CN1284743C - 通过热引发可完全硬化的至少两个部分的灰浆料和在固定的底座加固锚杆、钢筋等的方法 - Google Patents
通过热引发可完全硬化的至少两个部分的灰浆料和在固定的底座加固锚杆、钢筋等的方法 Download PDFInfo
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- CN1284743C CN1284743C CNB021412170A CN02141217A CN1284743C CN 1284743 C CN1284743 C CN 1284743C CN B021412170 A CNB021412170 A CN B021412170A CN 02141217 A CN02141217 A CN 02141217A CN 1284743 C CN1284743 C CN 1284743C
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- Prior art keywords
- mortar
- ammonium
- acrylate
- compound
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- 239000004570 mortar (masonry) Substances 0.000 title claims abstract description 84
- 230000000977 initiatory effect Effects 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 14
- 230000003014 reinforcing effect Effects 0.000 title claims description 13
- 229910000831 Steel Inorganic materials 0.000 title 1
- 239000010959 steel Substances 0.000 title 1
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 13
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical class [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000945 filler Substances 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 30
- 239000007858 starting material Substances 0.000 claims description 15
- -1 vinyl compound Chemical class 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 14
- 239000004160 Ammonium persulphate Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 11
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 208000034189 Sclerosis Diseases 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 claims description 8
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 claims description 6
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
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- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 5
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
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- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004902 Softening Agent Substances 0.000 claims description 4
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 4
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 239000006004 Quartz sand Substances 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 230000036571 hydration Effects 0.000 claims description 3
- 238000006703 hydration reaction Methods 0.000 claims description 3
- 229910000765 intermetallic Inorganic materials 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid group Chemical group C(C=1C(C(=O)O)=CC=CC1)(=O)O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910002001 transition metal nitrate Inorganic materials 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 2
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
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- 150000001869 cobalt compounds Chemical class 0.000 claims description 2
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 2
- 229910000271 hectorite Inorganic materials 0.000 claims description 2
- 239000012442 inert solvent Substances 0.000 claims description 2
- 239000012766 organic filler Substances 0.000 claims description 2
- 239000008188 pellet Substances 0.000 claims description 2
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 239000004254 Ammonium phosphate Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims 1
- TTZLKXKJIMOHHG-UHFFFAOYSA-M benzyl-decyl-dimethylazanium;chloride Chemical class [Cl-].CCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 TTZLKXKJIMOHHG-UHFFFAOYSA-M 0.000 claims 1
- AJSHDAOMUKXVDC-UHFFFAOYSA-N butan-1-amine;sulfuric acid Chemical compound CCCC[NH3+].OS([O-])(=O)=O AJSHDAOMUKXVDC-UHFFFAOYSA-N 0.000 claims 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims 1
- 239000012933 diacyl peroxide Substances 0.000 claims 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims 1
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
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- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 2
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- 125000003118 aryl group Chemical group 0.000 description 2
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- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/06—Inhibiting the setting, e.g. mortars of the deferred action type containing water in breakable containers ; Inhibiting the action of active ingredients
- C04B40/0666—Chemical plugs based on hydraulic hardening materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/06—Acrylates
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16B—DEVICES FOR FASTENING OR SECURING CONSTRUCTIONAL ELEMENTS OR MACHINE PARTS TOGETHER, e.g. NAILS, BOLTS, CIRCLIPS, CLAMPS, CLIPS OR WEDGES; JOINTS OR JOINTING
- F16B13/00—Dowels or other devices fastened in walls or the like by inserting them in holes made therein for that purpose
- F16B13/14—Non-metallic plugs or sleeves; Use of liquid, loose solid or kneadable material therefor
- F16B13/141—Fixing plugs in holes by the use of settable material
- F16B13/142—Fixing plugs in holes by the use of settable material characterised by the composition of the setting material or mixture
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymerisation Methods In General (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Joining Of Building Structures In Genera (AREA)
- Polymerization Catalysts (AREA)
Abstract
描述了通过热引发可完全硬化的,至少两个部分的灰浆料,它含有至少一种可聚合的单体和/或至少一种可硬化的树脂,至少一种用于可聚合单体和/或可硬化树脂的聚合引发剂和任选地含一种填料,其特征在于,作为聚合引发剂含有至少一种有机取代的铵盐作为一种灰浆部分的组成部分和至少一种我机的过硫酸盐作为另一灰浆部分的组成部分,它们在这两种灰浆部分就地混合后生成有机取代的过硫酸铵,其中有机取代的铵盐和无机的过硫酸盐以及可聚合的单体和可硬化的树脂的种类和用量是这样选择的,即生成通过热的作用可自由基聚合的灰浆料,以及用此灰浆料在固定的底座加固锚杆,钢筋或诸如此类元件的方法。
Description
本发明的主题是通过热引发可完全硬化的,至少两个部分的灰浆料,它含有至少一种可聚合的单体和/或至少一种可硬化的树脂,至少一种用于可聚合单体和/或可硬化树脂的聚合引发剂和任选地至少含有一种填料,和用此灰浆料在固定的底座加固锚杆、钢筋或诸如此类元件的方法。
为在含矿物底座,如混凝土制件或砌体制件的钻孔中加固锚杆,钢筋或类似的元件,通常用以甲基丙烯酸酯或环氧树脂为基础的两部分灰浆料。此灰浆料在反应性的成份相互混合后有一定的有效时间,当要加固的部件放入时,在继续一段时间间隔后达到它的最终强度。所谓的有效时间在通常的条件下在几分钟的范围。完全硬化一般在几分钟至几小时内完成。在任何情况下两种作用相互配合,即较长的有效时间导致较长的完全硬化时间,其中此时间可取决于环境条件,尤其是随温度而变化。
为克服对温度的依赖性,老的德国专利申请10002 367.3建议通过前期聚合(Frontalpolymerisation)按热引发可完全硬化的灰浆料,它除了含可聚合的单体或可硬化的树脂和任选地含至少一种填料外含有一种在温度30℃以上热可活化的和/或热可释放的聚合引发剂用于单体和/或含有硬化加速剂用于可硬化树脂,其中单体或树脂的品种和用量和聚合引发剂或硬化加速剂的品种和用量可这样选择,即在聚合引发后聚合前期的速度(前期速度)至少为10cm/min。
从US-A-6 057 406中可知,在单体混合物的前期聚合中可使用三辛基甲基过硫酸铵作引发剂,其优点是,在分解时它不产生气体。但这种非常活泼的聚合引发剂在它与可聚合的单体混合存放时就已引发聚合。
此外,不仅对前期聚合而且也对其它热引发的,自由基聚合在使用的灰浆存放稳定性和物料必要的高活性之间基本上形成一个矛盾。因此通常,灰浆的组成部分至少是两个部分和或者一种活性较低的引发剂在一部分中与一种加速剂在第二部分中相结合或活泼的引发剂在惰性物质(通常是增塑剂)中与可聚合单体或树脂分开存放。
因为采用的增塑剂影响完全硬化的灰浆的机械性能,故它的量必须维持很低,这又导致对均匀混合不利的混合比1∶10至1∶7。因此建议用不同方法,采用活性的载体物质,这又使得在其它部分中需要完全特殊的反应部分。
曾经建议过用水作载体物质。另方面WO-A-94/19397公开了用环氧化合物和/或异氰酸酯作载体物质。
由于这样的载体物质很昂贵且有缺点,因为它可与灰浆料的其余部分发生反应,因此本发明的根本的任务是,提供一种通过热引发可完全硬化的灰浆料,它对聚合引发剂无需附加的载体物质和解决了均匀混合的问题和在良好的存放稳定性下具有高的反应活性,使均匀的完全硬化的最终产品具有高的机械强度。
对热引发可理解为,通过在分开的部分中存在成分的混合得到的灰浆料在任意的时刻在它形成后可通过热输入引发灰浆的聚合反应,这样产生很长的灰浆料有效时间和达到在所需时间点开始完全硬化。因此有可能,首先用灰浆料填充大量的钻孔,随后放入加固元件,进行调节和然后引发硬化,这样使这有可能达到最佳的非常一致的完全硬化和因此使安装的加固元件达到很大程度均匀的拉伸强度。
令人惊讶的表明,用非常简单和完美的方法有可能完成此任务,即作为聚合引发剂采用有机取代的过硫酸铵,但是它仅以所需的原料的形式存在于灰浆料分开的部分中和仅在就地混合至少两个部分时在灰浆料中形成。其中灰浆料的一个部分含有至少一种有机取代的铵盐,而另一部分至少含有无机的过硫酸盐,它在很快的反应中形成有机取代的过硫酸铵,然后它提供作为灰浆料的自由基硬化的引发剂。
因此本发明的主题是通过热引发可完全硬化的至少两个部分的灰浆料。本发明的主题还包括对加固元件,如锚杆,钢筋或诸如此类元件在固定的底座用此灰浆加固的方法。
因此本发明涉及一种通过热引发可完全硬化的,至少两个部分的灰浆料,它含有
a)至少一种可聚合的单体和/或至少一种可硬化的树脂,
b)至少一种用于可聚合的单体和/或可硬化的树脂的聚合引发剂,和
c)任选地至少一种填料,其特征在于,作为聚合引发剂含有至少一种有机取代的铵盐作为灰浆部分的组成部分和含有至少一种无机过硫酸盐作为另外的灰浆部分的组成部分,它在灰浆部分就地混合后产生有机取代的过硫酸铵,其中有机取代的铵盐和无机过硫酸盐以及可聚合的单体和可硬化的树脂的种类和用量这样来选择,使之形成通过热作用自由基可聚合的灰浆料。
按本发明的优选的实施方式,灰浆料含有
a)10至98%(重量)的至少一种化合物(A),它至少具有一个可聚合的乙烯基,作为可聚合单体或可硬化的树脂
b)1至15%(重量)的至少一种有机取代的铵盐(B)
c)1至15%(重量)的至少一种无机过硫酸盐(C)
d)0至60%(重量)的至少一种填料(D)
e)0至10%(重量)的至少一种增稠剂(E)
f)0至30%(重量)的至少一种其它的在温度高于30℃可热活化和/或可热释放的聚合引发剂(F)和自加速-分解温度(FADT)至少30℃,用于乙烯基化合物(A)
g)0至10%(重量)的至少一种聚合加速剂(G)
h)0至10%(重量)的至少一种溶剂或稀释剂(H),其中有机取代的铵盐(B)和无机过硫酸盐(C)存在于相互密闭分开的部分中。
本发明使用的可聚合的单体及可硬化的树脂特别从以下化合物中挑选:丙烯酸,甲基丙烯酸,苯乙烯,二乙烯基苯,醋酸乙烯,丙烯酰胺,过渡金属硝酸盐/丙烯酰胺-络合物,丙烯酸酯,如丙烯酸丁酯,丙烯酸2-(2-乙氧基乙氧基)乙酯(EOEOEA),丙烯酸四氢糠基酯(THFA),丙烯酸月桂酯,丙烯酸苯氧基乙酯,丙烯酸异癸酯,丙烯酸十三烷酯,乙氧基化的丙烯酸壬基苯酯,丙烯酸异冰片酯(IBOA),乙氧基化的双酚-A-二丙烯酸酯,聚乙二醇二丙烯酸酯(PEGDA),烷氧基化的二丙烯酸酯,丙氧基化的新戊二醇二丙烯酸酯(NPGPODA),乙氧基化的新戊二醇二丙烯酸酯(NPGEODA),1,6-己二醇二丙烯酸酯(HDDA),四甘醇二丙烯酸酯(TTEGDA),三甘醇二丙烯酸酯(TIEGDA),三丙二醇二丙烯酸酯(TPGDA),二丙二醇二丙烯酸酯(DPGDA),二-(三羟甲基丙烷)四丙烯酸酯(DiTMPTTA),三(α-羟乙基)异氰尿酸三丙烯酸酯(THEIC-TA),二季戊四醇五丙烯酸酯(DiPEPA),乙氧基化的三羟甲基丙烷-三丙烯酸酯(TMPEOTA),丙氧基化的三羟甲基丙烷三丙烯酸酯(TMPPOTA),乙氧基化的季戊四醇四丙烯酸酯(PPTTA),丙氧基化的甘油三丙烯酸酯(GPTA),季戊四醇四丙烯酸酯(PETTA),三羟甲基丙烷三丙烯酸酯(TMPTA)和改性的季戊四醇三丙烯酸酯;甲基丙烯酸酯,如甲基丙烯酸烯丙基酯(AMA),甲基丙烯酸四氢糠酯(THFMA),甲基丙烯酸苯氧基乙基酯,甲基丙烯酸异冰片基酯,甲基丙烯酸甲酯(MMA),三甘醇二甲基丙烯酸酯(TIEGDMA),乙二醇二甲基丙烯酸酯(EGDMA),四甘醇二甲基丙烯酸酯(TTEGDMA),聚乙二醇二甲基丙烯酸酯(PEGDMA),丁二醇二甲基丙烯酸酯(BDDMA),二甘醇二甲基丙烯酸酯(DEGDMA),己二醇二甲基丙烯酸酯(HDDMA),聚乙二醇二甲基丙烯酸酯(PEG600DMA),丁二醇二甲丙烯酸酯(BGDMA),乙氧基化的双酚-A-二甲基丙烯酸酯,三羟甲基丙烷三甲基丙烯酸酯(TMPTMA);和/或齐聚物或预聚物,如双酚-A-环氧丙烯酸酯。环氧化的豆油丙烯酸酯,环氧基-酚醛清漆丙烯酸酯齐聚物,脂肪酸改性的双酚-A-环氧丙烯酸酯,芳族的单丙烯酸酯齐聚物,脂肪族的二丙烯酸酯-齐聚物,四官能团的环氧丙烯酸酯,胺改性的聚醚丙烯酸酯-齐聚物,脂肪族的氨基甲酸酯三丙烯酸酯(Urethantriacrylat),脂肪族的氨基甲酸酯四丙烯酸酯,脂肪族的氨基甲酸酯二丙烯酸酯,六官能团的芳族氨基甲酸酯丙烯酸酯,芳族的氨基甲酸酯二丙烯酸酯,芳族的氨基甲酸酯四丙烯酸酯和四官能团的聚酯丙烯酸酯。
根据本发明的特别优选的实施方式,作为至少一种可聚合的具有乙烯基的化合物(A)灰浆料含有丙烯酸,甲基丙烯酸,丙烯酸酯,如丙烯酸正丁基酯,1,6-己二醇二丙烯酸酯,三羟甲基丙烷三丙烯酸酯或季戊四醇四丙烯酸酯,甲基丙烯酸酯,如甲基丙烯酸甲酯,三甘醇二甲基丙烯酸酯,二甘醇二甲基丙烯酸酯,三甘醇二甲基丙烯酸酯或三羟甲基丙烷三甲基丙烯酸酯,苯乙烯,二乙烯基苯,乙酸乙烯酯,丙烯酰胺,过渡金属硝酸盐/丙烯酰胺-络合物,齐聚的脂肪族的氨基甲酸酯-(甲基)丙烯酸酯,环氧-(甲基)丙烯酸酯,聚醚-(甲基)丙烯酸酯和/或聚酯-(甲基)丙烯酸酯。
此外优选的是,使用三-或尤其是四烷基-,-芳基或-芳基-烷基铵盐,例如-卤代铵例如-氯代铵,-乙酸铵,-(甲基)丙烯酸铵和/或硫酸氢铵作为有机取代的铵盐(B)。特别优选的是采用四丁基氯化铵,苄基三乙基氯化铵,四丁基-硫酸氢铵,十四烷基二甲基苄基氯化铵或三甲基-辛基氯化铵或这些化合物的混合物。
作为无机过硫酸盐(C)优选采用过硫酸钠,过硫酸钾,不取代或弱取代的过硫酸铵,如单或二烷基-,芳基或/和芳基烷基过硫酸铵。
优选的是,所描述的灰浆料作为填料含有石英砂,石英粉,热解的二氧化硅,金刚砂,玻璃小球,碳酸盐,硫酸盐,水泥,金属粉末或颗粒,水合层状硅酸盐如蒙脱石,锂蒙脱石和膨润土,一种有机填料和/或它们的混合物。
作为增稠剂(E)优选采用硅酸和/或硅酸盐,如由Laporte Ltd.销售的Laponit(一种合成层状硅酸镁)或膨润土。
按本发明的其它优选的实施方式有可能,为改善硬化在灰浆料中作为附加的聚合引发剂(F)加入过氧化物,特别是二烷基过氧化物,如二-叔丁基过氧化物,过氧化二酰,如过氧化二苯甲酰,氢过氧化物,如叔-丁基过氧化氢或枯烯过氧化氢,过碳酸酯,如过苯甲酸丁基酯,过缩酮(Perketal),如1,1-二-叔-丁基-过氧-3,3,5-三甲基环己烷,和/或偶氮化合物,如偶氮二异丁基腈,具有自加速-分解温度(SADT)至少为30℃,优选为55至120℃。
此外优选的是,在使用聚合加速剂(G)的情况采用这样的化合物,它在温度30℃以上,特别是在55-120℃温度范围可热活化和/或可热释放。这特别是涉及胺,尤其是叔胺,如叔苯胺,优选二甲基苯胺,硫化物,硫脲或硫醇和/或金属化合物,如钴-或钒化合物。
此外可能的是,为调节粘度附加装入惰性溶剂和/或稀释剂(L),例如增塑剂,尤其是二烷基苯二甲酸酯或二烷基己二酸酯和/或二甲基甲酰胺。
本发明另外的主题是加固元件如锚杆、钢筋或诸如此类元件在固定底座的加固方法,其特征在于,上面阐明的灰浆料装到销孔中,并将锚杆,钢筋和诸如此类元件放入和通过加热灰浆料引起完全硬化。
这里灰浆料部分的混合可用例如静态混合器进行,其结果是,一个灰浆部分的有机取代铵盐与至少另外一个灰浆部分的无机过硫酸盐自发地就地完全反应成相应的有机取代的过硫酸铵,这样通过热的作用生成自由基可聚合的灰浆料。这种灰浆料然后放入到在固定底座已有的销孔中,加固元件要固定在此底座上。随后将锚杆,钢筋或类似的加固元件放入填充有灰浆料的销孔中,在其上通过加热灰浆料到过硫酸盐反应温度以上,任选地在附加的聚合引发剂和/或聚合加速剂的反应温度以上引起完全硬化。
热引发是通过灰浆料的表面层的逐点或逐面的加热或通过热输入到灰浆料的内部而引起的。在此有可能,灰浆料的热引发通过用导热的加固元件带入热量而实现,可通过导热,通过电阻加热或借助于加固元件辐射的能量场,如电场,磁场或电磁场,例如通过微波辐射。
在按本发明方法的实施中钻孔和锚杆的尺寸选择相应于注射体系的技术水平。其中按本发明装入准备好的钻孔中灰浆料的量要以装入待固定的元件后环隙完全填满为准。按本发明元件的调整是可能的,因灰浆料在几秒钟的短时间加热后至少在80℃才完全硬化。
用此方法有可能,大量的加固元件装入准备好的和已经用灰浆料填满的销孔中,在加固和校准全部的加固元件后通过上面提到的热引发实现灰浆料的快速和完全的,尤其是均匀完全硬化,因此装入的加固元件达到高度均匀性和强度的稳定性。
以下实例用于进一步解释本发明
实例1
通过前期聚合完全硬化的物料:混合比部分A∶部分B为1∶1
总数 部分A 部分B
季戊四醇四丙烯酸酯(SR 295) 86 45 41
改性的硅酸(Cab-O-Sil) 2 1 1
过硫酸铵 8 0 8
四丁基氯化铵 4 4 0
100 50 50
首先在应用上表确定的组成部分的情况下部分A和部分B分开制备。
在两个部分用静态混合器混合后得到自由可聚合的灰浆料,因为过硫酸铵自发地与四丁基氯化铵反应生成四丁基过硫酸铵。用此方法得到的灰浆料在从静态混合器排出后加入钻孔中的质量C20的混凝土中,钻孔的深度为130mm和钻孔直径为14mm。在放入外径为12mm的锚杆后和在用钎焊的烙铁加热在钻孔上面存在的灰浆料到150℃而引发聚合后,在30秒的时间内物料发生完全的硬化。锚杆的拉伸力在完全硬化后约为29.5kN。
实例2
通过前期聚合完全硬化的物料;混合比部分A∶部分B为1∶1
总数 部分A 部分B
季戊四醇四丙烯酸酯(SR 295) 66.25 33.75 32.5
改性的硅酸(Cab-O-Sil) 2.75 1.75 1
石英砂 15 7.5 7.5
二甲基甲酰胺 3 3 0
过氧化物(DHBP(45%)Trigenox 101) 1 0 1
过硫酸铵 8 0 8
四丁基氯化铵 4 4 0
100 50 50
首先在应用上表确定的组成部分的情况下部分A和B分开制备。
在灰浆料的两个部分混合后将其按实例1中描述的锚杆加固方法放在混凝土-钻孔中。锚杆的拉伸强力在完全硬化后约为39kN。
Claims (24)
1.通过热引发可完全硬化的,至少两部分的灰浆料,它含有
a)至少一种可聚合的单体和/或至少一种可硬化的树脂,
b)至少一种用于可聚合的单体和/或可硬化的树脂的聚合引发剂和
c)任选的至少一种填料,其特征在于,作为聚合引发剂含有至少一种有机取代的铵盐作为灰浆部分的组成部分和至少一种无机过硫酸盐作为另一灰浆部分的组成部分,它们在就地混合后产生有机取代的过硫酸铵,其中有机取代的铵盐和无机过硫酸盐的种类和用量以及可聚合单体及可硬化树脂的种类和用量是这样来选择的,使之生成通过热作用自由基可聚合的灰浆料。
2.按权利要求1的灰浆料,其特征在于,它含有:
a)10至98%(重量)的至少一种化合物(A),它至少具有一个可聚合的乙烯基,作为可聚合的单体和可硬化的树脂,
b)1至15%(重量)的至少一种有机取代的铵盐(B),
c)1至15%(重量)的至少一种无机过硫酸盐(C),
d)0至60%(重量)的至少一种填料(D),
e)0至10%(重量)的至少一种增稠剂(E),
f)0至30%(重量)的至少另外一种在温度30℃以上可热活化的和/或可热释放的聚合引发剂(F),其自加速分解温度至少为30℃,用于乙烯基化合物(A),
g)0至10%(重量)的至少一种聚合加速剂(G),
h)0至10%(重量)的至少一种溶剂或稀释剂(H),其中有机取代的铵盐(B)和无机的过硫酸盐(C)存在于相互密闭分开的部分中。
3.按权利要求2的灰浆料,其特征在于,作为可聚合的乙烯基化合物(A)它含有丙烯酸,甲基丙烯酸,丙烯酸酯,甲基丙烯酸酯,苯乙烯,二-乙烯基苯,乙酸乙烯酯,丙烯酰胺,过渡金属硝酸盐/丙烯酰胺-络合物,齐聚的脂肪族氨基甲酸酯-丙烯酸酯或-甲基丙烯酸酯,环氧-丙烯酸酯或-甲基丙烯酸酯,聚醚-丙烯酸酯或-甲基丙烯酸酯和/或聚酯-丙烯酸酯或-甲基丙烯酸酯。
4.按权利要求3的灰浆料,其特征在于,所述丙烯酸酯是丙烯酸正丁酯,1,6-己二醇二丙烯酸酯,三羟甲基丙烷三丙烯酸酯或季戊四醇四丙烯酸酯;和所述甲基丙烯酸酯是甲基丙烯酸甲酯,丁二醇二甲基丙烯酸酯,三甘醇二甲基丙烯酸酯,二甘醇二甲基丙烯酸酯,三甘醇二甲基丙烯酸酯或三羟甲基丙烷三甲基丙烯酸酯。
5.按权利要求2的灰浆料,其特征在于,作为有机取代的铵盐(B)它含有三-或四-烷基,-芳基,或-芳基-烷基卤化铵,-乙酸铵,-碳酸铵,-碳酸氢铵,-磷酸铵,-磷酸氢铵,-硫酸铵,-硫酸氢铵,-丙烯酸铵,-甲基丙烯酸铵或这些化合物的混合物。
6.按权利要求5的灰浆料,其特征在于,作为有机取代的铵盐(B)它含有四丁基氯化铵,苄基三乙基氯化铵,四丁基硫酸氢铵,四癸基二甲基苄基氯化铵或三甲基辛基氯化铵或这些化合物的混合物。
7.按权利要求2的灰浆料,其特征在于,作为无机过硫酸盐(C)它含有过硫酸铵,过硫酸钾或过硫酸钠或它们的混合物。
8.按权利要求2的灰浆料,其特征在于,作为填料(D)它含有石英砂,石英粉,热解的二氧化硅,金刚砂,玻璃小球,碳酸盐,硫酸盐,水泥,金属粉或金属粒子,水合的层状硅酸盐,有机填料和/或它们的混合物。
9.按权利要求8的灰浆料,其特征在于,所述水合的层状硅酸盐是蒙脱石,锂蒙脱石或膨润土。
10.按权利要求2的灰浆料,其特征在于,作为增稠剂(E)它含有硅酸和/或硅酸盐。
11.按权利要求10的灰浆料,其特征在于,作为增稠剂(E)它含有Laponit或膨润土。
12.按权利要求2的灰浆料,其特征在于,作为附加的聚合引发剂(F)它含有过氧化物,和/或偶氮化合物,它具有自加速-分解温度至少为30℃。
13.按权利要求12的灰浆料,其特征在于,所述过氧化物是二烷基过氧化物,二-酰基过氧化物,氢过氧化物,过碳酸酯,过缩酮,和所述偶氮化合物是偶氮二异丁腈,并且所述引发剂(F)具有自加速-分解温度为55至80℃。
14.按权利要求13的灰浆料,其特征在于,所述二烷基过氧化物为二叔丁基过氧化物;所述二酰基过氧化物为二苯甲酰基过氧化物;所述氢过氧化物为叔-丁基过氧化氢或枯烯过氧化氢;所述过碳酸酯为过苯甲酸丁基酯;所述过缩酮为1,1-二-叔-丁基-过氧-3,3,5-三甲基环己烷。
15.按权利要求2的灰浆料,其特征在于,作为聚合加速剂(G)它含有胺和/或硫化物。
16.按权利要求2的灰浆料,其特征在于,作为聚合加速剂(G)它含有硫脲或硫醇和/或金属化合物。
17.按权利要求15的灰浆料,其特征在于,所述胺为叔苯胺。
18.按权利要求17的灰浆料,其特征在于,所述胺为二甲基苯胺。
19.按权利要求16的灰浆料,其特征在于,所述金属化合物是钴化合物。
20.按权利要求2的灰浆料,其特征在于,作为惰性溶剂(H)它含有增塑剂,水和/或二甲基甲酰胺。
21.按权利要求20的灰浆料,其特征在于,所述增塑剂是苯二甲酸二烷基酯或己二酸二烷基酯。
22.在固定的底座加固锚杆,钢筋的方法,其特征在于,将按前面述及的权利要求之一的灰浆料装入销孔中,再放入锚杆,钢筋和通过加热灰浆料引起完全硬化。
23.按权利要求22的方法,其特征在于,灰浆料的加热是通过经加固元件输入能量而完成的。
24.按权利要求22或23的方法,其特征在于,通过电阻加热和/或电场,磁场或电磁场实行热量输入。
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US (1) | US6815517B2 (zh) |
EP (1) | EP1273617B1 (zh) |
JP (1) | JP2003064321A (zh) |
KR (1) | KR20030004109A (zh) |
CN (1) | CN1284743C (zh) |
AT (1) | ATE310045T1 (zh) |
DE (2) | DE10132336C2 (zh) |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002046291A1 (en) * | 2000-11-15 | 2002-06-13 | Henkel Loctite Corporation | Multi-functional alpha-alkoxyalkyl acrylate and methacrylate ester compositions and reworkable polymers formed therefrom |
DE10232762A1 (de) * | 2002-07-18 | 2004-02-12 | Kew Kunststofferzeugnisse Gmbh Wilthen | Befestigungsmasse zum Fixieren eines Befestigungselementes und Verfahren |
DE10340394B4 (de) * | 2003-09-02 | 2005-09-29 | Hilti Ag | Vorrichtung zur Befestigung von Verankerungsmitteln |
US7319410B2 (en) * | 2004-06-28 | 2008-01-15 | Intelliserv, Inc. | Downhole transmission system |
JP5192174B2 (ja) * | 2007-04-27 | 2013-05-08 | アビオス株式会社 | 丸太材およびその他の多孔質材料の体積改質法 |
US8215393B2 (en) * | 2009-10-06 | 2012-07-10 | Schlumberger Technology Corporation | Method for treating well bore within a subterranean formation |
CN101759389B (zh) * | 2009-12-29 | 2012-06-20 | 上海东升新材料有限公司 | 流变降粘剂及其制备方法 |
EP2357162B1 (en) * | 2010-02-11 | 2012-09-05 | HILTI Aktiengesellschaft | Resin mortar suitable for construction purposes, especially for chemical anchoring |
DE102010008971B4 (de) * | 2010-02-24 | 2013-10-10 | Hilti Aktiengesellschaft | Verwendung einer Zweikomponenten-Mörtelmasse |
WO2012174370A2 (en) * | 2011-06-17 | 2012-12-20 | M-I L.L.C. | Composition of polybutadiene-based formula for downhole applications |
US10023783B2 (en) * | 2012-06-23 | 2018-07-17 | Pumprock, Llc | Compositions and processes for downhole cementing operations |
DE102012221441A1 (de) * | 2012-11-23 | 2014-05-28 | Hilti Aktiengesellschaft | Verfahren zur Herstellung von modifizierten Epoxy(meth)acrylatharzen und ihre Verwendung |
DE102012221446A1 (de) * | 2012-11-23 | 2014-05-28 | Hilti Aktiengesellschaft | Harzmischung auf Epoxy(meth)acrylatharz-Basis und deren Verwendung |
EP2851352A1 (de) * | 2013-09-19 | 2015-03-25 | HILTI Aktiengesellschaft | Durch Frontalpolymerisation aushärtbarer Reaktionsharzmörtel und Verfahren zur Befestigung von Ankerstangen |
US10174223B2 (en) * | 2013-11-30 | 2019-01-08 | Hrl Laboratories, Llc | Formulations, methods, and apparatus for remote triggering of frontally cured polymers |
EP2980037A1 (de) * | 2014-07-31 | 2016-02-03 | HILTI Aktiengesellschaft | Zweikomponenten-Mörtelmasse und deren Verwendung |
US10487446B2 (en) | 2016-03-18 | 2019-11-26 | The Board Of Trustees Of The University Of Illinois | Frontal polymerization for fiber-reinforced composites |
US11015057B2 (en) * | 2019-04-03 | 2021-05-25 | Prc-Desoto International, Inc. | Dual-cure compositions |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2367C (de) | O. LILIENTHAL, Ingenieur, In Berlin | Zirkel für Metallarbeiter mit Vorrichtung zum Anreifsen von Mittellinien | ||
US4326049A (en) * | 1979-09-18 | 1982-04-20 | Minnesota Mining And Manufacturing Company | Phase transfer free-radical polymerization |
IE52230B1 (en) * | 1981-12-11 | 1987-08-19 | Loctite Ireland Ltd | Two-part,two-tier cure adhesive composition |
DE3812814A1 (de) * | 1988-04-16 | 1989-11-02 | Hilti Ag | Verwendung von zweikomponenten-reaktionsharzen fuer befestigungszwecke |
DE3940309A1 (de) * | 1989-12-06 | 1991-06-13 | Hilti Ag | Moertelmasse |
DE4121832C1 (zh) * | 1991-07-02 | 1992-06-11 | Upat Gmbh & Co, 7830 Emmendingen, De | |
KR960000046B1 (ko) * | 1992-10-16 | 1996-01-03 | 한국과학기술원 | 테트라 부틸 암모늄 퍼옥시 디술페이트(n-tetrabutylammonium peroxydisulfate), 그 제조방법 |
US6067406A (en) * | 1995-05-03 | 2000-05-23 | Agfa-Gevaert N.V. | Automatic calibration for output devices based on device output mode |
US6057406A (en) * | 1998-08-03 | 2000-05-02 | The University Of Southern Mississippi | Functionally gradient polymeric materials |
DE10002367C1 (de) * | 2000-01-20 | 2001-07-19 | Hilti Ag | Durch Frontalpolymerisation aushärtbare Mörtelmasse und Verfahren zur Befestigung von Ankerstangen |
-
2001
- 2001-07-04 DE DE10132336A patent/DE10132336C2/de not_active Expired - Fee Related
-
2002
- 2002-06-21 AT AT02405515T patent/ATE310045T1/de active
- 2002-06-21 EP EP02405515A patent/EP1273617B1/de not_active Expired - Lifetime
- 2002-06-21 DE DE50204922T patent/DE50204922D1/de not_active Expired - Lifetime
- 2002-07-01 JP JP2002191802A patent/JP2003064321A/ja active Pending
- 2002-07-01 US US10/188,203 patent/US6815517B2/en not_active Expired - Lifetime
- 2002-07-02 KR KR1020020037871A patent/KR20030004109A/ko not_active Application Discontinuation
- 2002-07-03 CN CNB021412170A patent/CN1284743C/zh not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
US20030027900A1 (en) | 2003-02-06 |
US6815517B2 (en) | 2004-11-09 |
CN1394825A (zh) | 2003-02-05 |
EP1273617B1 (de) | 2005-11-16 |
DE10132336A1 (de) | 2003-01-23 |
EP1273617A3 (de) | 2003-05-02 |
JP2003064321A (ja) | 2003-03-05 |
DE50204922D1 (de) | 2005-12-22 |
EP1273617A2 (de) | 2003-01-08 |
ATE310045T1 (de) | 2005-12-15 |
DE10132336C2 (de) | 2003-07-31 |
KR20030004109A (ko) | 2003-01-14 |
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