CN111518362A - High-temperature flame-retardant glass fiber reinforced plastic and preparation method thereof - Google Patents
High-temperature flame-retardant glass fiber reinforced plastic and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-temperature flame-retardant glass fiber reinforced plastic and a preparation method thereof. The high-temperature flame-retardant glass fiber reinforced plastic comprises the following raw materials in percentage by weight: 50-60% of glass fiber, 30-45% of silicon modified phenolic resin, 1-3% of aluminum hydroxide and/or magnesium hydroxide, 1-5% of kaolin, 0.1-0.5% of fumed silica and 1-3% of talcum powder. According to the invention, the silicon modified phenolic resin is used as the resin matrix of the glass fiber reinforced plastic, and the aluminum hydroxide, the magnesium hydroxide, the kaolin, the fumed silica and the talcum powder are added as inorganic additives, so that the synergistic effect among the components is fully exerted, and the obtained high-temperature flame-retardant glass fiber reinforced plastic has higher normal-temperature bending strength, the oxygen index is more than 60, and the fire structural integrity is first grade.
Description
Technical Field
The invention relates to the technical field of preparation of high-temperature composite materials, in particular to high-temperature flame-retardant glass fiber reinforced plastic and a preparation method thereof.
Background
At present, the main system of the evaluation indexes of the flame retardant performance of the domestic high-temperature flame retardant material is in the aspects of oxygen index, vertical and horizontal combustion, smoke density, smoke toxicity and the like, and the evaluation indexes do not provide specific requirements for the performance of the flame retardant material during or after combustion. With the gradual and deep research on fire safety, people find that the mechanical property of materials or structures plays a crucial role in taking rescue measures, emergency evacuation, escape and the like after fire occurs. Relevant standards have been established abroad, for example, the standard "Fiber Reinforced Polymer (FRP) grids for ships" which puts requirements on the integrity of structural members in fires, and which also brings the mechanical properties of materials when and after being heated into flame resistance assessment requirements.
The high-temperature flame retardant property of the glass fiber composite material is limited by the property of the resin matrix used by the glass fiber composite material. Currently, a high-temperature glass fiber composite material is generally prepared by adding various additives to a high-temperature resin and using glass fibers as a framework. However, the glass fiber composite material taking the phenolic resin as the matrix has the structural integrity greatly reduced after the resin is carbonized when the heating temperature reaches 927 ℃, and the structural integrity is not obviously improved even if the conventional additive is added. Therefore, the conventional phenolic resin-based glass fiber composite material has poor mechanical property and structural integrity after being heated.
Disclosure of Invention
The invention aims to overcome the technical defects, provides a high-temperature flame-retardant glass fiber reinforced plastic and a preparation method thereof, and solves the technical problems of poor mechanical property and structural integrity of the conventional phenolic resin-based glass fiber composite material after being heated in the prior art.
In order to achieve the technical purpose, the first aspect of the invention provides a high-temperature flame-retardant glass fiber reinforced plastic, which comprises the following raw materials in percentage by weight:
the second aspect of the invention provides a preparation method of high-temperature flame-retardant glass fiber reinforced plastic, which comprises the following steps:
uniformly mixing silicon modified phenolic resin, aluminum hydroxide and/or magnesium hydroxide, kaolin, fumed silica and talcum powder to obtain a mixture;
and paving the mixture and the glass fiber in a mold in a layered overlapping mode, and finally curing to obtain the high-temperature flame-retardant glass fiber reinforced plastic.
The preparation method of the high-temperature flame-retardant glass fiber reinforced plastic provided by the second aspect of the invention is used for obtaining the high-temperature flame-retardant glass fiber reinforced plastic provided by the first aspect of the invention.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the silicon modified phenolic resin is used as the resin matrix of the glass fiber reinforced plastic, and the aluminum hydroxide, the magnesium hydroxide, the kaolin, the fumed silica and the talcum powder are added as inorganic additives, so that the synergistic effect among the components is fully exerted, and the obtained high-temperature flame-retardant glass fiber reinforced plastic has higher normal-temperature bending strength, the oxygen index is more than 60, and the fire structural integrity is first grade.
Drawings
FIG. 1 is a process flow diagram of one embodiment of a method for preparing a high temperature flame retardant glass fiber reinforced plastic provided by the present invention;
FIG. 2 is a graph of the temperature rise of ASTM E119-2018 used in the structural integrity test of fires according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a high-temperature flame-retardant glass fiber reinforced plastic, which comprises the following raw materials in percentage by weight:
in the system, the glass fiber plays a role in supporting the framework, so that the continuity and the strength uniformity of the material are ensured; the silicon modified phenolic resin has great advantages in the aspects of high temperature resistance and flame retardance, a carbonization area, a cracking area and an original area are formed from the surface to the inside in the combustion process, the oxygen-containing and highly cross-linked chemical structure ensures that a phenolic matrix mainly has free radical transfer, high-temperature decarbonylation and dehydrogenation to form a carbon reaction in the thermal cracking process, and a porous carbonization layer is formed in the carbonization area and the cracking area on the surface layer of the material by means of the bridging action of fibers, so that the permeation of oxygen and the escape of inflammable micromolecules generated by thermal cracking are effectively prevented, a condensed phase flame retardance effect is realized, after organic silicon is introduced, the melting point of the resin can be further improved, and the flame retardance of the resin is enhanced; compared with other flame retardants, the aluminum hydroxide/magnesium hydroxide can be decomposed into aluminum oxide/magnesium oxide and water at high temperature, and the water forms steam at high temperature, so that the concentration of combustible gas is reduced, air is isolated, kaolin is hydrated and dissolved, the distribution is uniform and compact, a compact protective layer is formed on the surface, and the resin is prevented from being further degraded; the rheological property of the resin can be changed by adding the fumed silica, the fumed silica can be used as an anti-caking agent for other powder materials in a system to prevent the powder from settling in the resin, and meanwhile, the fumed silica can resist high temperature and can improve the high temperature resistance of the reinforced plastic due to the nanoscale size distribution in the system; the talcum powder has good compatibility with phenolic resin, can improve the rigidity of a product, reduce the thermal expansion coefficient, promote the flow, have the lubricating effect, reduce the fiber damage degree in the forming process, and simultaneously, the talcum powder contains a large amount of silicate and silicon dioxide to further improve the high temperature resistance of the system.
Preferably, the high-temperature flame-retardant glass fiber reinforced plastic comprises the following raw materials in percentage by weight:
within the range, the obtained high-temperature flame-retardant glass fiber reinforced plastic has better high-temperature resistance.
Preferably, the glass fiber is continuous alkali-free glass fiber, which has better high temperature resistance and can ensure the continuity and uniformity of the strength of the composite material.
Preferably, the silicon-modified phenolic resin is obtained by reacting silane with phenolic resin.
Further, the silane is one or more of hexadecyl trimethoxy silane, amino propyl triethoxy silane, propyl trimethoxy silane and hexamethyl disiloxane.
Preferably, the viscosity of the silicon modified phenolic resin is 8-10 Pa, and after other additives are added into the silicon modified phenolic resin with the viscosity, the fluidity and the thixotropy are good, so that the preparation of the composite material is facilitated, and the composite material has excellent performance.
Further, the silicon-modified phenolic resin is obtained by the following steps:
(1) uniformly mixing a phenol solution, a formaldehyde solution and sodium hydroxide, heating to 70-90 ℃, preserving heat for 2-3 hours, and continuously reacting for 1-2 hours under the conditions of vacuum and 70-80 ℃ to obtain a phenolic resin intermediate;
(2) uniformly mixing silane, water and methanol, adjusting the pH value to 3-5, stirring for 3-5 h at 25-35 ℃, standing for layering, and obtaining an oil phase which is pretreated silane;
(3) uniformly mixing the phenolic resin intermediate and the pretreated silane, heating to 70-80 ℃, continuing to react until the viscosity reaches 20 Pa.s, stopping the reaction, cooling to 35-45 ℃, adding absolute ethyl alcohol, and adjusting the viscosity to 8-10 Pa.s to obtain the silicon modified phenolic resin.
Furthermore, the molar ratio of the phenol to the formaldehyde is 1 (1-1.5).
Further, the amount of the sodium hydroxide added is 0.5 to 1.5% of the sum of the amounts of the phenol solution and the formaldehyde solution added.
Furthermore, the adding amount of the silane is 1-5% of the sum of the adding amounts of the phenol solution and the formaldehyde solution.
Specifically, the mass fraction of the phenol solution is 98%, and the mass fraction of the formaldehyde solution is 37%.
Furthermore, the volume ratio of the silane, the water and the methanol is 1 (0.8-1.2) to 2-4.
Further, the vacuum condition was such that the relative degree of vacuum reached-0.01 MPa.
Preferably, the particle size of the kaolin is 0.8 to 2 μm. If the particle size is too large, the compactness of the obtained high-temperature flame-retardant glass fiber reinforced plastic is poor, and the bending strength of the high-temperature flame-retardant glass fiber reinforced plastic is reduced; if the particle size is too small, the flow property of the resin matrix is reduced, the contact area with the glass fiber is reduced, and the mechanical property and the fire integrity grade of the obtained high-temperature flame-retardant glass fiber reinforced plastic are influenced.
Referring to fig. 1, a second aspect of the present invention provides a method for preparing a high-temperature flame-retardant glass fiber reinforced plastic, comprising the following steps:
s1, uniformly mixing the silicon modified phenolic resin, aluminum hydroxide and/or magnesium hydroxide, kaolin, fumed silica and talcum powder to obtain a mixture;
and S2, laying the mixture and the glass fiber in a mold in a layered overlapping mode, and finally curing to obtain the high-temperature flame-retardant glass fiber reinforced plastic.
The preparation method of the high-temperature flame-retardant glass fiber reinforced plastic provided by the second aspect of the invention is used for obtaining the high-temperature flame-retardant glass fiber reinforced plastic provided by the first aspect of the invention.
Preferably, in the curing process, the curing temperature is 160-170 ℃, and the curing time is 2-3 h.
For avoiding redundancy, the preparation methods of the silicon modified phenolic resin used in the following examples and comparative examples of the present invention are summarized as follows:
preparation of hexadecyl trimethoxy silane modified phenolic resin:
(11) 96g of 98 percent phenol solution, 97g of 37 percent formaldehyde solution and 1.93g of sodium hydroxide are uniformly mixed, heated to 80 ℃, kept at the temperature for 3 hours and then continuously reacted for 1.5 hours under the conditions of vacuum and 75 ℃ to obtain the phenolic resin intermediate.
(21) Uniformly mixing hexadecyl trimethoxy silane, water and methanol according to the volume ratio of 1:1:3, adjusting the pH to 4, stirring for 4 hours at the temperature of 30 ℃, standing and layering, wherein the obtained oil phase is pretreated silane; wherein the mass of the hexadecyl trimethoxy silane used was 5.79 g.
(31) And uniformly mixing the phenolic resin intermediate and the pretreated silane, heating to 75 ℃ for continuous reaction until the viscosity reaches 20 Pa.s, stopping the reaction, cooling to 40 ℃, adding absolute ethyl alcohol, and adjusting the viscosity to 8-10 Pa.s to obtain the silicon modified phenolic resin.
Preparation of aminopropyltriethoxysilane modified phenolic resin:
(21) 96g of 98 percent phenol solution, 97g of 37 percent formaldehyde solution and 1.93g of sodium hydroxide are uniformly mixed, heated to 80 ℃, kept at the temperature for 3 hours and then continuously reacted for 1.5 hours under the conditions of vacuum and 75 ℃ to obtain the phenolic resin intermediate.
(22) Uniformly mixing aminopropyltriethoxysilane, water and methanol according to the volume ratio of 1:0.8:4, adjusting the pH to 4.5, stirring for 3 hours at 35 ℃, standing for layering, and obtaining an oil phase which is pretreated silane; wherein the mass of the aminopropyltriethoxysilane used is 2.895 g.
(23) And uniformly mixing the phenolic resin intermediate and the pretreated silane, heating to 80 ℃, continuing to react until the viscosity reaches 20 Pa.s, stopping the reaction, cooling to 45 ℃, adding absolute ethyl alcohol, and adjusting the viscosity to 8-10 Pa.s to obtain the silicon modified phenolic resin.
Preparation of hexamethyldisiloxane modified phenolic resin:
(31) 96g of 98 percent phenol solution, 97g of 37 percent formaldehyde solution and 1.93g of sodium hydroxide are uniformly mixed, heated to 80 ℃, kept at the temperature for 3 hours and then continuously reacted for 1.5 hours under the conditions of vacuum and 75 ℃ to obtain the phenolic resin intermediate.
(32) Uniformly mixing hexamethyldisiloxane, water and methanol according to the volume ratio of 1:1.2:2.5, adjusting the pH value to 3.5, stirring for 5 hours at 25 ℃, standing and layering to obtain an oil phase which is pretreated silane; the mass of hexamethyldisiloxane used was 8.69 g.
(33) And uniformly mixing the phenolic resin intermediate and the pretreated silane, heating to 70 ℃, continuing to react until the viscosity reaches 20 Pa.s, stopping the reaction, cooling to 35 ℃, adding absolute ethyl alcohol, and adjusting the viscosity to 8-10 Pa.s to obtain the silicon modified phenolic resin.
The silicon-modified phenol resins used in examples 1 to 5 and comparative examples 1 to 7 were all hexadecyltrimethoxysilane-modified phenol resins, the silicon-modified phenol resin used in example 6 was an aminopropyltriethoxysilane-modified phenol resin, and the silicon-modified phenol resin used in example 7 was a hexamethyldisiloxane-modified phenol resin.
Example 1
The embodiment provides a high-temperature flame-retardant glass fiber reinforced plastic which comprises the following raw materials in percentage by weight:
the preparation method of the high-temperature flame-retardant glass fiber reinforced plastic comprises the following steps:
s11, weighing the raw materials according to the weight percentage, adding fumed silica into the silicon modified phenolic resin, uniformly mixing the mixture by using an electric stirrer, sequentially adding aluminum hydroxide, kaolin and talcum powder, and uniformly mixing the mixture by using the electric stirrer to obtain a mixture;
s12, brushing the mixture into a mold, spreading glass fiber on the mold, repeating the steps alternately until the thickness reaches 2mm, finally curing the mixture at 170 ℃ for 2h, and cooling the mixture at room temperature to obtain the high-temperature flame-retardant glass fiber reinforced plastic.
Wherein the silicon modified phenolic resin is hexadecyl trimethoxy silane modified phenolic resin.
Example 2
The embodiment provides a high-temperature flame-retardant glass fiber reinforced plastic which comprises the following raw materials in percentage by weight:
the preparation method of the high-temperature flame-retardant glass fiber reinforced plastic comprises the following steps:
s21, weighing the raw materials according to the weight percentage, adding fumed silica into the silicon modified phenolic resin, uniformly mixing the mixture by using an electric stirrer, sequentially adding aluminum hydroxide, kaolin and talcum powder, and uniformly mixing the mixture by using the electric stirrer to obtain a mixture;
s22, brushing the mixture into a mold, spreading glass fiber on the mold, repeating the steps alternately until the thickness reaches 2mm, finally curing the mixture at 170 ℃ for 2h, and cooling the mixture at room temperature to obtain the high-temperature flame-retardant glass fiber reinforced plastic.
Wherein the silicon modified phenolic resin is hexadecyl trimethoxy silane modified phenolic resin.
Example 3
The embodiment provides a high-temperature flame-retardant glass fiber reinforced plastic which comprises the following raw materials in percentage by weight:
the preparation method of the high-temperature flame-retardant glass fiber reinforced plastic comprises the following steps:
s31, weighing the raw materials according to the weight percentage, adding fumed silica into the silicon modified phenolic resin, uniformly mixing the mixture by using an electric stirrer, sequentially adding aluminum hydroxide, kaolin and talcum powder, and uniformly mixing the mixture by using the electric stirrer to obtain a mixture;
s32, brushing the mixture into a mold, spreading glass fiber on the mold, repeating the steps alternately until the thickness reaches 2mm, finally curing the mixture at 170 ℃ for 2h, and cooling the mixture at room temperature to obtain the high-temperature flame-retardant glass fiber reinforced plastic.
Wherein the silicon modified phenolic resin is hexadecyl trimethoxy silane modified phenolic resin.
Example 4
The embodiment provides a high-temperature flame-retardant glass fiber reinforced plastic which comprises the following raw materials in percentage by weight:
the preparation method of the high-temperature flame-retardant glass fiber reinforced plastic comprises the following steps:
s41, weighing the raw materials according to the weight percentage, adding fumed silica into the silicon modified phenolic resin, uniformly mixing the mixture by using an electric stirrer, sequentially adding magnesium hydroxide, kaolin and talcum powder, and uniformly mixing the mixture by using the electric stirrer to obtain a mixture;
s42, brushing the mixture into a mold, spreading glass fiber on the mold, repeating the steps alternately until the thickness reaches 2mm, finally curing the mixture at 170 ℃ for 2h, and cooling the mixture at room temperature to obtain the high-temperature flame-retardant glass fiber reinforced plastic.
Wherein the silicon modified phenolic resin is hexadecyl trimethoxy silane modified phenolic resin.
Example 5
The embodiment provides a high-temperature flame-retardant glass fiber reinforced plastic which comprises the following raw materials in percentage by weight:
the preparation method of the high-temperature flame-retardant glass fiber reinforced plastic comprises the following steps:
s51, weighing the raw materials according to the weight percentage, adding fumed silica into the silicon modified phenolic resin, uniformly mixing the mixture by using an electric stirrer, sequentially adding aluminum hydroxide, magnesium hydroxide, kaolin and talcum powder, and uniformly mixing the mixture by using the electric stirrer to obtain a mixture;
s52, brushing the mixture into a mold, spreading glass fiber on the mold, repeating the steps alternately until the thickness reaches 2mm, finally curing the mixture at 170 ℃ for 2h, and cooling the mixture at room temperature to obtain the high-temperature flame-retardant glass fiber reinforced plastic.
Wherein the silicon modified phenolic resin is hexadecyl trimethoxy silane modified phenolic resin.
Example 6
The embodiment provides a high-temperature flame-retardant glass fiber reinforced plastic which comprises the following raw materials in percentage by weight:
the preparation method of the high-temperature flame-retardant glass fiber reinforced plastic comprises the following steps:
s61, weighing the raw materials according to the weight percentage, adding fumed silica into the silicon modified phenolic resin, uniformly mixing the mixture by using an electric stirrer, sequentially adding aluminum hydroxide, kaolin and talcum powder, and uniformly mixing the mixture by using the electric stirrer to obtain a mixture;
s62, brushing the mixture into a mold, spreading glass fiber on the mold, repeating the steps alternately until the thickness reaches 2mm, finally curing the mixture at 170 ℃ for 2h, and cooling the mixture at room temperature to obtain the high-temperature flame-retardant glass fiber reinforced plastic.
Wherein the silicon modified phenolic resin is aminopropyl triethoxysilane modified phenolic resin.
Example 7
The embodiment provides a high-temperature flame-retardant glass fiber reinforced plastic which comprises the following raw materials in percentage by weight:
the preparation method of the high-temperature flame-retardant glass fiber reinforced plastic comprises the following steps:
s71, weighing the raw materials according to the weight percentage, adding fumed silica into the silicon modified phenolic resin, uniformly mixing the mixture by using an electric stirrer, sequentially adding aluminum hydroxide, kaolin and talcum powder, and uniformly mixing the mixture by using the electric stirrer to obtain a mixture;
s72, brushing the mixture into a mold, spreading glass fiber on the mold, repeating the steps alternately until the thickness reaches 2mm, finally curing the mixture at 170 ℃ for 2h, and cooling the mixture at room temperature to obtain the high-temperature flame-retardant glass fiber reinforced plastic.
Wherein the silicon modified phenolic resin is hexamethyldisiloxane modified phenolic resin.
Comparative example 1
The comparative example provides a high-temperature flame-retardant glass fiber reinforced plastic which comprises the following raw materials in percentage by weight:
the preparation method of the high-temperature flame-retardant glass fiber reinforced plastic comprises the following steps:
s11a, weighing the raw materials according to the weight percentage, adding fumed silica into the silicon modified phenolic resin, uniformly mixing the materials by using an electric stirrer, sequentially adding aluminum hydroxide, kaolin and talcum powder, and uniformly mixing the materials by using the electric stirrer to obtain a mixture;
s21a, coating the mixture in a mold, spreading glass fiber on the mixture, repeating the steps alternately until the thickness reaches 2mm, finally curing the mixture at 170 ℃ for 2 hours, and cooling the mixture at room temperature to obtain the high-temperature flame-retardant glass fiber reinforced plastic.
Wherein the silicon modified phenolic resin is hexadecyl trimethoxy silane modified phenolic resin.
Comparative example 2
The comparative example provides a high-temperature flame-retardant glass fiber reinforced plastic which comprises the following raw materials in percentage by weight:
the preparation method of the high-temperature flame-retardant glass fiber reinforced plastic comprises the following steps:
s11b, weighing the raw materials according to the weight percentage, adding fumed silica into the silicon modified phenolic resin, uniformly mixing the materials by using an electric stirrer, sequentially adding aluminum hydroxide, kaolin and talcum powder, and uniformly mixing the materials by using the electric stirrer to obtain a mixture;
s21b, coating the mixture in a mold, spreading glass fiber on the mixture, repeating the steps alternately until the thickness reaches 2mm, finally curing the mixture at 170 ℃ for 2 hours, and cooling the mixture at room temperature to obtain the high-temperature flame-retardant glass fiber reinforced plastic.
Wherein the silicon modified phenolic resin is hexadecyl trimethoxy silane modified phenolic resin.
Comparative example 3
The comparative example provides a high-temperature flame-retardant glass fiber reinforced plastic which comprises the following raw materials in percentage by weight:
the preparation method of the high-temperature flame-retardant glass fiber reinforced plastic comprises the following steps:
s11c, weighing the raw materials according to the weight percentage, adding fumed silica into the silicon modified phenolic resin, uniformly mixing the materials by using an electric stirrer, sequentially adding antimony trioxide, kaolin and talcum powder, and uniformly mixing the materials by using the electric stirrer to obtain a mixture;
s21c, coating the mixture in a mold, spreading glass fiber on the mixture, repeating the steps alternately until the thickness reaches 2mm, finally curing the mixture at 170 ℃ for 2 hours, and cooling the mixture at room temperature to obtain the high-temperature flame-retardant glass fiber reinforced plastic.
Wherein the silicon modified phenolic resin is hexadecyl trimethoxy silane modified phenolic resin.
Comparative example 4
The comparative example provides a high-temperature flame-retardant glass fiber reinforced plastic which comprises the following raw materials in percentage by weight:
the preparation method of the high-temperature flame-retardant glass fiber reinforced plastic comprises the following steps:
s11d, weighing the raw materials according to the weight percentage, adding fumed silica into the silicon modified phenolic resin, uniformly mixing the materials by using an electric stirrer, sequentially adding aluminum hydroxide, bentonite and talcum powder, and uniformly mixing the materials by using the electric stirrer to obtain a mixture;
s21d, coating the mixture in a mold, spreading glass fiber on the mixture, repeating the steps alternately until the thickness reaches 2mm, finally curing the mixture at 170 ℃ for 2 hours, and cooling the mixture at room temperature to obtain the high-temperature flame-retardant glass fiber reinforced plastic.
Wherein the silicon modified phenolic resin is hexadecyl trimethoxy silane modified phenolic resin.
Comparative example 5
The comparative example provides a high-temperature flame-retardant glass fiber reinforced plastic which comprises the following raw materials in percentage by weight:
the preparation method of the high-temperature flame-retardant glass fiber reinforced plastic comprises the following steps:
s11e, weighing the raw materials according to the weight percentage, adding fumed silica into the silicon modified phenolic resin, uniformly mixing the materials by using an electric stirrer, sequentially adding aluminum hydroxide, kaolin and talcum powder, and uniformly mixing the materials by using the electric stirrer to obtain a mixture;
s21e, coating the mixture in a mold, spreading glass fiber on the mixture, repeating the steps alternately until the thickness reaches 2mm, finally curing the mixture at 170 ℃ for 2 hours, and cooling the mixture at room temperature to obtain the high-temperature flame-retardant glass fiber reinforced plastic.
Wherein the silicon modified phenolic resin is hexadecyl trimethoxy silane modified phenolic resin.
Comparative example 6
The comparative example provides a high-temperature flame-retardant glass fiber reinforced plastic which comprises the following raw materials in percentage by weight:
the preparation method of the high-temperature flame-retardant glass fiber reinforced plastic comprises the following steps:
s11f, weighing the raw materials according to the weight percentage, adding fumed silica into phenolic resin, uniformly mixing by using an electric stirrer, sequentially adding aluminum hydroxide, kaolin and talcum powder, and uniformly mixing by using the electric stirrer to obtain a mixture;
s21f, coating the mixture in a mold, spreading glass fiber on the mixture, repeating the steps alternately until the thickness reaches 2mm, finally curing the mixture at 170 ℃ for 2 hours, and cooling the mixture at room temperature to obtain the high-temperature flame-retardant glass fiber reinforced plastic.
Wherein the phenolic resin is a conventional phenolic resin which is not modified by silicon.
Comparative example 7
The comparative example provides a high-temperature flame-retardant glass fiber reinforced plastic which comprises the following raw materials in percentage by weight:
the preparation method of the high-temperature flame-retardant glass fiber reinforced plastic comprises the following steps:
s11g, weighing the raw materials according to the weight percentage, sequentially adding aluminum hydroxide, kaolin and talcum powder into the silicon modified phenolic resin, and uniformly mixing by using an electric stirrer to obtain a mixture;
s21g, coating the mixture in a mold, spreading glass fiber on the mixture, repeating the steps alternately until the thickness reaches 2mm, finally curing the mixture at 170 ℃ for 2 hours, and cooling the mixture at room temperature to obtain the high-temperature flame-retardant glass fiber reinforced plastic.
Wherein the silicon modified phenolic resin is hexadecyl trimethoxy silane modified phenolic resin.
The raw materials used in each of examples 1 to 7 and comparative examples 1 to 7 are summarized in table 1, and the data in table 1 are counted in mass percentage.
TABLE 1
Test group
The materials obtained in examples 1 to 7 and comparative examples 1 to 7 were subjected to flexural strength test, oxygen index test and fire structural integrity test, and the results are shown in Table 2. The test method comprises the following steps:
1. the bending strength test method comprises the following steps:
using the three point bend test procedure, the test specimens should have a flexural strength of 50000psi (344738kPa) or greater.
Sample size: 305mm by 478mm of the sample,
2. oxygen index test method:
the test is carried out according to GB/T8924-2005 oxygen index method which is a glass fiber reinforced plastic combustion performance test method.
3. The fire disaster structural integrity testing method comprises the following steps:
sample size: 203mm 305mm
Applying a concentrated static load at the center position of the unsupported span of the sample, keeping for 60min according to a temperature rise curve, and recording the collapse time of the sample; if the sample does not collapse within 60min, the fire integrity of the first-level structure is considered to be met; if collapsed, level 0 is assumed. The load was 88lbf (391N) and the contact surface with the sample was 0.09m2Square of (2).
Furnace temperature control curve: the temperature was raised to 927 ℃ at 60min according to the ASTME119-2018 heating system (see FIG. 2 in particular).
TABLE 2
(oxygen > 60% in the table means that the sample did not burn when the oxygen content reached 60%, and was not tested further and recorded as having an oxygen index greater than 60.)
As can be seen from Table 2, examples 1 to 7 all have higher normal temperature bending strength, the oxygen index reaches more than 60%, and the structural integrity of the fire can reach one level. Compared with the embodiment 1, the embodiment 4 and the embodiment 5 respectively use the magnesium hydroxide to completely or partially replace the aluminum hydroxide, still obtain higher normal temperature bending strength, the oxygen index reaches more than 60 percent, and the structural integrity of the fire can reach one level. In example 4, the room temperature flexural strength was lower than that of example 1 because the compatibility of magnesium hydroxide with the resin matrix was slightly lower than that of aluminum hydroxide. Compared with the embodiment 1, the embodiment 6 and the embodiment 7 respectively replace hexadecyl trimethoxy silane modified phenolic resin with aminopropyl triethoxy silane modified phenolic resin and hexamethyldisiloxane modified phenolic resin, still obtain higher normal temperature bending strength, the oxygen index reaches more than 60 percent, and the fire structural integrity reaches the first level, which shows that the silicon modified phenolic resin can improve the high temperature resistance. Compared with the embodiment 1, the comparative example 1 adds less silicon modified phenolic resin, so that the surface of the glass fiber is not wrapped by enough resin, the prepared composite material has the problem that the glass fiber is exposed, local mechanical defects are caused, and the bending strength of the material is reduced; meanwhile, in a fire integrity test, because the addition amount of the silicon modified phenolic resin is less, the carbon formation amount of a system after combustion is reduced, and the heat release is increased, so that the flame retardance is finally lower. Compared with example 1, the comparative example 2 has the advantages that more silicon modified phenolic resin is added, so that the brittleness of the high-temperature flame-retardant glass fiber reinforced plastic is higher; meanwhile, the addition amount of the glass fiber used as the framework is small, so that the normal-temperature bending strength of the high-temperature flame-retardant glass fiber reinforced plastic is low, and the high-temperature flame-retardant glass fiber reinforced plastic is very easy to collapse in a fire structural integrity test. Compared with the example 1, the antimony trioxide is adopted to replace the aluminum hydroxide in the comparative example 3, so that the curing time of the system is long, and the curing degree is low; meanwhile, antimony trioxide can not be decomposed at high temperature to generate water vapor, so that the hydration degree of kaolin is reduced, and a protective layer for preventing resin from further degrading can not be further formed, thereby reducing the bending strength at normal temperature and the oxygen index. Compared with the prior art, the bentonite is adopted to replace kaolin in the comparative example 4, and the bentonite has obvious thickening performance, so that the formed mixture has poor fluidity and is not fully infiltrated with the surface of the glass fiber, and the bending strength at normal temperature is influenced. Comparative example 5, in which less kaolin was added as compared to example 1, failed to sufficiently form a protective layer on the surface of the resin, resulting in poor bending strength at temperature, poor oxygen index, and poor structural integrity in fire. Compared with the embodiment 1, the ordinary phenolic resin is selected to replace the silicon modified phenolic resin in the comparative example 6, so that the silicon content in the system is obviously reduced, the oxygen index is reduced, the fire integrity level is reduced, and the interface effect of the phenolic resin and inorganic matters is poor, so that the normal-temperature bending strength is reduced; in comparison with example 1, in comparative example 7 in which fumed silica was not used, the dispersion uniformity of inorganic substances in the resin matrix was deteriorated, so that the room-temperature bending strength was lowered, the high-temperature resistance of fumed silica was not exhibited, the oxygen index was lowered, and the structural integrity of fire was of class 0.
In conclusion, the silicon modified phenolic resin is used as the resin matrix of the glass fiber reinforced plastic, the aluminum hydroxide, the magnesium hydroxide, the kaolin, the fumed silica and the talcum powder are added as the inorganic additives, the synergistic effect among the components is fully exerted, and the obtained high-temperature flame-retardant glass fiber reinforced plastic has higher normal-temperature bending strength, the oxygen index of more than 60 and the fire structural integrity of the first level.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The high-temperature flame-retardant glass fiber reinforced plastic is characterized by comprising the following raw materials in percentage by weight:
2. the high-temperature flame-retardant glass fiber reinforced plastic as claimed in claim 1, which comprises the following raw materials in percentage by weight:
3. the high temperature flame retardant fiberglass reinforced plastic of claim 1, wherein said glass fibers are continuous alkali free glass fibers.
4. The high-temperature flame-retardant glass fiber reinforced plastic as claimed in claim 1, wherein the silicon-modified phenolic resin is obtained by reacting silane with phenolic resin.
5. The high temperature flame retardant glass fiber reinforced plastic of claim 4, wherein the silane is one or more of hexadecyl trimethoxy silane, amino propyl triethoxy silane, propyl trimethoxy silane, and hexamethyl disiloxane.
6. The high-temperature flame-retardant glass fiber reinforced plastic according to claim 1, wherein the silicon-modified phenolic resin is obtained by the following steps:
(1) uniformly mixing a phenol solution, a formaldehyde solution and sodium hydroxide, heating to 70-90 ℃, preserving heat for 2-3 hours, and continuously reacting for 1-2 hours under the conditions of vacuum and 70-80 ℃ to obtain a phenolic resin intermediate;
(2) uniformly mixing silane, water and methanol, adjusting the pH value to 3-5, stirring for 3-5 h at 25-35 ℃, standing for layering, and obtaining an oil phase which is pretreated silane;
(3) uniformly mixing the phenolic resin intermediate and the pretreated silane, heating to 70-80 ℃, continuing to react until the viscosity reaches 20 Pa.s, stopping the reaction, cooling to 35-45 ℃, adding absolute ethyl alcohol, and adjusting the viscosity to 8-10 Pa.s to obtain the silicon modified phenolic resin.
7. The high-temperature flame-retardant glass fiber reinforced plastic as claimed in claim 6, wherein the silane is added in an amount of 1-5% of the sum of the phenol solution and the formaldehyde solution.
8. The high-temperature flame-retardant glass fiber reinforced plastic as claimed in claim 1, wherein the particle size of the kaolin is 0.8-2 μm.
9. A preparation method of the high-temperature flame-retardant glass fiber reinforced plastic as claimed in any one of claims 1 to 8, characterized by comprising the following steps:
uniformly mixing silicon modified phenolic resin, aluminum hydroxide and/or magnesium hydroxide, kaolin, fumed silica and talcum powder to obtain a mixture;
and paving the mixture and the glass fiber in a mold in a layered overlapping mode, and finally curing to obtain the high-temperature flame-retardant glass fiber reinforced plastic.
10. The preparation method of the high-temperature flame-retardant glass fiber reinforced plastic as claimed in claim 9, wherein in the curing process, the curing temperature is 160-170 ℃ and the curing time is 2-3 h.
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