JP5467859B2 - Method for producing cement dispersant - Google Patents
Method for producing cement dispersant Download PDFInfo
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- JP5467859B2 JP5467859B2 JP2009293683A JP2009293683A JP5467859B2 JP 5467859 B2 JP5467859 B2 JP 5467859B2 JP 2009293683 A JP2009293683 A JP 2009293683A JP 2009293683 A JP2009293683 A JP 2009293683A JP 5467859 B2 JP5467859 B2 JP 5467859B2
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- itaconic anhydride
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- 239000004568 cement Substances 0.000 title claims description 64
- 239000002270 dispersing agent Substances 0.000 title claims description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 50
- 229920000642 polymer Polymers 0.000 claims description 41
- 239000007795 chemical reaction product Substances 0.000 claims description 27
- 239000003960 organic solvent Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 15
- 238000005886 esterification reaction Methods 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 230000032050 esterification Effects 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 7
- 230000000379 polymerizing effect Effects 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000012615 aggregate Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 61
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 150000008064 anhydrides Chemical class 0.000 description 17
- 239000000178 monomer Substances 0.000 description 15
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 14
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 12
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000003377 acid catalyst Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 229940098779 methanesulfonic acid Drugs 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 125000006353 oxyethylene group Chemical group 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 150000002148 esters Chemical group 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 229920001515 polyalkylene glycol Polymers 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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 2
- NAEBGSZDTZXVPT-UHFFFAOYSA-N C1CO1.C(C(=C)CC(=O)O)(=O)O Chemical compound C1CO1.C(C(=C)CC(=O)O)(=O)O NAEBGSZDTZXVPT-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- NCEXYHBECQHGNR-UHFFFAOYSA-N chembl421 Chemical compound C1=C(O)C(C(=O)O)=CC(N=NC=2C=CC(=CC=2)S(=O)(=O)NC=2N=CC=CC=2)=C1 NCEXYHBECQHGNR-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000002012 dioxanes Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011440 grout Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- XXROGKLTLUQVRX-UHFFFAOYSA-N hydroxymethylethylene Natural products OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 230000014759 maintenance of location Effects 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
-
- 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
- C04B24/2664—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers
- C04B24/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers containing polyether side chains
-
- 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
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
Landscapes
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明はセメント分散剤の製造方法に関する。 The present invention relates to a method for producing a cement dispersant.
セメント分散剤としてポリカルボン酸系分散剤が用いられている。ポリカルボン酸系分散剤は、例えば、ポリアルキレングリコールメタクリル酸エステルとメタクリル酸との共重合体、アリルアルコールのアルキレンオキシド付加物とマレイン酸の共重合体等が代表的な構造として挙げられる。 A polycarboxylic acid-based dispersant is used as a cement dispersant. Typical examples of the polycarboxylic acid dispersant include a copolymer of polyalkylene glycol methacrylate and methacrylic acid, a copolymer of allyl alcohol alkylene oxide adduct and maleic acid, and the like.
これらの製造方法としては、主鎖となる重合体にポリアルキレングリコールをグラフトする方法や不飽和結合を有する単量体を共重合する方法等が知られている。例えば、特許文献1には、添加効果で従来品より優れ、かつ製造技術面でも簡素で問題の少ない新タイプのセメント分散剤を提供することを課題とし、数平均分子量が1,000〜5,000で、無水マレイン酸に対するスチレンの共重合比が1〜5のスチレン・無水マレイン酸共重合体と、ポリアルキレンオキシドモノアルキルエーテルとの反応生成物、及び/又は該反応生成物の塩を含有するセメント分散剤が開示されている。そして、この分散剤の製造方法として、スチレン・無水マレイン酸共重合体へのポリアルキレンオキシドモノアルキルエーテルの付加反応が開示されている。 As these production methods, a method of grafting a polyalkylene glycol to a polymer as a main chain, a method of copolymerizing a monomer having an unsaturated bond, and the like are known. For example, Patent Document 1 aims to provide a new type of cement dispersant that is superior to conventional products in terms of additive effect and that is simple and less problematic in terms of manufacturing technology, and has a number average molecular weight of 1,000 to 5, 000, a reaction product of a styrene / maleic anhydride copolymer having a copolymerization ratio of styrene to maleic anhydride of 1 to 5 and a polyalkylene oxide monoalkyl ether, and / or a salt of the reaction product A cement dispersant is disclosed. As a method for producing this dispersant, an addition reaction of polyalkylene oxide monoalkyl ether to a styrene / maleic anhydride copolymer is disclosed.
また、特許文献2には、分散性、スランプ保持性及び硬化遅延に優れた性能を課題として、炭素数2〜3のオキシアルキレン基を平均付加モル数で2〜300モル付加したジカルボン酸系単量体の単独重合体、又は炭素数2〜3のオキシアルキレン基を平均付加モル数で2〜300モル付加したジカルボン酸系単量体とジカルボン酸系単量体との共重合体が開示されている。そして、この文献の実施例ではイタコン酸とイタコン酸エチレンオキシド5モル付加物との共重合により得られた重合体とその製造方法として溶媒と重合体原料反応容器に仕込み、重合開始剤を滴下して重合する方法が開示されている。 Further, Patent Document 2 discloses a dicarboxylic acid-based monomer obtained by adding 2 to 300 moles of an average addition mole number of an oxyalkylene group having 2 to 3 carbon atoms for the purpose of achieving excellent performance in dispersibility, slump retention and curing delay. A homopolymer of a monomer or a copolymer of a dicarboxylic acid monomer and a dicarboxylic acid monomer obtained by adding 2 to 300 moles of an average addition mole number of an oxyalkylene group having 2 to 3 carbon atoms is disclosed. ing. In the examples of this document, a polymer obtained by copolymerization of itaconic acid and an itaconic acid ethylene oxide 5-mole adduct and a production method thereof were charged into a solvent and a polymer raw material reaction vessel, and a polymerization initiator was dropped. A method of polymerizing is disclosed.
特許文献2に開示されたイタコン酸とイタコン酸エチレンオキシド付加物との共重合による方法では反応率が低いことから残存モノマーが多くなる傾向があり、その結果セメントを十分分散させるのに必要な添加量が多くなる。 The method based on the copolymerization of itaconic acid and itaconic acid ethylene oxide adduct disclosed in Patent Document 2 tends to increase the residual monomer due to the low reaction rate. As a result, the addition amount necessary to sufficiently disperse the cement Will increase.
本発明の課題は、より少ない添加量でセメントを効率よく分散できるイタコン酸が主鎖骨格となるセメント分散剤の製造方法を提供することである。 An object of the present invention is to provide a method for producing a cement dispersant in which itaconic acid which can efficiently disperse cement with a smaller addition amount is a main chain skeleton.
本発明は、無水イタコン酸を重合してポリ無水イタコン酸を得る工程(A)と、得られたポリ無水イタコン酸と一般式(1)で表されるアルコールとをエステル化させる工程(B)とを有する、セメント分散剤の製造方法に関する。
R1−(OR2)nOH (1)
(式中、R1は炭素数1〜4のアルキル基を表し、OR2は炭素数1〜12のオキシアルキレン基を表し、nはオキシアルキレン基の平均付加モル数であって9〜300の数を表す。)
The present invention includes a step (A) for polymerizing itaconic anhydride to obtain polyitaconic anhydride, and a step (B) for esterifying the obtained polyitaconic anhydride and the alcohol represented by the general formula (1). And a method for producing a cement dispersant.
R 1- (OR 2 ) n OH (1)
(In the formula, R 1 represents an alkyl group having 1 to 4 carbon atoms, OR 2 represents an oxyalkylene group having 1 to 12 carbon atoms, and n represents an average added mole number of the oxyalkylene group, which is 9 to 300. Represents a number.)
また、本発明は、上記本発明の製造方法で得られた反応生成物からなるセメント分散剤組成物であって、反応生成物中の固形分に対する重合体の重量割合(重合体/固形分)が、60〜100%であるセメント分散剤組成物に関する。 Further, the present invention is a cement dispersant composition comprising the reaction product obtained by the production method of the present invention, wherein the weight ratio of the polymer to the solid content in the reaction product (polymer / solid content). However, the present invention relates to a cement dispersant composition that is 60 to 100%.
また、本発明は、水硬性粉体、骨材、水及び上記本発明の製造方法で得られるセメント分散剤を含有する水硬性組成物に関する。 The present invention also relates to a hydraulic composition containing hydraulic powder, aggregate, water, and a cement dispersant obtained by the production method of the present invention.
本発明によれば、より少ない添加量でセメントを効率よく分散できるイタコン酸が主鎖骨格となるセメント分散剤の製造方法が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the cement dispersant from which itaconic acid which can disperse | distribute a cement efficiently with a smaller addition amount becomes a main chain skeleton is provided.
本発明は、ポリ無水イタコン酸を得る工程(A)と、該ポリ無水イタコン酸と一般式(1)で表されるアルコールとのエステル化反応を行う工程(B)とを有するセメント分散剤の製造方法である。 The present invention provides a cement dispersant having a step (A) for obtaining polyitaconic anhydride and a step (B) for performing an esterification reaction between the polyitaconic anhydride and an alcohol represented by the general formula (1). It is a manufacturing method.
工程(A)では、無水イタコン酸を有機溶媒(I)の存在下で重合して得られた反応生成物を、前記有機溶媒(I)よりも極性の低い有機溶媒(II)と混合してポリ無水イタコン酸を析出させて得ることが好ましい。例えば、無水イタコン酸を有機溶媒(I)の存在下で、重合開始剤とともに窒素雰囲気下、一定温度で一定時間攪拌して重合して得られた反応生成物を、前記有機有機溶媒(I)よりも極性の低い有機溶媒(II)中に加えて生成した析出物を単離して得る方法が挙げられる。ここで、有機溶媒(I)、(II)の極性は、スワイン(Swain)のパラメーター(「大学院 有機化学 上」、岩村秀他著、講談社サイエンティフィク社、1988年6月20日発行、236〜237頁)により高低を対比するものとする。 In the step (A), a reaction product obtained by polymerizing itaconic anhydride in the presence of the organic solvent (I) is mixed with an organic solvent (II) having a lower polarity than the organic solvent (I). It is preferable to obtain it by precipitating poly itaconic anhydride. For example, the reaction product obtained by polymerizing itaconic anhydride in the presence of the organic solvent (I) and stirring with a polymerization initiator under a nitrogen atmosphere at a constant temperature for a fixed time is used as the organic organic solvent (I). And a method in which a precipitate formed by addition in a less polar organic solvent (II) is isolated. Here, the polarities of the organic solvents (I) and (II) are the parameters of Swain (“Graduate School of Organic Chemistry”, Hide Iwamura et al., Kodansha Scientific Co., Ltd., issued June 20, 1988, 236 ~ 237 pages).
工程(A)で得られるポリ無水イタコン酸の重合度は、セメントの分散性と分散剤の製造の観点から30〜1000が好ましく、50〜500がより好ましい。ポリ無水イタコン酸は実質的に無水イタコン酸の構成単位からなるものであればよく、本発明の効果を損なわない範囲で無水イタコン酸以外の重合性単量体を共重合してもよい。 The polymerization degree of the poly itaconic anhydride obtained in the step (A) is preferably 30 to 1000, more preferably 50 to 500, from the viewpoints of dispersibility of the cement and production of the dispersant. The poly itaconic anhydride may be any one that substantially consists of a structural unit of itaconic anhydride, and a polymerizable monomer other than itaconic anhydride may be copolymerized within a range not impairing the effects of the present invention.
無水イタコン酸の重合に用いる有機溶媒(I)は、比較的極性が高いものが好ましく、反応温度を高くできる点で沸点の高い溶媒が好ましい。例えば、環状エーテルが挙げられ、沸点は70℃以上が好ましい。具体的にはジオキサンが好ましい。有機溶媒(I)の量は、無水イタコン酸と該溶媒の合計量に対して、反応率向上及び無水イタコン酸の粘度低減の観点から、5〜20重量%が好ましく、5〜15重量%がより好ましい。重合開始剤は、アゾビスイソブチロニトリル(AIBN)が好ましく、その添加量は無水イタコン酸100モルに対して、1〜10モルが好ましく、3〜6モルがより好ましい。また反応温度は60〜100℃が好ましく、70〜90℃が更に好ましい。反応温度を上げると重合度、即ち分子量が小さくなる傾向があり、反応温度を下げると重合度、即ち分子量が大きくなる傾向がある。攪拌して反応させる時間は4〜10時間が好ましく、5〜8時間が更に好ましい。なお、更に反応率を高めるために、前記反応時間の経過後、更に重合開始剤(AIBN等)を反応系に添加することが好ましく、その添加量は無水イタコン酸100モルに対して1〜5モルが好ましく、2〜4モルがより好ましい。AIBN追加後の反応時間は2〜4時間が好ましい。 The organic solvent (I) used for the polymerization of itaconic anhydride is preferably a solvent having a relatively high polarity, and a solvent having a high boiling point is preferable because the reaction temperature can be increased. For example, cyclic ether is mentioned, and the boiling point is preferably 70 ° C. or higher. Specifically, dioxane is preferable. The amount of the organic solvent (I) is preferably 5 to 20% by weight, and 5 to 15% by weight, based on the total amount of itaconic anhydride and the solvent, from the viewpoint of improving the reaction rate and reducing the viscosity of itaconic anhydride. More preferred. The polymerization initiator is preferably azobisisobutyronitrile (AIBN), and the addition amount is preferably 1 to 10 mol, more preferably 3 to 6 mol, per 100 mol of itaconic anhydride. The reaction temperature is preferably 60 to 100 ° C, more preferably 70 to 90 ° C. Increasing the reaction temperature tends to decrease the degree of polymerization, that is, the molecular weight, and decreasing the reaction temperature tends to increase the degree of polymerization, that is, the molecular weight. The time for stirring and reacting is preferably 4 to 10 hours, more preferably 5 to 8 hours. In order to further increase the reaction rate, it is preferable to further add a polymerization initiator (AIBN or the like) to the reaction system after the reaction time has elapsed, and the addition amount is 1 to 5 with respect to 100 mol of itaconic anhydride. Mole is preferable, and 2 to 4 mol is more preferable. The reaction time after addition of AIBN is preferably 2 to 4 hours.
反応終了後、未反応モノマー及び重合開始剤の除去を目的として、合成時に用いた有機溶媒(I)とは異なる有機溶媒中へ反応終了後の反応生成物を加え、沈殿により精製することができる。ポリ無水イタコン酸の沈殿に用いる有機溶媒としては、重合に用いた有機溶媒よりも極性の低い有機溶媒(II)であることが好ましく、更に、反応終了後のモノマー及び重合開始剤が溶解し、かつ合成したポリ無水イタコン酸が溶解しない極性を有する有機溶媒がより好ましい。具体的にはジエチルエーテルが好ましい。 After completion of the reaction, the reaction product after completion of the reaction can be added to an organic solvent different from the organic solvent (I) used at the time of synthesis for the purpose of removing unreacted monomer and polymerization initiator, and purified by precipitation. . The organic solvent used for precipitation of poly itaconic anhydride is preferably an organic solvent (II) having a lower polarity than the organic solvent used for the polymerization, and further, the monomer and the polymerization initiator after the reaction are dissolved, An organic solvent having a polarity that does not dissolve the synthesized polyitaconic anhydride is more preferable. Specifically, diethyl ether is preferable.
工程(B)では、工程(A)で得られたポリ無水イタコン酸と一般式(1)で表されるアルコールとをエステル化させる。一般式(1)において、R1は炭素数1〜4のアルキル基を表し、セメント分散性の観点から好ましくはメチル基である。OR2は炭素数1〜12のオキシアルキレン基を表し、好ましくは炭素数2のオキシエチレン基である。nはOR2の平均付加モル数を表し、セメント分散性の観点から9〜300であり、9〜120が好ましく、15〜50がより好ましく、20〜30が更に好ましい。 In the step (B), the polyitaconic anhydride obtained in the step (A) and the alcohol represented by the general formula (1) are esterified. In the general formula (1), R 1 represents an alkyl group having 1 to 4 carbon atoms, and is preferably a methyl group from the viewpoint of cement dispersibility. OR 2 represents an oxyalkylene group having 1 to 12 carbon atoms, preferably an oxyethylene group having 2 carbon atoms. n represents an average addition number of moles of OR 2, a 9-300 in terms of cement dispersibility, preferably 9-120, more preferably from 15 to 50, more preferably 20 to 30.
一般式(1)の化合物は、アルコキシポリアルキレングリコールであり、具体的には、メトキシポリエチレングリコール、メトキシポリエチレングリコールポリプロピレングリコール、エトキシポリエチレングリコール、プロポキシポリエチレングリコール、ブトキシポリエチレングリコール等が挙げられる。 The compound of the general formula (1) is an alkoxy polyalkylene glycol, and specific examples thereof include methoxy polyethylene glycol, methoxy polyethylene glycol polypropylene glycol, ethoxy polyethylene glycol, propoxy polyethylene glycol, and butoxy polyethylene glycol.
ポリ無水イタコン酸と一般式(1)で表されるアルコールとのエステル化反応は、例えば、反応容器に原料を仕込み、酸触媒を用いて有機溶媒中窒素雰囲気下、一定温度で一定時間攪拌させることで行うことができる。有機溶媒を用いることで原料の粘度を低くでき攪拌を容易となり反応温度を低くできる。また、有機溶媒の沸点以上の温度に反応器の温度を設定し、還流状態で反応させることもできる。有機溶媒の使用量は、反応系の固形分が好ましくは30〜70重量%、より好ましくは40〜60重量%になるように用いる。原料として用いるポリ無水イタコン酸は、重合体の製造時に副生される異性体等の不純物を含んでいても良いが、ポリ無水イタコン酸の純分として50重量%以上含むことが好ましい。前述した無水イタコン酸を有機溶媒(I)の存在下で重合して得られた反応生成物は、無水イタコン酸を80重量%以上含んでおり、通常はそのままエステル化反応に用いることができ、得られるセメント分散剤はセメントを効率よく分散できる。本発明の製造方法では、ポリ無水イタコン酸を原料として用いるためエステル化による水が反応系に生成せず、反応時の脱水処理は不要である。 For example, the esterification reaction of polyitaconic anhydride and the alcohol represented by the general formula (1) is performed by, for example, charging a raw material in a reaction vessel and using an acid catalyst to stir at a constant temperature for a certain time in a nitrogen atmosphere in an organic solvent. Can be done. By using an organic solvent, the viscosity of the raw material can be lowered, stirring can be facilitated, and the reaction temperature can be lowered. Alternatively, the temperature of the reactor can be set to a temperature equal to or higher than the boiling point of the organic solvent, and the reaction can be performed in a reflux state. The amount of the organic solvent used is such that the solid content of the reaction system is preferably 30 to 70% by weight, more preferably 40 to 60% by weight. The polyitaconic anhydride used as a raw material may contain impurities such as isomers produced as a by-product during the production of the polymer, but is preferably contained in an amount of 50% by weight or more as a pure content of polyitaconic anhydride. The reaction product obtained by polymerizing the above-mentioned itaconic anhydride in the presence of the organic solvent (I) contains at least 80% by weight of itaconic anhydride, and can usually be used for the esterification reaction as it is. The resulting cement dispersant can disperse cement efficiently. In the production method of the present invention, polyitaconic anhydride is used as a raw material, so that water by esterification is not generated in the reaction system, and dehydration during the reaction is unnecessary.
エステル化に用いる一般式(1)で表されるアルコールの量は、ポリ無水イタコン酸中の無水イタコン酸単位100モルに対して一般式(1)で表されるアルコールを好ましくは1〜100モル、より好ましくは5〜50モル、更に好ましくは10〜30モルである。なお、無水イタコン酸単位1モルとは重合体の無水イタコン酸からなる構成単位1ユニットのことを意味する。 The amount of the alcohol represented by the general formula (1) used for esterification is preferably 1 to 100 moles of the alcohol represented by the general formula (1) with respect to 100 moles of the itaconic anhydride unit in the polyitaconic anhydride. More preferably, it is 5-50 mol, More preferably, it is 10-30 mol. In addition, 1 mol of itaconic anhydride units means 1 unit of structural units composed of itaconic anhydride of a polymer.
酸触媒はスルホン酸系触媒が好ましく、結晶水等の水を含まないものがより好ましい。具体的にはメタンスルホン酸が好ましい。酸触媒の添加量はポリ無水イタコン酸中の無水イタコン酸単位100モルに対して、好ましくは5〜15モルである。 The acid catalyst is preferably a sulfonic acid-based catalyst, and more preferably contains no water such as crystal water. Specifically, methanesulfonic acid is preferable. The addition amount of the acid catalyst is preferably 5 to 15 mol with respect to 100 mol of itaconic anhydride units in poly itaconic anhydride.
ポリ無水イタコン酸と一般式(1)で表されるアルコールとのエステル化の反応温度は100〜120℃が好ましく、105〜115℃がより好ましい。前記反応温度より沸点が低い溶媒を用いる際には、反応容器の温度を前記温度に設定し還流状態で反応させることもできる。反応時間は反応温度によっても異なるが、5〜20時間が好ましく、7〜15時間がより好ましい。 100-120 degreeC is preferable and, as for the reaction temperature of esterification with polyitaconic anhydride and alcohol represented by General formula (1), 105-115 degreeC is more preferable. When using a solvent having a boiling point lower than the reaction temperature, the temperature of the reaction vessel can be set to the temperature and the reaction can be carried out in a reflux state. Although reaction time changes also with reaction temperature, 5 to 20 hours are preferable and 7 to 15 hours are more preferable.
工程(B)で用いる有機溶媒は沸点が高く、ポリ無水イタコン酸、一般式(1)で表されるアルコール及び酸触媒を全て溶解できる溶媒が好ましく、反応温度を高くできる点で沸点が90℃以上の溶媒が好ましい。例えば、環状エーテルが好ましく、具体的にはジオキサンが好ましい。 The organic solvent used in the step (B) has a high boiling point and is preferably a solvent capable of dissolving all of polyitaconic anhydride, the alcohol represented by the general formula (1) and the acid catalyst, and has a boiling point of 90 ° C. in that the reaction temperature can be increased. The above solvents are preferred. For example, a cyclic ether is preferable, and specifically, dioxane is preferable.
反応終了後、塩基によって中和を行うことができる。塩基としては水酸化ナトリウムが好ましく、中和終了後のpHは5〜7が好ましい。中和後、得られた重合体を溶解させる観点から、極性の高い溶媒を加えることが好ましい。加える溶媒としては、水が好ましい。 After completion of the reaction, neutralization can be performed with a base. The base is preferably sodium hydroxide, and the pH after neutralization is preferably 5-7. From the viewpoint of dissolving the obtained polymer after neutralization, it is preferable to add a highly polar solvent. The solvent to be added is preferably water.
得られた重合体はセメント分散剤として用いることができる。また、重合体を含む反応生成物が水溶液等の場合、そのままセメント分散剤(セメント分散剤の水溶液)としてもよい。本発明では、工程(A)、(B)により得られた反応生成物をセメント分散剤組成物とすることが好ましい。本発明の製造方法により反応生成物中の残存モノマーや未反応のアルコール等の重合体以外の成分を少なくすることができる。セメント分散剤として用いる反応生成物中の固形分に対する重合体の重量割合(重合体/固形分)は、セメント分散性の観点から60〜100%が好ましく、セメント分散性と生産性の観点から70〜95%がより好ましい。 The obtained polymer can be used as a cement dispersant. Moreover, when the reaction product containing a polymer is an aqueous solution or the like, a cement dispersant (an aqueous solution of a cement dispersant) may be used as it is. In the present invention, the reaction product obtained by the steps (A) and (B) is preferably used as a cement dispersant composition. By the production method of the present invention, components other than the polymer such as residual monomer and unreacted alcohol in the reaction product can be reduced. The weight ratio of the polymer to the solid content in the reaction product used as a cement dispersant (polymer / solid content) is preferably 60 to 100% from the viewpoint of cement dispersibility, and 70 from the viewpoint of cement dispersibility and productivity. -95% is more preferable.
重合体の重量平均分子量は、セメント分散性の観点から、3000〜100000が好ましく、5000〜50000がより好ましい。重合体のエステル化度は、セメント分散性の観点から1〜100が好ましく、10〜30がより好ましい。ここで、エステル化度は重合体中の無水イタコン酸単位(モノマーユニット)の数を100として、エステル化されたカルボキシル基の割合を表すものである。すなわち、ポリ無水イタコン酸の場合、1つの無水イタコン酸単位中に、2個のカルボキシル基の無水構造を1個有するので、重合体中の全てのカルボキシル基がエステル化された場合、エステル化度は200となる。 The weight average molecular weight of the polymer is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, from the viewpoint of cement dispersibility. The degree of esterification of the polymer is preferably 1 to 100 and more preferably 10 to 30 from the viewpoint of cement dispersibility. Here, the degree of esterification represents the ratio of esterified carboxyl groups, where the number of itaconic anhydride units (monomer units) in the polymer is 100. That is, in the case of poly itaconic anhydride, since it has one anhydrous structure of two carboxyl groups in one itaconic anhydride unit, when all the carboxyl groups in the polymer are esterified, the degree of esterification Becomes 200.
本発明で得られるセメント分散剤は、水和反応により硬化する物性を有する水硬性粉体を分散させる目的で用いることができる。水硬性粉体として、例えば普通ポルトランドセメント、中庸熱セメント、早強セメント、超早強セメント、高ビーライト含有セメント、高炉セメント、フライアッシュセメント、アルミナセメント、シリカフュームセメントなどの水硬性粉体セメントや石膏が挙げられる。 The cement dispersant obtained in the present invention can be used for the purpose of dispersing a hydraulic powder having physical properties that are cured by a hydration reaction. Examples of hydraulic powders include hydraulic powder cements such as ordinary Portland cement, medium heat cement, early strength cement, very early strength cement, cement containing high belite, blast furnace cement, fly ash cement, alumina cement, silica fume cement, and the like. Gypsum.
本発明により得られるセメント分散剤と、水硬性粉体と、水とを含有する水硬性組成物が提供される。水硬性組成物は、モルタル、コンクリート、グラウト等が挙げられる。水硬性組成物は、セメント、水、細骨材、粗骨材、炭酸カルシウム等フィラー等を含有することができる。また、フライアッシュ、高炉スラグ、シリカヒフューム、石灰石等の微粉体を添加したものであってもよい。かかる水硬性組成物において、本発明により製造されたセメント分散剤、好ましくは重合体は、水硬性粉体100重量部に対して0.01〜10重量部、更に0.05〜8重量部、更に0.1〜5重量部使用することができる。 The hydraulic composition containing the cement dispersant obtained by this invention, hydraulic powder, and water is provided. Examples of the hydraulic composition include mortar, concrete, and grout. The hydraulic composition can contain cement, water, fine aggregate, coarse aggregate, filler such as calcium carbonate, and the like. Moreover, what added fine powders, such as a fly ash, blast furnace slag, a silica hifume, and limestone, may be used. In such a hydraulic composition, the cement dispersant produced according to the present invention, preferably the polymer, is 0.01 to 10 parts by weight, more preferably 0.05 to 8 parts by weight, based on 100 parts by weight of the hydraulic powder. Furthermore, 0.1 to 5 parts by weight can be used.
実施例1
〔工程(A)〕
温度計、攪拌機、窒素導入管及び還流冷却器を備えたガラス製反応容器に、無水イタコン酸224.2g(2.0モル)(本工程(A)では、以下のモル%はこの量の無水イタコン酸を100モル%とした量である)[東京化成社製]に対し、5モル%のAIBN16.42g(0.1モル)[和光純薬工業社製、試薬1級]及び全体の固形分が90%となるよう脱水ジオキサン26.74g[和光純薬工業社製]を加え、窒素雰囲気下、80℃にて重合を行った。反応開始6時間後(AIBNの残存率が0.5%となる時間)に、未反応モノマーの反応を促進させるためAIBNを無水イタコン酸に対し3モル%(9.85g、0.06モル)加え、更に3時間攪拌を続け、開始から9時間後反応を停止した。反応の進行度を高速液体クロマトグラフィによる無水イタコン酸の残存率で確認した結果、反応率は87%であった。精製はジオキサンを加え固形分を50重量%とした後、ジエチルエーテル中に滴下してポリマーを沈殿させ、ろ過をし、最後に溶媒を留去し乾燥させた。その結果ポリマー粉末が29.6%で得られ、NMR測定により、モノマーのピークがほぼ消失していることから、無水イタコン酸の反応率が高く、純度の高いポリマーが得られたことが確かめられた。合成したポリ無水イタコン酸を含む反応生成物の組成は、ポリマー粉末を105℃2時間保存した際の重量変化からジオキサン(残溶媒)17重量%であった。更に、1H−NMR測定結果のポリマーのメチレン部のプロトン(1ユニット当り4H)とモノマーの二重結合のプロトン(1ユニット当り2H)の積分値の比率からポリ無水イタコン酸と無水イタコン酸の含有量を計算したところ、ポリ無水イタコン酸79.8重量%、無水イタコン酸(残存モノマー)3.2重量%であった。なお、ポリ無水イタコン酸の重合度は174.56であった。また、ポリ無水イタコン酸の純度は96%であった。
Example 1
[Process (A)]
In a glass reaction vessel equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 224.2 g (2.0 mol) of itaconic anhydride (in this step (A), the following mol% is the amount of anhydrous (It is the quantity which made itaconic acid 100 mol%) [Tokyo Kasei Co., Ltd.] 5 mol% AIBN 16.42g (0.1 mol) [Wako Pure Chemical Industries Ltd., reagent grade 1] and the whole solid 26.74 g of dehydrated dioxane [manufactured by Wako Pure Chemical Industries, Ltd.] was added so that the content was 90%, and polymerization was performed at 80 ° C. in a nitrogen atmosphere. Six hours after the start of the reaction (time when the residual ratio of AIBN becomes 0.5%), AIBN is added in an amount of 3 mol% (9.85 g, 0.06 mol) with respect to itaconic anhydride to promote the reaction of the unreacted monomer. In addition, stirring was continued for another 3 hours, and the reaction was stopped after 9 hours from the start. As a result of confirming the progress of the reaction by the residual rate of itaconic anhydride by high performance liquid chromatography, the reaction rate was 87%. For purification, dioxane was added to adjust the solid content to 50% by weight, and the resulting solution was dropped into diethyl ether to precipitate a polymer, filtered, and finally the solvent was distilled off and dried. As a result, a polymer powder was obtained at 29.6%, and the peak of the monomer was almost disappeared by NMR measurement, so it was confirmed that a polymer having a high reaction rate of itaconic anhydride and a high purity was obtained. It was. The composition of the synthesized reaction product containing polyitaconic anhydride was 17% by weight of dioxane (residual solvent) from the change in weight when the polymer powder was stored at 105 ° C. for 2 hours. Furthermore, from the ratio of the integral value of the proton of the methylene part (4H per unit) of the polymer as a result of 1 H-NMR measurement and the proton of the double bond of the monomer (2H per unit), polyitaconic anhydride and itaconic anhydride The content was calculated to be 79.8% by weight of polyitaconic anhydride and 3.2% by weight of itaconic anhydride (residual monomer). The polymerization degree of poly itaconic anhydride was 174.56. The purity of poly itaconic anhydride was 96%.
〔工程(B)〕
温度計、攪拌機、窒素導入管及び還流冷却器を備えたガラス製反応容器に、工程(A)で得られたポリマー粉末30.1g(ポリ無水イタコン酸と無水イタコン酸の合計量25.0g[無水イタコン酸単位換算0.223モル]、ジオキサン5.1g)、ポリマー粉末中の無水イタコン酸単位100モルに対して20モル(20モル%)のメトキシポリエチレングリコール(オキシエチレン基の平均付加モル数23)46.43g(0.0446モル)[新中村化学社製]、酸触媒としてポリマー粉末中の無水イタコン酸単位100モルに対して10モル(10モル%)のメタンスルホン酸2.14g(0.0223モル)をそれぞれ加え、ジオキサン68.47gを加えて固形分50重量%とし、窒素雰囲気下、110℃で還流しながら反応を行った。反応は10時間攪拌後冷却してから48重量%水酸化ナトリウム水溶液及び水を加え、pH5.71、固形分32.6重量%の反応生成物(セメント分散剤A−1)を得た。1H−NMRのピークの積分値で求めたところ、反応率は88%であり、得られたポリマーの構造は、エステル化されていない無水イタコン酸単位(以下、酸ユニットという)が82モル%、エステル化された無水イタコン酸単位(以下、エステルユニットという)18モル%であり、エステル化度は18であった。また、反応生成物中の固形分に対するポリマーの重量割合は89%であった。
[Process (B)]
In a glass reaction vessel equipped with a thermometer, a stirrer, a nitrogen introduction tube and a reflux condenser, 30.1 g of the polymer powder obtained in the step (A) (total amount of polyitaconic anhydride and itaconic anhydride 25.0 g [ Itaconic anhydride unit conversion 0.223 mol], dioxane 5.1 g), 20 mol (20 mol%) of methoxypolyethylene glycol (average added mole number of oxyethylene group) per 100 mol of itaconic anhydride unit in the polymer powder 23) 46.43 g (0.0446 mol) [manufactured by Shin-Nakamura Chemical Co., Ltd.], 2.14 g of 10 mol (10 mol%) of methanesulfonic acid per 100 mol of itaconic anhydride units in the polymer powder as an acid catalyst ( 0.0223 mol) and 68.47 g of dioxane were added to give a solid content of 50% by weight, and the mixture was refluxed at 110 ° C. in a nitrogen atmosphere. It was carried out. The reaction was stirred for 10 hours and then cooled, and then a 48 wt% aqueous sodium hydroxide solution and water were added to obtain a reaction product (cement dispersant A-1) having a pH of 5.71 and a solid content of 32.6 wt%. The reaction rate was 88% as determined from the integrated value of the peak of 1 H-NMR, and the structure of the obtained polymer was 82 mol% of itaconic anhydride units that were not esterified (hereinafter referred to as acid units). The esterified itaconic anhydride unit (hereinafter referred to as ester unit) was 18 mol%, and the degree of esterification was 18. The weight ratio of the polymer to the solid content in the reaction product was 89%.
実施例2(セメント分散剤A−2の製造)
工程(B)におけるメトキシポリエチレングリコールの量を表2のように変更した以外は実施例1と同様に合成を行い、セメント分散剤A−2を得た。得られたポリマーを1H−NMR測定のピークの積分値で求めたところ、反応率は67%であり、得られたポリマーの構造は酸ユニットが66モル%、エステルユニットが34モル%であり、エステル化度は34であった。また、反応生成物中の固形分に対するポリマーの重量割合は71%であった。
Example 2 (Production of cement dispersant A-2)
Synthesis was performed in the same manner as in Example 1 except that the amount of methoxypolyethylene glycol in the step (B) was changed as shown in Table 2 to obtain a cement dispersant A-2. When the obtained polymer was determined by the integrated value of the peak of 1 H-NMR measurement, the reaction rate was 67%, and the structure of the obtained polymer was 66 mol% of acid units and 34 mol% of ester units. The degree of esterification was 34. The weight ratio of the polymer to the solid content in the reaction product was 71%.
比較例1(比較セメント分散剤B−1の製造)
温度計、攪拌機、窒素導入管及び還流冷却器を備えたガラス製反応容器に、ポリイタコン酸15.9g(イタコン酸単位換算0.122モル)[イワタ化学社製]とメトキシポリエチレングリコール(オキシエチレン基の平均付加モル数23)152.5g(0.146モル)とをガラス製反応容器内で攪拌させながら110℃に昇温させた後、メタンスルホン酸1.17g(0.012モル)を加え、真空ポンプによる減圧条件下、11時間110℃にて反応させた。なお生成した水はトラップ管にて回収した。得られた重合体溶液を、逆滴定にて反応率を確認した。すなわち、水酸化カリウムを過剰に加えた後、塩酸で滴定した。終点はフェノールフタレイン溶液にて確認した。その結果、反応率は31.7%であった。得られた反応生成物をセメント分散剤B−1とした。本例では、反応により生じる水のために反応が進行しにくいと考えられたため、メトキシポリエチレングリコールを増量したが、反応率は悪かった。なお、ポリマーの構造の酸ユニット、エステルユニット及び反応生成物中の固形分に対するポリマーの重量割合は測定しなかった。
Comparative Example 1 (Production of Comparative Cement Dispersant B-1)
In a glass reaction vessel equipped with a thermometer, stirrer, nitrogen inlet tube and reflux condenser, 15.9 g of polyitaconic acid (0.122 mol of itaconic acid unit conversion) [manufactured by Iwata Chemical Co., Ltd.] and methoxypolyethylene glycol (oxyethylene group) The average added mole number of 23) 152.5 g (0.146 mol) was heated to 110 ° C. while stirring in a glass reaction vessel, and 1.17 g (0.012 mol) of methanesulfonic acid was added. The mixture was reacted at 110 ° C. for 11 hours under reduced pressure using a vacuum pump. The produced water was collected with a trap tube. The reaction rate of the obtained polymer solution was confirmed by back titration. That is, potassium hydroxide was added in excess and titrated with hydrochloric acid. The end point was confirmed with a phenolphthalein solution. As a result, the reaction rate was 31.7%. The obtained reaction product was designated as a cement dispersant B-1. In this example, it was thought that the reaction was difficult to proceed due to water generated by the reaction, so the amount of methoxypolyethylene glycol was increased, but the reaction rate was poor. In addition, the weight ratio of the polymer with respect to the solid content in the acid unit, ester unit and reaction product of the polymer structure was not measured.
比較例2(比較セメント分散剤B−2の製造)
(1)メトキシポリエチレングリコールイタコネートの製造
温度計、攪拌機、窒素導入管及び還流冷却器を備えたガラス製反応容器に、無水イタコン酸106.1g(0.95モル)、メトキシポリエチレングリコール(オキシエチレン基の平均付加モル数23)984.9g(0.95モル)、及び酸触媒としてメタンスルホン酸9.1g(0.095モル)を加え、窒素雰囲気下、110℃で攪拌してエステル化を行った。反応中、メトキシポリエチレングリコールの反応率を酸価の測定により経時的に解析した。反応開始6時間後にメトキシポリエチレングリコールの反応率が95.1%となったところで反応を停止させ、そのときのイタコン酸の反応率を1H−NMRのピークの積分値で求めたところ、79.6%であった。これらの結果から、メトキシポリエチレングリコールイタコネートの組成は、モノエステル:64.5重量%(56.8モル%)、ジエステル:27.9重量%(12.9モル%)、残存無水イタコン酸:1.9重量%(17.2モル%)、メトキシポリエチレングリコール:4.8重量%(4.6モル%)、メタンスルホン酸:0.8重量%(8.5モル%)であることがわかった。また、反応生成物中の固形分に対するポリマーの重量割合は41%であった。
Comparative Example 2 (Production of Comparative Cement Dispersant B-2)
(1) Production of methoxypolyethylene glycol itaconate In a glass reaction vessel equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, itaconic anhydride 106.1 g (0.95 mol), methoxypolyethylene glycol (oxyethylene) The average number of moles added 23) 984.9 g (0.95 mol) and 9.1 g (0.095 mol) of methanesulfonic acid as an acid catalyst were added, and the mixture was stirred at 110 ° C. in a nitrogen atmosphere for esterification. went. During the reaction, the reaction rate of methoxypolyethylene glycol was analyzed over time by measuring the acid value. When the reaction rate of methoxypolyethylene glycol reached 95.1% 6 hours after the start of the reaction, the reaction was stopped, and the reaction rate of itaconic acid at that time was determined by the integrated value of the peak of 1 H-NMR. It was 6%. From these results, the composition of methoxypolyethylene glycol itaconate was as follows: monoester: 64.5% by weight (56.8 mol%), diester: 27.9% by weight (12.9 mol%), residual itaconic anhydride: 1.9 wt% (17.2 mol%), methoxypolyethylene glycol: 4.8 wt% (4.6 mol%), methanesulfonic acid: 0.8 wt% (8.5 mol%) all right. Further, the weight ratio of the polymer to the solid content in the reaction product was 41%.
次に、ガラス製反応容器に水124gを加え、窒素置換した後80℃まで加温したところへ、(イ)合成したメトキシポリエチレングリコールイタコネート85.65g(モノエステル:0.048モル、ジエステル:0.011モル、残存無水イタコン酸:0.013モル、メトキシポリエチレングリコール:0.0016モル、メタンスルホン酸:0.0074モル)を48重量%水酸化ナトリウム水溶液0.61g(0.0074モル)で中和した後水60gを加えた水溶液と、(ロ)イタコン酸28.6g(0.22モル)を48重量%水酸化ナトリウム水溶液17.4g(0.20モル)で中和した後、水50gを加えた水溶液と、(ハ)過流酸ナトリウム2.3g(0.0094モル)に水30gを加えた水溶液とを、それぞれ同時に二時間かけて滴下し、熟成1時間後、更に過流酸ナトリウム0.57g(0.0023モル)に水10gを加えた水溶液を30分かけて滴下し、最後に熟成1時間させ、重合を行った。得られた反応生成物をセメント分散剤B−2とした。反応率を1H−NMRのピークの積分値で求めたところ、イタコン酸が42.7%、エステルが44.4%であった。また得られたポリマーの構造は酸ユニットが79モル%、エステルユニットが21モル%、エステル化度21であった。 Next, 124 g of water was added to a glass reaction vessel, and after substituting with nitrogen, the mixture was heated to 80 ° C. (i) 85.65 g of synthesized methoxypolyethylene glycol itaconate (monoester: 0.048 mol, diester: 0.011 mol, residual itaconic anhydride: 0.013 mol, methoxypolyethylene glycol: 0.0016 mol, methanesulfonic acid: 0.0074 mol), 48% by weight aqueous sodium hydroxide solution 0.61 g (0.0074 mol) After neutralizing the solution with 60 g of water and (b) itaconic acid 28.6 g (0.22 mol) with 17.4 g (0.20 mol) of a 48 wt% aqueous sodium hydroxide solution, An aqueous solution in which 50 g of water was added, and (c) an aqueous solution in which 30 g of water was added to 2.3 g (0.0094 mol) of sodium persulfate, Occasionally added dropwise over 2 hours, and after 1 hour of aging, an aqueous solution obtained by adding 10 g of water to 0.57 g (0.0023 mol) of sodium persulfate was further added dropwise over 30 minutes. Went. The obtained reaction product was designated as a cement dispersant B-2. When the reaction rate was determined by the integral value of the peak of 1 H-NMR, itaconic acid was 42.7% and ester was 44.4%. The structure of the obtained polymer was 79 mol% of acid units, 21 mol% of ester units, and a degree of esterification of 21.
参考例1(比較セメント分散剤X−1の製造)
ガラス製反応容器に水2070gを加え、窒素置換した後78℃まで加温したところへ、アクリル酸315.29g(4.33モル)とメトキシポリエチレングリコールアクリレート(オキシエチレン基の平均付加モル数23)2266.67g(1.44モル)の混合液、メルカプトプロピオン酸13.48g(0.127モル)に水56.52gを加えた水溶液及び過流酸アンモニウム13.17g(0.0577モル)に水56.83gを加えた水溶液をそれぞれ同時に一時間半かけて滴下し、その後過硫酸アンモニウム6.59g(0.0289モル)に水28.42gを加えた水溶液を30分かけて滴下後、1時間熟成し、48%水酸化ナトリウム水溶液を216.59g(2.60モル)加えて中和した。得られた反応生成物をセメント分散剤X−1とした。
Reference Example 1 (Production of Comparative Cement Dispersant X-1)
To a glass reaction vessel, 2070 g of water was added, and after purging with nitrogen, the mixture was heated to 78 ° C., and then 315.29 g (4.33 mol) of acrylic acid and methoxypolyethylene glycol acrylate (average number of moles of oxyethylene group added 23) A mixture of 2266.67 g (1.44 mol), an aqueous solution obtained by adding 56.52 g of water to 13.48 g (0.127 mol) of mercaptopropionic acid, and water of 13.17 g (0.0577 mol) of ammonium persulfate An aqueous solution containing 56.83 g was simultaneously added dropwise over one and a half hours, and then an aqueous solution obtained by adding 28.42 g of water to 6.59 g (0.0289 mol) of ammonium persulfate was added dropwise over 30 minutes, followed by aging for 1 hour. Then, 216.59 g (2.60 mol) of a 48% aqueous sodium hydroxide solution was added for neutralization. The obtained reaction product was designated as a cement dispersant X-1.
参考例2(比較セメント分散剤X−2の製造)
ガラス製反応容器にメトキシポエリエチレングリコール(オキシエチレン基の平均付加モル数23)246.72g(0.237モル)を加え、100℃まで加熱・均一溶解した後にパラトルエンスルホン酸・一水和物5.85g(0.031モル)[和光純薬工業社製、試薬特級]及びポリアクリル酸33.3%水溶液190.0g(0.878モル)を加え、110℃まで昇温した。一時間後、系中に生成する水を除去するために減圧を開始した。減圧度は400mmHg(53.3kPa)から開始し、最終的には100mmHg(13.3kPa)とした。12時間後反応容器をバスから出し、冷却後48%水酸化ナトリウム水溶液で中和し、最後に水を加え希釈した。反応率は97.4%であった。得られた反応生成物をセメント分散剤X−2とした。
Reference Example 2 (Production of Comparative Cement Dispersant X-2)
Add 246.72 g (0.237 mol) of methoxypolyethylene glycol (average number of moles of oxyethylene group added) of 23 to a glass reaction vessel, heat to 100 ° C and dissolve uniformly, then p-toluenesulfonic acid monohydrate 5.85 g (0.031 mol) [manufactured by Wako Pure Chemical Industries, reagent grade] and 190.0 g (0.878 mol) of 33.3% polyacrylic acid aqueous solution were added, and the temperature was raised to 110 ° C. After 1 hour, vacuum was started to remove the water formed in the system. The degree of vacuum started from 400 mmHg (53.3 kPa) and was finally 100 mmHg (13.3 kPa). After 12 hours, the reaction vessel was taken out of the bath, cooled and neutralized with a 48% aqueous sodium hydroxide solution, and finally diluted with water. The reaction rate was 97.4%. The obtained reaction product was designated as a cement dispersant X-2.
実施例1、2、比較例1、2、及び参考例1、2の反応条件等を表2にまとめた。 The reaction conditions of Examples 1 and 2, Comparative Examples 1 and 2, and Reference Examples 1 and 2 are summarized in Table 2.
本発明の製造方法による実施例1、2では、比較例1、2と比べて、高い反応率で重合体が得られていることがわかる。一方、参考例のアクリル酸の場合は、ポリアクリル酸のエステル化する方法とアクリル酸とアクリル酸エステルの共重合する方法のいずれの方法でも高い反応率で重合体が得られることがわかる。 In Examples 1 and 2 by the manufacturing method of this invention, it turns out that the polymer is obtained with the high reaction rate compared with Comparative Examples 1 and 2. On the other hand, in the case of acrylic acid of the reference example, it can be seen that a polymer can be obtained with a high reaction rate by either the method of esterifying polyacrylic acid or the method of copolymerizing acrylic acid and acrylic acid ester.
試験例(セメント分散性の評価)
普通ポルトランドセメント300gを500ml樹脂製ビーカに入れ、そこへ表2に示すセメント分散剤を含む水道水90gを加えた。ハンドミキサー[National社製]低速回転で2分間混練した。混練されたペーストを50mmコーン(径50mm×高さ51mm)に詰め、混練開始から3分後にコーンを垂直に引き上げた。ペーストが拡がったフローの最長径とそれに垂直方向の径を測定し、それらの平均値をペーストフロー値(流動性)とした。なお、セメント分散剤の添加量はペーストフローが160mmになることを目標として調整した。表2に、用いた分散剤と試験結果を示す。
Test example (evaluation of cement dispersibility)
300 g of ordinary Portland cement was put into a 500 ml resin beaker, and 90 g of tap water containing a cement dispersant shown in Table 2 was added thereto. A hand mixer [manufactured by National] was kneaded for 2 minutes at low speed. The kneaded paste was packed into a 50 mm cone (diameter 50 mm × height 51 mm), and the cone was pulled up vertically 3 minutes after the start of kneading. The longest diameter of the flow in which the paste spreads and the diameter in the direction perpendicular thereto were measured, and the average value thereof was defined as the paste flow value (fluidity). The amount of cement dispersant added was adjusted with the goal of a paste flow of 160 mm. Table 2 shows the dispersants used and the test results.
表中、添加量は、分散剤(反応生成物)のセメント100重量部に対する重量部である。 In the table, the addition amount is parts by weight with respect to 100 parts by weight of the cement of the dispersant (reaction product).
本発明により製造された分散剤A−1は、比較例の分散剤B−2と比べると、同じフローを得るための添加量が少なく、セメント分散性に優れることがわかる。 It can be seen that the dispersant A-1 produced according to the present invention has a small amount of addition for obtaining the same flow and is excellent in cement dispersibility as compared with the dispersant B-2 of the comparative example.
Claims (6)
R1−(OR2)nOH (1)
(式中、R1は炭素数1〜4のアルキル基を表し、OR2は炭素数2のオキシアルキレン基を表し、nはオキシアルキレン基の平均付加モル数であって9〜300の数を表す。) The step (A) of polymerizing itaconic anhydride to obtain poly itaconic anhydride, and the resulting poly itaconic anhydride and the alcohol represented by the general formula (1) are esterified to give a weight average molecular weight of 3000 to And a step (B) of obtaining a reaction product containing a polymer having an esterification degree of 1 to 100, and a method for producing a cement dispersant.
R 1- (OR 2 ) n OH (1)
(In the formula, R 1 represents an alkyl group having 1 to 4 carbon atoms, OR 2 represents an oxyalkylene group having 2 carbon atoms, and n represents an average added mole number of the oxyalkylene group, and represents a number of 9 to 300. Represents.)
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