WO2015074341A1 - 一种以酚醛树脂为壁材的环氧微胶囊的制备方法 - Google Patents

一种以酚醛树脂为壁材的环氧微胶囊的制备方法 Download PDF

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WO2015074341A1
WO2015074341A1 PCT/CN2014/071279 CN2014071279W WO2015074341A1 WO 2015074341 A1 WO2015074341 A1 WO 2015074341A1 CN 2014071279 W CN2014071279 W CN 2014071279W WO 2015074341 A1 WO2015074341 A1 WO 2015074341A1
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preparation
wall material
epoxy
phenol
phenolic resin
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朱光明
周玉明
汤皎宁
董必钦
王险峰
韩宁旭
邢峰
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Shenzhen University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking

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  • the invention relates to the field of self-repairing materials, in particular to the field of self-repairing concrete, in particular to a method for preparing epoxy microcapsules using phenolic resin as a wall material.
  • the self-healing material is a smart material that can repair its own defects such as voids and cracks.
  • a main method for realizing the self-repairing function of materials is to pre-embed the repairing agent in the matrix material. When the matrix material is cracked or void due to some physical or chemical factors, the repairing agent will be automatically released. Self-repairing defects.
  • microcracks There are a large number of microcracks in the concrete members, and these microcracks are difficult to be detected and manually repaired. In humid atmospheres, especially in coastal environments, their presence accelerates the corrosion of steel bars, reduces the durability of concrete works, and shortens project life.
  • Phenolic resin is a polymer widely used in the industry, which is obtained by a polycondensation reaction of a phenol with an aldehyde. According to a synthesis method, a phenol resin is classified into a Novolak resin and a Resole resin. Novolak resin requires the addition of a curing agent to crosslink to form the wall of the capsule, while the Resole resin can be cured to form a wall by heating and conditioning. Since the curing agent of Novolak resin also cures the epoxy, a resole resin such as a phenolic resin is generally used as a phenolic precursor to prepare an epoxy microcapsule with a phenolic resin as a wall material.
  • the first-order Resole resin is sensitive to pH when it is acidified and cured.
  • the inappropriate pH value often does not form a phenolic capsule wall.
  • a large amount of methylol in the resole resin is easy to be epoxy.
  • the epoxy end group of the resin undergoes an addition reaction to cure the epoxy. Therefore, it is difficult to prepare an epoxy microcapsule using a phenol resin as a wall material by using a resole resin as a precursor.
  • the object of the present invention is to disclose a method for preparing an epoxy microcapsule using a phenolic resin as a wall material to solve the deficiencies of the prior art.
  • the technical solution adopted by the present invention to solve the above technical problem is to provide a method for preparing an epoxy microcapsule using a phenolic resin as a wall material, comprising the following steps:
  • step S3 adding polyphenol, curing accelerator, pH adjuster II to the solution obtained in step S2, adjusting the pH to 2 ⁇ 4, reacting for 2 ⁇ 3 hours, cooling, standing, filtering, drying, then obtaining phenolic resin Epoxy microcapsules for wall materials.
  • the beneficial effects of the technical scheme of the present invention are as follows: (1) selecting a surfactant having a specific molecular structure as an emulsifier, which not only can emulsify the epoxy resin well under the reaction condition, but also is a good cover for the epoxy group.
  • the agent prevents the reaction of the epoxy group with a large amount of methylol groups contained in the phenolic resin precursor A-step Resole resin; (2) the specific process conditions of the present invention also effectively prevent the curing reaction between the core material and the wall material It ensures the formation of microcapsules; (3) phenolic resin is obtained by polycondensation reaction of phenol and aldehyde, and the process is simple and inexpensive; the cured phenolic is a highly crosslinked brittle structure polymer, which meets the requirements of stress triggering. (4) The epoxy microcapsules prepared by the method with phenolic resin as the wall material have good morphology and high coverage.
  • Example 1 is an SEM image of an epoxy microcapsule prepared by using a phenol resin as a wall material in Example 1 of the present invention
  • Example 2 is an SEM image of an epoxy microcapsule prepared by using a phenol resin as a wall material in Example 2 of the present invention.
  • the object of the present invention is to disclose a method for preparing an epoxy microcapsule using a phenolic resin as a wall material to solve the deficiencies of the prior art.
  • the technical solution adopted by the present invention to solve the above technical problem is to provide a method for preparing an epoxy microcapsule using a phenolic resin as a wall material, comprising the following steps:
  • step S3 adding polyphenol, curing accelerator, pH adjuster II to the solution obtained in step S2, adjusting the pH to 2 ⁇ 4, reacting for 2 ⁇ 3 hours, cooling, standing, filtering, drying, then obtaining phenolic resin Epoxy microcapsules for wall materials.
  • the emulsifier in the step S1 is a polyhydroxy compound selected from at least one of polyvinyl alcohol, polyacryl alcohol, polysaccharide, and alkyl glycoside. Further, the mass ratio of the epoxy resin, the emulsifier, and the water in the step S1 is 1: 0.05 ⁇ 0.2: 10 ⁇ 30; for sufficient emulsification, the stirring time is 30 ⁇ 60 min.
  • the phenol in the step S2 is at least one selected from the group consisting of phenol, cresol and mixed cresol, preferably phenol;
  • the aldehyde is at least one selected from the group consisting of formaldehyde, paraformaldehyde, furfural and acetaldehyde, preferably formaldehyde.
  • the molar ratio of phenol to aldehyde is 1: 1.2 ⁇ 2.5, preferably the molar ratio is 1:2; the mass ratio of the phenol to the epoxy resin in the step S1 is 1:1.5 ⁇ 12.
  • the pH adjuster I in the step S2 is preferably 5 A wt% aqueous ammonia solution is adjusted so that the pH of the reaction solution in this step is 7-9.
  • the polyphenol in step S3 is preferably resorcinol, tea polyphenol, and the amount of the polyphenol is 5.5 to 30 of the aldehyde in step S2. %; the curing accelerator is ammonium chloride, the mass fraction of the curing accelerator is 10-40% of the aldehyde in S2; the pH adjuster II in step S3 is preferably 3.7 The aqueous solution of wt% hydrochloric acid is adjusted so that the pH of the reaction solution in this step is 2 to 4.
  • the epoxy microcapsules prepared by the present invention having a phenolic resin as a wall material have a good morphology and a high coating ratio, and the present invention will be further explained below in conjunction with specific examples.
  • reaction liquid After the reaction liquid is cooled, it is allowed to stand 30 Min, filter, dry at 40 ⁇ 50 °C for 1-2 hours to obtain the target product. Scanning electron microscope observation, as shown in Figure 1, the formed microcapsule particles in good shape, high coverage, particle size between 30 ⁇ 60 microns.
  • Example 2 was essentially the same as Example 1, except that the pH was adjusted to 8 in the stage A resole phenolic resin formation stage and the pH was adjusted to 3 in the cross-linking curing stage. Specific steps are as follows:
  • the reaction liquid After the reaction liquid is cooled, it is allowed to stand 30 Min, filter, dry at 40 ⁇ 50 °C for 1-2 hours to obtain the target product. Scanning electron microscope observation, as shown in Fig. 2, the microcapsules formed have a particle size of 10 to 40 ⁇ m, and the morphology is good, and the coating ratio is high. Compared with the product obtained in Example 1, the capsule wall is wrinkled, and there is no The smoothness of Example 1.

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  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Abstract

一种以酚醛树脂为壁材的环氧微胶囊的制备方法，包括以下步骤：将环氧树脂、乳化剂、水混合，搅拌制成乳液；在所述乳液中加入酚、醛和pH值调节剂I，调节pH值至7∼9，搅拌；在所得溶液中再加入多元酚、固化促进剂、pH值调节剂II，调节pH值至2∼4，反应2∼3小时，经冷却、静置、过滤、干燥，即得以酚醛树脂为壁材的环氧微胶囊。本制备方法避免了壁材与芯材之间发生的固化反应，成功地合成了形态好、包覆率高的以酚醛树脂为壁材的环氧微胶囊。

Description

一种以酚醛树脂为壁材的环氧微胶囊的制备方法 技术领域
本发明涉及自修复材料领域，尤其涉及到自修复混凝土领域，具体地说，涉及一种以酚醛树脂为壁材的环氧微胶囊的制备方法。
 背景技术
自修复材料是一种智能材料，它能自主修复自身出现的空洞、裂纹等缺陷。在技术上，实现材料自主修复功能的一个主要方法是：将修复剂预先包埋在基体材料中，当基体材料因某种物理或化学因素而产生裂纹或者空洞时，修复剂将被自动释放，自主修补缺陷。混凝土构件中存在大量的微裂纹，且这些微裂纹难以被一一探测和进行人工修补。如在潮湿的大气环境，尤其是滨海环境下，它们的存在将加速钢筋的锈蚀，降低混凝土工程的耐久性，缩短工程寿命。
酚醛树脂是工业上广泛使用的一种聚合物，它通过酚与醛的缩聚反应而得，按合成方法，酚醛树脂分Novolak树脂和Resole树脂。Novolak树脂需要加入固化剂才能交联形成囊壁，而Resole树脂只需在加热调酸即可固化形成囊壁。由于Novolak树脂的固化剂也会使环氧固化，故一般选用甲阶Resole树脂作为酚醛前驱体制备以酚醛树脂为壁材的环氧微胶囊。甲阶Resole树脂在调酸固化时对pH值很敏感，不合适的pH值往往形不成酚醛囊壁；在加热促进其固化反应时，甲阶Resole树脂中大量的羟甲基，易与环氧树脂的环氧端基发生加成反应，使环氧固化，因此，以甲阶Resole树脂为前驱体制备以酚醛树脂为壁材的环氧微胶囊较为困难。
 技术问题
本发明的目的在于公开一种以酚醛树脂为壁材的环氧微胶囊的制备方法，以解决现有技术的不足。
技术解决方案
本发明解决上述技术问题所采用的技术方案为是提供一种以酚醛树脂为壁材的环氧微胶囊的制备方法，包括以下步骤：
S1：将环氧树脂、乳化剂、水混合，搅拌制成乳液；
S2：在所述乳液中加入酚、醛和pH值调节剂I，调节pH值至7~9，搅拌；
S3：在步骤S2所得溶液中加入多元酚、固化促进剂、pH值调节剂II，调节pH值至2~4，反应2~3小时，经冷却、静置、过滤、干燥，即得以酚醛树脂为壁材的环氧微胶囊。
 有益效果
本发明技术方案的有益效果在于：（1）选择具有特定分子结构的表面活性剂作为乳化剂，在反应条件下它不仅能很好地乳化环氧树脂，而且是环氧基团很好的掩护剂，阻止环氧基团与酚醛树脂前体甲阶Resole树脂中所含有的大量羟甲基的反应；（2）本发明特定工艺条件也有效地避免了芯材与壁材之间发生固化反应，保障了微胶囊的生成；（3）酚醛树脂是它通过酚与醛的缩聚反应而得，工艺简单、价格低廉；固化的酚醛是高度交联的脆性体结构聚合物，符合应力触发的要求；（4）本法所制得以酚醛树脂为壁材的环氧微胶囊形态好、包覆率高。
附图说明
图1是本发明实施例1所制备以酚醛树脂为壁材的环氧微胶囊的SEM图；
图2是本发明实施例2所制备以酚醛树脂为壁材的环氧微胶囊的SEM图。
 本发明的实施方式
为了使本发明所要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明的目的在于公开一种以酚醛树脂为壁材的环氧微胶囊的制备方法，以解决现有技术的不足。
本发明解决上述技术问题所采用的技术方案为是提供一种以酚醛树脂为壁材的环氧微胶囊的制备方法，包括以下步骤：
S1：将环氧树脂、乳化剂、水混合，搅拌制成乳液；
S2：在所述乳液中加入酚、醛和pH值调节剂I，调节pH值至7~9，搅拌；
S3：在步骤S2所得溶液中加入多元酚、固化促进剂、pH值调节剂II，调节pH值至2~4，反应2~3小时，经冷却、静置、过滤、干燥，即得以酚醛树脂为壁材的环氧微胶囊。
其中，步骤S1中乳化剂为多羟基化合物，选自聚乙烯醇、聚丙烯醇、多聚糖、烷基糖苷中的至少一种。进一步地，步骤S1中环氧树脂、乳化剂、水的质量比为1: 0.05~0.2 : 10~30；为充分乳化，所述搅拌的时间为30~60 min。
其中，步骤S2中所述酚选自苯酚、甲酚、混甲酚中的至少一种，优选苯酚；所述醛选自甲醛、多聚甲醛、糠醛、乙醛中的至少一种，优选甲醛；酚和醛的摩尔比为1: 1.2~2.5，优选摩尔比为1: 2；酚与步骤S1中环氧树脂的质量比为1:1.5~12。该步骤S2中pH值调节剂I优选5 wt%氨水水溶液，调节使该步骤反应溶液pH值为7~9。
其中，步骤S3中多元酚优选为间苯二酚、茶多酚，多元酚的物质的量分数为步骤S2中所述醛的5.5~30 %；固化促进剂为氯化铵，固化促进剂的质量分数为S2中所述醛的10~40 %；该步骤S3中pH值调节剂II优选3.7 wt%盐酸水溶液，调节使该步骤反应溶液的pH值为2~4。
本发明所制得以酚醛树脂为壁材的环氧微胶囊形态好、包覆率高，以下结合具体实施例进一步解释本发明。
实施例1
在250 ml的三口烧瓶中，加入10 ml 5 wt%的聚乙烯醇（PVA-1788）水溶液，100 ml去离子水，搅拌均匀后，缓慢加入2.1 g（0.022 mol）苯酚，待其溶解后，用氨水（NH3•H2O）将溶液的pH值调到7，随后缓慢加入6.5 g环氧树脂，在高速搅拌乳化60 min，转速大于1000 rpm，得均一稳定的水包油环氧乳液。
将转速调到400 rpm，向乳液里面缓慢的滴加3.35 g（0.041 mol）质量浓度为37 %的甲醛（CH2O）水溶液，同时将温度缓慢升到65℃，保温反应3 h，形成水溶性的甲阶Resole酚醛树脂。随后用3.7 %的盐酸溶液将pH值调至4，加入0.5 g间苯二酚，反应30 min，再加入0.5 g NH4Cl，继续反应2.5 h，形成以酚醛树脂为壁材的环氧微胶囊。
待反应液冷却后静置30 min，过滤，40~50℃干燥1~2小时，得目标产物。扫描电子显微镜观察，如图1所示，所形成的微胶囊颗粒形态良好，包覆率高，粒径在30~60微米之间。
实施例2
实施例2与实施例1过程基本相同，只是在甲阶Resole酚醛树脂形成阶段将pH调节至8，在交联固化阶段将pH调节至3。具体步骤如下：
在250 ml的三口烧瓶中，加入10 ml 5 wt%的聚乙烯醇（PVA）水溶液，100 ml去离子水，搅拌均匀后，缓慢加入2.1 g（0.022 mol）苯酚，待其溶解后，用氨水（NH3•H2O）将溶液的pH值调到8，随后缓慢加入6.5 g环氧树脂，在高速搅拌乳化60 min，转速大于1000 rpm，得均一稳定的水包油环氧乳液。
将转速调到400 rpm，向乳液里面缓慢的滴加3.35 g（0.041 mol）质量浓度为37 %的甲醛（CH2O）水溶液，同时将温度缓慢升到65℃，保温反应3 h，形成水溶性的甲阶Resole酚醛树脂。随后用3.7 %的盐酸溶液将pH值调至3，加入0.5 g间苯二酚，反应30 min，再加入0.5 g NH4Cl，继续反应2.5 h，形成以酚醛树脂为壁材的环氧微胶囊。
待反应液冷却后静置30 min，过滤，40~50℃干燥1~2小时，得目标产物。扫描电子显微镜观察，如图2所示，所形成微胶囊粒径在10~40微米之间，形态良好，包覆率高，与实施例1所制得产物相比，囊壁起皱，没有实施例1的光滑。
实施例3
实施例3与实施例1过程的主要不同点是使用烷基糖苷（Alkyl Polyglycoside，APG）作为乳化剂。具体步骤如下：
在250 ml的三口烧瓶中，加入10 ml 5 wt%的APG水溶液，100 ml去离子水，搅拌均匀后，缓慢加入2.1 g（0.022 mol）苯酚，待其溶解后，用氨水（NH3•H2O）将溶液的pH值调到8，随后缓慢加入6.5 g环氧树脂，在高速搅拌乳化60 min，转速大于1000 rpm，得均一稳定的水包油环氧乳液。
将转速调到400 rpm，向乳液里面缓慢的滴加3.35 g（0.041 mol）质量浓度为37%的甲醛（CH2O）水溶液，同时将温度缓慢升到65℃，保温反应3h，形成水溶性的甲阶Resole酚醛树脂。随后用3.7%的盐酸溶液将pH值调至4，加入0.5 g间苯二酚，反应30 min，再加入0.5 g NH4Cl，继续反应2.5 h，形成以酚醛树脂为壁材的环氧微胶囊。
待反应液冷却后静置30min，过滤，40~50℃干燥1~2小时，得目标产物。扫描电子显微镜观察，胶囊囊壁光滑，粒径在50~80微米之间。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种以酚醛树脂为壁材的环氧微胶囊的制备方法，包括以下步骤：
    S1：将环氧树脂、乳化剂、水混合，搅拌制成乳液；
    S2：在所述乳液中加入酚、醛和pH值调节剂I，调节pH值至7 ~ 9，搅拌；
    S3：在步骤S2所得溶液中加入多元酚、固化促进剂、pH值调节剂II，调节pH值至2 ~ 4，反应2~3小时，经冷却、静置、过滤、干燥，即得以酚醛树脂为壁材的环氧微胶囊。
  2. 根据权利要求1所述的制备方法，其特征在于，所述乳化剂为多羟基化合物，所述多羟基化合物选自聚乙烯醇、聚丙烯醇、多聚糖、烷基糖苷中的一种。
  3. 根据权利要求1或2所述的制备方法，其特征在于，步骤S1中所述环氧树脂、乳化剂、水的质量比为1: 0.05~ 0.2 : 10~30。
  4. 根据权利要求1所述的制备方法，其特征在于，步骤S2中所述酚选自苯酚、甲酚、混甲酚中的至少一种；所述醛选自甲醛、多聚甲醛、糠醛、乙醛中的至少一种；所述酚与所述醛的摩尔比为1: 1.2~2.5。
  5. 根据权利要求1所述的制备方法，其特征在于，步骤S2中所述酚与步骤S1中所述环氧树脂的质量比为1: 1.5~12。
  6. 根据权利要求1所述的制备方法，其特征在于，步骤S3中所述多元酚为间苯二酚、茶多酚，所述多元酚的质量分数为步骤S2中所述醛的5.5~30 %。
  7. 根据权利要求1所述的制备方法，其特征在于，步骤S3中所述固化促进剂为氯化铵，所述固化促进剂的质量分数为步骤S2中所述醛的10~40%。
  8. 根据权利要求1所述的制备方法，其特征在于，步骤S2中所述pH值调节剂I为5 wt%氨水水溶液，所述pH值调节剂II为3.7 wt%盐酸水溶液。
  9. 根据权利要求1所述的制备方法，其特征在于，步骤S1中所述搅拌的时间为30~60 min。
  10. 一种根据权利要求1~9中任一项所述的制备方法所制备的以酚醛树脂为壁材的环氧微胶囊，其特征在于，所述微胶囊的芯材和壁材的质量比为0.5~3 : 1。
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CN120854050A (zh) * 2025-09-25 2025-10-28 长春职业技术大学 一种高性能多功能电缆及其制备方法

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CN120854050B (zh) * 2025-09-25 2025-11-28 长春职业技术大学 一种高性能多功能电缆及其制备方法

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