TW202000626A - Additive for hydraulic composition - Google Patents
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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
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Description
本發明係關於一種水硬性組合物用添加物。特別係關於一種水硬性組合物用添加劑,其本身作為水溶液之穩定性高,且與既有之水硬性組合物用添加劑之相溶性優異,並可提升由水硬性組合物所得混凝土硬化體等之抗凍融性。 The present invention relates to an additive for hydraulic compositions. In particular, it relates to an additive for hydraulic compositions, which itself has high stability as an aqueous solution, and is excellent in compatibility with existing additives for hydraulic compositions, and can improve concrete hardened bodies obtained from hydraulic compositions, etc. Freeze-thaw resistance.
近年來,大多要求自水硬性組合物所得到的硬化體,像是混凝土硬化體需具有高耐久性。已知有「抗凍融性」為顯示該高耐久性的指標之一。因此,以謀求提高混凝土硬化體的抗凍融性為其目的,製造了在混凝土硬化體內部混入細微氣泡而形成的AE混凝土。但是,隨著混凝土硬化體中所使用的各種材料或者各種材料的混合比例等各種條件的不同,即使是AE混凝土有時也會無法具有充分的抗凍融性。因此,會因應製造條件進行空氣量的增加或配方的修改等各種調整作業。 In recent years, most of the hardened bodies obtained from hydraulic compositions are required, such as concrete hardened bodies, which require high durability. It is known that "freeze-thaw resistance" is one of the indexes showing this high durability. Therefore, for the purpose of improving the freeze-thaw resistance of the concrete hardened body, AE concrete formed by mixing fine air bubbles inside the concrete hardened body was manufactured. However, depending on various conditions such as various materials used in the concrete hardened body or the mixing ratio of various materials, even AE concrete may not have sufficient freeze-thaw resistance. Therefore, various adjustment operations, such as increasing the air volume or modifying the formula, are carried out in accordance with the manufacturing conditions.
例如,在製造AE混凝土的過程中,使用添加劑以調整空氣量。此時,因應所使用的添加劑的種類,所得到的混凝土硬化體的抗凍融性個別不同。在此,作為抗凍融性優異之添加劑,已提出將磷酸酯類添加劑作為AE調整劑使用之方法(參考專利文獻1~3)。 For example, in the process of manufacturing AE concrete, additives are used to adjust the amount of air. At this time, the freeze-thaw resistance of the obtained concrete hardened body varies depending on the type of additives used. Here, as an additive excellent in freeze-thaw resistance, a method of using a phosphate-based additive as an AE regulator has been proposed (refer to Patent Documents 1 to 3).
專利文獻 Patent Literature
專利文獻1:日本發明公開昭61-048480號公報 Patent Literature 1: Japanese Invention Publication No. 61-048480
專利文獻2:日本發明公開2010-100478號公報 Patent Document 2: Japanese Invention Publication No. 2010-100478
專利文獻3:日本發明公開2010-285291號公報 Patent Document 3: Japanese Patent Publication No. 2010-285291
【發明內容】 [Invention content]
然而,上述專利文獻1~3所示之磷酸酯類添加劑,與水及既有之水硬性組合物用添加劑的相溶性不良,結果,依舊產生混凝土硬化體等之抗凍融性不充分等問題。 However, the phosphate ester additives shown in the above Patent Documents 1 to 3 have poor compatibility with water and the additives for existing hydraulic compositions, and as a result, problems such as insufficient freeze-thaw resistance of the concrete hardened body still occur. .
鑒於上述實情,本發明之水硬性組合物用添加劑,以提供一種本身作為水溶液之穩定性高,且與既有之水硬性組合物用添加劑的相溶性優異,並且所得之混凝土硬化體等可表現良好抗凍融性數值之水硬性組合物用添加劑為課題。 In view of the above facts, the additive for hydraulic composition of the present invention provides a high stability as an aqueous solution in itself, and has excellent compatibility with the existing additive for hydraulic composition, and the resulting concrete hardened body can be expressed Additives for hydraulic compositions with good freeze-thaw resistance values are the subject.
本發明者等為解決上述課題,經潛心研究結果,發現特佳為含有特定脂肪醇磷酸酯及特定有機胺之水硬性組合物用添加劑。 In order to solve the above-mentioned problems, the inventors have made intensive studies and found that it is particularly preferable to use an additive for a hydraulic composition containing a specific fatty alcohol phosphate ester and a specific organic amine.
也就是說,本發明係關於一種水硬性組合物用添加劑,其構成成分為:包含至少一種以上之分別由以下化學式1、化學式2及化學式3所示之脂肪醇磷酸酯之第一成分;以及,以包含由以下化學式4所示之有機胺之第二成分所中和之脂肪醇磷酸酯之有機胺鹽。 That is, the present invention relates to an additive for a hydraulic composition, the constituent components of which are: a first component comprising at least one fatty alcohol phosphate represented by the following Chemical Formula 1, Chemical Formula 2, and Chemical Formula 3; and , An organic amine salt containing a fatty alcohol phosphate ester neutralized by the second component of the organic amine shown in the following Chemical Formula 4.
化學式1
唯,在上述化學式1~化學式3當中,R1~R5表示碳數為6~24之脂肪族醇在去除氫氧基後之殘基或以每莫耳之碳數為6~24之脂肪族醇,附加總計1~10莫耳之環氧乙烷及/或環氧丙烷之比例後,再去除氫氧基後之殘基;n表示2或3之整數;M1~M4表示氫、鹼金屬及鹼土族金屬,且,M1~M4之至少一個,表示為含鹼金屬或鹼土族金屬者。 However, in the above Chemical Formula 1 to Chemical Formula 3, R 1 to R 5 represent the residue of the aliphatic alcohol having 6 to 24 carbon atoms after removing the hydroxyl group or the fat having 6 to 24 carbon atoms per mole Group alcohol, after adding a total of 1 to 10 moles of ethylene oxide and/or propylene oxide, the residue after removing the hydroxyl group; n represents an integer of 2 or 3; M 1 to M 4 represents hydrogen , Alkali metals and alkaline earth metals, and at least one of M 1 to M 4 is expressed as containing alkali metals or alkaline earth metals.
化學式4
唯,於上述化學式4中,R6表示碳數為1~30之烷基及/或碳數為2~30之烯基,AO、BO各表氧伸烷基,a、b為0以上之整數,且,滿足a+b≦100之條件。 However, in the above Chemical Formula 4, R 6 represents an alkyl group having a carbon number of 1 to 30 and/or an alkenyl group having a carbon number of 2 to 30, AO and BO each represent an oxyalkylene group, and a and b are at least 0. Integer, and satisfy the condition of a+b≦100.
在此,如前所述,於上述化學式1當中,R1表示碳數為6~24之脂肪族醇在去除氫氧基後之殘基或以每莫耳之碳數為6~24之脂肪族醇,附加總計1~10莫耳之環氧乙烷及/或環氧丙烷之比例後,再去除氫氧基後之殘基。 Here, as mentioned above, in the above Chemical Formula 1, R 1 represents the residue of an aliphatic alcohol having 6 to 24 carbon atoms after removal of hydroxyl groups or a fat having 6 to 24 carbon atoms per mole Group alcohol, after adding a total of 1 to 10 moles of ethylene oxide and/or propylene oxide, the residue after removing the hydroxyl group.
作為此般R1,例如可列舉:1)己醇、庚醇、辛醇、2-乙-己醇、壬醇、癸醇、2-丙-庚醇、十一醇、十二醇、2-丁-辛醇、十三醇、十四醇、十六醇、十八醇、異十八醇、油醇、二十醇、二十二醇、二十四醇等碳數為6~24之脂肪族醇在去除氫氧基後之殘基;2)己醇、庚醇、辛醇、2-乙-己醇、壬醇、癸醇、2-丙-庚醇、十一醇、十二醇、2-丁-辛醇、十三醇、十四醇、十六醇、十八醇、異十八醇、油醇、二十醇、二十二醇、二十四醇等以每莫耳之碳數為6~24之脂肪族醇,附加總計1~10莫耳之環氧乙烷及/或環氧丙烷之比例後,再去除氫氧基後之殘基。其中作為R1,較佳為辛醇、2-乙-己醇、壬醇、十二醇、2-丁-辛醇、十三醇、十四醇、十六醇、十八醇、異十八醇、油醇等碳數為8~22之脂肪族醇在去除氫氧基後之殘 基。 Examples of such R 1 include: 1) hexanol, heptanol, octanol, 2-ethyl-hexanol, nonanol, decanol, 2-propan-heptanol, undecyl alcohol, dodecanol, 2 -Butane-octanol, tridecyl alcohol, tetradecyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, eicosyl alcohol, behenyl alcohol, tetracosyl alcohol and other carbon numbers are 6~24 The residue of the aliphatic alcohol after removing the hydroxyl group; 2) hexanol, heptanol, octanol, 2-ethyl-hexanol, nonanol, decanol, 2-propan-heptanol, undecyl alcohol, ten Glycol, 2-butan-octanol, tridecyl alcohol, tetradecyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, eicosanol, behenyl alcohol, tetracosyl alcohol, etc. Molar aliphatic alcohols with a carbon number of 6 to 24, after adding a total of 1 to 10 moles of ethylene oxide and/or propylene oxide, then remove the residue after the hydroxyl group. Among them, R 1 is preferably octanol, 2-ethyl-hexanol, nonanol, dodecanol, 2-butan-octanol, tridecanol, tetradecanol, hexadecanol, stearyl alcohol, isodecyl alcohol Residues of aliphatic alcohols with 8 to 22 carbon atoms, such as octanol and oleyl alcohol, after the removal of hydroxyl groups.
作為化學式1所示脂肪醇磷酸酯,可列舉:磷酸單己酯、磷酸單辛酯、單2-乙-磷酸己酯、磷酸單壬酯、磷酸單癸酯、磷酸單十二酯、單2-丁-磷酸辛酯、磷酸單十三酯、磷酸單十四酯、磷酸單十六酯、磷酸單十八酯、磷酸單異十八酯、磷酸單油酯等。 Examples of the fatty alcohol phosphate represented by Chemical Formula 1 include monohexyl phosphate, monooctyl phosphate, mono-2-ethyl-hexyl phosphate, monononyl phosphate, monodecyl phosphate, monododecyl phosphate, and mono 2 -Butyl-octyl phosphate, monotridecyl phosphate, monotetradecyl phosphate, monohexadecyl phosphate, monooctadecyl phosphate, monoisostearyl phosphate, monooleic phosphate, etc.
於化學式2中,R2、R3與化學式1中之R1描述者相同。因此,以下省略詳細說明。 In Chemical Formula 2, R 2 and R 3 are the same as the description of R 1 in Chemical Formula 1. Therefore, detailed description is omitted below.
作為化學式2所示脂肪醇磷酸酯,例如可列舉:二磷酸辛酯、二2-乙-己磷酸酯、二壬磷酸酯、二癸磷酸酯、二十二磷酸酯、二2-丁-磷酸辛酯、二十三磷酸酯、二十四磷酸酯、二十六磷酸酯、二十八磷酸酯、二異十八磷酸酯、二油磷酸酯、二癸油磷酸酯等。 Examples of the fatty alcohol phosphate represented by Chemical Formula 2 include octyl diphosphate, di-2-ethyl-hexyl phosphate, dinonyl phosphate, didecyl phosphate, behenyl phosphate, and di 2-butyric acid. Octyl ester, tricosyl phosphate, tetracosyl phosphate, hexadecyl phosphate, octacosyl phosphate, diisooctadecyl phosphate, dioleic phosphate, didecyl phosphate, etc.
於化學式3中,R4、R5與化學式1中之R1描述者相同。因此,以下省略詳細說明。此外,n為2或3之整數。 In Chemical Formula 3, R 4 and R 5 are the same as the description of R 1 in Chemical Formula 1. Therefore, detailed description is omitted below. In addition, n is an integer of 2 or 3.
作為化學式3所示脂肪醇磷酸酯,可列舉:焦磷酸單辛酯、焦磷酸二辛酯、單-2-乙基己基焦磷酸鹽、二-2-乙基-己基焦磷酸鹽、單壬基焦磷酸鹽、二壬基焦磷酸鹽、單十二烷基焦磷酸鹽、二十二烷基焦磷酸鹽、單油基焦磷酸鹽、二油基焦磷酸鹽、十二烷基油基焦磷酸鹽、二油基多磷酸鹽等。 Examples of the fatty alcohol phosphate represented by Chemical Formula 3 include monooctyl pyrophosphate, dioctyl pyrophosphate, mono-2-ethylhexyl pyrophosphate, di-2-ethyl-hexyl pyrophosphate, and mononon Pyrophosphate, dinonyl pyrophosphate, monododecyl pyrophosphate, behenyl pyrophosphate, monooleyl pyrophosphate, dioleyl pyrophosphate, lauryl pyrophosphate Pyrophosphate, dioleyl polyphosphate, etc.
於化學式4中,R6係碳數為1~30之烷基及/或碳數為2~30之烯基。作為此般R6,可列舉:甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一基、十二基、十三基、十四基、十五基、十六基、十七基、十八基、十九基、二十基、二十一基、二十二基、 二十三基、二十四基、十八碳烯基、十八碳二烯基等。R6亦可為自牛脂胺、氫化牛脂胺、椰子油胺、棕櫚油胺或大豆油胺等胺中除去氨基而獲得的基團。 In Chemical Formula 4, R 6 is an alkyl group having 1 to 30 carbon atoms and/or an alkenyl group having 2 to 30 carbon atoms. Examples of R 6 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, Fourteen base, fifteen base, sixteen base, seventeen base, eighteen base, nineteen base, twenty base, twenty one base, twenty two base, twenty three base, twenty four base, eighteen base Carboalkenyl, octadecadienyl, etc. R 6 may also be a group obtained by removing amino groups from amines such as tallow amine, hydrogenated tallow amine, coconut oleamine, palm oleamine, or soybean oleamine.
R6亦可由直鏈或分支鏈之任一構造所構成。R6之碳數為1~30,唯最佳為6~22。若R6之碳數超過30,將增加有機胺之疏水性。 R 6 may also be composed of any structure of straight chain or branched chain. The carbon number of R 6 is 1~30, but the best is 6~22. If the carbon number of R 6 exceeds 30, it will increase the hydrophobicity of the organic amine.
於化學式4中,AO、BO為碳數為2~4之氧化烯基,唯較佳為氧化乙烯基或氧化丙烯基,尤佳為氧化乙烯。a、b表示氧伸烷基之附加莫耳數。 In the chemical formula 4, AO and BO are oxyalkylene groups having 2 to 4 carbon atoms, preferably oxyethylene groups or oxypropylene groups, and particularly preferably oxyethylene groups. a, b represent the additional mole number of oxyalkylene.
於化學式4中,a、b為0以上之整數,且為滿足a+b≦100之整數。較佳為滿足1≦a+b≦50之整數,尤佳為滿足2≦a+b≦50之整數,特佳為滿足2≦a+b≦35之整數,最佳為滿足3≦a+b≦35之整數。 In Chemical Formula 4, a and b are integers of 0 or more, and are integers satisfying a+b≦100. Preferably it is an integer satisfying 1≦a+b≦50, particularly preferably an integer satisfying 2≦a+b≦50, particularly preferably an integer satisfying 2≦a+b≦35, and most preferably satisfying 3≦a+ b≦35 integer.
並且,於第一成分之脂肪醇磷酸酯中,上述化學式1~化學式3中之R1~R5亦可為碳數為8~22之烷基及/或烯基。 In addition, in the fatty alcohol phosphate ester of the first component, R 1 to R 5 in the above Chemical Formula 1 to Chemical Formula 3 may also be an alkyl group and/or alkenyl group having 8 to 22 carbon atoms.
另外,於第二成分之有機胺中,上述化學式4中之R6亦可為碳數為6~22之烷基及/或烯基。 In addition, in the organic amine of the second component, R 6 in the above Chemical Formula 4 may be an alkyl group and/or alkenyl group having 6 to 22 carbon atoms.
此外,第一成分之脂肪醇磷酸酯之酸價無特殊限制,唯例如可為0.1~500mg/g之範圍內。其中較佳為40~400mg/g、尤佳為100~250mg/g之範圍內。 In addition, the acid value of the fatty alcohol phosphate ester of the first component is not particularly limited, but it may be in the range of 0.1 to 500 mg/g, for example. Among them, it is preferably 40 to 400 mg/g, and particularly preferably 100 to 250 mg/g.
在此,酸價,例如係將異丙醇及二甲苯/異丙醇(容量比1/1)之混合液、溶解於水等溶劑之試劑以及0.1N氫氧化鉀及乙二醇/異丙醇(容量比1/1)之混合溶液,以電位滴定儀進行電位滴定,測量滴定終點(ml),將試劑1g中所含磷酸酯之酸性基中和時所需之氫氧化鉀的 mg數透過以下算式1所計算出的值。 Here, the acid value is, for example, a mixture solution of isopropyl alcohol and xylene/isopropyl alcohol (volume ratio 1/1), a reagent dissolved in a solvent such as water, and 0.1N potassium hydroxide and ethylene glycol/isopropyl Potentiometric titration of a mixed solution of alcohol (volume ratio 1/1) with a potentiometric titrator, measuring the titration end point (ml), and the number of mg of potassium hydroxide required to neutralize the acidic group of the phosphate ester contained in 1g of the reagent The value calculated by Equation 1 below.
算式1酸價(KOH mg/g)=(A1×f1×5.61)/W1 Formula 1 Acid value (KOH mg/g) = (A1×f1×5.61)/W1
上述算式1中,A1:滴定量(ml) In the above formula 1, A1: titration amount (ml)
f1:0.1N氫氧化鉀溶液的滴定度 f1: Titer of 0.1N potassium hydroxide solution
W1:試劑量(g) W1: Reagent amount (g)
此外,第二成分之有機胺之胺價無特殊限制,唯,例如可為20~200mg/g之範圍內。其中較佳可為30~150mg/g之範圍內,尤佳可為50~100mg/g之範圍內。 In addition, the amine value of the organic amine of the second component is not particularly limited, but, for example, it may be in the range of 20 to 200 mg/g. Among them, it is preferably in the range of 30 to 150 mg/g, and particularly preferably in the range of 50 to 100 mg/g.
胺價,例如為將異丙醇、二甲苯/異丙醇(容量比1/1)之混合液、溶解於水等溶劑之試劑以及0.1N鹽酸及乙二醇/異丙醇(容量比1/1)之混合溶液,以電位滴定儀進行電位滴定,測量滴定終點(ml),試劑1g中所含有機胺之胺基中和時所需之鹽酸與等量之氫氧化鉀的mg數透過以下算式2所計算出的值。 The amine value is, for example, a mixed solution of isopropyl alcohol, xylene/isopropyl alcohol (volume ratio 1/1), a reagent dissolved in a solvent such as water, and 0.1N hydrochloric acid and ethylene glycol/isopropyl alcohol (volume ratio 1) /1) The mixed solution is potentiometrically titrated with a potentiometric titrator to measure the end point of titration (ml). The number of mg of hydrochloric acid and equal amount of potassium hydroxide required for the neutralization of the amine group of the organic amine contained in 1g of the reagent permeates The value calculated by Equation 2 below.
算式2胺價(KOH mg/g)=(A2×f2×5.61)/W2 Formula 2 Amine price (KOH mg/g) = (A2×f2×5.61)/W2
於上述算式2中,A2:滴定量(ml) In the above formula 2, A2: titration amount (ml)
f2:0.1N氫氧化鉀溶液的滴定度 f2: Titer of 0.1N potassium hydroxide solution
W2:試劑量(g) W2: Reagent amount (g)
並且,將第二成分之胺價以第一成分之酸價除之,再乘以 100之值(以下稱「胺價/酸價×100」)可為10~300之範圍。其中較佳可為30~250之範圍,尤佳可為50~150之範圍。 In addition, the amine value of the second component is divided by the acid value of the first component, and then multiplied by a value of 100 (hereinafter referred to as "amine value/acid value × 100") can be in the range of 10 to 300. Among them, the range from 30 to 250 is preferable, and the range from 50 to 150 is particularly preferable.
構成本發明之水硬性組合物用添加劑之脂肪醇磷酸酯之有機胺鹽,係將碳數為6~24之脂肪族醇或將每莫耳之碳數為6~24之脂肪族醇附加總計1~10莫耳環氧乙烷及/或環氧丙烷之比例,加上例如五氧化二燐進行反應獲得脂肪醇磷酸酯後,再將此般脂肪醇磷酸酯以氫氧化鉀等鹼性成分及化學式4所示有機胺中和所得之。該脂肪醇磷酸酯,一般會形成化學式1所示脂肪醇磷酸酯與化學式2所示脂肪醇磷酸酯之混合物,唯某些情況下會形成更含有化學式3所示脂肪醇磷酸酯之混合物。 The organic amine salt of the fatty alcohol phosphate ester constituting the additive for the hydraulic composition of the present invention is an aliphatic alcohol having a carbon number of 6 to 24 or an aliphatic alcohol having a carbon number of 6 to 24 per mole. The ratio of 1-10 molar ethylene oxide and/or propylene oxide, for example, by reacting dioxo pentoxide to obtain fatty alcohol phosphate ester, and then using the basic components such as potassium hydroxide and other alkaline alcohol phosphate ester It is obtained by neutralizing the organic amine represented by Chemical Formula 4. The fatty alcohol phosphate ester generally forms a mixture of the fatty alcohol phosphate ester represented by Chemical Formula 1 and the fatty alcohol phosphate ester represented by Chemical Formula 2, but in some cases, a mixture further containing the fatty alcohol phosphate ester represented by Chemical Formula 3 is formed.
本發明之水硬性組合物用添加劑係用於土木、建築、二次製品等,為含水硬性膠合劑之水硬性組合物。作為此般水硬性組合物,可列舉:水泥漿(paste)、水泥砂漿(mortar)、混凝土等。 The additive for the hydraulic composition of the present invention is used in civil engineering, construction, secondary products, etc., and is a hydraulic composition of an aqueous hard adhesive. Examples of such a hydraulic composition include paste, cement mortar, and concrete.
本發明之水硬性組合物用添加劑可與既有之水硬性組合物用添加劑合併使用。作為此般水硬性組合物用添加劑,可列舉:AE減水劑、高性能AE減水劑、作為含氣量調整劑之AE劑、消泡劑、收縮抑制劑、增黏劑、硬化加速劑等。 The additive for hydraulic compositions of the present invention can be used in combination with the existing additive for hydraulic compositions. Examples of additives for hydraulic compositions in this way include AE water reducers, high-performance AE water reducers, AE agents as gas content regulators, defoamers, shrinkage inhibitors, thickeners, hardening accelerators, and the like.
作為用於調製本發明之水硬性組合物用添加劑之使用對象-水硬性組合物之水硬性膠合劑,可列舉:普通卜特蘭水泥、早強卜特蘭水泥、中庸熱水泥等各種卜特蘭水泥;以及高爐水泥、飛灰水泥、矽灰水泥等各種混合水泥。此外,亦可將高爐爐碴細粉、飛灰、矽灰等各種混和材與前述所示之各種水泥合併使用。 As the object of use for preparing the additive for the hydraulic composition of the present invention, the hydraulic binder of the hydraulic composition includes various Ports such as ordinary Portland cement, early strength Portland cement, and moderate heat cement Blue cement; and various mixed cements such as blast furnace cement, fly ash cement and silica fume cement. In addition, various blended materials such as fine powder of blast furnace slag, fly ash, silica fume, etc. can be used in combination with the various cements shown above.
此外,若調製水硬性組合物之過程中使用粒料時,粒料可列 舉細粒料與粗粒料。作為細粒料,可列舉河砂、山砂、海砂、碎砂、爐碴細粒料等;作為粗粒料,可列舉河礫、碎石、輕量粒料等。 In addition, when pellets are used in the process of preparing the hydraulic composition, the pellets may include fine pellets and coarse pellets. As fine particles, river sand, mountain sand, sea sand, crushed sand, ballast fine particles, etc. may be mentioned; as coarse particles, river gravel, crushed stone, lightweight particles, etc. may be mentioned.
另外,水硬性組合物之水膠比通常為70%以下,較佳為20~60%,尤佳為30~55%,特佳為35~55%。一般而言,水膠比愈大,水硬性組合物之抗凍融性愈低,一旦高於70%,多數情況下會無法獲得抗凍融性。 In addition, the water-to-binder ratio of the hydraulic composition is usually 70% or less, preferably 20-60%, particularly preferably 30-55%, and particularly preferably 35-55%. Generally speaking, the greater the water-gel ratio, the lower the freeze-thaw resistance of the hydraulic composition. Once it exceeds 70%, the freeze-thaw resistance will not be obtained in most cases.
藉由本發明,可獲如下效果:本身作為水溶液之穩定性高,且與既有之水硬性組合物用添加劑的相溶性亦高,使所得之混凝土硬化體具備優異之抗凍融性。 According to the present invention, the following effects can be obtained: the stability as an aqueous solution itself is high, and the compatibility with existing additives for hydraulic compositions is also high, so that the resulting concrete hardened body has excellent freeze-thaw resistance.
以下,為更具體說明本發明之架構及效果而列舉實施例,唯本發明不限於諸等實施例。另,以下實施例及比較例當中,若無特別記載,“份”係表示質量份、“%”係表示質量%。 In the following, embodiments are listed to more specifically explain the architecture and effects of the present invention, but the present invention is not limited to the various embodiments. In addition, in the following examples and comparative examples, unless otherwise specified, "parts" means mass parts, and "%" means mass %.
1.聚羧酸類減水劑之合成 1. Synthesis of polycarboxylic acid water reducer
將離子交換水244.3份,及聚(平均附加莫耳數為53莫耳)乙二醇單(3-甲基-3-丁烯基)醚368.3份加入反應容器,並將反應容器內氣體以氮氣取代後,攪拌並慢慢加溫。將反應系統溫度以溫水浴保持70℃,再用3小時時間滴入3.5%過氧化氫水溶液23.5份,與此同時,用3小時時間滴入離子交換水117.5份、溶解丙烯酸23.5份之水溶液,與此同時,用4小時時間滴入離子交換水15.0份、溶解L-抗壞血酸1.9g與3-巰基丙酸1.9g之水溶液使其反應。最後將所得之共聚物加入30%氫氧化鈉水溶液45.5份、離 子交換水,獲得40%水溶性乙烯基共聚物水溶液(減水劑B液)。分析該水溶性乙烯基共聚物時,測得其質量平均分子量為45000。另,共聚物之重量平均分子量係透過凝膠滲透層析術進行測量。 Add 244.3 parts of ion-exchanged water and 368.3 parts of poly(average additional mole number of 53 moles) ethylene glycol mono(3-methyl-3-butenyl) ether to the reaction vessel, and After replacing with nitrogen, stir and slowly warm up. The temperature of the reaction system was maintained at 70°C in a warm water bath, and then 23.5 parts of 3.5% aqueous hydrogen peroxide solution was added dropwise over 3 hours. At the same time, an aqueous solution of 117.5 parts of ion exchanged water and 23.5 parts of dissolved acrylic acid was added dropwise over 3 hours. At the same time, an aqueous solution of 15.0 parts of ion-exchanged water, 1.9 g of L-ascorbic acid and 1.9 g of 3-mercaptopropionic acid was added dropwise over 4 hours to react. Finally, the obtained copolymer was added to 45.5 parts of 30% sodium hydroxide aqueous solution and ion-exchanged water to obtain a 40% water-soluble vinyl copolymer aqueous solution (water-reducing agent B solution). When this water-soluble vinyl copolymer was analyzed, its mass average molecular weight was measured to be 45,000. In addition, the weight average molecular weight of the copolymer is measured by gel permeation chromatography.
2.測量條件 2. Measurement conditions
裝置:Shodex GPC-101(昭和電工製) Device: Shodex GPC-101 (manufactured by Showa Denko)
管柱:OHpak SB-G+SB-806M HQ+SB-806M HQ(昭和電工製) Column: OHpak SB-G+SB-806M HQ+SB-806M HQ (manufactured by Showa Denko)
偵測器:差示折光儀(RI) Detector: Differential Refractometer (RI)
溶析液:50MM硝酸鈉水溶液 Dissolution solution: 50MM sodium nitrate aqueous solution
流量:0.7ml/分 Flow rate: 0.7ml/min
試劑濃度:試劑濃度為0.5質量%之溶析液溶液 Reagent concentration: 0.5% by mass of eluent solution
標準物質:PEG/PEO(Agilent Technologies製) Standard material: PEG/PEO (manufactured by Agilent Technologies)
3.實施例1(AE-1)(調製脂肪醇磷酸酯之有機胺鹽等) 3. Example 1 (AE-1) (preparation of organic amine salt of fatty alcohol phosphate, etc.)
於反應容器內加入1-辛醇41.6份,於120℃、0.05MPa之條件下經2小時脫水處理後,使其恢復正常大氣壓,於60±5℃環境下,用0.5小時時間投入五氧化二燐18.1份並持續攪拌。於80℃環境下熟成3小時後,投入離子交換水1.2份再熟成0.5小時。接著在50℃環境下滴入48%氫氧化鉀水溶液18.8份進行中和反應。以電位滴定測量酸價之結果為222mg/g。接著在50℃環境下滴入十二胺-聚氧化乙烯20莫耳加成物(胺價55mg/g)182.4質量份進行中和反應,加入離子交換水,調製成25%水硬性組合物用添加劑水溶液(實施例(AE-1))。 Add 41.6 parts of 1-octanol to the reaction vessel, and after 2 hours of dehydration treatment at 120°C and 0.05MPa, restore it to normal atmospheric pressure, and put in pentoxide in 0.5 hours at 60±5°C Pour 18.1 parts and keep stirring. After aging for 3 hours in an environment of 80°C, 1.2 parts of ion-exchanged water was put in and aging was continued for 0.5 hours. Next, 18.8 parts of 48% potassium hydroxide aqueous solution was added dropwise at 50° C. to carry out the neutralization reaction. The result of measuring acid value by potentiometric titration was 222 mg/g. Next, 182.4 parts by mass of dodecylamine-polyoxyethylene 20 mole adduct (amine value 55 mg/g) was added dropwise at 50° C. to perform neutralization reaction, and ion-exchanged water was added to prepare a 25% hydraulic composition. Additive aqueous solution (Example (AE-1)).
4.實施例2~17((AE-2~AE-17)及比較例1(RAE-1)、比較例2(RAE-2) 4. Examples 2 to 17 ((AE-2 to AE-17) and Comparative Example 1 (RAE-1), Comparative Example 2 (RAE-2)
與上述實施例1同樣,調製實施例2~17((AE-2)~(AE-17))及比較例1(RAE-1)、比較例2(RAE-2)的25%水硬性組合物用添加劑水溶液。 As in Example 1 above, 25% hydraulic combinations of Examples 2 to 17 ((AE-2) to (AE-17)), Comparative Examples 1 (RAE-1), and Comparative Examples 2 (RAE-2) were prepared Aqueous additive solution.
5.比較例3(RAE-3) 5. Comparative Example 3 (RAE-3)
於反應容器內加入135.8質量份1-辛醇,於120℃、0.05MPa之條件下經2小時脫水處理後,使其恢復正常大氣壓,於60±5℃環境下,用0.5小時時間投入五氧化二燐59.1份並持續攪拌。於80℃環境下熟成3小時後,投入離子交換水4.1份再熟成0.5小時。接著在50℃環境下滴入48%氫氧化鉀水溶液153.4份進行中和反應後,加入離子交換水,調製成25%水硬性組合物用添加劑水溶液(比較例3(RAE-3))。 Add 135.8 parts by mass of 1-octanol into the reaction vessel, and after 2 hours of dehydration treatment at 120°C and 0.05MPa, return it to normal atmospheric pressure. Put it into pentoxide in an environment of 60±5°C for 0.5 hours 59.1 parts of dioxin and keep stirring. After aging for 3 hours in an environment of 80°C, 4.1 parts of ion-exchanged water was added and aging was continued for 0.5 hour. Next, 153.4 parts of 48% potassium hydroxide aqueous solution was added dropwise in a 50° C. environment to perform neutralization reaction, and ion-exchanged water was added to prepare a 25% additive aqueous solution for hydraulic composition (Comparative Example 3 (RAE-3)).
6.比較例4(RAE-4)、比較例(RAE-5) 6. Comparative Example 4 (RAE-4), Comparative Example (RAE-5)
與比較例3(RAE-3)同樣,分別調製比較例4(RAE-4)及比較例5(RAE-5)各25%水溶液。 As in Comparative Example 3 (RAE-3), 25% aqueous solutions of Comparative Example 4 (RAE-4) and Comparative Example 5 (RAE-5) were prepared.
7.比較例6(RAE-6) 7. Comparative Example 6 (RAE-6)
於反應容器內加入離子交換水701.7份、48%氫氧化鉀水溶液76.3份後,加溫至90℃。此時添加松香(和光純藥製)222.0份並同時攪拌。添加後,進行1小時的熟成,調製成25%松香鉀鹽水溶液(Rosin K)。 After adding 701.7 parts of ion-exchanged water and 76.3 parts of 48% potassium hydroxide aqueous solution to the reaction vessel, it was heated to 90°C. At this time, 222.0 parts of rosin (manufactured by Wako Pure Chemicals) was added while stirring. After the addition, aging was carried out for 1 hour to prepare a 25% aqueous solution of rosin potassium salt (Rosin K).
將以上第1.~6.項調製之各例脂肪醇磷酸酯之有機胺鹽等內容彙整如以下表1所示。此外,P核積分比率,係於脂肪醇磷酸酯之有機胺鹽等加入過量KOH使其pH值處於12以上之條件下,再使用31P-NMR(VALIAN公司製,商品名稱為MERCURY plus NMR Spectrometor System,300MHz)時的測量值,透過以下算式3~算式5所計算。溶媒係使用重水 /四氫呋喃=8/2(體積比)之混合溶媒。 The contents of the organic amine salts of the fatty alcohol phosphate esters prepared in the above items 1. to 6. are summarized in Table 1 below. In addition, the P nuclear integration ratio is based on the addition of excess KOH to the pH value of 12 or more for the organic amine salt of fatty alcohol phosphate, etc., and then uses 31 P-NMR (manufactured by Valian Corporation, trade name MERCURY plus NMR Spectrometor System, 300MHz), the measured value is calculated by the following formula 3 to formula 5. The solvent system uses a mixed solvent of heavy water/tetrahydrofuran=8/2 (volume ratio).
在此,上述算式3~算式5當中,P化1、P化2、P化3各表如下:「P化1:歸屬於化學式1所示脂肪醇磷酸酯之有機胺鹽等之P核NMR積分值」、「P化2:歸屬於化學式2所示脂肪醇磷酸酯之有機胺 鹽等之P核NMR積分值」及「P化3:歸屬於化學式3所示脂肪醇磷酸酯之有機胺鹽等之P核NMR積分值」。 Here, in the above formula 3 to formula 5, the tables of P1, P2, and P3 are as follows: "P1: P nuclear NMR attributed to the organic amine salt of fatty alcohol phosphate shown in Chemical formula 1 "Integral value", "P2: P nuclear NMR integral value attributed to the organic amine salt of fatty alcohol phosphate shown in Chemical Formula 2" and "P3: Organic amine attributed to fatty alcohol phosphate shown in Chemical Formula 3" P nuclear NMR integral value of salt etc.".
並且,上述表1當中,化1、化2、化3各表如下:「化1:自算式3所計算出之P核積分比率」、「化2:自算式4所計算出之P核積分比率」及「化3:自算式5所計算出之P核積分比率」。 In addition, in the above Table 1, the tables of Chem1, Chem2, and Chem3 are as follows: "Chem1: P-core score ratio calculated by self-calculation formula 3", "Chem2: P-core score calculated by self-calculation formula 4" Ratio" and "Chemical 3: P-core points ratio calculated from Equation 5".
此外,於表1之第一成分(脂肪醇磷酸酯)中,C8、C9、C12、C18各表如下:「C8:辛醇」、「C9:壬醇」、「C12:十二醇」、「C18:油醇(唯,AE-13、AE-15之C18為油醇-聚氧化乙烯4莫耳加成物)」;第二成分(有機胺)之R6當中,C12、C18、C8各表如下:「C12:十二基」、「C18:硬脂基」及「C8:辛基」;其他K、Na、EO各表如下:「K:鉀鹽」、「Na:鈉鹽」及「EO:氧化乙烯」。 In addition, in the first component (fatty alcohol phosphate) of Table 1, the C8, C9, C12, and C18 tables are as follows: "C8: Octanol", "C9: Nonanol", "C12: Dodecanol", "C18: oleyl alcohol (only, AE-13, AE-15 C18 is oleyl alcohol-polyoxyethylene 4 mole adduct)"; Among the R 6 of the second component (organic amine), C12, C18, C8 The tables are as follows: "C12: dodecyl", "C18: stearyl" and "C8: octyl"; other K, Na, EO are as follows: "K: potassium salt", "Na: sodium salt" And "EO: ethylene oxide".
10.水硬性組合物用添加劑之水溶液的穩定性及與減水劑(既有之水硬性組合物用添加劑)之相溶性 10. Stability of the aqueous solution of additives for hydraulic compositions and compatibility with water reducing agents (existing additives for hydraulic compositions)
10-1.水硬性組合物用添加劑之水溶液的穩定性 10-1. Stability of aqueous solutions of additives for hydraulic compositions
將表1調製成的25%水硬性組合物用添加劑水溶液震盪混勻後,倒入透明容器內,分別以5℃、20℃、40℃等條件靜置一週,以目視確認溶解性,並使用後述之評價基準實施評價。其結果彙整如以下表2所示。 After the 25% hydraulic composition prepared in Table 1 was shaken and mixed with an aqueous additive solution, it was poured into a transparent container and allowed to stand at 5°C, 20°C, 40°C, etc. for one week to confirm the solubility visually and use Evaluation will be carried out according to the evaluation criteria described later. The results are summarized in Table 2 below.
10-2.水硬性組合物用添加劑與水溶液及減水劑之相溶性 10-2. Compatibility of additives for hydraulic compositions with aqueous solutions and water reducers
分別於聚羧酸類高性能AE減水劑「CHUPOL HP-11(TAKEMOTO OIL & FAT CO.,LTD製-減水劑A液)」、減水劑B液、變性木質素磺酸與聚羧酸類化合物之複合體的磺酸減水劑「CHUPOL EX60(TAKEMOTO OIL & FAT CO.,LTD製-減水劑C液)」中,添加25%水硬性組合物用添加劑水溶 液使其為1質量%,在20℃環境下靜置一週,以目視確認溶解性,並使用後述之評價基準實施評價。其結果彙整如以下表2所示。 Compounded in polycarboxylic acid high-performance AE water reducer "CHUPOL HP-11 (made by TAKEMOTO OIL & FAT CO., LTD-water reducer A liquid)", water reducer B liquid, modified lignin sulfonic acid and polycarboxylic acid compound The sulfonic acid water-reducing agent "CHUPOL EX60 (made by TAKEMOTO OIL & FAT CO., LTD-water-reducing agent C solution)" was added with 25% of the aqueous solution of the additive for the hydraulic composition to 1% by mass in a 20°C environment After standing for one week, the solubility was visually confirmed, and the evaluation was performed using the evaluation criteria described later. The results are summarized in Table 2 below.
10-3.穩定性及相溶性之評價基準 10-3. Evaluation criteria for stability and compatibility
A:經1週溶解 A: Dissolve after 1 week
B:經1天溶解 B: Dissolve in 1 day
C:1天內分離 C: Separation within 1 day
11.混凝土組合物之調製及評價 11. Preparation and evaluation of concrete composition
11-1.AE混凝土組合物之調製 11-1. Preparation of AE concrete composition
於表3所述混合條件下,於50L圓盤強制式攪拌機內,將規定量之普通卜特蘭水泥(太平洋水泥製、宇份三菱水泥製及住友大阪水泥製之普通卜特蘭水泥之等量混合物,密度=3.16g/cm3)、陸砂(大井川水系產,密度=2.58g/cm3)、碎石(岡崎產碎石,密度=2.66g/cm3)、減水劑A液或減水劑B液、25%水硬性組合物用添加劑水溶液,以及水泥質量0.0005%之消泡劑「AFK-2(TAKEMOTO OIL & FAT CO.,LTD製)」、攪拌水(自來水)共同投入並攪拌90秒,調製成假定坍流度為18±1cm、假定含氣量為4.5±0.5%範圍內之AE混凝土組合物,求得作為坍流度、含氣量及抗凍融性之指標的抗凍融性指數(300循環)(詳如後述)後,其結果彙整如表4所示。另,針對使用減水劑C液之情況,根據表5所示混合條件實施相同試驗。其結果彙整如表6所示。 Under the mixing conditions described in Table 3, a prescribed amount of ordinary Portland cement (made by Pacific Cement, Ufen Mitsubishi Cement, and ordinary Portland Cement made by Sumitomo Osaka Cement, etc.) in a 50L disc forced mixer Amount of mixture, density = 3.16g/cm 3 ), land sand (from Oigawa River system, density = 2.58g/cm 3 ), crushed stone (Okazaki gravel, density = 2.66g/cm 3 ), water reducer A or Water-reducing agent B solution, 25% additive aqueous solution for hydraulic composition, and 0.0005% defoamer "AFK-2 (manufactured by TAKEMOTO OIL & FAT CO., LTD) of cement quality", stirring water (tap water) are added and stirred together 90 seconds, prepared into an AE concrete composition with an assumed slump of 18±1cm and an assumed gas content of 4.5±0.5%, to obtain freeze-thaw resistance as an indicator of slump, gas content and freeze-thaw resistance After sex index (300 cycles) (details will be described later), the results are summarized in Table 4. In addition, for the case of using the water reducing agent C liquid, the same test was carried out according to the mixing conditions shown in Table 5. The results are summarized in Table 6.
11-2.含氣量、坍流度及抗凍融性指數之測量。 11-2. Measurement of gas content, slump and freeze-thaw resistance index.
含氣量(容量%):根據JIS A 1128標準測量攪拌後不久之AE混凝土組合物。 Gas content (volume %): AE concrete composition measured shortly after stirring according to JIS A 1128 standard.
坍流度(cm):測量含氣量之同時,根據JIS A 1101標準進行測量。 Slump (cm): While measuring the gas content, it is measured according to the JIS A 1101 standard.
抗凍融性指數:針對使用各例之25%水硬性組合物用添加劑水溶液調製而成之AE混凝土組合物硬化體,使用以JIS A 1148標準測量的值,再運用ASTM-C-666-75耐久性指數計算出抗凍融性指數值。該數值之最大值為100,愈接近100,呈現出愈優異之抗凍融性。 Freeze-thaw resistance index: For the hardened body of AE concrete composition prepared by using 25% hydraulic composition with additive aqueous solution in each case, the value measured according to JIS A 1148 standard is used, and then ASTM-C-666-75 is used The durability index calculates the freeze-thaw resistance index value. The maximum value of this value is 100, the closer to 100, the more excellent freeze-thaw resistance is exhibited.
在此,於表4、表6中,減水劑之用量,及25%水硬性組合物用添加劑水溶液之用量,係表示相對於水泥(C)之百分比。 Here, in Tables 4 and 6, the amount of water-reducing agent and the amount of 25% additive aqueous solution for hydraulic composition represent the percentage relative to cement (C).
11-3.抗凍融性指數之評價基準 11-3. Evaluation criteria for freeze-thaw resistance index
抗凍融性之評價,係根據後述評價基準實施。也就是說,抗凍融性指數達80%以上者,評為“A”;另一方面,抗凍融性指數未滿80%者,評為“B”。 The evaluation of freeze-thaw resistance is carried out according to the evaluation criteria described below. In other words, those with a freeze-thaw resistance index of over 80% are rated "A"; on the other hand, those with a freeze-thaw resistance index of less than 80% are rated "B".
如表2、表4及表6所示結果可明顯得知,本發明之水硬性組合物用添加劑,本身具有優異之穩定性,且與既有之水硬性組合物用添加劑之溶解性(相溶性)良好,並確認結果獲得具備優異抗凍融性之混凝土硬化體等。 As shown in the results shown in Table 2, Table 4 and Table 6, it is obvious that the additive for hydraulic composition of the present invention has excellent stability itself, and the solubility with the existing additive for hydraulic composition (phase Solubility) is good, and it is confirmed that a hardened concrete body with excellent freeze-thaw resistance is obtained.
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