JPH01121314A - Sulfone group-containing melamine formaldehyde resin - Google Patents
Sulfone group-containing melamine formaldehyde resinInfo
- Publication number
- JPH01121314A JPH01121314A JP27840087A JP27840087A JPH01121314A JP H01121314 A JPH01121314 A JP H01121314A JP 27840087 A JP27840087 A JP 27840087A JP 27840087 A JP27840087 A JP 27840087A JP H01121314 A JPH01121314 A JP H01121314A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- added
- sulfite
- melamine
- formaldehyde resin
- 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.)
- Granted
Links
- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 31
- 125000001174 sulfone group Chemical group 0.000 title claims description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 31
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 17
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012736 aqueous medium Substances 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 18
- 239000004568 cement Substances 0.000 abstract description 16
- 238000006482 condensation reaction Methods 0.000 abstract description 10
- 238000003860 storage Methods 0.000 abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 6
- 235000011121 sodium hydroxide Nutrition 0.000 abstract description 6
- 239000000243 solution Substances 0.000 abstract description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 abstract description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000010517 secondary reaction Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000006277 sulfonation reaction Methods 0.000 description 7
- 239000004567 concrete Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 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
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-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
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000036772 blood pressure Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006326 desulfonation Effects 0.000 description 1
- 238000005869 desulfonation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000011372 high-strength concrete Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- -1 methylol groups Chemical group 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002893 slag 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
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Landscapes
- 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、スルホン基含有メラミンホルムアルデヒド樹
脂に関するものである。さらに詳しくはコンクリートや
モルタルのペーストのワーカビリチーの経時による低下
を防止し、その施工性、作業性を改善することを可能と
すると共に、極めて良好な貯蔵安定性を有する、セメン
ト減水剤として有用なスルホン基含有メラミンホルムア
ルデヒド樹脂を製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a sulfone group-containing melamine formaldehyde resin. More specifically, sulfone is useful as a cement water-reducing agent that prevents the workability of concrete and mortar paste from decreasing over time, improves its workability and workability, and has extremely good storage stability. The present invention relates to a method for producing a group-containing melamine formaldehyde resin.
セメント、水及び砂利、混和剤または混和材とを混合し
てなるセメント配合物は、混練後、時間の経過と共にセ
メントの物理的化学的凝集が進行し、流動性を失い、施
工性、作業性が経時的に低下する０例えばセメント配合
物のポンプ圧送に際し何らかの理由により圧送を中止し
、その後圧送を再開しようとする場合、配管中のセメン
ト配合物の流動性が低下し、圧送再開時に圧送圧力の急
上昇や閉塞を生じることもある。Cement mixtures made by mixing cement, water, gravel, admixtures, or admixtures undergo physical and chemical aggregation of the cement over time after mixing, and lose fluidity, resulting in poor workability and workability. For example, when pumping cement mixture, if you stop pumping for some reason and then try to restart pumping, the fluidity of the cement mixture in the piping will decrease, and the pumping pressure will decrease when pumping resumes. It may also cause a sudden increase in blood pressure or blockage.
水の配合量を増やせば流動性は、改善されるがこれでは
コンクリート強度の低下が著しい。Fluidity can be improved by increasing the amount of water mixed, but this results in a significant decrease in concrete strength.
これらの問題解決のために従来セメント減水剤として、
リグニンスルホン酸塩、オキシカルボン酸塩、ナフタリ
ンスルホン酸ホルマリン縮合物、スルホン基含有メラミ
ンホルムアルデヒド樹脂、などが提案されている。しか
しこれらの従来技術では近年の建築土木技術の進歩に対
応できる分散流動性、スランプ保持力、貯蔵安定性等を
十分に満足するものとは言い難く、その改良が強く望ま
れてきた。To solve these problems, as a conventional cement water reducer,
Lignin sulfonates, oxycarboxylate salts, naphthalene sulfonic acid formalin condensates, sulfonic group-containing melamine formaldehyde resins, and the like have been proposed. However, these conventional techniques cannot be said to fully satisfy the dispersion fluidity, slump holding power, storage stability, etc. that are compatible with recent advances in construction and civil engineering technology, and improvements have been strongly desired.
本発明の目的は、１８ケ月以上の長期貯蔵安定性ををし
、かつ優れたセメント減水性能を持ち、高強度コンクリ
ート減水剤水溶液として好適なスルホン基含有メラミン
ホルムアルデヒド樹脂を簡易に、かつ効率的に製造する
方法を提供することにある。The purpose of the present invention is to easily and efficiently produce a sulfonic group-containing melamine formaldehyde resin that has long-term storage stability of 18 months or more, has excellent cement water-reducing performance, and is suitable as an aqueous solution of a high-strength concrete water-reducing agent. The purpose is to provide a manufacturing method.
本発明者らは、スルホン基含有メラミンホルムアルデヒ
ド樹脂の貯蔵安定性、分散流動性等について改善すべく
鋭意検討の結果、縮合反応後の反応液のｐ）Ｉ及び該反
応後の亜硫酸塩の添加が生成液のセメン）ｉ％！２水剤
としての性能に著しく影響を与えることを見いだし本発
明を完成した。The present inventors have conducted intensive studies to improve the storage stability, dispersion fluidity, etc. of sulfonic group-containing melamine formaldehyde resins, and have found that the addition of p)I to the reaction solution after the condensation reaction and sulfite after the reaction Cement of produced liquid) i%! The present invention was completed based on the discovery that this significantly affects the performance as a two-water solution.
すなわち本発明は、次の第１〜４次の反応工程よりなる
スルホン基含有メラミンホルムアルデヒド樹脂の製造方
法である。That is, the present invention is a method for producing a sulfone group-containing melamine formaldehyde resin, which comprises the following first to fourth reaction steps.
（ａ）水媒体中で、メラミンとホルムアルデヒドをモル
比１．０ ： ２．６〜３．４ 、ｐＨ３〜１１で反応
させる第１次反応工程、
（ｂ）ついで亜硫酸塩をメラミン１モルに対して０゜７
〜１．３モル加えてｐＨ９〜１３、温度５０〜９０”Ｃ
で１〜５時間反応させる第２次反応工程、
（ｃ）ついで’ｐＨ３，５〜６．５ 、温度４０〜９０
”Ｃで１〜５時間時間間応を行う第３次反応工程、
（ｄ）この後ｐｉを９〜１３に調節した後、亜硫酸塩を
さらに０．０１〜０．３０モル加えて０〜６０分反応さ
せる第４次反応工程。(a) A first reaction step in which melamine and formaldehyde are reacted in an aqueous medium at a molar ratio of 1.0:2.6 to 3.4 and a pH of 3 to 11. (b) Then, sulfite is reacted with respect to 1 mole of melamine. te0゜7
~1.3 mol added, pH 9-13, temperature 50-90"C
A second reaction step of reacting for 1 to 5 hours at pH 3.5 to 6.5 and temperature 40 to 90.
(d) After adjusting the pi to 9 to 13, add another 0.01 to 0.30 mol of sulfite to give 0 to 60 mol of sulfite. 4th reaction step of reacting for minutes.
本発明に使用するホルムアルデドは、市販工業製品のホ
ルマリン、パラホルムアルデヒド等で十分である。また
メラミンも通常の市販品でよい。As the formaldede used in the present invention, commercially available industrial products such as formalin and paraformaldehyde are sufficient. Also, melamine may be a commercially available product.
亜硫酸塩は重亜硫酸塩も含むものとし、市販工業製品の
亜硫酸アンモニウム、亜硫酸ソーダ、重亜硫酸ソーダ、
重亜硫酸アンモニウム、ピロ亜硫酸ソーダ等がある。Sulfites include bisulfites, including commercially available industrial products such as ammonium sulfite, sodium sulfite, sodium bisulfite,
Examples include ammonium bisulfite and sodium pyrosulfite.
本明細書においては、ホルムアルデヒドはその形態にか
かわらずＨＣＨｏ １モルを提供する化合物を１モルと
して、メラミンはトリアジン環を１モル提供する化合物
を１モルとして、亜硫酸塩としては、１モルのＳＯ！基
を提供する化合物を１モルとして計算する。In this specification, formaldehyde is defined as 1 mole of a compound that provides 1 mole of HCHo regardless of its form, melamine is defined as 1 mole of a compound that provides 1 mole of triazine ring, and sulfite is defined as 1 mole of SO! Calculated based on 1 mole of compound providing the group.
本発明のスルホン基含有メラミンホルムアルデヒド樹脂
の製造法は、まず水媒体中で、ホルムアルデヒドとメラ
ミンを反応させる第一次反応工程を行なう。第一次反応
工程は、メラミンとホルムアルデヒドからトリメチロー
ルメラミンを効率よく生成させる工程である。この反応
のｐｉは３〜１１、望ましくは４〜９である。３未満で
は、メチロール化反応が進みにくく、１１を越えると副
反応が起こりやすい、メラミンとホルムアルデヒドのモ
ル比はｔ、ｏ： ２．６〜３．４、好ましくは１．０
： ２．９〜３．１である０モル比が２．６未満ではメ
チロール化が不十分となり、３．４を越えるとフリーの
ホルムアルデヒドが増加し、次に述べるスルホン化反応
に於いて亜硫酸塩と反応してしまい好ましくない０反応
時間は５〜６０分、望ましくは１５〜２５分である。５
分未満ではメチロール化が不十分であり、６０分を越え
ると沈殿などを生じやすい。In the method for producing a sulfonic group-containing melamine-formaldehyde resin of the present invention, a first reaction step is first performed in which formaldehyde and melamine are reacted in an aqueous medium. The first reaction step is a step of efficiently producing trimethylolmelamine from melamine and formaldehyde. The pi of this reaction is 3-11, preferably 4-9. When it is less than 3, the methylolation reaction is difficult to proceed, and when it exceeds 11, side reactions tend to occur.The molar ratio of melamine and formaldehyde is t, o: 2.6 to 3.4, preferably 1.0.
: If the molar ratio of 2.9 to 3.1 is less than 2.6, methylolization will be insufficient, and if it exceeds 3.4, free formaldehyde will increase, and sulfite will be formed in the sulfonation reaction described below. The undesirable reaction time is 5 to 60 minutes, preferably 15 to 25 minutes. 5
If it is less than 60 minutes, methylolization is insufficient, and if it exceeds 60 minutes, precipitation etc. tend to occur.
この第一次反応工程に続き、亜硫酸塩を加えスルホン化
を行う第二次反応工程を行う。メラミンと亜硫酸塩のモ
ル比はｔ、ｏ： ０．７〜１．３望ましくは、１．０
： ０．９〜１．１である。０．７未満の場合スルホン
化が不十分となり、次に説明する縮合反応に於いてゲル
化又は異常増粘してしまう、１．３を越えると必要以上
にスルホン化が進み、次に説明する縮合反応が起こりに
（（なり、得られるスルホン基含有メラミンホルムアル
デヒド樹脂は十分にコンクリート等の流動性を改善し得
ない。反応ｐ＋１は９〜１３、望ましくは１０〜１２で
ある。９未満では、スルホン化が進まず、１３を越える
と脱スルホン化してしまうので好ましくない。反応温度
は５０〜９０’Ｃ，望ましくは７０〜８０℃である。５
０℃未満では、非常に長い反応時間を要し、９０℃を越
えると反応のコントロールが困難になる０反応時間は１
〜５時間、望ましくは２〜３時間である。１時間未満で
は、スルホン化反応が不十分である。５時間程度でスル
ホン化反応はほぼ終了するので５時間を越える必要がな
い、上記反応におけるｐＨの調整は、苛性ソーダ、苛性
カリ等の通常のアルカリ性物質の添加によって容易に行
われる。Following this first reaction step, a second reaction step is performed in which sulfite is added and sulfonation is carried out. The molar ratio of melamine and sulfite is t, o: 0.7 to 1.3, preferably 1.0
: 0.9 to 1.1. If it is less than 0.7, the sulfonation will be insufficient, resulting in gelation or abnormal thickening in the condensation reaction explained next.If it exceeds 1.3, the sulfonation will proceed more than necessary, which will be explained next. A condensation reaction occurs ((), and the resulting sulfone group-containing melamine formaldehyde resin cannot sufficiently improve the fluidity of concrete, etc. Reaction p+1 is 9 to 13, preferably 10 to 12. If it is less than 9, Sulfonation does not proceed, and if the temperature exceeds 13, desulfonation occurs, which is undesirable.The reaction temperature is 50 to 90'C, preferably 70 to 80'C.5
At temperatures below 0°C, a very long reaction time is required, and at temperatures above 90°C, it becomes difficult to control the reaction.
-5 hours, preferably 2-3 hours. If the time is less than 1 hour, the sulfonation reaction will be insufficient. Since the sulfonation reaction is almost completed in about 5 hours, there is no need to exceed 5 hours.Adjustment of the pH in the above reaction is easily carried out by adding a common alkaline substance such as caustic soda or caustic potash.
これに続き縮合反応を行う第三次反応工程は、ｐＨを３
．５〜６．５、望ましくは５〜６に調節する。In the third reaction step, which is followed by a condensation reaction, the pH is adjusted to 3.
．． Adjust to 5-6.5, preferably 5-6.
３．５未満の場合はゲル化、増粘しやすく、６．５を越
えると縮合反応がほとんど進まない０反応温度は４０〜
９０℃、望ましくは６０〜８０℃である。４０℃未満で
は縮合反応が進まず、９０℃を越えると反応のコントロ
ールが難しい。反応時間は、１〜５時間、望ましくは２
〜３時間である。１時間以下では、縮合反応が不十分で
理想の分子量に達せず、貯蔵安定性が著しく悪くなる。If it is less than 3.5, gelation and thickening will occur easily, and if it exceeds 6.5, the condensation reaction will hardly proceed.
The temperature is 90°C, preferably 60-80°C. If the temperature is lower than 40°C, the condensation reaction will not proceed, and if the temperature exceeds 90°C, it will be difficult to control the reaction. The reaction time is 1 to 5 hours, preferably 2 hours.
~3 hours. If the time is less than 1 hour, the condensation reaction will be insufficient and the ideal molecular weight will not be reached, resulting in significantly poor storage stability.
５時間程度で縮合反応は、はぼ終了してしまうのでこれ
を越えて行う必要がない、この反応のｐｎの調整には塩
酸、硫酸等の通常の鉱酸や、蟻酸、酢酸等の有機酸の添
加によって容易に行われる。The condensation reaction will be completed in about 5 hours, so there is no need to continue it beyond this time.To adjust the pn of this reaction, use ordinary mineral acids such as hydrochloric acid and sulfuric acid, and organic acids such as formic acid and acetic acid. This can be easily done by adding .
三次反応工程終了後、直ちに、反応液ｐＨを９〜１３に
調整し、亜硫酸塩を０．０１〜０．３０モル、望ましく
は０．０２〜０．０７モル加える。 ０．０１モル以下
では、貯蔵安定性を十分に改善できない、 ０．３０モ
ルを越えるとコンクリートの耐久性に悪影響を与えるの
で好ましくない、このｐＨの調整は、苛性ソーダ等の通
常のアルカリ性物質の添加によって容易に行われる。そ
の後４０〜７０℃に冷却し、０〜６０分間熟成反応させ
た後冷却する。この熟成反応は、必ずしも行わな′くと
も構わないが、２０〜３０分間反応を行うことが望まし
い、この後、更に所定のＰＨに調節することも可能であ
る。Immediately after the completion of the tertiary reaction step, the pH of the reaction solution is adjusted to 9 to 13, and 0.01 to 0.30 mol, preferably 0.02 to 0.07 mol of sulfite is added. If it is less than 0.01 mol, the storage stability cannot be sufficiently improved, and if it exceeds 0.30 mol, it will adversely affect the durability of the concrete, which is undesirable.This pH adjustment is done by adding ordinary alkaline substances such as caustic soda. easily done by Thereafter, the mixture is cooled to 40 to 70°C, subjected to aging reaction for 0 to 60 minutes, and then cooled. Although this aging reaction does not necessarily have to be carried out, it is desirable to carry out the reaction for 20 to 30 minutes.After this, it is also possible to further adjust the pH to a predetermined value.
最後に亜硫酸塩を添加する処理によって特に１８ヶ月以
上もの長期にわたる貯蔵安定性を有し、かつ優れたセメ
ント減水性能を持つスルホン基含有メラミンホルムアル
デヒド樹脂が得られる。Finally, by adding sulfite, a sulfonic group-containing melamine formaldehyde resin can be obtained which has long-term storage stability of 18 months or more and has excellent cement water reduction performance.
さらに、本発明のスルホン基含有メラミンホルムアルデ
ヒド樹脂は、必要に応じて噴霧乾燥を行い、粉末とする
ことも可能である。Furthermore, the sulfone group-containing melamine formaldehyde resin of the present invention can be spray-dried as necessary to form a powder.
本発明のスルホン基含有メラミンホルムアルデヒド樹脂
の添加量は固形分として、セメントに対して０．０５〜
２．５重量％が適当である。 ０．０５％未満では、十
分なワーカビリチーを得ることはできず、２．５％を越
えると経済的に不利である。The amount of the sulfonic group-containing melamine formaldehyde resin of the present invention added as solid content is 0.05 to 0.05 to
2.5% by weight is suitable. If it is less than 0.05%, sufficient workability cannot be obtained, and if it exceeds 2.5%, it is economically disadvantageous.
さらに、本発明のスルホン基含有メラミンホルムアルデ
ヒド樹脂をセメントに添加する場合、−船釣な混和剤や
混和材つまり空気連行剤、早強剤、遅延剤、防水剤、防
錆剤、保水剤、着色剤、防腐剤、グラスファイバー、フ
ライアッシュ、高炉スラグ、シリカ粉末等と併用するこ
とが可能である。さらに、本発明のスルホン基含有メラ
ミンホルムアルデヒド樹脂は、コンクリートのほかにも
例えば石膏の減水剤としても用いられる。Furthermore, when the sulfonic group-containing melamine formaldehyde resin of the present invention is added to cement, it may be used as an admixture or admixture, such as an air entraining agent, an early strength agent, a retarder, a waterproofing agent, a rust preventive agent, a water retention agent, or a coloring agent. It can be used in combination with additives, preservatives, glass fiber, fly ash, blast furnace slag, silica powder, etc. Furthermore, the sulfonic group-containing melamine formaldehyde resin of the present invention can be used as a water reducing agent for, for example, plaster in addition to concrete.
本発明の学理的作用効果は不明であるが、縮合反応後、
再添加された亜硫酸塩が、未反応のメチロール基やフリ
ーのホルムアルデヒドと反応することで優れたコンクリ
ート減水性能に関連する分子量分布や優れた貯蔵安定性
を有するようになると推定される。Although the theoretical effects of the present invention are unknown, after the condensation reaction,
It is presumed that the re-added sulfite reacts with unreacted methylol groups and free formaldehyde, resulting in a molecular weight distribution and excellent storage stability related to excellent concrete water reduction performance.
以下に、実施例および比較例を挙げてさらに詳述するが
本発明の技術的範囲は、これに限定されない。The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the technical scope of the present invention is not limited thereto.
実施例１〜１３．比較例１〜６
温度計、撹拌機、コンデンサー、を備えた反応容器に３
７％ホルマリンを投入し、２０％苛性ソーダを加え所定
のｐＨに調整し、撹拌下、メラミンを投入した後、所定
温度まで昇温し反応させて第一次反応工程を行った。Examples 1-13. Comparative Examples 1 to 6 3 in a reaction vessel equipped with a thermometer, a stirrer, and a condenser.
7% formalin was added, 20% caustic soda was added to adjust the pH to a predetermined value, melamine was added under stirring, and the temperature was raised to a predetermined temperature to cause a reaction, thereby carrying out the first reaction step.
次に３５％重亜硫酸ナトリウムを加えた後２０％苛性ソ
ーダを加え所定のｐ）Ｉに調整し、所定温度で反応させ
て第２次反応工程を行った。Next, 35% sodium bisulfite was added, and then 20% caustic soda was added to adjust to a predetermined p)I, and the mixture was reacted at a predetermined temperature to perform a second reaction step.
次に反応溶液を４０℃まで冷却した後、２％硫酸を加え
所定のｐＨに調整し、所定温度で反応させて第３次反応
工程を行った。Next, after cooling the reaction solution to 40° C., 2% sulfuric acid was added to adjust the pH to a predetermined value, and the reaction was carried out at a predetermined temperature to perform a third reaction step.
次に２０％苛性ソーダを加え所定のｐＨに調整し、所定
温度で３５％重亜硫酸ナトリウムを加えた後反応させて
第４次反応工程を行い冷却した。Next, 20% caustic soda was added to adjust the pH to a predetermined value, and 35% sodium bisulfite was added and reacted at a predetermined temperature to carry out a fourth reaction step, followed by cooling.
但し比較例１は所定のｐＨに調整した後３５％重亜硫酸
ナトリウムを加えずにそのまま冷却した。However, in Comparative Example 1, after adjusting the pH to a predetermined value, the solution was cooled without adding 35% sodium bisulfite.
反応条件の詳細を表１〜３に示す。Details of the reaction conditions are shown in Tables 1 to 3.
実施例および比較例でえられた各樹脂液についてセメン
ト減水剤としての性能をＪＩＳ−Ｒ−５２０１の方法に
従って試験した。すなわち、普通ポルトランドセメント
ＩＫｇに、セメントに対して固形分として５ｇのスルホ
ン酸基含有メラミンホルムアルデヒド樹脂を含む水２６
０ｇを加えモルタルミキサーで３分間撹拌した後セメン
トペーストのフロー値を測定した０表１〜３に製造直後
、製造９ケ月後、製造１８ケ月後のフロー値及び粘度を
示す、無添加の場合のセメントペーストのフロー値は、
１５９だうた。The performance of each resin liquid obtained in Examples and Comparative Examples as a cement water reducing agent was tested according to the method of JIS-R-5201. That is, 26 kg of ordinary Portland cement and 26 kg of water containing 5 g of sulfonic acid group-containing melamine formaldehyde resin as a solid content based on the cement.
Tables 1 to 3 show the flow value and viscosity immediately after production, 9 months after production, and 18 months after production, in the case of no additives. The flow value of cement paste is
159 songs.
表１〜３より、本発明によるスルホン酸基含有メラミン
ホルムアルデヒド樹脂が極めて優れたセメント減水剤で
あることを示している。Tables 1 to 3 show that the sulfonic acid group-containing melamine formaldehyde resin of the present invention is an extremely excellent cement water reducing agent.
特許出願人 三井東圧化学株式会社Patent applicant Mitsui Toatsu Chemical Co., Ltd.
Claims (1)
ミンホルムアルデヒド樹脂の製造方法。 （ａ）水媒体中で、メラミンとホルムアルデヒドをモル
比１．０：２．６〜３．４、ｐＨ３〜１１で反応させる
第１次反応工程、 （ｂ）ついで亜硫酸塩をメラミン１モルに対して０．７
〜１．３モル加えてｐＨ９〜１３、温度５０〜９０℃で
１〜５時間反応させる第２次反応工程、 （ｃ）ついでｐＨ３．５〜６．５、温度４０〜９０℃で
１〜５時間縮合反応を行う第３次反応工程、 （ｄ）この後ｐＨを９〜１３に調節した後、亜硫酸塩を
さらに０．０１〜０．３０モル加えて０〜６０分反応さ
せる第４次反応工程。[Scope of Claims] A method for producing a melamine formaldehyde resin containing a sulfone group, which comprises the following first to fourth reaction steps. (a) A first reaction step in which melamine and formaldehyde are reacted in an aqueous medium at a molar ratio of 1.0:2.6 to 3.4 and a pH of 3 to 11. (b) Then, sulfite is added to 1 mole of melamine. Te 0.7
A second reaction step in which ~1.3 mol is added and reacted for 1 to 5 hours at a pH of 9 to 13 and a temperature of 50 to 90°C, (c) followed by a reaction of 1 to 5 at a pH of 3.5 to 6.5 and a temperature of 40 to 90°C (d) After adjusting the pH to 9 to 13, 0.01 to 0.30 mol of sulfite is further added and the reaction is carried out for 0 to 60 minutes. Process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27840087A JPH0627173B2 (en) | 1987-11-05 | 1987-11-05 | Method for producing melamine formaldehyde resin containing sulfonic acid group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27840087A JPH0627173B2 (en) | 1987-11-05 | 1987-11-05 | Method for producing melamine formaldehyde resin containing sulfonic acid group |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01121314A true JPH01121314A (en) | 1989-05-15 |
| JPH0627173B2 JPH0627173B2 (en) | 1994-04-13 |
Family
ID=17596819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27840087A Expired - Fee Related JPH0627173B2 (en) | 1987-11-05 | 1987-11-05 | Method for producing melamine formaldehyde resin containing sulfonic acid group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0627173B2 (en) |
-
1987
- 1987-11-05 JP JP27840087A patent/JPH0627173B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0627173B2 (en) | 1994-04-13 |
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