Intrinsic structure damping integrated material with reversible shape memory property and preparation method thereof
阅读说明：本技术 一种具有可逆形状记忆性质的本征结构阻尼一体化材料及其制备方法 (Intrinsic structure damping integrated material with reversible shape memory property and preparation method thereof ) 是由 邹华维 周勣 陈洋 衡正光 梁梅 于 2019-11-28 设计创作，主要内容包括：本发明提供了一种具有形状记忆性质的本征结构阻尼一体化材料。与普通固化环氧树脂E51-DMM相比,本发明采用“硬质填充”的方法制得的固化环氧树脂PEE-DMM与PDE-DMM同时有显著拓宽的阻尼温域、优良的力学性能(特别是弯曲模量)和可逆的形状记忆特性,是一种优异的本征型结构阻尼一体化材料,在航空航天等领域具有广阔的应用前景。(The invention provides an intrinsic structure damping integrated material with shape memory property. Compared with the common cured epoxy resin E51-DMM, the cured epoxy resin PEE-DMM and the PDE-DMM prepared by the method of 'hard filling' have remarkably widened damping temperature range, excellent mechanical properties (particularly bending modulus) and reversible shape memory characteristics, are excellent intrinsic structure damping integrated materials, and have wide application prospects in the fields of aerospace and the like.)
1. A structural damping integrated material is characterized in that: the structural damping integrated material is obtained by carrying out a curing reaction on epoxy resin and a curing agent, wherein the structure of the epoxy resin is shown as a formula 3 or a formula 4:
the epoxy value of the epoxy resin shown in the formula 3 is 0.25-0.40, and the epoxy value of the epoxy resin shown in the formula 4 is 0.15-0.30.
2. The structural damping integrated material of claim 1, wherein: the epoxy value of the epoxy resin shown in the formula 3 is 0.32, and the epoxy value of the epoxy resin shown in the formula 4 is 0.23;
and/or the curing agent is an aromatic amine curing agent, preferably DDM;
and/or the molar ratio of the epoxy resin to the curing agent is 1: (0.8 to 1.2), preferably 1: 1.
3. the structural damping integrated material of claim 1 or 2, wherein: the epoxy resin is prepared from bisphenol compounds and epoxy chloropropane, wherein the structure of the bisphenol compounds is shown in formula 1 or formula 2:
preferably, the raw materials for preparing the epoxy resin also comprise a catalyst, and preferably, the catalyst is benzyltrimethylammonium chloride;
the molar ratio of the bisphenol compound to the epichlorohydrin to the catalyst is 10: (300-500): (0.3-1), preferably 10:400: 0.5.
4. a method for preparing the structural damping integrated material as described in any one of claims 1 to 3, wherein: the method comprises the following steps:
(1) uniformly mixing bisphenol compounds and epoxy chloropropane, and reacting to obtain the epoxy resin of any one of claims 1 to 3; the structure of the bisphenol compound is shown in formula 1 or formula 2:
(2) and (2) uniformly mixing the epoxy resin obtained in the step (1) with a curing agent, and curing to obtain the epoxy resin.
5. The method of claim 4, wherein: in the step (1), the reaction is carried out under the action of a catalyst, preferably, the catalyst is benzyltrimethylammonium chloride;
the reaction temperature is 80-100 ℃ and the reaction time is 20-30 hours, preferably, the reaction temperature is 90 ℃ and the reaction time is 24 hours;
the epoxy value of the epoxy resin represented by formula 3 is 0.32, and the epoxy value of the epoxy resin represented by formula 4 is 0.23.
6. The method according to claim 4 or 5, characterized in that: in the step (2), the curing conditions are as follows: curing was carried out at 135 ℃ for 3 hours and then at 180 ℃ for 3 hours.
7. Bisphenol compounds of formula 2:
8. an epoxy resin represented by formula 3 or formula 4:
wherein the epoxy value of the epoxy resin shown in the formula 3 is 0.25-0.40, preferably 0.32;
the epoxy value of the epoxy resin represented by formula 4 is 0.15 to 0.30, preferably 0.23.
9. A process for the preparation of the bisphenols as claimed in claim 7, wherein: the method comprises the following steps: mixing 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 4-hydroxyacetophenone and phenol uniformly, and reacting to obtain the final product;
preferably, the reaction is carried out under the action of a catalyst, namely p-hydroxybenzene sulfonic acid;
the reaction temperature is 110-150 ℃, and the reaction time is 20-30 hours;
the reaction is carried out under the protection of inert gas;
the molar ratio of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the 4-hydroxyacetophenone to the phenol (0.5-1.5): (0.5-1.5): 100, preferably 1: 1: 100.
10. the process for producing an epoxy resin according to claim 8, wherein: the method comprises the following steps: uniformly mixing the bisphenol compound shown in the formula 1 or the bisphenol compound shown in the formula 2 with epoxy chloropropane, and reacting to obtain the bisphenol compound;
preferably, the reaction is carried out under the action of a catalyst, and the catalyst is benzyltrimethylammonium chloride;
the bisphenol compound shown in the formula 1 or the bisphenol compound shown in the formula 2, epichlorohydrin and a catalyst are in a molar ratio of 10: (300-500): (0.3-1), preferably 10:400: 0.5;
the reaction temperature is 80-100 ℃ and the reaction time is 20-30 hours, and preferably the reaction temperature is 90 ℃ and the reaction time is 24 hours.
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to an intrinsic structure damping integrated material with reversible shape memory property and a preparation method thereof.
Background
With the development of aerospace equipment towards light weight, high speed, automation and multiple functions, the requirements on the composite material and the composite material matrix in special equipment are higher and higher. The application environments of the application fields are severe, and the high-frequency vibration and noise can deteriorate the dynamic environment of precise electronic instruments and meters on aerospace products, reduce the precision and reliability of navigation and control systems, and bring great challenges to the working stability of precise instruments. Damping materials have attracted attention because they can convert mechanical vibrational energy into thermal energy for dissipation, effectively controlling vibration and noise. However, most damping materials have limited application temperature, and the mechanical properties of the damping materials are sharply reduced at a slightly high temperature, so that the requirements of structural materials on rigidity and strength cannot be met.
Epoxy resin is used as the most common thermosetting resin, has good mechanical property, and can not be decomposed or melted along with the rise of temperature, so that the epoxy resin is widely applied to composite materials such as aerospace equipment. However, the damping performance of the traditional bisphenol A type epoxy resin (DGEBA) is relatively poor, and the effective damping temperature range (Tan delta >0.3) is only 20 ℃ around the glass transition temperature (Tg), which means that the damping performance of the epoxy resin is poor in a wide range of use temperatures.
In modern diversified resin application environments, more and more situations require that the material has excellent damping and shock absorption characteristics and excellent mechanical properties at the same time under the use temperature, so that the preparation of the structural damping integrated composite material becomes a research hotspot in recent decades.
From the last 90 s, scholars at home and abroad put forward a plurality of technical schemes around the preparation of structural damping integrated composite materials, and materials with two or more Tg peaks are prepared by a method of blending rubber, plastic and resin in the early stage so as to widen the damping temperature range of the materials. In recent years, researchers try to prepare a novel structural damping integrated material by adopting a microstructure design, such as preparing a submicron powder frame structure based on epoxy by adopting a laser photoetching technology, or intercalating viscoelastic macromolecules into high-rigidity montmorillonite layers to form a rigid/viscoelastic alternative layered structure and introducing a structural resin system, or realizing structural damping integration of the material by spontaneously forming a specific microstructure in epoxy resin through block copolymers. The German research group introduces a pendant chain into an elastomer by a controllable free polymerization method to obtain a damping elastomer with a wide damping peak, and the Japanese research group obtains a micro-phase-separated elastomer by introducing a hydrocarbon chain pendant chain and also widens the effective damping temperature range of the material. However, the above methods all achieve the widening of the effective damping temperature range by introducing additional structural variables into the matrix material, and the preparation method is complex and has high cost. And the methods cannot simultaneously improve the mechanical modulus of the material and widen the damping temperature range of the material. At present, no intrinsic structure damping integrated material with both mechanical property and damping property remarkably improved is reported.
In addition, the shape memory material as a novel intelligent high polymer material can respond to the triggering of external stimulation such as heat, chemistry, machinery, light, magnetism or electricity and the like to perform shape remodeling, so that the technical parameters of the shape memory material are changed, and the shape memory material has wide application in the fields of aerospace, biomedicine, power electronics, packaging, intelligent control systems and the like. However, most of the existing epoxy resins have high glass transition temperature (Tg), have poor remolding property, and even if the epoxy resins are heated to the vicinity of the Tg, the shapes of the epoxy resins are difficult to be freely remolded, which limits the application of the epoxy resins to a certain extent. Therefore, the preparation of the intrinsic structure damping integrated material which has high damping performance, excellent mechanical property and reversible plastic shape memory performance has very important significance.
Disclosure of Invention
The invention aims to provide an intrinsic structure damping integrated material which not only has high damping performance, but also has excellent mechanical property and reversible plastic shape memory performance.
The invention provides a structural damping integrated material, which is obtained by carrying out a curing reaction on epoxy resin and a curing agent, wherein the structure of the epoxy resin is shown as a
the epoxy value of the epoxy resin shown in the
Further, the epoxy value of the epoxy resin represented by
and/or the curing agent is an aromatic amine curing agent, preferably DDM;
and/or the molar ratio of the epoxy resin to the curing agent is 1: (0.8 to 1.2), preferably 1: 1.
further, the epoxy resin is prepared from bisphenol compounds and epichlorohydrin, wherein the structure of the bisphenol compounds is shown in
preferably, the raw materials for preparing the epoxy resin also comprise a catalyst, and preferably, the catalyst is benzyltrimethylammonium chloride;
the molar ratio of the bisphenol compound to the epichlorohydrin to the catalyst is 10: (300-500): (0.3-1), preferably 10:400: 0.5.
the invention provides a method for preparing the damping integrated material with the structure, which comprises the following steps:
(1) uniformly mixing bisphenol compounds and epoxy chloropropane, and reacting to obtain the epoxy resin; the structure of the bisphenol compound is shown in
(2) and (2) uniformly mixing the epoxy resin obtained in the step (1) with a curing agent, and curing to obtain the epoxy resin.
Further, in the step (1), the reaction is carried out under the action of a catalyst, preferably, the catalyst is benzyltrimethylammonium chloride;
the reaction temperature is 80-100 ℃ and the reaction time is 20-30 hours, preferably, the reaction temperature is 90 ℃ and the reaction time is 24 hours;
the epoxy value of the epoxy resin represented by
Further, in the step (2), the curing conditions are as follows: curing was carried out at 135 ℃ for 3 hours and then at 180 ℃ for 3 hours.
The present invention also provides bisphenol compounds represented by formula 2:
the invention also provides an epoxy resin shown in
wherein the epoxy value of the epoxy resin shown in the
the epoxy value of the epoxy resin represented by
The invention also provides a preparation method of the bisphenol compound shown in the
preferably, the reaction is carried out under the action of a catalyst, namely p-hydroxybenzene sulfonic acid;
the reaction temperature is 110-150 ℃, and the reaction time is 20-30 hours;
the reaction is carried out under the protection of inert gas;
the molar ratio of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the 4-hydroxyacetophenone to the phenol (0.5-1.5): (0.5-1.5): 100, preferably 1: 1: 100.
the invention also provides a preparation method of the epoxy resin, which comprises the following steps: uniformly mixing the bisphenol compound shown in the
preferably, the reaction is carried out under the action of a catalyst, and the catalyst is benzyltrimethylammonium chloride;
the bisphenol compound shown in the
the reaction temperature is 80-100 ℃ and the reaction time is 20-30 hours, and preferably the reaction temperature is 90 ℃ and the reaction time is 24 hours.
The invention prepares two novel cured epoxy resins PEE-DMM and PDE-DMM by a phase transfer catalyst method. In the invention, a rigid structure is introduced into a molecular chain structure of the thermosetting resin as a suspension chain, the rigid structure plays a role of supporting in a microstructure of a material, and a large number of rigid suspension chains play a similar 'filling dilution' effect on a cross-linked network, which is called as 'hard filling'. The 'hard filling' method does not need to introduce extra substances to change the structure of the epoxy resin, has simple process and low cost, and is suitable for industrial expanded production.
Experimental results show that compared with the common epoxy resin E51-DMM, the cured epoxy resin PEE-DMM and the PDE-DMM prepared by the method of 'hard filling' have remarkably widened damping temperature range, excellent mechanical properties (particularly bending modulus) and reversible shape memory characteristics, are excellent intrinsic structure damping integrated materials, and have wide application prospects in the fields of aerospace and the like.
Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Drawings
FIG. 1 is a schematic diagram of the preparation of E51-DMM, PEE-DMM and PDE-DMM according to the present invention.
FIG. 2. Synthesis procedure for PEE.
FIG. 3 Synthesis steps of BDP and PDE.
FIG. 4 is an infrared spectrum of PDE, BPD, PEE and BPP.
FIG. 5 of BPD and BPP1H nuclear magnetic resonance spectrogram.
FIG. 6 dynamic mechanical analysis of three epoxy resins E51-DMM, PEE-DMM, PDE-DMM: a) storage moduli of the three epoxy resins, b) loss factor versus temperature curves of the three epoxy resins.
FIG. 7 shows the PEE-DMM bent into different shapes after being heated to 130 ℃.
FIG. 8 shows three epoxy resins E51-DMM, PEE-DMM, PDE-DMM a) first relaxation peak broken lines with temperature change, b) relaxation time curves at different temperatures.
FIG. 9 three epoxy resins E51-DMM, PEE-DMM, PDE-DMM a) dielectric loss versus temperature curves, b) fitting a Havriliak-Negami equation.
FIG. 10 is a logic model for modeling three epoxy resin free volume fraction analysis, E51-DMM, PEE-DMM, and PDE-DMM.
FIG. 11 is a plot of the fractional free volumes of three epoxy resins, E51-DMM, PEE-DMM, and PDE-DMM, as a function of temperature.
Detailed Description
The raw materials and equipment used in the invention are known products and are obtained by purchasing commercial products.
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