WO2017049750A1 - 一种四臂星形结构高效重钙研磨分散剂的制备方法及其产物和应用 - Google Patents

一种四臂星形结构高效重钙研磨分散剂的制备方法及其产物和应用 Download PDF

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WO2017049750A1
WO2017049750A1 PCT/CN2015/094782 CN2015094782W WO2017049750A1 WO 2017049750 A1 WO2017049750 A1 WO 2017049750A1 CN 2015094782 W CN2015094782 W CN 2015094782W WO 2017049750 A1 WO2017049750 A1 WO 2017049750A1
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cyano
reaction
solvent
heavy calcium
pentaerythritol
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French (fr)
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施晓旦
邵威
金霞朝
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上海东升新材料有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/04—Acids; Metal salts or ammonium salts thereof
    • C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations

Definitions

  • the invention relates to a preparation method of a grinding dispersant, in particular to a preparation method of a four-arm star structure high-efficiency heavy calcium grinding dispersing agent, and a product prepared according to the method and application of the product.
  • Dispersants have been widely used in the wet grinding production of ultra-fine calcium, which can significantly reduce the grinding viscosity of heavy calcium slurry, reduce anti-stick after grinding, increase the stability of the slurry, reduce wear and improve product quality. Has an important role.
  • the current research shows that the dispersion mechanism of heavy calcium grinding dispersant is: 1 polymer polycarboxylate molecules adsorbed on the surface of calcium carbonate particles to form an electric double layer, which has electrostatic repulsion; 2 polymer adsorbed on the surface of the particles, in each The particles play a certain steric hindrance.
  • the star polymer can effectively reduce the viscosity of the fluid, increase the volume to weight ratio of the polymer, and more efficiently due to the branched structure of the star polymer.
  • Adsorption on the surface of the calcium carbonate particles enhances the steric effect between the particles, thereby improving the dispersion performance.
  • calcium hydroxide or magnesium hydroxide is introduced during the neutralization process. Because of the low degree of freedom of calcium and magnesium ions in the polycarboxylate dispersion system of calcium and magnesium, and the very good compatibility with the calcium carbonate grinding system, Therefore, the free counter ion effect can be lowered to improve the dispersing property of the dispersant.
  • Reversible-addition-fragmentation chain transfer (RAFT) polymerization is an excellent activity-controlled polymerization method, which can efficiently synthesize a molecular weight polymer, and can accurately obtain the polymer of the target molecular weight by adjusting the reaction conditions. At the same time, a very narrow molecular weight distribution can be ensured.
  • the reaction step is simple and the reaction conditions are mild. Therefore, the inventors decided to use the RAFT method to prepare a high-efficiency heavy calcium grinding dispersant after analysis and experiment.
  • a method for preparing a four-arm star structure high-efficiency heavy calcium grinding dispersant is provided, and the reaction formula of the main steps of the method is as follows:
  • the method includes the following steps:
  • the parts by mass of each reactant are as follows:
  • the amount of the solvent is such that the concentration of the vinyl carboxylic acid monomer is maintained at 1 to 8 mol/L.
  • the bubbling time is 15-30 minutes; in the step (3), the temperature is 60-80 ° C, and the reaction period is 8 to 16 hours. .
  • the base for neutralization is calcium hydroxide and magnesium hydroxide, and the calcium hydroxide and magnesium hydroxide are added in the following parts by mass:
  • the vinyl carboxylic acid monomer is acrylic acid or methacrylic acid.
  • the initiator is selected from the group consisting of azobisisobutyronitrile, azobisisoheptanenitrile, azobisisobutylvaleric acid, dibenzoyl peroxide, cyclohexanone peroxide, and t-butyl peroxide.
  • One or more of hydrogen peroxide is selected from the group consisting of azobisisobutyronitrile, azobisisoheptanenitrile, azobisisobutylvaleric acid, dibenzoyl peroxide, cyclohexanone peroxide, and t-butyl peroxide.
  • One or more of hydrogen peroxide is selected from the group consisting of azobisisobutyronitrile, azobisisoheptanenitrile, azobisisobutylvaleric acid, dibenzoyl peroxide, cyclohexanone peroxide, and t-butyl peroxide.
  • the solvent is one or more selected from the group consisting of tetrahydrofuran, benzene, toluene, N,N-dimethylformamide, ethylbenzene, xylene, and 1,4-dioxane.
  • the dispersant obtained according to the above method can be used for both heavy calcium grinding and light calcium dispersion.
  • the resulting ultrafine calcium carbonate can be used in the fields of papermaking, coatings, plastics, rubber, sealants, medicine, food, and cosmetics.
  • the invention adopts a reversible-addition-fragmentation chain transfer (RAFT) polymerization method to synthesize a polyethylene carboxylic acid with a controlled molecular weight and a narrow molecular weight distribution of a molecule having a four-arm star structure, and is introduced in the neutralization process.
  • RAFT reversible-addition-fragmentation chain transfer
  • Alkali calcium hydroxide / magnesium hydroxide to obtain a polyvinyl carboxylate high efficiency heavy calcium grinding and dispersing agent.
  • the four-arm star structure polymer synthesized by the method can adsorb on the surface of calcium carbonate particles efficiently, and the steric hindrance effect after adsorption is large, so the dispersion effect is better than the conventional linear polycarboxylic acid, and the synthesis method
  • the molecular weight is precisely controllable, the molecular weight distribution is narrow, and no free counter ions are introduced during the initiation process.
  • the use of calcium hydroxide/magnesium hydroxide in the neutralization process effectively reduces the influence of the free counterion on the calcium carbonate dispersion system. Combining the above characteristics, the dispersant obtained by the method has excellent performance.
  • a method for preparing a four-arm star structure high-efficiency heavy calcium grinding dispersant comprising the steps of:
  • the parts by mass of each reactant are as follows:
  • the amount of the solvent is such that the concentration of the vinyl carboxylic acid monomer is maintained at 1 to 8 mol/L.
  • the bubbling is for a period of time of 15 to 30 minutes; in the step (3), the temperature is 60 to 80 ° C, and the reaction is for a period of time. It is 8 to 16 hours.
  • the base for neutralization is calcium hydroxide and magnesium hydroxide, and the calcium hydroxide and magnesium hydroxide are added in the following parts by mass:
  • the vinyl carboxylic acid monomer is acrylic acid or methacrylic acid.
  • the initiator is selected from the group consisting of azobisisobutyronitrile, azobisisoheptanenitrile, azobisisobutylvaleric acid, dibenzoyl peroxide, cyclohexanone peroxide One or more of t-butyl hydroperoxide.
  • the solvent is selected from one or more of tetrahydrofuran, benzene, toluene, N,N-dimethylformamide, ethylbenzene, xylene, and 1,4-dioxane.
  • tetrahydrofuran benzene, toluene, N,N-dimethylformamide, ethylbenzene, xylene, and 1,4-dioxane.
  • a dithioester chain transfer agent pentaerythritol tetrakis 4-cyano-4-dithiobenzoyloxyvalerate 8.07 g and an initiator azobisisobutyronitrile 1.71 g were added to the reaction vessel. 288.0 g of hexacyclohexane and 172 g of monomeric acrylic acid. The system was bubbled with nitrogen for 20 minutes, sealed, and then heated to 70 ° C for 12 hours.
  • the obtained dispersant has a number average molecular weight of 6,420.
  • the molecular weight distribution index was 1.25.
  • the obtained dispersant had a number average molecular weight of 5,620 and a molecular weight distribution index of 1.21.
  • the obtained dispersant had a number average molecular weight of 8,320 and a molecular weight distribution index of 1.37.
  • dispersant prepared in accordance with Examples 1 to 3 and the comparative sample were at 98.
  • Application in heavy calcium milling (dispersant solids are 25%).

Abstract

本发明公开了一种四臂星形结构高效重钙研磨分散剂的制备方法，包括如下步骤：(1)往溶剂中加入季戊四醇和4-氰基-4-二硫代苯甲酰氧基戊酸，再加入吸水剂DCC和催化剂DMAP，反应完成后，经浓缩和分离得到四臂RAFT链转移剂季戊四醇四4-氰基-4-二硫代苯甲酰氧基戊酸酯；(2)加入乙烯基羧酸单体、季戊四醇四4-氰基-4-二硫代苯甲酰氧基戊酸酯、引发剂，并在低温下氮气鼓泡一定时间，密封；(3)加热反应；(4)反应结束后蒸馏除去溶剂；(5)再加入一种或者多种中和用碱溶液调节体系的pH为5～8，再加水调节固含量至20％～50％，即可获得高效重钙研磨分散剂。该方法制得的产物，反离子效应低，分子量和分子量分布精确可控，具有优异的分散性能。

Description

一种四臂星形结构高效重钙研磨分散剂的制备方法及其产物和应用 技术领域
本发明涉及一种研磨分散剂的制备方法，尤其涉及一种四臂星形结构高效重钙研磨分散剂的制备方法，及依据该方法制备的产物和该产物的应用。
背景技术
分散剂已经广泛用于超细重钙的湿法研磨生产当中，其可以显著降低重钙浆料的研磨粘度、减少磨后反粘、增加浆料的稳定性，对于降低磨耗和提高产品品质都有着重要作用。
目前研究表明，重钙研磨分散剂的分散机理为：1聚合物聚羧酸盐分子吸附在碳酸钙微粒表面从而形成双电层，其具有静电排斥作用；2聚合物吸附在微粒表面，在各微粒之间起到一定的位阻作用。
目前市场上绝大部分重钙研磨用分散剂都是直链型的聚羧酸钠水溶液，反应引发剂多是无机的钠盐，中和过程中大多使用氢氧化钠水溶液，从而在以上过程中引入了大量的自由反离子钠离子，自由反离子的引入能够有效降低静电排斥作用从而降低分散剂的性能。
相比与传统的直链型结构的分散剂聚合物分子，星形聚合物，由于其结构的支链化，可以有效的降低其流体的粘度、增加聚合物的体积重量比、更加高效率地吸附在碳酸钙微粒的表面、使微粒间的位阻效应增强，从而提高分散性能。同时在中和过程中引入氢氧化钙或者氢氧化镁，由于在钙镁的聚羧酸盐分散体系中，钙镁离子的自由度低，而且与碳酸钙研磨体系有着非常好的相容性，因此，可以降低自由反离子效应从而提高分散剂的分散性能。
传统分散剂最主要的合成方法是传统的溶液自由基聚合。但是该法所合成的聚合物分子量分布很宽，且对分子量控制性较差。据文献报道，分散剂的分子量及其分布对于其分散效果具有很大的影响。J.Loiseau[Macromolecules 2003，36，3066-3077]的研究结果表明，接近分子量单分散的聚丙烯酸钠比多分散的聚丙烯酸钠具有更好的分散作用，前者可以不可逆的全部吸附到碳酸钙粒子的表面上， 从而达到很好的分散碳酸钙；而后者只能部分选择性的吸附到碳酸钙粒子表面，分散剂的利用效率大大降低，甚至会出现沉淀。
可逆-加成-断裂链转移(RAFT)聚合是一种优良的活性-控制聚合方法，该方法可以有效的合成目分子量的聚合物，可以通过对反应条件的调节精确得到目标分子量的聚合物且同时可以保证很窄的分子量分布。反应步骤简单、反应条件较温和。因此，发明人经过分析和实验，决定采用RAFT法以制备一种高效重钙研磨分散剂。
发明内容
为了能够克服上述现有技术中存在的问题，本发明的第一方面，提供了一种四臂星形结构高效重钙研磨分散剂的制备方法，该方法主要步骤的反应通式如下所示：
Figure PCTCN2015094782-appb-000001
所述方法包括如下步骤：
(1)以1∶4的摩尔比往溶剂中加入季戊四醇和4-氰基-4-二硫代苯甲酰氧基戊酸，再加入吸水剂DCC和催化剂DMAP，在一定反应温度下反应一段时间后，经浓缩和简单的柱色谱分离得到四臂RAFT链转移剂季戊四醇四4-氰基-4-二硫代苯甲酰氧基戊酸酯；
(2)在溶剂中加入乙烯基羧酸单体、季戊四醇四4-氰基-4-二硫代苯甲酰氧基戊酸酯、引发剂，并在低温下氮气鼓泡一定时间，密封；
(3)加热至一定温度反应一段时间；
(4)反应结束后蒸馏除去溶剂；
(5)再加入一种或者多种中和用碱溶液调节体系的pH为5～8，再加水调节固含量至20％～50％，即可获得高效重钙研磨分散剂。
优选地，所述步骤(1)中，以下物质的摩尔比为[季戊四醇]∶[4-氰基-4-二 硫代苯甲酰氧基戊酸]∶[DCC]∶[DMAP]＝1∶4∶0.5∶0.1，所述溶剂为二氯甲烷，所述反应温度为室温，所述反应一段时间为6～12小时。
优选地，所述步骤(2)中，各反应物的质量份数如下：
乙烯基羧酸单体 30～100份
季戊四醇四4-氰基-4-二硫代苯甲酰氧基戊酸酯  0.1～2份
引发剂         0.01～2份
并且，溶剂的用量使得乙烯基羧酸单体的浓度保持为1～8mol/L。
优选地，所述步骤(2)中，所述鼓泡一定时间为15-30分钟；所述步骤(3)中，所述温度为60～80℃，所述反应一段时间为8至16小时。
优选地，所述步骤(5)中，所述中和用碱为氢氧化钙和氢氧化镁，并且所述氢氧化钙和氢氧化镁的加入量依据以下质量份数：
氢氧化钙       0～100份
氢氧化镁       0～100份
进一步优选地，所述乙烯基羧酸单体为丙烯酸或者甲基丙烯酸。
进一步优选地，所述引发剂选引偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁基戊酸、过氧化二苯甲酰、过氧化环己酮、叔丁基过氧化氢中的一种或者多种。
进一步优选地，所述溶剂选自四氢呋喃、苯、甲苯、N，N-二甲基甲酰胺、乙苯、二甲苯、1，4-二氧六环中的一种或者多种。
另外，以上所有的质量份数均按照原料有效含量为100％计算而标明的，实际用量需按照原料的实际有效含量折算。
本发明的第二方面，提供了一种采用上述方法制得的四臂星形结构高效重钙研磨分散剂。
本发明的第三方面，提供了上述四臂星形结构高效重钙研磨分散剂在超细重钙的湿法研磨生产中的应用。
当然，依据上述方法所获得的分散剂，既可用于重钙研磨，也可用于轻钙分散。所得的超细碳酸钙可用于造纸、涂料、塑料、橡胶、密封胶、医药、食品和化妆品等领域。
本发明采用可逆-加成-断裂链转移(RAFT)聚合的方法合成四臂星形结构的分子的分子量量可控、分子量分布较窄的聚乙烯基羧酸，再在中和过程中引入 碱氢氧化钙/氢氧化镁从而得到聚乙烯基羧酸盐高效重钙研磨分散剂。该法所合成的四臂星形结构聚合物能够高效地吸附在碳酸钙微粒表面，吸附后产生的位阻效应大，所以在分散效果上比传统的直链型聚羧酸要好，同时合成方法与传统的自由基聚合相比优点为分子量精确可控、分子量分布较窄，引发过程中不引入自由反离子。在中和过程中使用氢氧化钙/氢氧化镁，有效的降低了自由反离子对碳酸钙分散体系的影响，综合以上特点，该方法得到的分散剂具有优异的性能。
具体实施方式
下面结合具体实施方式对本发明作进一步阐述，但本发明并不限于以下实施方式。
本发明的第一方面，提供了一种四臂星形结构高效重钙研磨分散剂的制备方法，包括如下步骤：
(1)以1∶4的摩尔比往溶剂中加入季戊四醇和4-氰基-4-二硫代苯甲酰氧基戊酸，再加入吸水剂DCC和催化剂DMAP，在一定反应温度下反应一段时间后，经浓缩和简单的柱色谱分离得到四臂RAFT链转移剂季戊四醇四4-氰基-4-二硫代苯甲酰氧基戊酸酯；
(2)在溶剂中加入乙烯基羧酸单体、季戊四醇四4-氰基-4-二硫代苯甲酰氧基戊酸酯、引发剂，并在低温下氮气鼓泡一定时间，密封；
(3)加热至一定温度反应一段时间；
(4)反应结束后蒸馏除去溶剂；
(5)再加入一种或者多种中和用碱溶液调节体系的pH为5～8，再加水调节固含量至20％～50％，即可获得高效重钙研磨分散剂。
在一个优选的实施例中，所述步骤(1)中，以下物质的摩尔比为[季戊四醇]∶[4-氰基-4-二硫代苯甲酰氧基戊酸]∶[DCC]∶[DMAP]＝1∶4∶0.5∶0.1，所述溶剂为二氯甲烷，所述反应温度为室温，所述反应一段时间为6～12小时。
在一个优选的实施例中，所述步骤(2)中，各反应物的质量份数如下：
乙烯基羧酸单体 30～100份
季戊四醇四4-氰基-4-二硫代苯甲酰氧基戊酸酯  0.1～2份
引发剂         0.01～2份
并且，溶剂的用量使得乙烯基羧酸单体的浓度保持为1～8mol/L。
在一个优选的实施例中，所述步骤(2)中，所述鼓泡一定时间为15-30分钟；所述步骤(3)中，所述温度为60～80℃，所述反应一段时间为8至16小时。
在一个优选的实施例中，所述步骤(5)中，所述中和用碱为氢氧化钙和氢氧化镁，并且所述氢氧化钙和氢氧化镁的加入量依据以下质量份数：
氢氧化钙        0～100份
氢氧化镁        0～100份
在一个进一步优选的实施例中，所述乙烯基羧酸单体为丙烯酸或者甲基丙烯酸。
在一个进一步优选的实施例中，所述引发剂选自偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁基戊酸、过氧化二苯甲酰、过氧化环己酮、叔丁基过氧化氢中的一种或者多种。
在一个进一步优选的实施例中，所述溶剂选自四氢呋喃、苯、甲苯、N，N-二甲基甲酰胺、乙苯、二甲苯、1，4-二氧六环中的一种或者多种。
本发明的第二方面，提供了一种采用上述方法制得的四臂星形结构高效重钙研磨分散剂。
本发明的第三方面，提供了上述四臂星形结构高效重钙研磨分散剂在超细重钙的湿法研磨生产中的应用。
实施例1低分子量窄分布的四臂星形聚丙烯酸盐的制备
在200g二氯甲烷中加入季戊四醇1.36g、4-氰基-4-二硫代苯甲酰氧基戊酸12.0g，再加入3g吸水剂二环己基碳二亚胺(DCC)和0.54g催化剂4-二甲氨基吡啶(DMAP)。室温下反应8小时后，经浓缩和简单的柱色谱分离得到四臂RAFT链转移剂季戊四醇四4-氰基-4-二硫代苯甲酰氧基戊酸酯12.97g。后再在反应容器中加入二硫代酯链转移剂季戊四醇四4-氰基-4-二硫代苯甲酰氧基戊酸酯8.07g，引发剂偶氮二异丁腈1.71g，溶剂二氧六环288.0g以及单体丙烯酸172g。体系用氮气鼓泡20分钟后密封，之后升温至70℃条件下反应12小时。反应结束后将所得溶液减压蒸馏，除去溶剂后，加少量水稀释，再加入摩尔比[氢氧化钙]∶[氢氧化镁]＝2∶1的中和用碱混合悬浮液调节pH为6.89，并且加水调节聚合物溶液固含量为25％，得到最终的分散剂样品。所得分散剂数均分子量为6420， 分子量分布指数为1.25。
实施例2低分子量窄分布的四臂星形聚甲基丙烯酸盐的制备：
在250g二氯甲烷中加入季戊四醇1.91g、4-氰基-4-二硫代苯甲酰氧基戊酸16.8.0g，再加入4.2g吸水剂二环己基碳二亚胺(DCC)和0.76g催化剂4-二甲氨基吡啶(DMAP)。室温下反应8小时后，经浓缩和简单的柱色谱分离得到四臂RAFT链转移剂季戊四醇四4-氰基-4-二硫代苯甲酰氧基戊酸酯17.81g。后再在石英反应容器中加入季戊四醇四4-氰基-4-二硫代苯甲酰氧基戊酸10.45g，引发剂偶氮二异丁腈2.34g，溶剂四氢呋喃400.21g以及单体甲基丙烯酸215.00g。体系用氮气鼓泡20分钟后密封，之后升温至80℃条件下反应8小时。反应结束后将所得溶液减压蒸馏，除去溶剂后，加少量水稀释，再加入摩尔比[氢氧化钙]∶[氢氧化镁]＝1∶1的中和用碱混合悬浮液调节pH为7.11，并且加水调节聚合物溶液固含量为25％，得到最终的分散剂样品。所得分散剂数均分子量为5620，分子量分布指数为1.21。
实施例3低分子量窄分布的四臂星形聚(丙烯酸钠-co-甲基丙烯酸盐)的制备
在200g二氯甲烷中加入季戊四醇1.09g、4-氰基-4-二硫代苯甲酰氧基戊酸10.8g，再加入2.4g吸水剂二环己基碳二亚胺(DCC)和0.43g催化剂4-二甲氨基吡啶(DMAP)。室温下反应8小时后，经浓缩和简单的柱色谱分离得到四臂RAFT链转移剂季戊四醇四4-氰基-4-二硫代苯甲酰氧基戊酸酯10.98g。之后再在石英反应容器中加入季戊四醇四4-氰基-4-二硫代苯甲酰氧基戊酸7.22g，引发剂偶氮二异庚腈1.91g，溶剂1，4-二氧六环322.24g以及单体甲基丙烯酸112.0g、丙烯酸90.23g。体系用氮气鼓泡20分钟后密封，之后升温至65℃条件下反应16小时。反应结束后将所得溶液减压蒸馏，除去溶剂后，加少量水稀释，再加入摩尔比[氢氧化钙]∶[氢氧化镁]＝1∶2的中和用碱混合悬浮液调节pH为7.01，并且加水调节聚合物溶液固含量为25％，得到最终的分散剂样品。所得分散剂数均分子量为8320，分子量分布指数为1.37。
研磨效果检测
将按照实施例1～3制得的分散剂以及对比样(按美国专利20020019329A1公开的方法制备的分散剂，数均分子量4400，而分子量分布指数1.43)在98级 重钙研磨中进行应用(分散剂固含均为25％)。
在15升研磨罐中加入计算量的水，开启搅拌，加入计算量的分散剂，搅拌均匀后加入计算量的重质碳酸钙粉料，研磨2小时后出料，进行粘度和粒径数据检测，其中分散剂用量和研磨浆料其他各组分的比例保持一致。粒径和分散后静止1小时粘度数据如下：
Figure PCTCN2015094782-appb-000002
表1
从表1的数据结果中可以看出：使用本发明实施例1～3制备的分散剂的研磨效果要明显优于对比样分散剂。
以上对本发明的具体实施例进行了详细描述，但是，其只是作为范例，本发明并不限制于以上描述的具体实施例。对于本领域技术人员而言，任何对本发明进行的等同修改和替代也都在本发明的范畴之中。因此，在不脱离本发明的精神和范围下所作的均等变换和修改，都应涵盖在本发明的范围内。

Claims (10)

  1. 一种四臂星形结构高效重钙研磨分散剂的制备方法，其特征在于，包括如下步骤：
    (1)以1∶4的摩尔比往溶剂中加入季戊四醇和4-氰基-4-二硫代苯甲酰氧基戊酸，再加入吸水剂DCC和催化剂DMAP，在一定反应温度下反应一段时间后，经浓缩和简单的柱色谱分离得到四臂RAFT链转移剂季戊四醇四4-氰基-4-二硫代苯甲酰氧基戊酸酯；
    (2)在溶剂中加入乙烯基羧酸单体、季戊四醇四4-氰基-4-二硫代苯甲酰氧基戊酸酯、引发剂，并在低温下氮气鼓泡一定时间，密封；
    (3)加热至一定温度反应一段时间；
    (4)反应结束后蒸馏除去溶剂；
    (5)再加入一种或者多种中和用碱溶液调节体系的pH为5～8，再加水调节固含量至20％～50％，即可获得高效重钙研磨分散剂。
  2. 根据权利书要求1所述的方法，其特征在于，所述步骤(1)中，以下物质的摩尔比为[季戊四醇]∶[4-氰基-4-二硫代苯甲酰氧基戊酸]∶[DCC]∶[DMAP]＝1∶4∶0.5∶0.1，所述溶剂为二氯甲烷，所述反应温度为室温，所述反应一段时间为6～12小时。
  3. 根据权利要求1所述的方法，其特征在于，所述步骤(2)中，各反应物的质量份数如下：
    乙烯基羧酸单体  30～100份
    季戊四醇四4-氰基-4-二硫代苯甲酰氧基戊酸酯  0.1～2份
    引发剂          0.01～2份
    并且，溶剂的用量使得乙烯基羧酸单体的浓度保持为1～8mol/L。
  4. 根据权利要求1所述的方法，其特征在于，所述步骤(2)中，所述鼓泡一定时间为15-30分钟；所述步骤(3)中，所述温度为60～80℃，所述反应一段时间为8至16小时。
  5. 根据权利要求1所述的方法，其特征在于，所述步骤(5)中，所述中和用碱为氢氧化钙和氢氧化镁，并且所述氢氧化钙和氢氧化镁的加入量依据以下质量份数：
    氢氧化钙       0～100份
    氢氧化镁       0～100份
  6. 根据权利要求1-5中任一项所述的方法，其特征在于，所述乙烯基羧酸单体为丙烯酸或者甲基丙烯酸。
  7. 根据权利要求1-5中任一项所述的方法，其特征在于，所述引发剂选自偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁基戊酸、过氧化二苯甲酰、过氧化环己酮、叔丁基过氧化氢中的一种或者多种。
  8. 根据权利要求1-5中任一项所述的方法，其特征在于，所述溶剂选自四氢呋喃、苯、甲苯、N，N-二甲基甲酰胺、乙苯、二甲苯、1，4-二氧六环中的一种或者多种。
  9. 根据权利要求1～8中任一项所述的方法制备的四臂星形结构高效重钙研磨分散剂。
  10. 根据权利要求9所述的四臂星形结构高效重钙研磨分散剂在超细重钙的湿法研磨生产中的应用。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115073637A (zh) * 2022-07-25 2022-09-20 济宁明升新材料有限公司 一种含有多种反离子的聚丙烯酸系分散剂及其制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111440259A (zh) * 2020-04-23 2020-07-24 济宁明升新材料有限公司 一种多分支型分散剂及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000037168A1 (en) * 1998-12-18 2000-06-29 3M Innovative Properties Company Polyelectrolyte dispersants for hydrophobic particles in water-based systems
CN101020132A (zh) * 2006-05-31 2007-08-22 北京盖雅技术中心有限公司 碳酸钙分散剂
CN103030729A (zh) * 2012-12-06 2013-04-10 永港伟方（北京）科技股份有限公司 研磨重质碳酸钙用分散剂及其合成方法和应用
EP2657264A1 (en) * 2010-12-22 2013-10-30 Jiangsu Bote New Materials Co., Ltd Preparation method of hyperbranched polycarboxylic acid type copolymer cement dispersant
CN104017119A (zh) * 2014-06-12 2014-09-03 东升新材料（山东）有限公司 支化结构重钙研磨用分散剂及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1833868B1 (en) * 2004-10-25 2013-04-17 The Lubrizol Corporation Star polymers and compositions thereof
CN103709283B (zh) * 2013-12-17 2015-12-02 聊城大学 一种四臂星形聚合物蜂窝状多孔膜及制备方法
CN104031190A (zh) * 2014-06-12 2014-09-10 东升新材料（山东）有限公司 光引发室温raft聚合制备高效重钙研磨分散剂
CN105669912B (zh) * 2016-03-03 2018-03-13 江苏中铁奥莱特新材料股份有限公司 一种制备星型聚羧酸系减水剂的方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000037168A1 (en) * 1998-12-18 2000-06-29 3M Innovative Properties Company Polyelectrolyte dispersants for hydrophobic particles in water-based systems
CN101020132A (zh) * 2006-05-31 2007-08-22 北京盖雅技术中心有限公司 碳酸钙分散剂
EP2657264A1 (en) * 2010-12-22 2013-10-30 Jiangsu Bote New Materials Co., Ltd Preparation method of hyperbranched polycarboxylic acid type copolymer cement dispersant
CN103030729A (zh) * 2012-12-06 2013-04-10 永港伟方（北京）科技股份有限公司 研磨重质碳酸钙用分散剂及其合成方法和应用
CN104017119A (zh) * 2014-06-12 2014-09-03 东升新材料（山东）有限公司 支化结构重钙研磨用分散剂及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PENG, ZHIPING ET AL.: "Synthesi and characterization of double-hydrophilic triblock copolymers of PSS-b-PEG-b-PSS via RAFT polymerization in aqueous solution", JOURNAL OF UNIVERSITY OF SCIENCE AND TECHNOLOGY BEIJING, vol. 28, 31 October 2006 (2006-10-31), pages 352 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115073637A (zh) * 2022-07-25 2022-09-20 济宁明升新材料有限公司 一种含有多种反离子的聚丙烯酸系分散剂及其制备方法

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