GB2028451A - Sealing Cartridge for Anchoring Bolts or Sealing Solid Structures - Google Patents
Sealing Cartridge for Anchoring Bolts or Sealing Solid Structures Download PDFInfo
- Publication number
- GB2028451A GB2028451A GB7833767A GB7833767A GB2028451A GB 2028451 A GB2028451 A GB 2028451A GB 7833767 A GB7833767 A GB 7833767A GB 7833767 A GB7833767 A GB 7833767A GB 2028451 A GB2028451 A GB 2028451A
- Authority
- GB
- United Kingdom
- Prior art keywords
- capsules
- cartridge
- rod
- sealing
- cylindrical array
- 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.)
- Withdrawn
Links
- 238000007789 sealing Methods 0.000 title claims abstract description 21
- 238000004873 anchoring Methods 0.000 title claims abstract description 14
- 239000007787 solid Substances 0.000 title claims abstract description 13
- 239000002775 capsule Substances 0.000 claims abstract description 44
- 239000012634 fragment Substances 0.000 claims abstract description 35
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 7
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000013467 fragmentation Methods 0.000 claims description 8
- 238000006062 fragmentation reaction Methods 0.000 claims description 8
- 230000000977 initiatory effect Effects 0.000 claims description 4
- 239000011435 rock Substances 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 description 23
- 229920005989 resin Polymers 0.000 description 21
- 239000011347 resin Substances 0.000 description 21
- 239000000376 reactant Substances 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 239000006260 foam Substances 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 238000011049 filling Methods 0.000 description 9
- 238000003780 insertion Methods 0.000 description 9
- 230000037431 insertion Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- -1 polyethylene Polymers 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000007903 gelatin capsule Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000003094 microcapsule Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004927 clay Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 230000002787 reinforcement Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 3
- 239000007767 bonding agent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 2
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical compound C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 description 2
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/241—Preventing premature crosslinking by physical separation of components, e.g. encapsulation
-
- 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
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21D—SHAFTS; TUNNELS; GALLERIES; LARGE UNDERGROUND CHAMBERS
- E21D20/00—Setting anchoring-bolts
- E21D20/02—Setting anchoring-bolts with provisions for grouting
- E21D20/025—Grouting with organic components, e.g. resin
- E21D20/026—Cartridges; Grouting charges
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16B—DEVICES FOR FASTENING OR SECURING CONSTRUCTIONAL ELEMENTS OR MACHINE PARTS TOGETHER, e.g. NAILS, BOLTS, CIRCLIPS, CLAMPS, CLIPS OR WEDGES; JOINTS OR JOINTING
- F16B13/00—Dowels or other devices fastened in walls or the like by inserting them in holes made therein for that purpose
- F16B13/14—Non-metallic plugs or sleeves; Use of liquid, loose solid or kneadable material therefor
- F16B13/141—Fixing plugs in holes by the use of settable material
- F16B13/143—Fixing plugs in holes by the use of settable material using frangible cartridges or capsules containing the setting components
- F16B13/145—Fixing plugs in holes by the use of settable material using frangible cartridges or capsules containing the setting components characterised by the composition of the setting agents contained in the frangible cartridges or capsules
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mining & Mineral Resources (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Mechanical Engineering (AREA)
- Structural Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Analytical Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
A process for reinforcing or sealing solid structures or for anchoring bolts using macrocapsules which contain at least one part of a multi-part curable polymer system and which fracture under pressure to produce flake-like fragments that aid in mixing the components of the multi-part curable polymer system. The macrocapsules are made into a sealing cartridge for ease of use, e.g. can be contained in a paper tube or can be held together adhesively to form a cylindrical mass. In securing, e.g. a rock bolt, the capsules are placed on the borehole with another part of the system, e.g. in liquid form, if all parts are not contained in capsules and shattered by inserting the bolt. Rotation of the bolt is unnecessary. <IMAGE>
Description
SPECIFICATION
Method for Reinforcing or Sealing Solid Structures or for Anchoring Bolts Therein and Cartridges for Use in Such Method
The present invention relates to a resin anchored rod system, to a rod anchoring process and to a curable resin containing cartridge which can be inserted into a hole and penetrated by the insertion of a rod, causing curing of the resin and securing of the rod therein.
The use of organic resins for rock stabilization and for anchoring rods in rock or masonry is well known, e.g., U.S. Pat. 2,952,129. In the 1959 United States Bureau of Mines Report of Investigation 5439 ("Cementation of Bituminous Coal Mine Roof Strata", Injection of Epoxy and Polyester Type
Resins, E. R. Maize, R. M. Oitto, Jr.) the pumping of curable two-part epoxy or polyester resin systems into rock was shown to produce rock stabilization. Various approaches have been made to introduce a two-part resin system into a bore hole as represented in U.S. Letters Patent Nos. 3,108,443; 3,324,663; 3,698,196; 3,877,235 and 3,925,996. However, to insure intimate mixing of the several resin forming components the rod or anchor has been rapidly rotated in the bore hole, a cumbersome step which caused loss of time and required auxiliary equipment.
In U.S. Pat. 3,731,791 the reactive components have been placed in a frangible container where their separation is accomplished solely by a layer of reaction product, but rod rotation is still required to achieve full mixing. In order to increase the mixing of the various parts of the curable polymer system
German OLS 2,249,834 describes the use of microcapsules (polyethylene polyamide or similar polymer) with a curable resin system encapsulated therein, the diameter of the microcapsules being as large as 8 mm., preferably less than 1 mm. to create a satisfactory mixture of the proper proportions.
As the rod is inserted into the hole, the microcapsules rupture and the resin system cures to reinforce the surrounding structure. Although in such a system the dispersion of the extremely small diameter microcapsules (i.e., less than 1 mm.) does tend to insure better initial mixing, such small microcapsules tend to be difficult to rupture with the bolt or rod.
This invention provides an improvement in a rod anchoring process and in cartridges for fixing rods in solid structures, reinforcing solid structures and the like with the use of a multi-component curable polymer system (i.e., two or more components which when mixed together effect the reaction or cure to form a polymer or resin of higher molecular weight than any of the initial reactive components). The cartridges of this invention are generally cylindrical in shape and comprise a cylindrical array of relatively nonmobile, pressure fragmentable, non-friable capsules containing at least one part of the multi-part curable polymer system. The cylindrical array may have cross sectional diameter from about 5 mm. to about 10 cm., generally corresponding to (but slightly less than) the diameter of the holes in which they may be inserted.Although the shape of the capsules is not critical (e.g., spherical, elongated, etc.), their major dimension must be in the range from 4.75 mm., preferably at least 8 mm. (most preferably at least 10 mm.) to about 95% of the cross sectional diameter of the cylindrical array, usually up to about 2 cm. major dimension. Because of their size such capsules are referred to as "macrocapsules". When placed under increasing pressure, the capsules must fragment with the wall portion forming flake-like fragments.
Because the macrocapsules of this invention are relatively large, they are more readily ruptured by pressure, are less mobile in liquid media, are easily prepared from a variety of materials in a variety of shapes, and generally have more controllable wall thicknesses. However even though the larger sized capsules initially provide a lesser degree of dispersion of the severai components in the curable polymer system compared to smaller microcapsules, it has been found that the use of relatively large capsules which fragment under pressure to produce flake-like wall fragments rather than powder (as obtained from friable materials) compensates for their lesser degree of initial dispersion.This is attributed to the action of the flake-like fragments which serve, at least transitorily, as static mixers causing turbulence of the curable components released from the fractured macrocapsules and hence improved mixing of those components as the cylindrical array of macrocapsules is penetrated in the bore hole by the bolt or rod. In fact, such mixing is sufficiently thorough that rotation of the bolt or rod is unnecessary.
Figure 1 is a side elevation view of a cartridge having no container and having macrocapsules bonded together at points of contact.
Figure 2 is a side elevation view, with partial cross-section, of a cartridge containing macrocapsules in a container.
In the cartridge of the present invention the cylindrical array of macrocapsules generally has a circular cross section to conform with the normal cross section of a drill hole. However, the edges may be fluted, serrated or of some other variant if one desires to vary the amount of the annular space between the cartridge and the drill hole while maintaining some contact of the cartridge with, or proximate relationship of the cartridge to, the walls of the drill hole, for example, to position or center the cartridge in the drill hole. The end of the cylindrical array need not be flat, and in some instances a conical or rounded end portion may make it easier to insert the cartridge into the bore hole.Within the cartridge the macrocapsules are distributed, preferably in a fixed three dimensional relationship either in a segregated or layered manner but preferably uniformly, in a generally cylindrical array. The macrocapsules therefore are restricted in space and are capable of at most only slight motion relative to each other. By bonding or adhesively securing the macrocapsules to each other, the array may be made self-supporting, as shown in Figure 1. Alternatively, as shown in Figure 2, they may be placed in a container which ruptures under pressure, such as an open mesh tube of friable material as shown in
U.S. Patent No.3,699,687, a paper tube or a glass cylinder.A rigid, liquid permeable container which does not rupture readily under pressure (e.g. cylindrical metal screen) may be used if the rod used to rupture the macrocapsules therein has a smaller cross sectional area than the container, and preferably a rounded or conical nose portion, so it can move into the container. A pressure rupturable container which is fluid impermeable (e.g. sealed glass tube) is particularly useful if one or more fluid components of the curable system are not contained within the macrocapsules. For most applications, such as in mine roof reinforcement, rock consolidations and anchoring rods or bolts in solid structures, the cross sectional diameter of these cylindrical arrays, and normally also the approximate cross sectional diameter of the cartridge, is in the range of from 8 mm. to 10 cm., preferably from 10 mm. to 50 mm.
The macrocapsule walls must be impervious to the curable system component to be contained therein. If the basic wall material is not itself impervious, an impervious coating (e.g. wax, varnish, etc.) may be deposited thereon. It is also essential that such wall material be non-friable, since friable materials crumble directly into a powder upon disintegration under pressure, and powder will not serve as static mixers for the various components of the curable system.Furthermore, the wall material must break under pressure to form, at least initialy, flake-like fragments (i.e., fragments of a shape which, if projected onto a plane so as to form a surface of maximum area, that area can be inscribed in a rectangle having dimensions X and Y, where X is at least four times the average fragment thickness and Y is at least four times the average fragment thickness, preferably Y is at least 10 times the
average thickness, the average thickness being at least 100 microns). These initial fragments may be further broken into smaller pieces under continued pressure, and these pieces may ultimately no longer be fiake-like. The flake-like fragments apparently serve as static mixers immediately after their formation, while the macrocapsule contents are released and commingled with the contents released from the surrounding macrocapsules.Illustrative of useful macrocapsules are two-part gelatin capsules of the type used for pharmaceuticals; organic and inorganic macrocapsules of the type described in
West German OLS 2,603,534 (corresponds to U.S. Serial No. 544,965, filed January 29, 1975); hollow structures of the type shown in U.S. Pat. 3,864,443; and fired clay pillows of the type described
in U.S. Serial No. 761,265, filed January 21, 1977, incorporated herein by reference. The suitability of
any macrocapsule can readily be determined by subjecting an individual capsule to pressure and/or
impact and examining the shape of the fragments to determine if any have flake-like shape.
Macrocapsule walls of materials such as polyethylene polyamide (e.g. nylon), polyethylene and elastomers would not form the desired flake-like fragments and are therefore not useful in this invention.
Any multi-part organic curable resin system in which the major components are liquid and which is capable of forming a hard resin upon curing can be used in the cartridge and macrocapsules of this invention. Although systems curable under ambient conditions are greatly preferred, in some
applications, it may be possible to supply heat to the mixture, for example by heating the rod or anchor
bolt before insertion. Curable systems which generate gas upon curing produce a foamed resin, and the
pressure generated by the gas is advantageous in assisting the mixing of the components and in forcing the resin-forming mixture into any cracks or fissures in the walls of the bore hole, which
reinforces the surrounding solid structure. Foaming curable systems are therefore particularly desirable for many applications, such as mine roof reinforcement.Epoxy resin systems are described in United States Bureau of IVTinesRepoifs oflnvestigationNos, 5439 (E. R. Maize and R. H. Oitto, Jr., 1959) and 7907 (R. V. Subramanian, H. Austin, R. A. V. Raff and J. C. Franklin, 1973), the former also including
polyester type resins. Polyurethane, melamine- or urea-formaldehyde systems are also very useful, see
U.S. Pat. 3,698,196 and Gluechauf, Vol. 108 pages 582-4 (Alfons Jankowski). Liquid curable
systems in which all the reactants are liquid under the ambient conditions of use are preferred to facilitate mixing and to improve resin impregnation of the surrounding solid structure. The water
curable systems have the advantage of curing in water-wetted structures, e.g., rock formations in
mines.Not every part of the multi-part curable system need be contained in the macrocapsules; some
parts may be added to the cure site before inserting the cartridge into the bore hole, and
unencapsulated liquid components, as mentioned earlier, may be retained, in the cartridge if a liquid
impermeable rupturable container is used.
The cartridges normally are used in a bore hole which is slightly larger in diameter than the
cartridge to facilitate insertion. The rod or bolt used to rupture the macrocapsules in the cartridge is
also selected to have a diameter slightly smaller than the bore hole and may have a rounded or conical
nose portion.If the surrounding structure is relatively porous or contains fissures, it may be desirable to
use a rod having a diameter very close to that of the bore hole to permit a maximum build-up of
pressure upon insertion of the rod, which can assist in forcing the curing polymer system into the pores orfissures. However, a greater difference between the hole diameter and the rod diameter will make
the rod insertion somewhat easier and will allow more of the curing polymer system to flow into the annular space between the rod and the hole, thereby more effectively anchoring the rod therein.After positioning the cartridge, or a plurality of individual macrocapsules, in the hole, the operator inserts the rod or bolt until it abuts the cartridge or macrocapsules at the end of the hole, then forces the bolt or rod into the cartridge or macrocapsules by hand or with a hammer or by machine, depending on the force required to break the macrocapsules, with no bolt or rod rotation required for mixing the reactive components of the curable polymer system. However, some rotation may be used to disintegrate the cartridge or ease insertion of the rod into the bore hole. After the insertion is completed, the mixed system is permitted to cure without any rod rotation.
Although the mechanism of the macrocapsule fragmentation is not fully understood, it is believed that the initial effect of the rod penetrating the cartridge or individual macrocapsules is to selectively fragment by pressure those macrocapsules in the zone immediately adjacent the rod end, creating from the macrocapsules a plurality of flake-like fragments that promote turbulence and mixing of the various parts of the liquid curable polymer system in that zone. As the rod penetrates further, the mixed curing system is forced into the surrounding porous structure of the hole and/or into the annular space between the rod and the hole wall.This process is repeated as the rod progressively penetrates the cartridge or individual macrocapsules until its further motion is stopped by the end of the hole, by the compacted macrocapsule fragments accumulating at the end of the hole and/or by the progress of the polymer cure to a solid. However, whatever the dynamics of the macrocapsule fragmentation mechanism and of the mixing of the curable components, it is essential that the macrocapsule fragmentation generates in situ flake-like fragments rather than powder particles, which fragments facilitate mixing.
The practice of this invention is valuable not only for anchoring rods or bolts in solid structures but also in sealing or reinforcing the surrounding solid structures. When only sealing or reinforcement is desired, the rod can be removed from the hole before the resin cure is complete.
Example 1
Macrospheres of phenolic resin-hollow glass microspheres, prepared as described in Ex. 22 of
German OLS 2,603,534, having a nominal diameter of 0.48 cm., were filled with the following:
Part A
Parts by Weight
Polyether triol of approximately 700 molecular weight, hydroxyl
equivalent of 240, viscosity of about 300 cps@250C. ("Niax LHT
240", a trademarked product of Union Carbide Corporation) 36.7 25 weight % potassium acetate in diethylene glycol 1
N,N-dimethylcyclohexylamine 0.76
The filling operation was accomplished by placing the macrospheres in a flask, covering the macrospheres completely with the Part A mixture, drawing a vacuum on the flask to remove air from the hollow macrospheres, then releasing the vacuum to allow the Part A mixture to fill the macrospheres.
The macrospheres were then poured into a 2.5 cm. diameter hole (14 cm. deep) in a concrete block, filling approximately one-third of the hole volume. Into the hole was poured a second mixture (Part B) of the following composition:
Part B
Parts by Weight
Polymethylene polyphenylisocyanate NCO equivalent weight of 132, NCO%=31.5%, approximately tri-functional in NCO groups ("Mondur
MRS", a trademarked product of Mobay Chemical Co.) 23.3
Silicone surfactant ("Surfactant L 540", a product of Union Carbide
Corporation) 0.1
The ratio of Part to Part B was 16.7 parts by weight to 23.4 parts by weight. Parts A and B are liquid coreactants which, upon mixing, react to produce a solid product or, if a trace of water is present, a rigid foam. The amount of foam is proportional to the amount of water present.
A 1.9 cm. diameter rod was then pushed, without rod rotation, into the hole through the macrpcapsules and Part B liquid mixture. The macrocapsules were crushed by the rod penetration releasing their contents, and the reactants together with some of the flake-like macrocapsule wall fragments were forced into the annulus between the rod and the wall of the hole. Within five minutes the reaction had taken place, and foam filled the annulus. After the reaction was complete the concrete block was sectioned to expose the foamed resin, revealing an essentially homogeneous foam with flake-like macrocapsule wall fragments scattered throughout with an accumulation of fragments at the bottom of the hole. Sufficient mixing of the reactants had occurred without rod rotation because of the wall fragments serving as mixers.
Example 2
Three runs were made using transparent polymethylmethacrylate tubes (2.5 cm. diameter and 30 cm. length) to allow observation of the mixing caused by macrocapsule fragments as a rod penetrates the macrocapsule array. Macrocapsules of the type described in Example 1, but with a diameter ranging from 0.32 to 0.95 cm., were filled using the same procedure described in Example 1. Some of the macrocapsules were filled with the Part A reactants of Example 1, and others were filled with the
Part B reactants of Example 1.
31 grams of the Part B filled macrocapsules were mixed gently with 21 g. of the Part A filled macrocapsules, after which the mixture was placed in one of the transparent tubes. Approximately 22 cm. of the tube height was filled with the macrocapsule mixture. A 1.9 cm. diameterx61 cm. length iron rod was pushed downwardly without rotation through the macrocapsules until it reached the accumulated macrocapsule fragments at the bottom of the tube. After one minute foam was formed and started to rise in the tube. The enhanced mixing of the faster moving liquid reactants by the slower moving macrocapsule wall fragments was observed visually. After two minutes foam spilled over the top of the tube, and after seven minutes the hardness of the foam indicated the reaction was complete.
Into a second transparent tube was placed Part A filled macrocapsules, and the Part B liquid was poured over the macrocapsules. When the iron rod was inserted without rotation, as before, similar results were observed, with the foam density being higher than in the first run above.
Into a third transparent tube was placed Part B filled macrocapsules, and the Part A liquid was poured over the macrocapsules. After the iron rod was inserted without rotation, results similar to those obtained in the second transparent tube run were achieved.
Example 3
Dry Clay powder (M Er D Ball Clay, a product of Kentucky-Tennessee Clay Co.) was mixed with successive increments of water until it was sufficiently plastic to be readily extrudable as a hollow tube.
The extruded tube is cut into "pillows" by pinching the tube together at the desired intervals with a gear type cutter. The ends of the resulting pillows were flattened and closed so as to leave a hollow cavity inside the pillow shell. These pillows were then weighed, air dried, and then oven dried at 1 1 OOC. for 5-10 minutes. Finally the dried pillows were fired in a small electric kiln equipped with a thermocouple and galvanometer reading temperature directly in the kiln. The pillows were fired at 11 000C. for about two hours, after which power to the kiln was shut off. The pillows, after cooling overnight in the kiln, had a water impervious shell about 0.95 cm. in diameter and 1.9 cm. in length with 0.38 mm. wall thickness. Such clay pillows are described in U.S. Patent Application Serial No.
761,265, incorporated herein by reference.
A corner of each pillow was broken off to permit filling. One portion of the pillows was filled with
Part A, "Epon 815" (a trademarked product of Shell Chemical Co.) consisting of a mixture of 89 parts by weight of diglycidyl ether of bisphenol A and 11 parts by weight of butyl glycidyl ether and having an epoxy equivalent weight of 175-195 and a viscosity of 500 to 700 cps at 25 or. A second portion of the pillows was filled with Part B, consisting of 1 part by weight of the polyether triol used in
Example 1 ("Niax LHT 240") and 1 part by weight of diethylenetriamine, having a viscosity of 34 cps at250C.
113 grams of the Part A filled pillows (containing a total of 58 grams of Part A reactant) were then carefully mixed together with 25 grams of the Part B filled pillows (containing a total of 11.6 grams of Part B reactant). 94 grams of the pillow mixture was poured into a transparent plastic tube (2.54 cm. diameter and 30.5 cm. length). A 1.9 cm., diameter iron rod was inserted to a depth of 17.8 cm. and then forced without rotation into the pillow mixture by hammering. One hour later the exothermic reaction was complete, and the cured epoxy resin was transparent with flake-like pillow fragments throughout, with some accumulation of fragments at the bottom of the tube, indicating good mixing of the reactants.
The viscosity of the epoxy resin reactants is generally higher than that of the isocyanate systems.
For higher viscosity curable resins it may be desirable to introduce thinners or diluents or reduce the viscosity and thereby improve the mixing.
Example 4
This example illustrates the use of standard commercially available gelatin capsules used in the drug industry (#2 gelatin capsules, 1 7.5 mm. length, 1 00 microns wall thickness, 6 mm. diameter, a product of Eli Lilly). The Part A reactant mixture contained:
Parts by Weight
Bisphenol A glycidyl methacrylate 50
Triethyleneglycol dimethacrylate 50
N,N-2 dihydroxyethyl paratoluidine 2.4
and the Part B reactant mixture contained:
Bisphenol A glycidyl methacrylate 50
Triethyleneglycol dimethacrylate 50 Benzoyl peroxide 1.1
Butylated hydroxy toluene stabilizer 500 parts per million parts (ppm)
This reactant system utilizes a free radical initiated vinyl polymerization mechanism.
The two halves of each gelatin capsule were separated, and the fill material was placed in the smaller diameter half. One fraction of the gelatin capsules was filled with the Part A reactant mixture, and the other was filled with the Part B mixture. Approximately 37 grams of each part filled 95 capsules. The larger half of each capsule was then inserted over the filled smaller half, with no special provision for sealing the two halves together. 95 Part A filled capsules were mixed with 95 Part B filled capsules, and the resulting mixture was placed in a 2.5 cm. diameter and 31 cm. length transparent plastic tube. The capsule mixture was activated by insertion of a 1.9 cm. diameter iron rod, without rod rotation. Virtually all of the gelatin capsules fractured and generated flake-like capsule fragments.After about 5 minutes the exothermic reaction had taken place to produce a hard, clear resin which bonded the rod to the clear plastic tube.
Example 5
This sample illustrates a rigid sealing cartridge having the macrocapsules in a container.
Macrospheres of the type described in Example 1 (about 7.9 mm. diameter) were filled with the same procedures and same Part A and Part B reactants described in Example 1, but with a small hole made in each macrosphere to ease filling and with subsequent sealing of each macrosphere. The Part
A filled capsules were dipped into a Part B solution to seal off the filling holes. Similarly, the Part B filled capsules were dipped into a Part A solution to seal the filling holes. A mixture of the Part A filled and Part B filled macrocapsules (same reactant ratios as in Example 1) was packed tightly into a paper tube (0.7 mm. paper thickness, slightly less than 25 mm. tube diameter and 630 mm. tube length).
Clay pillows of the type described in Example 3 (except each contains a 0.125 mm. hole on one end and each has a 19 mm. length and 7.9 mm. diameter) were filled with the Part A and Part B reactants described above, using the filling and sealing procedures described above. A mixture of the
Part A filled and the Part B filled pillows was tightly packed into a paper tube, as above, to provide a cylindrical array of the pillows and each end of the paper tube was closed with adhesive tape.
Three tubes of each type, i.e., macrosphere and clay pillow types, were placed in deep ddfl holes (25 mm. diameter, 122 cm. deep) in the roof structure of an operating copper mine. At a mine temperature of 12-1 30C., a Joy bolter machine was used to force standard roof bolts (19 mm.
diameter, 120 cm. length) into the drill holes and through the tubes, causing rupture of the macrocapsules and pillows and initiating reaction. None of the samples showed any sign of unreacted resin running out of the holes. Approximately one week later the bolts were pulled with a standard bolt puli apparatus. Even at an extraction force of 11 tons, the bolts had a 2.5-5 mm. deflection but did not release, which indicated good bonding of the bolts to the rock structure.
Example 6
This example illustrates a rigid sealing cartridge having no container, the capsules being bonded to each other to form a rigid assembly.
Clay pillows of the type described in Example 5, having a diameter of 8 mm. and a length of 1 9 mm., with a wall thickness of 0.5 mm., were filled with either Part A or Part B reactant system. Part A consisted of:
Parts by Weight
Polyether triol of Part A in Ex. 1 367 25 weight % potassium acetate in diethylene glycol solution 20
N,N-dimethylcyclohexylamine 7.6
Part B consisted of the polymethylene polyphenylisocyanate of Part B in Example 1. Pillows were filled, some with Part A and some with Part B, using the vacuum filling procedure described in Example 1.
After each type of pillow was filled with reactant, it was sealed by dipping it into the other liquid reactant to form a fiim over the pillow, as described in Example 5.
Two parts by weight of the Part A filled pillows were mixed carefully to avoid breakage with three parts by weight of the Part B filled pillows. Then the pillow mixture was poured into a preformed tube made of 0.1 mm. polyethylene (24 mm. diameter and 300 mm. length). The filled tube was contained in a 25 mm. diameter rigid wall tube to maintain a circular cross section and a straight axis. A bonding agent was poured through the polyethylene tube, coating each pillow, and allowed to drain out of the bottom of the tube. The bonding agent was a two-part curable mixture having the following components:
Parts by Weight
Part 1
"Epon 815" (as defined in Ex. 3) 90
Phenyl glycidyl ether 10
Part 2
Diethylene triamine 10
The drained assembly was allowed to cure at 250C. for 1 6 hours.After cure the rigid tube mold was removed and the polyethylene film tube was stripped off. A totally self-supporting cylindrical array of the pillows (24 mm. diameter and 300 mm. length) was formed by bonding agent holding the pillows together without filling the voids between the pillows.
A 200 mm. length of the above cylindrical array was placed in a 25 mm. diameter hole (200 mm.
length) in a concrete block. A 1 9 mm. diameter iron rod was inserted without rotation into the hole, using a hammer for the final distance. Within one minute after rod insertion, foam appeared in the annul us, indicating sufficient mixing and reaction. After five minutes the foam was hard, indicating complete reaction.
Example 7
This example illustrates the mixing obtained with larger macrospheres.
Phenolic macrospheres of the type described in Ex. 1, but with a diameter of 12.7 mm.+0.25 mm., were separated into two lots. The macrospheres of the first lot were punctured and filled from a
syringe containing a fluorescent dye (rhodamine B) in water. The macrospheres in the second lot were filled in similar manner with a glycerol. A total of 24 macrospheres was then placed in a 30.5 cm. high, 1 3.5 mm. inside diameter glass tube, alternating macrocapsules from each lot as the tube was filled.
A 9.5 mm. diameter steel rod (of the type used for cement reinforcement) was pushed into the glass tube and through the capsules, causing capsule fragmentation, without rod rotation. A series of photographs shows uniform mixing of the dye solution and the glycerol. If the macrocapsules were filled with two curable resin components rather than the dye and glycerol, similarly effective mixing can be achieved, with resulting cure of the components.
Claims (14)
1. A sealing cartridge for reinforcing or sealing solid structure, anchoring bolts or the like
comprising a cylindrical array of pressure fragmentable capsules in a fixed three dimensional
relationship, said cylindrical array having a cross sectional diameter from 5 mm. to 10 cm., said capsules containing at least one part of a multi-part curable polymer system, having a major dimension in the range of 4.75 mm. to about 95% of the cross sectional diameter of said cylindrical array and forming flake-like fragments from the walls of the capsules upon their pressure fragmentation and release of their contents.
2. The cartridge of claim 1-in which the cylindrical array has a cross sectional diameter from 10
mm. to 50 mm.
3. The cartridge of claim 2 in which the capsules have a major dimension in the range of 8 mm. to 2 cm.
4. The cartridge of claim 1 in which the capsules are generally spherical.
5. The cartridge of claim 1 in which the capsules are generally elongated.
6. The cartridge of claim 1 in which a portion of the capsules contain one part of said multi-part
curable polymer system and another portion of the capsules contain a second part of said multi-part
curable polymer system.
7. The cartridge of claim 1 in which said cylindrical array of capsules is a unitary and cohesive
mass.
8. The cartridge of claim 1 in which said cylindrical array of capsules is confined in a container
having a shape in conformity with said cylindrical array.
9. The cartridge of claim 8 in which said cylindrical array of capsules is confined in a rigid liquid
permeable cylindrical container.
10. The cartridge of claim 8 in which said container is a pressure rupturable container.
11. The cartridge of claim 8 in which said container is a tubular paper container.
12. The cartridge of claim 8 in which said cylindrical array of capsules is confined in a liquid
impermeable, pressure rupturable cylindrical container and one part of said multi-part curable polymer
system therein is a liquid outside of said capsules.
13. A process for sealing a hole, anchoring a rod or the like which comprises (a) inserting into a
hole of a diameter from about 5 mm. to 10 cm. the components of a multi-part curable polymer system
and a plurality of pressure fragmentable capsules containing at least one part of a said multi-part
curable polymer system, having a major dimension in the range of 4.75 mm. to about 95% of the cross
sectional diameter of said hole and forming flake-like fragments from the capsule walls upon pressure
fragmentation of the capsules and release of the capsule contents, (b) inserting a rod into said hole
until the end thereof contacts said plurality of capsules, (c) forcing the rod into said capsules so as to
cause their fragmentation into flake-like fragments, thereby releasing and mixing the capsule contents
and initiating the curing of the multi-part curing system, and (d) permitting the curing to proceed to
completion without rotation of said rod.
14. A process for sealing a hole, anchoring a rod or the like which comprises (a) inserting into a
hole the components of a multi-part curable polymer system and a sealing cartridge comprising a
cylindrical array of pressure fragmentable capsules in a fixed three dimensional relationship, said
cylindrical array having a cross sectional diameter from 5 mm. to 10 cm., said capsules containing at least one part of said multi-part curable polymer system, having a major dimension in the range of 4.75 mm. to about 95% of the cross sectional diameter of said cylindrical array and forming flake-like fragments from the walls of the capsules upon their pressure fragmentation and release of their contents, (b) inserting a rod into said hole until the end thereof contacts the sealing cartridge, (c) forcing the rod into said cartridge so as to fragment said macrocapsules into flake-like fragments, thereby releasing and mixing the capsule contents and initiating the curing of said multi-part curing system, and (d) permitting the curing reaction to proceed to completion without rotation of said rod.
1 5. A sealing cartridge substantially as herein described with reference to the accompanying drawings for reinforcing or sealing solid structure, anchoring bolts or the like.
1 6. A process substantially as herein described for sealing a hole or anchoring a rod or the like.
1 7. Any novel element, or combination of elements, herein described and/or shown in the accompanying drawings, irrespective of whether the present claim is within the scope of, or relates to the same invention as, any of the preceding claims.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB7833767A GB2028451A (en) | 1978-08-17 | 1978-08-17 | Sealing Cartridge for Anchoring Bolts or Sealing Solid Structures |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB7833767A GB2028451A (en) | 1978-08-17 | 1978-08-17 | Sealing Cartridge for Anchoring Bolts or Sealing Solid Structures |
Publications (1)
Publication Number | Publication Date |
---|---|
GB2028451A true GB2028451A (en) | 1980-03-05 |
Family
ID=10499130
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB7833767A Withdrawn GB2028451A (en) | 1978-08-17 | 1978-08-17 | Sealing Cartridge for Anchoring Bolts or Sealing Solid Structures |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB2028451A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61243876A (en) * | 1985-04-18 | 1986-10-30 | ヒルテイ・アクチエンゲゼルシヤフト | Adhesive based on acrylic compound |
EP0366103A2 (en) * | 1988-10-26 | 1990-05-02 | Ism International Inc. | Material for setting anchoring bolts |
EP0502348A2 (en) * | 1991-02-28 | 1992-09-09 | MÄCHTLE GmbH | Anchoring device |
EP0713015A1 (en) | 1994-10-28 | 1996-05-22 | Basf Aktiengesellschaft | Self-supporting mastic for dowels used in the chemical fastening technology |
DE19507381A1 (en) * | 1995-03-03 | 1996-09-05 | Stahl Gmbh | Multicomponent adhesive cartridge for bonding anchor in stone or concrete |
US20130327464A1 (en) * | 2011-05-18 | 2013-12-12 | Illinois Tool Works Inc. | Isocyanurate vinyl ester anchoring adhesive composition |
-
1978
- 1978-08-17 GB GB7833767A patent/GB2028451A/en not_active Withdrawn
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61243876A (en) * | 1985-04-18 | 1986-10-30 | ヒルテイ・アクチエンゲゼルシヤフト | Adhesive based on acrylic compound |
EP0199671A3 (en) * | 1985-04-18 | 1988-04-06 | Hilti Aktiengesellschaft | Acrylic resin-based anchoring agent, and its use in anchorings |
EP0366103A2 (en) * | 1988-10-26 | 1990-05-02 | Ism International Inc. | Material for setting anchoring bolts |
EP0366103A3 (en) * | 1988-10-26 | 1991-08-07 | Ism International Inc. | Material for setting anchoring bolts |
DE4106311C1 (en) * | 1991-02-28 | 1992-10-01 | Maechtle Gmbh, 7015 Korntal-Muenchingen, De | |
EP0502348A3 (en) * | 1991-02-28 | 1992-09-16 | MÄCHTLE GmbH | Anchoring device |
EP0502348A2 (en) * | 1991-02-28 | 1992-09-09 | MÄCHTLE GmbH | Anchoring device |
US5282697A (en) * | 1991-02-28 | 1994-02-01 | Maechtle Gmbh | Compound anchor |
EP0713015A1 (en) | 1994-10-28 | 1996-05-22 | Basf Aktiengesellschaft | Self-supporting mastic for dowels used in the chemical fastening technology |
US5731366A (en) * | 1994-10-28 | 1998-03-24 | Dsm Resins B.V. | Self-supporting plugging compound |
DE19507381A1 (en) * | 1995-03-03 | 1996-09-05 | Stahl Gmbh | Multicomponent adhesive cartridge for bonding anchor in stone or concrete |
US20130327464A1 (en) * | 2011-05-18 | 2013-12-12 | Illinois Tool Works Inc. | Isocyanurate vinyl ester anchoring adhesive composition |
US9644123B2 (en) * | 2011-05-18 | 2017-05-09 | Illinois Tool Works Inc. | Isocyanurate vinyl ester anchoring adhesive composition |
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Legal Events
Date | Code | Title | Description |
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WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |