AU2003203844A1 - Method for strengthening geological formations - Google Patents

Method for strengthening geological formations Download PDF

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Publication number
AU2003203844A1
AU2003203844A1 AU2003203844A AU2003203844A AU2003203844A1 AU 2003203844 A1 AU2003203844 A1 AU 2003203844A1 AU 2003203844 A AU2003203844 A AU 2003203844A AU 2003203844 A AU2003203844 A AU 2003203844A AU 2003203844 A1 AU2003203844 A1 AU 2003203844A1
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AU
Australia
Prior art keywords
oil
oils
fatty acid
component
acid triglycerides
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Application number
AU2003203844A
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AU2003203844B2 (en
Inventor
Wolfgang Cornely
Oliver Czysollek
Petra Samek
Wolfgang Schnorbus
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Minova International Ltd
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CARBOTECH FOSROC GmbH
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Publication of AU2003203844A1 publication Critical patent/AU2003203844A1/en
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Assigned to MINOVA INTERNATIONAL LIMITED reassignment MINOVA INTERNATIONAL LIMITED Request for Assignment Assignors: MINOVA CARBOTECH GMBH
Assigned to MINOVA CARBOTECH GMBH reassignment MINOVA CARBOTECH GMBH Request for Assignment Assignors: CARBOTECH FOSROC GMBH
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00Soil-conditioning materials or soil-stabilising materials
    • C09K17/14Soil-conditioning materials or soil-stabilising materials containing organic compounds only
    • C09K17/18Prepolymers; Macromolecular compounds
    • C09K17/30Polyisocyanates; Polyurethanes
    • EFIXED CONSTRUCTIONS
    • E21EARTH OR ROCK DRILLING; MINING
    • E21DSHAFTS; TUNNELS; GALLERIES; LARGE UNDERGROUND CHAMBERS
    • E21D9/00Tunnels or galleries, with or without linings; Methods or apparatus for making thereof; Layout of tunnels or galleries
    • E21D9/001Improving soil or rock, e.g. by freezing; Injections
    • E21D9/002Injection methods characterised by the chemical composition used

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Mining & Mineral Resources (AREA)
  • General Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Consolidation Of Soil By Introduction Of Solidifying Substances Into Soil (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)

Description

AUSTRALIA
PATENTS ACT 1990 COMPLETE SPECIFICATION NAME OF APPLICANT(S):: CarboTech Fosroc GmbH ADDRESS FOR SERVICE: DAVIES COLLISON CAVE Patent Attorneys 1 Little Collins Street, Melbourne, 3000.
INVENTION TITLE: Method for strengthening geological formations The following statement is a full description of this invention, including the best method of performing it known to me/us:- 5102 The invention relates to a method for strengthening geological formations in accordance with the preamble of Claim 1.
From DE 34 33 928 C2 a method is known using polyurethane resin mixtures for strengthening geological formations in black (hard) coal mining. By this method the coal-bearing rock and also the coal are stabilised. In individual cases fires have occurred as a consequence of these applications. These events were found to have been caused since the reaction heat of the hardening resin created favourable conditions for the spontaneous combustion of the coal. The reaction heat and the reaction temperature in polyurethane resin mixtures is a result of the reaction of the polyisocyanate component B and the OH groups of the polyol component A and by the reaction of the polyisocyanates with water. Conventional polyurethane resins for strengthening geological formations contain a significant excess of NCO groups. Thus, in accordance with DE34 33 928 C2, reaction mixtures with an isocyanate index of between 120 and 140 are preferred. Temperatures of between 130 and 150 0 C can occur as reaction temperatures, starting out from approx. 30 0 C. In the event however that water or hydrous substances are added whereby an isocyanate index of approx. 100 results, i.e. stoichiometric turnover, the temperatures can rise up to 180 0
C.
In order to reduce the reaction temperature, a variety of options are known in principle: One option is to admix low-boiling inert substances, for instance fluorocarbons, which evaporate due to the reaction heat generated and due to the enthalpy of vaporisation contribute to reducing the reaction temperature. In addition a "dilution effect" occurs. When applying this 2 method, a light polyurethane foam is produced which in view of itI inferior strength is not suitable for reinforcing rocks.
A further alternative to achieve a reduction in the reaction temperature is the addition of non-volatile inert substances. The easiest method is the addition of liquid inert substances. Towards this end, high-boiling plasticisers are used as a rule of the type customarily applied in the chemistry of plastics.
They can be added to both components. The mechanical properties of the polyurethane resin product are however in most cases impaired thereby, in particular the hardness of the resulting end product deteriorates. In higher concentrations, the inert substance tends to exude from the polymer matrix.
This effect results above all in an undesirable impairment of the adhesion properties.
It is also possible to admix solid fillers of the type customarily used in the chemistry of plastics. Whilst the pressure-related mechanical properties are generally improved thereby, the tension-related properties deteriorate, in particular the adhesion strength of the resins. In practical applications designed to strengthen rocks, it is of a great disadvantage that the solid fillers have the tendency of settling from the liquid phase. A homogenisation of such separated systems in situ is not possible as a rule.
To achieve a stable dispersion is difficult above all in view of the low viscosities required in the pumping and injection technology. Liquids with a viscosity of >1000 mPa s cannot be processed with selfpriming pumps of the type customarily used in injection technology.
A further alternative for temperature reduction is the reduction of the number of reactive groups by using components with higher molecular weight. This can be done simultaneously in both components where, on the polyol side, polyols with a lower OH-content or lower OH-number can be used and, on the isocyanate side, prepolymers, i.e. preadducts between polyol and excess isocyanate, can be used. In this way the viscosity is significantly increased on the one hand, and on the other hand the substances become softer so that upon a significant reduction of the reaction temperature they no longer possess the stiffness required for rock reinforcement.
The decisive factor for the enthalpy of reaction generated is the molar turnover relative to the total mass of the components. The molar turnover is limited by that particular component which contains the lowest number of reactive groups. Reactive groups which represent a stoichiometric excess in the other component do not contribute to the heat evolution. In the event the molecular weight of only one component is increased whilst the volume ratio of I 1 is retained, the stoichiometric ratio, which is expressed by the isocyanate index, is changed. Generally, the isocyanate index in rock strengthening systems is between 120 and 200, i.e. there is an excess of isocyanate, which is either lysed in secondary reactions (allophanate or biuret reaction) or in reactions with water from the environment, if present, or are preserved as unreacted isocyanate group.
In the event the number of reactive groups on the polyol side are reduced, for instance by application of polyols with a lower OH number, and therefore the isocyanate index is increased, this leads to a temperature reduction under laboratory conditions. In practical applications this is however very problematic since the reaction with water from the environment leads to an additional temperature increase. For this reason it is advisable to keep the isocyanate index as low as possible.
If, on the other hand, the number of the reactive groups on the isocyanate side is reduced, for instance by using prepolymers, a reduction of the chemical turnover does not occur and, consequently, also no reduction of the reaction temperature, when starting out from an original isocyanate index of 160 until reaching an isocyanate index of 100 stoichiometric reaction). Only at lower isocyanate indices does a temperature reduction effect occur. The products thereby created are however too soft for rock stabilisation.
It is the object of the invention to provide polyurethane resin mixtures wherein the reaction heat and therefore the reaction temperature are reduced and which react to produce at the same time a polyurethane resin product which is at least equally well suited for the strengthening of geological formations in coal mining, in particular with a view to the adhesion strength, as the traditional polyurethane resin systems. Further aims are easy production, sufficient storage stability as well as easy pumping capability and suitability for application in multiple use container systems customary in coal mining situations.
The object of the invention is achieved by the characteristics of Claim 1.
Further developments are described in the characteristics of the subclaims.
In accordance with the invention, fatty acid triglycerides, which do not contain isocyanate reactive groups are added to the polyisocyanate component B. The fatty acid triglycerides reduce the proportion of the isocyanate groups in the B component, that is the B component is diluted by the fatty acid triglycerides with regard to the isocyanate groups. This dilution effect normally causes, as described above, a lesser adhesion, i.e.
the products obtained are too soft for stabilisations in a mountain.
It was surprisingly found during tests that the addition of fatty acid triglycerides to the isocyanate component only caused an inessential reduction of the mechanical strength.
Fatty acid triglycerides to be considered in the first place are native (virgin) oils, in particular vegetable oils, so for instance olive oil, peanut oil, rape oil, linseed oil, soy oil, sunflower oil and sesame oil. These oils are comparatively inexpensive and easily available. A decisive criterion for the selection of the suitable oil is the proportion of unsaturated fatty acids. Oils with a high proportion of these acids are particularly well suited, since they have a superior solubility in the isocyanate component.
The invention is described below by reference to examples.
Examples The following raw materials were used: Polyol 1: trifunctional polyether polyol based on glycerine and propylene oxide with an OH number of 380 and a viscosity (25 0 C) of 450 mPa s.
Polyol 2 trifunctional polypropylene glycol with an OH number of 27 and a viscosity (25°C) of 1150 mPa s Polyol 3 tetrafunctional polypropylene glycol with an OH number of 60 and a viscosity (25 0 C) of 555 mPa s.
glycerine with an OH number of 1810 and a viscosity (20 0 C) of 1400 mPas dibutyl tin dilaurate
PMDI
polymeric diphenyl methane diisocyanate with an NCO content of 31.5% by weight and with a viscosity (25 0 C) of 200 mPas.
Softener 1 dibutyl phthalate with a viscosity (25°C) of 19 mPas Softener 2 diisopropyl naphthalene with a viscosity (25°C) of 10 mPas Softener 3 terphenyl with a viscosity (25°C) of 92 mPas Softener 4 solvent naphtha with a viscosity (25 0 C) of 800 1000 mPas Softener dioctyladipate with a viscosity (25 0 C) of 14 mPas Triglyceride 1 linseed oil (linum usitatissimum) Triglyceride 2 sunflower oil (helianthus annuus) Triglyceride 3 rape seed oil (brassica oleifera) Triglyceride 4 soy oil (soja hispida) Component A: Component B 1: 28.8 polyol 1 13.8 polyol 2 46.8 polyol 3 softener 1.0 glycerine 0.8 dibutyl tin dilaurate 0.8 water viscosity (25 0 C) 390 mPa s 80 PMDI softener 1 Component B2: Component B3: 80 PMDI softener 2 80 PMDI softener 3 80 PMDI softener 4 80% PMDI softener Component B4: Component B5: Component B6: Component B7: Component B8: 80% PMDI triglyceride 1 80% PMDI triglyceride 2 80 PMDI triglyceride 3 80% PMDI triglyceride 4 Component B9: The polyol components A and the polyisocyanate components B were mixed in a volume ratio 1 1 and the properties of the reaction mixture were determined as follows: Adhesion: A rock prism of the dimensions 160 mm x 40 mm x 40 mm is broken in half and stored for 24 hours at 30 0 C and 80 relative humidity. The fractured surfaces are joined leaving a gap of 3 mm and this gap is sealed with the homogeneous reaction mixtures at a 30 0 C starting temperature. Following storage at 30 0 C and 80 relative humidity, the bonded prism is subjected to a flexural stress test according to DIN EN 196, Part 1, wherein the load increase is 50 10 N/s. The adhesion strength is measured after 30 minutes and after 7 days.
Gross density The gross density is determined from the foam in the joints, whose volume is 3 mm x 40 mm x 40 mm.
Maximum reaction temperature 100 ml of each of the components are homogeneously mixed at 23 °C starting temperature in a 250 ml jar and the temperature change is observed by means of a Ni-Cr-Ni thermo element whose measuring junction is arranged in the centre of the foam and the maximum reaction temperature is determined.
Test results The test recipes were selected such that the stoichiometric ratio of NCO to the OH groups was around 1.45 (isocyanate index 145).
The tests results are specified in the table below Example Recipe Adhesion at 0 C after 30 min [Mpa]
A+BI
A+B2 A+B3 A+ B4 A+B6 A+B7 A+B8 A+B9 Adhesion at 30 0 C after 7 days [Mpa] 1.1 1.6 1.7 1.4 1.5 4.1 4.6 4.8 4.7 Gross density of the foam [kg/m 3 205 220 215 200 220 335 365 360 350 Max reaction temperature 0
C]
103 102 103 104 102 104 103 103 103 Examples 6 to 9 show that with the use of triglycerides in accordance with the invention compared with the use of customarily used commercially available softeners an improvement of the adhesion strength is achieved.
9 Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.
The reference to any prior art in this specification is not, and should not be taken as, an acknowledgement or any form of suggestion that that prior art forms part of the common general knowledge in Australia.

Claims (5)

1. A method for strengthening geological formations in underground black (hard) coal mines by which polyurethane-producing reaction mixtures, which contain a polyol component A and a polyisocyanate component B, are introduced into the formations to be reinforced via previously made boreholes where the reaction mixtures are caused to react, characterised in that fatty acid triglycerides, which do not contain any isocyanate-reactive groups, are added to the polyisocyanate component B.
2. A method according to Claim 1, characterised in that, as the fatty acid triglycerides, native (virgin) oils, in particular vegetable oils, are used.
3. A method according to Claim 2, characterised in that, as the native (virgin) oils, olive oil, peanut oil, rape oil, linseed oil, soy oil, sunflower oil or sesame oil or blends of these oils are used.
4. A method according to claims 1 to 3, characterised in that the fatty acid triglycerides are used at the rate of between I and 30 of the polyisocyanate component B. A method substantially as hereinbefore described with reference to the Examples.
6. The steps, features, compositions and compounds disclosed herein or referred to or indicated in the specification and/or claims of this application, individually or collectively, and any and all combinations of any two or more of said steps or features. DATED this TWENTY THIRD day of APRIL 2003 CarboTech Fosroc GmbH by DAVIES COLLISON CAVE Patent Attorneys for the applicant(s) 5108
AU2003203844A 2002-04-26 2003-04-23 Method for strengthening geological formations Expired AU2003203844B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10218718.5 2002-04-26
DE2002118718 DE10218718C1 (en) 2002-04-26 2002-04-26 Consolidation of geological formation in underground coal mining using a polyurethane-forming mixture of polyol and polyisocyanate components with an added fatty acid triglyceride without isocyanate-reactive groups

Publications (2)

Publication Number Publication Date
AU2003203844A1 true AU2003203844A1 (en) 2003-11-13
AU2003203844B2 AU2003203844B2 (en) 2009-04-02

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Country Status (3)

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AU (1) AU2003203844B2 (en)
DE (2) DE10218718C1 (en)
PL (1) PL203391B1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2470061C2 (en) * 2007-07-05 2012-12-20 Родиа Операсьон Oil composition for preventing influx of water into underground formations

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10218718C1 (en) * 2002-04-26 2003-03-27 Carbotech Fosroc Gmbh Consolidation of geological formation in underground coal mining using a polyurethane-forming mixture of polyol and polyisocyanate components with an added fatty acid triglyceride without isocyanate-reactive groups
EP1805395B1 (en) * 2004-10-21 2010-09-08 Minova International Limited Method for embedding rock anchors
US20070037955A1 (en) * 2005-08-15 2007-02-15 Richards James L Polymeric diluents for structural adhesives
KR100836606B1 (en) 2005-08-15 2008-06-10 롬 앤드 하아스 컴패니 Polymeric diluents for structural adhesives
WO2013073981A1 (en) * 2011-11-15 2013-05-23 Gridnev Alexei Alexeevich Adhesive composition, composite and foam made of this adhesive composition
WO2013115669A1 (en) * 2012-02-02 2013-08-08 Gridnev Alexei Alexeevich Adhesive composition, composite and foam made of this adhesive composition

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3433928C2 (en) * 1984-09-15 1994-01-20 Bergwerksverband Gmbh Process for the consolidation of geological formations
DE3815947C1 (en) * 1988-05-10 1989-10-05 Bayer Ag, 5090 Leverkusen, De
DE10114651C1 (en) * 2001-03-24 2002-05-08 Carbotech Fosroc Gmbh Consolidation of a geological formation in an underground coal mine by introducing a reaction mixture which forms a polyurethane, uses polyol component containing polyether polyol with solid organic filler formed in situ, and plasticizer
DE10218718C1 (en) * 2002-04-26 2003-03-27 Carbotech Fosroc Gmbh Consolidation of geological formation in underground coal mining using a polyurethane-forming mixture of polyol and polyisocyanate components with an added fatty acid triglyceride without isocyanate-reactive groups

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2470061C2 (en) * 2007-07-05 2012-12-20 Родиа Операсьон Oil composition for preventing influx of water into underground formations

Also Published As

Publication number Publication date
DE10315610A1 (en) 2003-11-27
AU2003203844B2 (en) 2009-04-02
PL359835A1 (en) 2003-11-03
DE10315610B4 (en) 2004-04-15
DE10218718C1 (en) 2003-03-27
PL203391B1 (en) 2009-09-30

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Owner name: MINOVA CARBOTECH GMBH

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Owner name: MINOVA INTERNATIONAL LIMITED

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Name of requester: BZ COMMERCIAL FINANCE DESIGNATED ACTIVITY COMPANY

MK14 Patent ceased section 143(a) (annual fees not paid) or expired