JPH0297446A - Air entraining cement dispersant - Google Patents
Air entraining cement dispersantInfo
- Publication number
- JPH0297446A JPH0297446A JP25054088A JP25054088A JPH0297446A JP H0297446 A JPH0297446 A JP H0297446A JP 25054088 A JP25054088 A JP 25054088A JP 25054088 A JP25054088 A JP 25054088A JP H0297446 A JPH0297446 A JP H0297446A
- Authority
- JP
- Japan
- Prior art keywords
- air
- acenaphthene
- methylnaphthalene
- mixture
- dispersant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 26
- 239000004568 cement Substances 0.000 title claims abstract description 21
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 claims abstract description 32
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 claims abstract description 31
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 28
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 150000001239 acenaphthenes Chemical class 0.000 claims abstract description 4
- 230000005494 condensation Effects 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 9
- 239000007859 condensation product Substances 0.000 abstract 2
- 239000004567 concrete Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000004570 mortar (masonry) Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000006277 sulfonation reaction Methods 0.000 description 3
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000006072 paste Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical compound COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- -1 acenaphthenesulfonic acid formaldehyde Chemical compound 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- RRDQTXGFURAKDI-UHFFFAOYSA-N formaldehyde;naphthalene-2-sulfonic acid Chemical compound O=C.C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 RRDQTXGFURAKDI-UHFFFAOYSA-N 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 239000011396 hydraulic cement Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、空気連行性セメント分散剤、ざらに詳しくは
セメントペースト、モルタルおよびコンクリートに使用
する空気連行性セメント分散剤に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to air-entraining cement dispersants, and more particularly to air-entraining cement dispersants for use in cement pastes, mortars and concrete.
〈従来の拮術〉
水硬性セメント配合物は、セメントと砂、砂利などを水
と混練し、成型することにより得られる。 成型後の強
度、耐久性は材料の品質にもよるが、特に重要な条件の
一つは水の配合割合であり、できるだけ少ない水で練る
ことが望ましい。 ところが、近年のボンブエ法の普及
などにより、単位水量を多くした軟練り化の傾向が強ま
り、強度、耐久性の低下が問題となっている。 そこで
、少ない水量で高流動性を与えるコンクリート混和剤が
強く要望されている。<Conventional Comparison> Hydraulic cement mixtures are obtained by kneading cement, sand, gravel, etc. with water and molding the mixture. The strength and durability after molding depend on the quality of the material, but one particularly important condition is the proportion of water, and it is desirable to knead with as little water as possible. However, in recent years, with the spread of the Bombouet method, there has been a growing trend towards soft kneading by increasing the amount of water per unit, resulting in problems such as a decrease in strength and durability. Therefore, there is a strong demand for a concrete admixture that provides high fluidity with a small amount of water.
一般的に空気連行性セメント分散剤は、コンクリート中
に微細な空気を連行し、かつセメント粒子への吸着によ
るセメント粒子間の静電反発により、流動性を向上させ
る。 その結果、成型物中の微細な空気泡により凍結融
解抵抗性が向上し、流動性向上に伴う単位水量の低減が
、高強度、高耐久性を有するコンクリートの製造を可能
にする。In general, air-entraining cement dispersants entrain fine air into concrete and improve fluidity by electrostatic repulsion between cement particles due to adsorption to cement particles. As a result, the freeze-thaw resistance is improved by the fine air bubbles in the molded product, and the reduction in unit water volume due to improved fluidity makes it possible to produce concrete with high strength and high durability.
代表的なセメント分散剤としては、β−ナフタレンスル
ホン酸ホルムアルデヒド縮合物、メラミン樹脂スルホン
酸およびリグニンスルホン酸などが知られている。As typical cement dispersants, β-naphthalene sulfonic acid formaldehyde condensates, melamine resin sulfonic acids, lignin sulfonic acids, and the like are known.
〈発明が解決しようとする課題〉
空気連行性セメント分散剤としてはリグニンスルホン酸
が挙げられるが、連行空気の安定性、セメント分散性能
は十分ではなく、また、凝結遅延性があるウ β−ナフ
タレンスルホン酸ホルムアルデヒド縮合物およびメラミ
ン樹脂スルホン酸は分散性能は高いが、非空気連行性で
あり、空気連行性を必要としないコンクリート2吹製品
においては有効であるが、空気連行性を必要とするモル
タルおよびコンクリート製品には空気連行剤(以下、A
E剤という)の併用を必要とする。<Problems to be Solved by the Invention> Lignosulfonic acid is an example of an air-entraining cement dispersant, but the stability of entrained air and cement dispersion performance are insufficient, and β-naphthalene has a setting retardant property. Sulfonic acid formaldehyde condensate and melamine resin sulfonic acid has high dispersion performance, but is non-air entraining, and is effective for two-shot concrete products that do not require air entrainment, but is effective for mortar that requires air entrainment. and air entraining agents (hereinafter referred to as A) for concrete products.
(referred to as Agent E).
染料、顔料およびコンクリートの分散剤として、アセナ
フテンスルホン酸ホルムアルデヒド縮金物が有効である
ことが知られているが(例えば、特公昭40−2624
9号公報参照)、この化合物は非空気連行性であり、空
気連行性を必要とするモルタルおよびコンクリート製品
にはAE剤の併用を必要とする。It is known that acenaphthenesulfonic acid formaldehyde condensates are effective as dispersants for dyes, pigments, and concrete (for example, Japanese Patent Publication No. 40-2624
9), this compound is non-air entraining, and requires the combined use of an AE agent in mortar and concrete products that require air entrainment.
本発明は、上記従来の問題を解決して、より高性能を有
する空気連行性セメント分散剤を提供することを目的と
している。The present invention aims to solve the above-mentioned conventional problems and provide an air-entraining cement dispersant having higher performance.
く課題を解決するための手段〉
本発明者らは、鋭意検討の結果、アセナフテンの縮合反
応性が極めて高く、縮合反応性の低い物質とも容易に共
縮合し、高縮合物を得ることができること、また、アル
キルナフタレン類との共縮合物が、セメントペースト、
モルタルおよびコンクリートに対して優れた分散性能を
示し、かつ良好な空気連行作用を有することを見い出し
、本発明を完成させるに至った。Means for Solving the Problems As a result of intensive studies, the present inventors have discovered that acenaphthene has extremely high condensation reactivity and can be easily co-condensed with substances having low condensation reactivity to obtain a high condensate. , Also, co-condensates with alkylnaphthalenes can be used as cement pastes,
The present inventors have discovered that they exhibit excellent dispersion performance in mortar and concrete and have good air entrainment effects, leading to the completion of the present invention.
即ち、上記目的を達成するために本発明によれば、アセ
ナフテンとメチルナフタレンとの重量比が20:80〜
70 : 30であるスルホン化されたアセナフテンと
メチルナフタレンの混合物を、ホルムアルデヒド縮合し
て得られる生成物を主成分とする空気連行性セメント分
散剤が提供される。That is, in order to achieve the above object, according to the present invention, the weight ratio of acenaphthene and methylnaphthalene is 20:80 to 20:80.
An air-entraining cement dispersant is provided which is based on a product obtained by formaldehyde condensation of a 70:30 mixture of sulfonated acenaphthene and methylnaphthalene.
以下に本発明をさらに詳細に説明する。The present invention will be explained in more detail below.
まず、本発明の分散剤を製造する方法について説明する
。 原料としては、アセナフテンとメチルナフタレンと
の重量比が20:80〜70:30の範囲にある混合物
をスルホン化して用いるか、またはアセナフテンとメチ
ルナフタレンをそれぞれスルホン化した後、アセナフテ
ンとメチルナフタレンの重量比が20 : 80〜70
:30の範囲にあるように混合したものを用いる。First, a method for producing the dispersant of the present invention will be explained. As a raw material, a mixture of acenaphthene and methylnaphthalene with a weight ratio in the range of 20:80 to 70:30 may be sulfonated, or acenaphthene and methylnaphthalene may be sulfonated, and then the weight ratio of acenaphthene and methylnaphthalene may be sulfonated. Ratio is 20:80-70
: Use a mixture in the range of 30.
アセナフテン、メチルナフタレンおよびアセナフテンと
メチルナフタレンの混合物のスルホン化は、原料に対し
、1.0〜1.5モル倍量の濃硫酸あるいは発煙硫酸を
添加し、140〜160℃で2〜4hr反応を行う。Sulfonation of acenaphthene, methylnaphthalene, and a mixture of acenaphthene and methylnaphthalene is performed by adding 1.0 to 1.5 molar amount of concentrated sulfuric acid or fuming sulfuric acid to the raw materials, and carrying out the reaction at 140 to 160°C for 2 to 4 hours. conduct.
次いで、アセナフテンとメチルナフタレンの割合が20
:80〜70:30の範囲にあるそれぞれのスルホン化
物の混合物に、ホルムアルデヒドを0.9〜1.1モル
倍量の割合で添加し、反応温度95〜105℃、反応時
間3〜6時間で縮合反応を行う。 縮合反応の際、必要
に応じ、希釈水および触媒として濃硫酸を添加する。
反応終了後、消石灰を加えて反応液中の硫酸を石膏とし
て除去し、次いで、前記生成スルホン酸と等モルの炭酸
ナトリウムまたは水酸化ナトリウムを添加して、ナトリ
ウム塩とした空気連行性セメント分散剤が得られる。Next, the ratio of acenaphthene and methylnaphthalene is 20
Formaldehyde was added at a ratio of 0.9 to 1.1 moles to a mixture of each sulfonate in the range of 80 to 70:30, and the reaction temperature was 95 to 105°C and the reaction time was 3 to 6 hours. Perform a condensation reaction. During the condensation reaction, dilution water and concentrated sulfuric acid are added as a catalyst, if necessary.
After the reaction is completed, slaked lime is added to remove the sulfuric acid in the reaction solution as gypsum, and then sodium carbonate or sodium hydroxide is added in an equimolar amount to the generated sulfonic acid to form an air-entraining cement dispersant. is obtained.
アセナフテンの重量比が20%未満の場合は、縮合反応
性が低下し、高縮合物を得難く、セメント分散性が低下
するとともに、必要以上の空気を連行し、好ましくない
。If the weight ratio of acenaphthene is less than 20%, the condensation reactivity decreases, it is difficult to obtain a high condensate, the cement dispersibility decreases, and more air than necessary is entrained, which is not preferable.
また、アセナフテンの重量比が70%より高くなると、
セメント分散性は優れるものの空気連行性が著しく低下
する。Moreover, when the weight ratio of acenaphthene is higher than 70%,
Although cement dispersibility is excellent, air entrainment properties are significantly reduced.
本発明分散剤の使用に際しては、AE剤を併用すること
なく所定の空気を連行させることが可能であるが、原料
中のメチルナフタレン分の割合が比較的低く、所定の空
気量が得られない場合は、AE剤との併用も差し支えな
い。 また、本発明による分散剤は、他の分散剤、遅延
剤などとの併用も可能である。When using the dispersant of the present invention, it is possible to entrain a specified amount of air without using an AE agent together, but the proportion of methylnaphthalene in the raw material is relatively low, making it impossible to obtain the specified amount of air. If necessary, it may be used in combination with an AE agent. Further, the dispersant according to the present invention can be used in combination with other dispersants, retarders, etc.
〈実施例〉
以下に本発明を実施例に基づき具体的に説明するが、あ
くまでも本発明はこれに限定されるものではない。<Examples> The present invention will be specifically described below based on Examples, but the present invention is not limited thereto.
アセナフテンおよびメチルナフタレンをそれぞれ第1表
に示す各割合に混合し、130℃に加熱したところに濃
硫酸150重量部を滴下し、150℃に昇温して3時間
スルホン化反応を行った。Acenaphthene and methylnaphthalene were mixed in the proportions shown in Table 1, heated to 130°C, 150 parts by weight of concentrated sulfuric acid was added dropwise, and the mixture was heated to 150°C to carry out a sulfonation reaction for 3 hours.
次いで、100℃ま°で冷却したところで第1表に示す
各割合で希釈水と濃硫酸を加え、80℃に保持し、37
wt%ホルムアルデヒド85重量部を加え、100℃で
第1表に示す各時間の縮合反応を行った。 反応終了後
、常法に従いライジング、ソーデイジョンを行い、ナト
リウム塩とした分散剤を得た(本発明例1〜6)。 な
お、アセナフテンおよびβ−メチルナフタレンの各単独
原料について、アセナフテンのスルホン化用濃硫酸に1
30重量部、縮合にホルマリン80重量部を用いた他は
本発明例と同様にしてナトリウム塩とした分散剤を得た
(比較例1.2)。 この場合の原料量、ホルムアルデ
ヒド縮合の条件は第1表に併記したとおりである。Next, after cooling to 100°C, dilution water and concentrated sulfuric acid were added in the proportions shown in Table 1, and the temperature was maintained at 80°C.
85 parts by weight of wt% formaldehyde was added, and a condensation reaction was carried out at 100° C. for each time shown in Table 1. After the reaction was completed, rising and sodium dispersion were carried out according to conventional methods to obtain dispersants in the form of sodium salts (Examples 1 to 6 of the present invention). In addition, for each individual raw material of acenaphthene and β-methylnaphthalene, 1 ml of concentrated sulfuric acid for sulfonation of acenaphthene
A dispersant in the form of a sodium salt was obtained in the same manner as in the present invention except that 30 parts by weight of formalin and 80 parts by weight of formalin were used for condensation (Comparative Example 1.2). The amounts of raw materials and conditions for formaldehyde condensation in this case are as listed in Table 1.
上記本発明例および比較例の各分散剤を予め練りまぜ水
に溶解し、第2表に示す構成比になるようセメント、砂
を配合し、モルタル混練機により練りまぜてモルタルを
得、JISR5201に準じ、モルタルフロー(mm)
および空気量を測定した。 その結果を第3表に示す。The above-mentioned dispersants of the present invention examples and comparative examples are mixed in advance and dissolved in water, and cement and sand are mixed so that the composition ratios shown in Table 2 are obtained. Accordingly, mortar flow (mm)
and measured the amount of air. The results are shown in Table 3.
なお、ナフタレンを原料とした市販の分散剤(参考例
1)、市販の空気連行性分散剤(参考例2)を配合した
モルタルおよび分散剤を配合しないモルタル(参考例3
)についての測定値を第3表に併記した。In addition, mortar containing a commercially available dispersant made from naphthalene (Reference Example 1), a commercially available air-entraining dispersant (Reference Example 2), and a mortar containing no dispersant (Reference Example 3)
) are also listed in Table 3.
第3表に示すとおり本発明例の分散剤は良好な空気連行
作用を示し、かつ優れたセメント分散能力を有すること
が明白である。As shown in Table 3, it is clear that the dispersants of the present invention exhibit good air entrainment action and have excellent cement dispersion ability.
〈発明の効果〉
本発明は、以上説明したように構成されているので、空
気連行性分散剤として、AE剤を併用しなくても優れた
分散性能を示し、良好な空気連行作用を有するという効
果を奏する。<Effects of the Invention> Since the present invention is configured as described above, it is said that as an air-entraining dispersant, it exhibits excellent dispersion performance even without the use of an AE agent and has a good air-entraining effect. be effective.
Claims (1)
0:80〜70:30であるスルホン化されたアセナフ
テンとメチルナフタレンの混合物を、ホルムアルデヒド
縮合して得られる生成物を主成分とする空気連行性セメ
ント分散剤。(1) The weight ratio of acenaphthene and methylnaphthalene is 2
An air-entraining cement dispersant whose main component is a product obtained by formaldehyde condensation of a mixture of sulfonated acenaphthene and methylnaphthalene in a ratio of 0:80 to 70:30.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP25054088A JPH0297446A (en) | 1988-10-04 | 1988-10-04 | Air entraining cement dispersant |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP25054088A JPH0297446A (en) | 1988-10-04 | 1988-10-04 | Air entraining cement dispersant |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0297446A true JPH0297446A (en) | 1990-04-10 |
Family
ID=17209428
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP25054088A Pending JPH0297446A (en) | 1988-10-04 | 1988-10-04 | Air entraining cement dispersant |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0297446A (en) |
-
1988
- 1988-10-04 JP JP25054088A patent/JPH0297446A/en active Pending
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