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Número de publicaciónCN105271880 A
Tipo de publicaciónSolicitud
Número de solicitudCN 201510802875
Fecha de publicación27 Ene 2016
Fecha de presentación19 Nov 2015
Fecha de prioridad19 Nov 2015
También publicado comoCN105271880B
Número de publicación201510802875.8, CN 105271880 A, CN 105271880A, CN 201510802875, CN-A-105271880, CN105271880 A, CN105271880A, CN201510802875, CN201510802875.8
Inventores陈礼平
Solicitante杭州立平工贸有限公司
Exportar citaBiBTeX, EndNote, RefMan
Enlaces externos:  SIPO, Espacenet
水泥助磨剂 Cement grinding aids traducido del chino
CN 105271880 A
Resumen
The invention discloses a cement grinding aid which is prepared from, by weight, 5-30 parts of modified triethanolamine, 5-20 parts of molasses, 1-4 parts of lignin derivatives, 3-8 parts of chlorinated hydrocarbon and 60-80 parts of water. The cement grinding aid has the advantages that part of modified triethanolamine and chlorinated hydrocarbon act to form quaternary ammonium salt, and accordingly chloride ions are generated in the cement grinding aid under the condition that chlorine salt is not added; the chloride ions can remarkably enhance early strength and the grinding aid effect of cement. Meanwhile, quaternary ammonium salt is not stable, so that the quaternary ammonium salt formed in the cement after construction is decomposed into triethanolamine and chlorinated hydrocarbon again; chlorinated hydrocarbon is volatile so that chlorinated hydrocarbon can volatilize after the cement is constructed, and the problems that steel ribs in concrete are corroded because of the chloride ions, and the service life and durability of the concrete are affected are avoided.
Reclamaciones(8)  traducido del chino
1. 一种水泥助磨剂,其特征是:包括由以下重量份数为主组分的原料制备而成: 改性三乙醇胺5-30份糖蜜5-20份木质素衍生物1-4份氯代烃3-8份水60-80份。 1. A cement grinding aid, characterized in that: Preparation dominated by comprising the following raw materials in parts by weight of components: 1-4 parts of the modified parts of triethanolamine 5-30 molasses 5-20 parts of lignin derivatives chlorinated hydrocarbons 3-8 parts 60-80 parts of water.
2. 根据权利要求1所述的水泥助磨剂,其特征是:包括由以下重量份数为主组分的原料制备而成: 改性三乙醇胺5-20份糖蜜5-15份木质素衍生物1-4份氯代烃3-6份水60-80份。 The cement grinding aid according to claim 1, wherein: preparing a raw material comprising mainly consists of the following parts by weight of components from: 5-20 parts of triethanolamine modification 5-15 parts of lignin-derived molasses 1-4 parts of chlorinated hydrocarbons was 3-6 parts 60-80 parts of water.
3. 根据权利要求1所述的水泥助磨剂,其特征是:按照重量比,所述改性三乙醇胺由辛酸三乙醇胺酯:双月桂酸三乙醇胺酯=0-1:1-0组成。 Cement grinding aid according to claim 1, characterized in that: in a weight ratio of said modified by the triethanolamine ester of triethanolamine octoate: lauric acid triethanolamine ester = 0-1: 1-0 Composition.
4. 根据权利要求1所述的水泥助磨剂,其特征是:所述糖蜜选用甜菜糖蜜、甘蔗糖蜜、 葡糖糖糖蜜中的其中一种。 Cement grinding aid according to claim 1, wherein: said selected one of molasses sugar beet molasses, cane molasses, sugar glucose in honey.
5. 根据权利要求1所述的水泥助磨剂,其特征是:所述木质素衍生物优选为木质素磺酸钠。 Cement grinding aid according to claim 1, characterized in that: said lignin derivatives, preferably sodium lignosulfonate.
6. 根据权利要求1所述的水泥助磨剂,其特征是:所述氯代烃选用二氯甲烷、1,1-二氯乙烷、1,2-二氯乙烷中的其中一种或几种。 Cement grinding aid according to claim 1, characterized in that: said selection chlorinated hydrocarbon methylene chloride, 1,1-dichloroethane, 1,2-dichloroethane one or more.
7. -种如权利要求1所述的改性三乙醇胺的制备方法,其特征是:包括如下步骤: 步骤一:按照摩尔比,辛酸:三乙醇胺=1. 4-1. 6:1进行混合,将辛酸和三乙醇胺的混合物以及苯酚溶液置于圆底烧瓶中,进行减压、加热反应,反应温度控制在130-140°C,反应8h,蒸掉反应生成的水,残留物即为粗产品; 步骤二:减压蒸馏后所得为粗产品,将其溶于异辛烷中,顺次以NaOH水溶液和蒸馏水洗涤,以除去未反应的正辛酸,相应的溶剂及三乙醇胺,最后将溶剂异辛烷通过旋转蒸发仪蒸发掉得最终产物; 步骤三:按照月桂酸:三乙醇胺=1. 9-2. 3:1的摩尔比比例在电子天平上称量月桂酸和三乙醇胺,先在三口瓶中添加月桂酸和对甲苯酸,在三口瓶上架一滴液漏斗,恒速滴加三乙醇胺,在半小时内滴加完,装上回流冷凝管,反应温度控制在140°C,回流0. 5小时, 稍冷后, 7. - The kind of modification of the method for the preparation of triethanolamine claim, characterized in that: mixing 1: comprising the following steps: Step 1: a molar ratio of octanoic acid: Triethanolamine = 14-16. the mixture of caprylic acid and triethanolamine and phenol solution was placed in a round bottom flask, under reduced pressure, heating the reaction, the reaction temperature is controlled at 130-140 ° C, the reaction 8h, the water of reaction distilled off, the residue is the crude product; step two: after distillation under reduced pressure the resulting crude product, which was dissolved in iso-octane, successively washed with aqueous NaOH and distilled to remove the unreacted n-octanoic acid, triethanolamine and the corresponding solvent, and finally solvent isooctane evaporated off by rotary evaporator to give the final product; step three: according laurate: triethanolamine = 19-23: 1 ratio molar ratio of lauric acid and triethanolamine were weighed on an electronic balance, in the first three-neck flask was added p-toluenesulfonic acid and lauric acid, three-necked flask shelves dropping funnel, was added dropwise a constant rate triethanolamine, dropwise addition over half an hour, fitted with a reflux condenser, the reaction temperature is controlled at 140 ° C, reflux 0 after 5 hours, coolish, 为蒸馏装置,蒸馏反应11. 5h,蒸掉生成的水即为反应的粗产品; 步骤四:蒸馏后所得为粗产品,顺次以水溶液和蒸馏水洗涤,再用二氯甲烷为溶剂经硅胶柱分离纯化后得到双月桂酸三乙醇胺酯; 步骤五:将步骤二得到的辛酸三乙醇胺酯和步骤四得到的双月桂酸三乙醇胺酯按照重量比为辛酸三乙醇胺酯:双月桂酸三乙醇胺酯=0-1:1-0混合均匀。 A distillation device, distillation reactor 11. 5h, the crude product was distilled out of the reaction is the water produced; Step Four: The crude product obtained after distillation was sequentially washed with an aqueous solution and distilled water, with dichloromethane as the solvent by silica gel column after separation and purification to give bis lauric acid triethanolamine ester; step 5: octanoic acid obtained in step two and step four triethanolamine ester obtained lauric acid triethanolamine ester in a weight ratio of caprylic acid triethanolamine ester: lauric acid triethanolamine ester = 0-1: 1-0 mixed.
8. -种如权利要求1所述的水泥助磨剂的制备方法,其特征是:包括如下步骤: I先将5-30份改性三乙醇胺倒入反应釜中,再在搅拌状态下倒入3-8份氯代烃进行混合搅拌,加热回流12h,冷却待用; 8. - The method for producing species, such as grinding aids according to claim 1, characterized in that: comprising the following steps: I first modification 5-30 parts of triethanolamine was poured into the reaction vessel, and then pour with stirring state 3-8 parts of chlorinated hydrocarbons into the mixture stirred and heated at reflux for 12h, cooled and set aside;
Descripción  traducido del chino
水泥助磨齐I. Cement grinding aid Qi I.

技术领域 FIELD

[0001] 本发明设及一种外加剂,更具体地说,它设及一种水泥助磨剂。 [0001] The present invention is provided, and one additive, and more particularly, to a cement grinding aids, and it is disposed.

背景技术 Background technique

[0002] 水泥助磨剂是一种改善水泥粉磨效果和性能的化学添加剂,用于水泥物料的粉磨过程中,添加少量的助磨剂能够显著提高粉磨效率或降低能耗,并且显著提高水泥台时产量和各项技术指标,而又不损害水泥自身的性能。 [0002] cement grinding aid is a chemical additive to improve the effectiveness and performance of cement grinding, cement grinding process for the material, adding a small amount of grinding aids can significantly reduce energy consumption or to improve the grinding efficiency, and significantly increase cement production units and various technical indicators, without compromising the performance of the cement itself. 作为一种化学激发剂,助磨剂能改善水泥颗粒分布并激发水化动力,从而提高水泥早期强度和后期强度。 As a chemical activator, grinding aids can improve the particle size distribution of the cement hydration and excitation power, thereby improving the early strength of cement and late strength. 我国水泥工业生产的能耗占建材工业能耗的80%,占全国工业生产总能耗的8. 7%,水泥助磨剂的应用给水泥工业的"节能减排"W及水泥工业的可持续发展带来的效益,远远超过了它本身的价值,它已经成为水泥工业不可缺少的辅助材料。 China's cement industry energy production accounts for 80% of industrial energy consumption of building materials, accounting for 8.7 percent of the country's total energy consumption in industrial production, cement grinding aids applied to "energy saving" W cement industry and cement industry can the benefits of sustainable development, far more than the value of its own, it has become the cement industry indispensable auxiliary materials.

[0003] 对比文件CN201210265048. 6中公开了一种水泥助磨剂,该水泥助磨剂高物料在磨内的流动性,有效减少磨机过粉磨现象,改善物料对研磨体、衬板、隔仓扳的粘附作用和自身结团现象。 [0003] Comparative file CN201210265048. 6 discloses a cement grinding aid, cement grinding aids of the high material flow in the mill, and effectively reduce the phenomenon of over-grinding mill, for grinding materials improve, liner, compartment pull the adhesion and agglomeration phenomenon itself.

[0004] 但是,在对比文件中,需要用到氯化钢和氯化钟等含氯离子的盐来增加助磨剂的效果,但是氯离子的存在容易造成混凝±中钢筋腐蚀、影响混凝±的使用寿命和耐久性。 [0004] However, in contrast to the file, and the need to use chloride salts steel bell chloride containing chlorine ions to increase the effect of grinding aids, but the presence of chloride ions likely to cause corrosion of reinforcement coagulation ± influence mixed ± condensate life and durability.

发明内容 SUMMARY

[0005] 针对现有技术存在的不足,本发明的目的在于提供一种水泥助磨剂。 [0005] for the deficiencies of the prior art, an object of the present invention is to provide a cement grinding aids. 该水泥助磨剂未添加氯化钢和氯化钟等含氯离子的盐,却能够达到更好的助磨和增强效果。 The cement grinding aids chloride salt steel bell chloride and chlorine ions is not added, it is possible to achieve better grinding aid and reinforcing effect.

[0006] 为实现上述目的,本发明提供了如下技术方案: 一种水泥助磨剂,包括由W下重量份数为主组分的原料制备而成: 改性=乙醇胺5-30份糖蜜5-20份木质素衍生物1-4份氯代控3-8份水60-80份。 [0006] To achieve the above object, the present invention provides the following technical solutions: A cement grinding aids, including weight parts prepared from the W-based raw materials in the components: 5 to 30 parts diethanolamine-modified molasses = 5 1-4 parts to 20 parts chlorinated lignin derivative control parts 60-80 3-8 parts of water.

[0007] 包括由W下重量份数为主组分的原料制备而成: 改性=乙醇胺5-20份糖蜜5-15份木质素衍生物1-4份氯代控3-6份水60-80份。 [0007] prepared from the W comprises by weight parts of the main component material: 5 to 20 parts diethanolamine-modified molasses = 5-15 parts chlorinated lignin derivatives 1-4 parts Water 60 parts by control 3-6 80 parts.

[0008] 所述改性=乙醇胺由辛酸=乙醇胺醋:双月桂酸=乙醇胺醋=0-1:1-0组成。 [0008] The modification of octanoic acid = = ethanolamine diethanolamine acetate: lauric acid diethanolamine acetate = = 0-1: 1-0 Composition.

[0009] 所述糖蜜选用甜菜糖蜜、甘薦糖蜜、葡糖糖糖蜜中的其中一种。 [0009] The selection of beet molasses molasses, molasses Gan Jian, one glucose sugar in honey.

[0010] 所述木质素衍生物优选为木质素横酸钢。 [0010] The lignin derivative is preferably an acid lignin cross-steel.

[0011] 所述氯代控选用二氯甲烧、1,I-二氯乙烧、1,2-二氯乙烧中的其中一种或几种。 [0011] The burn-chloro-controlled selection dichloromethane, 1, I- burning dichloroacetyl, wherein one or more of 1,2-dichloroethane in the burning.

[0012] 一种改性=乙醇胺的制备方法,其特征是:包括如下步骤: 步骤一:按照摩尔比,辛酸乙醇胺=1. 4-1. 6:1进行混合,将辛酸和=乙醇胺的混合物W及苯酪溶液置于圆底烧瓶中,进行减压、加热反应,反应溫度控制在130-140°C,反应她,蒸掉反应生成的水,残留物即为粗产品; 步骤二:减压蒸馈后所得为粗产品,将其溶于异辛烧中,顺次W化OH水溶液和蒸馈水洗涂,W除去未反应的正辛酸,相应的溶剂及=乙醇胺,最后将溶剂异辛烧通过旋转蒸发仪蒸发掉得最终产物; 步骤=:按照月桂酸乙醇胺=1. 9-2. 3:1的摩尔比比例在电子天平上称量月桂酸和=乙醇胺,先在=口瓶中添加月桂酸和对甲苯酸,在=口瓶上架一滴液漏斗,恒速滴加= 乙醇胺,在半小时内滴加完,装上回流冷凝管,反应溫度控制在140°C,回流0. 5小时, 稍冷后,改为蒸馈装置,蒸馈反应11. 5h,蒸掉生成 [0012] The method of preparing a modified = ethanolamine, characterized in that: comprising the following steps: Step 1: 1 were mixed, the mixture = ethanolamine and octanoic acid: molar ratio of octanoic acid = 14-16 ethanolamine. W and casein benzene solution was placed in a round bottom flask, under reduced pressure, heating the reaction, the reaction temperature is controlled at 130-140 ° C, the reaction her, water produced by the reaction was distilled off, the residue is the crude product; step two: Save after the resulting crude product feed autoclave, which was dissolved in the isooctyl fired sequentially W of OH solution and distilled water-fed coating, W unreacted n-octanoic acid, and the corresponding solvent = ethanolamine, and finally the solvent was isooctyl burning evaporated off by rotary evaporator to give the final product; = step: ethanolamine according lauric = 19-23: 1 ratio molar ratio = lauric acid and ethanolamine were weighed on an electronic balance, in the first = jar. lauric acid and p-toluenesulfonic acid was added, the jar was added to = dropping funnel, was added dropwise a constant rate = ethanolamine, dropwise completed within half an hour, fitted with a reflux condenser, the reaction temperature is controlled at 140 ° C, refluxed for 0.5 hours, coolish, evaporated to feeding means, feeding reaction steam 11. 5h, generated was distilled off 的水即为反应的粗产品; 步骤四:蒸馈后所得为粗产品,顺次W水溶液和蒸馈水洗涂,再用二氯甲烧为溶剂经硅胶柱分离纯化后得到双月桂酸=乙醇胺醋; 步骤五:将步骤二得到的辛酸=乙醇胺醋和步骤四得到的双月桂酸=乙醇胺醋按照重量比为辛酸=乙醇胺醋:双月桂酸=乙醇胺醋=0-1:1-0混合均匀。 Water is the crude reaction product; Step Four: After distilling the resulting crude product is fed sequentially feeding water W evaporated and aqueous coating, and then after burning methylene separation solvent was purified by silica gel column to obtain bis lauric = ethanolamine vinegar; step 5: octanoic acid obtained in step two and step four = ethanolamine vinegar obtained dilaurate ethanolamine acetate = weight ratio of octanoic acid = ethanolamine acetate: lauric acid diethanolamine acetate = = 0-1: 1-0 mixed .

[0013] 一种水泥助磨剂的制备方法,包括如下步骤: I先将5-30份改性=乙醇胺倒入反应蓋中,再在揽拌状态下倒入3-8份氯代控进行混合揽拌,加热回流12h,冷却待用; II将步骤I得到的混合物转移到揽拌蓋中,加入5-20份糖蜜、1-4份木质素衍生物、 60-80份水,揽拌Ih后出料即得。 [0013] A process for preparing a cement grinding aids, comprising the following steps: I = First 5 to 30 parts of ethanolamine was poured into the reaction modifier lid, and then was poured into 3-8 parts embrace stirred at chloro control state embrace mixture stirred and heated at reflux for 12h, cooled stand; II the mixture obtained in step I is transferred to embrace cover mix, 5-20 parts of added molasses, lignin derivatives parts 1-4, 60-80 parts of water, mixed with football obtain the material after ih.

[0014] 通过采用上述技术方案,本发明具有W下几点效果: ① 部分改性=乙醇胺和氯代控作用形成季锭盐,从而在未加入氯盐的情况下在水泥助磨剂中产生氯离子,而氯离子能够做到显著增强水泥的的早强性能和助磨效果。 [0014] By adopting the above technical solution, the present invention has several effects W: ① = triethanolamine and partially modified chlorinated CONTROLLING ingot form a quaternary salt to produce cement grinding aid in the absence of added chloride salt chloride ions, chloride ions can achieve significantly enhanced early strength cement grinding aid and performance effects. 同时由于季锭盐具有不稳定的性质,因此在施工后的水泥中形成的季锭盐会重新分解为=乙醇胺和氯代控,而氯代控具有易挥发性,所W能够实现在水泥完成施工后,氯代烧挥发,从而不会存在氯离子造成混凝±中钢筋腐蚀、影响混凝±的使用寿命和耐久性的问题; ② 改性=乙醇胺和氯代控形成的季锭盐具有良好的抗菌性能,能够显著增强水泥的杀菌效果; ③ 改性=乙醇胺和氯代控形成的季锭盐能够显著增强糖蜜、木质素衍生物W及其他水泥外加剂在水中的溶解性能,所W能够在水泥施工时,增大糖蜜、木质素衍生物W及其他水泥外加剂在水泥中的分散度; ④ 改性=乙醇胺是由=乙醇胺与不同的酸醋化并进行复配得到,相比于=乙醇胺,改性=乙醇胺具有更好的助磨和提高强度的作用; ⑥木质素衍生物不仅能够显著增水泥的强度,同时可显著减少水泥使用过程 Quaternary salts have the same time as the ingot unstable, thus forming a quaternary salt of the ingot in the cement after the re-construction of ethanolamine and decomposition of chlorinated = control, and with control-chloro-volatile, they can be fulfilled in the cement W after construction, burning volatile chlorinated, whereby there will be no reinforcement corrosion caused by chloride ion ± coagulation, the life and durability problems ± coagulation effect; starter quaternary amine and salts ② = modified chlorinated formed having controlled good antibacterial properties, can significantly enhance the sterilizing effect of the cement; quaternary salt ingot = ③ modified chlorinated ethanolamine and control can significantly enhance the formation of molasses, lignin derivatives and other cement admixture W solubility in water, the W when cementing is possible, increasing the molasses, lignin derivatives W and other cement admixture in the cement dispersion; ④ is obtained by a modification = ethanolamine = ethanolamine vinegar of different and complex than to = ethanolamine, diethanolamine = modified grinding aid and have better strength improving effect; ⑥ lignin derivatives not only a significant increase in the strength of the cement while the cement can be significantly reduced using the procedure 中的水的用量。 The amount of water.

具体实施方式 detailed description

[0015]实施例1-5为改性S乙醇胺的制备实施例。 [0015] Example 1-5 Example of preparation of the modified S ethanolamine.

[001引实施例I 步骤一:按照摩尔比,辛酸乙醇胺=1. 4:1进行混合,将辛酸和=乙醇胺的混合物W及苯酪溶液置于圆底烧瓶中,进行减压、加热反应,反应溫度控制在130°C,反应化,蒸掉反应生成的水,残留物即为粗产品; 步骤二:减压蒸馈后所得为粗产品,将其溶于异辛烧中,顺次W化OH水溶液和蒸馈水洗涂,W除去未反应的正辛酸,相应的溶剂及=乙醇胺,最后将溶剂异辛烧通过旋转蒸发仪蒸发掉得最终产物; 步骤=:按照月桂酸乙醇胺=2. 2:1的摩尔比比例在电子天平上称量月桂酸和=乙醇胺,先在=口瓶中添加月桂酸和对甲苯酸,在=口瓶上架一滴液漏斗,恒速滴加=乙醇胺,在半小时内滴加完,装上回流冷凝管,反应溫度控制在140°C,回流0. 5小时,稍冷后,改为蒸馈装置,蒸馈反应11. 5h,蒸掉生成的水即为反应的粗产品; 步骤四:蒸馈后所得为粗产品,顺次 [Example I Step 001 a primer: a molar ratio of ethanolamine octanoic acid = 14: 1 were mixed, the mixture of octanoic acid and ethanolamine W = benzene and cheese was placed in a round bottom flask, under reduced pressure, heating the reaction, the reaction temperature was controlled at 130 ° C, of the reaction, the resulting reaction water was distilled off, the residue is the crude product; step two: feeding distilled off under reduced pressure the resulting crude product, which was dissolved in the isooctyl fired sequentially W OH solution and feeding of water vapor coating, W to remove the unreacted n-octanoic acid, and the corresponding solvent = ethanolamine, and finally the solvent was evaporated isooctyl burned by rotary evaporator to give the final product; step =: = 2 according lauric diethanolamine. 2: 1 molar ratio = ratio of lauric acid and ethanolamine were weighed on an electronic balance, lauric acid was added to the jar and p = acid, was added to the jar = dropping funnel, was added dropwise a constant rate = ethanolamine in after dropwise within half an hour, fitted with a reflux condenser, the reaction temperature is controlled at 140 ° C, reflux for 0.5 hours, coolish, evaporated to feeding means, feeding reaction steam 11. 5h, i.e., generated water was distilled off the crude reaction product; step four: after distilling the resulting crude product is fed sequentially W水溶液和蒸馈水洗涂,再用二氯甲烧为溶剂经硅胶柱分离纯化后得到双月桂酸=乙醇胺醋; 步骤五:将步骤二得到的辛酸=乙醇胺醋和步骤四得到的双月桂酸=乙醇胺醋按照重量比为辛酸S乙醇胺醋:双月桂酸S乙醇胺醋=0:1混合均匀。 W aqueous feed water and steam coating, then fired after methylene chloride solvent was separated and purified by silica gel column to obtain bis lauric = ethanolamine acetate; Step 5: octanoic acid obtained obtained in step two and step = ethanolamine vinegar four dilaurate = ethanolamine vinegar S weight ratio of caprylic acid ethanolamine acetate: lauric acid diethanolamine vinegar S = 0: 1 mixed.

[0017] 实施例2 步骤一:按照摩尔比,辛酸乙醇胺=1. 6:1进行混合,将辛酸和=乙醇胺的混合物W及苯酪溶液置于圆底烧瓶中,进行减压、加热反应,反应溫度控制在135°C,反应化,蒸掉反应生成的水,残留物即为粗产品; 步骤二:减压蒸馈后所得为粗产品,将其溶于异辛烧中,顺次W化OH水溶液和蒸馈水洗涂,W除去未反应的正辛酸,相应的溶剂及=乙醇胺,最后将溶剂异辛烧通过旋转蒸发仪蒸发掉得最终产物; 步骤=:按照月桂酸乙醇胺=2. 1:1的摩尔比比例在电子天平上称量月桂酸和=乙醇胺,先在=口瓶中添加月桂酸和对甲苯酸,在=口瓶上架一滴液漏斗,恒速滴加=乙醇胺,在半小时内滴加完,装上回流冷凝管,反应溫度控制在140°C,回流0. 5小时,稍冷后,改为蒸馈装置,蒸馈反应11. 5h,蒸掉生成的水即为反应的粗产品; 步骤四:蒸馈后所得为粗产品,顺次 [0017] Example 2 Step a: molar ratio of ethanolamine octanoic acid = 16: 1 were mixed, the mixture of octanoic acid and ethanolamine W = benzene and cheese was placed in a round bottom flask, under reduced pressure, heating the reaction, the reaction temperature was controlled at 135 ° C, of the reaction, the resulting reaction water was distilled off, the residue is the crude product; step two: feeding distilled off under reduced pressure the resulting crude product, which was dissolved in the isooctyl fired sequentially W OH solution and feeding of water vapor coating, W to remove the unreacted n-octanoic acid, and the corresponding solvent = ethanolamine, and finally the solvent was evaporated isooctyl burned by rotary evaporator to give the final product; step =: = 2 according lauric diethanolamine. 1: 1 ratio molar ratio of lauric acid were weighed on an electronic balance and = ethanolamine, lauric acid was added to the jar and p = acid, was added to the jar = dropping funnel, was added dropwise a constant rate = ethanolamine in after dropwise within half an hour, fitted with a reflux condenser, the reaction temperature is controlled at 140 ° C, reflux for 0.5 hours, coolish, evaporated to feeding means, feeding reaction steam 11. 5h, i.e., generated water was distilled off the crude reaction product; step four: after distilling the resulting crude product is fed sequentially W水溶液和蒸馈水洗涂,再用二氯甲烧为溶剂经硅胶柱分离纯化后得到双月桂酸=乙醇胺醋; 步骤五:将步骤二得到的辛酸=乙醇胺醋和步骤四得到的双月桂酸=乙醇胺醋按照重量比为辛酸=乙醇胺醋:双月桂酸=乙醇胺醋=0. 5:0. 5混合均匀。 W aqueous feed water and steam coating, then fired after methylene chloride solvent was separated and purified by silica gel column to obtain bis lauric = ethanolamine acetate; Step 5: octanoic acid obtained obtained in step two and step = ethanolamine vinegar four dilaurate = ethanolamine vinegar weight ratio of octanoic acid = ethanolamine acetate: lauric = ethanolamine acetate = 05: 05 mixed.

[001引实施例3 步骤一:按照摩尔比,辛酸乙醇胺=1. 5:1进行混合,将辛酸和=乙醇胺的混合物W及苯酪溶液置于圆底烧瓶中,进行减压、加热反应,反应溫度控制在140°C,反应化,蒸掉反应生成的水,残留物即为粗产品; 步骤二:减压蒸馈后所得为粗产品,将其溶于异辛烧中,顺次W化OH水溶液和蒸馈水洗涂,W除去未反应的正辛酸,相应的溶剂及=乙醇胺,最后将溶剂异辛烧通过旋转蒸发仪蒸发掉得最终产物; 步骤=:按照月桂酸乙醇胺=2. 3:1的摩尔比比例在电子天平上称量月桂酸和=乙醇胺,先在=口瓶中添加月桂酸和对甲苯酸,在=口瓶上架一滴液漏斗,恒速滴加=乙醇胺,在半小时内滴加完,装上回流冷凝管,反应溫度控制在140°C,回流0. 5小时,稍冷后,改为蒸馈装置,蒸馈反应11. 5h,蒸掉生成的水即为反应的粗产品; 步骤四:蒸馈后所得为粗产品,顺次 Example 3 Step [001 embodiment a primer: a molar ratio of ethanolamine octanoic acid = 15: 1 were mixed, the mixture of octanoic acid and ethanolamine W = benzene and cheese was placed in a round bottom flask, under reduced pressure, heating the reaction, the reaction temperature was controlled at 140 ° C, of the reaction, the resulting reaction water was distilled off, the residue is the crude product; step two: feeding distilled off under reduced pressure the resulting crude product, which was dissolved in the isooctyl fired sequentially W OH solution and feeding of water vapor coating, W to remove the unreacted n-octanoic acid, and the corresponding solvent = ethanolamine, and finally the solvent was evaporated isooctyl burned by rotary evaporator to give the final product; step =: = 2 according lauric diethanolamine. 3: 1 molar ratio = ratio of lauric acid and ethanolamine were weighed on an electronic balance, lauric acid was added to the jar and p = acid, was added to the jar = dropping funnel, was added dropwise a constant rate = ethanolamine in after dropwise within half an hour, fitted with a reflux condenser, the reaction temperature is controlled at 140 ° C, reflux for 0.5 hours, coolish, evaporated to feeding means, feeding reaction steam 11. 5h, i.e., generated water was distilled off the crude reaction product; step four: after distilling the resulting crude product is fed sequentially W水溶液和蒸馈水洗涂,再用二氯甲烧为溶剂经硅胶柱分离纯化后得到双月桂酸=乙醇胺醋; 步骤五:将步骤二得到的辛酸=乙醇胺醋和步骤四得到的双月桂酸=乙醇胺醋按照重量比为辛酸=乙醇胺醋:双月桂酸=乙醇胺醋=0. 2:0. 8混合均匀。 W aqueous feed water and steam coating, then fired after methylene chloride solvent was separated and purified by silica gel column to obtain bis lauric = ethanolamine acetate; Step 5: octanoic acid obtained obtained in step two and step = ethanolamine vinegar four dilaurate = ethanolamine vinegar weight ratio of octanoic acid = ethanolamine acetate: lauric = ethanolamine acetate = 02: 08 mixed.

[0019] 实施例4 步骤一:按照摩尔比,辛酸乙醇胺=1. 6:1进行混合,将辛酸和=乙醇胺的混合物W及苯酪溶液置于圆底烧瓶中,进行减压、加热反应,反应溫度控制在140°C,反应化,蒸掉反应生成的水,残留物即为粗产品; 步骤二:减压蒸馈后所得为粗产品,将其溶于异辛烧中,顺次W化OH水溶液和蒸馈水洗涂,W除去未反应的正辛酸,相应的溶剂及=乙醇胺,最后将溶剂异辛烧通过旋转蒸发仪蒸发掉得最终产物; 步骤=:按照月桂酸乙醇胺=2. 0:1的摩尔比比例在电子天平上称量月桂酸和=乙醇胺,先在=口瓶中添加月桂酸和对甲苯酸,在=口瓶上架一滴液漏斗,恒速滴加=乙醇胺,在半小时内滴加完,装上回流冷凝管,反应溫度控制在140°C,回流0. 5小时,稍冷后,改为蒸馈装置,蒸馈反应11. 5h,蒸掉生成的水即为反应的粗产品; 步骤四:蒸馈后所得为粗产品,顺次 [0019] Example 4 Step a: molar ratio of ethanolamine octanoic acid = 16: 1 were mixed, the mixture of octanoic acid and ethanolamine W = benzene and cheese was placed in a round bottom flask, under reduced pressure, heating the reaction, the reaction temperature was controlled at 140 ° C, of the reaction, the resulting reaction water was distilled off, the residue is the crude product; step two: feeding distilled off under reduced pressure the resulting crude product, which was dissolved in the isooctyl fired sequentially W OH solution and feeding of water vapor coating, W to remove the unreacted n-octanoic acid, and the corresponding solvent = ethanolamine, and finally the solvent was evaporated isooctyl burned by rotary evaporator to give the final product; step =: = 2 according lauric diethanolamine. 0: 1 molar ratio = ratio of lauric acid and ethanolamine were weighed on an electronic balance, lauric acid was added to the jar and p = acid, was added to the jar = dropping funnel, was added dropwise a constant rate = ethanolamine in after dropwise within half an hour, fitted with a reflux condenser, the reaction temperature is controlled at 140 ° C, reflux for 0.5 hours, coolish, evaporated to feeding means, feeding reaction steam 11. 5h, i.e., generated water was distilled off the crude reaction product; step four: after distilling the resulting crude product is fed sequentially W水溶液和蒸馈水洗涂,再用二氯甲烧为溶剂经硅胶柱分离纯化后得到双月桂酸=乙醇胺醋; 步骤五:将步骤二得到的辛酸=乙醇胺醋和步骤四得到的双月桂酸=乙醇胺醋按照重量比为辛酸=乙醇胺醋:双月桂酸=乙醇胺醋=0. 7:0. 3混合均匀。 W aqueous feed water and steam coating, then fired after methylene chloride solvent was separated and purified by silica gel column to obtain bis lauric = ethanolamine acetate; Step 5: octanoic acid obtained obtained in step two and step = ethanolamine vinegar four dilaurate = ethanolamine vinegar weight ratio of octanoic acid = ethanolamine acetate: lauric acid diethanolamine acetate = = 07: 03 mixed.

[0020] 实施例5 步骤一:按照摩尔比,辛酸乙醇胺=1. 4:1进行混合,将辛酸和=乙醇胺的混合物W及苯酪溶液置于圆底烧瓶中,进行减压、加热反应,反应溫度控制在138°C,反应化,蒸掉反应生成的水,残留物即为粗产品; 步骤二:减压蒸馈后所得为粗产品,将其溶于异辛烧中,顺次W化OH水溶液和蒸馈水洗涂,W除去未反应的正辛酸,相应的溶剂及=乙醇胺,最后将溶剂异辛烧通过旋转蒸发仪蒸发掉得最终产物; 步骤=:按照月桂酸乙醇胺=1.9:1的摩尔比比例在电子天平上称量月桂酸和=乙醇胺,先在=口瓶中添加月桂酸和对甲苯酸,在=口瓶上架一滴液漏斗,恒速滴加=乙醇胺,在半小时内滴加完,装上回流冷凝管,反应溫度控制在140°C,回流0. 5小时,稍冷后,改为蒸馈装置,蒸馈反应11. 5h,蒸掉生成的水即为反应的粗产品; 步骤四:蒸馈后所得为粗产品,顺次W [0020] Example 5 Step a: molar ratio of ethanolamine octanoic acid = 14: 1 were mixed, the mixture of octanoic acid and ethanolamine W = benzene and cheese was placed in a round bottom flask, under reduced pressure, heating the reaction, the reaction temperature was controlled at 138 ° C, of the reaction, the resulting reaction water was distilled off, the residue is the crude product; step two: feeding distilled off under reduced pressure the resulting crude product, which was dissolved in the isooctyl fired sequentially W OH solution and feeding of water vapor coating, W to remove the unreacted n-octanoic acid, and the corresponding solvent = ethanolamine, and finally the solvent was evaporated isooctyl burned by rotary evaporator to give the final product; = step: triethanolamine laurate = 1.9 according to: Comparative Example 1 molar ratio of lauric acid and weighed on an electronic balance = ethanolamine, first add the lauric acid and p = jar, the jar was added to = dropping funnel, was added dropwise a constant rate = ethanolamine, half an hour after the dropwise addition, fitted with a reflux condenser, the reaction temperature is controlled at 140 ° C, reflux for 0.5 hours, coolish, evaporated to feeding means, feeding reaction steam 11. 5h, generated water that is distilled off the reaction the crude product; step four: after distilling the resulting crude product is fed sequentially W 水溶液和蒸馈水洗涂,再用二氯甲烧为溶剂经硅胶柱分离纯化后得到双月桂酸=乙醇胺醋; 步骤五:将步骤二得到的辛酸=乙醇胺醋和步骤四得到的双月桂酸=乙醇胺醋按照重量比为辛酸S乙醇胺醋:双月桂酸S乙醇胺醋=1:0混合均匀。 Feeding an aqueous solution of distilled water and coating, and then after burning methylene chloride solvent was separated and purified by silica gel column to obtain bis lauric = ethanolamine acetate; Step 5: octanoic acid obtained in step two and step four = ethanolamine vinegar obtained dilaurate = ethanolamine vinegar S weight ratio of caprylic acid ethanolamine acetate: lauric acid diethanolamine vinegar S = 1: 0 mixed.

[0021] 实施例6-11为水泥助磨剂的制备实施例。 [0021] Example 6-11 Example preparing a cement grinding aid.

[002引实施例6 I先将按照实施例1制备的20份改性S乙醇胺倒入反应蓋中,再在揽拌状态下倒入8 份二氯甲烧进行混合揽拌,加热回流12h,冷却待用; II将步骤I得到的混合物转移到揽拌蓋中,加入20份甜菜糖蜜、4份木质素横酸钢、80 份水,揽拌Ih后出料即得。 [Example 6 I 002 cited first parts 20 according to the modified S prepared in Example 1 was poured into the reaction ethanolamine lid, and then was poured into 8 parts of methylene chloride stirred under a state embrace embrace burning mixed stirred and heated at reflux for 12h, cooling stand; II the mixture obtained in step I is transferred to embrace cover mix, 20 parts sugar beet molasses, 4 parts of lignin cross-steel acid, 80 parts of water, stirred for Ih embrace the material to obtain.

[002引实施例7 I先将按照实施例2制备的15份改性S乙醇胺倒入反应蓋中,再在揽拌状态下倒入4 份1,1-二氯乙烧进行混合揽拌,加热回流12h,冷却待用; II将步骤I得到的混合物转移到揽拌蓋中,加入15份葡糖糖糖蜜、1份木质素横酸钢、 60份水,揽拌Ih后出料即得。 [Example 7 I 002 cited first prepared in accordance with Example 2 15 parts of ethanolamine was poured into the reaction of the modified S lid, and then poured into 4 parts in a mixed state embrace vinylidene chloride were mixed embrace burning mix, was heated at reflux for 12h, cooled stand; II the mixture obtained in step I is transferred to embrace cover mix was added 15 parts of honey, glucose sugar, 1 part lignin cross-steel acid, 60 parts of water, stirred for Ih embrace the material to obtain .

[0024]实施例8 I先将按照实施例3制备的5份改性=乙醇胺倒入反应蓋中,再在揽拌状态下倒入3 份1,2-二氯乙烧进行混合揽拌,加热回流12h,冷却待用; II将步骤I得到的混合物转移到揽拌蓋中,加入10份甘薦糖蜜、2份木质素横酸钢、70 份水,揽拌Ih后出料即得。 [0024] Example 8 I first prepared according to Example 3 5 parts of the modified embodiment of the head = ethanolamine poured into the reaction, and then poured into 3 parts in a mixed state embrace 1,2-dichloroethane were mixed embrace burning mix, was heated at reflux for 12h, cooled stand; II the mixture obtained in step I is transferred to embrace cover mix was added 10 parts of Gan Jian molasses, 2 parts of lignin cross-steel acid, 70 parts of water, stirred for Ih embrace the material to obtain.

[00幼实施例9 I先将按照实施例4制备的10份改性S乙醇胺倒入反应蓋中,再在揽拌状态下倒入按照摩尔比,由二氯甲烧:1,1-二氯乙烧=1:1混合而成的5份混合溶液进行混合揽拌,加热回流12h,冷却待用; II将步骤I得到的混合物转移到揽拌蓋中,加入5份甘薦糖蜜、3份木质素横酸钢、75 份水,揽拌Ih后出料即得。 EXAMPLE 9 I [00 10 parts according to the first embodiment Immature modified S prepared in Example 4 was poured into the reaction ethanolamine lid, and then poured into a stirred state embrace the molar ratio, from the burning dichloromethane: 1,1-bis b = burn-chloro-1: 5 parts of a mixed solution obtained by mixing a mixed embrace stirred and heated at reflux for 12h, cooled stand; II the mixture obtained in step I is transferred to embrace cover mix, 5 parts of molasses Gan Jian, 3 acid lignin cross-steel parts, 75 parts of water, stirred for Ih embrace the material to obtain.

[002引实施例10 I先将按照实施例5制备的30份改性=乙醇胺倒入反应蓋中,再在揽拌状态下倒入按照摩尔比,由二氯甲烧:1,1-二氯乙烧:1,2-二氯乙烧=1:1 :1混合而成的6份混合溶液进行混合揽拌,加热回流12h,冷却待用; II将步骤I得到的混合物转移到揽拌蓋中,加入13份甜菜糖蜜、2份木质素横酸钢、65 份水,揽拌Ih后出料即得。 [Example 10 I 002 cited first reaction was poured into 30 parts of the modified according to Preparation Example 5 = ethanolamine embodiment of the cover, and then poured into a stirred state embrace the molar ratio, from the burning dichloromethane: 1,1-bis chloroacetamide burning: 1,2-dichloroethane burn = 1: 1: 6 parts of a mixed solution obtained by mixing a mixed embrace stirred and heated at reflux for 12h, cooled stand; II the mixture obtained in step I is transferred to embrace mixed cover, 13 parts sugar beet molasses, 2 parts of lignin cross-steel acid, 65 parts of water, stirred for Ih embrace the material to obtain.

[0027]对比实施例选用对比文件CN201210265048. 6中实施例4作为对比实施例按W下质量百分比称取各组分,二甘醇3. 3%、二乙醇胺3%、二乙醇单异丙醇胺23%、糖蜜4%、氯化钟1%、氯化钢7%、聚合醇胺25%、水33. 7%。 [0027] Comparative Example Comparative selected files embodiment CN201210265048. 6 Example 4 Comparative Example As in percentage by mass of each component weighed at W, diethylene glycol, 3.3%, 3% diethanolamine, diethanol embodiment monoisopropanol amine 23%, 4% molasses, 1% bell chloride, chlorinated steel 7%, 25% polymeric alcohol amine, water 33.7%.

[0028]常溫下,将大分子表面活性剂和水放入反应蓋内,加入糖蜜、氯化钟、氯化钢,均化(充分揽拌均匀)15分钟,加入二乙醇单异丙醇胺,均化(充分揽拌均匀)15分钟,再加入二甘醇、二乙醇胺,均化(充分揽拌均匀)30分钟后,经过200目滤网过滤后出料装桶。 [0028] at room temperature, the macromolecular surfactant and water in the reaction cap, was added molasses, bell chloride, chlorinated steel, a homogenizer (embrace sufficiently uniform mix) for 15 minutes, diethanol monoisopropanolamine homogenizer (embrace sufficiently uniform mix) for 15 minutes, was added diethylene glycol, diethanolamine, homogenizer (embrace sufficiently uniform mix) for 30 minutes, after the material 200 mesh screen filter barreling.

[002引助磨实验将等量的按照实施例6至实施例10制备的水泥助磨剂S6至SlO和对比实施例制备的水泥助磨剂Dl应用到水泥小磨试验中,水泥原料的配方为(按质量百分比混配):水泥熟料58. 0%、石膏4. 0%、石灰石23. 0%、高娃砂岩4. 0%、儘渣1. 0%和炉底渣10. 0%。 [002 cited experiment equal amounts of grinding aid are applied in the cement grinding aids Examples 6 to 10 Preparation of embodiment Dl S6 to SlO cement grinding aids and Comparative Examples Preparation of the embodiment and cement grinding test, the formulation of the cement raw material is (compounding percentage by mass): 58.0% clinker, 4.0% gypsum, limestone 23.0%, 4.0% Gaowa sandstone, 1.0% slag to make slag and bottom 10.0 %. 将水泥原料分6组分别置于小磨机中,每组依次标记为对比样、试样6、试样7、……试样10,分别向对比样和试样6至10内按水泥原料质量的0. 05%添加水泥助磨剂Dl和S6至S10,并分别进行粉磨成水泥,记录粉磨过程中水的使用量,计算用水量占水泥的比值。 The cement material is divided into six groups were placed in a small mill, labeled sequentially as each control sample, Sample 6, Sample 7, Sample 10 ......, cement raw material respectively into the control sample and Sample 6-10 0.05% by mass is added to the cement grinding aids Dl S6 and SlO, and grinding into cement were recorded usage of water during the grinding, calculated water at the ratio of cement. 对制成的水泥按GB175-2007《普通娃酸盐水泥》进行检测,所得的水泥的检验数据见表1,再根据Duncan多范围检验法的单因素方差分析方法(差异显著性水平a=0. 05)、使用SPSS17.O数据处理软件进行差异显著性分析,分析结果见表1。 GB175-2007 cement made by the "baby ordinary Portland cement" is detected, the resulting cement test data in Table 1, then according to Duncan multiple range test of single factor variance analysis method (difference significance level a = 0 05), using data processing software SPSS17.O significant difference analysis and the results are shown in Table 1.

[0030] 表1 [0030] TABLE 1

Figure CN105271880AD00091

抗菌实验步骤1 :将大肠杆菌放在LB培养基中培养,分散浓度为80c化.mL1,将菌液均分为6 份,记录大肠杆菌的初始浓度Cl。 Antimicrobial Test Step 1: A culture of E. coli in LB medium, a dispersion of a concentration of 80c .mL1, the bacteria were divided into 6 parts, Cl recording initial concentration of E. coli. 在每份菌液中分别加入等量的按照对比实施例和实施例6-10制作的水泥助磨剂,经过化后测定大肠杆菌的浓度C2,并按照公式计算并记录浓度减少率。 They were added each in the same amount of bacteria in the embodiment according to Examples 6-10 and Comparative Examples produced cement grinding aids embodiment, after measuring the concentration of E. coli C2, and calculates a reduction rate and recording density according to the equation.

[0031] 公式:浓度减少率=(C1-C2) /C1。 [0031] Formula: concentration reduction rate = (C1-C2) / C1.

[0032] 步骤2 :再取肺炎杆菌、枯草杆菌重复大肠杆菌的实验。 [0032] Step 2: then take Bacilli, Escherichia coli Bacillus subtilis repeated experiments.

[0033] 表2浓度减少率 [0033] Table 2 density decrease rate

Figure CN105271880AD00101

从表I可W看出,相比于对比实施例,本发明在细度、比表面积等助磨效果的表征数据上都具有更好的效果。 W can be seen from Table I, in comparison to the Comparative Examples, the fineness of the present invention, the specific surface area and other characterization data grinding aid effect have better results. 同时,本发明在3d抗压强度和28d抗压强度上也具有比对比实施例更好的效果,在用水量上比对比实施例普遍减少5个百分点(与水泥的重量比)。 Meanwhile, the present invention also has an effect better than Comparative Example in the embodiment 3d 28d compressive strength and compressive strength in the water than that of Comparative Example 5 percentage points generally reduced (the weight ratio of cement). 同时本发明在抗菌性能上更是明显优于对比实施例。 While the invention on the antibacterial performance is significantly better than the comparative examples. 同时由于使用本发明水泥助磨剂的水泥在施工完成后不存在氯离子腐蚀的问题,因此能够极大增加水泥的使用时间和使用强度。 At the same time the use of cement grinding aids of the present invention the Corrosion problems not present in the construction is completed, it is possible to significantly increase the use time and the use of cement strength.

[0034] 从W上几点优点可W看出,本发明水泥助磨剂具有极大的市场前景,应该予W推广应用。 [0034] Several advantages can be seen from the W W, cement grinding aids of the present invention has great market potential, should I W application.

[0035] W上所述仅是本发明的优选实施方式,本发明的保护范围并不仅局限于上述实施例,凡属于本发明思路下的技术方案均属于本发明的保护范围。 [0035] W on only the preferred embodiment of the present invention, the scope of the present invention is not limited to the above embodiments, where the aspect belonging to the idea of the present invention belong to the scope of the present invention. 应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理前提下的若干改进和润饰,运些改进和润饰也应视为本发明的保护范围。 It should be noted that one of ordinary skill in the art, in several improvements and modifications without departing from the principles of the invention under the premise of some transportation improvements and modifications should be the scope of the invention.

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Clasificaciones
Clasificación internacionalC04B103/52, C04B24/12
Eventos legales
FechaCódigoEventoDescripción
27 Ene 2016C06Publication
24 Feb 2016C10Entry into substantive examination
13 Jun 2017GR01