WO2013123811A1 - Process for preparing amphiphilic block copolymer - Google Patents

Process for preparing amphiphilic block copolymer Download PDF

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Publication number
WO2013123811A1
WO2013123811A1 PCT/CN2012/087228 CN2012087228W WO2013123811A1 WO 2013123811 A1 WO2013123811 A1 WO 2013123811A1 CN 2012087228 W CN2012087228 W CN 2012087228W WO 2013123811 A1 WO2013123811 A1 WO 2013123811A1
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Prior art keywords
microemulsion
monomer
block copolymer
amphiphilic block
acrylate polymer
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PCT/CN2012/087228
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French (fr)
Chinese (zh)
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孙雯雯
薛建设
舒适
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京东方科技集团股份有限公司
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Publication of WO2013123811A1 publication Critical patent/WO2013123811A1/en

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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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters

Definitions

  • the present invention relates to a process for preparing amphiphilic block copolymers. Background technique
  • the amphiphilic block copolymer refers to a copolymer containing both a hydrophilic segment and a hydrophobic segment in the same polymer. Compared to ordinary polymers, the 3 -individual block copolymer has many special properties such as surface activity, solubilization and thickening.
  • Emulsion polymerization is a synthetic method commonly used in the synthesis of polymers because it uses water as a solvent and is very beneficial to the environment.
  • the emulsion polymerization is a polymerization in which an monomer is dispersed in water to form an emulsion under the action of an emulsifier and mechanically stirred, and is initiated by an initiator.
  • Chinese patent application CN 101870759 A discloses a method for synthesizing a amphiphilic block copolymer which is synthesized by a conventional emulsion polymerization method.
  • the emulsion is a turbid unstable system
  • the thermodynamic system is unstable
  • the size of the dispersed phase is large, which makes the chemical reaction system unstable, and has a certain influence on the distribution and stability of the dispersed pigment particle size.
  • the technical problem to be solved by the present invention is how to enhance the thermodynamic stability of the amphiphilic block copolymer system.
  • an aspect of the present invention provides a method of preparing an amphiphilic block copolymer.
  • the method of preparing an amphiphilic block copolymer according to the present invention comprises the steps of:
  • Preparing a seed microemulsion and a pre-emulsified mixed monomer wherein the seed microemulsion and the pre-emulsified mixed monomer respectively contain a propionic acid-based hydrophobic monomer;
  • the prepared acrylate polymer is reacted with a hydrophilic monomer to obtain an amphiphilic block copolymer.
  • the seed microemulsion is prepared by the following steps: mixing 60 75% of the emulsifier with water, The mixture was stirred by magnetic force to obtain an emulsion, and 25-40% of an acrylic hydrophobic monomer was added under ultrasonic stirring to obtain a seed microemulsion.
  • the volume ratio of the emulsifier, water and the acrylic hydrophobic monomer is preferably (1 to 2): (25 to 50): (10 to 20).
  • the magnetic stirring speed is 300 ⁇ 330rad/min; the magnetic stirring time is 25 ⁇ 35min.
  • the pre-emulsified mixed monomer is prepared by mixing 25 to 40% of an emulsifier with water, and adding 60 to 75% of an acrylic hydrophobic monomer under magnetic stirring to obtain a pre-emulsified mixed monomer.
  • the volume ratio of the emulsifier, water, and acrylic hydrophobic monomer is preferably (1 to 2): (50-100): (50 to 80).
  • the magnetic stirring speed is 40 (30 rad/min; the magnetic stirring time is 25 to 35 min.
  • the acrylate polymer is prepared by adding a base, a catalyst, a ligand and an initiator to the seed microemulsion to initiate microemulsion polymerization; when the seed microemulsion exhibits blue light, the temperature is raised to 80 to 85 ° C; Pre-emulsified mixed monomer; after 2 ⁇ 3h, the temperature is lowered, the temperature is lowered after 0.5 ⁇ lh, the pH is adjusted to 9 ⁇ 11, the reaction product is vacuumed, cooled under protective gas, filtered, washed and dried to obtain acrylate. polymer.
  • the volume ratio of the seed microemulsion, the pre-emulsified mixed monomer, the base, the catalyst, the ligand, and the initiator is preferably (72 to 144): (101-182): (0.05-0.15): (1-2) ): (2-3): (1 ⁇ 2).
  • the amphiphilic block copolymer is obtained by mixing an acrylate polymer with a hydrophilic monomer, reacting in a water bath under a protective gas of 50 to 80 mm, cooling, suction filtration, washing, and drying.
  • the temperature of the water bath is preferably 25 to 35 °C.
  • the volume ratio of the acrylate polymer to the hydrophilic monomer is 1: (2-4) 0
  • the acrylic hydrophobic monomer is preferably selected from one or more of decyl acrylate, ethyl acrylate, isobutyl acrylate, decyl methacrylate and ethyl methacrylate.
  • the hydrophilic monomer is preferably selected from one or more of acrylamide, methacrylamide, propylene glycol, and glycerin.
  • the initiator is selected from the group consisting of perfuate or hydrogen peroxide, or a derivative thereof.
  • the initiator is sodium persodium or potassium perruthenate.
  • the emulsifier is selected from one or more of sodium secondary alkyl ketone, sodium dodecyl benzene sulfonate and Triton X-100.
  • the catalyst is selected from one or more of copper bromide, iron bromide, copper chloride, and ferric chloride.
  • the ligand is selected from one of 2-methyl-5-vinylpyridine, 3-vinylpyridine, 4,4-bipyridine, and pentadecyldiethylenetriamine.
  • the base is selected from one or more of sodium hydrogencarbonate, sodium carbonate, and sodium hydroxide.
  • the shielding gas is nitrogen or an inert gas.
  • the inert gas includes those commonly found in the art, preferably argon.
  • the present invention synthesizes amphiphilic block copolymers by microemulsion polymerization.
  • Microemulsion polymerization is to disperse the droplet size of the dispersed phase to a smaller extent, so that the droplet diameter of the dispersed phase is in the range of 10 to 100 nm.
  • the microbeads are maintained by a layer of composite film and interface layer formed by an emulsifier and a co-emulsifier.
  • the amphiphilic block polymer system obtained by the microemulsion method is thermodynamically stable, and the dispersed phase is small in size, at 21.5 to 33 nm.
  • the size distribution is stable and stable.
  • the amphiphilic block copolymer synthesized by this method has good affinity for hydrophilic fibers and hydrophobic pigments, can modify the surface of natural fibers, and has excellent stability to the organic pigment dispersion system. Therefore, it can be used as a pigment dispersant for a color film in a liquid crystal display.
  • Another aspect of the invention relates to an amphiphilic block copolymer prepared according to the process of the invention.
  • Still another aspect of the invention relates to the use of the above parent block copolymer in a pigment dispersant. detailed description
  • the properties of the amphiphilic block copolymer obtained by the synthesis method of the present invention can be detected by the following indicators:
  • Copolymer Viscosity The viscosity of the binder emulsion was measured using a BROOKFIELD DV-C digital viscometer.
  • Copolymer particle size and particle size distribution The particle size and particle size distribution of the block copolymer emulsion were determined by a Nano ZS particle size analyzer.
  • Copolymer molecular weight and distribution index The molecular weight and molecular weight distribution of the polymer were measured by Waters 515 gel permeation chromatography at a test temperature of 25 ° C, a mobile phase of tetrahydrofuran, a flow rate of 1.0 ml/min, and a standard sample of polystyrene.
  • acrylic hydrophobic The monomer is selected from the group consisting of methyl acrylate, isobutyl acrylate and methyl methacrylate; the hydrophilic monomer is selected from the group consisting of acrylamide, methacrylamide and propylene glycol; and the initiator is selected from the group consisting of sodium persulfate and potassium perruthenate.
  • the emulsifier is selected from the group consisting of sodium secondary alkyl sulfate and sodium dodecylbenzene sulfonate;
  • the catalyst is selected from the group consisting of copper bromide and iron bromide;
  • the ligand is selected from the group consisting of 2-methyl-5-ethyl pyridine, 3-ethylene Pyridine and 4,4-bipyridine;
  • the base used is selected from the group consisting of argon carbonate] and sodium carbonate.
  • the volume ratio of the emulsifier, water, and acrylic hydrophobic monomer is (1 ⁇ 2): (25 ⁇ 50) ): (10-20);
  • the volume ratio of the emulsifier, water, and acrylic hydrophobic monomer is (1 ⁇ 2): (50-100): (50-80);
  • the volume ratio of the seed 3 ⁇ 4 emulsion, pre-emulsified mixed monomer, base, catalyst, ligand, and initiator used is (72 to 144): (101-182): (0.05-0.15) : (1-2): (2-3): (1-2);
  • the volume ratio of acrylate polymer to hydrophilic monomer is 1: (2-4)
  • each of the solutions used is a common usable solvent unless otherwise specified, as long as it does not affect the reaction or method of the present invention. It is generally preferred to formulate each substance to be used in the form of an aqueous solution, i.e., water is preferably used as the solvent.
  • the emulsifier used is preferably formulated into an aqueous solution with an acrylic hydrophobic monomer and water (preferably deionized water).
  • the volume ratio of each substance may refer to the volume ratio of the aqueous solution of each substance.
  • the temperature is lowered after 0.5 h of heat preservation, and the pH is adjusted to 10, and the reaction product is sealed and vacuumed, so that the vacuum degree reaches 40 kPa and then argon gas is filled to normal pressure.
  • the reaction product was cooled in ice water for 20 min, and the reaction product was suction filtered after the temperature was lowered to 20 ° C; the solid obtained by suction filtration was rinsed 3 times with deionized water at 50 ° Under the condition of C, vacuum drying for 4 hours to obtain an acrylate polymer;
  • Example 2 The concentrations corresponding to the materials used hereinafter are the same as those used in Example 1, unless otherwise stated.
  • Example 2 The concentrations corresponding to the materials used hereinafter are the same as those used in Example 1, unless otherwise stated.
  • 3-vinylpyridine 1 ml potassium persulfate, initiated microemulsion polymerization; when the seed microemulsion showed blue light, the temperature was raised to 85 ° C, and the pre-emulsified mixed monomer obtained in step (2) was added dropwise, and the mixture was dropped within 2 hours. After heating for 0.5h, the temperature is lowered, the pH is adjusted to 10, and the reaction product is sealed and vacuumed, so that the vacuum reaches 40 kPa, then the argon gas is refilled to normal pressure, and repeated three times; in the presence of argon, the reaction product is in water.
  • the reaction product was suction filtered after the temperature was lowered to 20 ° C; the solid obtained by suction filtration was washed 3 times with deionized water, and vacuum-dried for 4 h under 50 Torr to obtain an acrylate polymer;
  • step (3) adding 0.15 ml of sodium hydrogencarbonate, 2 ml of iron bromide, 3 ml of 4,4-bipyridine, 2 ml of sodium persulfate to the seed microemulsion obtained in the step (1) to initiate microemulsion polymerization; After the emulsion is blue light, the temperature is raised to 80 ° C, and the pre-emulsified mixed monomer obtained in the step (2) is added dropwise, and the mixture is dripped in 3 hours, the temperature is lowered after the heat preservation for 1 hour, the pH is adjusted to 9, and the reaction product is sealed and vacuumed.
  • the argon gas is further filled to normal pressure and repeated three times; in the presence of argon, the reaction product is cooled in ice water for 15 mm, and the reaction product is subjected to suction filtration after the temperature is lowered to 20 Torr; the solid obtained by suction filtration Rinse with deionized water for 3 times, and vacuum dry at 50 ° C for 4 h to obtain an acrylate polymer;
  • step (3) adding 1 ml of sodium carbonate, 20 ml of copper bromide, 20 ml of 3-vinylpyridine, and 20 ml of potassium persulfate to the seed microemulsion obtained in the step (1) to initiate microemulsion polymerization; when the seed microemulsion is present After blue light, the temperature is raised to 85 °C, and the pre-emulsified mixed monomer obtained by the step (2) is added dropwise. After 2 hours, the temperature is lowered after heating for 0.5 h, the pH is adjusted to 11, and the reaction product is sealed and evacuated.
  • the nitrogen gas is further filled to normal pressure for three times; in the presence of nitrogen, the reaction product is cooled in water for 20 minutes, and the reaction product is subjected to suction filtration after the temperature is lowered to 20 ° C; Rinse with deionized water for 3 times, and vacuum dry at 50 ° C for 4 h to obtain an acrylate polymer;
  • the amphiphilic block copolymer prepared by the invention has a particle size distribution width of 21.5 to 33 nm and a small dispersed phase size range; the obtained amphiphilic block copolymer is hydrophilic to the fiber and hydrophobic. Pigments have good affinity.
  • the inventors also characterized their dispersion stability by long-term follow-up testing of the viscosity and particle size of the pigment. As a result, it has been found that, when the amphiphilic block copolymer produced by the method of the present invention is used as a pigment dispersant in a period of six months to one year, the viscosity and particle size of the pigment hardly increase significantly, which indicates the use according to the present invention.
  • the pigment dispersant of the amphiphilic block copolymer prepared by the method has good Stability.
  • the above is only an exemplary embodiment of the present invention, and is not intended to limit the scope of the present invention.
  • the scope of the present invention is defined by the appended claims.

Abstract

A process for preparing an amphiphilic block copolymer, comprises the following steps: preparing a seeded microemulsion and a pre-emulsified monomer mixture; initiating the microemulsion polymerization of the seeded microemulsion; adding the pre-emulsified monomer mixture to obtain an acrylate polymer; and reacting the acrylate polymer with a hydrophilic monomer to obtain the amphiphilic block copolymer. The microemulsion polymerization system is thermodynamically stable, and the size of dispersed phase is small. Thus the polymer emulsion is stable with uniform particle sizedistribution. The block copolymer synthesized by said method has a good affinity for both hydrophilic fiber and hydrophobic pigment, and can be used to modify the surface of the natural fiber while plays a key role in stabilizing the organic pigment dispersion system.

Description

双亲嵌段共聚物的制备方法 技术领域  Method for preparing amphiphilic block copolymers
本发明涉及一种制备双亲嵌段共聚物的方法。 背景技术  The present invention relates to a process for preparing amphiphilic block copolymers. Background technique
双亲嵌段共聚物是指在同一高分子中既含有亲水链段， 又含有疏水链段 的共聚物。 与普通的聚合物相比， 3又亲嵌段共聚物具有许多特殊性质， 如表 面活性、 增溶性和增稠性。 The amphiphilic block copolymer refers to a copolymer containing both a hydrophilic segment and a hydrophobic segment in the same polymer. Compared to ordinary polymers, the 3 -individual block copolymer has many special properties such as surface activity, solubilization and thickening.
乳液聚合 (emulsion polymerization)是高分子合成过程中常用的一种合成 方法， 因为它以水作溶剂， 对环境十分有利。 乳液聚合反应是在乳化剂的作 用下并借助机械搅拌， 使单体在水中分散成乳状液， 由引发剂引发而进行的 聚合反应。  Emulsion polymerization is a synthetic method commonly used in the synthesis of polymers because it uses water as a solvent and is very beneficial to the environment. The emulsion polymerization is a polymerization in which an monomer is dispersed in water to form an emulsion under the action of an emulsifier and mechanically stirred, and is initiated by an initiator.
中国专利申请 CN 101870759 A公开了一种合成双亲嵌段共聚物的方法， 此方法釆用的是普通的乳液聚合法合成欢亲嵌段聚合物。 然而该乳液是浑浊 的不稳定体系， 其热力学体系不稳定， 且分散相尺寸较大， 使化学反应体系 不稳定， 对分散的颜料粒子尺寸的分布及稳定性有一定的影响。 发明内容  Chinese patent application CN 101870759 A discloses a method for synthesizing a amphiphilic block copolymer which is synthesized by a conventional emulsion polymerization method. However, the emulsion is a turbid unstable system, the thermodynamic system is unstable, and the size of the dispersed phase is large, which makes the chemical reaction system unstable, and has a certain influence on the distribution and stability of the dispersed pigment particle size. Summary of the invention
本发明要解决的技术问题是如何增强双亲嵌段共聚物体系的热力学稳定 性。  The technical problem to be solved by the present invention is how to enhance the thermodynamic stability of the amphiphilic block copolymer system.
为了解决上述技术问题， 本发明的一个方面提供一种制备双亲嵌段共聚 物的方法。  In order to solve the above technical problems, an aspect of the present invention provides a method of preparing an amphiphilic block copolymer.
根据本发明的制备双亲嵌段共聚物的方法包括如下步骤：  The method of preparing an amphiphilic block copolymer according to the present invention comprises the steps of:
制备种子微乳液和预乳化混合单体， 其中所述种子微乳液和所述预乳化 混合单体分别含有丙浠酸类疏水性单体；  Preparing a seed microemulsion and a pre-emulsified mixed monomer, wherein the seed microemulsion and the pre-emulsified mixed monomer respectively contain a propionic acid-based hydrophobic monomer;
引发种子微乳液进行微乳聚合反应， 加入预乳化混合单体以制备丙烯酸 酯聚合物，  Initiating a microemulsion of the seed to carry out microemulsion polymerization, adding a pre-emulsified mixed monomer to prepare an acrylate polymer,
将所制备的丙烯酸酯聚合物与亲水性单体反应， 得到双亲嵌段共聚物。 所述种子微乳液通过如下步骤制备： 将 60 75%的乳化剂与水混合， 通 过磁力搅拌得到乳液， 在超声搅拌下加入 25~40%的丙烯酸类疏水性单体， 得到种子微乳液。 The prepared acrylate polymer is reacted with a hydrophilic monomer to obtain an amphiphilic block copolymer. The seed microemulsion is prepared by the following steps: mixing 60 75% of the emulsifier with water, The mixture was stirred by magnetic force to obtain an emulsion, and 25-40% of an acrylic hydrophobic monomer was added under ultrasonic stirring to obtain a seed microemulsion.
其中， 乳化剂、 水和丙烯酸类疏水性单体的体积比优选为（1~2)： (25〜50)： (10~20)。 优选地， 磁力搅拌的转速为 300~330rad/min; 磁力搅拌的时间为 25〜35min。  Among them, the volume ratio of the emulsifier, water and the acrylic hydrophobic monomer is preferably (1 to 2): (25 to 50): (10 to 20). Preferably, the magnetic stirring speed is 300~330rad/min; the magnetic stirring time is 25~35min.
所述预乳化混合单体通过如下步骤制备： 将 25〜40%的乳化剂与水混合， 在磁力搅拌下加入 60〜75%的丙烯酸类疏水性单体， 得到预乳化混合单体。  The pre-emulsified mixed monomer is prepared by mixing 25 to 40% of an emulsifier with water, and adding 60 to 75% of an acrylic hydrophobic monomer under magnetic stirring to obtain a pre-emulsified mixed monomer.
其中乳化剂、 水、 丙烯酸类疏水性单体的体积比优选为（1~2)： (50-100): (50~80)。 优选地， 磁力搅拌的转速为 40( 30rad/min; 磁力搅拌的时间为 25~35min。  The volume ratio of the emulsifier, water, and acrylic hydrophobic monomer is preferably (1 to 2): (50-100): (50 to 80). Preferably, the magnetic stirring speed is 40 (30 rad/min; the magnetic stirring time is 25 to 35 min.
所述丙烯酸酯聚合物通过如下步骤制备： 向种子微乳液中加入碱、 催化 剂、配体和引发剂，引发微乳聚合；当种子微乳液呈现蓝光后升温至 80〜85°C ; 缓慢滴加预乳化混合单体； 2〜3h内滴完， 保温熟化 0.5〜lh后降温， 调节 pH 为 9〜11， 将反应产物抽真空， 在保护气体下冷却， 抽滤， 洗涤， 干燥， 得到 丙烯酸酯聚合物。  The acrylate polymer is prepared by adding a base, a catalyst, a ligand and an initiator to the seed microemulsion to initiate microemulsion polymerization; when the seed microemulsion exhibits blue light, the temperature is raised to 80 to 85 ° C; Pre-emulsified mixed monomer; after 2~3h, the temperature is lowered, the temperature is lowered after 0.5~lh, the pH is adjusted to 9~11, the reaction product is vacuumed, cooled under protective gas, filtered, washed and dried to obtain acrylate. polymer.
其中， 所用的种子微乳液、 预乳化混合单体、 碱、 催化剂、 配体、 引发 剂的体积比优选为（72〜144)： (101-182): (0.05-0.15): (1-2): (2-3): (1〜2)。  Wherein, the volume ratio of the seed microemulsion, the pre-emulsified mixed monomer, the base, the catalyst, the ligand, and the initiator is preferably (72 to 144): (101-182): (0.05-0.15): (1-2) ): (2-3): (1~2).
通过将丙烯酸酯聚合物与亲水性单体混合， 在保护气体下， 在水浴中反 应 50〜80mm, 冷却， 抽滤， 洗涤， 干燥， 得到双亲嵌段共聚物。  The amphiphilic block copolymer is obtained by mixing an acrylate polymer with a hydrophilic monomer, reacting in a water bath under a protective gas of 50 to 80 mm, cooling, suction filtration, washing, and drying.
其中， 优选水浴的温度为 25〜35°C。 优选地， 丙烯酸酯聚合物与亲水性 单体的体积比为 1: (2-4) 0 Among them, the temperature of the water bath is preferably 25 to 35 °C. Preferably, the volume ratio of the acrylate polymer to the hydrophilic monomer is 1: (2-4) 0
所述丙烯酸类疏水性单体优选选自丙烯酸曱酯、 丙烯酸乙酯、 丙烯酸异 丁酯、 甲基丙烯酸曱酯和甲基丙烯酸乙酯中的一种或多种。  The acrylic hydrophobic monomer is preferably selected from one or more of decyl acrylate, ethyl acrylate, isobutyl acrylate, decyl methacrylate and ethyl methacrylate.
所述亲水性单体优选选自丙烯酰胺、 甲基丙烯酰胺、 丙二醇和丙三醇中 的一种或多种。  The hydrophilic monomer is preferably selected from one or more of acrylamide, methacrylamide, propylene glycol, and glycerin.
所述引发剂选自过 ^f酸盐或过氧化氢， 或其衍生物。 优选地， 所述引发 剂为过 ^酸钠或过 υ酸钾。  The initiator is selected from the group consisting of perfuate or hydrogen peroxide, or a derivative thereof. Preferably, the initiator is sodium persodium or potassium perruthenate.
所述乳化剂选自仲烷基克酸钠、 十二烷基苯磺酸钠和曲拉通 X- 100中的 一种或多种。  The emulsifier is selected from one or more of sodium secondary alkyl ketone, sodium dodecyl benzene sulfonate and Triton X-100.
所述催化剂选自溴化铜、 溴化铁、 氯化铜和氯化铁中的一种或多种。 所述配体选自 2-甲基 -5-乙烯基吡啶、 3-乙烯基吡啶、 4,4-联吡啶和五曱 基二乙烯三胺中的一种。 The catalyst is selected from one or more of copper bromide, iron bromide, copper chloride, and ferric chloride. The ligand is selected from one of 2-methyl-5-vinylpyridine, 3-vinylpyridine, 4,4-bipyridine, and pentadecyldiethylenetriamine.
所述碱选自碳酸氢钠、 碳酸钠和氢氧化钠中的一种或多种。  The base is selected from one or more of sodium hydrogencarbonate, sodium carbonate, and sodium hydroxide.
所述保护气体为氮气或惰性气体。 所述惰性气体包括本领域中常见的那 些， 优选为氩气。  The shielding gas is nitrogen or an inert gas. The inert gas includes those commonly found in the art, preferably argon.
本发明通过釆用微乳液聚合法合成双亲嵌段共聚物。 微乳液聚合是将分 散相的珠滴尺寸分散的更小， 可使分散相的珠滴直径在 10~100nm范围内。 在微乳液体系中， 微珠滴是通过乳化剂与助乳化剂形成的一层复合薄膜和界 面层来维持其稳定的。  The present invention synthesizes amphiphilic block copolymers by microemulsion polymerization. Microemulsion polymerization is to disperse the droplet size of the dispersed phase to a smaller extent, so that the droplet diameter of the dispersed phase is in the range of 10 to 100 nm. In the microemulsion system, the microbeads are maintained by a layer of composite film and interface layer formed by an emulsifier and a co-emulsifier.
由于微乳液聚合具有热力学稳定的特性， 及微乳液中分散相尺寸较小的 特点， 本发明利用微乳液方法聚合得到的双亲嵌段聚合物体系热力学稳定， 分散相尺寸较小， 在 21.5〜33nm之间， 尺寸分布均勾且稳定。 用此方法合成 的双亲嵌段共聚物对亲水性的纤维和疏水性的颜料都有较好的亲和力， 可对 天然纤维表面进行改性， 同时对有机颜料分散体系有优异的稳定作用。 因此， 可用作液晶显示器中彩膜的颜料分散剂。  Due to the thermodynamically stable properties of the microemulsion polymerization and the small size of the dispersed phase in the microemulsion, the amphiphilic block polymer system obtained by the microemulsion method is thermodynamically stable, and the dispersed phase is small in size, at 21.5 to 33 nm. The size distribution is stable and stable. The amphiphilic block copolymer synthesized by this method has good affinity for hydrophilic fibers and hydrophobic pigments, can modify the surface of natural fibers, and has excellent stability to the organic pigment dispersion system. Therefore, it can be used as a pigment dispersant for a color film in a liquid crystal display.
因此， 本发明的另一个方面涉及根据本发明的方法所制备的双亲嵌段共 聚物。  Accordingly, another aspect of the invention relates to an amphiphilic block copolymer prepared according to the process of the invention.
本发明的再一个方面涉及上述双亲嵌段共聚物在颜料分散剂中的用途。 具体实施方式  Still another aspect of the invention relates to the use of the above parent block copolymer in a pigment dispersant. detailed description
以下实施例用于说明本发明， 但不用来限制本发明的范围。  The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
本发明所述的合成方法得到的双亲嵌段共聚物的各项性能可采用以下指 标进行检测：  The properties of the amphiphilic block copolymer obtained by the synthesis method of the present invention can be detected by the following indicators:
1. 共聚物粘度：采用 BROOKFIELD DV-C数显粘度计测定粘合剂乳液 的粘度。  1. Copolymer Viscosity: The viscosity of the binder emulsion was measured using a BROOKFIELD DV-C digital viscometer.
2. 共聚物粒子粒径及粒径分布： 采用 Nano ZS粒度仪测定嵌段共聚物 乳液的粒径与粒径分布。  2. Copolymer particle size and particle size distribution: The particle size and particle size distribution of the block copolymer emulsion were determined by a Nano ZS particle size analyzer.
3. 共聚物分子量及分布指数： 采用 Waters515凝胶渗透色谱测试聚合物分 子量及分子量分布， 测试温度为 25°C， 流动相为四氢呋喃， 流速为 1.0ml/min， 标准样为聚苯乙烯。  3. Copolymer molecular weight and distribution index: The molecular weight and molecular weight distribution of the polymer were measured by Waters 515 gel permeation chromatography at a test temperature of 25 ° C, a mobile phase of tetrahydrofuran, a flow rate of 1.0 ml/min, and a standard sample of polystyrene.
为了示例性但非限制性地说明本发明， 在以下实施例中， 丙烯酸类疏水 性单体选自丙烯酸甲酯、 丙烯酸异丁酯和曱基丙烯酸甲酯； 亲水性单体选自 丙烯酰胺、 甲基丙烯跣胺和丙二醇； 引发剂选自过硫酸钠和过 υ酸钾； 乳化 剂选自仲烷基硫酸钠和十二烷基苯磺酸钠； 催化剂选自溴化铜和溴化铁； 配 体选自 2-甲基 -5-乙婦基吡啶、 3-乙烯基吡啶和 4,4-联吡啶； 所用的碱选自碳酸 氬 ]和碳酸納。 For illustrative but non-limiting illustration of the invention, in the following examples, acrylic hydrophobic The monomer is selected from the group consisting of methyl acrylate, isobutyl acrylate and methyl methacrylate; the hydrophilic monomer is selected from the group consisting of acrylamide, methacrylamide and propylene glycol; and the initiator is selected from the group consisting of sodium persulfate and potassium perruthenate. The emulsifier is selected from the group consisting of sodium secondary alkyl sulfate and sodium dodecylbenzene sulfonate; the catalyst is selected from the group consisting of copper bromide and iron bromide; and the ligand is selected from the group consisting of 2-methyl-5-ethyl pyridine, 3-ethylene Pyridine and 4,4-bipyridine; the base used is selected from the group consisting of argon carbonate] and sodium carbonate.
为了示例性但非限制性地说明本发明， 在以下实施例中， 在制备种子微 乳液时，乳化剂、水、丙烯酸类疏水性单体的体积比为（1~2)： (25~50)： (10-20); 在制备预乳化混合单体时，乳化剂、水、丙烯酸类疏水性单体的体积比为（1~2)： (50-100): (50-80); 在制备丙烯酸酯聚合物时， 所用的种子 ¾乳液、 预乳化混 合单体、碱、催化剂、配体、引发剂的体积比为 (72〜144)： (101-182): (0.05-0.15): (1-2): (2-3): (1-2); 丙烯酸酯聚合物与亲水性单体的体积比为 1 : (2-4)„  To illustrate the invention by way of example and not limitation, in the following examples, in the preparation of the seed microemulsion, the volume ratio of the emulsifier, water, and acrylic hydrophobic monomer is (1~2): (25~50) ): (10-20); When preparing the pre-emulsified mixed monomer, the volume ratio of the emulsifier, water, and acrylic hydrophobic monomer is (1~2): (50-100): (50-80); In the preparation of the acrylate polymer, the volume ratio of the seed 3⁄4 emulsion, pre-emulsified mixed monomer, base, catalyst, ligand, and initiator used is (72 to 144): (101-182): (0.05-0.15) : (1-2): (2-3): (1-2); The volume ratio of acrylate polymer to hydrophilic monomer is 1: (2-4) „
在本文中， 如无具体说明， 使用的各种溶液中的溶剂均为常见的可用溶 剂， 只要其不影响本发明的反应或方法即可。 一般优选将使用的各物质与水 配制成水溶液， 即优选使用水作为溶剂。  Herein, the solvent in each of the solutions used is a common usable solvent unless otherwise specified, as long as it does not affect the reaction or method of the present invention. It is generally preferred to formulate each substance to be used in the form of an aqueous solution, i.e., water is preferably used as the solvent.
例如，优选将所用的乳化剂与丙烯酸类疏水性单体与水 (优选为去离子水) 配制成水溶液。  For example, the emulsifier used is preferably formulated into an aqueous solution with an acrylic hydrophobic monomer and water (preferably deionized water).
在本文中， 各物质的体积比可以指各物质的水溶液的体积比。 实施例 1  Herein, the volume ratio of each substance may refer to the volume ratio of the aqueous solution of each substance. Example 1
(1)将 4 ml仲烷基硫酸钠、 100 ml去离子水加入到带支管烧瓶中， 在转 速为 300rad/min的磁力搅拌下搅拌 30min得到乳液，在超声波搅拌下加入 30 ml丙烯酸甲酯得到半透明的种子微乳液；  (1) 4 ml of sodium secondary alkyl sulfate and 100 ml of deionized water were added to a flask with a branch tube, stirred under magnetic stirring at a speed of 300 rad/min for 30 minutes to obtain an emulsion, and 30 ml of methyl acrylate was added under ultrasonic stirring. Translucent seed microemulsion;
(2)将 2 ml仲烷基硫酸钠、 100 ml去离子水加入到带支管烧瓶中， 在转 速为 400rad/min的磁力搅拌下加入 60 ml丙烯酸甲酯， 磁力搅拌 30min得到 预乳化混合单体；  (2) 2 ml of sodium secondary alkyl sulfate and 100 ml of deionized water were added to a flask with a branch tube. 60 ml of methyl acrylate was added under magnetic stirring at a speed of 400 rad/min, and magnetically stirred for 30 minutes to obtain a pre-emulsified mixed monomer. ;
(3)向步骤 (1)得到的种子微乳液中加入 0.1 ml (浓度为 40%)碳酸钠、 2 ml 溴化铜 (浓度为 30%)、 2 ml 2-甲基 -5-乙婦基吡啶 (本身）、 2 ml过硫酸钠 (浓度 为 40%), 引发微乳聚合； 当种子微乳液呈现蓝光后升温至 85°C， 緩慢滴加 步骤 (2)得到的预乳化混合单体， 2h内滴完， 保温熟化 0.5h后降温， 调节 pH 至 10, 将反应产物密封抽真空， 使真空度达到 40kPa后再充氩气至常压， 反 复三次； 在氩气存在条件下， 将反应产物在冰水中冷却 20min, 至温度降温 至 20°C后对反应产物进行抽滤； 抽滤得到的固体用去离子水冲洗 3 次， 在 50 °C条件下真空烘千 4h得到丙烯酸酯聚合物； (3) To the seed microemulsion obtained in the step (1), 0.1 ml (concentration: 40%) sodium carbonate, 2 ml of copper bromide (concentration: 30%), and 2 ml of 2-methyl-5-ethylglycol are added. Pyridine (self), 2 ml of sodium persulfate (concentration: 40%), initiate microemulsion polymerization; when the seed microemulsion exhibits blue light, the temperature is raised to 85 ° C, and the pre-emulsified mixed monomer obtained in the step (2) is slowly added dropwise. After 2 hours, the temperature is lowered after 0.5 h of heat preservation, and the pH is adjusted to 10, and the reaction product is sealed and vacuumed, so that the vacuum degree reaches 40 kPa and then argon gas is filled to normal pressure. Three times; in the presence of argon, the reaction product was cooled in ice water for 20 min, and the reaction product was suction filtered after the temperature was lowered to 20 ° C; the solid obtained by suction filtration was rinsed 3 times with deionized water at 50 ° Under the condition of C, vacuum drying for 4 hours to obtain an acrylate polymer;
(4)将 1份 (250 ml)丙烯酸酯聚合物 (浓度为 20%的乙醇溶液)和 2份 (500 ml) 甲基丙烯酰胺 (浓度为 20%的乙醇溶液)在带支管烧瓶中混合， 密封抽真空， 使真空度达到 20kPa后再充氩气至常压， 反复三次； 在氩气存在的条件下， 将烧^ L丈入 30°C水浴中反应 50min， 取出烧 入冰水浴中冷却 30min， 至 温度降至 20°C， 转移出得到的反应产物并抽滤， 将得到的固体用去离子水沖 洗 4次后， 在 50°C条件下真空烘干 4h得到双亲嵌段共聚物。  (4) Mix 1 part (250 ml) of an acrylate polymer (20% ethanol solution) and 2 parts (500 ml) of methacrylamide (20% ethanol solution) in a tube flask, Seal the vacuum, make the vacuum reach 20kPa, then refill the argon to the normal pressure, repeat three times; in the presence of argon, the calcination into the 30 ° C water bath for 50min, take out into the ice water bath to cool After 30 min, the temperature was lowered to 20 ° C, and the obtained reaction product was transferred and suction filtered. The obtained solid was washed 4 times with deionized water, and then dried under vacuum at 50 ° C for 4 hours to obtain an amphiphilic block copolymer.
下文中使用物质对应的浓度如无另有说明 , 均与实施例 1中使用的浓度 相同。 实施例 2  The concentrations corresponding to the materials used hereinafter are the same as those used in Example 1, unless otherwise stated. Example 2
(1)将 2 ml十二烷基苯磺酸钠 (浓度为 60〜75%)、 50 ml去离子水加入到带 支管烧瓶中， 在转速为 330rad/min的磁力搅拌下搅拌 30min得到乳液， 在超 声波搅拌下加入 20 ml丙烯酸曱酯得到半透明的种子微乳液；  (1) 2 ml of sodium dodecylbenzenesulfonate (concentration: 60 to 75%) and 50 ml of deionized water were placed in a flask with a branch, and stirred under magnetic stirring at a speed of 330 rad/min for 30 minutes to obtain an emulsion. 20 ml of decyl acrylate was added under ultrasonic stirring to obtain a translucent seed microemulsion;
(2) 1 ml十二烷基^黄酸钠、 50 ml去离子水加入到带支管烧瓶中， 在 转速为 430rad/min的磁力搅拌下加入 50 ml丙烯酸甲酯， 磁力搅拌 30min得 到预乳化混合单体；  (2) 1 ml of sodium dodecyl sulphate and 50 ml of deionized water were added to a flask with a branch tube. 50 ml of methyl acrylate was added under magnetic stirring at a speed of 430 rad/min, and magnetically stirred for 30 min to obtain a pre-emulsified mixture. Monomer
(3)向步骤 (1)得到的种子微乳液中加入 0.05 ml碳酸钠、 1 ml溴化铜、 2 ml (3) Add 0.05 ml of sodium carbonate, 1 ml of copper bromide, 2 ml to the seed microemulsion obtained in the step (1).
3-乙烯基吡啶、 1 ml过硫酸钾， 引发微乳聚合； 当种子微乳液呈现蓝光后升 温至 85°C， 缓曼滴加步骤 (2)得到的预乳化混合单体， 2h 内滴完， 保温熟化 0.5h后降温， 调节 pH至 10， 将反应产物密封抽真空， 使真空度达到 40kPa 后再充氩气至常压， 反复三次； 在氩气存在条件下， 将反应产物在水水中冷 却 20min, 至温度降温至 20°C后对反应产物进行抽滤； 抽滤得到的固体用去 离子水冲洗 3次， 在 50Ό条件下真空烘干 4h得到丙烯酸酯聚合物； 3-vinylpyridine, 1 ml potassium persulfate, initiated microemulsion polymerization; when the seed microemulsion showed blue light, the temperature was raised to 85 ° C, and the pre-emulsified mixed monomer obtained in step (2) was added dropwise, and the mixture was dropped within 2 hours. After heating for 0.5h, the temperature is lowered, the pH is adjusted to 10, and the reaction product is sealed and vacuumed, so that the vacuum reaches 40 kPa, then the argon gas is refilled to normal pressure, and repeated three times; in the presence of argon, the reaction product is in water. After cooling for 20 min, the reaction product was suction filtered after the temperature was lowered to 20 ° C; the solid obtained by suction filtration was washed 3 times with deionized water, and vacuum-dried for 4 h under 50 Torr to obtain an acrylate polymer;
(4)将 1份 (100 ml)丙烯酸酯聚合物和 2份 (200 ml)丙二醇在带支管烧瓶中 混合， 密封抽真空， 使真空度达到 20kPa后再充氩气至常压， 反复三次； 在 氩气存在的条件下， 将烧瓶放入 30°C水浴中反应 50min, 取出烧瓶放入冰水 浴中冷却 30min, 至温度降至 20°C , 转移出得到的反应产物并抽滤， 将得到 的固体用去离子水冲洗 4次后， 在 50°C条件下真空烘干 4h得到双亲嵌段共 聚物。 实施例 3 (4) 1 part (100 ml) of acrylate polymer and 2 parts (200 ml) of propylene glycol were mixed in a branching flask, sealed and evacuated, and the vacuum was brought to 20 kPa, and then argon gas was added to normal pressure, and repeated three times; In the presence of argon, the flask was placed in a 30 ° C water bath for 50 min. The flask was taken out and placed in an ice water bath for 30 min. The temperature was lowered to 20 ° C. The obtained reaction product was transferred and suction filtered. The solid was washed 4 times with deionized water and then vacuum dried at 50 ° C for 4 h to obtain an amphiphilic block copolymer. Example 3
(1)将 6 ml仲烷基硫酸钠、 150 ml去离子水加入到带支管烧瓶中， 在转 速为 300rad/min的磁力搅拌下搅拌 35min得到乳液，在超声波搅拌下加入 45 ml甲基丙烯酸甲酯得到半透明的种子微乳液；  (1) Add 6 ml of sodium secondary alkyl sulfate and 150 ml of deionized water to a flask with a branch tube, stir for 35 minutes under magnetic stirring at a speed of 300 rad/min to obtain an emulsion, and add 45 ml of methacrylic acid under ultrasonic stirring. The ester gives a translucent seed microemulsion;
(2)将 3 ml仲烷基 酸钠、 150 ml去离子水加入到带支管烧瓶中， 在转 速为 400rad/min的磁力搅拌下加入 0 ml甲基丙烯酸甲酯， 磁力搅拌 30min 得到预乳化混合单体；  (2) Add 3 ml of sodium secondary alkylate and 150 ml of deionized water to the flask with a branch tube, add 0 ml of methyl methacrylate under magnetic stirring at a speed of 400 rad/min, and magnetically stir for 30 min to obtain pre-emulsified mixture. Monomer
(3)向步骤 (1)得到的种子微乳液中加入 0.15 ml碳酸氢钠、 2 ml溴化铁、 3 ml 4,4-联吡啶、 2 ml过硫酸钠， 引发微乳聚合； 当种子微乳液呈现蓝光后升 温至 80°C , 缓曼滴加步骤 (2)得到的预乳化混合单体， 3h 内滴完， 保温熟化 lh后降温， 调节 pH至 9， 将反应产物密封抽真空， 使真空度达到 40kPa后 再充氩气至常压， 反复三次； 在氩气存在条件下， 将反应产物在冰水中冷却 15mm, 至温度降温至 20Ό后对反应产物进行抽滤； 抽滤得到的固体用去离 子水冲洗 3次， 在 50°C条件下真空烘干 4h得到丙烯酸酯聚合物；  (3) adding 0.15 ml of sodium hydrogencarbonate, 2 ml of iron bromide, 3 ml of 4,4-bipyridine, 2 ml of sodium persulfate to the seed microemulsion obtained in the step (1) to initiate microemulsion polymerization; After the emulsion is blue light, the temperature is raised to 80 ° C, and the pre-emulsified mixed monomer obtained in the step (2) is added dropwise, and the mixture is dripped in 3 hours, the temperature is lowered after the heat preservation for 1 hour, the pH is adjusted to 9, and the reaction product is sealed and vacuumed. After the vacuum degree reaches 40 kPa, the argon gas is further filled to normal pressure and repeated three times; in the presence of argon, the reaction product is cooled in ice water for 15 mm, and the reaction product is subjected to suction filtration after the temperature is lowered to 20 Torr; the solid obtained by suction filtration Rinse with deionized water for 3 times, and vacuum dry at 50 ° C for 4 h to obtain an acrylate polymer;
(4)将 1份 (400 ml)丙烯酸酯聚合物和 2份 (800 ml)丙烯酰胺在带支管烧瓶 中混合， 密封抽真空， 使真空度达到 20kPa后再充氩气至常压， 反复三次； 在氩气存在下的条件下， 将烧瓶放入 25Ό水浴中反应 60min， 取出烧瓶放入 ；水水浴中冷却 30mm， 至温度降至 20°C， 转移出得到的反应产物并抽滤， 将 得到的固体用去离子水冲洗 4次后， 在 50°C条件下真空烘干 4h得到双亲嵌 段共聚物。 实施例 4  (4) Mix 1 part (400 ml) of acrylate polymer and 2 parts (800 ml) of acrylamide in a tube with a branch tube, seal and evacuate, and make the vacuum reach 20 kPa, then refill with argon to normal pressure, repeat three times. In the presence of argon, the flask was placed in a 25 Ό water bath for 60 min, the flask was taken out, cooled in a water bath for 30 mm, and the temperature was lowered to 20 ° C. The obtained reaction product was transferred and suction filtered. The obtained solid was washed 4 times with deionized water, and then vacuum-dried at 50 ° C for 4 hours to obtain an amphiphilic block copolymer. Example 4
( 1 )将 40 ml十二烷基苯磺酸钠、 1000 ml去离子水加入到带支管烧瓶中， 在转速为 320rad/min的磁力搅拌下搅拌 25min得到乳液，在超声波搅拌下加 入 300 ml丙烯酸异丁酯得到半透明的种子 £乳液； (1) Add 40 ml of sodium dodecylbenzene sulfonate and 1000 ml of deionized water to a flask with a branch tube, stir for 25 minutes under magnetic stirring at a speed of 320 rad/min to obtain an emulsion, and add 300 ml under ultrasonic stirring. Isobutyl acrylate gives a translucent seed emulsion;
(2)将 20 ml十二烷基苯磺酸钠、 1000 ml去离子水加入到带支管烧瓶中， 在转速为 420rad/mm 的磁力搅拌下加入 600 ml 丙烯酸异丁酯， 磁力搅拌 30mm得到预乳化混合单体； (2) Add 20 ml of sodium dodecylbenzene sulfonate and 1000 ml of deionized water to a flask with a branch, and add 600 ml of isobutyl acrylate under magnetic stirring at a speed of 420 rad/mm. 30mm to obtain a pre-emulsified mixed monomer;
(3)向步骤 (1)得到的种子微乳液中加入 1 ml碳酸钠、 20 ml溴化铜、 20 ml 3-乙烯基吡啶、 20 ml过硫酸钾， 引发微乳聚合； 当种子微乳液呈现蓝光后升 温至 85 °C , 緩' ft滴加步骤 (2)得到的预乳化混合单体， 2h 内滴完， 保温熟化 0.5h后降温， 调节 pH至 11 , 将反应产物密封抽真空， 使真空度达到 40kPa 后再充氮气至常压， 反复三次； 在氮气存在条件下， 将反应产物在水水中冷 却 20min， 至温度降温至 20°C后对反应产物进行抽滤； 抽滤得到的固体用去 离子水沖洗 3次， 在 50°C条件下真空烘干 4h得到丙烯酸酯聚合物；  (3) adding 1 ml of sodium carbonate, 20 ml of copper bromide, 20 ml of 3-vinylpyridine, and 20 ml of potassium persulfate to the seed microemulsion obtained in the step (1) to initiate microemulsion polymerization; when the seed microemulsion is present After blue light, the temperature is raised to 85 °C, and the pre-emulsified mixed monomer obtained by the step (2) is added dropwise. After 2 hours, the temperature is lowered after heating for 0.5 h, the pH is adjusted to 11, and the reaction product is sealed and evacuated. After the vacuum degree reaches 40 kPa, the nitrogen gas is further filled to normal pressure for three times; in the presence of nitrogen, the reaction product is cooled in water for 20 minutes, and the reaction product is subjected to suction filtration after the temperature is lowered to 20 ° C; Rinse with deionized water for 3 times, and vacuum dry at 50 ° C for 4 h to obtain an acrylate polymer;
(4)将 1份 (1200 ml)丙烯酸酯聚合物和 2份 (2400 ml)丙二醇在带支管烧瓶 中混合， 密封抽真空， 使真空度达到 20kPa后再充氮气至常压， 反复三次； 在氮气存在的条件下， 将烧瓶放入 25 °C水浴中反应 80min , 取出烧瓶放入冰 水浴中冷却 30mm, 至温度降至 20Ό , 转移出得到的反应产物并抽滤， 将得 到的固体用去离子水冲洗 4次后， 在 50°C条件下真空烘千 4h得到双亲嵌段 共聚物。  (4) Mix 1 part (1200 ml) of acrylate polymer and 2 parts (2400 ml) of propylene glycol in a tube with a branch tube, seal and evacuate, and make the vacuum degree reach 20 kPa, then refill with nitrogen to normal pressure, and repeat three times; In the presence of nitrogen, the flask was placed in a 25 ° C water bath for 80 min. The flask was taken out and placed in an ice water bath to cool for 30 mm until the temperature dropped to 20 Torr. The obtained reaction product was transferred and suction filtered, and the obtained solid was used. After rinsing with ion water for 4 times, the amphiphilic block copolymer was obtained by vacuum drying at 50 ° C for 4 h.
对实施例 1〜4得到的双亲嵌段共聚物进行性能测试， 结果见表 1 : 表 1  The performance of the amphiphilic block copolymers obtained in Examples 1 to 4 was tested. The results are shown in Table 1: Table 1
Figure imgf000008_0001
由表 1可知，本发明制备的双亲嵌段共聚物，其粒径分布宽度在 21.5〜33nm 之间， 分散相尺寸范围较小； 所得双亲嵌段共聚物对亲水性的纤维和疏水性 的颜料都有较好的亲和力。 发明人还通过对颜料的粘度和粒度的长期跟踪测试对其分散稳定性进行 了表征。 结果发现， 在半年至一年的时间内， 本发明方法所制得的双亲嵌段 共聚物用作颜料分散剂时， 颜料的粘度和粒度值几乎不发生明显的增长， 这 说明使用根据本发明方法所制得的双亲嵌段共聚物的颜料分散剂具有良好的 稳定性。 以上所述仅是本发明的示范性实施方式， 而非用于限制本发明的保护范 围， 本发明的保护范围由所附的权利要求确定。
Figure imgf000008_0001
It can be seen from Table 1 that the amphiphilic block copolymer prepared by the invention has a particle size distribution width of 21.5 to 33 nm and a small dispersed phase size range; the obtained amphiphilic block copolymer is hydrophilic to the fiber and hydrophobic. Pigments have good affinity. The inventors also characterized their dispersion stability by long-term follow-up testing of the viscosity and particle size of the pigment. As a result, it has been found that, when the amphiphilic block copolymer produced by the method of the present invention is used as a pigment dispersant in a period of six months to one year, the viscosity and particle size of the pigment hardly increase significantly, which indicates the use according to the present invention. The pigment dispersant of the amphiphilic block copolymer prepared by the method has good Stability. The above is only an exemplary embodiment of the present invention, and is not intended to limit the scope of the present invention. The scope of the present invention is defined by the appended claims.

Claims

权利要求书 Claim
1、 一种制备双亲嵌段共聚物的方法， 其中， 包括如下步骤： A method for preparing an amphiphilic block copolymer, comprising the steps of:
制备种子微乳液和预乳化混合单体， 其中所述种子微乳液和预乳化混合 单体分别含有丙烯酸类疏水性单体；  Preparing a seed microemulsion and a pre-emulsified mixed monomer, wherein the seed microemulsion and the pre-emulsified mixed monomer respectively contain an acrylic hydrophobic monomer;
引发所述种子微乳液进行微乳聚合反应， 加入所述预乳化混合单体以制 备丙烯酸酯聚合物，  Initiating the microemulsion of the seed to carry out microemulsion polymerization, adding the pre-emulsified mixed monomer to prepare an acrylate polymer,
将所制备的丙烯酸酯聚合物与亲水性单体反应， 得到双亲嵌段共聚物。 The prepared acrylate polymer is reacted with a hydrophilic monomer to obtain an amphiphilic block copolymer.
2、根据权利要求 1所述的方法，其中， 所述丙烯酸类疏水性单体优选选 自丙烯酸曱酯、 丙烯酸乙酯、 丙烯酸异丁酯、 甲基丙烯酸甲酯和甲基丙烯酸 乙酯中的一种或多种； 以及所述亲水性单体优选选自丙烯酰胺、 甲基丙烯酰 胺、 丙二醇和丙三醇中的一种或多种。 The method according to claim 1, wherein the acrylic hydrophobic monomer is preferably selected from the group consisting of decyl acrylate, ethyl acrylate, isobutyl acrylate, methyl methacrylate and ethyl methacrylate. One or more; and the hydrophilic monomer is preferably selected from one or more of acrylamide, methacrylamide, propylene glycol, and glycerin.
3、根据权利要求 1或 2所迷的方法， 其中， 所述种子微乳液通过如下步 骤制备： 将 60〜75%的乳化剂与水混合， 通过磁力搅拌得到乳液， 在超声搅 拌下加入 25〜40%的丙烯酸类疏水性单体， 得到所述种子微乳液。  3. The method according to claim 1 or 2, wherein the seed microemulsion is prepared by the following steps: mixing 60 to 75% of the emulsifier with water, obtaining the emulsion by magnetic stirring, and adding 25~ under ultrasonic stirring. 40% of an acrylic hydrophobic monomer gives the seed microemulsion.
4、根据权利要求 3所述的方法， 其中， 所述乳化剂、 所述水与所述丙烯 酸类疏水性单体的体积比为（1〜2)： (25-50): (10~20)。 The method according to claim 3, wherein the emulsifier, the volume ratio of the water to the acrylic hydrophobic monomer is (1 to 2 ): (25-50): (10~ 2) 0).
5、 根据权利要求 3 或 4 所述的方法， 其中， 所述磁力搅拌的转速为 300~330rad/min, 所述磁力搅拌的时间为 25~35mm。  5. The method according to claim 3 or 4, wherein the magnetic stirring speed is 300 to 330 rad/min, and the magnetic stirring time is 25 to 35 mm.
6、根据权利要求 1-5中任一项所述的方法， 其中， 所述预乳化混合单体 通过如下步骤制备： 将 25 40%的乳化剂与水混合， 在磁力搅拌下加入 60〜75%的丙烯酸类疏水性单体， 得到所述预乳化混合单体。  The method according to any one of claims 1 to 5, wherein the pre-emulsified mixed monomer is prepared by the following steps: mixing 25 40% of the emulsifier with water, and adding 60 to 75 under magnetic stirring % of the acrylic hydrophobic monomer, the pre-emulsified mixed monomer is obtained.
7、根据权利要求 6所述的方法， 其中， 所述乳化剂、 所述水与所述丙烯 酸类疏水性单体的体积比为（1~2)： (50-100): (50-80) 0 The method according to claim 6, wherein the emulsifier, the volume ratio of the water to the acrylic hydrophobic monomer is (1 to 2 ): (50-100): (50-80) ) 0
8、 根据权利要求 6 或 7 所述的方法， 其中， 所述磁力搅拌的转速为 8. The method according to claim 6 or 7, wherein the magnetic stirring speed is
400~430rad/min, 所述磁力搅拌的时间为 25〜35mm。 400~430rad/min, the magnetic stirring time is 25~35mm.
9、根据权利要求 3-8所述的方法，其中，所述乳化剂选自仲烷基硫酸钠、 十二烷基苯磺酸钠和曲拉通 X-100中的一种或多种。  9. A method according to claims 3-8 wherein the emulsifier is selected from one or more of the group consisting of sodium secondary alkyl sulfate, sodium dodecylbenzene sulfonate and Triton X-100.
10、 根据权利要求 1-9中任一项所述的方法， 其中， 所述丙烯酸酯聚合 物通过如下步骤制备： 向所述种子微乳液中加入碱、催化剂、 配体和引发剂， 引发微乳聚合； 当种子微乳液呈现蓝光后升温至 80〜85 °C ; 緩慢滴加所述预 乳化混合单体； 2〜3h内滴完， 保温熟化 0.5〜lh后降温， 调节 pH为 9〜11 , 将反应产物抽真空， 在保护气体下冷却， 抽滤， 洗涤， 干燥， 得到丙烯酸酯 聚合物。 The method according to any one of claims 1 to 9, wherein the acrylate polymer is prepared by adding a base, a catalyst, a ligand and an initiator to the seed microemulsion, Initiating microemulsion polymerization; when the seed microemulsion exhibits blue light, the temperature is raised to 80~85 °C; the pre-emulsified mixed monomer is slowly added dropwise; after 2~3h, the temperature is lowered, the temperature is lowered after 0.5~lh, and the pH is adjusted to 9 ～11, the reaction product was evacuated, cooled under a protective gas, suction filtered, washed, and dried to obtain an acrylate polymer.
11、根据权利要求 10所述的方法， 其中， 所用的种子微乳液、 预乳化混 合单体、 碱、 催化剂、 配体和引发剂的体积比为（72~144)： (101-182): (0.05-0.15): (1-2): (2-3): (1~2)。  The method according to claim 10, wherein the volume ratio of the seed microemulsion, the pre-emulsified mixed monomer, the base, the catalyst, the ligand and the initiator used is (72 to 144): (101-182): (0.05-0.15): (1-2): (2-3): (1~2).
12、根据权利要求 10或 11所述的方法，其中， 所述催化剂选自溴化铜、 溴化铁、 氯化铜和氯化铁中的一种或多种； 所述配体选自 2-甲基 -5-乙婦基吡 啶、 3-乙婦基吡啶、 4,4-联吡啶和五甲基二乙烯三胺中的一种； 所述碱选自碳 酸氢钠、 碳酸钠和氢氧化钠中的一种或多种； 所述保护气体选自氮气和惰性 气体。  The method according to claim 10 or 11, wherein the catalyst is selected from one or more of copper bromide, iron bromide, copper chloride and iron chloride; the ligand is selected from 2 - one of methyl-5-ethyl pyridine, 3-ethyl pyridine, 4,4-bipyridine and pentamethyldiethylene triamine; the base is selected from the group consisting of sodium hydrogencarbonate, sodium carbonate and hydrogen One or more of sodium oxide; the shielding gas is selected from the group consisting of nitrogen and an inert gas.
13、 根据权利要求 1-12中任一项所述的方法， 其中， 通过将丙烯酸酯聚 合物与亲水性单体混合， 在保护气体下， 在水浴中反应 50〜80min, 冷却， 抽 滤， 洗涤， 干燥， 得到双亲嵌段共聚物。  The method according to any one of claims 1 to 12, wherein the acrylate polymer is mixed with a hydrophilic monomer, reacted in a water bath for 50 to 80 minutes under a protective gas, cooled, and filtered. Washed and dried to obtain an amphiphilic block copolymer.
14、 据权利要求 13所述的方法， 其中， 水浴的温度为 25~35°C。  14. The method of claim 13 wherein the temperature of the water bath is between 25 and 35 °C.
15、 根据权利要求 13或 14所述的方法， 其中， 丙烯酸酯聚合物与亲水 性单体的体积比为 1 : (2〜4)。  The method according to claim 13 or 14, wherein the volume ratio of the acrylate polymer to the hydrophilic monomer is 1: (2 to 4).
16、根据权利要求 1-15中任一项所述的制备双亲嵌段共聚物的方法所制 备的双亲嵌段共聚物。  The amphiphilic block copolymer prepared by the process for producing an amphiphilic block copolymer according to any one of claims 1 to 15.
17、 根据权利要求 16所述的双亲嵌段共聚物作为颜料分散剂的应用。  17. Use of an amphiphilic block copolymer according to claim 16 as a pigment dispersant.
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