CN109280334B - Composite material with flame retardant and shape memory performance and preparation method thereof - Google Patents
Composite material with flame retardant and shape memory performance and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of multifunctional composite materials, and particularly relates to a composite material with flame retardant and shape memory properties and a preparation method thereof. The composite material comprises the following components in parts by weight: 30-40 parts of water-based epoxy resin, 3-30 parts of flame retardant and 7-10 parts of curing agent. The composite material adopts the water-based epoxy resin as a matrix, and is molded by compression and solidification after freeze drying through the blending of the water-based epoxy resin and the flame retardant, so that the preparation method is simple and the molding efficiency is high; the prepared composite material has both flame retardant and shape memory properties.
Description
Technical Field
The invention belongs to the technical field of multifunctional composite materials, and particularly relates to a composite material with flame retardant and shape memory properties and a preparation method thereof.
Background
Epoxy Resin (ER) is one of important thermosetting polymers, and is widely used in many fields such as coatings, adhesives, electronic insulating materials, and advanced materials due to its excellent mechanical rigidity and toughness, good solvent resistance and chemical resistance, and excellent adhesion. However, its wide use is limited by its high flammability. The common epoxy resin material has high inflammability, once ignited, the flame propagation speed is high, the heat release rate is high, low-falling objects with flames are easily generated and generated along with thick smoke, and potential threats are caused to fire expansion and personnel escape.
With the increasing demand for the safety of materials, the demand for the heat-resistant and flame-retardant properties of epoxy resins is also increasing. However, the traditional additive type flame retardant can not meet the requirements of flame retardance, insulation, excellent mechanical property, good compatibility with a matrix and the like; the use of reactive flame retardants, i.e., flame retardant elements such as chlorine and bromine are introduced into the epoxy resin matrix, which can effectively increase the oxygen index of the epoxy resin, however, halogen-based flame retardants emit toxic hydrogen halides and halogenated dibenzodioxins during combustion, and cause environmental pollution after disposal, and thus, the use of the reactive flame retardants is limited. The current research and application are turned to environment-friendly halogen-free flame-retardant epoxy resin, wherein the epoxy resin mainly contains phosphorus epoxy resin and silicon flame-retardant epoxy resin, so that the epoxy resin composite material with flame retardant property has wide application in copper clad laminates, packaging materials, adhesives and the like. For example, patent document No. CN107057517A discloses a silsesquioxane-crosslinked silicon-nitrogen-phosphorus synergistic flame retardant aqueous epoxy resin, which is composed of 40-80 wt% of an epoxy resin base material, 2-12 wt% of a silsesquioxane epoxy resin curing agent containing silicon, nitrogen and phosphorus, 0.5-2 wt% of a curing accelerator, 5-20 wt% of a foaming agent, 5-20 wt% of a char forming agent, 3-20 wt% of a char forming catalyst, 2-12 wt% of a pigment and filler, and 0.1-2.5 wt% of a leveling agent, wherein the silsesquioxane epoxy resin containing silicon, nitrogen and phosphorus is used as the curing agent, and the synergistic char forming agent, the foaming agent, and the char forming catalyst significantly improve the flame retardant performance of the aqueous epoxy resin.
In the currently developed flame retardant epoxy resins, there is no shape memory effect yet. The shape memory material is an important functional material, is rapidly developed since the 80 s of the 20 th century, and has wide application in the fields of aerospace, power electronics, medical treatment, packaging, intelligent control systems and the like. Therefore, there is a need in the art to develop a composite material having both shape memory and flame retardant properties.
Disclosure of Invention
Based on the defects in the prior art, the invention provides a composite material with flame retardant and shape memory properties and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a composite material with flame retardant and shape memory properties comprises the following components in parts by weight: 30-40 parts of water-based epoxy resin, 3-30 parts of flame retardant and 7-10 parts of curing agent.
Preferably, the composite material further comprises: 0.2-0.5 part of water-soluble graphene.
Preferably, the water-soluble graphene is polydopamine-modified reduced graphene oxide.
Preferably, the flame retardant is ammonium polyphosphate, hexaphenoxycyclotriphosphazene or melamine phosphate.
Preferably, the curing agent is an amine curing agent.
Preferably, the curing agent is tetraethylenepentamine, diethylenetriamine or m-phenylenediamine.
Preferably, the solid content of the water-based epoxy resin is 50-60%.
The invention also provides a preparation method of the composite material with flame retardant and shape memory performance, which comprises the following steps:
(1) mixing the waterborne epoxy resin, the flame retardant and the curing agent in parts by weight, and uniformly mixing to obtain a mixed material;
(2) freeze-drying the mixed material;
(3) and (3) pressing and curing the freeze-dried mixed material by a vulcanizing machine to obtain the composite material with flame retardance and shape memory performance.
Preferably, the step (1) further comprises: modifying graphene oxide to obtain polydopamine-modified reduced graphene oxide; and (2) adding polydopamine modified reduced graphene oxide in the material mixing process of the step (1).
Preferably, the curing process of the pressing die of the vulcanizing machine in the step (3) comprises pre-curing and high-temperature curing, wherein the pre-curing temperature is 70-80 ℃, and the heat preservation time is 20-40 min; the temperature of the high-temperature curing is 90-120 ℃, and the heat preservation time is 100-120 min.
Preferably, the temperature of the freeze drying is-10 to-30 ℃, and the time of the freeze drying is 165-180 h.
Compared with the prior art, the invention has the beneficial effects that:
the composite material with flame retardant and shape memory performance has good flame retardant performance and good shape memory performance.
The preparation method of the composite material with flame retardant and shape memory performance adopts the water-based epoxy resin as the matrix, and the composite material is molded by compression molding and curing after the water-based epoxy resin and the flame retardant are blended, frozen and dried, so that the preparation method is simple and the molding efficiency is high.
Drawings
Fig. 1 is a comparative schematic of the flame retardant properties of the composite material made in example 2 of the present invention and commercially available WEP materials and a graph showing the shape memory function of the composite material made in example 2 of the present invention.
Detailed Description
In order to more clearly illustrate the embodiments of the present invention, the following description will explain the embodiments of the present invention with reference to the accompanying drawings. It is obvious that the drawings in the following description are only some examples of the invention, and that for a person skilled in the art, other drawings and embodiments can be derived from them without inventive effort.
Example 1:
the preparation method of the composite material with flame retardant and shape memory performance of the embodiment comprises the following steps:
(1) selecting a container with proper capacity, adding 40 parts of waterborne epoxy resin with 50% of solid content into the container, then adding 3.33 parts of ammonium polyphosphate APP into the container, mixing under high-speed magnetic stirring, then adding 10 parts of epoxy resin curing agent tetraethylenepentamine after uniformly mixing, and continuously and uniformly stirring to obtain a mixed material;
(2) freezing the mixed material by using liquid nitrogen, and then putting the frozen mixed material into a freeze drying box at the temperature of-20 ℃ for freeze drying for 170 hours to obtain mixture powder;
(3) and then, softening the mixture powder obtained by freeze drying at room temperature into a long strip, placing the long strip in a mold of a stainless steel iron plate, precuring the long strip at 75 ℃ for 30min under the action of a vulcanizing machine, then curing the long strip at 120 ℃ for 120min, cooling the long strip to room temperature, and taking the long strip out to obtain the composite material with flame retardance and shape memory performance, wherein the ammonium polyphosphate accounts for 10 percent of the content of the composite material.
Example 2:
the preparation method of the composite material with flame retardant and shape memory performance of the embodiment comprises the following steps:
(1) selecting a container with proper capacity, adding 40 parts of waterborne epoxy resin with the solid content of 50% into the container, then adding 7.5 parts of ammonium polyphosphate into the container, mixing under high-speed magnetic stirring, then adding 10 parts of epoxy resin curing agent tetraethylenepentamine after uniformly mixing, and continuously and uniformly stirring to obtain a mixed material;
(2) freezing the mixed material by using liquid nitrogen, and then putting the frozen mixed material into a freeze drying box at the temperature of-20 ℃ for freeze drying for 170 hours to obtain mixture powder;
(3) and then, softening the mixture powder obtained by freeze drying at room temperature into a long strip, placing the long strip in a mold of a stainless steel iron plate, precuring the long strip at 75 ℃ for 30min under the action of a vulcanizing machine, then curing the long strip at 120 ℃ for 120min, cooling the long strip to room temperature, and taking the long strip out to obtain the composite material with flame retardance and shape memory performance, wherein the ammonium polyphosphate accounts for 20 percent of the content of the composite material. A comparison graph before and after the combustion performance of the composite material prepared by the embodiment and a structural graph reflecting the shape memory function are shown in fig. 1, and fig. 1 also shows the flame retardant performance of the WEP material without the addition of ammonium polyphosphate, and as is obvious from fig. 1(a), the flame retardant performance of the WEP composite material after the addition of APP is remarkably improved; as is apparent from fig. 1(b), the composite material of the present example has an excellent shape memory function.
Example 3:
the preparation method of the composite material with flame retardant and shape memory performance of the embodiment comprises the following steps:
(1) selecting a container with proper capacity, adding 40 parts of waterborne epoxy resin with 50% of solid content into the container, then adding 12.86 parts of ammonium polyphosphate into the container, mixing under high-speed magnetic stirring, then adding 10 parts of epoxy resin curing agent tetraethylenepentamine after uniformly mixing, and continuously and uniformly stirring to obtain a mixed material;
(2) freezing the mixed material by using liquid nitrogen, and then putting the frozen mixed material into a freeze drying box at the temperature of-20 ℃ for freeze drying for 170 hours to obtain mixture powder;
(3) and then, softening the mixture powder obtained by freeze drying at room temperature into a long strip, placing the long strip in a mold of a stainless steel iron plate, precuring the long strip at 75 ℃ for 30min under the action of a vulcanizing machine, then curing the long strip at 120 ℃ for 120min, cooling the long strip to room temperature, and taking the long strip out to obtain the composite material with flame retardance and shape memory performance, wherein the ammonium polyphosphate accounts for 30 percent of the content of the composite material.
Example 4:
the preparation method of the composite material with flame retardant and shape memory performance of the embodiment comprises the following steps:
(1) selecting a container with proper capacity, adding 40 parts of waterborne epoxy resin with the solid content of 50% into the container, then adding 20 parts of ammonium polyphosphate into the container, mixing under high-speed magnetic stirring, then adding 10 parts of epoxy resin curing agent tetraethylenepentamine after uniformly mixing, and continuously and uniformly stirring to obtain a mixed material;
(2) freezing the mixed material by using liquid nitrogen, and then putting the frozen mixed material into a freeze drying box at the temperature of-20 ℃ for freeze drying for 170 hours to obtain mixture powder;
(3) and then, softening the mixture powder obtained by freeze drying at room temperature into a long strip, placing the long strip in a mold of a stainless steel iron plate, precuring the long strip at 75 ℃ for 30min under the action of a vulcanizing machine, then curing the long strip at 120 ℃ for 120min, cooling the long strip to room temperature, and taking the long strip out to obtain the composite material with flame retardance and shape memory performance, wherein the ammonium polyphosphate accounts for 40% of the content of the composite material.
Example 5:
the preparation method of the composite material with flame retardant and shape memory performance of the embodiment comprises the following steps:
(1) selecting a container with proper capacity, adding 40 parts of waterborne epoxy resin with the solid content of 50% into the container, then adding 30 parts of ammonium polyphosphate into the container, mixing under high-speed magnetic stirring, then adding 10 parts of epoxy resin curing agent tetraethylenepentamine after uniformly mixing, and continuously and uniformly stirring to obtain a mixed material;
(2) freezing the mixed material by using liquid nitrogen, and then putting the frozen mixed material into a freeze drying box at the temperature of-20 ℃ for freeze drying for 170 hours to obtain mixture powder;
(3) and then, softening the mixture powder obtained by freeze drying at room temperature into a long strip, placing the long strip in a mold of a stainless steel iron plate, precuring the long strip at 75 ℃ for 30min under the action of a vulcanizing machine, then curing the long strip at 120 ℃ for 120min, cooling the long strip to room temperature, and taking the long strip out to obtain the composite material with flame retardance and shape memory performance, wherein the ammonium polyphosphate accounts for 50 percent of the content of the composite material.
Example 6:
the preparation method of the composite material with flame retardant and shape memory performance of the embodiment comprises the following steps:
(1) preparing polydopamine modified reduced graphene oxide: firstly, ultrasonically dispersing graphene oxide in deionized water for 20min, and then adding a solvent with the mass ratio of (graphene oxide: dopamine hydrochloride) being 2: 1, dopamine hydrochloride, and stirring for 10min by magnetic force; then regulating the pH value to 8.0-8.5 by a tris-cl buffer solution, heating to 60 ℃, and violently stirring for 24 hours; then centrifugally washing for 5 times, freeze-drying and vacuum-drying into powder to obtain polydopamine-modified reduced graphene oxide (PDA-RGO); wherein the freeze drying time is 12h, and the vacuum drying time is 2 h;
(2) selecting a container with proper capacity, adding 40 parts of waterborne epoxy resin with the solid content of 50% into the container, then adding 3.33 parts of ammonium polyphosphate and 0.2 part of polydopamine-modified reduced graphene oxide into the container, mixing under high-speed magnetic stirring, then adding 10 parts of epoxy resin curing agent tetraethylenepentamine after uniformly mixing, and continuously and uniformly stirring to obtain a mixed material;
(2) freezing the mixed material by using liquid nitrogen, and then putting the frozen mixed material into a freeze drying box at the temperature of-20 ℃ for freeze drying for 170 hours to obtain mixture powder;
(3) and then, softening the mixture powder obtained by freeze drying at room temperature into a long strip, placing the long strip in a mold of a stainless steel iron plate, pre-curing the long strip at 75 ℃ for 30min under the action of a vulcanizing machine, then curing the long strip at 120 ℃ for 120min, cooling the long strip to room temperature, and taking the long strip out to obtain the composite material with flame retardance and shape memory performance, wherein the content of the polydopamine modified reduced graphene oxide in the composite material is 0.6%.
Example 7:
the preparation method of the composite material with flame retardant and shape memory performance of the embodiment comprises the following steps:
(1) preparing polydopamine modified reduced graphene oxide: firstly, ultrasonically dispersing graphene oxide in deionized water for 20min, and then adding a solvent with the mass ratio of (graphene oxide: dopamine hydrochloride) being 2: 1, dopamine hydrochloride, and stirring for 10min by magnetic force; then regulating the pH value to 8.0-8.5 by a tris-cl buffer solution, heating to 60 ℃, and violently stirring for 24 hours; then centrifugally washing for 5 times, freeze-drying and vacuum-drying into powder to obtain polydopamine-modified reduced graphene oxide (PDA-RGO); wherein the freeze drying time is 12h, and the vacuum drying time is 2 h;
(2) selecting a container with proper capacity, adding 40 parts of waterborne epoxy resin with the solid content of 50% into the container, then adding 3.33 parts of ammonium polyphosphate and 0.3 part of polydopamine-modified reduced graphene oxide into the container, mixing under high-speed magnetic stirring, then adding 10 parts of epoxy resin curing agent tetraethylenepentamine after uniformly mixing, and continuously and uniformly stirring to obtain a mixed material;
(3) freezing the mixed material by using liquid nitrogen, and then putting the frozen mixed material into a freeze drying box at the temperature of-20 ℃ for freeze drying for 170 hours to obtain mixture powder;
(4) and then, softening the mixture powder obtained by freeze drying at room temperature into a long strip, placing the long strip in a mold of a stainless steel iron plate, pre-curing the long strip at 75 ℃ for 30min under the action of a vulcanizing machine, then curing the long strip at 120 ℃ for 120min, cooling the long strip to room temperature, and taking the long strip out to obtain the composite material with flame retardance and shape memory performance, wherein the content of the polydopamine modified reduced graphene oxide in the composite material is 0.89%.
Example 8:
the preparation method of the composite material with flame retardant and shape memory performance of the embodiment comprises the following steps:
(1) preparing polydopamine modified reduced graphene oxide: firstly, ultrasonically dispersing graphene oxide in deionized water for 20min, and then adding a solvent with the mass ratio of (graphene oxide: dopamine hydrochloride) being 2: 1, dopamine hydrochloride, and stirring for 10min by magnetic force; then regulating the pH value to 8.0-8.5 by a tris-cl buffer solution, heating to 60 ℃, and violently stirring for 24 hours; then centrifugally washing for 5 times, freeze-drying and vacuum-drying into powder to obtain polydopamine-modified reduced graphene oxide (PDA-RGO); wherein the freeze drying time is 12h, and the vacuum drying time is 2 h;
(2) selecting a container with proper capacity, adding 40 parts of waterborne epoxy resin with the solid content of 50% into the container, then adding 3.33 parts of ammonium polyphosphate and 0.35 part of polydopamine-modified reduced graphene oxide into the container, mixing under high-speed magnetic stirring, then adding 10 parts of epoxy resin curing agent tetraethylenepentamine after uniformly mixing, and continuously and uniformly stirring to obtain a mixed material;
(3) freezing the mixed material by using liquid nitrogen, and then putting the frozen mixed material into a freeze drying box at the temperature of-20 ℃ for freeze drying for 170 hours to obtain mixture powder;
(4) and then, softening the mixture powder obtained by freeze drying at room temperature into a long strip, placing the long strip in a mold of a stainless steel iron plate, pre-curing the long strip at 75 ℃ for 30min under the action of a vulcanizing machine, then curing the long strip at 120 ℃ for 120min, cooling the long strip to room temperature, and taking the long strip out to obtain the composite material with flame retardance and shape memory performance, wherein the content of the polydopamine modified reduced graphene oxide in the composite material is 1.0%.
Example 9:
the preparation method of the composite material with flame retardant and shape memory performance of the embodiment comprises the following steps:
(1) preparing polydopamine modified reduced graphene oxide: firstly, ultrasonically dispersing graphene oxide in deionized water for 20min, and then adding a solvent with the mass ratio of (graphene oxide: dopamine hydrochloride) being 2: 1, dopamine hydrochloride, and stirring for 10min by magnetic force; then regulating the pH value to 8.0-8.5 by a tris-cl buffer solution, heating to 60 ℃, and violently stirring for 24 hours; then centrifugally washing for 5 times, freeze-drying and vacuum-drying into powder to obtain polydopamine-modified reduced graphene oxide (PDA-RGO); wherein the freeze drying time is 12h, and the vacuum drying time is 2 h;
(2) selecting a container with proper capacity, adding 40 parts of waterborne epoxy resin with the solid content of 50% into the container, then adding 3.33 parts of ammonium polyphosphate and 0.4 part of polydopamine-modified reduced graphene oxide into the container, mixing under high-speed magnetic stirring, then adding 10 parts of epoxy resin curing agent tetraethylenepentamine after uniformly mixing, and continuously and uniformly stirring to obtain a mixed material;
(3) freezing the mixed material by using liquid nitrogen, and then putting the frozen mixed material into a freeze drying box at the temperature of-20 ℃ for freeze drying for 170 hours to obtain mixture powder;
(4) and then, softening the mixture powder obtained by freeze drying at room temperature into a long strip, placing the long strip in a mold of a stainless steel iron plate, pre-curing the long strip at 75 ℃ for 30min under the action of a vulcanizing machine, then curing the long strip at 120 ℃ for 120min, cooling the long strip to room temperature, and taking the long strip out to obtain the composite material with flame retardance and shape memory performance, wherein the content of the polydopamine modified reduced graphene oxide in the composite material is 1.19%.
Example 10:
the preparation method of the composite material with flame retardant and shape memory performance of the embodiment comprises the following steps:
(1) preparing polydopamine modified reduced graphene oxide: firstly, ultrasonically dispersing graphene oxide in deionized water for 20min, and then adding a solvent with the mass ratio of (graphene oxide: dopamine hydrochloride) being 2: 1, dopamine hydrochloride, and stirring for 10min by magnetic force; then regulating the pH value to 8.0-8.5 by a tris-cl buffer solution, heating to 60 ℃, and violently stirring for 24 hours; then centrifugally washing for 5 times, freeze-drying and vacuum-drying into powder to obtain polydopamine-modified reduced graphene oxide (PDA-RGO); wherein the freeze drying time is 12h, and the vacuum drying time is 2 h;
(2) selecting a container with proper capacity, adding 40 parts of waterborne epoxy resin with the solid content of 50% into the container, then adding 3.33 parts of ammonium polyphosphate and 0.5 part of polydopamine-modified reduced graphene oxide into the container, mixing under high-speed magnetic stirring, then adding 10 parts of epoxy resin curing agent tetraethylenepentamine after uniformly mixing, and continuously and uniformly stirring to obtain a mixed material;
(3) freezing the mixed material by using liquid nitrogen, and then putting the frozen mixed material into a freeze drying box at the temperature of-20 ℃ for freeze drying for 170 hours to obtain mixture powder;
(4) and then, softening the mixture powder obtained by freeze drying at room temperature into a long strip, placing the long strip in a mold of a stainless steel iron plate, precuring the long strip at 75 ℃ for 30min under the action of a vulcanizing machine, then curing the long strip at 120 ℃ for 120min, cooling the long strip to room temperature, and taking the long strip out to obtain the composite material with flame retardance and shape memory performance, wherein the content of the polydopamine modified reduced graphene oxide in the composite material is 1.48%.
Comparative example 1:
comparative example 1 differs from example 1 in that: no flame retardant is added in the preparation process, and the obtained water-based epoxy resin material, called WEP material for short.
Table 1 summary of relevant parameters for the composite material of the examples and for the WEP material of comparative example 1
Table 1 shows the flame retardant performance and the shape memory performance of each example, and it can be seen that the limiting oxygen index LOI of comparative example 1 (pure WEP) is 18.2%, while the LOI of examples 1-5 shows a gradual trend with increasing APP content, and the LOI can reach 27% or more when the flame retardant APP is added to 20% (see example 2). The addition of the APP obviously improves the LOI of the composite material, mainly because the APP serves as an acid source in an expansion flame-retardant system to catalyze WEP to form carbon in the combustion process of the composite material, a stable expansion carbon layer is formed, and the effects of heat insulation and oxygen isolation are achieved. In examples 6-10, the LOI showed a tendency to increase and then decrease, and these five examples were based on example 1, and the addition of PDA-rGO as a synergistic flame retardant effect was continued, and it was found that when the content of the polydopamine modified reduced graphene oxide in the composite material is 1.0%, the LOI of the composite material is 27.4%, which is the best formulation, mainly due to the fact that PDA-rGO has the best dispersibility in WEP and forms an effective "tortuous path" under the formulation of the components. Thus, APP and PDA-rGO form a better synergistic effect, and the flame retardant performance is optimal. And when the content of the polydopamine modified reduced graphene oxide in the composite material is 1.0%, the polydopamine modified reduced graphene oxide shows a descending trend, and mainly due to the fact that the polydopamine modified reduced graphene oxide is increased to cause agglomeration in WEP, an effective 'tortuous path' cannot be formed in the combustion process, and LOI is reduced. From the table we can see that as the APP content (examples 1-5) increases, the shape fixation rate shows a decreasing trend, while the shape recovery rate does not change much, relative to comparative example 1. The increase in the content of APP mainly results in a decrease in the crosslinking density, which leads to a decrease in the stationary phase which plays a role in fixing and maintaining the shape memory, and thus a decrease in the shape memory fixation rate. In examples 6 to 10, the shape fixation rate and recovery rate tended to increase and decrease, and the shape memory fixation rate and recovery rate in example 8 were the best. The PDA-rGO mainly belonging to the component has the best dispersibility in a matrix, and the PDA-rGO plays a role in enhancing the shape memory performance of the composite material. When the addition amount is too large, the PDA-rGO is agglomerated in the matrix, and the shape memory property is reduced.
The invention adopts the water-based epoxy resin as a matrix and the ammonium polyphosphate as a flame retardant, and prepares the composite material with uniformity, flame retardant property and excellent shape memory property by blending the water-based epoxy resin and the ammonium polyphosphate in a water solvent well (with good uniform dispersibility), then completely removing water when completely drying by controlling the freeze drying time and mechanically stirring into powder. Because the freeze drying process is carried out under the conditions of vacuum pumping and low temperature of-10 to-30 ℃, water in the waterborne epoxy resin is sublimated in the form of ice, and the residual amount of water in the waterborne epoxy resin can be controlled by controlling the freeze drying time. Meanwhile, the curing reaction of the water-based epoxy resin cured at normal temperature can be inhibited.
Ammonium polyphosphate and other flame retardants containing P and N elements promote the crosslinking of the surface of the aqueous epoxy resin into carbon in the combustion process of the composite material, and simultaneously release ammonia and other non-combustible gases to form a porous foam expanded carbon layer, thereby playing roles in condensed phase and gas phase flame retardance. And the expanded carbon layer can play the roles of heat insulation, oxygen insulation, smoke suppression and molten drop prevention.
Due to the unique lamellar structure of graphene, excellent flame retardant effect can be obtained only by adding a small amount of graphene. The carbon layer can be formed on the surface of the polymer in the combustion process of the graphene composite material, when the graphene is better dispersed in the composite material, the graphene forms a 'tortuous path', and can effectively isolate oxygen and heat, inhibit the release of smoke and prevent combustible gas from entering combustion gas, so that the flame-retardant effect is achieved.
Therefore, the flame retardant property is effectively improved by improving the dispersibility of the graphene in the composite material, and the interface compatibility of the ammonium polyphosphate in the aqueous epoxy resin is improved by modifying the graphene. Graphene oxide is modified by polydopamine, wherein the polydopamine is good in compatibility, and N element is provided to further improve the flame retardance. The modified graphene is combined with ammonium polyphosphate, so that the dispersibility of the ammonium polyphosphate in the aqueous epoxy resin is obviously improved, and the interface compatibility of the ammonium polyphosphate in the aqueous epoxy resin is improved. In addition, the flame retardance is effectively improved by the synergistic effect of the graphene and the ammonium polyphosphate.
In the above examples and alternatives, the waterborne epoxy resin may also be used in amounts of 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts.
In the above examples and alternatives, the amount of ammonium polyphosphate may also be 3 parts, 3.5 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 15 parts, 18 parts, 21 parts, 23 parts, 25 parts, 28 parts.
In the above examples and alternatives, the epoxy resin curing agent tetraethylenepentamine may also be used in amounts of 7 parts, 7.5 parts, 7.8 parts, 8 parts, 8.2 parts, 8.5 parts, 8.8 parts, 9 parts, 9.3 parts, 9.5 parts, 9.6 parts, 9.8 parts.
In the above embodiments and alternatives, the polydopamine-modified reduced graphene oxide may also be used in amounts of 0.25 parts, 0.28 parts, 0.32 parts, 0.39 parts, 0.43 parts, 0.45 parts, 0.48 parts, 0.52 parts, 0.55 parts, 0.6 parts.
In the above examples and alternatives, the solids content of the waterborne epoxy resin may also be 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%.
In the above embodiments and alternatives, the pre-curing temperature may also be 70 ℃, 72 ℃, 76 ℃, 78 ℃, 80 ℃; the pre-curing heat preservation time can be 20min, 25min, 35min and 40 min.
In the above embodiments and their alternatives, the temperature of the high temperature curing may also be 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, and the holding time of the high temperature curing may also be 100min, 105min, 110min, 115 min.
In the above embodiment and its alternative, the temperature of freeze drying may be-10 deg.C, -15 deg.C, -25 deg.C, -30 deg.C during the freeze drying process of the mixed material; the freeze-drying time can also be 165h, 168h, 172h, 175h, 178h and 180 h.
In the above embodiments and alternatives thereof, the polydopamine-modified reduced graphene oxide may also be replaced by ethylenediamine-modified reduced graphene oxide.
In the above examples and alternatives, ammonium polyphosphate may also be replaced with hexaphenoxycyclotriphosphazene or melamine phosphate.
In the above examples and alternatives thereof, tetraethylenepentamine may also be replaced with diethylenetriamine or m-phenylenediamine.
It should be noted that the above embodiments can be freely combined as necessary. The foregoing has outlined rather broadly the preferred embodiments and principles of the present invention and it will be appreciated that those skilled in the art may devise variations of the present invention that are within the spirit and scope of the appended claims.
Claims (6)
1. The preparation method of the composite material with flame retardant and shape memory properties is characterized in that the composite material comprises the following components in parts by weight: 30-40 parts of water-based epoxy resin, 3-30 parts of a flame retardant and 7-10 parts of a curing agent; the preparation method comprises the following steps:
(1) mixing the waterborne epoxy resin, the flame retardant and the curing agent in parts by weight, and uniformly mixing to obtain a mixed material;
(2) freeze-drying the mixed material;
(3) the mixture after freeze drying is pressed and solidified by a vulcanizer to obtain the composite material with flame retardant and shape memory properties;
the composite material further comprises: the graphene comprises water-soluble graphene, wherein the water-soluble graphene is polydopamine-modified reduced graphene oxide; the step (1) is also preceded by: modifying graphene oxide to obtain polydopamine-modified reduced graphene oxide; adding polydopamine modified reduced graphene oxide in the burdening process of the step (1);
wherein the content of the polydopamine modified reduced graphene oxide in the composite material is 1.0%.
2. The preparation method according to claim 1, wherein the curing process of the press mold of the vulcanizer in the step (3) comprises pre-curing and high-temperature curing, wherein the pre-curing temperature is 70-80 ℃, and the holding time is 20-40 min; the temperature of the high-temperature curing is 90-120 ℃, and the heat preservation time is 100-120 min.
3. The method of claim 1, wherein the flame retardant is ammonium polyphosphate, hexaphenoxycyclotriphosphazene or melamine phosphate.
4. The method according to claim 1, wherein the curing agent is an amine curing agent.
5. The method according to claim 4, wherein the curing agent is tetraethylenepentamine, diethylenetriamine or m-phenylenediamine.
6. The preparation method of claim 1, wherein the solid content of the water-based epoxy resin is 50-60%.
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| CN109705528B (en) * | 2018-11-30 | 2021-05-11 | 浙江理工大学 | Water-based epoxy resin composite film, preparation method thereof and temperature difference energy collector |
| CN109880295B (en) * | 2019-02-22 | 2021-08-06 | 四川大学 | Amino-terminated modified graphene oxide and epoxy nanocomposite thereof |
| CN109824942B (en) * | 2019-02-26 | 2021-04-20 | 西北师范大学 | Preparation and application of organic-inorganic hybrid material composite flame retardant |
| CN109824971B (en) * | 2019-03-07 | 2021-09-07 | 华东理工大学 | Bionic modified graphene flame-retardant reinforced elastomer and preparation method thereof |
| CN110204864B (en) * | 2019-06-12 | 2022-06-03 | 北威(重庆)科技股份有限公司 | Antistatic fireproof composite material, preparation method thereof and semiconductor equipment |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104927302A (en) * | 2014-03-20 | 2015-09-23 | 江南大学 | Graphene-toughened epoxy resin composite material and preparation method thereof |
| CN106380144A (en) * | 2016-08-29 | 2017-02-08 | 万卓（武汉）新材料有限公司 | Semi-interpenetrating polymer cement-based flexible facing brick and manufacturing method thereof |
| CN106497311A (en) * | 2016-09-29 | 2017-03-15 | 沈阳化工大学 | A kind of preparation method of Graphene fire-resisting coating material |
| CN108034332A (en) * | 2017-12-28 | 2018-05-15 | 湖北楚禾新材料有限公司 | A kind of Waterborne Fire Retardant Coatings for Steel and preparation method thereof |
-
2018
- 2018-08-27 CN CN201810982353.4A patent/CN109280334B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104927302A (en) * | 2014-03-20 | 2015-09-23 | 江南大学 | Graphene-toughened epoxy resin composite material and preparation method thereof |
| CN106380144A (en) * | 2016-08-29 | 2017-02-08 | 万卓（武汉）新材料有限公司 | Semi-interpenetrating polymer cement-based flexible facing brick and manufacturing method thereof |
| CN106497311A (en) * | 2016-09-29 | 2017-03-15 | 沈阳化工大学 | A kind of preparation method of Graphene fire-resisting coating material |
| CN108034332A (en) * | 2017-12-28 | 2018-05-15 | 湖北楚禾新材料有限公司 | A kind of Waterborne Fire Retardant Coatings for Steel and preparation method thereof |
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