WO2021041271A1 - Système de prépolymères monoconstituants pénétrants - Google Patents

Système de prépolymères monoconstituants pénétrants Download PDF

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Publication number
WO2021041271A1
WO2021041271A1 PCT/US2020/047540 US2020047540W WO2021041271A1 WO 2021041271 A1 WO2021041271 A1 WO 2021041271A1 US 2020047540 W US2020047540 W US 2020047540W WO 2021041271 A1 WO2021041271 A1 WO 2021041271A1
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WIPO (PCT)
Prior art keywords
water
soil
foam
aggregates
interstices
Prior art date
Application number
PCT/US2020/047540
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English (en)
Inventor
Peter Kempenaers
Jan LIEKENS
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Gcp Applied Technologies Inc.
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Filing date
Publication date
Application filed by Gcp Applied Technologies Inc. filed Critical Gcp Applied Technologies Inc.
Publication of WO2021041271A1 publication Critical patent/WO2021041271A1/fr

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Classifications

    • E—FIXED CONSTRUCTIONS
    • E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
    • E02D—FOUNDATIONS; EXCAVATIONS; EMBANKMENTS; UNDERGROUND OR UNDERWATER STRUCTURES
    • E02D3/00—Improving or preserving soil or rock, e.g. preserving permafrost soil
    • E02D3/12—Consolidating by placing solidifying or pore-filling substances in the soil
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/302—Water
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
    • C09K17/18—Prepolymers; Macromolecular compounds
    • C09K17/30—Polyisocyanates; Polyurethanes
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21D—SHAFTS; TUNNELS; GALLERIES; LARGE UNDERGROUND CHAMBERS
    • E21D1/00—Sinking shafts
    • E21D1/10—Preparation of the ground
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21D—SHAFTS; TUNNELS; GALLERIES; LARGE UNDERGROUND CHAMBERS
    • E21D9/00—Tunnels or galleries, with or without linings; Methods or apparatus for making thereof; Layout of tunnels or galleries
    • E21D9/001—Improving soil or rock, e.g. by freezing; Injections
    • E21D9/002—Injection methods characterised by the chemical composition used
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/005—< 50kg/m3
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
    • C09K17/48—Organic compounds mixed with inorganic active ingredients, e.g. polymerisation catalysts

Definitions

  • the invention relates to the field of soil or aggregate stabilization, and more particularly to the use of a fast penetrating single component polyurethane prepolymer system for consolidating loose soil and aggregates (e.g . , rock, coal, mineral), especially in subterranean applications such as tunnels and/or mining.
  • a fast penetrating single component polyurethane prepolymer system for consolidating loose soil and aggregates (e.g . , rock, coal, mineral), especially in subterranean applications such as tunnels and/or mining.
  • a method for soil stabilization which entailed the injection of polyurethane prepolymer having terminal isocyanate groups, alone or in admixture with water, obtained by the reaction of compounds having at least two terminal hydroxy groups and a polyoxyalkylene chain with polyisocyanate compounds, in a molar amount at least equal to the number of hydroxyl groups and reacting the polyurethane prepolymer with water in the soil to solidify/stabilize/consolidate the soil.
  • the polyurethane prepolymer within the cavity has a limited distance of travel upon injection, thus decreasing time efficiency of the project.
  • Kubens et al. (Bayer Aktiengesellshaft) disclosed a process for the reinforcement of geological formations and loose rock and earth masses by introducing, into the cavities of the geological formations or rock or earth masses that were required to be reinforced, organic polyhydroxyl compounds and organic poly isocyanates through separate chambers. The constituent compounds reacted in the cavities to form polyurethanes.
  • the reaction process is said to be characterized in that the polyisocyanate component used is a polyisocyanate mixture containing from about 10 to 80%, by weight, of 2,4’- diisocyanato-diphenylmethane.
  • Kubens required the use of a cartridge having two chambers separated from each other, the first chamber containing the polyisocyanate component and the second chamber containing the polyol component. The quantitative proportions of the two components were calculated so that when the cartridge was destroyed, a reaction mixture which reacted to yield a polyurethane was obtained.
  • This two-component type system is disadvantageous due to increased complexity in equipment needed, along with storage and transportation difficulties.
  • very precise quantities of the polyol and polyisocyanate must be used to conduct the appropriate reaction. These precise quantities must be dispensed at the jobsite, thus further relying on the skill of the user/operator.
  • Kubens et al. (Bayer Aktiengesellshaft) disclosed a further process for consolidating geological formations, heaped rock and earth masses which involved applying a polyurethane reaction system.
  • the reaction system comprised a polyisocyanate component and a polyol component containing 5 to 50 wt.% of a special poly ether with an OH number under about 100.
  • This poly ether was said to be produced by the reaction of a compound having more than one reactive hydrogen atom per molecule and a molecular excess of a 1,2-alkylene oxide.
  • the reaction system could also contain conventional polyurethane additives such as foaming agents, fillers, foam stabilizers and catalysts.
  • the special poly ether was produced from ethylene diamine or triethanol amine.
  • Kubens also described that in forming the polyurethane, polyols were typically used having an average molecular weight of 400-600 and an OH number of 350-400. These polyols may be replaced up to about 15% or even completely by a plasticizer, such as castor oil.
  • a plasticizer such as castor oil.
  • castor oils have the disadvantage of relatively high viscosity, which could impede penetration into the smallest cracks and crevices and wetting of the surfaces within the rocks and soil.
  • Kubens also explicitly teaches a two-component type of system where the polyisocyanate and polyol component are injected separately into the geological formations, heaped rock and earth masses.
  • Janssen et al. Minnesota Mining and Manufacturing Company
  • superficial aggregate material e.g., soil and sand
  • a water-insoluble, moisture-curable NCO-terminated prepolymer having defined physical properties.
  • prepolymers are generally very viscous liquids and though they can be used by themselves in its application, it is preferred to employ the same in the form of a solution in a suitable vehicle or solvent which is nonreactive with the isocyanate moiety.
  • organic solvents, or any other organic compounds, which contain active hydrogen atoms are to be avoided in preparing the fluid agent used herein.
  • the solvent or vehicle should contain less than 0.05% by weight of water.
  • these solvents can be either water-miscible or water-immiscible and are preferably volatile at ambient conditions.
  • Representative solvents which can be used include acetone, 2-butanone and other ketones, toluene and other aromatic hydrocarbons, aliphatic hydrocarbons, esters, chlorinated aromatic hydrocarbons and chlorinated aliphatic hydrocarbons, tetrahydrofuran and other known ethers and glycol ethers, dimethyl formamide and other such solvents. See e.g., Col. 2, 11. 20-44.
  • Wiser-Halladay disclosed a method employing what was termed a polyurethane quasi prepolymer for proppant consolidation.
  • This method involved preparing a polyurethane prepolymer for consolidating a proppant in a subterranean formation about a well, employing the improvement characterized by the quasi prepolymer being formed by reacting a diol with a stoichiometric excess of isomeric methylene diphenylene diisocyanate and a diluent; and allowing the reactants to stand for a period in excess of two hours at 25 °C, forming oligomers of polyurethane chains.
  • the method enables consolidating a proppant in fractures by a slow polymerization process, whereby the curing agent can be added at the same time the proppant is placed.
  • diluents and curing agents are also disclosed.
  • Wiser-Halladay specifically taught use of methyl formamide, propylene carbonate, and dimethyl sulfoxide, all of which are hydrophilic in nature. Their hydrophilicities result in dissolution in water, causing the mixture to potentially flow away from the target region in the proppant.
  • GCP Applied Technologies Inc. (current applicant hereof) had developed polyurethane foam-based compositions and methodologies used for stabilizing soils in tunnels, excavations, and other subterranean applications. However, improvements can be made and are disclosed herein.
  • compositions and methodologies for stabilizing loose earthen mass using low-viscosity, water-reactive polyurethane prepolymers are needed.
  • the present invention may address one or more of the problems and deficiencies of the prior art discussed above. However, it is contemplated that the invention may prove useful in addressing other problems and deficiencies in a number of technical areas. Therefore, the claimed invention should not necessarily be construed as limited to addressing any of the particular problems or deficiencies discussed herein.
  • Exemplary embodiments of the current invention are compositions and method for stabilizing loose earthen mass.
  • a single component liquid resin system including a mixture of polyurethane prepolymers and a hydrophobic plasticizer, is prepared and transported to the jobsite.
  • Additives may optionally be included in the mixture of polyurethane prepolymers and plasticizer.
  • the mixture is injected into the loose earthen mass and comes into contact with water, which causes polymerization and expansion of the resin into a polyurethane foam that stabilizes the loose earthen mass.
  • the resulting foam includes unique properties that facilitate the stabilization.
  • An exemplary method of the current invention for stabilizing or reinforcing soil or aggregates in a subterranean formation comprises: infiltrating into interstices between loose particles of the soil or aggregates, a single component liquid resin system comprising a fluid mixture of polyurethane prepolymers and a hydrophobic, water-insoluble plasticizer; and allowing the infiltrated mixture to remain within the interstices to contact water or moisture, causing polymerization and expansion into a polyurethane foam that stabilizes the loose particles of the soil or aggregates, wherein the polyurethane foam has the following properties: a foam penetration of about 10 mm or less at a force of about 28 N or less, a density of about 30 kg/m 3 or more, a compressive strength of about 30 kPa or more, and a heat production of about 150°C or less upon completion of polymerization.
  • Another exemplary method of the current invention for stabilizing or reinforcing soil or aggregates in a subterranean formation comprises: injecting into interstices between loose particles of the soil or aggregates, a single component liquid resin system comprising the following components mixed uniformly together into a pumpable liquid suspension: a polyisocyanate component comprising a methylene diphenylene diisocyanate (“MDI”) compound, a polyol component comprising a polyether polyol compound, wherein the MDI compound is present in an amount of about 40- 70 parts to about 1-20 parts of the poly ether polyol compound, and a hydrophobic, water-insoluble plasticizer component comprising a plasticizer comprising a monoester of benzoic acid and isodecyl alcohol, present in the amount of about 5% to about 80% by weight of the single component liquid resin system; and allowing the infiltrated mixture to remain within the interstices to contact water or moisture, causing polymerization and expansion into a polyurethane foam
  • An exemplary subterranean soil- or aggregate-stabilizing precursor composition of the current invention comprises: a single component liquid resin system that includes polyurethane prepolymers and a hydrophobic, water-insoluble plasticizer, wherein the polyurethane prepolymers are formed by reacting polyol polyether with a stoichiometric excess of methylene diphenyl diisocyanate (MDI) to form both urethane linkage therebetween and residual MDI, the MDI compound is present in an amount of about 40-70 parts to about 1-20 parts of the poly ether polyol compound, and the hydrophobic, water-insoluble plasticizer is a plasticizer comprising a monoester of benzoic acid and isodecyl alcohol, present in the amount of about 5% to about 80% by weight of the single component liquid resin system.
  • MDI methylene diphenyl diisocyanate
  • the Figure is a flowchart depicting a general process utilizing a single component resin system, according to an embodiment of the current invention.
  • any range of numbers recited in the specification or claims, such as that representing a particular set of properties, units of measure, conditions, physical states or percentages, is intended to literally incorporate expressly herein by reference or otherwise, any number falling within such range, including any subset of numbers within any range so recited.
  • any number R falling within the range is specifically disclosed.
  • any numerical range represented by any two values of R, as calculated above, is also specifically disclosed.
  • the present invention teaches a single component water-reactive injection resin for stabilizing or consolidating soil particles, rocks, earth masses, or other loose aggregates in below-grade or subterranean applications, such as tunnels and excavations.
  • the present invention teaches a process of stabilizing or consolidating soil particles, rocks, earth masses, or other loose aggregates in subterranean applications, comprising sealing, strengthening, and consolidating subterranean structures — including but not limited to tunnels, galleries in mines, and loose strata — by injecting a 1 -component, low viscosity water-reactive polyurethane-based injection resin (see the Figure).
  • aggregates refers to particles, rocks, earth masses, strata, stones, slag, gravel, or other material that are in need to be stabilized, consolidated, or otherwise reinforced to form a more homogenous structure between the aggregates.
  • An exemplary single component injectable resin of the present invention comprises polymeric methylene diphenyl diisocyanate (MDI), reaction products of polymeric MDI and polyols and a plasticizer, and combinations thereof.
  • MDI polymeric methylene diphenyl diisocyanate
  • the present invention is a water-reactive composition
  • a water-reactive composition comprising polymeric MDI, polyurethane prepolymers, and a plasticizer, which are injected to seal, consolidate, and strengthen subterranean structures, for example including but not limited to tunnels, mines, soils and loose strata.
  • Certain embodiments of the current invention include single component resins that were surprisingly found to have low viscosity, permitting better permeation and penetration of the injected area or structures. Compared to two component polyurethane injection resins, the current single component resins develop less heat when reacting and curing.
  • compositions and methods discussed herein resulted in unique foam properties upon reaction with water and showed low migration values of substances into the environment when in contact with groundwater or any aquifer in the subterranean structure where it was injected.
  • Certain embodiments of the invention contemplate the on-site formation of a urethane- or urea-based foam via a single component system comprising urethane or urea prepolymers formed from the reaction of polyols or polyamines in an excess of isocyanates, preferably with a viscosity-decreasing amount of hydrophobic plasticizer.
  • urethane- or urea-based refers to a composition containing urethane and/or urea linkages.
  • the resulting prepolymer product is cured on site (i.e., at the site of injection or application), where the residual isocyanate reacts with water on site (i.e.. naturally present, pre-injected, or concurrently injected with the prepolymer) to form urea and/or urethane linkages and release carbon dioxide, resulting in the urethane/urea-based foam.
  • prepolymers refers to monomers, oligomers, or polymers that are capable of further polymerization. Accordingly, prepolymers are present in an intermediate molecular mass state prior to being fully cured. Upon addition of a curing agent, reactive agents within the prepolymers continue to polymerize.
  • polyurethane prepolymers for example include polyol hydroxyl end groups that have been reacted with isocyanate groups, in turn leaving isocyanate functionality at the termini instead of hydroxyls.
  • a reaction of isocyanate and polyols takes place (e.g., within a chemical reactor), where the reaction includes an amount of polyol that is lower than an amount that is stoichiometrically needed to form the full polyurethane polymer. In other words, an excess of isocyanate is reacted with polyols. Upon exposure to water or moisture, polymerization continues, and an expanding polyurethane foam is formed.
  • viscosity refers to a measure of a fluid’s resistance to deformation at a given rate. A liquid with a lower viscosity flows more freely /readily than a liquid with a higher viscosity. Viscosity is typically recorded as centipoise (cps) or mPa-s.
  • the viscosity of a liquid such as the resin containing prepolymers disclosed herein, may be determined by methods known in the art. Within the context of the present disclosure, viscosity measurements are acquired according to ISO 3219:1993 standards, unless otherwise stated. Furthermore, spindle 2 is used for viscosity measurements, at a speed 60 rpm.
  • the resin taught by the present disclosure has a viscosity (at 25°C) of about 200 mPa-s or less, about 180 mPa-s or less, about 160 mPa-s or less, about 140 mPa-s or less, about 120 mPa-s or less, about 100 mPa-s or less, about 80 mPa-s or less, about 60 mPa-s or less, or in a range between any two of these values.
  • the viscosity is between about 60 mPa-s and about 200 mPa-s, more preferably between about 125 mPa-s and about 175 mPa-s at 25°C, or even more preferably between about 135 mPa-s and about 160 mPa-s at 25°C.
  • plasticizer refers to materials that can be added before, during, or after the formation of a liquid resin, in order to decrease the viscosity of the resulting resin.
  • Hydrophobic plasticizers in particular, can be added to alter or improve desirable properties of the resin, for example so that the resin is less likely to wash out or become less diluted when contacting flowing water.
  • the polyurethane prepolymers include isocyanates comprising polymeric MDI, p-phenylenediisocynate (PPDI), isophorone diisocyanate (IPDI), and hydrogenated MDI, among others.
  • the isocyanates comprise polymeric MDI, which is also known to one of ordinary skill in the art as crude MDI.
  • Polymeric MDI may include a blend of 0%-80% of 4,4 methylenediphenyl diisocyanate with 20%-100% of isocyanic acid polymethylenepolyphenylene ester, for example including but not limited to diphenylmethane, isomers thereof, homologues thereof, or combinations thereof.
  • polyurethane prepolymers can be formed from a reaction of an excess of polymeric MDI with polyamines or more preferably polymeric MDI with polyols.
  • the term “excess” refers to an amount of reactant that is beyond what is needed to complete a reaction with a given amount of a limiting reactant.
  • an excess of polymeric MDI may be combined with a given amount of polyether polyol, such that there is residual polymeric MDI remaining after the reaction with the polyol has been completed. This residual isocyanate may then react with water/moisture to form polyurethane/polyurea foam.
  • the excess of polymeric MDI reacted with polyol can be performed at a concentration of about 40-70 parts polymeric MDI reacted with about 1-20 parts of polyol, and preferably about 55-65 parts polymeric MDI reacted with about 5-10 parts of the polyol.
  • the polyurethane prepolymers include polyols comprising, for example, castor oil, polyether polyols, or polyester polyols, among others.
  • the polyols comprise polyether polyols, due to better hydrolytic stability of polymers made with poly ether polyols, though other polyols may be utilized as well.
  • polyether polyols include, but are not limited to, polypropylene oxide homopolymers (PPG polyols), glycerin-based polyethertriols, sucrose-based polyols, sorbitol-based polyols, aminopolyols, Mannich base polyols, or combinations thereof.
  • the polyether polyol preferably comprises glycerin-based polyethertriols.
  • the hydroxyl value of the polyols can be in the range of about 100 -700 mg KOH/g, more preferably in the range of about 300-600 mg KOH/g, and even more preferably in the range of about 360-450 mg KOH/g.
  • the viscosity of the polyols can be in the range of about 60-40000 mPa- s at 25°C, preferably in the range of about 200-2000 mPa-s at 25°C, and even more preferably in the range of about 300-500 mPa-s at 25°C.
  • the molecular weight of the polyols can be in the range of about 100-7000 g/mol, more preferably in the range of about 250-2000 g/mol, and even more preferably in the range of about 350-450 g/mol.
  • the molecular weight of the polyols or polyamines can be in the range of about 100-1000 g/mol, more preferably in the range of about 200-500 g/mol, and even more preferably in the range of about 350-450 g/mol.
  • An example of an amine functional catalyst is diamine, for instance 4,4’-methylenebis(2- chloroanibne) (MBOCA).
  • MOCA 4,4’-methylenebis(2- chloroanibne)
  • a stabilizer can be added to avoid gelation of the reaction mixture and improve stability of the resulting prepolymer. The amount of stabilizer depends on the alkalinity of the used polyol.
  • stabilizers examples include phosphoric acid (in a concentration of about 80%-100%) and benzoylchloride, among other suitable stabilizers. With the stabilizer added, the reaction components (isocyanate + polyol/polyamine) can be mixed at a given temperature.
  • a catalyst can also be added subsequently, for example including but not limited to organometal compounds, tin catalysts and tertiaire amines for about (2) hours with the temperature maintained at about 75°C-85°C.
  • the urethane- or urea-based prepolymers further include a hydrophobic plasticizer to improve (1) ease of injection, (2) penetration and permeation through the target region by reducing the viscosity (i.e., greater distance traveled by lower viscous liquid), and (3) the hydrophobic character of the liquid during application and upon curing.
  • a hydrophobic plasticizer to improve (1) ease of injection, (2) penetration and permeation through the target region by reducing the viscosity (i.e., greater distance traveled by lower viscous liquid), and (3) the hydrophobic character of the liquid during application and upon curing.
  • the enhanced hydrophobic character of the injected/applied liquid composition helps avoid wash out or dilution when the resin is injected into areas with flowing or gushing water, and it will avoid shrinkage of the cured polymer by migration of water soluble ingredients into the environment.
  • the choice of the right plasticizer contributes to the desired foam properties after curing.
  • hydrophobic plasticizers examples include, but are not limited to, phthalates such as diisononylphthalate (DINP) and diisodecylphthalate (DIDP); 1,2 cy cl ohexanedi carboxylic acid, dinonylester, branched or linear (DINCH); citrates such as acetyltributylcitrate; maleates such as diethylmelate, dipropylmaleate, dibutylmaleate, and dipentylmaleate; adipates such as dioctyladipate and dimethyladipate; succinates such as dimethylsuccinate, diisobutylsuccinate, and dioctylsuccinate; butyrates such as 2,2,4 trimethyl-1,3 pentanediol diisobutyrate; propylene carbonate; dibasic ester; sebacates such as dibutyls
  • the plasticizer comprises phthaltes, terephthalates, citrates, adipates, benzoates, maleates. Even more preferably, the plasticizer comprises benzoic acid, C9- Cll, branched alkyl esters (e.g, a monoester of benzoic acid and isodecyl alcohol (JAYFLEX MB 10)). It is contemplated herein that each of the foregoing plasticizers sufficiently decreases viscosity of the liquid composition that is applied on-site and also is sufficiently hydrophobic for the purposes stated herein.
  • the amount of plasticizer utilized can be about 5-80% by weight, preferably about 15-55% by weight, and even more preferably about 35-45% by weight of the liquid resin system.
  • the term “sufficiently hydrophobic” refers to a measurement of the ability of a material or composition to repel water, to the extent that the material helps avoid wash out or dilution when the composition (including the hydrophobic element) is injected into areas with flowing or gushing water, and avoid shrinkage of the cured polymer by migration of water soluble ingredients into the environment.
  • the composition Upon preparation of the urethane- or urea-based prepolymer composition, the composition is transported to the jobsite for injection or application to a target region in need of that is in need of solidification, stabilization, consolidation, or reinforcement.
  • an accelerator for reactivity control and surfactants e.g., silicone surfactant
  • these components are known to the skilled persons in polyurethane technology and comprise catalysts, such as but not limited to tertiary amines, organometal compounds, dibutyltindilaurate, dibutyltinoctoate and polyethersilicones as foam stabilizers.
  • Preferred accelerators are available from GCP APPLIED TECHNOLOGIES under the trade names HA CUT CAT AF and HA CUT CAT SXF AF.
  • the prepolymer composition water reacts with the composition and functions as a curing agent, stimulating expansion of the composition and forming a foam resin.
  • This foam resin has a high compressive strength and stabilizes/reinforces the target region by consolidating soil and/or loose strata and rocks within the target region. It can be understood that the source of water is dependent on need and characteristics of the target region. If the target region has flowing or exposed water, then an external source of water may not be necessary, as the prepolymer composition can react with the water naturally present within the target region. On the other hand, if the target region does not contain available water or moisture, then an external source of water may be used for curing the prepolymer composition.
  • module and “compressive strength” refer to the capacity of a material to withstand loads or forces intended to compress the material. Compressive strength is typically recorded as kPa and may be determined by methods known in the art. Within the context of the present disclosure, compressive strength measurements are acquired according to ISO 844:2014 standards, unless otherwise stated.
  • the polyurethane foam taught by the present disclosure has a compressive strength of about 30 kPa or more, 40 kPa or more, 50 kPa or more, 60 kPa or more, 70 kPa or more, 80 kPa or more, 90 kPa or more, 100 kPa or more, 110 kPa or more, or in a range between any two of these values.
  • the term “density” refers to a measurement of the mass per unit volume of a material (e.g., foam) or composition (e.g., prepolymer).
  • a material e.g., foam
  • composition e.g., prepolymer
  • density generally refers to the true density of a polyurethane foam material. Density is typically recorded as kg/m 3 or g/cc. The density of a foam may be determined by methods known in the art. Within the context of the present disclosure, density measurements are acquired according to ISO 845:2006 standards, unless otherwise stated.
  • the foam taught by the present disclosure has a density of about 20 kg/m 3 or more, about 30 kg/m 3 or more, about 40 kg/m 3 or more, about 50 kg/m 3 or more, about 60 kg/m 3 or more, about 70 kg/m 3 or more, about 80 kg/m 3 or more, about 90 kg/m 3 or more, or in a range between any two of these values.
  • the term “foam penetration” refers to a measurement of the distance that an object can pierce or enter into a foam without damaging or tearing the skin of the foam. Foam penetration is recorded herein in millimeters (mm) and the force at which the skin breaks is recorded in Newtons (N). Unless otherwise stated, the foam penetration is measured herein through indentation of a foam with a test probe.
  • the test probe used herein is a cylindrical stainless steel probe that is about 60 mm long, with a flat contact surface and a diameter of about 15 mm. The probe is fixed to a load cell of about 5000-N capacity, and the penetration rate is 5 mm/min.
  • the test temperature of material and equipment is 23°C + 2°C.
  • the foam taught by the present disclosure has a foam penetration of about 10.0 mm or less, about 9.5 mm or less, about 9.0 mm or less, about 8.5 mm or less, about 8.0 mm or less, about 7.5 mm or less, about 7.0 mm or less, about 6.5 mm or less, about 6.0 mm or less, about 5.5 mm or less, about 5.0 mm or less, about 4.5 mm or less, about 4.0 mm or less, about 3.5 mm or less, about 3.0 mm or less, about 2.5 mm or less, or in a range between any two of these values.
  • foam penetration is between about 2.5 mm and about 8.5 mm at a force of about 28 N or less.
  • the term “susceptibility to migration into water” refers to the likelihood of a foam’s soluble components migrating into or with water that contacts the foam. Susceptibility to migration into water is recorded herein as mgC/dm 2 .day and typically decreases upon subsequent test cycles due to a majority of the soluble components migrating into water during the first test cycle. Within the context of the present disclosure, measurements of susceptibility to migration into water are acquired according to EN 12873-2, unless otherwise stated.
  • the foam taught by the present disclosure has a susceptibility to migration into water of about 10 mgC/dm 2 .day or less after the first test cycle, 8 mgC/dm 2 .day or less, 6 mgC/dm 2 .day or less, 4 mgC/dm 2 .day or less, 2 mgC/dm 2 .day or less, 1 mgC/dm 2 .day or less, 0.8 mgC/dm 2 .day or less, 0.6 mgC/dm 2 .day or less, 0.4 mgC/dm 2 .day or less, 0.2 mgC/dm 2 .day or less, 0.1 mgC/dm 2 .day or less, or in a range between any two of these values.
  • the term “heat production” refers to the internal core temperature of a foam upon completion of polymerization (i.e., expansion of foam has ceased). Heat production is typically recorded as °C and is measured by inserting a temperature probe/sensor into the substantial center of the foam.
  • the foam taught by the present disclosure has a heat production of about 150°C or less, about 140°C or less, about 130°C or less, about 120°C or less, about 110°C or less, about 100°C or less, about 90°C or less, about 80°C or less, about 70°C or less, about 60°C or less, about 50°C or less, or in a range between any two of these values.
  • heat production is between about 50°C and about 100°C. It should be noted that in many countries, regulations permit up to about 140°C for mining applications, where certain embodiments of the current invention can be effectively utilized.
  • additives may be added at certain points during the foregoing process.
  • the term “additive” refers to materials that can be added to a composition before, during, or after production of the prepolymer composition or formation of the foam. Additives can be added to alter or improve desirable properties in the prepolymer composition or in the foam, or to counteract undesirable properties therein.
  • additives includes, but are not limited to, fillers, UV stabilizers, degassers, antistatic agents, plasticizers, accelerants, catalysts, stabilizers, fire retardants, pH adjusters, reinforcing agents, thickening or thinning agents, elastic compounds, radiation absorbing or reflecting compounds, and other additives known in the art.
  • Example 1 To obtain polyurethane prepolymers according to an embodiment of the current invention, an excess of polymeric MDI (e.g., SUPRASEC 5025, VORANATE M220, or similar) was reacted with a stochiometrically limiting amount of polyether polyol (e.g, DESMOPHEN 1400BT, CARADOL ET380, or similar), at a concentration of about 59.5 parts polymeric MDI reacted with about 4.5 parts of polyether polyol.
  • the polyether polyol was characterized by a hydroxyl value of about 400 mg KOH/g, a viscosity of about 400 mPa-s at 25°C, and a molecular weight of about 420 g/mol.
  • the polymeric MDI was mixed with the polyether polyol for about two (2) hours at a temperature of about 75°C-85°C.
  • the head space in the reaction recipient was filled with nitrogen gas to avoid unwanted side reactions of air moisture with the polymeric MDI.
  • a viscosity -reducing hydrophobic plasticizer comprising a monoester of benzoic acid and isodecyl alcohol (JAYFLEX MB 10) was added at an amount of about 36% by weight.
  • Example 2 To obtain polyurethane prepolymers according to an embodiment of the current invention, an excess of polymeric MDI (e.g., SUPRASEC 5025, VORANATE M220, or similar) was reacted with a stochiometrically limiting amount of polyether polyol (e.g., PETOL PZ 4004G or similar), at a concentration of about 59.5 parts polymeric MDI reacted with about 4.4 parts of polyether polyol.
  • the polyether polyol was characterized by a hydroxyl value of about 400-450 mg KOH/g, a viscosity of about 5175 mPa-s at 25°C, and a molecular weight of about 630 g/mol.
  • the polymeric MDI was mixed with the polyether polyol for about two (2) hours at a temperature of about 75°C-85°C.
  • the head space in the reaction recipient was filled with nitrogen gas to avoid unwanted side reactions of air moisture with the polymeric MDI.
  • a viscosity-reducing hydrophobic plasticizer comprising 2,2,4-trimethyl-l,3-pentanediol diisobutyrate was added at an amount of about 36% by weight.
  • Example 3 To obtain polyurethane prepolymers according to an embodiment of the current invention, an excess of polymeric MDI (e.g., SUPRASEC 5025, VORANATE M220, or similar) was reacted with a stochiometrically limiting amount of polyether polyol (e.g., PETOL PS 400 4G or similar), at a concentration of about 59.5 parts polymeric MDI reacted with about 4.4 parts of polyether polyol.
  • the polyether polyol was characterized by a hydroxyl value of about 400-450 mg KOH/g, a viscosity of about 4000 mPa-s at 25°C, and a molecular weight of about 630 g/mol.
  • the polymeric MDI was mixed with the polyether polyol for about two (2) hours at a temperature of about 75°C-85°C.
  • the head space in the reaction recipient was filled with nitrogen gas to avoid unwanted side reactions of air moisture with the polymeric MDI.
  • a viscosity-reducing hydrophobic plasticizer comprising 2,2,4-trimethyl-l,3-pentanediol diisobutyrate was added at an amount of about 36% by weight.
  • Example 4 To obtain polyurethane prepolymers according to an embodiment of the current invention, an excess of polymeric MDI (e.g., SUPRASEC 5025, VORANATE M220, or similar) was reacted with a stochiometrically limiting amount of poly ether polyol (e.g., PETOL PM 410N or similar), at a concentration of about 59.5 parts polymeric MDI reacted with about 4.4 parts of polyether polyol.
  • the polyether polyol was characterized by a hydroxyl value of about 400-440 mg KOH/g, a viscosity of about 10400 mPa-s at 25°C, and a molecular weight of about 530 g/mol.
  • the polymeric MDI was mixed with the polyether polyol for about two (2) hours at a temperature of about 75°C-85°C.
  • the head space in the reaction recipient was filled with nitrogen gas to avoid unwanted side reactions of air moisture with the polymeric MDI.
  • a viscosity-reducing hydrophobic plasticizer comprising 2,2,4-trimethyl-l,3-pentanediol diisobutyrate was added at an amount of about 36% by weight.
  • Example 5 To obtain polyurethane prepolymers according to an embodiment of the current invention, an excess of polymeric MDI (e.g., SUPRASEC 5025, VORANATE M220, or similar) was reacted with a stochiometrically limiting amount of polyether polyol (e.g., PETOL PA450-3T or similar), at a concentration of about 59.5 parts polymeric MDI reacted with about 4.4 parts of polyether polyol.
  • the polyether polyol was characterized by a hydroxyl value of about 400-500 mg KOH/g, a viscosity of about 380 mPa-s at 25°C, and a molecular weight of about 375 g/mol.
  • the polymeric MDI was mixed with the polyether polyol for about two (2) hours at a temperature of about 75°C-85°C.
  • the head space in the reaction recipient was filled with nitrogen gas to avoid unwanted side reactions of air moisture with the polymeric MDI.
  • a viscosity-reducing hydrophobic plasticizer comprising 2,2,4-trimethyl-l,3-pentanediol diisobutyrate was added at an amount of about 36% by weight.
  • Example 6 (comparative).
  • polymeric MDI e.g., SUPRASEC 5025, VORANATE M220, or similar
  • the polymeric MDI was stored for about two (2) hours at a temperature of about 75°C-85°C.
  • the head space in the reaction recipient was filled with nitrogen gas to avoid unwanted side reactions of air moisture with the polymeric MDI.
  • a viscosity-reducing hydrophobic plasticizer comprising 2,2,4-trimethyl-l,3-pentanediol diisobutyrate was added at an amount of about 36% by weight vs about 64% of polymeric MDI.
  • Example 7 (comparative].
  • polymeric MDI e.g., SUPRASEC 5025, VORANATE M220, or similar
  • polyether polyol e.g, DESMOPHEN 1400 BT, PETOL 400-3 or similar
  • the polyether polyol was characterized by a hydroxyl value of about 400 mg KOH/g, a viscosity of about 400 mPa-s at 25°C, and a molecular weight of about 420 g/mol.
  • the polymeric MDI was mixed with the polyether polyol for about two (2) hours at a temperature of about 75°C-85°C.
  • the head space in the reaction recipient was filled with nitrogen gas to avoid unwanted side reactions of air moisture with the polymeric MDI.
  • a viscosity-reducing hydrophilic plasticizer comprising propylene carbonate was added at an amount of about 36% by weight.
  • the polyurethane prepolymers — containing a reaction mixture of isocyanates, polyols, and plasticizers — is characterized by about 59.5% isocyanate by weight, about 4.5% polyol by weight, and about 36.0% plasticizer by weight.
  • Viscosity Brookfield viscosity was measured according ISO 3219: 1993 and was found to be about 135-160 mPa-s at 25°C for the polyurethane prepolymers, inclusive of the isocyanates, polyols, and plasticizers.
  • the prepared resin comprising the polyurethane prepolymers are subsequently transported to the jobsite and injected into the target region.
  • the source of the curing agent water/moisture
  • the nature of the target region i.e.. whether water/moisture is naturally present in the target region).
  • Foam Penetration Foam penetration was measured through indentation with a test probe.
  • a foam of the prepared resin was made by mixing about 50 grams resin with about 5 grams accelerator (HA CUT CAT AF) in an open cup. Subsequently, about 2 grams water was added, and the liquid was stirred with a wooden spoon until the foaming (i.e.. expansion) started. The foam was allowed to rise/expand, and after curing, the foam was stored in lab conditions at about 20°C-22°C at approximately 50% relative humidity (RH) for 24 hours. For example, the cured foam of Example 1 was found to have an indentation of about 1.5-3.5 mm at a maximum force of about 20-25 N.
  • a foam of the prepared resin was made by mixing 50g resin with 5g of HA CUT CAT SXF AF. Subsequently, about 2g water was added, and the liquid was stirred with a wooden spoon until the foaming (i.e. , expansion) started. The foam was allowed to cure at about 20°C-22°C at approximately 50% RH for 24 hours. For example, the cured foam of Example 1 was found to have an indentation of about 7-10 mm at a maximum force of 25-30 N.
  • Foam Density and Compressive Strength Foam density was measured according ISO 845:2006, and compressive strength was measured according ISO 844:2014.
  • the foam was prepared as follows: about 125 grams of the prepared resin was mixed in an open cup with about 12.5 grams accelerator, preferably HA CUT CAT AF or HA CUT CAT SXF AF. Subsequently, about 6.25 grams water was added to the mixture, followed by 15 seconds of mixing with an overhead stirrer at 1000 rpm. A cylindrical tube with a diameter of about 10 cm and a height of about 40 cm was placed over the recipient, allowing the foam to rise within the cylinder. The foam was allowed to cure at about 20°C-22°C at approximately 50% RH for 24 hours. Subsequently, the foam cylinder is cut to form test foam cylinders each having a height of about 10 cm. The compressive strength was measured at 10% deformation.
  • Example 1 the foam that was prepared with HA CUT CAT AF as accelerator has a foam density of about 35-45 kg/m 3 measured according ISO 845:2006 and a compressive strength of about 30-35 kPa measured according to ISO 844:2014.
  • the foam of Example 1 that was prepared with HA CUT CAT SXF as accelerator has a foam density of about 30-40 kg/m 3 measured according ISO 845:2006 and a compressive strength of about 40-50 kPa measured according to ISO 844:2014.
  • the migration of the foam of Example 1 measured according to EN12873-2 was found to be less than about 20 mgC/dm 2 .day after the first test cycle, less than about 2 mgC/dm 2 .day after the second test cycle, and less than about 1 mgC/dm 2 .day after the third test cycle.

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Abstract

L'invention concerne une composition et un procédé permettant de stabiliser ou de consolider un sol, une roche, du charbon, un minéral ou d'autres agrégats meubles, en particulier dans un environnement souterrain. Un mélange d'hydrogonflement de prépolymères de polyuréthannes et d'un plastifiant hydrophobe est injecté ou pompé dans les interstices d'agrégats meubles. Le mélange est un système monoconstituant et présente une faible viscosité. Le mélange réagit avec l'eau qui est naturellement présente dans l'environnement souterrain ou avec l'eau qui est simultanément introduite par pompage, avant ou en même temps que le mélange. Après la réaction, le produit polymérise et gonfle afin de donner une mousse de polyuréthanne, dans le but de stabiliser les agrégats meubles.
PCT/US2020/047540 2019-08-26 2020-08-21 Système de prépolymères monoconstituants pénétrants WO2021041271A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4114382A (en) * 1974-07-26 1978-09-19 Bayer Aktiengesellschaft Process for the consolidation of geological formations and loosened rock and earth masses
US4475847A (en) * 1981-10-03 1984-10-09 Bergwerksverband Gmbh Process for consolidation and sealing of geological formations and artificial beds of rock, earth, and coal
US4904125A (en) * 1988-05-10 1990-02-27 Bayer Aktiengesellschaft Process for strengthening geological formations
AU2001260175B2 (en) * 2000-04-13 2005-07-21 Bayer Aktiengesellschaft Polyurethane foams with reduced exothermy
JP2010031280A (ja) * 2009-07-30 2010-02-12 Daido Kasei Kogyo Kk 一液湿気硬化型道床安定剤
US20150322314A1 (en) * 2013-01-25 2015-11-12 Henkel Ag & Co. Kgaa Moisture-Curing Polyurethane Composition Comprising Sustainably Produced Raw Materials
CN107083228A (zh) * 2017-04-28 2017-08-22 上海鹤城高分子科技有限公司 一种单组份透明不黄变聚氨酯密封胶及其制备方法
RU2641553C1 (ru) * 2016-12-30 2018-01-18 Федеральное государственное бюджетное учреждение науки Институт горного дела им. Н.А. Чинакала Сибирского отделения Российской академии наук (ИГД СО РАН) Полимерный состав для изоляции и укрепления горных пород

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4114382A (en) * 1974-07-26 1978-09-19 Bayer Aktiengesellschaft Process for the consolidation of geological formations and loosened rock and earth masses
US4475847A (en) * 1981-10-03 1984-10-09 Bergwerksverband Gmbh Process for consolidation and sealing of geological formations and artificial beds of rock, earth, and coal
US4904125A (en) * 1988-05-10 1990-02-27 Bayer Aktiengesellschaft Process for strengthening geological formations
AU2001260175B2 (en) * 2000-04-13 2005-07-21 Bayer Aktiengesellschaft Polyurethane foams with reduced exothermy
JP2010031280A (ja) * 2009-07-30 2010-02-12 Daido Kasei Kogyo Kk 一液湿気硬化型道床安定剤
US20150322314A1 (en) * 2013-01-25 2015-11-12 Henkel Ag & Co. Kgaa Moisture-Curing Polyurethane Composition Comprising Sustainably Produced Raw Materials
RU2641553C1 (ru) * 2016-12-30 2018-01-18 Федеральное государственное бюджетное учреждение науки Институт горного дела им. Н.А. Чинакала Сибирского отделения Российской академии наук (ИГД СО РАН) Полимерный состав для изоляции и укрепления горных пород
CN107083228A (zh) * 2017-04-28 2017-08-22 上海鹤城高分子科技有限公司 一种单组份透明不黄变聚氨酯密封胶及其制备方法

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