1930-03-04 | Aluminum Co Of America | Balloon envelope |
US2126818A (en) * | 1936-08-22 | 1938-08-16 | Theron P Sager | Gas-retaining fabric |
US2282827A (en) * | 1939-11-13 | 1942-05-12 | Du Pont | Resinous product and method of making |
US2523312A (en) * | 1940-05-28 | 1950-09-26 | Leboime Rene | Balloon envelope fabric |
US2424883A (en) * | 1941-10-14 | 1947-07-29 | Ici Ltd | Paraformaldehyde modified reaction products of diisocyanates with linear polyester polyamide |
US2729618A (en) * | 1952-11-18 | 1956-01-03 | Bayer Ag | Isocyanate-modified polyesters reacted with glycols |
US2751363A (en) * | 1953-04-02 | 1956-06-19 | Us Rubber Co | Flock-filled isocyanate-containing elastomer |
US2749960A (en) * | 1953-09-18 | 1956-06-12 | Du Pont | Composite structures |
US2805182A (en) * | 1955-12-22 | 1957-09-03 | Goodrich Co B F | Elastic polyurethane elastomer composites |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3178560A (en) * | 1960-11-18 | 1965-04-13 | Dowty Rotol Ltd | Electrical de-icing devices |
US3486966A (en) * | 1965-07-06 | 1969-12-30 | Chem Seal Corp Of America | Cloth ballistic penetrating resistance laminate |
US3509016A (en) * | 1966-02-16 | 1970-04-28 | Goodyear Tire & Rubber | Self-sealing fuel cell wall |
US3974989A (en) * | 1975-04-10 | 1976-08-17 | E. I. Du Pont De Nemours And Company | Inflatable lighter-than-air article composed of a coated triaxial weave construction |
US4149921A (en) * | 1976-01-26 | 1979-04-17 | Stannard Donald H | Elastomer coated fabric provided by a casting process |
US4125233A (en) * | 1977-05-04 | 1978-11-14 | Raven Industries, Inc. | Tethered aerodynamic balloon with integral fins |
US4235444A (en) * | 1978-09-11 | 1980-11-25 | Meyer Leonard S | Target particularly for archery |
US4282283A (en) * | 1979-10-29 | 1981-08-04 | Textured Products, Inc. | Laminated fiberglass fabric |
US4463465A (en) * | 1982-12-23 | 1984-08-07 | The United States Of America As Represented By The Administrator Of National Aeronautics And Space Administration | Fire blocking systems for aircraft seat cushions |
US6074722A (en) * | 1994-09-30 | 2000-06-13 | Lockheed Martin Corporation | Flexible material for use in an inflatable structure |
US20060084336A1 (en) * | 1999-08-10 | 2006-04-20 | Warwick Mills, Inc. | High strength lightweight composite fabric with low gas permeability |
US6474595B1 (en) * | 2000-02-01 | 2002-11-05 | Harnessing Energy/Storm Reduction, Inc. | Electrical energy depletion/collection system |
US6979479B2 (en) | 2003-03-14 | 2005-12-27 | Lockheed Martin Corporation | Flexible material for lighter-than-air vehicles |
US20040180161A1 (en) * | 2003-03-14 | 2004-09-16 | Lavan Charles K. | Flexible material for lighter-than-air vehicles |
US20060134359A1 (en) * | 2003-03-14 | 2006-06-22 | Lavan Charles K | Flexible laminate material for lighter-than-air vehicles |
US7354636B2 (en) | 2003-03-14 | 2008-04-08 | Lockheed Martin Corporation | Flexible laminate material for lighter-than-air vehicles |
US20070128963A1 (en) * | 2005-08-23 | 2007-06-07 | Vogt Kirkland W | Flexible sheet-like composites |
US7713890B2 (en) | 2005-08-23 | 2010-05-11 | Milliken & Company | Flexible sheet-like composites |
US20090042037A1 (en) * | 2005-09-21 | 2009-02-12 | Liggett Paul E | Metallized Flexible Laminate Material for Lighter-Than-Air Vehicles |
US8524621B2 (en) | 2005-09-21 | 2013-09-03 | Lockheed Martin Corporation | Metallized flexible laminate material for lighter-than-air vehicles |
US20070281570A1 (en) * | 2006-05-30 | 2007-12-06 | Liggett Paul E | Reduced weight flexible laminate material for lighter-than-air vehicles |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3127135A (en) | Polyurethane | |
US2766164A (en) | Adhesion of synthetic polymers to polymerizable materials | |
US2749960A (en) | Composite structures | |
US3462328A (en) | Method of making vehicle tire tread | |
US4594286A (en) | Coated fabric | |
US2467322A (en) | Tie gum for polymer-rubber articles | |
US3322433A (en) | Sealing ring and method of making same | |
US3300421A (en) | Resilient cellular material and method for making same | |
US5011902A (en) | Co-catalyst system for preparing polyurethane based plywood-patch compositions | |
US3951190A (en) | Heat-resistant fuel cell | |
US3940528A (en) | Rigid plastics tile with textured surface | |
US3772071A (en) | Liquid container cells | |
US3616189A (en) | Liquid container cells with cured nitrile inner layer and cured polyether-polyurethane elastomer outside layer | |
JP2007523232A (en) | Filled polymer composite and synthetic building material composition | |
CA2442002A1 (en) | Polyurethane in intimate contact with fibrous material | |
EP0705287B1 (en) | Polyureaurethane primerless structural adhesive | |
US3905944A (en) | Polyurethane prepared with 4,4{40 -diamino diphenyl disulfide | |
US6499745B2 (en) | Solid sealant with environmentally preferable corrosion resistance | |
US4123582A (en) | Building form for molded articles having a urethane coating | |
CN1386815A (en) | Preparing process and application of wet-solidifying single-component polyurethane adhesive | |
CN108864923B (en) | Low-temperature low-humidity curing solvent-free single-component polyurethane waterproof coating and preparation method thereof | |
CN110256653A (en) | A kind of high performance concrete piston sealing member material and preparation process | |
Schollenberger | Polyurethane-and isocyanate-based adhesives | |
US2389641A (en) | Method of adhering rubbery material to smcoth surfaces | |
US2816055A (en) | Fuel cell and method of making same |