阅读说明：本技术 一种纳米核壳粒子增韧改性环氧树脂的制备工艺 (Preparation process of nano core-shell particle toughening modified epoxy resin ) 是由 陈阳 于 2021-09-23 设计创作，主要内容包括：本发明提供了一种纳米核壳粒子增韧改性环氧树脂的制备工艺,包括如下步骤：步骤一：将30-70份的环氧树脂、0.1-0.3份的分散剂加入到80-120份的溶剂中；步骤二：将1-20份的纳米核壳粒子加入到上述的树脂溶液中,再经过高速分散机分散；步骤三：在进行继续高速搅拌,边搅拌边滴加0.06-0.1份的催化剂溶液；步骤四：在对上述产品进行抽真空去除溶剂,得到壳核粒子改性环氧树脂。本发明克服了现有技术的不足,设计合理,结构紧凑,本发明专利操作步骤简单,通过对核壳粒子表面进行反应接枝,核壳表面羧基与环氧基反应,可以将核壳表面改性为与环氧树脂相容性更好的结构,提高了环氧树脂的冲击强度、拉伸强度和剥离强度。(The invention provides a preparation process of a nano core-shell particle toughening modified epoxy resin, which comprises the following steps: the method comprises the following steps: adding 30-70 parts of epoxy resin and 0.1-0.3 part of dispersant into 80-120 parts of solvent; step two: adding 1-20 parts of nano core-shell particles into the resin solution, and dispersing by using a high-speed dispersion machine; step three: continuously stirring at high speed, and dropwise adding 0.06-0.1 part of catalyst solution while stirring; step four: and vacuumizing the product to remove the solvent to obtain the shell-core particle modified epoxy resin. The invention overcomes the defects of the prior art, has reasonable design and compact structure, has simple operation steps, can modify the surface of the core-shell into a structure with better compatibility with the epoxy resin by carrying out reaction grafting on the surface of the core-shell particles and reacting carboxyl on the surface of the core-shell with epoxy groups, and improves the impact strength, the tensile strength and the peel strength of the epoxy resin.)

1. A preparation process of a nano core-shell particle toughening modified epoxy resin is characterized by comprising the following steps:

the method comprises the following steps: adding 30-70 parts of epoxy resin and 0.1-0.3 part of dispersant into 80-120 parts of solvent, and fully and uniformly stirring;

step two: adding 1-20 parts of nano core-shell particles into the resin solution, and dispersing by using a high-speed dispersion machine to enable the particles to be in a monodisperse state to obtain a suspension;

step three: continuously stirring at high speed, heating to 60-100 ℃ for reflux, dropwise adding 0.06-0.1 part of catalyst solution while stirring, and continuously reacting for 1 hour;

step four: and vacuumizing the product to remove the solvent to obtain the shell-core particle modified epoxy resin.

2. The preparation process of the nano core-shell particle toughening-modified epoxy resin according to claim 1, characterized in that: the epoxy resin is bisphenol F type epoxy resin or bisphenol A type epoxy resin.

3. The preparation process of the nano core-shell particle toughening-modified epoxy resin according to claim 1, characterized in that: the radius of the nanometer core-shell particle is between 50 nm and 200 nm.

4. The preparation process of the nano core-shell particle toughening-modified epoxy resin according to claim 1, characterized in that: the dispersant is one or more of BYK-109, BYK-163, BYK-166, BYK-220S, BYK-2100 and BYK-2105.

5. The preparation process of the nano core-shell particle toughening-modified epoxy resin according to claim 1, characterized in that: the solvent is one or more of acetone, toluene, cyclohexanone, cyclohexane, toluene, xylene, ethyl acetate and butyl acetate.

6. The preparation process of the nano core-shell particle toughening-modified epoxy resin according to claim 1, characterized in that: the catalyst is one or more of triphenylphosphine, triphenylphosphine oxide, DBU salt and DBN salt.

7. The preparation process of the nano core-shell particle toughening-modified epoxy resin according to claim 1, characterized in that: the content of the core-shell particles is 15-20% of the epoxy resin.

8. The preparation process of the nano core-shell particle toughening-modified epoxy resin according to claim 1, characterized in that: the core-shell particles are butadiene rubber particles or acrylic rubber particles.

9. The preparation process of the nano core-shell particle toughening-modified epoxy resin according to claim 1, characterized in that: the catalyst solution refers to a catalyst solution in which 100% of solid catalyst is diluted with a solvent to 50%.

Technical Field

The invention relates to the technical field of epoxy resin equipment, in particular to a preparation process of nano core-shell particle toughening modified epoxy resin.

Background

The core-shell particles are toughening particles with rubber particles as a core and polymethyl methacrylate as a surface shell, and are widely applied to toughening of epoxy resin. The toughening modification of the epoxy resin is carried out by adopting the core-shell particles, at present, the modification is basically carried out by simple physical blending, the toughening core-shell particles are directly added into the epoxy resin and are uniformly stirred, and the toughening particles are dispersed in the epoxy resin by a mixing machine such as a dispersion machine, a grinding machine and the like so as to achieve the purpose of modification.

The aim of toughening and modifying the epoxy resin can be achieved through a simple physical blending mode, but the toughening core-shell particles are difficult to disperse completely in the form of primary particles and are difficult to disperse in the form of multiple particle agglomeration through simple physical blending. The primary particle size of the toughening core-shell particles is 50-200nm, if the toughening core-shell particles are dispersed in the form of primary particles, the toughening core-shell particles can show a nano-size effect and have the characteristics of high toughness, high strength and the like, and the multi-time agglomerated particles do not have the characteristics. The invention aims to disperse nanometer core-shell particles in epoxy resin in the form of primary particles and improve the toughness of the epoxy resin to the maximum extent.

Therefore, a preparation process of the nano core-shell particle toughening modified epoxy resin is provided.

Disclosure of Invention

It is an object of the present invention to solve or at least alleviate problems in the prior art.

In order to achieve the purpose, the invention is realized by the following technical scheme:

a preparation process of a nano core-shell particle toughening modified epoxy resin is characterized by comprising the following steps:

the method comprises the following steps: adding 30-70 parts of epoxy resin and 0.1-0.3 part of dispersant into 80-120 parts of solvent, and fully and uniformly stirring;

step two: adding 1-20 parts of nano core-shell particles into the resin solution, and dispersing by using a high-speed dispersion machine to enable the particles to be in a monodisperse state to obtain a suspension;

step three: continuously stirring at high speed, heating to 60-100 ℃ for reflux, dropwise adding 0.06-0.1 part of catalyst solution while stirring, and continuously reacting for 1 hour;

step four: and vacuumizing the product to remove the solvent to obtain the shell-core particle modified epoxy resin.

Optionally, the epoxy resin is bisphenol F type epoxy resin, bisphenol a type epoxy resin.

Optionally, the radius of the nano core-shell particles is between 50 nm and 200 nm.

Optionally, the dispersant is one or more of BYK-109, BYK-163, BYK-166, BYK-220S, BYK-2100, and BYK-2105.

Optionally, the solvent is one or more of acetone, toluene, cyclohexanone, cyclohexane, toluene, xylene, ethyl acetate, and butyl acetate.

Optionally, the catalyst is one or more of triphenylphosphine, triphenylphosphine oxide, DBU salt and DBN salt.

Optionally, the content of the core-shell particles is 15-20% of the epoxy resin.

Optionally, the core-shell particles are butadiene rubber particles or acrylic rubber particles.

Alternatively, the catalyst solution refers to a catalyst solution in which 100% solid catalyst is diluted with a solvent to 50%.

The embodiment of the invention provides a preparation process of a nano core-shell particle toughening modified epoxy resin. The method has the following beneficial effects: the method has simple operation steps, and can modify the surface of the core-shell into a structure with better compatibility with the epoxy resin by carrying out reaction grafting on the surface of the core-shell particles and reacting carboxyl on the surface of the core-shell with epoxy groups, so that the core-shell particles can stably keep a primary particle dispersed state in the epoxy resin without agglomeration, thereby improving the impact strength, the tensile strength and the peel strength of the epoxy resin.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

A preparation process of a nano core-shell particle toughening modified epoxy resin comprises the following steps:

the method comprises the following steps: adding 30-70 parts of epoxy resin (such as bisphenol F type epoxy resin and bisphenol A type epoxy resin) and 0.1-0.3 part of dispersant (such as BYK-109, BYK-163, BYK-166, BYK-220S, BYK-2100, BYK-2105) into 80-120 parts of solvent (such as acetone, toluene, cyclohexanone, cyclohexane, toluene, xylene, ethyl acetate and butyl acetate), and stirring thoroughly;

the purpose of adding the dispersant is to make the nanoparticles in a monodisperse state: the core-shell particles can reach a primary particle dispersion state in the solution by selecting a proper dispersant;

step two: adding 1-20 parts of nano core-shell particles (with the particle diameter of 50-200 nm) into the resin solution, and dispersing by a high-speed dispersion machine to enable the particles to be in a monodisperse state to obtain a suspension.

The content of the core-shell particles is 15-20% of the epoxy resin; the core-shell particles are butadiene rubber particles or acrylic rubber particles.

Step three: continuously stirring at high speed, heating to 60-100 deg.C, refluxing, dropwise adding 0.06-0.1 part of catalyst solution (such as triphenylphosphine, triphenylphosphine oxide, DBU salt, DBN salt, etc.) while stirring, and continuously reacting for 1 hr;

the catalyst solution refers to a catalyst solution in which 100% of solid catalyst is diluted with a solvent to 50%.

Step four: and vacuumizing the product to remove the solvent to obtain the shell-core particle modified epoxy resin.

The catalyst is added, so that a small amount of carboxyl groups left on the surfaces of the shell-core particles can react with the epoxy groups, the compatibility of the shell-core particles and the epoxy resin is improved, and the shell-core particles can be stably dispersed in the epoxy resin in a primary particle form.

By carrying out reactive grafting on the surface of the core-shell particles and reacting carboxyl on the surface of the core-shell with epoxy groups, the surface of the core-shell can be modified into a structure with better compatibility with epoxy resin, so that the core-shell particles can stably keep a primary particle dispersed state in the epoxy resin without agglomeration.

Example 1

The method comprises the following steps: adding 50 parts of epoxy resin and 0.18 part of BYK wetting dispersant into 100 parts of toluene, and fully and uniformly stirring;

step two: and adding 10 parts of nano core-shell particles into the resin solution, and dispersing by using a high-speed dispersion machine to enable the particles to be in a monodisperse state to obtain a suspension.

Step three: continuously stirring at high speed, heating to 60-100 ℃ for reflux, dropwise adding 0.09 part of triphenylphosphine solution while stirring, and continuously reacting for 1 hour;

step four: and vacuumizing the product to remove toluene to obtain the shell-core particle modified epoxy resin.

Example 2

The method comprises the following steps: adding 30 parts of epoxy resin and 0.1 part of BYK wetting dispersant into 80 parts of toluene, and fully and uniformly stirring;

step two: and (3) adding 1 part of nano core-shell particles into the resin solution, and dispersing by using a high-speed dispersion machine to enable the particles to be in a monodisperse state to obtain a suspension.

Step three: continuously stirring at high speed, heating to 60-100 ℃ for reflux, dropwise adding 0.06 part of triphenylphosphine solution while stirring, and continuously reacting for 1 hour;

step four: and vacuumizing the product to remove toluene to obtain the shell-core particle modified epoxy resin.

Example 3

The method comprises the following steps: adding 70 parts of epoxy resin and 0.3 part of BYK wetting dispersant into 120 parts of toluene, and fully and uniformly stirring;

step two: and adding 20 parts of nano core-shell particles into the resin solution, and dispersing by using a high-speed dispersion machine to enable the particles to be in a monodisperse state to obtain a suspension.

Step three: continuously stirring at high speed, heating to 60-100 ℃ for reflux, dropwise adding 0.1 part of triphenylphosphine solution while stirring, and continuously reacting for 1 hour;

step four: and vacuumizing the product to remove toluene to obtain the shell-core particle modified epoxy resin.

Example 4

The method comprises the following steps: adding 50 parts of epoxy resin and 0.18 part of BYK wetting dispersant into 100 parts of toluene, and fully and uniformly stirring;

step two: and (3) adding 1 part of nano core-shell particles into the resin solution, and dispersing by using a high-speed dispersion machine to enable the particles to be in a monodisperse state to obtain a suspension.

Step three: continuously stirring at high speed, heating to 60-100 ℃ for reflux, dropwise adding 0.09 part of triphenylphosphine solution while stirring, and continuously reacting for 1 hour;

step four: and vacuumizing the product to remove toluene to obtain the shell-core particle modified epoxy resin.

Example 5

The method comprises the following steps: adding 50 parts of epoxy resin and 0.18 part of BYK wetting dispersant into 100 parts of toluene, and fully and uniformly stirring;

step two: and adding 20 parts of nano core-shell particles into the resin solution, and dispersing by using a high-speed dispersion machine to enable the particles to be in a monodisperse state to obtain a suspension.

Step three: continuously stirring at high speed, heating to 60-100 ℃ for reflux, dropwise adding 0.09 part of triphenylphosphine solution while stirring, and continuously reacting for 1 hour;

step four: and vacuumizing the product to remove toluene to obtain the shell-core particle modified epoxy resin.

Example 6

The method comprises the following steps: adding 50 parts of epoxy resin and 0.1 part of BYK wetting dispersant into 100 parts of toluene, and fully and uniformly stirring;

step two: and adding 10 parts of nano core-shell particles into the resin solution, and dispersing by using a high-speed dispersion machine to enable the particles to be in a monodisperse state to obtain a suspension.

Step three: continuously stirring at high speed, heating to 60-100 ℃ for reflux, dropwise adding 0.09 part of triphenylphosphine solution while stirring, and continuously reacting for 1 hour;

step four: and vacuumizing the product to remove toluene to obtain the shell-core particle modified epoxy resin.

Example 7

The method comprises the following steps: adding 50 parts of epoxy resin and 0.3 part of BYK wetting dispersant into 100 parts of toluene, and fully and uniformly stirring;

step two: and adding 10 parts of nano core-shell particles into the resin solution, and dispersing by using a high-speed dispersion machine to enable the particles to be in a monodisperse state to obtain a suspension.

Step three: continuously stirring at high speed, heating to 60-100 ℃ for reflux, dropwise adding 0.09 part of triphenylphosphine solution while stirring, and continuously reacting for 1 hour;

step four: and vacuumizing the product to remove toluene to obtain the shell-core particle modified epoxy resin.

A comprehensive analysis of examples 1 to 7 according to the invention gives the following table

As can be seen from the above table, in example 1, the impact strength, tensile strength and peel strength were all the best.

Meanwhile, as can be seen from examples 1, 4 and 5, when the number of core-shell particles is small or large, the impact strength, tensile strength and peel strength are reduced, and when the content of the core-shell particles is 15-20% of that of the epoxy resin, the performance is the best.

On the other hand, it can be seen from examples 1, 6 and 7 that when the amount of the dispersant is small or large, the tensile strength and peel strength tend to decrease.

It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.

The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.