KR100372041B1 - Polymer based cement superplasticizer - Google Patents
Polymer based cement superplasticizer Download PDFInfo
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- KR100372041B1 KR100372041B1 KR10-2000-0015952A KR20000015952A KR100372041B1 KR 100372041 B1 KR100372041 B1 KR 100372041B1 KR 20000015952 A KR20000015952 A KR 20000015952A KR 100372041 B1 KR100372041 B1 KR 100372041B1
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- South Korea
- Prior art keywords
- hydrogen
- integer
- coom
- methyl
- general formula
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- 239000004568 cement Substances 0.000 title claims abstract description 25
- 229920000642 polymer Polymers 0.000 title claims abstract description 11
- 239000008030 superplasticizer Substances 0.000 title description 2
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 14
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 8
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 7
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 7
- 125000003277 amino group Chemical group 0.000 claims abstract description 7
- 150000008064 anhydrides Chemical group 0.000 claims abstract description 7
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 6
- 150000008378 aryl ethers Chemical class 0.000 claims abstract description 5
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 229920000090 poly(aryl ether) Polymers 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- BOGWUJBGKVPNKD-BTVCFUMJSA-N O1CC1.O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO Chemical compound O1CC1.O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO BOGWUJBGKVPNKD-BTVCFUMJSA-N 0.000 claims 1
- QUANRIQJNFHVEU-UHFFFAOYSA-N oxirane;propane-1,2,3-triol Chemical compound C1CO1.OCC(O)CO QUANRIQJNFHVEU-UHFFFAOYSA-N 0.000 claims 1
- 239000004567 concrete Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000002002 slurry Substances 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- -1 alkylene glycol Chemical compound 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011372 high-strength concrete Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 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 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000005418 aryl aryl group Chemical group 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- CTPXHNFFGNDMCM-UHFFFAOYSA-M ctk4f5363 Chemical compound [Na+].[O-]O CTPXHNFFGNDMCM-UHFFFAOYSA-M 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000011396 hydraulic cement Substances 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- 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
- F16B2/00—Friction-grip releasable fastenings
- F16B2/20—Clips, i.e. with gripping action effected solely by the inherent resistance to deformation of the material of the fastening
- F16B2/22—Clips, i.e. with gripping action effected solely by the inherent resistance to deformation of the material of the fastening of resilient material, e.g. rubbery material
-
- 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
- F16B37/00—Nuts or like thread-engaging members
- F16B37/08—Quickly-detachable or mountable nuts, e.g. consisting of two or more parts; Nuts movable along the bolt after tilting the nut
- F16B37/0871—Quickly-detachable or mountable nuts, e.g. consisting of two or more parts; Nuts movable along the bolt after tilting the nut engaging the bolt laterally, i.e. without the need to engage the end of the bolt
- F16B37/0878—Quickly-detachable or mountable nuts, e.g. consisting of two or more parts; Nuts movable along the bolt after tilting the nut engaging the bolt laterally, i.e. without the need to engage the end of the bolt in one piece, e.g. C-shaped nuts
Landscapes
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
불포화카르복실 단량체와 다가 알콜/당류·폴리 알킬렌 글리콜 모노(메타)아릴에테르 단량체를 공중합시키므로 얻어지는 일반식(Ⅲ)으로 표시되는 고분자 중합체로된 시멘트 유동화제Cement fluidizing agent made of a high molecular polymer represented by the general formula (III) obtained by copolymerizing an unsaturated carboxyl monomer with a polyhydric alcohol / saccharide / polyalkylene glycol mono (meth) arylether monomer.
여기서 X, Y는 각각 수소, 메틸, -COOM3이거나 X나 Y가 -COOM2와 무수물 환을 만들고, Z는 수소, 메틸 또는 CH2COOM3이며, M2, M3는 각각 수소, 알칼리금속, 암모늄, 유기아민기와 같은 것 중의 하나를 나타낸다.Where X and Y are hydrogen, methyl and -COOM 3 respectively, or X or Y is -COOM 2 and anhydride rings, Z is hydrogen, methyl or CH 2 COOM 3 and M 2 and M 3 are hydrogen and alkali metal, respectively. Or one such as ammonium or an organic amine group.
또한 R1, R2는 각각 수소 혹은 메틸이고, R3는 탄소수 2-4의 알킬렌기, A는 탄소수 3-6의 알코올/당류이며, m은 1-100의 정수, n은 0, 1의 정수, a, b는 1-20의 정수이며, k는 1-6의 정수이다.R 1 and R 2 are each hydrogen or methyl, R 3 is an alkylene group having 2-4 carbon atoms, A is an alcohol / saccharide having 3-6 carbon atoms, m is an integer of 1-100, n is 0, 1 The integer, a, b is an integer of 1-20, k is an integer of 1-6.
Description
본 발명은 수경성 시멘트에 배합하므로서 시멘트 슬러리에 유동성을 부여하고 슬럼프 로스를 방지하는 고분자 중합체로된 시멘트 유동화제에 관한 것으로 더욱 구체적으로는 일반식(I)로 표시되는 불포화 카르복실 단량체 및 일반식(Ⅱ)로 표시되는 다가알콜/당류·폴리 알킬렌 글리콜 모노(메타) 아릴에테르계 단량체로 부터 중합반응에 의하여 얻어지는 일반식(Ⅲ)으로 표시되는 고분자 중합체로된 시멘트 유동화제에 관한 것이다.The present invention relates to a cement fluidizing agent made of a high-molecular polymer which provides fluidity to a cement slurry and prevents slump loss by blending with a hydraulic cement. More specifically, the unsaturated carboxyl monomer represented by general formula (I) and general formula ( The present invention relates to a cement fluidizing agent comprising a polymer polymer represented by the general formula (III) obtained by a polymerization reaction from a polyhydric alcohol / saccharide / polyalkylene glycol mono (meth) arylaryl monomer represented by II).
여기서 X, Y는 각각 수소, 메틸, -COOM3이거나 X나 Y가 -COOM2와 무수물 환을 만들고, Z는 수소, 메틸 또는 CH2COOM3이며, M2, M3는 각각 수소, 알칼리금속, 암모늄, 유기아민기와 같은 것 중의 하나를 나타낸다.Where X and Y are hydrogen, methyl and -COOM 3 respectively, or X or Y is -COOM 2 and anhydride rings, Z is hydrogen, methyl or CH 2 COOM 3 and M 2 and M 3 are hydrogen and alkali metal, respectively. Or one such as ammonium or an organic amine group.
여기서 R1, R2는 각각 수소 혹은 메틸이고, R3는 탄소수 2-4의 알킬렌기, A는 탄소수 3-6의 알코올/당류이며, m은 1-100의 정수, n은 0, 1의 정수이며, k는 1-6의 정수이다.Where R 1 and R 2 are each hydrogen or methyl, R 3 is an alkylene group of 2-4 carbon atoms, A is an alcohol / saccharide of 3-6 carbon atoms, m is an integer of 1-100, n is 0, 1 It is an integer and k is an integer of 1-6.
여기서 X, Y는 각각 수소, 메틸, -COOM3이거나 X나 Y가 -COOM2와 무수물 환을 만들고, Z는 수소, 메틸 또는 CH2COOM3이며, M2, M3는 각각 수소, 알칼리금속, 암모늄, 유기아민기와 같은 것 중의 하나를 나타낸다.Where X and Y are hydrogen, methyl and -COOM 3 respectively, or X or Y is -COOM 2 and anhydride rings, Z is hydrogen, methyl or CH 2 COOM 3 and M 2 and M 3 are hydrogen and alkali metal, respectively. Or one such as ammonium or an organic amine group.
또한 R1, R2는 각각 수소 혹은 메틸이고, R3는 탄소수 2-4의 알킬렌기, A는 탄소수 3-6의 알코올/당류이며, m은 1-100의 정수, n은 0, 1 정수, a, b는 1-20의 정수이며, k는 1-6의 정수이다.R 1 and R 2 are each hydrogen or methyl, R 3 is an alkylene group having 2-4 carbon atoms, A is an alcohol / saccharide having 3-6 carbon atoms, m is an integer of 1-100, n is 0, 1 integer , a, b are integers of 1-20, k is an integer of 1-6.
현재 시멘트용 감수 분산제로는 리그닌 술폰산계, 폴리올계, 글루콘산계, 폴리카르본산계, 나프탈렌 술폰산계 및 멜라민수지 술폰산계등이 알려져 있으며, 이들 감수 분산제의 장단점을 상호 보완하기 위하여 특히 가격이 저렴하고 공기 연행성이 큰 리그닌 술폰산계, 고분산성이면서 저공기연행성, 저수화지연성, 안정성이 우수한 나프탈렌 술폰산계와 고분산성이면서 슬럼프 보지력이 뛰어난 폴리카르본산계가 혼합된 고성능 감수 분산제가 제품화되고 있다.Currently, sensitizing dispersants for cement are known as lignin sulfonic acid, polyol, gluconic acid, polycarboxylic acid, naphthalene sulfonic acid, and melamine resin sulfonic acid. High performance sensitizing dispersant which combines lignin sulfonic acid system with high air degradability, naphthalene sulfonic acid system with high dispersibility, low air continuity, low hydration delay and stability, and polycarboxylic acid system with high dispersibility and excellent slump holding power. .
대한민국 특허 공고번호 86-1647에서는 평균 분자량 1,000-10,000의 알칼리금속 폴리아크릴레이트 5-95%와 알칼리 또는 알칼리토류금속 나프탈렌술포네이트-포름알데히드 축합물과 알칼리 또는 알칼리토류금속 리그닌 술포네이트 90 : 10 - 10 : 90의 중량비로 배합함을 특징으로 하는 수퍼플라스티사이저 시멘트 조성물을 제시하고 있으며, 미국 특허 5087287에서는 말레인산 또는 푸마르산과 같은 불포화디카르복실산과 알킬렌 글리콜 또는 비이온 계면활성제를 첨가하여 수경화성 시멘트의 강도가 증가하는 것을 나타내었으며, 미국특허 4978392에서는 폴리옥시에틸렌글리콜과 폴리머릭 지방산의 폴리카르복실레이트가 유동성과 분산성이 개량됨을 나타내고 있다.Korean Patent Publication No. 86-1647 discloses 5-95% of alkali metal polyacrylates having an average molecular weight of 1,000-10,000 and alkali or alkaline earth metal naphthalenesulfonate-formaldehyde condensates and alkali or alkaline earth metal lignin sulfonates. A superplasticizer cement composition is characterized by blending at a weight ratio of 10:90, and US Patent 5087287 discloses a hydroponic solution by adding an unsaturated dicarboxylic acid such as maleic acid or fumaric acid and an alkylene glycol or nonionic surfactant. It was shown that the strength of the chemical conversion cement, US Patent 4978392 shows that the polycarboxylate of the polyoxyethylene glycol and the polymeric fatty acid improved the fluidity and dispersibility.
미국특허 5661206에서는 폴리 카르복실산 단량체 혼합물의 공중합물 및 알콕시 폴리 알킬렌 글리콜 모노(메타)아릴 에테르계 단량체와 폴리카르복실산 단량체 혼합물의 공중합물을 유동화제로 사용하여 시멘트 슬러리의 유동성을 높이고 경시적인 슬럼프 감소 문제를 해결할 수 있음을 제시하고 있다.U.S. Patent No. 5661206 uses a copolymer of a polycarboxylic acid monomer mixture and a copolymer of an alkoxy poly alkylene glycol mono (meth) aryl ether monomer and a polycarboxylic acid monomer mixture as a fluidizing agent to increase the fluidity of the cement slurry over time. It suggests that the slump reduction problem can be solved.
콘크리트 시공시의 작업성 개선, 경화 콘크리트의 강도 및 내구성의 향상이 강하게 요망되었는데 근래에 이러한 요구를 달성하여 고유동이고, 고강도의 콘크리트가 보급되고 있다.The improvement of workability at the time of concrete construction and the improvement of the strength and durability of hardened concrete were strongly desired, and in recent years, these requirements have been achieved, and high-flow, high-strength concrete has been spread.
이 고유동, 고강도 콘크리트를 제조하는 경우, 폴리카르본산계의 고성능 AE 감수제가 일반적으로 사용되고 있다.When producing this high flow, high strength concrete, polycarboxylic acid-based high performance AE water reducing agents are generally used.
그렇지만 이러한 혼화제는 모두 초기의 유동성을 얻기 위해 다량의 첨가량이 필요하고 또한 물의 첨가량을 증대시킬 필요가 있으며, 따라서 시멘트의 경화 특성이 악화되어 강도는 저하되게 된다.However, all of these admixtures require a large amount of addition to increase the initial fluidity, and an increase in the amount of water added. Therefore, the curing properties of the cement deteriorate and the strength decreases.
콘크리트의 유동성은 초기에서부터 타설까지 필요하다.The fluidity of concrete is necessary from the beginning to casting.
슬러리 내의 알카리 분위기에서 기존의 폴리카르본산계 유동화제는 결합력이 쉽게 약화되어 해리되고 슬럼프 로스를 발생시키는 단점이 있어 이를 해결하기 위하여 W/C 높이거나 유동화제를 과량투입하여 작업성을 높혔으나 강도의 저하 및 재료의 분리현상 등의 문제점을 내포하였다.Existing polycarboxylic acid-based fluidizing agent in the alkali atmosphere in the slurry has the disadvantage of dissociation and slump loss due to the weakening of the binding force. Therefore, the workability is increased by increasing the W / C or excessively adding the fluidizing agent to solve this problem. Problems such as degradation of the material and separation of materials.
본 발명에서는 이를 보완하여 콘크리트 슬러리 내의 강알카리 분위기에서도 강한 결합력을 유지하여 초기의 유동성이 타설까지 유지되도록 즉 경시적인 슬럼프 로스가 발생하지 않도록하여 타설시의 작업성을 높히고 W/C를 높히거나 과량의 유동화제를 첨가하므로서 발생하는 콘크리트 강도의 저하 및 재료의 분리현상 등을 방지할 수 있는 고분자중합체로된 시멘트 유동화제를 제공함에 있다 하겠다.In the present invention to compensate for this to maintain a strong bonding force even in the strong alkali atmosphere in the concrete slurry to maintain the initial fluidity to pour, that is to prevent the occurrence of slump loss over time to increase the workability at the time of pouring and to increase the W / C or excessive It is an object of the present invention to provide a cement fluidizing agent made of a polymer polymer capable of preventing a decrease in concrete strength and material separation caused by adding a fluidizing agent.
본 발명은 콘크리트 슬러리 내의 강알카리 분위기에서도 강한 결합력을 유지하여 초기의 유동성이 타설까지 유지되도록 다시 말하면 경시적인 슬럼프 로스가 발생하지 않도록하므로서 타설시의 작업성을 높히고 물/시메트 비를 높히거나 과량의 유동화제를 첨가하므로써 발생하는 콘크리트 강도의 저하 및 재료의 분리현상을 방지할 수 있고 슬러리 상태에서 시공성을 개선하고 경화콘크리트의 강도와 내구성을 향상시킬 수 있는 고분자 물질의 유동화제를 제공하는 것으로 구체적으로는 다음의 일반식(I)로 표시되는 불포화 카르복실산계 단량체 10-70wt%와 다음의 일반식(Ⅱ)로 표시되는 다가알콜/당류·폴리 알킬렌 글리콜 모노(메타) 아릴에테르계 단량체 30-90%의 중량비로 중합시키므로서 얻어지는 일반식(Ⅲ)으로 표시되는 고분자 중합체로된 시멘트 유동화제에 관한 것이다.The present invention maintains a strong bonding force even in the strong alkali atmosphere in the concrete slurry, so that the initial fluidity is maintained until casting, that is, to prevent the occurrence of slump loss over time to increase the workability at the time of pouring and to increase the water / system ratio or excessive It is to provide a fluidizing agent of a polymer material that can prevent the reduction of concrete strength and material separation caused by the addition of a fluidizing agent, and improve the workability in the slurry state and improve the strength and durability of the hardened concrete. Examples of the polyhydric alcohol / saccharides / polyalkylene glycol mono (meth) arylether monomers represented by 10-70wt% of unsaturated carboxylic acid monomers represented by the following general formula (I) and the following general formula (II) 30 Cemen of a high molecular polymer represented by the general formula (III) obtained by polymerization at a weight ratio of -90% It relates to a fluidizing agent.
여기서 X, Y는 각각 수소, 메틸, -COOM3이거나 X나 Y가 -COOM2와 무수물 환을 만들고, Z는 수소, 메틸 또는 CH2COOM3이며, M2, M3는 각각 수소, 알칼리금속, 암모늄, 유기아민기와 같은 것 중의 하나를 나타낸다.Where X and Y are hydrogen, methyl and -COOM 3 respectively, or X or Y is -COOM 2 and anhydride rings, Z is hydrogen, methyl or CH 2 COOM 3 and M 2 and M 3 are hydrogen and alkali metal, respectively. Or one such as ammonium or an organic amine group.
여기서 R1, R2는 각각 수소 혹은 메틸이고, R3는 탄소수 2-4의 알킬렌기, A는 탄소수 3-6의 알코올/당류이며, m은 1-100의 정수, n은 0, 1의 정수이며, k는 1-6의 정수이다.Where R 1 and R 2 are each hydrogen or methyl, R 3 is an alkylene group of 2-4 carbon atoms, A is an alcohol / saccharide of 3-6 carbon atoms, m is an integer of 1-100, n is 0, 1 It is an integer and k is an integer of 1-6.
여기서 X, Y는 각각 수소, 메틸, -COOM3이거나 X나 Y가 -COOM2와 무수물 환을 만들고, Z는 수소, 메틸 또는 CH2COOM3이며, M2, M3는 각각 수소, 알칼리금속, 암모늄, 유기아민기와 같은 것 중의 하나를 나타낸다.Where X and Y are hydrogen, methyl and -COOM 3 respectively, or X or Y is -COOM 2 and anhydride rings, Z is hydrogen, methyl or CH 2 COOM 3 and M 2 and M 3 are hydrogen and alkali metal, respectively. Or one such as ammonium or an organic amine group.
또한 R1, R2는 각각 수소 혹은 메틸이고, R3는 탄소수 2-4의 알킬렌기, A는 탄소수 3-6의 알코올/당류이며, m은 1-100의 정수, n은 0, 1정수, a, b는 1-20의 정수이며, k는 1-6의 정수이다.R 1 and R 2 are each hydrogen or methyl, R 3 is an alkylene group having 2-4 carbon atoms, A is an alcohol / saccharide having 3-6 carbon atoms, m is an integer of 1-100, n is 0, 1 integer , a, b are integers of 1-20, k is an integer of 1-6.
상기 일반식 (I)과 (Ⅱ)의 공중합 반응은 자유 라디칼 중합 촉매를 첨가함으로써 시작된다.The copolymerization reaction of the general formulas (I) and (II) is started by adding a free radical polymerization catalyst.
수용액 내에서 중합이 이루어질 때 필요한 중합개시제로는 암모늄퍼설페이트, 소듐 퍼설페이트, 하이드로진 퍼옥사이드, 아조아미딘 화합물등이 사용된다.As the polymerization initiator required when the polymerization is carried out in an aqueous solution, ammonium persulfate, sodium persulfate, hydroperoxide, azoamidine compound and the like are used.
가속제로는 소듐 하이드로진 퍼옥사이드, 소듐 하이드로진 설파이트 등을 중합개시제와 함께 투입한다.As the accelerator, sodium hydroperoxide, sodium hydrosulfite, and the like are added together with the polymerization initiator.
유기용매를 사용할 경우에는 퍼옥사이드, 하이드로퍼옥사이드, 아조화합물 등이 중합개시제로 사용된다.When an organic solvent is used, peroxides, hydroperoxides, azo compounds and the like are used as polymerization initiators.
이 경우 가속제로는 아민 화합물 등이 사용된다.In this case, an amine compound or the like is used as the accelerator.
반응 온도는 대개 0-120℃ 정도가 바람직하다고 더욱 좋기로는 40°- 90℃가 적절하다.As for reaction temperature, about 0-120 degreeC is preferable normally, More preferably, 40 degreeC-90 degreeC is suitable.
중합시 사용되는 용매로서는 물, 에탄올과 같은 알코올, 벤젠, n-헥산과 같은 방향족 또는 지방족 탄화수소, 아세톤과 같은 케톤등이 있으며, 물과 탄소수 1-3의 알코올의 혼합물 또는 톨루엔을 사용하는 것이 바람직하다.Examples of the solvent used in the polymerization include water, alcohols such as ethanol, benzene, aromatic or aliphatic hydrocarbons such as n-hexane, ketones such as acetone, and a mixture of water and an alcohol having 1-3 carbon atoms or toluene is preferable. Do.
반응 완료 후 필요한 경우 고형분 조정을 위하여 소정의 물을 첨가한다.After completion of the reaction, water is added if necessary to adjust the solids.
본 발명에서는 전체 반응 혼합물에 대해 15 내지 50 중량 퍼센트로 조정하였다.In the present invention it was adjusted to 15 to 50% by weight relative to the total reaction mixture.
공중합체의 질량 평균 분자량은 500-500000의 분포에 있으며, 더욱 바람직하게는 질량 평균 분자량은 5000-300000의 분포에 있는 것이 좋다.The mass average molecular weight of the copolymer is in the distribution of 500-500000, more preferably the mass average molecular weight is in the distribution of 5000-300000.
질량 평균 분자량이 500이하인 경우 슬럼프 로스 방지율이 작아지고 500000이상인 경우 감수율이 작아지게 되어 기대되는 시멘트 슬러리의 물성을 얻을 수 없게 된다.When the mass average molecular weight is 500 or less, the slump loss prevention rate becomes small, and when the molecular weight is 500000 or more, the susceptibility decreases, so that the expected properties of the cement slurry cannot be obtained.
실시예 1.Example 1.
온도계, 교반기, 환류장치, 모노머 및 촉매 적하장치 및 질소 투입관이 설치되어 있는 유리 반응기에 이소프로필 알코올 350부와 증류수 50부를 넣은 다음 교반하며 플라스크 내부를 질소 치환한 후 플라스크를 80℃까지 가온하여 이소프로필 알코올을 환류시킨다.350 parts of isopropyl alcohol and 50 parts of distilled water were added to a glass reactor equipped with a thermometer, agitator, reflux device, monomer and catalyst dropping device, and nitrogen inlet tube, and stirred. Isopropyl alcohol is refluxed.
아크릴산 70부, 글리세린 · 에틸렌옥사이드 부가물의 폴리 메타릴에테르(에틸렌옥사이드 부가몰수 : 23몰) 351부를 단량체 혼합물로 하고 5% 암모늄퍼설페이트 수용액 57.2부를 중합개시제로 하여 3시간 동안 주입한다.70 parts of acrylic acid and 351 parts of poly metharyl ether of glycerine and ethylene oxide adducts (23 moles of ethylene oxide added mole number) are used as a monomer mixture, and 57.2 parts of 5% aqueous ammonium persulfate solution is injected for 3 hours.
주입이 완료되면 2시간 동안 온도를 유지하여 반응을 완료시킨다.When the injection is complete, the temperature is maintained for 2 hours to complete the reaction.
반응이 완료되면 진공 증류해서 이소프로필 알코올을 회수하고, 반응기의 온도를 실온까지 냉각시킨다.After completion of the reaction, vacuum distillation recovers the isopropyl alcohol, and the reactor is cooled to room temperature.
얻어진 공중합물(공중합체 a)의 고형분을 측정하여 45%가 되도록 증류수를 첨가한다.Solid content of the obtained copolymer (copolymer a) is measured and distilled water is added so that it may become 45%.
실시예 2.Example 2.
온도계, 교반기, 환류장치, 모노머 및 촉매 적하장치 및 질소 투입관이 설치되어 있는 유리 반응기에 톨루엔 500부를 넣은 다음 교반하며 무수말레인산 50부, 글루코오스 ·에틸렌옥사이드 부가물의 폴리 아릴에테르(에틸렌옥사이드 부가몰수 : 23몰) 260부를 반응기에 주입한 후 승온한다.500 parts of toluene was added to a glass reactor equipped with a thermometer, a stirrer, a reflux device, a monomer and a catalyst dropping device, and a nitrogen inlet tube, and then stirred. Polyaryl ether (50 mol of maleic anhydride and a glucose / ethylene oxide adduct) 23 moles) 260 parts is injected into the reactor and then heated.
계내의 온도가 60℃에 달하면 벤조일퍼옥사이드 7부를 주입한 다음 반응기의 온도가 80℃까지 다시 승온한다.When the temperature in the system reaches 60 ℃, 7 parts of benzoyl peroxide is injected, and then the temperature of the reactor is raised again to 80 ℃.
온도를 80℃로 유지하면서 중합반응을 4시간 동안 실시한 다음 반응이 종료되면 감압상태에서 가온하여 톨루엔을 제거하여 투명한 공중합물(공중합체 b)을 얻는다.The polymerization was carried out for 4 hours while maintaining the temperature at 80 ° C., and then, when the reaction was completed, the mixture was heated under reduced pressure to remove toluene to obtain a transparent copolymer (copolymer b).
얻어진 공중합물의 고형분을 측정하여 45%가 되도록 증류수를 첨가한다.Solid content of the obtained copolymer is measured and distilled water is added so that it may become 45%.
비교실시예 3.Comparative Example 3.
콘크리트 시험체를 제조하여 실시예(1)(2)에 의한 시멘트 유동화제와 PC,NS, LS의 유동화제를 각각 비교하여 성능을 알아보았다.Concrete test specimens were prepared to compare the cement fluidizing agent according to Example (1) (2) with the fluidizing agents of PC, NS and LS, respectively.
콘크리트 시험체 제조 20±2℃의 시험실 내에서 골재 혼합기에 굵은 골재(이하 "G"로 함), 잔골재(이하 "S"로 함), 시멘트(이하 "C"로함)와 혼화제 성분이 혼합되어 있는 물(이하 "W"로함)을 투입한 다음 3분간 교반 혼합하여 콘크리트 슬러리를 제조한다.Manufacture of Concrete Test Specimens A coarse aggregate (hereinafter referred to as "G"), fine aggregate (hereinafter referred to as "S"), cement (hereinafter referred to as "C") and admixture components are mixed in an aggregate mixer in a laboratory at 20 ± 2 ° C. Water (hereinafter referred to as "W") was added thereto, followed by stirring for 3 minutes to prepare a concrete slurry.
혼합이 완료되면 제조된 콘크리트 슬러리를 직후, 30분, 60분 후의 슬럼프 및 공기량을 측정하였으며 그 결과는 표 2에 나타내었다.When the mixing was completed, the prepared concrete slurry was measured immediately after 30 minutes and 60 minutes, the slump and the amount of air was measured and the results are shown in Table 2.
사용된 재료 :Material used:
W : 수돗물W: tap water
C : 통상의 포틀랜드 시멘트(비중 3.16)C: ordinary Portland cement (specific gravity 3.16)
S : 강모래(비중 2.63, 조립율 2.71)S: steel sand (specific gravity 2.63, assembly rate 2.71)
G : 쇄석(비중 2.67, 조립율 6.70)G: Crushed stone (specific gravity 2.67, assembly rate 6.70)
콘크리트 배합 :Concrete mix:
콘크리트의 배합율은 표 1에 나타내었다.The mixing ratio of the concrete is shown in Table 1.
표 1. 콘크리트 배합율Table 1. Concrete mix ratio
콘크리트 시험방법 :Concrete test method:
슬럼프 시험 : KS F 2402Slump Test: KS F 2402
공기량 측정 : KS F 2409Air volume measurement: KS F 2409
표 1 콘크리트 배합율은 동일하게하고 여기에 실시예(1) 및 (2)에 의한 시멘트 혼화제(유동화제)와 기존 시멘트 혼화제(유동화제)를 각각 투입하여 직후, 30분, 60분 후의 슬럼프 및 공기량을 측정하였으며 그 결과는 표 2와 같다.Table 1 Concrete mixing rate is the same and the amount of slump and air after 30 minutes and 60 minutes immediately after adding the cement admixture (fluidizing agent) and the existing cement admixture (fluidizing agent) according to Examples (1) and (2), respectively Was measured and the results are shown in Table 2.
표 2. 혼화제 첨가량 및 경시적 슬럼프, 공기량 변화Table 2. Changes in Admixture and Slump and Air Volume over Time
PC : 폴리카르본산계 시멘트 분산제 Na염 (시판품)PC: Polycarboxylic acid cement dispersant Na salt (commercially available)
NS : 나프탈렌술폰산계 시멘트 분산제 Na염 (시판품)NS: Naphthalene sulfonic acid cement dispersant Na salt (commercially available)
LS : 리그닌술폰산계 시멘트 분산제 Na염(시판품)LS: Lignin sulfonic acid cement dispersant Na salt (commercially available)
본 발명에 의한 고분자 물질의 유동화제는 종래의 콘크리트용 감수제에 비하여 콘크리트 슬러리의 유동성 유지가 오랜시간 가능하며, 경시적 저하를 방지하며 작업성, 시공성을 크게 개선할 수 있으며, 시멘트의 경화 후에도 우수한 강도와 내구성을 향상시킬 수 있는 고분자 중합체로된 시멘트 유동화제라 할 수 있다.The fluidizing agent of the polymer material according to the present invention can maintain the fluidity of the concrete slurry for a long time as compared to the conventional concrete water reducing agent, prevents deterioration over time and can greatly improve workability and workability, and excellent even after the hardening of cement Cement fluidizing agent made of a high molecular polymer that can improve the strength and durability.
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