JPH03290343A - Water reducing agent for cement - Google Patents
Water reducing agent for cementInfo
- Publication number
- JPH03290343A JPH03290343A JP9333390A JP9333390A JPH03290343A JP H03290343 A JPH03290343 A JP H03290343A JP 9333390 A JP9333390 A JP 9333390A JP 9333390 A JP9333390 A JP 9333390A JP H03290343 A JPH03290343 A JP H03290343A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- cement
- mol
- water reducing
- reducing agent
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000004568 cement Substances 0.000 title claims abstract description 25
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 21
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 11
- 239000007859 condensation product Substances 0.000 claims abstract description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000002270 dispersing agent Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims 2
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims 1
- 239000001294 propane Substances 0.000 claims 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 92
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 239000004567 concrete Substances 0.000 description 10
- 235000010265 sodium sulphite Nutrition 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VKOUCJUTMGHNOR-UHFFFAOYSA-N Diphenolic acid Chemical compound C=1C=C(O)C=CC=1C(CCC(O)=O)(C)C1=CC=C(O)C=C1 VKOUCJUTMGHNOR-UHFFFAOYSA-N 0.000 description 2
- 229920001732 Lignosulfonate Chemical class 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920005646 polycarboxylate Polymers 0.000 description 2
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 125000001174 sulfone group Chemical group 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 description 1
- ZYZWCJWINLGQRL-UHFFFAOYSA-N 4-phenylcyclohexa-2,4-diene-1,1-diol Chemical group C1=CC(O)(O)CC=C1C1=CC=CC=C1 ZYZWCJWINLGQRL-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012615 aggregate Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000008054 sulfonate salts Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/20—Sulfonated aromatic compounds
- C04B24/22—Condensation or polymerisation products thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (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〕
本発明はセメントペースト、モルタル、コンクリートな
とセメント組成物に関するものであり、特に減水性が高
く、また流動性の経時的低下が少なく、施工性、作業性
の改善されたセメント用減水剤に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to cement compositions such as cement paste, mortar, and concrete. This invention relates to a water reducing agent for cement with improved properties and workability.
セメントペースト、モルタル、コンクリート等は、土木
、建築等に大量に使用されている。Cement paste, mortar, concrete, etc. are used in large quantities in civil engineering, construction, etc.
そして、その作業性の改善、強度や耐久性の向上、ひび
割れ性の減少等諸物性の向上を目的として各種の減水剤
が用いられているが、さらに高性能なセメント用減水剤
が要求されている。Various water reducing agents are used to improve various physical properties such as improving workability, increasing strength and durability, and reducing cracking resistance, but there is a need for even higher performance water reducing agents for cement. There is.
このうちスルホン化メラミン樹脂塩は減水効果自体が小
さく、多量の添加を必要とする。Among these, sulfonated melamine resin salts have a small water-reducing effect and require a large amount to be added.
ポリカルボン酸塩、リグニンスルホン酸塩、ナフタレン
スルホン酸ホルマリン高縮合物塩は減水効果は大きいが
、このうち
・ポリカルボン酸塩の場合は添加量を増大すると著しい
凝結遅延を起こし場合によっては硬化不良となる。Polycarboxylate salts, lignin sulfonate salts, and formalin naphthalene sulfonate high condensate salts have a large water-reducing effect; however, in the case of polycarboxylate salts, increasing the amount added may cause a significant setting delay and, in some cases, result in poor curing. becomes.
・リグニンスルホン酸塩は、空気混入量が大きく、モル
タルやコンクリートの物性に悪影響を与えることがある
。・Lignosulfonate contains a large amount of air, which may have a negative effect on the physical properties of mortar and concrete.
・ナフタレンスルホン酸ホルマリン高縮合物塩は、凝結
遅延を起こさず、空気連行性も非常に小さいが、モルタ
ル、コンクリートの流動性の経時的低下が著しい。・Naphthalenesulfonic acid formalin high condensate salt does not cause setting delay and has very low air entrainment, but the fluidity of mortar and concrete decreases significantly over time.
等の問題点があった。There were problems such as.
そこで本発明者等は、減水効果が大きく、凝結遅延も起
こさずまた空気連行性も小さく、しかもモルタル、コン
クリートの流動性の経時的低下が少ないセメント用減水
剤について鋭意検討の結果、本発明に到達したものであ
る。Therefore, the present inventors have conducted intensive studies on a water reducing agent for cement that has a large water reducing effect, does not cause setting delay, has low air entrainment, and has less deterioration in the fluidity of mortar and concrete over time, and has developed the present invention. It has been reached.
すなわち
一般式(1)
[式中Xは
OOH
のいずれかを示す(但し、nは1から5の整数、R,、
R3は夫々独立して水素、またはアルキル基、R2,R
4は夫々独立してアルキル基を示す)]で示される化合
物の1種、または2種以上と、亜鉛酸塩、及びアルデヒ
ド類とを必要に応じてアルカリの存在下、任意の順序で
反応させて得られる縮合生成物を分散剤として含有する
ことを特徴とするセメント用減水剤を提供するものであ
る。That is, general formula (1) [wherein X represents any one of OOH (where n is an integer from 1 to 5, R,
R3 is each independently hydrogen or an alkyl group, R2, R
4 each independently represents an alkyl group)], a zincate, and an aldehyde are reacted in any order in the presence of an alkali as necessary. The present invention provides a water reducing agent for cement, which contains a condensation product obtained as a dispersant.
本発明に用いる一般式(1)で表される化合物としては
2,2−ビス(4−ヒドロキシフェニル)プロパン、4
.4’ −ジヒドロキシジフェニルメタン、4.4’
−ジヒドロキシジフェニルスルホン、4.4’ −ジ
ヒドロキシビフェニル、44′−ビス(4−ヒドロキシ
フェニル)吉草酸が好んで用いられ、またこれらを組み
合わせて用いることもできる。The compounds represented by the general formula (1) used in the present invention include 2,2-bis(4-hydroxyphenyl)propane, 4
.. 4'-dihydroxydiphenylmethane, 4.4'
-dihydroxydiphenylsulfone, 4,4'-dihydroxybiphenyl, and 44'-bis(4-hydroxyphenyl)valeric acid are preferably used, and they can also be used in combination.
亜硫酸塩としては、亜硫酸ナトリウム、亜硫酸アンモニ
ウム、亜硫酸水素ナトリウム、ピロ亜硫酸ナトリウム、
重亜硫酸カリウム、重亜硫酸アンモニウム等があげられ
る。Sulfites include sodium sulfite, ammonium sulfite, sodium bisulfite, sodium pyrosulfite,
Examples include potassium bisulfite and ammonium bisulfite.
アルデヒド類としては、ホルムアルデヒド、パラホルム
アルデヒド、ヘキサンメチレンテトラミン等のホルムア
ルデヒド重合及び縮合物、アセトアルデヒド等か有用で
あり、特に好ましくは、ホルムアルデヒド及びその誘導
体である。Useful aldehydes include formaldehyde, paraformaldehyde, formaldehyde polymerization and condensation products such as hexamethylenetetramine, acetaldehyde, etc., and formaldehyde and derivatives thereof are particularly preferred.
また、その使用割合は以下のモル比で行うことが好まし
い。Moreover, it is preferable to use the following molar ratio.
一般式(1)で表される化合物 :A亜硫酸
塩 二Bアルデヒド
:CA:B:C=1+3〜02
:6〜1.2なお、一般式f1.)て表される化合物2
種以上で行う場合は、2種以上の合計のモル数を、単体
のモル数として、上記割合を適用すればよい。Compound represented by general formula (1): A sulfite B aldehyde
:CA:B:C=1+3~02
:6-1.2 Furthermore, general formula f1. ) Compound 2
When using more than one species, the above-mentioned ratio may be applied with the total number of moles of the two or more species as the number of moles of the single substance.
また、反応液pHは7〜14であることが好ましく、必
要に応じてアルカリを用いて調整すればよい。その場合
アルカリとしては水酸化ナトリウム、アンモニア及び水
酸化アンモニウム等が挙げられる。Further, the pH of the reaction solution is preferably 7 to 14, and may be adjusted using an alkali if necessary. In that case, examples of the alkali include sodium hydroxide, ammonia and ammonium hydroxide.
これらの使用割合で、水性条件下、常圧ないしは加圧下
に温度30〜140℃で通常1〜60時間、反応させる
ことにより縮合物を得ることができる。A condensate can be obtained by reacting in these proportions under aqueous conditions at normal pressure or elevated pressure at a temperature of 30 to 140°C for usually 1 to 60 hours.
本発明のセメント用減水剤は以下の効果を有する。The water reducing agent for cement of the present invention has the following effects.
・減水性が大きく、また凝結遅延を生じない。・High water reduction properties and no delay in setting.
・空気連行性か小さく、またモルタル、コンクリートの
流動性の経時的変化が少ない。・Air entrainment is small, and the fluidity of mortar and concrete changes less over time.
なお、本発明のセメント用減水剤は、セメント・重量の
0.01%〜2.0%、好ましくは0.1%〜06%の
割合で使用される。配合量が少なすぎると期待した効果
は得られず、多すぎるとセメントが過度に分散し、分離
現象を起こし好ましくない。The water reducing agent for cement of the present invention is used in a proportion of 0.01% to 2.0%, preferably 0.1% to 0.6%, based on the weight of the cement. If the amount is too small, the expected effect will not be obtained, and if it is too large, the cement will be excessively dispersed, causing a separation phenomenon, which is undesirable.
セメントは、普通ポルトランドセメント、早強セメント
、超早強セメント、高炉セメント、中庸熱セメント、フ
ライアッシュセメント、耐硫酸塩セメントなどが用いら
れる。また他のセメント用添加剤、例えば減水剤、空気
連行剤、凝結遅延剤、防水剤、膨張剤、シリカヒユーム
、石粉等と併用することもできる。As the cement, ordinary Portland cement, early strength cement, ultra early strength cement, blast furnace cement, medium heat cement, fly ash cement, sulfate resistant cement, etc. are used. It can also be used in combination with other cement additives, such as water reducing agents, air entraining agents, setting retarders, waterproofing agents, swelling agents, silica humes, stone powder, etc.
本願発明は以上の如く一般式(1)で示される化合物の
1種、または2種以上と、亜硫酸塩及びアルデヒド類と
を、必要に応じてアルカリの存在下に任意の順序で反応
させて得られる縮合生成物を分散剤として含有すること
を特徴とするセメント用減水剤であるが、更に■一般式
(1)で示される化合物のスルホン化物の1種または2
種以上及びアルデヒド類とを反応させて得られる縮合生
成物、■一般式(1)で示される化合物のスルホン化物
の1種または2種以上と、一般式(1)で示される化合
物の1種または2種以上及びアルデヒド類とを反応させ
て得られる縮合生成物のいずれかを分散剤として含有さ
せることもできる。As described above, the present invention can be obtained by reacting one or more of the compounds represented by the general formula (1) with a sulfite and an aldehyde in an arbitrary order in the presence of an alkali as necessary. This water reducing agent for cement is characterized in that it contains a condensation product as a dispersant;
A condensation product obtained by reacting one or more species with an aldehyde, (1) one or more sulfonated compounds of the general formula (1), and one of the compounds represented by the general formula (1); Alternatively, any of the condensation products obtained by reacting two or more types with aldehydes can also be included as a dispersant.
これら一般式(1)で表される化合物のスルホン化物は
、硫酸、発煙硫酸等のスルホン化剤を用いる直接スルホ
ン化や、スルホアルキル化反応によるスルホン基の間接
連結で得られるが、好ましくは亜硫酸塩、及びアルデヒ
ド類とのスルホメチル化反応によるスルホン化物である
。またそのスルホン化度は以下の割合が好ましい。Sulfonated products of these compounds represented by general formula (1) can be obtained by direct sulfonation using a sulfonating agent such as sulfuric acid or oleum, or by indirect linkage of sulfone groups through a sulfoalkylation reaction, but preferably sulfurous acid It is a sulfonated product obtained by a sulfomethylation reaction with a salt and an aldehyde. Further, the degree of sulfonation is preferably in the following ratio.
一般式(1)で表わされる化合物:スルホン基=1=1
〜2また、その使用割合は以下のモル比で行うことが好
ましい。Compound represented by general formula (1): sulfone group=1=1
~2 Also, it is preferable to use the following molar ratio.
一般式(1)で表される化合物のスルホン化物: A
一般式(1)で表される化合物 二Bアルデ
ヒド :CA:B:C=1:
4〜0:10〜1
〔実施例〕
以下、実施例によって本発明の詳細な説明するが、実施
例中の部は重量部を示している。Sulfonated product of the compound represented by general formula (1): A Compound represented by general formula (1) 2B aldehyde :CA:B:C=1:
4-0:10-1 [Example] Hereinafter, the present invention will be explained in detail with reference to Examples, where parts in the Examples indicate parts by weight.
合成例fl)
2.2−ビス(4−ヒドロキシフェニル)プロパン22
8.3部(1モル)と亜硫酸ナトリウム126、3部(
1モル)を水826部に加える。この固液に温度100
℃にて37%ホルマリン811部(ホルムアルデヒド
1モル)を1時間で滴下する。次にこの溶液を温度80
℃に冷却後、37%ホルマリン1622部(ホルムアル
デヒド 2モル)を1時間で滴下し、その温度で15時
間反応させて分散剤の水溶液を得た。Synthesis example fl) 2.2-bis(4-hydroxyphenyl)propane 22
8.3 parts (1 mol) and 126.3 parts (1 mol) of sodium sulfite (
1 mol) is added to 826 parts of water. This solid liquid has a temperature of 100
811 parts of 37% formalin (formaldehyde
1 mol) was added dropwise over 1 hour. Next, this solution was heated to 80°C.
After cooling to .degree. C., 1,622 parts of 37% formalin (2 moles of formaldehyde) was added dropwise over 1 hour, and the mixture was reacted at that temperature for 15 hours to obtain an aqueous solution of a dispersant.
合成例(2)
4.4′−ジヒドロキシジフェニルスルホン2503部
(1モル)と亜硫酸ナトリウム1263部(1モル)を
水860部に加える。この固液に温度90℃にて37%
ホルマリン243.3部(ホルムアルデヒド 3モル)
を1時間で滴下する。これを温度100℃に昇温し10
時間反応させて分散剤の水溶液を得た。Synthesis Example (2) 2503 parts (1 mol) of 4.4'-dihydroxydiphenylsulfone and 1263 parts (1 mol) of sodium sulfite are added to 860 parts of water. This solid-liquid contains 37% at a temperature of 90℃.
Formalin 243.3 parts (formaldehyde 3 moles)
Drop in for 1 hour. This was heated to 100℃ and 10
The reaction was carried out for a period of time to obtain an aqueous solution of the dispersant.
合成例(3)
4.4′−ジヒドロキシジェニルメタン2002部(1
モル)と亜硫酸ナトリウム157.9部(1,25モル
)を水790部に加える。この固液に温度100℃にて
37%ホルマリン2433部(ホルムアルデヒド 3モ
ル)を1時間で滴下する。Synthesis example (3) 2002 parts of 4.4'-dihydroxygenylmethane (1
mol) and 157.9 parts (1.25 mol) of sodium sulfite are added to 790 parts of water. To this solid liquid, 2433 parts of 37% formalin (3 moles of formaldehyde) was added dropwise at a temperature of 100° C. over 1 hour.
これを温度100℃に昇温し15時間反応させて分散剤
の水溶液を得た。This was heated to 100°C and reacted for 15 hours to obtain an aqueous solution of a dispersant.
合成例(4)
4.4′−ジヒドロキシジフェニルエーテル2042部
(1モル)と亜硫酸ナトリウム101.0部(08モル
)を水780部に加える。この固液に温度100℃にて
37%ホルマリン64.9部(ホルムアルデヒド0.8
モル)を1時間で滴下する。Synthesis Example (4) 2042 parts (1 mol) of 4.4'-dihydroxydiphenyl ether and 101.0 parts (08 mol) of sodium sulfite are added to 780 parts of water. Add 64.9 parts of 37% formalin (0.8 parts of formaldehyde) to this solid liquid at a temperature of 100°C.
mol) dropwise over 1 hour.
次にこの溶液を温度80°Cに冷却後37%ホルマリン
1622部(ホルムアルデヒド 2モル)を1時間で滴
下し、その温度で15時間反応させて分散剤の水溶液を
得た。Next, after cooling this solution to a temperature of 80°C, 1622 parts of 37% formalin (formaldehyde 2 mol) was added dropwise over 1 hour, and the reaction was allowed to proceed at that temperature for 15 hours to obtain an aqueous solution of a dispersant.
合成例(5)
亜硫酸ナトリウム126J部(1モル)を水826部に
溶解し、47%水酸化ナトリウム水溶液でpH14に調
整する。この溶液に2,2−ビス(4−ヒドロキシフェ
ニル)プロパン228.3部(1モル)を加え、温度1
00℃にて37%ホルマリン811部(ホルムアルデヒ
ド 1モル)を1時間で滴下する。さらにこの溶液を温
度80℃に冷却後、37%ホルマリン162.2部(ホ
ルムアルデヒド 2モル)を1時間で滴下し、その温度
で15時間反応させて分散剤の水溶液を得た。Synthesis Example (5) 126 J parts (1 mol) of sodium sulfite is dissolved in 826 parts of water, and the pH is adjusted to 14 with a 47% aqueous sodium hydroxide solution. 228.3 parts (1 mol) of 2,2-bis(4-hydroxyphenyl)propane was added to this solution, and the temperature was 1
At 00°C, 811 parts of 37% formalin (1 mol of formaldehyde) was added dropwise over 1 hour. After further cooling this solution to a temperature of 80°C, 162.2 parts of 37% formalin (2 moles of formaldehyde) was added dropwise over 1 hour, and the reaction was allowed to proceed at that temperature for 15 hours to obtain an aqueous solution of a dispersant.
合成例(6)
亜硫酸水素ナトリウム104.[1部(1モル)を水7
60部に溶解し、47%水酸化ナトリウム水溶液でpH
l0に調整する。この溶液に4,4−ジヒドロキシビフ
ェニル186.2部(1モル)を加えて、温度100℃
にて37%ホルマリン81.1部(ホルムアルデヒド
1モル)を1時間で滴下する。さらにこの溶液を温度8
0℃に冷却後、37%ホルマリン162.2部(ホルム
アルデヒド 2モル)を1時間で滴下し、その温度で1
0時間反応させて分散剤の水溶液を得た。Synthesis example (6) Sodium hydrogen sulfite 104. [1 part (1 mol) of water 7
Dissolve in 60 parts and adjust pH with 47% aqueous sodium hydroxide solution.
Adjust to l0. 186.2 parts (1 mol) of 4,4-dihydroxybiphenyl was added to this solution, and the temperature was 100°C.
81.1 parts of 37% formalin (formaldehyde
1 mol) was added dropwise over 1 hour. Furthermore, this solution was heated to 8
After cooling to 0°C, 162.2 parts of 37% formalin (2 moles of formaldehyde) was added dropwise over 1 hour, and at that temperature
The reaction was carried out for 0 hours to obtain an aqueous solution of a dispersant.
合成例(7)
2.2−ビス(4−ヒドロキシフェニル)プロパン17
1.2部(0,75モル)と、4.4−ビス(4−ヒド
ロキシフェニル)吉草酸71.6部(0,25モル)、
及び亜硫酸ナトリウム126.3部(1モル)を水85
0部に加える。この固液に温度80℃にて37%ホルマ
リン243.3部(3モル)を1時間で滴下する。これ
を温度100℃に昇温し10時間反応させて分散剤の水
溶液を得た。Synthesis example (7) 2.2-bis(4-hydroxyphenyl)propane 17
1.2 parts (0.75 mol) and 71.6 parts (0.25 mol) of 4,4-bis(4-hydroxyphenyl)valeric acid.
and 126.3 parts (1 mol) of sodium sulfite in 85 parts of water.
Add to 0 parts. 243.3 parts (3 moles) of 37% formalin are added dropwise to this solid liquid at a temperature of 80° C. over 1 hour. This was heated to 100° C. and reacted for 10 hours to obtain an aqueous solution of a dispersant.
合成例(8)
2.2−ビス(4−ヒドロキシフェニル)プロパン11
4.2部(0,5モル)と4.4′ −ジヒドロキシジ
フェニルスルホン125.1部(0,5モル)、及び亜
硫酸す) l)ラム126.3部(1モル)を水834
部に加える。この固液に温度80℃にて37%ホルマリ
ン243.3(3モル)を1時間で滴下する。これを温
度90℃に昇温しIn時間反応させて分散剤の水溶液を
得た。Synthesis example (8) 2.2-bis(4-hydroxyphenyl)propane 11
4.2 parts (0.5 mol) and 125.1 parts (0.5 mol) of 4.4'-dihydroxydiphenylsulfone, and sulfite) l) 126.3 parts (1 mol) of rum and 834 parts of water
Add to section. To this solid liquid, 37% formalin 243.3 (3 mol) was added dropwise at a temperature of 80° C. over 1 hour. This was heated to 90° C. and reacted for an In period to obtain an aqueous solution of a dispersant.
合成例(9)
22−ビス(4−ヒドロキシフェニル)プロパン228
.3部(1モル)と亜硫酸ナトリウム1263部(1モ
ル)を水940部に加える。この固液に温度90℃にて
37%ホルマリン81.1部(ホルムアルデヒド 1モ
ル)を1時間で滴下する。Synthesis example (9) 22-bis(4-hydroxyphenyl)propane 228
.. 3 parts (1 mole) and 1263 parts (1 mole) of sodium sulfite are added to 940 parts of water. To this solid liquid, 81.1 parts of 37% formalin (1 mol of formaldehyde) was added dropwise at a temperature of 90° C. over 1 hour.
これを温度100 ’Cに昇温し3時間反応させる。This was heated to 100'C and reacted for 3 hours.
この後この反応物に4,4−ビス(4−ヒドロキシフェ
ニル)吉草酸71,6部(0,25モル)を加え、37
%ホルマリン202.7部(ホルムアルデヒド2.5モ
ル)を1時間で滴下する。これを10時間反応させて分
散剤の水溶液を得た。Thereafter, 71.6 parts (0.25 mol) of 4,4-bis(4-hydroxyphenyl)valeric acid was added to the reaction mixture, and 37
% formalin (2.5 moles of formaldehyde) was added dropwise over 1 hour. This was reacted for 10 hours to obtain an aqueous solution of a dispersant.
合成例(圃
2.2−ビス(4−ヒドロキシフェニル)プロパン22
83部(1モル)と亜硫酸ナトリウム126.3部(1
モル)を水940部に加える。この固液に温度9G’C
にて37%ホルマリン186.5部(ホルムアルデヒド
2.3モル)を1時間で滴下する。これを温度100℃
に昇温し8時間反応させる。この後この反応物に4,4
′−ジヒドロキシジフェニルスルホン25.0部(01
モル)を加え、37%ホルマリン16,2部(ホルムア
ルデヒド0.2モル)を1時間で滴下する。これを5時
間反応させて分散剤の水溶液を得た。Synthesis example (field 2.2-bis(4-hydroxyphenyl)propane 22
83 parts (1 mol) and 126.3 parts (1 mol) of sodium sulfite
mol) to 940 parts of water. This solid liquid has a temperature of 9G'C.
186.5 parts of 37% formalin (2.3 moles of formaldehyde) was added dropwise over 1 hour. This temperature is 100℃
The temperature was raised to 100%, and the mixture was allowed to react for 8 hours. After this, add 4,4 to this reactant.
'-dihydroxydiphenylsulfone 25.0 parts (01
16.2 parts of 37% formalin (0.2 mole of formaldehyde) was added dropwise over 1 hour. This was reacted for 5 hours to obtain an aqueous solution of a dispersant.
合成例(1υ
亜硫酸水素ナトリウム2080部(2モル)を水970
部に溶解し、47%水酸化ナトリウム水溶液でpH12
に調整する。この溶液に2.2−ビス(4−ヒドロキシ
フェニル)プロパン228.3部(1モル)を加えて、
温度100°Cにて37%ホルマリン1622部(ホル
ムアルデヒド 2モル)を1時間で滴下し、2時間反応
させる。さらにこの溶液に、37%ホルマリン162.
2部(ホルムアルデヒド 2モル)を1時間で滴下し、
56時間反応させて分散剤の水溶液を得た。Synthesis example (1υ 2080 parts (2 mol) of sodium hydrogen sulfite to 970 parts of water
pH 12 with 47% aqueous sodium hydroxide solution.
Adjust to. Adding 228.3 parts (1 mol) of 2,2-bis(4-hydroxyphenyl)propane to this solution,
At a temperature of 100°C, 1622 parts of 37% formalin (formaldehyde 2 mol) was added dropwise over 1 hour, and the mixture was allowed to react for 2 hours. Furthermore, 162% of 37% formalin was added to this solution.
2 parts (2 moles of formaldehyde) were added dropwise over 1 hour,
The reaction was carried out for 56 hours to obtain an aqueous solution of a dispersant.
コンクリート試験
本発明の減水剤を添加したコンクリートのコンシスチン
シーを、比較例としてナフタレンスルホン酸ホルマリン
高縮合物(出隅国策パルプサンフローPS)のコンシス
チンシーと比較し、コンクリートのスランプロス(流動
性の経時変化)を比較した。Concrete Test The consistency of concrete to which the water reducing agent of the present invention was added was compared with the consistency of naphthalene sulfonic acid formalin high condensate (Desumi Kokusaku Pulp Sunflow PS) as a comparative example. Changes in sex over time) were compared.
配合を表1に示す。The formulation is shown in Table 1.
表1
コンクリートは、セメント、骨材、及び減水剤を含む水
を1001可搬傾胴式ミキサーにいて3分間混練し、直
後、30.60分後にスランプを測定シた。コンクリー
トのスランプ、空気量、及び凝結時間はJISに準拠し
て行った。測定結果を表2に示す。Table 1 For concrete, cement, aggregate, and water containing a water reducing agent were mixed in a 1001 portable tilting mixer for 3 minutes, and the slump was measured immediately and 30.60 minutes later. The concrete slump, air amount, and setting time were determined in accordance with JIS. The measurement results are shown in Table 2.
1) Cセメント:普通ポルトランドセメント比重3
.16
W 水 :水道水
S 細骨材 :島根産川砂 比重2.59FM、2.6
0
G 粗骨材 :山口症砕石 比重2.71FM、6.l
16
〔発明の効果〕
本発明の減水剤は、比較例(サンフロ−PS)の減水剤
より少ない添加率で目標スランプを得ることができ、こ
れは分散性(減水性)に優れていることを示している。1) C cement: Ordinary Portland cement specific gravity 3
.. 16 W Water: Tap water S Fine aggregate: Shimane river sand Specific gravity 2.59FM, 2.6
0 G Coarse aggregate: Yamaguchi crushed stone, specific gravity 2.71FM, 6. l
16 [Effects of the Invention] The water reducing agent of the present invention can obtain the target slump at a lower addition rate than the water reducing agent of the comparative example (Sunflow-PS), which indicates that it has excellent dispersibility (water reducing ability). It shows.
またスランプの経時変化から、本発明の減水剤は、比較
例(サンフローPS)の減水剤より流動性の経時的低下
が少ないことを示している。Further, the change in slump over time shows that the water reducing agent of the present invention shows less decrease in fluidity over time than the water reducing agent of the comparative example (Sunflow PS).
さらに本発明の減水剤は、凝結遅延を起こさず、空気連
行性も比較例(サンフローPS)と同等である。Further, the water reducing agent of the present invention does not cause retardation of setting, and its air entrainment property is equivalent to that of the comparative example (Sunflow PS).
これらの結果より本発明の減水剤が優れた効果を有する
のは明らかである。From these results, it is clear that the water reducing agent of the present invention has excellent effects.
Claims (2)
、R_3は夫々独立して水素、またはアルキル基、R_
2、R4は夫々独立してアルキル基を示す)]で示され
る化合物の1種、または2種以上と、亜硫酸塩、及びア
ルデヒド類とを、必要に応じてアルカリの存在下、任意
の順序で反応させて得られる縮合生成物を分散剤として
含有することを特徴とするセメント用減水剤。(1) General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, X indicates either ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or O (however, n is from 1 to An integer of 5, R_1
, R_3 are each independently hydrogen or an alkyl group, R_3
2, R4 each independently represents an alkyl group)], a sulfite, and an aldehyde in any order, optionally in the presence of an alkali. A water reducing agent for cement, characterized in that it contains a condensation product obtained by the reaction as a dispersant.
ヒドロキシフェニル)プロパンである請求項1記載のセ
メント用減水剤。(2) The compound represented by general formula 1 is 2,2-bis(4-
The water reducing agent for cement according to claim 1, which is hydroxyphenyl)propane.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9333390A JPH03290343A (en) | 1990-04-09 | 1990-04-09 | Water reducing agent for cement |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9333390A JPH03290343A (en) | 1990-04-09 | 1990-04-09 | Water reducing agent for cement |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH03290343A true JPH03290343A (en) | 1991-12-20 |
Family
ID=14079343
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9333390A Pending JPH03290343A (en) | 1990-04-09 | 1990-04-09 | Water reducing agent for cement |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH03290343A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009086194A (en) * | 2007-09-28 | 2009-04-23 | Sumitomo Bakelite Co Ltd | Highly heat-resistant radiation-sensitive resist composition |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5112819A (en) * | 1974-05-02 | 1976-01-31 | Cassella Farbwerke Mainkur Ag | Nikanfuenooruruino fuorumuarudehidotonoshukugoseiseibutsuofukumu kenzaihojozaisoseibutsu |
-
1990
- 1990-04-09 JP JP9333390A patent/JPH03290343A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5112819A (en) * | 1974-05-02 | 1976-01-31 | Cassella Farbwerke Mainkur Ag | Nikanfuenooruruino fuorumuarudehidotonoshukugoseiseibutsuofukumu kenzaihojozaisoseibutsu |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009086194A (en) * | 2007-09-28 | 2009-04-23 | Sumitomo Bakelite Co Ltd | Highly heat-resistant radiation-sensitive resist composition |
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