WO2002070591A2 - Polymeric excavation structural support membrane - Google Patents

Polymeric excavation structural support membrane Download PDF

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Publication number
WO2002070591A2
WO2002070591A2 PCT/EP2002/001213 EP0201213W WO02070591A2 WO 2002070591 A2 WO2002070591 A2 WO 2002070591A2 EP 0201213 W EP0201213 W EP 0201213W WO 02070591 A2 WO02070591 A2 WO 02070591A2
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WO
WIPO (PCT)
Prior art keywords
monomer
membrane
modifier
structural support
defoamer
Prior art date
Application number
PCT/EP2002/001213
Other languages
French (fr)
Other versions
WO2002070591A3 (en
Inventor
Frank V. Apicella
Lynn E. Brower
Hendrick J. G. Pretorius
Original Assignee
Mbt Holding Ag
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mbt Holding Ag filed Critical Mbt Holding Ag
Priority to MXPA03007105A priority Critical patent/MXPA03007105A/en
Priority to DE60204564T priority patent/DE60204564T2/en
Priority to EP02700214A priority patent/EP1390427B1/en
Priority to BR0206812-5A priority patent/BR0206812A/en
Priority to CA002435676A priority patent/CA2435676A1/en
Priority to JP2002570625A priority patent/JP4098631B2/en
Priority to AT02700214T priority patent/ATE297434T1/en
Publication of WO2002070591A2 publication Critical patent/WO2002070591A2/en
Publication of WO2002070591A3 publication Critical patent/WO2002070591A3/en

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Classifications

    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21D—SHAFTS; TUNNELS; GALLERIES; LARGE UNDERGROUND CHAMBERS
    • E21D11/00—Lining tunnels, galleries or other underground cavities, e.g. large underground chambers; Linings therefor; Making such linings in situ, e.g. by assembling
    • E—FIXED CONSTRUCTIONS
    • E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
    • E02D—FOUNDATIONS; EXCAVATIONS; EMBANKMENTS; UNDERGROUND OR UNDERWATER STRUCTURES
    • E02D17/00—Excavations; Bordering of excavations; Making embankments
    • E02D17/02—Foundation pits
    • E02D17/04—Bordering surfacing or stiffening the sides of foundation pits

Definitions

  • the present invention is directed to structural support coverings for excavations, such as mines. More particularly, the present invention is directed to a polymeric membrane that is applied to the surfaces of an excavation to provide structural support.
  • the excavation however, exposes natural rock features, such as faults and joints, and can damage the ground by digging or blasting. Minor rock falls can occur between the main supports. Even though they may be isolated or relatively small, they still pose a hazard to people working in the excavation.
  • wire screens or mesh have been installed between the main supports.
  • the screen requires labor intensive, installation.
  • the screen offers no protection against weathering of the rock face. Because of the uneveimess of the rock face, the screen is not fully flush with the rock face. The screen only becomes effective after considerable rock movement puts tension on the screen.
  • the screen is prone to corrosion and deterioration.
  • the screen is prone to blasting damage if it is installed close to the advancing face. Because it cannot be installed remotely, it is hazardous to install because of falling rock. It can be difficult to shotcrete over which causes relatively high rebound and lower substrate adhesion.
  • One possible alternative to a wire mesh would be to spray concrete (shotcrete) onto the rock face. However, this would be cost prohibitive to apply to all surfaces in an excavation. Also, shotcreting may not be able to be applied in all locations.
  • Sealants have been used in mines to prevent air leaks. Sealants, however, are not capable of providing structural support to a surface in an excavation. Generally, sealants are polymer in water dispersions. As a result, they cannot be applied to a surface at a thickness sufficient to provide support because of the water content. Also, the polymer in water dispersion prohibits quick setting of the polymer on the surface, which in turn does not provide sufficient tensile strength.
  • What is needed in the art is a structural membrane that can be installed with minimal labor, can be installed remotely from the exposed rock face, offers weathering protection to the rock face, does not corrode, becomes effective with minimal rock deformation, can be applied near the advancing face, is less prone to blast damage, and can be covered with shotcrete if deemed necessary.
  • the present invention provides a polymeric excavation structural support membrane comprising a polymer that is an initiator-induced reaction product of a monomer; a self- extinguishing agent; and optionally at least one of a crosslinking agent, a second monomer, a smoke retardant, a rheology modifier, a reaction rate modifier, a plasticizer, an emulsifier, a defoamer, a filler, a wet surface adhesion modifier, and a colouring agent; wherein the monomer is selected from the group consisting of aryloxy alkyl acrylates, aryloxy alkyl methacrylates, and mixtures thereof; wherein the second monomer does not homopolymerize in the presence of the reaction rate modifier or the initiator; and wherein the membrane has a tensile strength (ASTM D638) greater than 1 MPa after 24 hours and an adhesion strength (ASTM D4142) greater than 0.5 MPa after 24 hours.
  • the invention also provides a method of rein
  • the present invention also provides a polymeric structural support membrane formed from a process comprising: applying to an exposed surface in an excavation a mixture as hereinabove described.
  • the monomer is selected from the group consisting of monofunctional aryloxy alkyl acrylates, monofunctional aryloxy alkyl methacrylates, and mixtures thereof.
  • the present invention is directed to a polymeric structural support membrane for excavations.
  • the membrane includes a polymer and a self-extinguishing agent.
  • the polymer is a reaction product of a monomer selected from the group consisting of monofunctional monomers, di-functional monomers, tri-functional monomers, tetra- functional monomers, and mixtures thereof.
  • a monomer selected from the group consisting of monofunctional monomers, di-functional monomers, tri-functional monomers, tetra- functional monomers, and mixtures thereof.
  • functional it is meant that the monomer has at least one double bond reactive group that can react in a polymerization reaction to form a polymer.
  • the monomer can include another functional group, which can be a double bond or another reactive group, that reacts to link one polymer chain to another polymer chain.
  • the polymer is present in the membrane in an amount that provides the membrane with a tensile strength, a thickness, and a molecular weight sufficient to provide support to exposed surfaces in an excavation.
  • the polymer is generally present in an amount from 30% to 70% based on the weight of the membrane. In one embodiment, the polymer is present in the membrane from 51 % to 70% based on the weight of the membrane.
  • the monofunctional monomers used according to the present invention are monofunctional esters, particularly monofunctional aryloxy alkyl acrylates, monofunctional aryloxy alkyl methacrylates, and mixtures thereof. The methacrylates are preferred because they produce less odour.
  • Examples of useful monofunctional aryloxy alkyl acrylates and monofunctional aryloxy alkyl methacrylates include, but are not limited to, 2-phenoxyethyl methacrylate, 2- phenoxy-propyl-methacrylate, and mixtures thereof.
  • Other monofunctional monomers that can be reacted to form the membrane of the present invention include, but are not limited to, tri-propylene glycol diacrylate, tri-ethylene glycol dimethacrylate, and mixtures thereof.
  • the di-functional monomers can be any di-functional ester.
  • Di-functional esters that can be used are di-functional aryloxy alkyl acrylates, di-functional aryloxy alkyl methacrylates, and mixtures thereof.
  • Examples of useful di-functional monomers include, but are not limited to, tri-ethylene glycol dimethacrylate, neopentyl glycol diacrylate or methacrylate, and tri-propylene glycol diacrylate.
  • the tri-functional monomers can be any tri-functional ester.
  • Tri-functional esters that can be used are tri-functional acrylates, tri-functional methacrylates, and mixtures thereof.
  • Examples of useful tri-functional monomers include, but are not limited to, propoxylated trimethylolpropane triacrylate, ethoxylated trimethylpropane triacrylate, and propoxylated glyceryl triacrylate.
  • the tetra-functional monomers can be any tetra-functional esters. Tetra-functional esters that can be used are tetra-functional acrylates, tetra-functional methacrylates, and mixtures thereof. Examples of useful tri-functional monomers include, but are not limited to, di-trimethylolpropane tetra acrylate, and dipentaerythritol penta acrylate.
  • the polymer is the reaction product of a monomer selected from the group consisting of monofunctional aryloxy alkyl acrylates, monofunctional aryloxy alkyl methacrylates, and mixtures thereof, and a crosslinking agent.
  • a monomer selected from the group consisting of monofunctional aryloxy alkyl acrylates, monofunctional aryloxy alkyl methacrylates, and mixtures thereof.
  • a crosslinking agent is reacted with the monomer to provide crosslinking between the polymer chains to provide structural support.
  • crosslinking agent examples include, but are not limited to, methylene bis acrylamide, polymethylmethacrylate, butadiene styrene acrylate, styrene butyl acrylate copolymer, 1,6-hexanediol dimethacrylate, ethoxylated bisphenol A dimethacrylate, polyethylene glycol dimethacrylate, and mixtures thereof.
  • the crosslinking agent can be present up to 30% based on the weight of the monomer.
  • a second monomer may be included in the reaction product that forms the membrane of the present invention.
  • the second monomer preferably does not homopolymerize in the presence of the reaction rate modifier or the initiator.
  • Suitable examples of the second monomer include, but are not limited to, diethylene glycol monoethyl ether dimethacrylate, diethylene glycol monobutyl ether dimethacrylate, and mixtures thereof.
  • the membrane is being applied in an excavation, particularly in a mine, there is the potential for fire. In each jurisdiction, there are requirements that the membrane be self -extinguishing. The test is performed by holding the membrane to a flame for a fixed period of time. The membrane must then self-extinguish itself within a set maximum time.
  • the fire retardant can be any material that provides self-extinguishing properties to the membrane.
  • Suitable examples of the self- extinguishing agent include, but are not limited to, phosphates, such as triphenyl phosphate, polyammonium phosphate, monoammonium phosphate, or tri(2-chloroethyl) phosphate, exfoliated graphite (which can be acid treated natural graphite flakes), and mixtures thereof.
  • the fire retardant is preferably present in the membrane from 5 to 40% based on the weight of the membrane.
  • the fire retardant can be a liquid or a solid.
  • the fire retardant is a solid.
  • the solid is micronized.
  • micronized it is meant that the solid is ground to a micron size.
  • the micronized self-extinguishing agent can also be used with polymeric membranes other than the polymeric membrane of the present invention.
  • the other polymeric membranes include, but are not limited to, polyurethane and polyurea.
  • a preferred fire retardant is polyammonium phosphate.
  • a smoke retardant can be provided in the membrane.
  • a preferred smoke retardant is aluminium oxide (Al 2 O 3 ).
  • the smoke retardant is present in the membrane from 2% to 15% based on the weight of the membrane.
  • the combination of a polyammonium phosphate fire retardant and aluminium oxide smoke retardant is particularly preferred.
  • the gel and set time of the membrane can be controlled by adding at least one initiator.
  • the initiator can be an oxidizing agent. Suitable oxidizing agents include, but are not limited to, peroxides, such as benzoyl peroxide, dibenzoyl peroxide, hydroperoxides, such as cumyl hydroperoxide, persulfates, such as ammonium persulfate, and mixtures thereof.
  • the initiator is preferably added in an amount from 1% to 10% based on the weight of the monomer.
  • reaction rate modifier such as an accelerator
  • the reaction rate .modifier can be a reducing agent.
  • Suitable reducing agents include, but are not limited to, aniline-containing compounds, amines, glycols, octoates, and mixtures thereof.
  • Suitable examples of the reaction rate modifier include, but are not limited to, triethanolamine, N,N-dimethyl-p-toluidme, and tripropyl amines.
  • the reaction rate modifier can be present in an amount up to 10% based on the weight of the monomer.
  • the materials to form the membrane can either be provided as a single composition, or the materials can be provided as a multi-component (two or more) formulation.
  • the multi-component system may be desired when an initiator and a reaction rate modifier are being provided in the membrane. In this instance, the initiator would be supplied in one component, and the reaction rate modifier could be supplied in another component.
  • the membrane can also include a rheology modifier to increase the viscosity of the membrane materials immediately after application to excavation surfaces. This may be desired to prevent the membrane from slumping before it cures when it is applied to a surface in an excavation.
  • a rheology modifier include fumed silica, hydroxyethyl cellulose, hydroxypropyl cellulose, fly ash (as defined in ASTM C618), mineral oils (such as light naphthenic), tetra alkyl ammonium hectorite clay, any other solids that are inert to the other materials in the membrane, and mixtures thereof.
  • the rheology modifier can be present in an amount up to 20 %based on the weight of the membrane.
  • the membrane can also include an emulsifier. It may be desired to add an emulsifier to increase the adhesion of the membrane to a surface.
  • the emulsifier can be any anionic surfactant or nonionic surfactant. Suitable examples of the emulsifier include, but are not limited to, ethoxylated nonyl phenol (preferably, the ethoxylated nonyl phenol contains from 4 to 10 ethylene oxide groups), lauryl sulfates and mixtures thereof.
  • the emulsifier can be present in an amount up to 5% based on the weight of the monomer.
  • the membrane can also contain a plasticizer to make the membrane more flexible.
  • the plasticizer can be any material that plasticizes the polymer in the membrane.
  • the plasticizer allows the polymer to be self plasticizing. In this instance, the monomer is reacted with the plasticizer that incorporates itself into the reaction product.
  • the plasticizer can be present in an amount up to about 40% based on the weight of the monomer. Suitable examples of the plasticizer include, but are not limited to, lauryl methacrylates, stearyl methacrylates, and ethoxylated(4) nonyl phenol (meth)acrylate, as shown by the following formula:
  • R is H or CH 3 .
  • the membrane can also include a filler.
  • Suitable examples of the filler include, but are not limited to glass, such as crushed glass, metal, such as iron particles, quartz, silica, barytes, limestone, sulfates, alumina, various clays, diatomaceous earth, wollastonite, mica, perlite, flint powder, kryolite, alumina trihydrate, talc, sand, pyrophylite, granulated polyethylene, fibres, such as polypropylene or steel, zinc oxide, titanium dioxide, and mixtures thereof.
  • a preferred filler is titanium dioxide.
  • the filler can be present in an amount up to 40% based on the weight of the monomer.
  • the membrane can also include a wet surface adhesion modifier.
  • the wet surface adhesion modifier provides for increased adhesion to wet surfaces.
  • the wet surface adhesion modifier can be any material that increases the adhesion of the membrane to a wet surface. Suitable examples of the wet surface adhesion modifier include, but are not limited to, metallic acrylate or methacrylate at up to 10 % of total monomer content, ammonium oleate, magnesium oleate, ammonium acrylate and metal borates.
  • a preferred wet surface adhesion modifier is zinc borate.
  • the wet surface adhesion modifier is preferably present in an amount up to 3% based on the weight of the monomer.
  • the membrane can also include a coloring agent, such as a pigment or a dye, to provide a desired color to the membrane.
  • a coloring agent such as titanium dioxide, but other coloring agents are also useful.
  • the coloring agent can be present in an amount up to 3% based on the weight of the monomer.
  • the membrane can also include a defoamer such as modified silicones or petroleum oil mixtures.
  • a defoamer such as modified silicones or petroleum oil mixtures.
  • a preferred defoamer is FOAMASTERTM S available from Cognis Corporation, Cincinnati, Ohio.
  • the defoamer can be present in an amount up to 3% based on the weight of the monomer.
  • a preferred membrane is formed from a two-component reaction mixture.
  • the first component includes the monomer and the crosslinking agent that react to become the polymer and any other additive.
  • the second component includes the initiator and any other additive.
  • the two-component mixture is preferred so that the polymer does not prematurely react with the initiator.
  • the two components are mixed and allowed to react to form the polymer.
  • the membrane When applied to a surface, the membrane should be at least 1.5mm thick. Preferably, the membrane is 2mm to 6mm thick.
  • One property of the membrane is adequate elongation. Elongation is the percent increase in length of a membrane before it breaks (ASTM D638). It is desired to achieve elongation in the shortest amount of time.
  • the membrane has an elongation greater than 25% after 24 hours from being formed. More preferably, the membrane has an elongation greater than 50% after 8 hours. Most preferably, the membrane has an elongation greater than 75% after 2 hours. In some embodiments, however, the membrane has an elongation of about zero. In these instances, the membrane is substantially rigid.
  • Tensile strength is the maximum force that a membrane can withstand before breaking (ASTM D638). It is desired to achieve a high tensile strength.
  • the membrane has a tensile strength greater than 1 MPa after 24 hours. More preferably, the membrane has a tensile strength greater than 1 MPa after 6 hours. Most preferably, the membrane has a tensile strength greater than 1 MPa after 30 minutes or less.
  • the membrane also has an adequate adhesion property. Adhesion is measured by the force needed to remove the membrane from a surface (ASTM D4142). It is desired to achieve adhesion in the shortest amount of time.
  • the membrane has an adhesion strength greater than 0.5 MPa after 24 hours. More preferably, the membrane has an adhesion strength greater than 1 MPa after 8 hours. Most preferably the membrane has an adhesion strength greater than 0.5 MPa after 30 minutes or less.
  • the membrane have water resistance.
  • Water resistance can be determined by the following standards: ASTM D2247 (Standard Practice for Testing Water Resistance of Coatings in 100% Relative Humidity), ASTM D1735 (Standard Practice for Testing Water Resistance of Coatings Using Water Fog Apparatus), ASTM D4585 (Standard Practice for Testing Water Resistance of Coatings Using Controlled Condensation), or ASTM D870 (Standard Practice for Testing Water Resistance of Coatings Using Water Immersion).
  • the preferred standard is ASTM D870.
  • a sample of the membrane is immersed in room temperature water for a period of 24 hours.
  • the tensile strength of the membrane is then measured and compared to the tensile strength of .the membrane before immersion. Greater water resistance is indicated by having a lower loss in tensile strength.
  • Acceptable water resistance is having a loss in tensile strength less than 10%.
  • the loss in tensile strength is less than 5%. It has been found that aryloxy alkyl acrylates and aryloxy alkyl methacrylates provide acceptable water resistance to the membrane of the present invention.
  • the membrane is also capable of quick set.
  • quick set it is meant that the membrane achieves at least one of the tensile, elongation, and adhesive properties within the time referenced above.
  • the membrane have a useful service life greater than one year.
  • useful service life it is meant that the membrane has less than 10% loss of properties in one year.
  • membrane may be applied underground in a mine, it is preferred that membrane be non-toxic to human contact.
  • a method of reinforcing exposed surfaces in an excavation with a polymeric structural support membrane includes providing a mixture as hereinabove defined; applying said mixture to an exposed surface in an excavation, and causing the mixture to react. This method provides for applying the above-described polymeric structural support membrane on an exposed surface.
  • MBT Membrane Displacement Test is designed to provide load and displacement data on membrane performance to account for the combined effects of tensile strength, elongation and adhesion properties of spray-on membranes and provide performance data for evaluating such membranes. It is effective in comparing the relative performance of different membranes.
  • the membrane is sprayed onto the surface of a concrete slab.
  • the mixture can be applied by spraying, brushing, or rolling to provide the polymeric structural support membrane on an exposed surface.
  • a preferred embodiment of the present invention is prepared from the following formulation. It is provided in the preferred two-component formulation with the monomer and initiator being provided in separate parts to the formulation.
  • the present invention is prepared from the following formulation. Again, this embodiment is provided in the preferred two component formulation with the monomer and initiator being provided in separate parts to the formulation.
  • the present invention has the following formulation.
  • the formulation comprises four components. This embodiment is provided in a four-component formulation combined in two units of monomer, initiator and reaction rate modifier, as discussed below.
  • this embodiment can be reacted into the membrane of the present invention by supplying the four components through a pump that delivers the materials to a spraying apparatus to spray the formulation onto a surface.
  • the pump is designed to pump two components simultaneously. Parts A and B are supplied to one pumping chamber of the pump, and Parts C and D are supplied to a second pumping chamber of the pump.
  • the volumes of the components are sized such that the membrane is formed with the desired composition.
  • a pump is used that delivers two components in the volume ratio of about 3 to 1.
  • components one and two are sized to provide 3/4 of the total volume of the material delivered that forms the membrane, and components three and four are sized to provide 1/4 of the total volume.
  • An example of the present inventive polymeric structural support membrane is. tested for tensile strength ASTM D638 and elongation ASTM D638 both in the presence of water and without water.
  • the example of the invention comprises two components (3 parts of Part A to 1 part of Part B (by weight)) which are added together to react and form the support membrane.
  • part A three monomers are used in order to maximize the flexibility (elongation), strength (tensile strength) and water sensitivity of the structural support membrane.
  • 2 - phenoxy ethyl methacrylate imparts decreased water sensitivity but lacks strength and flexibility whereas, the remaining two monomers hydroxy propyl methacrylate and isobornyl methacrylate give the membrane strength and flexibility.
  • the example is tested for elongation (ASTM D638) - the percent increase in length of a membrane before it breaks, and tensile strength (ASTM D638) - the maximum force that a membrane can withstand before breaking expressed in megapascals (Mpa).
  • ASTM D638 the percent increase in length of a membrane before it breaks
  • tensile strength ASTM D638
  • Mpa megapascals
  • the polymeric structural support membrane achieves the desired tensile strength (greater than 1 MPa after 24 hours) and elongation (greater than about 25% after 24 hours). Therefore, the membrane will display the desired strength and flexibility for an underground structural support. Additionally, the test results demonstrate that the polymeric structural support membrane shows little or no strength loss when exposed to water (moisture sensitivity).

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Abstract

In excavations, such as mines, supports are needed to prevent rock falls. Structural beams provide the main support in the excavation to prevent major rock falls. However, between the main beams, minor rock falls can still occur. To provide structural support between the main beams, a polymeric structural support membrane can be applied. The membrane includes a polymer that is the reaction product of a monomer, an initiator, and optionally a crosslinking agent; and a self-extinguishing agent. The membrane can be applied by spraying, brushing, or rolling.

Description

POLYMERIC STRUCTURAL SUPPORT MEMBRANE
FIELD OF THE INVENTION
The present invention is directed to structural support coverings for excavations, such as mines. More particularly, the present invention is directed to a polymeric membrane that is applied to the surfaces of an excavation to provide structural support.
BACKGROUND OF THE INVENTION
When ground is excavated, structural supports are placed in the excavation to prevent the ground from collapsing into the excavated area. Mainly, the ground is supported by support rods that are placed along the excavation. These supports are typically steel reinforcing rods that are held in place by mechanical anchors and/or grouts. These supports provide the main protection against unplanned rock falls.
The excavation, however, exposes natural rock features, such as faults and joints, and can damage the ground by digging or blasting. Minor rock falls can occur between the main supports. Even though they may be isolated or relatively small, they still pose a hazard to people working in the excavation.
To prevent these minor rock falls between the supports, wire screens or mesh have been installed between the main supports. There are many disadvantages to using a wire screen. The screen requires labor intensive, installation. The screen offers no protection against weathering of the rock face. Because of the uneveimess of the rock face, the screen is not fully flush with the rock face. The screen only becomes effective after considerable rock movement puts tension on the screen. The screen is prone to corrosion and deterioration. The screen is prone to blasting damage if it is installed close to the advancing face. Because it cannot be installed remotely, it is hazardous to install because of falling rock. It can be difficult to shotcrete over which causes relatively high rebound and lower substrate adhesion. One possible alternative to a wire mesh would be to spray concrete (shotcrete) onto the rock face. However, this would be cost prohibitive to apply to all surfaces in an excavation. Also, shotcreting may not be able to be applied in all locations.
Sealants have been used in mines to prevent air leaks. Sealants, however, are not capable of providing structural support to a surface in an excavation. Generally, sealants are polymer in water dispersions. As a result, they cannot be applied to a surface at a thickness sufficient to provide support because of the water content. Also, the polymer in water dispersion prohibits quick setting of the polymer on the surface, which in turn does not provide sufficient tensile strength.
What is needed in the art is a structural membrane that can be installed with minimal labor, can be installed remotely from the exposed rock face, offers weathering protection to the rock face, does not corrode, becomes effective with minimal rock deformation, can be applied near the advancing face, is less prone to blast damage, and can be covered with shotcrete if deemed necessary.
It is an object of the invention to provide a polymeric structural support membrane for providing support to exposed surfaces in an excavation.
SUMMARY OF THE INVENTION
The present invention provides a polymeric excavation structural support membrane comprising a polymer that is an initiator-induced reaction product of a monomer; a self- extinguishing agent; and optionally at least one of a crosslinking agent, a second monomer, a smoke retardant, a rheology modifier, a reaction rate modifier, a plasticizer, an emulsifier, a defoamer, a filler, a wet surface adhesion modifier, and a colouring agent; wherein the monomer is selected from the group consisting of aryloxy alkyl acrylates, aryloxy alkyl methacrylates, and mixtures thereof; wherein the second monomer does not homopolymerize in the presence of the reaction rate modifier or the initiator; and wherein the membrane has a tensile strength (ASTM D638) greater than 1 MPa after 24 hours and an adhesion strength (ASTM D4142) greater than 0.5 MPa after 24 hours. The invention also provides a method of reinforcing exposed surfaces in an excavation with a polymeric structural support membrane comprising: applying to the exposed surface a mixture as hereinabove defined; and causing the mixture to react.
The present invention also provides a polymeric structural support membrane formed from a process comprising: applying to an exposed surface in an excavation a mixture as hereinabove described.
Preferably, the monomer is selected from the group consisting of monofunctional aryloxy alkyl acrylates, monofunctional aryloxy alkyl methacrylates, and mixtures thereof.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to a polymeric structural support membrane for excavations. The membrane includes a polymer and a self-extinguishing agent.
The polymer is a reaction product of a monomer selected from the group consisting of monofunctional monomers, di-functional monomers, tri-functional monomers, tetra- functional monomers, and mixtures thereof. By functional, it is meant that the monomer has at least one double bond reactive group that can react in a polymerization reaction to form a polymer. Additionally, the monomer can include another functional group, which can be a double bond or another reactive group, that reacts to link one polymer chain to another polymer chain.
The polymer is present in the membrane in an amount that provides the membrane with a tensile strength, a thickness, and a molecular weight sufficient to provide support to exposed surfaces in an excavation. The polymer is generally present in an amount from 30% to 70% based on the weight of the membrane. In one embodiment, the polymer is present in the membrane from 51 % to 70% based on the weight of the membrane. The monofunctional monomers used according to the present invention are monofunctional esters, particularly monofunctional aryloxy alkyl acrylates, monofunctional aryloxy alkyl methacrylates, and mixtures thereof. The methacrylates are preferred because they produce less odour.
Examples of useful monofunctional aryloxy alkyl acrylates and monofunctional aryloxy alkyl methacrylates include, but are not limited to, 2-phenoxyethyl methacrylate, 2- phenoxy-propyl-methacrylate, and mixtures thereof. Other monofunctional monomers that can be reacted to form the membrane of the present invention include, but are not limited to, tri-propylene glycol diacrylate, tri-ethylene glycol dimethacrylate, and mixtures thereof.
The di-functional monomers can be any di-functional ester. Di-functional esters that can be used are di-functional aryloxy alkyl acrylates, di-functional aryloxy alkyl methacrylates, and mixtures thereof. Examples of useful di-functional monomers include, but are not limited to, tri-ethylene glycol dimethacrylate, neopentyl glycol diacrylate or methacrylate, and tri-propylene glycol diacrylate.
The tri-functional monomers can be any tri-functional ester. Tri-functional esters that can be used are tri-functional acrylates, tri-functional methacrylates, and mixtures thereof. Examples of useful tri-functional monomers include, but are not limited to, propoxylated trimethylolpropane triacrylate, ethoxylated trimethylpropane triacrylate, and propoxylated glyceryl triacrylate.
The tetra-functional monomers can be any tetra-functional esters. Tetra-functional esters that can be used are tetra-functional acrylates, tetra-functional methacrylates, and mixtures thereof. Examples of useful tri-functional monomers include, but are not limited to, di-trimethylolpropane tetra acrylate, and dipentaerythritol penta acrylate.
Preferably, the polymer is the reaction product of a monomer selected from the group consisting of monofunctional aryloxy alkyl acrylates, monofunctional aryloxy alkyl methacrylates, and mixtures thereof, and a crosslinking agent. When a monofunctional monomer is selected, a crosslinking agent is reacted with the monomer to provide crosslinking between the polymer chains to provide structural support. Suitable examples of the crosslinking agent include, but are not limited to, methylene bis acrylamide, polymethylmethacrylate, butadiene styrene acrylate, styrene butyl acrylate copolymer, 1,6-hexanediol dimethacrylate, ethoxylated bisphenol A dimethacrylate, polyethylene glycol dimethacrylate, and mixtures thereof. The crosslinking agent can be present up to 30% based on the weight of the monomer.
A second monomer may be included in the reaction product that forms the membrane of the present invention. The second monomer preferably does not homopolymerize in the presence of the reaction rate modifier or the initiator. Suitable examples of the second monomer include, but are not limited to, diethylene glycol monoethyl ether dimethacrylate, diethylene glycol monobutyl ether dimethacrylate, and mixtures thereof.
Because the membrane is being applied in an excavation, particularly in a mine, there is the potential for fire. In each jurisdiction, there are requirements that the membrane be self -extinguishing. The test is performed by holding the membrane to a flame for a fixed period of time. The membrane must then self-extinguish itself within a set maximum time.
Provided in the membrane is a fire retardant. The fire retardant can be any material that provides self-extinguishing properties to the membrane. Suitable examples of the self- extinguishing agent include, but are not limited to, phosphates, such as triphenyl phosphate, polyammonium phosphate, monoammonium phosphate, or tri(2-chloroethyl) phosphate, exfoliated graphite (which can be acid treated natural graphite flakes), and mixtures thereof. The fire retardant is preferably present in the membrane from 5 to 40% based on the weight of the membrane.
The fire retardant can be a liquid or a solid. Preferably the fire retardant is a solid.
More preferably, the solid is micronized. By micronized it is meant that the solid is ground to a micron size. The micronized self-extinguishing agent can also be used with polymeric membranes other than the polymeric membrane of the present invention. The other polymeric membranes include, but are not limited to, polyurethane and polyurea. A preferred fire retardant is polyammonium phosphate.
A smoke retardant can be provided in the membrane. A preferred smoke retardant is aluminium oxide (Al2O3). Preferably, the smoke retardant is present in the membrane from 2% to 15% based on the weight of the membrane. The combination of a polyammonium phosphate fire retardant and aluminium oxide smoke retardant is particularly preferred.
The gel and set time of the membrane can be controlled by adding at least one initiator. The initiator can be an oxidizing agent. Suitable oxidizing agents include, but are not limited to, peroxides, such as benzoyl peroxide, dibenzoyl peroxide, hydroperoxides, such as cumyl hydroperoxide, persulfates, such as ammonium persulfate, and mixtures thereof. The initiator is preferably added in an amount from 1% to 10% based on the weight of the monomer.
In combination with the initiator, a reaction rate modifier, such as an accelerator, can be added. The reaction rate .modifier can be a reducing agent. Suitable reducing agents include, but are not limited to, aniline-containing compounds, amines, glycols, octoates, and mixtures thereof. Suitable examples of the reaction rate modifier include, but are not limited to, triethanolamine, N,N-dimethyl-p-toluidme, and tripropyl amines. The reaction rate modifier can be present in an amount up to 10% based on the weight of the monomer.
The materials to form the membrane can either be provided as a single composition, or the materials can be provided as a multi-component (two or more) formulation. The multi-component system may be desired when an initiator and a reaction rate modifier are being provided in the membrane. In this instance, the initiator would be supplied in one component, and the reaction rate modifier could be supplied in another component.
The membrane can also include a rheology modifier to increase the viscosity of the membrane materials immediately after application to excavation surfaces. This may be desired to prevent the membrane from slumping before it cures when it is applied to a surface in an excavation. Suitable examples of the rheology modifier include fumed silica, hydroxyethyl cellulose, hydroxypropyl cellulose, fly ash (as defined in ASTM C618), mineral oils (such as light naphthenic), tetra alkyl ammonium hectorite clay, any other solids that are inert to the other materials in the membrane, and mixtures thereof. The rheology modifier can be present in an amount up to 20 %based on the weight of the membrane.
The membrane can also include an emulsifier. It may be desired to add an emulsifier to increase the adhesion of the membrane to a surface. The emulsifier can be any anionic surfactant or nonionic surfactant. Suitable examples of the emulsifier include, but are not limited to, ethoxylated nonyl phenol (preferably, the ethoxylated nonyl phenol contains from 4 to 10 ethylene oxide groups), lauryl sulfates and mixtures thereof. The emulsifier can be present in an amount up to 5% based on the weight of the monomer.
The membrane can also contain a plasticizer to make the membrane more flexible. The plasticizer can be any material that plasticizes the polymer in the membrane. In one embodiment of the invention, the plasticizer allows the polymer to be self plasticizing. In this instance, the monomer is reacted with the plasticizer that incorporates itself into the reaction product. The plasticizer can be present in an amount up to about 40% based on the weight of the monomer. Suitable examples of the plasticizer include, but are not limited to, lauryl methacrylates, stearyl methacrylates, and ethoxylated(4) nonyl phenol (meth)acrylate, as shown by the following formula:
Figure imgf000008_0001
wherein R is H or CH3.
The membrane can also include a filler. Suitable examples of the filler include, but are not limited to glass, such as crushed glass, metal, such as iron particles, quartz, silica, barytes, limestone, sulfates, alumina, various clays, diatomaceous earth, wollastonite, mica, perlite, flint powder, kryolite, alumina trihydrate, talc, sand, pyrophylite, granulated polyethylene, fibres, such as polypropylene or steel, zinc oxide, titanium dioxide, and mixtures thereof. A preferred filler is titanium dioxide. The filler can be present in an amount up to 40% based on the weight of the monomer.
The membrane can also include a wet surface adhesion modifier. The wet surface adhesion modifier provides for increased adhesion to wet surfaces. The wet surface adhesion modifier can be any material that increases the adhesion of the membrane to a wet surface. Suitable examples of the wet surface adhesion modifier include, but are not limited to, metallic acrylate or methacrylate at up to 10 % of total monomer content, ammonium oleate, magnesium oleate, ammonium acrylate and metal borates. A preferred wet surface adhesion modifier is zinc borate. The wet surface adhesion modifier is preferably present in an amount up to 3% based on the weight of the monomer.
The membrane can also include a coloring agent, such as a pigment or a dye, to provide a desired color to the membrane. An example of a coloring agent is titanium dioxide, but other coloring agents are also useful. The coloring agent can be present in an amount up to 3% based on the weight of the monomer.
The membrane can also include a defoamer such as modified silicones or petroleum oil mixtures. A preferred defoamer is FOAMASTER™ S available from Cognis Corporation, Cincinnati, Ohio. The defoamer can be present in an amount up to 3% based on the weight of the monomer.
A preferred membrane is formed from a two-component reaction mixture. The first component includes the monomer and the crosslinking agent that react to become the polymer and any other additive. The second component includes the initiator and any other additive. The two-component mixture is preferred so that the polymer does not prematurely react with the initiator. To form the membrane, the two components are mixed and allowed to react to form the polymer.
When applied to a surface, the membrane should be at least 1.5mm thick. Preferably, the membrane is 2mm to 6mm thick. One property of the membrane is adequate elongation. Elongation is the percent increase in length of a membrane before it breaks (ASTM D638). It is desired to achieve elongation in the shortest amount of time. Preferably, the membrane has an elongation greater than 25% after 24 hours from being formed. More preferably, the membrane has an elongation greater than 50% after 8 hours. Most preferably, the membrane has an elongation greater than 75% after 2 hours. In some embodiments, however, the membrane has an elongation of about zero. In these instances, the membrane is substantially rigid.
Another property of the membrane is adequate tensile strength. Tensile strength is the maximum force that a membrane can withstand before breaking (ASTM D638). It is desired to achieve a high tensile strength. Preferably, the membrane has a tensile strength greater than 1 MPa after 24 hours. More preferably, the membrane has a tensile strength greater than 1 MPa after 6 hours. Most preferably, the membrane has a tensile strength greater than 1 MPa after 30 minutes or less.
The membrane also has an adequate adhesion property. Adhesion is measured by the force needed to remove the membrane from a surface (ASTM D4142). It is desired to achieve adhesion in the shortest amount of time. Preferably, the membrane has an adhesion strength greater than 0.5 MPa after 24 hours. More preferably, the membrane has an adhesion strength greater than 1 MPa after 8 hours. Most preferably the membrane has an adhesion strength greater than 0.5 MPa after 30 minutes or less.
It is preferred that the membrane have water resistance. Water resistance can be determined by the following standards: ASTM D2247 (Standard Practice for Testing Water Resistance of Coatings in 100% Relative Humidity), ASTM D1735 (Standard Practice for Testing Water Resistance of Coatings Using Water Fog Apparatus), ASTM D4585 (Standard Practice for Testing Water Resistance of Coatings Using Controlled Condensation), or ASTM D870 (Standard Practice for Testing Water Resistance of Coatings Using Water Immersion).
The preferred standard is ASTM D870. A sample of the membrane is immersed in room temperature water for a period of 24 hours. The tensile strength of the membrane is then measured and compared to the tensile strength of .the membrane before immersion. Greater water resistance is indicated by having a lower loss in tensile strength. Acceptable water resistance is having a loss in tensile strength less than 10%. Preferably, the loss in tensile strength is less than 5%. It has been found that aryloxy alkyl acrylates and aryloxy alkyl methacrylates provide acceptable water resistance to the membrane of the present invention.
The membrane is also capable of quick set. By quick set it is meant that the membrane achieves at least one of the tensile, elongation, and adhesive properties within the time referenced above.
It is also preferred that the membrane have a useful service life greater than one year. By useful service life, it is meant that the membrane has less than 10% loss of properties in one year.
Because the membrane may be applied underground in a mine, it is preferred that membrane be non-toxic to human contact.
In another embodiment of the present invention there is provided a method of reinforcing exposed surfaces in an excavation with a polymeric structural support membrane. The method includes providing a mixture as hereinabove defined; applying said mixture to an exposed surface in an excavation, and causing the mixture to react. This method provides for applying the above-described polymeric structural support membrane on an exposed surface.
Sufficient membrane tensile strength and thickness to provide support for exposed surfaces in an excavation can be measured using the testing method illustrated in A. Spearing, Jeffrey Ohler & Emmanuel Attiogbe, "The effective testing of thin support membranes (superskins) for use in underground mines", Australian Centre for Geomechanics, herein incorporated by reference. The test, referred to as MBT Membrane Displacement Test, is designed to provide load and displacement data on membrane performance to account for the combined effects of tensile strength, elongation and adhesion properties of spray-on membranes and provide performance data for evaluating such membranes. It is effective in comparing the relative performance of different membranes. The membrane is sprayed onto the surface of a concrete slab. An area of the applied membrane is then subjected to a load. Both short- and long-term (i.e., creep) tests can be performed with the test setup. For ease of developing a standard test that can be routinely used to assess the overall performance of spray-on membranes, pre-cast concrete slabs are used. These slabs are commercially available and are quite dense (relative to normal cast-in- place concrete) with a slightiy textured finish on one surface. Typical values of absorption and volume of permeable pore space for the slabs, as determined in accordance with ASTM C 642, are 5% and 11%, respectively. Using the pre-cast slab, the performance of the membrane can be evaluated for the effects of variations in membrane properties, as well as the effects of substrate moisture conditions.
The mixture can be applied by spraying, brushing, or rolling to provide the polymeric structural support membrane on an exposed surface.
A preferred embodiment of the present invention is prepared from the following formulation. It is provided in the preferred two-component formulation with the monomer and initiator being provided in separate parts to the formulation.
Figure imgf000012_0001
Figure imgf000013_0001
In another preferred embodiment, the present invention is prepared from the following formulation. Again, this embodiment is provided in the preferred two component formulation with the monomer and initiator being provided in separate parts to the formulation.
Figure imgf000013_0002
Figure imgf000014_0001
In another preferred embodiment, the present invention has the following formulation.
Figure imgf000014_0002
In another preferred embodiment the formulation comprises four components. This embodiment is provided in a four-component formulation combined in two units of monomer, initiator and reaction rate modifier, as discussed below.
Figure imgf000015_0001
Preferably, this embodiment can be reacted into the membrane of the present invention by supplying the four components through a pump that delivers the materials to a spraying apparatus to spray the formulation onto a surface. Generally, the pump is designed to pump two components simultaneously. Parts A and B are supplied to one pumping chamber of the pump, and Parts C and D are supplied to a second pumping chamber of the pump. The volumes of the components are sized such that the membrane is formed with the desired composition. In a preferred embodiment, a pump is used that delivers two components in the volume ratio of about 3 to 1. In this embodiment, components one and two are sized to provide 3/4 of the total volume of the material delivered that forms the membrane, and components three and four are sized to provide 1/4 of the total volume.
EXAMPLE
An example of the present inventive polymeric structural support membrane is. tested for tensile strength ASTM D638 and elongation ASTM D638 both in the presence of water and without water. The example of the invention comprises two components (3 parts of Part A to 1 part of Part B (by weight)) which are added together to react and form the support membrane. In part A, three monomers are used in order to maximize the flexibility (elongation), strength (tensile strength) and water sensitivity of the structural support membrane. 2 - phenoxy ethyl methacrylate imparts decreased water sensitivity but lacks strength and flexibility whereas, the remaining two monomers hydroxy propyl methacrylate and isobornyl methacrylate give the membrane strength and flexibility.
Table 1
Figure imgf000016_0001
Initiator benzoyl peroxide 14.93
Rheology modifier Bentone 38 7.46
Aerosil R 202 2.98
Table 2
Figure imgf000017_0001
The example is tested for elongation (ASTM D638) - the percent increase in length of a membrane before it breaks, and tensile strength (ASTM D638) - the maximum force that a membrane can withstand before breaking expressed in megapascals (Mpa). As illustrated by the results in Table 2, the polymeric structural support membrane achieves the desired tensile strength (greater than 1 MPa after 24 hours) and elongation (greater than about 25% after 24 hours). Therefore, the membrane will display the desired strength and flexibility for an underground structural support. Additionally, the test results demonstrate that the polymeric structural support membrane shows little or no strength loss when exposed to water (moisture sensitivity).
Although the invention has been described in detail through the above detailed description and the preceding formulations and example, these examples are for the purpose of illustration only and it is understood that variations and modifications can be made by one skilled in the art without departing from the spirit and the scope of the invention.

Claims

1. A polymeric excavation structural support membrane comprising a polymer that is an initiator-induced reaction product of a monomer; a self- extinguishing agent; and optionally at least one of a crosslinking agent, a second monomer, a smoke retardant, a rheology modifier, a reaction rate modifier, a plasticizer, an emulsifier, a defoamer, a filler, a wet surface adhesion modifier, and a colouring agent; wherein the monomer is selected from the group consisting of aryloxy alkyl acrylates, aryloxy alkyl methacrylates, and mixtures thereof; wherein the second monomer does not homopolymerize in the presence of the reaction rate modifier or the initiator; and wherein the membrane has a tensile strength, (ASTM D638) greater than 1 MPa after 24 hours and an adhesion strength (ASTM D4142) greater than 0.5 MPa after 24 hours.
2. The polymeric structural support membrane of claim 1, wherein the membrane comprises a polymer that is an initiator induced reaction product of a monomer, a crosslinking agent; a self extinguishing agent; and optionally at least one of a second monomer, a smoke retardant, a rheology modifier, reaction rate modifier, a plasticizer, emulsifier, defoamer, filler, wet surface adhesion modifier, and coloring agent; wherein the monomer is selected from the group consisting of monofunctional aryloxy alkyl acrylates, monofunctional aryloxy alkyl methacrylates, and mixtures thereof.
3. The polymeric structural support membrane of claim 2, wherein the monofunctional aryloxy alkyl methacrylates are selected from the group consisting of 2-phenoxyethyl methacrylate 2-phenoxy-propyl-methacrylate, and mixtures thereof.
4. The polymeric structural support membrane of any one of claims 1-3, wherein, if present, a. the crosslinking agent is present up to 30% by weight of the monomer; b. the rheology modifier is present up to 10% by weight of the monomer; c. the emulsifier is present up to 5% by weight of the monomer; d. the plasticizer is present up to 40% by weight of the monomer; e. the filler is present up to 40% by weight of the monomer; f. the wet surface adhesion modifier is present up to 3% by weight of the monomer; g. the coloring agent is present up to 3% by weight of the monomer; h. the defoamer is present up to 3% by weight of the monomer; i. the reaction rate modifier is present up to 10% by weight of the monomer; and j. the smoke retardant is present up to 10% by weight.
5. The polymeric structural support membrane of any one of claims 1-4, wherein the membrane is characterized by an elongation greater than 25% after 24 hours from being formed.
6. The polymeric structural support membrane of any one of claims 1-5, wherein the membrane is characterized by a water resistance as measured by having less than 5% loss of tensile strength when immersed in water at room temperature for 24 hours (ASTM D870).
7. The polymeric structural support membrane of any one of claims 1-6, wherein the membrane is a reaction product of a first component and a second component; wherein the first component comprises a monomer, a crosslinking agent, a reaction rate modifier, a self-extinguishing agent, a rheology modifier, filler, and a defoamer; and the second component comprises an initiator, a self-extinguishing agent, a rheology modifier, a wet surface adhesion modifier, and a defoamer.
8. The polymeric structural support membrane of claim 7, wherein the first component comprises 2-phenoxyethyl methacrylate, ethoxylated bisphenol A dimethacrylate,
N,N-Dimethyl-P-Toluidine, natural graphite flake, fumed silica, mineral oil, titanium dioxide, zinc borate, smoke retardant, and defoamer; and wherein the second component comprises tri(2-chloroethyl) phosphate, mineral oil, benzoyl peroxide, fumed silica, zinc borate, and defoamer.
9. The polymeric structural support membrane of claim 7, wherein the first component comprises 2-phenoxyethyl methacrylate, at least one of ethoxylated bisphenol A dimethacrylate and trimethylolpropane trimethacrylate, N,N-Dimethyl-P-Toluidine, ethoxylated(4) nonyl phenol (meth)acrylate, monoammonium phosphate, aluminum oxide, fumed silica, mineral oil, titanium dioxide, zinc borate, and defoamer; and wherein the second component comprises monoammonium phosphate, aluminum oxide, mineral oil, benzoyl peroxide, fumed silica, zinc borate, and defoamer.
10. A method of reinforcing exposed surfaces in an excavation with a polymeric structural support membrane comprising: a. applying to the exposed surface a mixture comprising a monomer; an initiator, a self extinguishing agent; and optionally at least one of a crosslinking agent, a second monomer, a smoke retardant, a rheology modifier, reaction rate modifier, a plasticizer, emulsifier, defoamer, filler, wet surface adhesion modifier, and coloring agent; wherein the monomer is selected from the group consisting of aryloxy alkyl acrylates, aryloxy alkyl methacrylates, and mixtures thereof, wherein the second monomer does not homopolymerize in the presence of the reaction rate modifier or the initiator; and b. causing the mixture to react; wherein the membrane has a tensile strength, (ASTM D638) greater than 1 MPa after
24 hours and an adhesion strength (ASTM D4142) greater than 0.5 MPa after 24 hours.
11. A polymeric structural support membrane formed from the process comprising: a. applying to an exposed surface in an excavation a mixture comprising a monomer; an initiator, a self extinguishing agent; and optionally at least one of a crosslinking agent, a second monomer, a smoke retardant, a rheology modifier, reaction rate modifier, a plasticizer, emulsifier, defoamer, filler, wet surface adhesion modifier, and coloring agent; wherein the monomer is selected from the group consisting of aryloxy alkyl acrylates, aryloxy alkyl methacrylates, and mixtures thereof, wherein the second monomer does not homopolymerize in the presence of the reaction rate modifier or the initiator; and b. causing the mixture to react; wherein the membrane has a tensile strength (ASTM D638) greater than 1 MPa after 24 hours and an adhesion strength (ASTM D4142) greater than 0.5 MPa after 24 hours.
PCT/EP2002/001213 2001-02-08 2002-02-05 Polymeric excavation structural support membrane WO2002070591A2 (en)

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