US2180971A - Waterproofing composition - Google Patents
Waterproofing composition Download PDFInfo
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- US2180971A US2180971A US2180971DA US2180971A US 2180971 A US2180971 A US 2180971A US 2180971D A US2180971D A US 2180971DA US 2180971 A US2180971 A US 2180971A
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- Prior art keywords
- solvent
- water
- repellent
- thickener
- crystallizable
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- Expired - Lifetime
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- 239000000203 mixture Substances 0.000 title description 134
- 238000004078 waterproofing Methods 0.000 title description 60
- 239000000463 material Substances 0.000 description 132
- 239000002904 solvent Substances 0.000 description 96
- 239000005871 repellent Substances 0.000 description 82
- 239000002562 thickening agent Substances 0.000 description 82
- 239000000470 constituent Substances 0.000 description 44
- 239000000126 substance Substances 0.000 description 34
- 239000007787 solid Substances 0.000 description 30
- 239000000499 gel Substances 0.000 description 26
- 235000021323 fish oil Nutrition 0.000 description 20
- 125000005456 glyceride group Chemical group 0.000 description 20
- 238000001704 evaporation Methods 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 239000010426 asphalt Substances 0.000 description 12
- 239000002270 dispersing agent Substances 0.000 description 12
- 239000003925 fat Substances 0.000 description 12
- 235000019197 fats Nutrition 0.000 description 12
- 150000002430 hydrocarbons Chemical class 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 12
- 239000004568 cement Substances 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 10
- HVYWMOMLDIMFJA-DPAQBDIFSA-N (3β)-Cholest-5-en-3-ol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 230000000149 penetrating Effects 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000005712 crystallization Effects 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000035515 penetration Effects 0.000 description 6
- 238000007711 solidification Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- 241000251468 Actinopterygii Species 0.000 description 4
- 229940063655 Aluminum stearate Drugs 0.000 description 4
- DSSYKIVIOFKYAU-UHFFFAOYSA-N Camphor Chemical compound C1CC2(C)C(=O)CC1C2(C)C DSSYKIVIOFKYAU-UHFFFAOYSA-N 0.000 description 4
- 229960000846 Camphor Drugs 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N Carbon tetrachloride Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 229940107161 Cholesterol Drugs 0.000 description 4
- 241000723346 Cinnamomum camphora Species 0.000 description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 4
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229930007890 camphor Natural products 0.000 description 4
- 235000012000 cholesterol Nutrition 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 125000000853 cresyl group Chemical class C1(=CC=C(C=C1)C)* 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 235000013311 vegetables Nutrition 0.000 description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-Ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 235000017060 Arachis glabrata Nutrition 0.000 description 2
- 240000005781 Arachis hypogaea Species 0.000 description 2
- 235000010777 Arachis hypogaea Nutrition 0.000 description 2
- 235000018262 Arachis monticola Nutrition 0.000 description 2
- 241001608519 Bursera fagaroides Species 0.000 description 2
- 241000283153 Cetacea Species 0.000 description 2
- 240000007170 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 239000004859 Copal Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- JXSJBGJIGXNWCI-UHFFFAOYSA-N Malathion Chemical compound CCOC(=O)CC(SP(=S)(OC)OC)C(=O)OCC JXSJBGJIGXNWCI-UHFFFAOYSA-N 0.000 description 2
- 229940061319 Ovide Drugs 0.000 description 2
- 241000779819 Syncarpia glomulifera Species 0.000 description 2
- 229940036248 Turpentine Drugs 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- IVFLBOOKXPVDAK-UHFFFAOYSA-L [Cl-].[Cl-].C=C.C(Cl)(Cl)Cl.C(Cl)(Cl)(Cl)Cl Chemical compound [Cl-].[Cl-].C=C.C(Cl)(Cl)Cl.C(Cl)(Cl)(Cl)Cl IVFLBOOKXPVDAK-UHFFFAOYSA-L 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- -1 amyl alcohols Chemical class 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000010775 animal oil Substances 0.000 description 2
- 230000001680 brushing Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229940110456 cocoa butter Drugs 0.000 description 2
- 235000019868 cocoa butter Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 235000005824 corn Nutrition 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 235000019688 fish Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 239000005445 natural product Substances 0.000 description 2
- 229930014626 natural products Natural products 0.000 description 2
- 230000001264 neutralization Effects 0.000 description 2
- AZBLNMZWDUZVKW-UHFFFAOYSA-N nitrobenzene;1,2-xylene Chemical compound CC1=CC=CC=C1C.[O-][N+](=O)C1=CC=CC=C1 AZBLNMZWDUZVKW-UHFFFAOYSA-N 0.000 description 2
- 235000020232 peanut Nutrition 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000001739 pinus spp. Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001105 regulatory Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 235000003441 saturated fatty acids Nutrition 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000001256 steam distillation Methods 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 150000004992 toluidines Chemical class 0.000 description 2
- 238000004450 types of analysis Methods 0.000 description 2
- 239000010698 whale oil Substances 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D195/00—Coating compositions based on bituminous materials, e.g. asphalt, tar, pitch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/005—Drying oils
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
Definitions
- Our invention relates to waterproofing compositions, and more particularly to waterproofing compositions that form, upon evaporation of their volatile constituents, fine-grained to glass-like 5 water-repellent films.
- One of the features of" our invention is the crystallization of a water-repellent crystalline material in the composition controlled by a noncrystalline water-repellent constituent present in o thickened form, whereby the normal growth of the crystals of the controlled material is arrested and that material deposits in the form of extremely fine size crystals.
- These fine crystals uniformly and intimately admix with the fine size particles of the controlling non-crystalline substance to form upon complete, solidification a continuous fine-grained to glass-like film the imperforate nature of which prevents moisture penetration.
- the rule or formula to be followed for producing the improved waterproofing compositions of our invention comprises selecting an organic solvent, acrystallizable water-repellent material, and-a normally solid or viscous sub 35 stance (preferably water-repellent) and that is chemically or physically so related that the mixture of this substance and the solvent will thicken upon concentration thereof; and to so proportion them that the thickening will occur 40 before the crystallizable water-repellent constituent or constituents in the liquid waterproofing composition begin to'crystallize.
- the waterproofing composition when the waterproofing composition is applied to a material to be waterproofed and the organic solvent begins' to evaporate, one of the constituents must first cause this substance and the solvent to thicken, either in the form of a gel or' a viscous mass, so that when the crystallizable water-repellent material subsequently begins to precipitate out of solution the thickener and solvent will be in thickened form to arrest the normal crystal growth of the precipitate so that the crystals of water-repellent material will be deposited in extremely fine size form, connormally fine size or amorphous particles of the water-repellent thickener to produce upon the material to be waterproofed a composite finegrained to glass-like water-repellent film.
- the waterproofing composition may be made from any two or more water-repellent constituents and a suitable solvent properly selected from large groups of such constituents subsequently denoted herein and, in general, the same degree of waterproofing effectiveness will be obtained in each case. Regardless of the constituents so selected, their maximum waterproofing effectiveness will always be produced so long as the crystallization of the crystallizable water-repellent material is .properly controlled to produce very fine size crystals and thereby fine-grained films.
- paraffin, waxes, and gums may now be used as constituents in highly effective waterproofing compositions.
- the field of effective waterproofing compositions has been markedly extended.
- compositions produced from various mixtures of the selected water-repellent constituents will vary somewhat inherently, they will each possess a high degree of water-repellency because of the fine-grained, uniform, compact structure of their deposited films. That is to say, these films are composed of extremely small particles so uniform in size, admixture and distribution that the film is practically homogeneous and substantially free of interstices. Consequently, the film ofiers a uniform high resistance to water over its entire surface and being practically nonporous it is impervious to water penetration.
- the crystallizable water-repellent material which constitutes one of the principal waterproofing ingredients in the composition, may be any organic water-repellent material that will. crystallize upon concentration in an organic sol Some of the water-repellent crystalliz-' vent. able materials that we have found satisfactory are as follows:
- Fatty materials e. g., both those natural fats I and the.artificially saturated animal, vegetable and marine fats and oils which crystallize and are substantially solid at normal atmospheric temperatures; such as lard, tallow, cocoa butter, fish and whale fats, hydrogenated animal oil, cotton seed, corn, cocoanut, peanut, fish and whale oils.
- Fatty acid glycerides e. g., both those natural glycerides and those artificially saturated jglyi'cerides'of the higher fatty acids found in ani-- -m al',' vegetable and marine: fats which crystalli'ze a n'd are substantially solid at normal at- "mosbheric temperatures, e. g., hydrogenated fish oil glycerides.
- Hydrocarbons e. g., paraflin, montan, ceresin, and others which are substantially solid at normal atmospheric temperatures.
- the solvent used may be any one of the organic evaporative solvents that will act as a common solvent for the water-repellent thickener and the crystallizable material; and with the thick- Benzol Tolulol Xylol Nitrobenzene 3. Oils derived by steam distillation of resinous woods; e. g., turpentine 4. Halogen derivatives of lower hydrocarbons;
- the thickener may be any organic, preferably waterproof, substance that with the solvent will thicken at the proper concentration to arrest the crystal -growth of the crystallizable waterrepellent material.
- water-repellent substances are of the type normally considered as amorphous, although X-ray analyses might show some or all of these I substances to have, at least in part, a crystalline structure.
- any waterproof substance whether of an organic or inorganic nature and whether of a crystalline or non-crystalline character, could be used as the thickener in accordance with our invention provided it served the purpose of controlling the crystal growth of the definitely crystalline water-repellent material or materials used in the composition.
- the principal requirement for the thickener is that regardless ofits chemical nature, the solvent and the thickener it will increase in viscosity at the proper concentration and time to effect the desired crystal growth control.
- the thickener may be either of a gel-forming type or of a non-gel-forming type. As far as the physical character of the thickener is concerned, it is only necessary that it and the solvent will be 'sufiiciently viscous tophysically interfere with the normal crystal growth of the crystallizable water-repellent material.
- thickeners that we have found Satisfactory or use in. our invention are the following:
- 35 mation of fine-grain films are as follows:
- Example I Y Per cent Aluminum'stearate (thickener) 2.0 3.0 Hydrogenated fish oil glycerides (crystallizable material) 1.0- 3.0 Petroleum naphtha (solvent) .1 96.5 93.5 Cresol (thinner) 0.5- 0.5
- Example III L Grams 55 Asphalt (thickener) 20-25 5 ficial asphalt.
- Gums and resins e. g., both the natural products such as rosin, copal, colophony, dammer,
- Cellulosic materials e. g., collodion (tetranitrate of cellulose).
- the thickener used in the waterproofing composition when the thickener used in the waterproofing compositionforms a gel or gel-like mass initially in the hydrocarbon solvent, i. e., before concentration in the solvent, we have found it desirable to use a thinner or dispersing agent to disperse the gel and produce a mobile colloidal solution.
- This initial breaking or dispersing of the gel] will not, however, if the proper dispersing agent is used, prevent the desired formation of gel or viscous mass for crystal growth control during evaporation-of the solvent when the composition is used.
- The-thinner used for dispersing the initial gel should be a substance that volatilizes on evaporation of the mixture. Examples of the thinners or dispersing agents that we have found satisfactory are the following: Methyl, ethyl, butyl and amyl alcohols, phenol, cresol, aniline, toluidine, acetone and acetic acid.
- Example V Duco" cellulosic cement (thickener) c.v c 15 Hydrogenated fish oil glycerides (crystallizable material) ,gram 0.1 Acetone (solvent) c. c
- Example VIII Per cent Aluminum stearate (thickener) 3 Cumar (thickener) 5.0 Hydrogenated fish oil glycerides (crystallizable material) 2.7 Hydrogenated fish oil. acids (crystallizable material) 0.3 Hydrogenated naphtha (solvent) 88.0 Ethyl alcohol (thinner) 1 It is to be understood that the above examples are'not to limit the scope of our invention and thatvarious other compositions may be prepared utilizing some of the other solvents, thickeners, crystallizable water-repellent materials, and thinners or dispersing agents listed hereinabove, and various combinations of these and like materials having the necessary characteristics above described for producing the fine-grain to glass-like films characteristic of our invention.
- a mixture is made of the thickener and thegs olvent that are desired to be used, and the mixture concentrated by evaporation to the point. at which the mixture shows a marked increase" in viscosity such as attended by gel formation or a definite tendency to string. If the mixture either gels or strings, the solvent and thickener are suitable.
- the concentration of the solvent -in the mixture of the crystallizable material and solvent is-a'ppreciably less than the concentration of the solvent in the mixture of the thickener and solvent, the relative propororder to delay its precipitation and thereby inl tions of thickener and crystallizable material are substantially correct. If the concentrations of sure precipitation. of the thickener before pre-.
- the mixture of thickener and. solvent gels or strings at a concentration of solventdess than the concentration of solvent in the mixture of crystallizexamination such as the following:
- a drop of the waterproofing composition containing the solvent, the water-repellent thickener, and the water-repellent crystallizable material is placed on' a slide and examined after solidification under a microscope with dark field illumination and a magnification of about 150 diameters. If under .these conditions the film appears fine-grained to glass-like, it is a satisfactory waterproofing film,
- the proportion of crystallizable material in the mixture is too high.
- a new mixture with slightly smaller proportion of crystallizable material should then be tried until a satisfactory film is obtained.
- the same efiect can be produced in some instances, by adding to the composition a certain proportion of another miscible solvent in which the crystallizable material is more soluble and the thickener not more soluble.
- a proportion of 0.1 gram of hydrogenated fish oil glycerides to 5 c. c. of cement gave a porphyritic structure.
- the film prepared with the same proportion of glycerides and cement was non-porphyritic; in other words, amorphous and glass-like.
- the proper proportioning of the thickener and the crystallizable materials is essential.
- the actual amounts of thickener and crystallizable material may vary from any useful small amount vup to the amounts just a short of those that would normally form supersaturated solutions, that is, amounts suflicient to cause precipitation of the solids in the waterproofing composition before it is applied for use.
- the fine-grained to glass-like films are produced by precipitation from solution, and any desired amounts of materials less than the amount that will not go into solution may be used.
- the actual amounts of thickener and crystallizable materials used will depend largely upon the thickness of the waterproofing film that it. is desired to produce and upon the degree of penetration required.
- the thickness of the film is proportional to the amounts of solid materials present in the composition.
- Thepenetrativeness of the composition is inversely proportional to the concentration of solids therein, the greater the concentration of solids the smaller the penetrativeness of the composition and vice versa.
- the waterproofing compositions of our invention may be applied according to any well known methods, such as brush, spray, and immersion processes.
- the waterproofing compositions of our invention may be prepared by any suitable admixing of the several constituents, once the proper proportions thereof have been determined in the manner described hereinabove.
- the thickener and the crystallizable material maybe ⁇ admixed in solid form and heated until at least one of the materials liquefies and causes all of the solids to mutually dissolve. The proper amount of solvent is then added to this mixture of the thickener and crystallizable material.
- the thickener used is of the gel forming type, a relatively small amount, such as for example 1% or less of the thinner or dispersing agent is added to the mixture, either before or after the solvent is added, for the purpose of producing a thin penetrative mobile type of solution suitable for brushing, spraying or dipping processes.
- Another method ofpreparing the composition comprises dissolving simultaneously the thickener and crystallizable material in the solvent, applying heat and agitation, if necessary, to effect so lution of the solids in the solvent.
- Still another method of preparing the composition when using as the thickener a gel-forming material, comprises heating the thickener and solvent mixture until a gel is formed, then adding to the' gel a relatively small amount of the dispersing agent to disperse the gel into a mobile colloidal solution, and then dissolving in this solution thec'rystallizable material.
- a mobile, liquid, penetrative waterproofing composition comprising a normally solid hydrogenated fish oil, a petroleum naphtha and a volatile constituents a fine-grained to glass-like water-repellent film, comprising a normally solid water-repellent crystallizable organic material selected from the group consisting -of fats and waxes of organic origin, an evaporating hydrocarbon solvent, and a naturalasphalt, mixed in such proportions that upon concentration 'of the composition said natural asphalt and hydrocar-- bon solvent will thicken before said crystallizable material beings to precipitate, whereby said natural asphalt arreststhe normal crystal growth of the crystallizable material as it precipitates from said solvent, and causes said crystallizable material to precipitate in the form of extremely fine size crystals.
- a mobile, liquid, penetrative waterproofing composition that forms upon evaporation of its volatile constituents a fine-grained to glass-like water-repellent film, comprising a normally solid water-repellent crystallizable organic material selected from the group consisting of fats and waxes of organic origin, an evaporative organic solvent, and asphalt, mixed in such proportions that upon concentration of the composition saidasphalt and organic solvent will thicken before 7 said crystallizab le material to precipitate,
- said asphalt arrests the normal crystal growth of the crystallizable material as it precipitates from said solvent, and causes said crystallizable material to precipitate in the form of extremely fine size crystals.
- a mobile, liquid, penetrative waterproofing composition that forms upon evaporation of its volatile constituents a fine-grained to 'glass like water-repellent film, comprising a normally solid water-repellent crystallizable material, an evapoporative organic solvent, an an asphaltic substance, mixed in such proportions that upon concentration of the composition said a'sphaltic substance and organic solvent will thicken before said crystallizable material begins to precipitate, whereby said asphaltic substance arrests the normal crystal growth of the crystallizable material as it precipitates from said solvent, and causes-said crystallizable material to precipitate in the form of extremely fine size crystals.
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- Organic Chemistry (AREA)
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Civil Engineering (AREA)
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Description
Patented Nov. 21, 1 939 WATERPROOFING COMPOSITION Arthur F. Taggart, Scarsdale, and Warley'L. Parrott, New York, N. Y.
No Drawing. Application April 22, 1937,
. Serial No. 138,364
4 Claims. (01. 134-13) Our invention relates to waterproofing compositions, and more particularly to waterproofing compositions that form, upon evaporation of their volatile constituents, fine-grained to glass-like 5 water-repellent films.
One of the features of" our invention is the crystallization of a water-repellent crystalline material in the composition controlled by a noncrystalline water-repellent constituent present in o thickened form, whereby the normal growth of the crystals of the controlled material is arrested and that material deposits in the form of extremely fine size crystals. These fine crystals uniformly and intimately admix with the fine size particles of the controlling non-crystalline substance to form upon complete, solidification a continuous fine-grained to glass-like film the imperforate nature of which prevents moisture penetration.
Preliminarily to the discovery upon which our invention is based, we prepared and observed microscopically numerous slides of different mixtures of water-repellent substances and tested these mixtures for comparative waterproofing effectiveness. We observed from these tests that the most effective waterproofing mixtures, whatever the ingredients used, were those that produced uniform fine-grained to glasslike films. Such films, generally speaking, are
composed of ingredients that are so finely divided that no definite crystalline structure can be detected in the film when it is viewed through a microscope with dark field'illumination and having a magnification of about 150 diameters. Following these observations, we discovered that highly eificient waterproofing compositions capable of producing the desired fine-grained to glass-like films may be consistently produced by admixing in the proper proportions an organic forming material, and a water-repellent, substance that will cause the solvent and this substance to thicken sufliciently, before the crys- 45 tallizable material begins to crystallize, to arrest the growth of crystals when the crystalliz- 55 An object of ou in en n s t p ovide a solvent,- an organic water-repellent crystal-' waterproofing composition containing an in'timate admixture of various water-repellent constituents so related in solubility in the solvent used and in concentration therein, that whatever the constituents used the-composition will 5 form, upon evaporation of its volatile constituents, a highly water-repellent fine-grained t glass-like film.
From the numerous microscopic observations that we have made of various waterproofing 10 compositions, we have noticed that if the composition does not contain, at the time of crystallization of the crystallizable water-repellent constituents, .a constituent that will interfere Y with the normal crystal growth of the ,crystalliz- 1 able material, the latter will deposit in the form of relatively large, irregular and separated crystals. The films produced by such compositions are non-uniform and have a porphyritic or per-' forated structure that permits moisture penetra- 20 tion. These films are not satisfactory since they do not completely waterproof the-materials to which they are applied. On the other hand, we have found that if thesolvent and waterrepellent constituents are properly chosen and 25 their concentrations properly regulated to effect the above mentioned crystal growth interference, the compositions will produce upon solidification uniform, fine-grained to glass-like, imperforate, highly water-repellent films. 30
The rule or formula to be followed for producing the improved waterproofing compositions of our invention comprises selecting an organic solvent, acrystallizable water-repellent material, and-a normally solid or viscous sub 35 stance (preferably water-repellent) and that is chemically or physically so related that the mixture of this substance and the solvent will thicken upon concentration thereof; and to so proportion them that the thickening will occur 40 before the crystallizable water-repellent constituent or constituents in the liquid waterproofing composition begin to'crystallize. In other words, when the waterproofing composition is applied to a material to be waterproofed and the organic solvent begins' to evaporate, one of the constituents must first cause this substance and the solvent to thicken, either in the form of a gel or' a viscous mass, so that when the crystallizable water-repellent material subsequently begins to precipitate out of solution the thickener and solvent will be in thickened form to arrest the normal crystal growth of the precipitate so that the crystals of water-repellent material will be deposited in extremely fine size form, connormally fine size or amorphous particles of the water-repellent thickener to produce upon the material to be waterproofed a composite finegrained to glass-like water-repellent film.
One of theimportant and commercially valuable features of our invention is that the waterproofing composition may be made from any two or more water-repellent constituents and a suitable solvent properly selected from large groups of such constituents subsequently denoted herein and, in general, the same degree of waterproofing effectiveness will be obtained in each case. Regardless of the constituents so selected, their maximum waterproofing effectiveness will always be produced so long as the crystallization of the crystallizable water-repellent material is .properly controlled to produce very fine size crystals and thereby fine-grained films.
Accordingly, a'number of watererepellent constituents wliich heretofore have been considered in ,someirespects undesirable, such as for example,
paraffin, waxes, and gums, may now be used as constituents in highly effective waterproofing compositions. As aresult, the field of effective waterproofing compositions has been markedly extended.
While the exact water resistance of compositions produced from various mixtures of the selected water-repellent constituents will vary somewhat inherently, they will each possess a high degree of water-repellency because of the fine-grained, uniform, compact structure of their deposited films. That is to say, these films are composed of extremely small particles so uniform in size, admixture and distribution that the film is practically homogeneous and substantially free of interstices. Consequently, the film ofiers a uniform high resistance to water over its entire surface and being practically nonporous it is impervious to water penetration.
' In view of the fact that the only essential requirement for producing the desired type of waterproofing composition is proper selection of a water-repellent substance that with the solvent will thicken sufiiciently at the proper concentrations to arrest the crystal growth ofthe water-repellent crystalizable material, it will be apparent that wide variations may be made in the several constituents used in thewaterproofing composition as illustrated by the following.
The crystallizable water-repellent material, which constitutes one of the principal waterproofing ingredients in the composition, may be any organic water-repellent material that will. crystallize upon concentration in an organic sol Some of the water-repellent crystalliz-' vent. able materials that we have found satisfactory are as follows:
Fatty materials, e. g., both those natural fats I and the.artificially saturated animal, vegetable and marine fats and oils which crystallize and are substantially solid at normal atmospheric temperatures; such as lard, tallow, cocoa butter, fish and whale fats, hydrogenated animal oil, cotton seed, corn, cocoanut, peanut, fish and whale oils.
Fatty acid glycerides, e. g., both those natural glycerides and those artificially saturated jglyi'cerides'of the higher fatty acids found in ani-- -m al',' vegetable and marine: fats which crystalli'ze a n'd are substantially solid at normal at- "mosbheric temperatures, e. g., hydrogenated fish oil glycerides.
Higher fatty acids; -e. g., both those natural acids and those artificially saturated fatty acids tially solid at normal atmospheric temperatures,
e. g., cholesterol, and camphor.
Hydrocarbons; e. g., paraflin, montan, ceresin, and others which are substantially solid at normal atmospheric temperatures.
The solvent used may be any one of the organic evaporative solvents that will act as a common solvent for the water-repellent thickener and the crystallizable material; and with the thick- Benzol Tolulol Xylol Nitrobenzene 3. Oils derived by steam distillation of resinous woods; e. g., turpentine 4. Halogen derivatives of lower hydrocarbons;
Carbon tetrachloride Chloroform Ethylene-dichloride 5. Cellosolve The thickener may be any organic, preferably waterproof, substance that with the solvent will thicken at the proper concentration to arrest the crystal -growth of the crystallizable waterrepellent material. We have found it advantageous to use water-repellent substances as thickeners. These substances are of the type normally considered as amorphous, although X-ray analyses might show some or all of these I substances to have, at least in part, a crystalline structure. We appreciate-that any waterproof substance whether of an organic or inorganic nature and whether of a crystalline or non-crystalline character, could be used as the thickener in accordance with our invention provided it served the purpose of controlling the crystal growth of the definitely crystalline water-repellent material or materials used in the composition. The principal requirement for the thickener is that regardless ofits chemical nature, the solvent and the thickener it will increase in viscosity at the proper concentration and time to effect the desired crystal growth control. The thickener may be either of a gel-forming type or of a non-gel-forming type. As far as the physical character of the thickener is concerned, it is only necessary that it and the solvent will be 'sufiiciently viscous tophysically interfere with the normal crystal growth of the crystallizable water-repellent material.
Examples of thickeners that we have found Satisfactory or use in. our invention are the following:
35 mation of fine-grain films are as follows:
Example I Y Per cent Aluminum'stearate (thickener) 2.0 3.0 Hydrogenated fish oil glycerides (crystallizable material) 1.0- 3.0 Petroleum naphtha (solvent) .1 96.5 93.5 Cresol (thinner) 0.5- 0.5
100.0-100.0 Example II Per cent Cumar (thickener) 80.00 Paraffin (crystallizable material) 0.75 50 Hydrogenated naphtha (solvent) 19.25
100.00 Example III L Grams 55 Asphalt (thickener) 20-25 5 ficial asphalt.
Gums and resins; e. g., both the natural products such as rosin, copal, colophony, dammer,
and the artificial neutral products such as the cumars.
cement.
Cellulosic materials; e. g., collodion (tetranitrate of cellulose).
when the thickener used in the waterproofing compositionforms a gel or gel-like mass initially in the hydrocarbon solvent, i. e., before concentration in the solvent, we have found it desirable to use a thinner or dispersing agent to disperse the gel and produce a mobile colloidal solution. This initial breaking or dispersing of the gel] will not, however, if the proper dispersing agent is used, prevent the desired formation of gel or viscous mass for crystal growth control during evaporation-of the solvent when the composition is used. The-thinner used for dispersing the initial gel should be a substance that volatilizes on evaporation of the mixture. Examples of the thinners or dispersing agents that we have found satisfactory are the following: Methyl, ethyl, butyl and amyl alcohols, phenol, cresol, aniline, toluidine, acetone and acetic acid.
Examples of various waterproofing composi-- tions illustrating the proportions of ingredients necessary for crystal growth control and the for- Hydrogenated fish oil glycerides (crystallizable material) Hydrogenated fish oil acids (crystallizable material) 1. 3
Hydrogenated naphtha (solvent) 100 Example IV Per cent Aluminum stearate 1.85
Hydrogenated fish oil glycerides 1.00-
Carbon tetrachloride 96.15
Ethyl alcohol 1.00
100.00 Example V Duco" cellulosic cement (thickener) c.v c 15 Hydrogenated fish oil glycerides (crystallizable material) ,gram 0.1 Acetone (solvent) c. c
75 Hydrogenated naphtha (solvent) c.c 5
Hydrocarbons; e. g., rubber, Duco household Example VI Collodion solution consisting of tetra-nitrate of cellulose, ethyl alcohol and ethyl ether (thickener) c.'c 5 Cholesterol (crystallizable material) gram 0.025 Example VII Collodion solution consisting of tetra-nitrate of cellulose, ethyl alcohol and ethyl ether (thickener) c. c 5 'Camphor (crystallizable material) gram 0.3
Example VIII Per cent Aluminum stearate (thickener) 3 Cumar (thickener) 5.0 Hydrogenated fish oil glycerides (crystallizable material) 2.7 Hydrogenated fish oil. acids (crystallizable material) 0.3 Hydrogenated naphtha (solvent) 88.0 Ethyl alcohol (thinner) 1 It is to be understood that the above examples are'not to limit the scope of our invention and thatvarious other compositions may be prepared utilizing some of the other solvents, thickeners, crystallizable water-repellent materials, and thinners or dispersing agents listed hereinabove, and various combinations of these and like materials having the necessary characteristics above described for producing the fine-grain to glass-like films characteristic of our invention.
The tests that we have found satisfactory to determine suitable solvents and thickeners (that.
is those capable of producing upon concentration a marked increase in viscosity-,sufiicientto interfere with the normal crystaljigrowth of the crystallizable water-repellent material and proper proportions thereof), are as follows: A mixture is made of the thickener and thegs olvent that are desired to be used, and the mixture concentrated by evaporation to the point. at which the mixture shows a marked increase" in viscosity such as attended by gel formation or a definite tendency to string. If the mixture either gels or strings, the solvent and thickener are suitable.
The concentration of the solvent in the mixture when it reaches this point is then noted. Next,
a mixture of a water-repellent crystallizable. material and solvent is made and evaporated to the point at which precipitation of the crystallizable material begins. The concentration of solvent in the mixture at this'point is noted;
If, at the above mentioned points of gelling or stringing andj crys tallizing, the concentration of the solvent -in the mixture of the crystallizable material and solvent is-a'ppreciably less than the concentration of the solvent in the mixture of the thickener and solvent, the relative propororder to delay its precipitation and thereby inl tions of thickener and crystallizable material are substantially correct. If the concentrations of sure precipitation. of the thickener before pre-.
cipitation of the crystallizable material. If the mixture of thickener and. solvent gels or strings at a concentration of solventdess than the concentration of solvent in the mixture of crystallizexamination, such as the following: A drop of the waterproofing composition containing the solvent, the water-repellent thickener, and the water-repellent crystallizable material is placed on' a slide and examined after solidification under a microscope with dark field illumination and a magnification of about 150 diameters. If under .these conditions the film appears fine-grained to glass-like, it is a satisfactory waterproofing film,
indicating that the crystal growthof the crystallizable water-repellent material has been properly arrested by the thickener.
However, if definite crystals are scattered in porphyritic fashion throughout the mass of the film, the proportion of crystallizable material in the mixture is too high. A new mixture with slightly smaller proportion of crystallizable material should then be tried until a satisfactory film is obtained. Alternatively, the same efiect can be produced in some instances, by adding to the composition a certain proportion of another miscible solvent in which the crystallizable material is more soluble and the thickener not more soluble. For example, when using the Duco" cement as the thickener with acetone as the solvent, a proportion of 0.1 gram of hydrogenated fish oil glycerides to 5 c. c. of cement gave a porphyritic structure. By adding to the mixture 1 c. c. of hydrogenated naphtha, which is a good solvent for the glycerides,, the film prepared with the same proportion of glycerides and cement was non-porphyritic; in other words, amorphous and glass-like.
In all of the compositions mentioned above, it will be understood that the proper proportioning of the thickener and the crystallizable materials is essential. The actual amounts of thickener and crystallizable material may vary from any useful small amount vup to the amounts just a short of those that would normally form supersaturated solutions, that is, amounts suflicient to cause precipitation of the solids in the waterproofing composition before it is applied for use. In other words, the fine-grained to glass-like films are produced by precipitation from solution, and any desired amounts of materials less than the amount that will not go into solution may be used. The actual amounts of thickener and crystallizable materials used will depend largely upon the thickness of the waterproofing film that it. is desired to produce and upon the degree of penetration required. The thickness of the film is proportional to the amounts of solid materials present in the composition. Thepenetrativeness of the composition is inversely proportional to the concentration of solids therein, the greater the concentration of solids the smaller the penetrativeness of the composition and vice versa.
\ The waterproofing compositions of our invention may be applied according to any well known methods, such as brush, spray, and immersion processes.
The waterproofing compositions of our invention may be prepared by any suitable admixing of the several constituents, once the proper proportions thereof have been determined in the manner described hereinabove. For example, the thickener and the crystallizable material maybe \admixed in solid form and heated until at least one of the materials liquefies and causes all of the solids to mutually dissolve. The proper amount of solvent is then added to this mixture of the thickener and crystallizable material. If the thickener used is of the gel forming type, a relatively small amount, such as for example 1% or less of the thinner or dispersing agent is added to the mixture, either before or after the solvent is added, for the purpose of producing a thin penetrative mobile type of solution suitable for brushing, spraying or dipping processes.
Another method ofpreparing the composition comprises dissolving simultaneously the thickener and crystallizable material in the solvent, applying heat and agitation, if necessary, to effect so lution of the solids in the solvent. Still another method of preparing the composition, when using as the thickener a gel-forming material, comprises heating the thickener and solvent mixture until a gel is formed, then adding to the' gel a relatively small amount of the dispersing agent to disperse the gel into a mobile colloidal solution, and then dissolving in this solution thec'rystallizable material.
From these examples it will be apparent that various other methods of preparing the compositions may be used and our invention is intended to cover any and all of such methods.
It is to m understood that the doctrine of equivalents applies with full force and effect to this application and the invention disclosed herein and that various modifications and changes may be made in the materials and methods used without departing from the scope of this invention. The appended claims are directed to some of the novel features of the invention.
We claim:
1. A mobile, liquid, penetrative waterproofing composition comprising a normally solid hydrogenated fish oil, a petroleum naphtha and a volatile constituents a fine-grained to glass-like water-repellent film, comprising a normally solid water-repellent crystallizable organic material selected from the group consisting -of fats and waxes of organic origin, an evaporating hydrocarbon solvent, and a naturalasphalt, mixed in such proportions that upon concentration 'of the composition said natural asphalt and hydrocar-- bon solvent will thicken before said crystallizable material beings to precipitate, whereby said natural asphalt arreststhe normal crystal growth of the crystallizable material as it precipitates from said solvent, and causes said crystallizable material to precipitate in the form of extremely fine size crystals.
3. A mobile, liquid, penetrative waterproofing composition that forms upon evaporation of its volatile constituents a fine-grained to glass-like water-repellent film, comprising a normally solid water-repellent crystallizable organic material selected from the group consisting of fats and waxes of organic origin, an evaporative organic solvent, and asphalt, mixed in such proportions that upon concentration of the composition saidasphalt and organic solvent will thicken before 7 said crystallizab le material to precipitate,
whereby said asphalt arrests the normal crystal growth of the crystallizable material as it precipitates from said solvent, and causes said crystallizable material to precipitate in the form of extremely fine size crystals.
4. A mobile, liquid, penetrative waterproofing composition that forms upon evaporation of its volatile constituents a fine-grained to 'glass like water-repellent film, comprising a normally solid water-repellent crystallizable material, an evapoporative organic solvent, an an asphaltic substance, mixed in such proportions that upon concentration of the composition said a'sphaltic substance and organic solvent will thicken before said crystallizable material begins to precipitate, whereby said asphaltic substance arrests the normal crystal growth of the crystallizable material as it precipitates from said solvent, and causes-said crystallizable material to precipitate in the form of extremely fine size crystals.
AR'I'HUR F. :TAGGART. WARLEY L. PARRO'I'I.
- CERTIFICATE OF CORRECTION, Patent No. 2,180,971. November 21, 1959.
ARTHUR F. TAGGART'.
It is hereby certified that'error appears in the printed specification of the above mgmbered patent requiring; correction as follows: Page L second column, line 55, claim 2, for the word "evaporating" read evaporative;
'page 5, first column, line 12, claim 11., for F'an an read arid an; and that th said Letters Patent should; be read with this. correction therein that the seine may oon form to therecord of the ,case in the Patent Office.
Sigped and sealed this 26th day of December, A. D.---1959.
Henry Van Arsdale,
(Seal) Acting Comxnissioner of Patents.
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US2180971A true US2180971A (en) | 1939-11-21 |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2847315A (en) * | 1955-09-26 | 1958-08-12 | Mohawk Ind Inc | Sealing composition |
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US2847315A (en) * | 1955-09-26 | 1958-08-12 | Mohawk Ind Inc | Sealing composition |
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