CN1067737C - Injection-type chemical composition for stabilization and reinforcement process using same - Google Patents
Injection-type chemical composition for stabilization and reinforcement process using same Download PDFInfo
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- CN1067737C CN1067737C CN92103414A CN92103414A CN1067737C CN 1067737 C CN1067737 C CN 1067737C CN 92103414 A CN92103414 A CN 92103414A CN 92103414 A CN92103414 A CN 92103414A CN 1067737 C CN1067737 C CN 1067737C
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 102100029028 Protoporphyrinogen oxidase Human genes 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- 241001074085 Scophthalmus aquosus Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical group C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003818 cinder Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 description 1
- 229940099364 dichlorofluoromethane Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- SHWINQXIGSEZAP-UHFFFAOYSA-N dimethyl heptanedioate Chemical compound COC(=O)CCCCCC(=O)OC SHWINQXIGSEZAP-UHFFFAOYSA-N 0.000 description 1
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical class [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036449 good health Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- NVQBAIMDGFLXBX-UHFFFAOYSA-N phosphoric acid;prop-1-ene Chemical compound CC=C.OP(O)(O)=O NVQBAIMDGFLXBX-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Consolidation Of Soil By Introduction Of Solidifying Substances Into Soil (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
An injection-type chemical composition comprises (A) an aqueous solution of alkali metal salt of silicic acid and (B) an organic polyisocyanate compound. The composition is used for the consolidation and stabilization of instable parts on rock mass, ground or artificial structure. A reinforcement method using the composition is further provided. The aqueous solution of alkali metal salt of silicic acid (A) is compatible with the organic polyisocyanate compound (B). The composition is suitable for the rock mass, ground or artificial structure, and has good penetrability to the rock mass and the like. The reinforced composite has high strength, ensuring the construction to be carried out safely.
Description
The present invention relates to a kind of reinforcing perfusion type Chemical composition that, it can be used for reinforcing with stable as the rock mass or the unsettled soft foundation that have crack area; Percolating water can take place or rock mass that water outwards overflows be arranged or the current in the ground in blocking-up; Artificial structure's thing with crack or slit such as the slit in the concrete structure are carried out reinforcement means such as packing.The invention still further relates to a kind of method of using above-mentioned Chemical composition that to reinforce.
A kind of as the stabilization and reinforcement facture in crack in the packing artificial structure thing or slit pours into inorganic or organic slurry has been that people use at present, and can obtain effect preferably to a certain extent.
Yet, when above-mentioned this method for filling is carried out scrutiny, can find to obtain satisfied effect.Such as, because be in suspended state in use as widely used cement paste, therefore its be penetrated into the crack in rock mass or the artificial structure's thing or the ability that resembles in the sandy ground basic unit just very poor, and curing rate is slower, needs could to obtain for a long time the intensity of being satisfied with like this.Therefore, use above-mentioned cement grout not reach in construction of tunnel or underground excavation project, to make its purpose of in a short time unstable ground being stablized and reinforced, above-mentioned engineering then to need in a short time apace and reach certain intensity ground stabilization.In addition, when percolating water occurring or have water to overflow, above-mentioned cement injection slurries just can be diluted by water, and outwards flow out.On the other hand, when using water glass dual-fluid system slurries as typical case's representative of inorganic slurry to carry out reperfusion reinforcement, then this slurries firming body intensity is very low, as 3-10kg/cm
2In addition, As time goes on, because above-mentioned firming body can contact meeting its main component of elution such as Na with water
2O and SiO
2Thereby, cause highly basic to pollute, or its intensity reduces greatly.
Organic slurry such as urea slurries, its solidification intensity is very poor, and has cure component or assistant, as sulfuric acid and the eluted shortcoming of formalin.At the special public clear 63-63687 of JP, or the special public clear 63-63688 of JP, the clear 63-7413 of TOHKEMY, the clear 63-7491 of TOHKEMY, the clear 63-8477 of TOHKEMY also discloses a kind of reinforcement means in these several pieces of patent documentations of the clear 63-35913 of TOHKEMY, and this method is a kind of can curing fast of perfusion, hard and expandable urethane is to reinforce rock mass, and the main component that above-mentioned urethane is is polyol and PIC.Though said method wishes to obtain good consolidation effect, above-mentioned urethane is tied to form this too costliness, and easy firing, need be to improve to above-mentioned urethane with regard to economy and safety perspective therefore.
A kind of perfusion type Chemical composition that is also disclosed in the clear 61-9482 of TOHKEMY and these two pieces of patent documentations of the clear 55-160079 of TOHKEMY, this Chemical composition that comprises PIC and water glass (sodium silicate aqueous solution), above-mentioned water glass comprises the Mannich salt as the trimer catalyst of above-mentioned PIC, as specific tertiary amine or amino alcohol.Though above-mentioned composition is nonflammable, still need the trimer catalyst of use cost costliness.In addition, in order to improve the flowability of PIC, also need to use a large amount of organic solvents to dilute above-mentioned PIC.In addition, because the capacitive of tertiary amine or amino alcohol and PIC or water glass is very poor, when above-mentioned two kinds of compositions mixed, they can be separated from one another immediately.In order to improve above-mentioned capacitive, then need to use the compound that involves great expense, such as the silicon polyol, and this compound cost is very expensive.
The object of the present invention is to provide a kind of perfusion type Chemical composition that, use it can obtain good effect, such as in the stabilization and reinforcement method of rock mass, ground and artificial structure's thing, and during the current in rock mass, ground and the artificial structure's thing are blocked, good solidification intensity is obtained in the capital, advantages of excellent stability and reinforcing property, long-term durability, and placeability is good, and is safe and economical.
Another object of the present invention is to provide a kind of method of utilizing mentioned component that rock mass, ground, artificial structure's thing are reinforced.
Above-mentioned purpose and other purpose of the present invention can draw in the following description easily.
At the problem that exists in the above-mentioned prior art, the present invention explores, find now when pour into comprise the perfusion type Chemical composition that of special component and form expansion inorganic-during organic composite curing body, can rock mass, ground and artificial structure's thing stable, reinforce and the processing procedure of blocking-up current wherein in reach good effect, as good solidification intensity, reliably stability and good reinforcing property, long-term durability, and placeability is good, economy and safety.
Reinforcing of the present invention comprises with perfusion type Chemical composition that:
A, silicate base aqueous metal salt;
B, organic polyisocyanate compounds.
Reinforcement means of the present invention comprises:
Above-mentioned composition is filled in rock mass, ground or the artificial structure's thing, above-mentioned composition is solidified or the shutoff crack.
Fig. 1 is the schematic cross-section that is used for the Rock anchor of one embodiment of the invention, and wherein label 1 is a Rock anchor, and label 5 is a perfusion type Chemical composition that of the present invention.
Here term " is blocked " to look like and is: fill a hole or crack with a kind of as composition, to stop up this hole or crack.
As mentioned above, perfusion type Chemical composition that of the present invention comprise (A), silicate base aqueous metal salt and (B), organic polyisocyanate compounds.
The above-mentioned aqueous solution (A) mainly is the silicic acid anhydride one urethane complex that forms by the isocyanates radical reaction in silanol group in the composition (A) and the composition (B).As composition (A), can use commercially available potassium silicate in market or silicate of soda as main component.And among them, use silicate of soda then better.Above-mentioned silicate of soda is a kind of mixture by following molecular formula statement: Na
2OXSinH
2O, wherein Na
2O and SiO
2Molar ratio be 2: 1-1: 4.The solid concentration of the best above-mentioned aqueous solution is counted by weight percentage and is 10%-70%, and is then best during 20%-40%.
Organic polyisocyanate compounds (B) has such character, composition (A) and the following tertiary amine that will describe (D) can be scatter equably or makes its emulsification, perhaps makes composition (A), (B) and (D) reacts equably.Preferably use organic PIC as composition (B).This organic PIC can be for example polymethylene polyphenylene PIC, the liquid methyl diphenylene diisocyanate, toluene di-isocyanate(TDI), natural toluene-2,4-diisocyanate, the xylyl vulcabond, IPDI, naphthalene diisocyanate, hydrogenated diphenyl methane diisocyanate.Above-mentioned PIC can be used alone or as a mixture.
Also can use urethane prepolymer as composition B in addition, this urethane prepolymer can be by obtaining above-mentioned organic PIC and polyoxyalkylene list alcohol or polyol reaction, and above-mentioned reaction can be undertaken by general fashion, and its NCO/OH equivalent proportion is 1.5-100, is preferably 2.0-50.Polyoxyalkylene list alcohol or polyol can pass through single alcohol (monool), dihydroxyl compound (diol), the composition of polyol (polyol) or above-claimed cpd and alkylene oxide carry out the known processing of polymerization once more and obtain, and this alkylene oxide can be oxirane, propylene oxide, butylene oxide, the composition of styrene oxide or above-claimed cpd, above-mentioned single alcohol can be methyl alcohol, ethanol, propyl alcohol, butanols, octanol or lauryl alcohol, above-mentioned dihydroxyl compound can be 1, the 2-ethylidene glycol, propane diols, 1, the 3-butanediol, 1,4-butanediol or 1,6-hexylene glycol, above-mentioned polyol can be glycerine, trimethylolpropane, pentaerythrite, diethanolamine, triethanolamine, diglycerol, anhydro sorbitol, sucrose.Preferably use polyethyleneglycol alcohol or polyol, count by weight percentage, the dioxy base chain that this compound had accounts for more than 5% of its oxyalkylene chain, is preferably 10%-100%.The above-mentioned urethane prepolymer that obtains usually has the NCO that does not react at its end.
Enter the main chain of urethane prepolymer by guiding dioxy base chain, can make above-mentioned prepolymer possess hydrophilic property, thereby can improve the capacitive of this urethane prepolymer and silicate base aqueous metal salt greatly, therefore can not take place employed composition can not be in grouting equipment well-mixed phenomenon, and this phenomenon can often take place when construction, adds solid uniformly thereby can form.In addition, in place when construction that the frequent seepage of water is arranged, also be well, and above-mentioned slurries can bond very firmly with above-mentioned rock mass, ground or artificial structure's thing after solidifying to the conformability of wet rock mass, ground or artificial structure's thing.
The consumption of composition (B) can be according to Na in composition (A) etc.
2O and SiO
2Ratio and change, therefore can not generally provide.Preferably composition (A) is 10/100-100/10 with the weight ratio of composition (B), and is then better when this ratio is between 20/100-100/20 certainly.When above-mentioned ratio less than 10/100 the time, then can make the composition cost costliness that is obtained, uneconomical, and the usage ratio grouting pump can be difficult to this weight ratio is controlled in the implementation process; On the other hand, when above-mentioned ratio greater than 100/10 the time, the perfusion Chemical composition that is then obtained can not fully solidify, that is to say that said composition can not be solidified, even said composition is solidified, the hardness of formed firming body is also very low, and frangible, so its exploitativeness is very poor.
According to the present invention, above-mentioned reinforcing with perfusion type Chemical composition that except that comprise mentioned component (A) and (B), also can comprise having expandable thinner (C).
The heat that this inflatable thinner (C) produces after can reacting owing to composition (A) with (B) volatilizees, formed so inorganic-organic complex just can expand, its volume is several times to tens times of original volume, this complex just can be penetrated in rock mass or the ground fully like this, has consequently increased the intensity of rock mass owing to the anchoring effect of above-mentioned slurries solidifying body.In addition, before expanding, above-mentioned thinner (C) has reduced the viscosity of said composition as composition (A) and thinner (B), and Chemical composition that just can be penetrated in the rock mass at an easy rate like this.
Expandable thinner (C) can be: acetone for example, butanone, carrene, trichloroethanes, a trifluorotrichloroethane, dicholorodifluoromethane, dichlorofluoromethane, dichlorotrifluoroethane, butane, pentane, hexane etc.The consumption of best mentioned component (C) and the weight ratio height to 50 of composition (A) and total consumption (B): 100.In general, because mentioned component (C) presents inertia in composition (B), and is dissolvable in water in this composition (B), therefore can in advance this composition (C) be dissolved in the composition (B).
According to the present invention above-mentioned perfusion type Chemical composition that except that comprise composition (A) and (B), also can comprise tertiary amine (D) and surfactant (E).
This tertiary amine (D) is a kind of reaction that can quicken composition (B) and water or silanol group, thereby shortens the composition of gelling time.Mentioned component (D) can be alkyl amine, cyclammonium etc.In above-claimed cpd, preferably adopt the dimethyl octylame, dimethyl lauryl amine, morpholine, N-methylmorpholine, piperazine, lupetazin, triethylenediamine, imidazoles, N methyldiethanol amine, N, N ＇-dimethylethanolamine, polymine etc.
Preferably composition (D) is 0.1-20 with the weight ratio of composition (B): 100, and this ratio is 0.5-15 certainly: 100 o'clock are then better.When the relative weight of composition (D) less than 0.1 the time, the composition that is then obtained can be able to not solidify, thereby can not obtain desirable effect.In addition when the relative weight of composition (D) greater than 20 the time, then the composition setting rate is too fast, thereby can not make composition (A), (B), (D) and (E) evenly mix.
Surfactant (E) is a kind ofly can make composition (A), (B) and (D) evenly scatter or make their emulsification, particularly makes composition (A) and (D) evenly scatter or make their emulsification, so that they react uniform composition.Composition (E) can be cationic surfactant, as four generations acid ammonium ester (guarternaly ammonium salt), isopropanolamine fatty acid ester; Anion surfactant, as oil or fatty acid sulfate, the alkyl sodium sulfate ester, the alkyl sodium sulfate ether-ether, alkyl sulfonic ester, alkyl allyl sulphonic acid ester, napsylate, sulphation or sulfonated aromatic compound, aliphatic carboxylic acid or carboxylate, sulfonated petroleum product, dialkyl sulfosuccinate carboxylic acid or its ester class, alkylphosphonate, oleoyl methyl touride sulphonic acid ester, sulphation or sulfonation acid amides; Carboxylic acid or sulfonic acid amphoteric surfactant; Non-ionic surface active agent with 4-10 HLB (hydrophilic lipophilic balance), as polyoxyethylene alkyl ether, polyxyethylated allyl ether, polyoxyethylene polyols ether, another kind of ethers non-ionic surface active agent, polyol ester, ester class non-ionic surface active agent or nitrogenous non-ionic surface active agent etc.Above-mentioned surfactant can use separately separately, also can mix use.
Composition (E) is preferably 1-200 with the weight ratio of composition (D): 100, certainly this ratio is 5-100: 100 o'clock then better, when the relative weight of mentioned component (E) less than 1 the time, then be difficult to composition (A), (B), (D) are evenly mixed, particularly be difficult to mix, thereby can obtain a kind of solidifying body heterogeneous with composition (A) with (D).In addition, when the relative weight of mentioned component (E) surpasses 200, then can't obtain solidifying body, even and obtain solidifying body, its physical property is also very poor.
Organic polyisocyanate compounds (B) can react well with composition (A), perhaps has good coagulability.Yet because composition (B) has higher viscosity, so it can not be penetrated in rock mass or the ground fully.In order to increase flowability or permeability, people have begun to add organic solvent such as the toluene as thinner, dimethylbenzene, 1,1,1-trichloroethanes, carrene or fluoroform at present.Yet above-mentioned organic solvent is volatile, because its volatilization can destroy the surrounding environment generation, does not therefore preferably use above-mentioned organic solvent after slurries solidify as far as possible.
By the present invention, composition (B) can be mixed mutually with reactive diluent, and this thinner can react with silicic acid metal alkyl salt, this thinner can not react with NCO when mixing with composition (B), and it with composition (B) when mixture contacts, can react with composition (A) immediately and solidification phenomenon takes place.Because above-mentioned reactive diluent can not react with NCO, so it helps to improve the shelf stability of composition (B), and can reduce its viscosity.Can react with composition (A) at once owing to this thinner in addition, so the environment around can influencing hardly.
Addible in the present invention reactive diluent can be ester or ether, because this thinner can produce diluting effect to organic polyisocyanate compounds (B), therefore when reperfusion serosity, it can play the effect that reduces its viscosity.In addition, above-mentioned reactive diluent also can help to form the solidifying body of harder inorganic-organic complex, and this complex mainly comprises silicic acid anhydride-urethane complex, with the mutually crosslinked silicic acid anhydride complex of urea or be cancellated silicic acid anhydride colloid.Specifically, when above-mentioned reactive diluent just can be made this thinner alkalization hydrolysis with silicate base aqueous metal salt (A) when contacting, the ester of this hydrolysis or ether can react with composition (A) and/or composition (B), reactive diluent has just played facilitation in composition (A) and composition (B) solidify reaction process like this, thereby can form harder firming body recited above.
As mentioned above, the alkaline hydrolyzate of above-mentioned reactive diluent has a palace energy base that reacts with composition (A) or composition (B) at least, and this palace can be alcoholic hydroxyl, carboxyl, amino, parahelium, thiol base etc. by base.For example, suppose when during as reactive diluent, just producing the pure and mild acetate of 1,2 ethylene as hydrolysate with ethylene acetate.1 of above-mentioned generation, 2 ethylidene glycols can react then to form and be 3 D cross-linked polyurethane with PIC (B), the acetate of above-mentioned generation can in and the silicate base slaine in the composition (A) or make its dehydration, generation siloxane bond net structure, thus quickened gelatinization.
As mentioned above, when reactive diluent mixes mutually with composition of the present invention, formed inorganic-solidifying body of organic complex has higher mechanical strength and hardness.
When containing the composition of reactive diluent and comparing with the composition that does not contain reactive diluent, the former has following advantage with above-mentioned:
1, because the viscosity of composition (B) reduces, its rock mass or ground permeability improve greatly.
2, be diluted to generation volatilization hardly, therefore can guarantee to have good health and security context around the job site.
3, improved the bin stability of composition (B).
4, can form the composite solidification body after reacting, thereby improve the intensity of this solidifying body greatly.
The reactive diluent that possesses following condition can preferentially use, be that thinner is in a liquid state, (about 5 ℃-40 ℃) have lower viscosity under its temperature when composition uses, its volatility is poor, it is inertia in composition (B), it can be by composition (A) hydrolysis, and the hydrolysate that is generated can react with composition (A) and/or composition (B).
Above-mentioned reactive diluent can for as have the binary acid diester class of lower molecular weight, list or polyol acid ester, alkylene carbonate, ether, cyclic ester, ester acid anhydride, various acrylate, various methacrylates etc.
Above-mentioned binary acid diester class with lower molecular weight can be for as binary acid dialkyl ester, and this binary acid dialkyl ester specifically can be dimethyl glutarate or oxalic acid, dimethyl succinate or diethylester, dimethyl adipate or diethylester, dimethyl malenate or diethylester, ethylene dimethyl or diethylester, Dimethyl 1,7-heptanedioate or diethylester etc.
Above-mentioned alcohol acetic ester can be for as glycol ether ethyl ester ester, and glycol ether wherein specifically can be glycol monomethyl ether, ethyl methyl ether, butyl cellosolve, propylene glycol monomethyl ether, ethyl carbitol or butyl carbinol; The alkoxyalkyl alcohol acetic ester, and alkoxyalkyl alcohol wherein is specifically as follows the 3-methoxybutanol, 3-methyl-3-methoxybutanol; The diacetate of di-alcohols, dihydroxylic alcohols wherein is specifically as follows 1,2 ethylidene glycol, diethylene glycol (DEG), triethylene glycol etc.
Above-mentioned alkylene carbonate can be for as propylene carbonate, and ethylene carbonate is dissolved in the propylene carbonate and the dilution that obtains etc.
Above-mentioned ether can be for as cyclic ethers, and this cyclic ethers specifically again can be for as oxolane, diox or dehydrated castor wet goods.
Above-mentioned naphthenic acid can be for as lactone, and this lactone specifically can be γ-butyl lactone again, lactams, and this lactams can be epsilon-caprolactams etc.
Above-mentioned various acrylate or methacrylate can be for as the acrylate or methacrylate methyl ester, as methyl acrylate, and acrylic acid methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl isocrotonate; Acrylate or methacrylate, alcohol ester, wherein the alcohol in the alcohol ester is specifically as follows 1,2 ethylidene glycol, diethylene glycol (DEG), polyethylene glycol again.Molecular weight that should poly-ethanol is 100-1000, propane diols, and DPG, polypropylene glycol, the molecular weight of this polypropylene glycol are 100-1000, oxirane, 1, the molecular weight of 2-expoxy propane polymerization is the glycol of 100-5000 or triol etc.
Above-mentioned acid anhydrides can be propionic andydride, butyric anhydride, cis-1 etc.
The preferably above-mentioned reactive diluent and the weight ratio of organic polyisocyanate compounds (B) they are 5-90: 100, and this ratio is 10-50 certainly: 100 o'clock are better.Above-mentioned consumption can be adjusted in above-mentioned scope according to the viscosity of composition (B) and the kind of composition (B) and the factors of wanting to use such as occasion.If the reactive diluent consumption is too little, the effect of its viscosity that reduces composition (B) is reduced, or reduce the effect that it improves the intensity of solidifying body.On the other hand, when consumption was too big, the intensity of solidifying body also can be lowered.
In order to carry above-mentioned reactive diluent or to make slurries have dilatancy, except that using above-mentioned reactive diluent, also can add known thinner.
By the present invention, can also contain the plasticizing agent that in the resin of extensive use, is added in the composition, this plasticizing agent can be dioctyl phthalate, dibutyl phthalate, dioctyl adipate, chlorinated paraffin wax, process oil.
The gross weight of best above-mentioned reactive diluent or plasticizing agent and composition (A) and composition (B) sum is than being 0-100: 100.
In addition, also can add inorganic filler in the composition of the present invention, as cement, blast-furnace cinder, gypsum, calcium carbonate, clay, aluminium hydroxide, antimony trioxide, quicklime, hydrated lime, swell soil etc.Above-mentioned inorganic filler can be solidified when mixing with composition (A), thereby forms compound firming body, has consequently improved the intensity of firming body and the effect of sealing crack or hole greatly.The weight ratio of above-mentioned inorganic filler and composition (B) is 0-80: 100, be preferably 0-50: 100.
As mentioned above, in perfusion type composition of the present invention, also can add tertiary amine (D) to quicken the reaction with composition (B) as curing catalysts.Except that above-mentioned tertiary amine (D), also can add as following curing accelerator, as two fourth tin dilaurates, triethylenediamine, imidazoles, MEA, diethanol amine, triethanolamine etc.The weight ratio of above-mentioned curing accelerator and composition (B) is 0.1-20: 100, and this ratio is 0.5-15 certainly: 100 o'clock are then better.
As mentioned above, for composition (A), (B), (D) uniformly emulsify in the above-mentioned perfusion type Chemical composition that or evenly scatter, can be to wherein adding surfactant (E).When during as curing accelerator, then using any surfactant with alkyl amine (D), as cation, anion, amphoteric surfactant or nonionic surface active agent.Above-mentioned surfactant can be for as alkylsurfuric acid sodium salt, amine salt or ammonium salt aqueous solution, alkyl benzene sulphonate sodium salt, amine salt or ammonium salt aqueous solution, ethoxy vinic acid sodium salt, amine salt or ammonium salt aqueous solution, or ethyoxyl alkyl phenyl-hydrogen-sulfate sodium salt, amine salt or ammonium salt aqueous solution; Alkylphosphonate; Non-ionic surface active agent etc.And this non-ionic surface active agent can be when using alcohol or alkyl phenol several moles oxirane carry out once more polymerization and handle and obtain.The weight ratio of above-mentioned surfactant and curing accelerator is 1-100: 100, and this ratio is 10-20 certainly: 100 o'clock are then better.
Also can add the siloxanes foaming control agent in addition at composition (A) or (B).
For elasticity or the mechanical strength that improves firming body, can be in when grouting, the various polymer of adding necessary amount to composition (A) and/or (B) in, can be solvent-borne type volatility or non-volatile rubber as this polymer, this rubber specifically can be butadiene rubber, chloroprene rubber; butadiene-styrene rubber, EP rubbers, the latex of above-claimed cpd; various acrylic resin latexes; polyvinyl alcohol, ethylene vinyl acetate latex, polyurethane resin dispersion; PEO, asphalt emulsion etc.
Can in composition (B), infiltrate stabilizing agent if desired, as various aging-proof agents, anti-thermit powder or antioxidant.The weight of above-mentioned various stabilizing agents accounts for the 0-2% of composition (B) usually.
Composition of the present invention in addition also can comprise phosphorus, and halogenated fire-retardants is as ester or lactone water glass etc.
The curing reaction of perfusion type Chemical composition that of the present invention is very complicated, therefore is not easy to make clear.Can think, the alkali metal aqueous solution (A) and polyisocyanate compounds (B) are when mixing mutually, the silanol group that is had in the silicate base aqueous metal salt just can react with the NCO in the polyisocyanate compounds, thereby form silicic acid anhydride-urethane complex, above-mentioned organic polyisocyanate compounds can form with the water reaction and have the crosslinked complex of polymer silicic acid anhydride-urea that the urea chain is connected simultaneously, can produce carbon dioxide simultaneously, the part of the above-mentioned carbon dioxide as byproduct that is produced can be dissolved in the silicate base aqueous metal salt, and because the effect of this carbon dioxide dissolved gas can generate the silicic acid anhydride colloid from the silicate base slaine.
In addition, above-mentioned silicic acid anhydride-urethane complex forms the firming body of expansion owing to the effect of carbon dioxide and steam, above-mentioned carbon dioxide produces in composition B and water react process, above-mentioned steam is formed by the heat that composition (A) and composition (B) produce when reacting, the volume of the complex of above-mentioned like this expansion will increase, and swelling has just taken place this moment.And because the bulbs of pressure that this expansion produced, above-mentioned silicic acid anhydride-urethane complex just can enter in the slit of the soil body, rock mass, brick, coal and artificial structure's thing at an easy rate.
When use contains the composition of the present invention of composition (C), because the heat of reaction that is produced when at composition (A) and (B) reacting can make composition (C) volatilize, therefore the compound that is generated by previous reaction just can expand, thereby has increased the volume of firming body.
Preferably use perfusion type Chemical composition that of the present invention as a kind of pair of composition (than assembly) composition, this pair of component composition comprises above-mentioned composition (A) and composition (B), this composition (A) and (B) in being filled into rock mass etc. before mix.
When employing contains the composition of above-mentioned composition (A), (B), (C), preferably use the composition be in two composition (two assembly) states, and wherein one of assembly contains composition (A), two of assembly contains composition (B) and (C).Before in being filled into rock mass etc. these two assemblys are mixed.The known mixed method that will describe below is applicable to the mixing of composition of the present invention, such as when needing long gelling time or irritating grouting amount hour, can adopt injection method one time, in the method at first and (B) with composition (A), perhaps add after composition (C) mixing in advance, this mixture is poured into.
When use contains the composition of composition (A), (B), (D), (E), then can the order by merging of composition (A), (B), (D), (E) be limited, such as using two compositions (two assembly) to constitute the composition of state, one of them assembly comprises the mixture of composition (A), (D), (E), and another assembly is composition (B), this sample ingredient (A), (D), (E) mix in advance, and composition (B) mixes with above-mentioned mixture again then.
The composition (A) that includes only the silicate base aqueous metal salt can prepare by following manner, is about to the silicate base slaine and is added to the water, and as mentioned above, the solid content in this water and the weight ratio of the above-mentioned aqueous solution are 10-70: 100.When preparation contains other composition, during as the composition (A) of curing accelerator, this composition can be stirred in the above-mentioned aqueous solution, can add surfactant so that it is dispersed in the aqueous solution safely in case of necessity.
Reactive diluent is added in the composition (B), can add the thinner of normal use again, mixture is fully stirred as needs.
Above-mentioned specific perfusion type Chemical composition that of the present invention is filled in the weak soil or unstable ground, rock mass, layer of sand, layer of gravel or artificial structure's thing with a lot of cracks or space, and makes its curing.When pouring into and solidifying above-mentioned composition of the present invention, can at will adopt known method.Such as, can use the ratio grouting pump of the mixing ratio that can control consumption, pressure or composition (A), (B), (C), (D), (E).When composition contains composition (A) and (B) time, in two jars, carry composition (A) and (B) respectively; When composition contains composition (A), (B), (C), carry composition (B) and mixture (C) and composition (A) to two jars respectively; When composition contains composition (A), (B), (D), (E), carry mixture and the composition (B) of composition (A), (D), (E) respectively to two jars.Then at 0.S-50kg/cm
2.G under the injection pressure condition, each composition in above-mentioned jar is filled into predetermined position (such as a plurality of holes of being bored every 0.5-3 rice) by rock bolt or Grouting Pipe, above-mentioned rock bolt or Grouting Pipe are equipped with static pressure mixture or one way valve in advance.At last, utilize the static pressure blender that the composition of the scheduled volume of two assemblys formations is fully stirred,, said composition is penetrated in the predetermined unstable rock mass afterwards and solidifies, thereby rock mass or ground are reinforced so that it can evenly be mixed.
If use the present composition that tunnel roof is poured into, then before perfusion, preferably use and have diameter and offer injected hole as the long screw auger of 42mm drill bit, the degree of depth of this injected hole is 2m, its bore angle is 10 °-30 °, the spacing of wells is 2m, as shown in Figure 1, hollow carbon steel rock bolt 1 (length is 3m) is placed in each injected hole, above-mentioned anchor pole 1 has hole 4, static pressure blender 2 and one way valve 3 be equipped with and, anchor pole 1 openend can be by useless cloth, rapid condensation cement or infiltration have useless cloth of expandable hard polyurethane resin etc. to seal, by aforementioned manner above-mentioned perfusion type Chemical composition that 5 is poured into then, when injection pressure increases suddenly or the composition groundwater increment surpasses scheduled volume to a certain degree, promptly composition groundwater increment volume surpasses scheduled volume 20%, has then just finished above-mentioned filling process.In general, the amount that is filled into the composition in each hole is 30-200kg.
When the artificial structure's thing that has the crack being reinforced or when wherein current are blocked, can utilize rig boring on the surface with crack, the bore dia that is bored is 10mm, and the degree of depth is 5-10cm, spacing is 20-50cm, with compressed air chip or powder is blown away from the hole afterwards; Placing thickness then in the hole is the water imbibition cotton of 5mm, and squeeze into a Grouting Pipe therein, and the diameter of this Grouting Pipe is 10mm, length is 20-30mm, part to be reinforced so just can be in such state, i.e. perfusion type Chemical composition that seepage can not take place.In addition, when crack or seepage part be shaped as U type shape or V-type shape, and its width then can use rapid solidification cement that Grouting Pipe is fixed when being the 30cm left and right sides.Afterwards, be 0.5-20kg/cm at grouting pressure
2.G, be preferably 0.5-2kg/cm
2.G the time, Y-piece by having the static pressure blender or U type pipe predetermined amounts adopt ratio grouting pump or hand pump, and the composition of the invention described above is poured into.Groundwater increment is the total amount that the hypothesis voidage of pipe adds α.
In reinforcement means of the present invention, because composition has lower viscosity, therefore be easy to be penetrated in unstable ground, crack or the cracking district, consequently can carry out large-area reinforcing, the blocking-up construction of current unsettled rock mass, ground or artificial structure's thing.In addition, last formed firming body intensity height, durability is long, with rock mass pipe bonding firmly, does not burn or have anti-flammability, and cost is low.Therefore method of the present invention has practical value.
To more specifically describe the present invention by example below, if wherein do not add special indicate then all percentage and shares are all calculated by weight.Can know, the invention is not restricted to following example, therefore can on the basis of not leaving spirit and scope of the invention, carry out various forms of improvement or change the present invention.
Reference example 1-4
Composition shown in the table 1 (B) is pre-mixed with additive in the table 1 and catalyzer by quantity shown in the table 1, the composition that obtains like this (B) is being equipped with static mixer (long 15cm with the composition (A) of quantity shown in the table 1 again, diameter 1cm) mix in the pump, with this mixture at 5-10kg/cm
2.G under the pressure with 7kg/m
2Quantity discharge.
For said composition, the needed gel time of the said composition that inspection discharges (time of setting), and the uniformity of said composition, for firming body, to carry out bend test and compression test according to JIS (Japanese Industrial Standards) R5201, expansion rate is calculated from the density that records according to JISK5400, and combustion test (burning time and burning extent) is carried out according to JISA9514.
No matter said composition by layering or do not have a layering, as long as said composition is not condensed, will estimate the uniformity of this combination.
For composition (A), use 40% No. 3 sodium silicate aqueous solutions.(Na
2O/SiO
2=1/3, mol ratio).
The result is as shown in table 1.
The make a din uniformity No of dimethyl octylame-(2.0) (1.5) (1.5)-composition of the table 1 reference example number free NCO content of the organic poly-isocyanide Me700C-MDI G5000-20.C-MDI G3000-30C-MDI N4000-50.C-MDI acid compounds of 1234 compositions (A) sodium silicate aqueous solutions (part), 100 100 100 100 compositions (B) (part) (148.0) (138.5) (88.5) (50) (%) 29.7 25.0 27.5 21.8 additives (part)-dioctyl phthalic acid fat ethylene glycol bisthioglycolate acetic acid fat propene phosphoric acid fat-(10) (10) (10) catalyst (part) dimethyl octylame N-methyl*No No No expansion rate 1.21 1.28 1.25 1.30 time of setting (20 ℃, second) 120 65 70 90 compressive strength (kg/cm
2) 90.0 105 88.2 72.5 bending strength (kg/cm
2) 41.2 34.6 45.5 30.8 60 60 60 60 burning extents burning time (second) (mm) 0000 (notes)
* 1: said composition is not divided into layer.
Me700.C-MDI: the urine gastral cavity prepolymer of single alcohol (the OH value is 190) (NCO content: 22%),
This prepolymer is ethylene oxide and the C-MDI by methyl alcohol and 6 moles
The addition reaction of (polyethylene polyphenol PIC) obtains
G5000-20.C-MDI: mean molecule quantity is 5000 polyoxyalkylene triols (the OH value is 34)
Urine gastral cavity prepolymer (NCO content: 25%), this urine gastral cavity prepolymer
Propylene oxide chain by 80% and 20% ethylene oxide chain and
C-MDI forms.
G3000-30.C-MDI: mean molecule quantity is that (the OH value is for 3000 polyoxyalkylene triols
56) urine gastral cavity prepolymer (NCO content is 24%), this urinates gastral cavity
Prepolymer is by 70% propylene oxide chain and 30% oxidation second
Alkene chain and C-MDI form.
N4000-50.C-MDI: mean molecule quantity is that (the OH value is for 4000 polyoxygenated chain triol
42) urine gastral cavity prepolymer (NCO content is 28%); This urine
The gastral cavity prepolymer is the propylene oxide with three ethanol gastral cavitys and 50%,
50% ethylene oxide and the addition reaction of C-MDI obtain.Reference example 5 and 6.
Except following variation, the method for repeated reference example 1 is made composition.This variation is that composition (B) is with 88 parts in polyethylene polyphenol polyisocyanate fat (C-MDI) and use the catalyzer shown in (in the reference example 5) table 2; Perhaps composition (B) uses 88.0 parts of polyols that do not contain oxyethyl chain, and uses additive and the catalyzer shown in (in example 6) table 2.
For said composition, its uniformity is estimated by reference example 1 same mode.The results are shown in table 2.
The organic ployisocyanate Compound C of table 2 reference example number 56 compositions (A) sodium silicate aqueous solutions (part), 100 100 compositions (B)-MDI D-2000.C-MDI (part) (98.0) (88.0) NCO content 31.0 28.0 (percentage by weight) additive-1; 1,1-trichloroethanes (part)-(10) catalyst two fourth tin glycerine two laurate fat uncle gastral cavity (part) (2.0) (2.0) uniformity Δs* 1Δ (notes) * 1: said composition has been divided into layer, yet and then said composition can used after the pressure stirring.D-2000.C-MDI: mean molecule quantity is the urine gastral cavity prepolymer (NCO content is 22%) of PPOX 1, the 2 one pure and mild C-MDI of ethylene of 2000 (the OH value is 56).
Reference example 7-10.
Be pre-mixed with the catalyzer shown in the table 3 with composition (B) with (C), subsequently the same composition (A) that uses in this mixture and the reference example 1 mixed in the pump that static mixer (long 15cm, diameter 1cm) is housed, at last with mixture at 5-10kg/cm
2.G under the pressure, with 7kg/m
2Quantity discharge.
For the uniformity and the setting time of said composition, and for the expansion rate of its firming body; Compressive strength, bending strength and combustion test are all by checking with mode identical in the reference example 1.
The results are shown in table 3.
The inflatable rare trichlorine fluoroethane methyl chloride acetone methyl of the table 3 reference example number free NCO content of 789 10 compositions (A) sodium metasilicate water 100 100 100 100 solution (part) compositions (B) organic polyisocyanate Me700C-MDI G5000-20.c-MDI esterified compounds of G3000-30C-MDI N4000-50.C-MDI (78.0) (138.5) (88.5) (190) (part) (%) 29.7 25.0 27.5 21.8 compositions (C), ethyl ketone are released the uniformity No of agent (part) (10) (10) (10) (10) catalyst dimethyl-octa gastral cavity N-methylmorpholine dimethyl-octa gastral cavity-(part) (2.0) (1.5) (1.5)-said composition* 1No No No expansion rate 1.50 2.10 1.90 3.05 setting times (20 ℃ time, second) 170 120 115 190 compression strength (kg/cm), 89.0 65.5 72.4 61.2 bending strengths (kg/cm), 38.5 31.0 35.1 29.7 60 60 60 60 burning extents burning time (second) (mm) 0000 (notes) * 1: said composition is not divided into layer.
Reference example 11 and 12
Except that following variation, the method in the repeated reference example 7 makes composition, and this variation is that composition (B) is with 88 parts in polyethylene polyphenol polyisocyanate fat and use composition (C) and the catalyzer (with reference to example 11) shown in the table 4; Perhaps composition (B) is with being polyol and composition shown in the table 4 (C) and the catalyzer (with reference to example 12) that does not contain oxyethyl chain.
The uniformity of said composition is by estimating with reference example 1 identical mode.
The results are shown in table 4.
The organic polyisocyanate fat Compound C of table 4 reference example number 11 12 compositions (A) water-soluble 100 100 liquid of silicate of soda (part) compositions (the B)-inflatable rare methyl chloride 1 of the free NCO content of MDI D-2000.C-MDI (part) (88.0) (88.0) (%) 31.0 28.0 compositions (C), 1, the 1-trichloroethanes is released agent (part) (10) (10) catalyzer two fourth tin glycerine uncle gastral cavitys two laurate fat (part) (2.0) (2.0) uniformity Δ * 1 Δ (notes) * 1: said composition has been divided into layer, yet said composition can be used after and then forcing to stir.
Reference example 13-16
Be pre-mixed composition (A) in the table 5, (D) and (E), subsequently this mixture mixed in the pump that static mixer (long 15cm, diameter 1cm) is housed with the composition in the table 5 (B), last, this mixture is at 5-10kg/cm
2.G under the pressure with 7kg/m
2Quantity be released out.
Use with reference example 1 in identical composition (A) as composition (A).
For the composition that is obtained, its uniformity and setting time; And for expansion rate, compressive strength, bending strength and the combustion test of firming body, all by with reference example 1 in identical mode check.
The results are shown in table 5.
5 13 14 15 16 ( A ) 100 100 100 100 ( ) ( B ) Me1200C-NDI D4000-50.C-MDI G5000-80C-MDI G40001-MDI ( ) ( 100 ) ( 150 ) ( 100 ) ( 200 ) ( D ) N- ( ) ( 5.0 ) ( 6.5 ) ( 5.0 ) ( 7.5 ) ( E ) N- -N,N- ( ) ( HLB8 ) ( 0.5 ) ( 0.3 ) ( 0.5 ) ( 0.5 ) No* 1No No No expansion rate 1.68 2.10 1.90 3.10 setting times (20 ℃ time, second) 170 105 110 250 compression strength (kg/cm), 72.5 75.3 70.5 35.0 bending strengths (kg/cm), 50.1 42.0 48.2 21.4 60 60 60 60 burning extents burning time (second) (mm) 0000 (notes)
* 1: composition is not divided into layer.
Me1200.C-MDI: a kind of urine gastral cavity prepolymer (NCO content is 29.5%) of single alcohol, should
Single alcohol is 6 moles ethylene oxide and methyl alcohol (the OH value is 190)
And the addition reaction product of C-MDI.
D4000-50.C-MDI: mean molecule quantity is the urine gastral cavity pre-polymerization of 4000 polyoxyalkylene diols
(NCO content: 23.0%), this urine gastral cavity prepolymer is by 70% oxygen for thing
Change propylene chain and 30% ethylene oxide chain (the OH value is 28.0) and
C-MDI forms.
G5000-80.C-MDI: mean molecule quantity is the urine gastral cavity prepolymer (NCO content is 20.5%) of 5000 polyoxyalkylene triols, this urine gastral cavity prepolymer by
20% propylene oxide chain and 80% ethylene oxide chain (OH value
Be 33.0) and the C-MDI composition.
G4000e-MDI: glycerine and propylene oxide (mean molecule quantity is 4000, and the OH value is 42.0)
And e-MDI (liquid diphenylmethane diisocyanate resin) addition reaction
The urine gastral cavity prepolymer (NCO content is 25.0%) that produces;
Reference example 17
Except that not using surfactant (E), the method for repeated reference example 16 makes composition.
Said composition is divided into layer, yet and then said composition still can used after the pressure stirring.
Reference example 18
Except following variation, the method in the repeated reference example 15 makes composition, and the addition reaction of the ethylene oxide (HLB is 14) of octyl phenol and 10 moles is promptly used in this variation, and replacing HLB is that 8 non-ionic surface active agent is as composition (E).
The separated stratification of said composition, however and then said composition still can used after the pressure stirring.
Example 1
At the tunnel top that the crack district is arranged, distance with the about 2m in interval, use has the long screw auger of 42mm φ drill bit, 5 holes are bored at the angle (with the excavation direction angulation in tunnel) that pierces with 25 to 35, as shown in Figure 1, (JISG 3445 for the carbon steel that will be used to pour into again, STKM17C) anchor pole, (external diameter 27.2mm, internal diameter 15mm, long 3m) be inserted in each hole, and then (the good cotton wastes cloth of braiding of two-liquid hard erpandable urine gastral cavity resin pushes in the hole from its opening (degree of depth 30cm) with an iron staff, and the hole is sealed will to be impregnated with hard expandable of two liquid.
The composition that perfusion type Chemical composition that reference example 1 is obtained and reference example 13 are obtained is with the quantity, about 20 to 50kg/cm of each hole about 80 to 120 kg
2.G injection pressure is filled into respectively in the fixing hole that will pour into, and with the composition that reference example 7 is obtained, removes perfusion pressure and adjusts to 5 to 10kg/cm
2.G outside, be filled in the hole in the same manner described above.After 120 minutes, excavate the tunnel end face that this has been poured this composition from the perfusion composition, can access what kind of improvement so that understand this end face.The result shows that consolidation zone is in the hemisphere that radius is 3m, and this zone is cured and has stablized.
By using a sampler, from cured portion, choose a garden cylindricality sample (5cm φ * 10cm), measure uniaxial compressive strength.The compressive strength of the composition in reference example 1 and the example 7 is respectively 120kg/cm
2, the compressive strength of the composition in the reference example 13 is 130kg/cm
2For the summit portion that does not make improvements, because the appearance of crack area, sampling is impossible.The result has fully proved the validity of Chemical composition that of the present invention, and has proved and formed stable curing.
Example 2
In order to stablize apertured granite crack district in the tunnel roof, stablize by each composition in the perfusion reference example 2,8 and 14, implementation method by with example 1 in identical mode carry out.
Promptly, in end face, bore 10 holes (hole depth 2m) with the spacing of about 2m with the long screw auger of a band 42mm φ drill bit.Piercing the angle is 20 °.To insert in these holes with the same carbon steel rock bolt (JOS G 3455, STKM 17C) that uses in the example 1, the opening in hole seals by the mode identical with example 1.
Each above-mentioned composition injected to the amounts of 110kg by 70 (injection pressure: the composition for reference example 2 and 14 is to 20kg/cm from 10
2.G, for the composition in the reference example 8, for from 2 to 10kg/cm
2.G).In order to confirm its stable state, from the perfusion composition after 150 minutes, to excavate and research has been poured the peripheral region in the hole of composition, this part in radius is the hemisphere of 2.5m has been cured, and its large fracture is by sealed with high density satisfactorily.For example, core is taken a sample out from this part, and (5cm φ * 10cm), this part produced king-sized crack to a garden post, with described hardening composition sealing, measured its unidirectional axial compressive strength and carried out combustion test.
The results are shown in table 6.
Table 6 reference example number 28 14 unidirectional axial compressive strengths
*250 223 230 (kg/cm
2) inflammability
*60 60 60 burning extents burning time (second) (mm) 000 (notes) * A sample: 4cm * 4cm * 4cm, compression speed are the 5mm/ branch
* is according to JISA 9514
From the result of example 2, can prove, when radius that each Chemical composition that is perfused in its slit greater than in the time in order to the granite crack district of the radius of the anchor pole of perfusion, this slit can be sealed fully, said composition has fully penetrated in the district of crack, and be cured, to stablize this rock mass.In other words, composition of the present invention has significant effect in the digging operation in tunnel.
Example 3
In a compound steel reinforced concrete building, on the angle of shingle, produced the crack, its low layer is seepage under the situation of raining.With diameter is the brill of 10mm, bores 15 holes (hole depth is about 5cm) with the spacing of about 20cm.After scraping or the dust in the hole being blown off with compressed air, thickness is put into each hole for the absorbent cotton of about 5mm, be that the pipe that is used to pour into of 10mm is squeezed into wherein with a wooden mallet with an external diameter then.The Y pipe that a static mixer is housed is installed in each pipe, use a hand charge pump then; Composition in reference example 1,7 and 15 is injected respectively by the amount of every about 2-3e in hole.When the composition in the use reference example 1, composition (A) is about 1/1.5 to the volume ratio of composition (B), when the composition in the use reference example 7, composition (A) is about 1/1 to composition (B) and volume ratio (C), during composition in using reference example 15, composition (A), (D) and (E) volume ratio of composition (B) is about 1/1.5.
After the perfusion, the pipe that will be used to pour into is extracted out, squeezes into cork, is coated with stuccoing, has just finished.After two weeks, heavy rain is arranged, water can not get off from seepage on the end face fully.Confirmed that just composition of the present invention is used for the crack sealing or cuts off current having a significant effect.
Example 4
On the fine sand spilling water ground that contains sand and stone of underground 7 to 10m (groundwater table is 5m) depths, carry out in the shield tunneling construction, in order to cut off current and stable spilling water zone ground on every side, use balanced grout pump, according to 1.5-injection method (1.5-shotmethod), by the iron staff (external diameter is 40.5mm) that is used to pour into and static mixer wherein is housed, composition in the reference example 16 is filled into ground that plan will excavate and on every side, and groundwater increment is 230m
3Injecting said composition, is 1/2 so that make composition (A), (D) and mixture (E) to the volume ratio of composition (B).Before perfusion and the perfusion after the ground state be shown in table 7.As shown in table 7, the stable and reinforcing of ground can be realized, and the effect of current can be obtained to cut off.Therefore, use composition of the present invention, can accelerate the operation of shield tunneling engineering.
Table 7
The 750m of ground is improved in the perfusion back before the perfusion
3750m
2Quantity (3m is long, and 5m is wide, (3m is long, the wide length of 5m (length) 50m) length (length) 50m) N value 3 to 10 45 to 60 transmission coefficients
*3.1 * 10
-16.2 * 10
-6(cm/ second) (notes) * is according to JIS A 1218
Stable and the reinforcement means of perfusion type Chemical composition that of the present invention and its has the effect of aspect, following (1)-(5).
(1) the silicate alkali metal aqueous solution (A) and organic polyisocyanate fat compound (B) are very compatible, and one forms anhydrous urea silicic acid compound surely, the composite curing body of anhydrous urine gastral cavity silicic acid compound and silicic acid anhydride.In addition, because their good compliance, the adhesion stress of rock mass, ground and artificial structure's thing also is improved.Equally, for except that comprise composition (A) and (B), also include the said composition of composition (C), composition (C) and composition (A) and (B) be compatible, so, can form certainly with the similar composite curing body of the composite curing body of above-mentioned combination.In addition, permeability is owing to the bulbs of pressure improve, and solidification intensity is significantly improved.In addition, for except that comprise composition (A) and (B), the said composition that also includes tertiary amine (D) and surfactant (E), because the use of composition (E), compatible more significantly between them, therefore, nature can form and the similar composite curing body of the composite curing body of above-mentioned composition.Also have, because composition is matched with rock mass or ground and artificial structure's thing, so its adhesion stress is improved, its effect of stopping up the crack is that tool is big.
So, solidify and maintenance performance height rock mass or ground stable and add that the good general is sure to be improved, and an effect that obtains surely at seepage place cut-out current.
(2) composition (A) and mixture (B), the viscosity of composition (A), (B) and mixture (C) and composition (A), (B), (D) and mixture (E) is all low, thus permeability separately is fine.
(3) owing to used the silicate alkali metal aqueous solution and because the expansion effect of this organic polyisocyanate fat compound, the cost of said composition per unit volume is low, and has advantage at economic aspect.Except that contain composition (A) and (B) also include the composition of inflatable thinner (C) because the expansion effect of composition (C), the cost of said composition per unit volume also will reduce, and is economical thereby use said composition.Similarly, comprise the composition of tertiary amine (D), owing to used composition (D), the meeting of said composition further reduces, and is economical thereby use said composition.
(4) the solidification intensity height of composition is so can stablize effectively and reinforce for the unsettled rock mass or the ground that require certain intensity.
(5) firming body is fine aspect durability, and is incombustible or perhaps fire-retardant.So, the worry of not catching fire too much.Equally, said composition also is being very outstanding aspect safety and the health in construction.
As mentioned above, method of the present invention has outstanding characteristics, for reliable, economical and realize the stable of unstable rock mass or ground and reinforce or cut off current that this method all has significant effect safely and with high strength ground.In the construction of tunnel operation of heavy in section or in the underground civil engineering operation of certain depth construction, and need carry out usually in the operation of constructing tunnel, this stable and reinforce and need.
Except employed composition in above-mentioned example, in order to obtain identical in fact effect, said other composition also can use in the example of manual in front.
Claims (11)
1. perfusion type Chemical composition that, it comprises:
(A) a kind of silicate base aqueous metal salt and
(B) a kind of hydrophilic urethane prepolymer that free isocyano group group is arranged, described prepolymer is obtained by following reaction:
(a) have the pure and mild polyol of list of oxyalkylene group chain, in this compound, comprise at least 5% weight oxygen ethylidene chain and
(b) organic PIC.
2. composition as claimed in claim 1, it also comprises (C) a kind of inflatable thinner.
3. as the composition of claim 1 or 2, it also comprises:
(D) a kind of tertiary amine and
(E) at least a from by cationic surfactant, anion surfactant, amphoteric surfactant agent and HLB being the surfactant of selecting the group formed of 4 to 10 non-ionic surface active agent.
4. composition as claimed in claim 1, wherein said component (A) is a sodium silicate aqueous solution.
5. composition as claimed in claim 1, wherein said component (B) comprises a kind of reaction diluent, this reaction diluent be a kind of can not be with described component (B) reaction but can be by the ester or the ether of described component (A) basic hydrolysis, resulting like this hydrolysate can be with described component (A) and/or described component (B) reaction.
6. reinforcement means, it comprises and is filled into perfusion type Chemical composition that in rock mass, ground or the artificial structure's thing and solidifies described composition,
Described composition comprises
(A) a kind of silicate metal saline solution and
(B) a kind of hydrophilic urethane prepolymer that free isocyano group group is arranged, described prepolymer is obtained by following reaction:
(a) have the pure and mild polyol of list of oxyalkylene group chain, in this compound, comprise at least 5% weight oxygen ethylidene chain and
(b) organic PIC.
7. method as claimed in claim 6, wherein said component (B) comprises a kind of reaction diluent, this reaction diluent be a kind of can not be with described component (B) reaction but can be by the ester or the ether of described component (A) basic hydrolysis, resulting like this hydrolysate can be with described component (A) and/or described component (B) reaction.
8. method as claimed in claim 6, wherein said composition also comprise (C) a kind of expandable thinner.
9. as the method for claim 6 or 7, wherein said composition also comprise (D) a kind of tertiary amine and (E) at least a be the surfactant of selecting the group formed of 4 to 10 non-ionic surface active agent from cationic surfactant, anion surfactant, amphoteric surfactant and HLB.
10. method as claimed in claim 6, described composition is filled in described rock mass, the ground by following method, make its curing, this method is to hole by preset space length on rock mass or ground, insert the hollow anchor bar be used to pour in each hole, the opening by this anchor pole is filled into described composition in each hole.
11. method as claimed in claim 6, wherein adopt the pipe that will be used for pouring into to insert described artificial structure's thing, and described composition is filled into method in this artificial structure's thing by this pipe, described composition is filled in artificial structure's thing so that its curing.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP75049/1991 | 1991-04-08 | ||
| JP7504991A JPH04309616A (en) | 1991-04-08 | 1991-04-08 | Filling chemical composition for stabilizing soil quality and method for sealing water to stabilize for reinforcement using the same |
| JP75049/91 | 1991-04-08 | ||
| JP85171/91 | 1991-04-17 | ||
| JP85171/1991 | 1991-04-17 | ||
| JP3085171A JPH0772271B2 (en) | 1991-04-17 | 1991-04-17 | Injectable liquid chemical composition for stabilizing soil, etc. and stable strengthening method using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1068163A CN1068163A (en) | 1993-01-20 |
| CN1067737C true CN1067737C (en) | 2001-06-27 |
Family
ID=26416202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92103414A Expired - Fee Related CN1067737C (en) | 1991-04-08 | 1992-04-08 | Injection-type chemical composition for stabilization and reinforcement process using same |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR100216686B1 (en) |
| CN (1) | CN1067737C (en) |
| AU (1) | AU648152B2 (en) |
| TW (1) | TW211598B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756291A (en) * | 2013-12-27 | 2014-04-30 | 中科院广州化灌工程有限公司 | Polyurethane-water glass composite grouting material as well as preparation method and application thereof |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19832668A1 (en) * | 1998-07-21 | 2000-01-27 | Hilti Ag | Organic-inorganic mortar |
| JP3600502B2 (en) * | 2000-04-04 | 2004-12-15 | 有限会社シモダ技術研究所 | Plastic grouting method |
| EP1391440B1 (en) * | 2002-08-22 | 2007-10-17 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Chemical grout composition for stabilization when digging tunnels and construction method for increasing stability using same |
| GB0822553D0 (en) * | 2008-12-11 | 2009-01-14 | Minova Int Ltd | Silicate isocyanate |
| CN102673737B (en) * | 2012-05-16 | 2014-12-24 | 上海交通大学 | Solidifying type anchor with ultrahigh holding power to weight ratio and mounting method thereof |
| CN102718462B (en) * | 2012-07-09 | 2013-11-06 | 杭州国电大坝安全工程有限公司 | Chemical grouting material for reinforcing loose and broken bedrock |
| CN102964565A (en) * | 2012-12-03 | 2013-03-13 | 山东东大一诺威新材料有限公司 | Silicate modified polyurethane high molecular material and preparation method thereof |
| CN103113080A (en) * | 2013-02-06 | 2013-05-22 | 山西誉邦新动力科技有限公司 | Preparation method of mine water glass reinforced water shutoff material |
| CN103113079A (en) * | 2013-02-06 | 2013-05-22 | 山西誉邦新动力科技有限公司 | Mine water glass reinforced water shutoff material |
| CN103304984B (en) * | 2013-06-15 | 2015-06-10 | 尤洛卡矿业安全工程股份有限公司 | Inorganic modified polyurethane grouting material and preparation method thereof |
| KR101339968B1 (en) * | 2013-10-28 | 2013-12-10 | 우경기술주식회사 | Swirl type grout mixing apparatus |
| CN103770909B (en) * | 2014-01-20 | 2016-06-01 | 上海交通大学 | The buried consolidation anchor of the Zi Luochong of oceanographic engineering |
| CN104558514B (en) * | 2014-12-26 | 2018-02-23 | 北京瑞诺安科新能源技术有限公司 | A kind of high-strength polyurethane modified Portland slip casting strengthening material and its preparation method and application |
| CN107201208A (en) * | 2017-04-28 | 2017-09-26 | 上海鹤城高分子科技有限公司 | A kind of dual-component polyurethane grout off glue and its preparation and application |
| CN108085011B (en) * | 2017-12-19 | 2021-02-26 | 山东鸿扬文物保护工程有限公司 | Reinforcing agent and reinforcing method for earthen site in semi-moist or moist area |
| CN112195803B (en) * | 2020-08-28 | 2022-07-05 | 江苏开岩路桥工程有限公司 | Road and bridge crack reinforcing apparatus based on municipal building |
| CN114215569B (en) * | 2021-12-17 | 2023-07-28 | 南京林业大学 | Prestressed anchor rod construction method utilizing magnesium oxide-carbon dioxide carbonization |
| CN114573783A (en) * | 2022-03-07 | 2022-06-03 | 河北浩威旭光新材料科技有限公司 | Filling reinforcing material for reinforcing coal rock mass in coal mine and using method thereof |
| CN116003019B (en) * | 2022-12-16 | 2024-07-05 | 新宁县金旺水泥粉磨有限责任公司 | Cement activator, cement using same and preparation method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2728074A1 (en) * | 1977-06-22 | 1979-01-11 | Bayer Ag | METHOD FOR MANUFACTURING MINERAL FIBER MATS |
| DE2908746C2 (en) * | 1979-03-06 | 1983-08-11 | Bayer Ag, 5090 Leverkusen | Process for consolidating and sealing geological and poured rock and earth formations |
| DE3421085C1 (en) * | 1984-06-06 | 1985-10-31 | F. Willich GmbH & Co, 4600 Dortmund | Process for solidifying and sealing coal and / or rock and earth formations |
-
1992
- 1992-03-30 AU AU13926/92A patent/AU648152B2/en not_active Ceased
- 1992-04-07 KR KR1019920005774A patent/KR100216686B1/en not_active IP Right Cessation
- 1992-04-08 CN CN92103414A patent/CN1067737C/en not_active Expired - Fee Related
- 1992-04-09 TW TW081102748A patent/TW211598B/zh active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756291A (en) * | 2013-12-27 | 2014-04-30 | 中科院广州化灌工程有限公司 | Polyurethane-water glass composite grouting material as well as preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| AU648152B2 (en) | 1994-04-14 |
| AU1392692A (en) | 1992-10-15 |
| KR920019906A (en) | 1992-11-20 |
| KR100216686B1 (en) | 1999-09-01 |
| CN1068163A (en) | 1993-01-20 |
| TW211598B (en) | 1993-08-21 |
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