CN111518362B - 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
- Publication number
- CN111518362B CN111518362B CN202010390741.0A CN202010390741A CN111518362B CN 111518362 B CN111518362 B CN 111518362B CN 202010390741 A CN202010390741 A CN 202010390741A CN 111518362 B CN111518362 B CN 111518362B
- Authority
- CN
- China
- Prior art keywords
- glass fiber
- reinforced plastic
- fiber reinforced
- phenolic resin
- temperature flame
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/14—Modified phenol-aldehyde condensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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 consists of the following raw materials in percentage by weight: 50 to 60 percent of glass fiber, 30 to 45 percent of silicon modified phenolic resin, 1 to 3 percent of aluminum hydroxide and/or magnesium hydroxide, 1 to 5 percent of kaolin, 0.1 to 0.5 percent of fumed silica and 1 to 3 percent of talcum powder. According to the invention, the silicon modified phenolic resin is adopted as a resin matrix of the glass fiber reinforced plastic, and aluminum hydroxide, magnesium hydroxide, kaolin, fumed silica and talcum powder are added as inorganic additives, so that the synergistic effect of the components is fully exerted, and the obtained high-temperature flame-retardant glass fiber reinforced plastic has higher normal-temperature bending strength, an oxygen index of more than 60 and primary fire structural integrity.
Description
Technical Field
The invention relates to the technical field of preparation of high-temperature composite materials, in particular to a high-temperature flame-retardant glass fiber reinforced plastic and a preparation method thereof.
Background
At present, the main system of the national flame retardant performance evaluation index of the high-temperature flame retardant material has no specific requirements on the performance of the flame retardant material in or after combustion in terms of oxygen index, vertical and horizontal combustion, smoke density, smoke toxicity and the like. With the gradual penetration of fire safety research, people find that the mechanical properties of materials or structures have important roles in taking rescue measures, emergency evacuation, escape and the like after the occurrence of fire. Related standards exist abroad, for example, the "Fiber Reinforced Polymer (FRP) grid for ships" standard sets forth requirements for the integrity of structural members in fire, and the mechanical properties of the materials when and after being heated also include flame retardant requirements.
The high-temperature flame retardant property of the glass fiber composite material is limited by the properties of the resin matrix used by the glass fiber composite material. At present, high-temperature glass fiber composite materials are generally prepared by adding various auxiliary agents into high-temperature resin and using glass fibers as a framework. However, the structural integrity of the glass fiber composite material taking phenolic resin as a matrix is greatly reduced after the resin is carbonized when the heated 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, and provides a high-temperature flame-retardant glass fiber reinforced plastic and a preparation method thereof, which solve the technical problems of poor mechanical property and poor structural integrity of a 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 (3) paving the mixture and glass fibers 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 adopted as a resin matrix of the glass fiber reinforced plastic, and aluminum hydroxide, magnesium hydroxide, kaolin, fumed silica and talcum powder are added as inorganic additives, so that the synergistic effect of the components is fully exerted, and the obtained high-temperature flame-retardant glass fiber reinforced plastic has higher normal-temperature bending strength, an oxygen index of more than 60 and primary fire structural integrity.
Drawings
FIG. 1 is a process flow diagram of an embodiment of a method for preparing a high temperature flame retardant glass fiber reinforced plastic provided by the invention;
FIG. 2 is a graph of the temperature rise of ASTME119-2018 used in the fire structural integrity test of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
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:
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 zone, a cracking zone and an original zone are formed from the surface to the inside in the combustion process, the oxygen-containing and highly crosslinked chemical structure enables a phenolic matrix to mainly undergo free radical transfer, high Wen Tuotang and dehydrogenation to form a carbon reaction in the thermal cracking process, a porous carbonization layer is formed in the carbonization zone and the cracking zone on the surface layer of the material by virtue of the bridging action of fibers, the permeation of oxygen and the escape of inflammable micromolecules generated by thermal cracking are effectively prevented, the condensation phase flame retardance is achieved, and after the 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, 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 further degradation of resin is prevented; the addition of the fumed silica can change the rheological property of the resin, can be used as an anti-caking agent for other powder materials in the system, prevents the powder from settling in the resin, and meanwhile, the fumed silica can resist high temperature, the nanoscale size is distributed in the system, and the high temperature resistance of the reinforced plastic can be improved; the talcum powder has good compatibility with phenolic resin, can improve the rigidity of products, reduce the thermal expansion coefficient, promote the flow, has lubricating effect, can reduce the damage degree of fibers in the forming process, and simultaneously, the talcum powder contains a large amount of silicate and silicon dioxide, so that the high temperature resistance of a system can be further improved.
Preferably, the high-temperature flame-retardant glass fiber reinforced plastic comprises the following raw materials in percentage by weight:
in the above 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 hexadecyltrimethoxysilane, aminopropyl triethoxysilane, propyl trimethoxysilane and hexamethyldisiloxane.
Preferably, the viscosity of the silicon modified phenolic resin is 8-10 Pa, and after other additives are added, the fluidity and the thixotropy of the silicon modified phenolic resin 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 through the following steps:
(1) Uniformly mixing a phenol solution, a formaldehyde solution and sodium hydroxide, heating to 70-90 ℃, preserving heat for 2-3 h, and then continuously reacting for 1-2 h under the conditions of vacuum and 70-80 ℃ to obtain a phenolic resin intermediate;
(2) Evenly mixing silane, water and methanol, regulating the pH value to 3-5, stirring for 3-5 h at 25-35 ℃, standing and layering, wherein the obtained oil phase is pretreated silane;
(3) Uniformly mixing the phenolic resin intermediate and the pretreated silane, heating to 70-80 ℃ to continue the reaction until the viscosity reaches 20 Pa.s, stopping the reaction, cooling to 35-45 ℃, adding absolute ethyl alcohol, and regulating the viscosity to 8-10 Pa.s to finally obtain the silicon modified phenolic resin.
Further, the molar ratio of the phenol to formaldehyde is 1 (1-1.5).
Further, the addition amount of the sodium hydroxide is 0.5 to 1.5 percent of the sum of the addition amounts of the phenol solution and the formaldehyde solution.
Further, the addition amount of the silane is 1 to 5% of the sum of the addition amounts of the phenol solution and the formaldehyde solution.
Specifically, the mass fraction of the phenol solution was 98%, and the mass fraction of the formaldehyde solution was 37%.
Further, the volume ratio of the silane, the water and the methanol is 1 (0.8-1.2) to 2-4.
Further, the vacuum condition is that the relative vacuum degree reaches-0.01 MPa.
Preferably, the kaolin has a particle size of 0.8 to 2. Mu.m. 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 flowability of the resin matrix is reduced, the contact area between the resin matrix and the glass fiber is reduced, and the mechanical property and fire integrity level of the obtained high-temperature flame-retardant glass fiber reinforced plastic are affected.
Referring to fig. 1, the 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 silicon modified phenolic resin, aluminum hydroxide and/or magnesium hydroxide, kaolin, fumed silica and talcum powder to obtain a mixture;
s2, paving the mixture and glass fibers 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.
In order to avoid 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% by mass of phenol solution, 97g of 37% by mass of formaldehyde solution and 1.93g of sodium hydroxide are uniformly mixed, heated to 80 ℃, kept at the temperature for 3 hours, and then reacted for 1.5 hours under the conditions of vacuum and 75 ℃ to obtain a phenolic resin intermediate.
(21) Uniformly mixing hexadecyl trimethoxy silane, water and methanol according to the volume ratio of 1:1:3, regulating the pH value to 4, stirring for 4 hours at 30 ℃, standing for layering, wherein the obtained oil phase is pretreated silane; wherein the mass of hexadecyltrimethoxysilane used was 5.79g.
(31) Uniformly mixing the phenolic resin intermediate and the pretreated silane, heating to 75 ℃ to continue the reaction until the viscosity reaches 20 Pa.s, stopping the reaction, cooling to 40 ℃, adding absolute ethyl alcohol, and regulating the viscosity to 8-10 Pa.s to finally obtain the silicon modified phenolic resin.
Preparation of aminopropyl triethoxysilane modified phenolic resin:
(21) 96g of 98% by mass of phenol solution, 97g of 37% by mass of formaldehyde solution and 1.93g of sodium hydroxide are uniformly mixed, heated to 80 ℃, kept at the temperature for 3 hours, and then reacted for 1.5 hours under the conditions of vacuum and 75 ℃ to obtain a phenolic resin intermediate.
(22) Uniformly mixing aminopropyl triethoxysilane, water and methanol according to the volume ratio of 1:0.8:4, regulating the pH value to 4.5, stirring for 3 hours at 35 ℃, standing and layering, wherein the obtained oil phase is pretreated silane; wherein the mass of the aminopropyl triethoxysilane used was 2.895g.
(23) Uniformly mixing the phenolic resin intermediate and the pretreated silane, heating to 80 ℃ to continue the reaction until the viscosity reaches 20 Pa.s, stopping the reaction, cooling to 45 ℃, adding absolute ethyl alcohol, and regulating the viscosity to 8-10 Pa.s to finally obtain the silicon modified phenolic resin.
Preparation of hexamethyldisiloxane modified phenolic resin:
(31) 96g of 98% by mass of phenol solution, 97g of 37% by mass of formaldehyde solution and 1.93g of sodium hydroxide are uniformly mixed, heated to 80 ℃, kept at the temperature for 3 hours, and then reacted for 1.5 hours under the conditions of vacuum and 75 ℃ to obtain a phenolic resin intermediate.
(32) Uniformly mixing hexamethyldisiloxane, water and methanol according to a volume ratio of 1:1.2:2.5, regulating pH to 3.5, stirring for 5h at 25 ℃, standing for layering, wherein the obtained oil phase is pretreated silane; wherein the mass of hexamethyldisiloxane used was 8.69g.
(33) Uniformly mixing the phenolic resin intermediate and the pretreated silane, heating to 70 ℃ for continuous reaction until the viscosity reaches 20 Pa.s, stopping the reaction, cooling to 35 ℃, adding absolute ethyl alcohol, and regulating the viscosity to 8-10 Pa.s, thus obtaining the silicon modified phenolic resin.
The silicon-modified phenolic resins used in examples 1 to 5 and comparative examples 1 to 7 were each hexadecyl trimethoxy silane-modified phenolic resins, the silicon-modified phenolic resin used in example 6 was amino propyl triethoxy silane-modified phenolic resin, and the silicon-modified phenolic resin used in example 7 was hexamethyldisiloxane-modified phenolic 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 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;
and S12, coating the mixture in a mold, spreading glass fibers on the mixture, repeating the steps alternately for a plurality of times until the thickness reaches 2mm, finally solidifying the mixture for 2 hours at 170 ℃, 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 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;
and S22, coating the mixture in a mold, spreading glass fibers on the mixture, repeating the steps alternately for a plurality of times until the thickness reaches 2mm, finally solidifying the mixture for 2 hours at 170 ℃, 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 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;
and S32, brushing the mixture in a mold, spreading glass fibers on the mixture, repeating the steps alternately for a plurality of times until the thickness reaches 2mm, finally curing the mixture for 2 hours at 170 ℃, 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 by using an electric stirrer, sequentially adding magnesium hydroxide, kaolin and talcum powder, and uniformly mixing by using the electric stirrer to obtain a mixture;
and S42, coating the mixture in a mold, spreading glass fibers on the mixture, repeating the steps alternately for a plurality of times until the thickness reaches 2mm, finally solidifying the mixture for 2 hours at 170 ℃, 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 by using an electric stirrer, sequentially adding aluminum hydroxide, magnesium hydroxide, kaolin and talcum powder, and uniformly mixing by using the electric stirrer to obtain a mixture;
and S52, coating the mixture in a mold, spreading glass fibers on the mixture, repeating the steps alternately for a plurality of times until the thickness reaches 2mm, finally solidifying the mixture for 2 hours at 170 ℃, 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 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;
and S62, coating the mixture in a mold, spreading glass fibers on the mixture, repeating the steps alternately for a plurality of times until the thickness reaches 2mm, finally solidifying the mixture for 2 hours at 170 ℃, 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 amino propyl triethoxy silane 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 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;
and S72, coating the mixture in a mold, spreading glass fibers on the mixture, repeating the steps alternately for a plurality of times until the thickness reaches 2mm, finally solidifying the mixture for 2 hours at 170 ℃, 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 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;
and S21a, brushing the mixture in a mold, spreading glass fibers on the mixture, repeating the steps alternately for a plurality of times until the thickness reaches 2mm, finally curing the mixture for 2 hours at 170 ℃, 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 the fumed silica into the silicon modified phenolic resin, uniformly mixing by using an electric stirrer, sequentially adding the aluminum hydroxide, the kaolin and the talcum powder, and uniformly mixing by using the electric stirrer to obtain a mixture;
and S21b, brushing the mixture in a mould, spreading glass fibers on the mixture, repeating the steps alternately for a plurality of times until the thickness reaches 2mm, finally solidifying the mixture for 2 hours at 170 ℃, 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 the fumed silica into the silicon modified phenolic resin, uniformly mixing by using an electric stirrer, sequentially adding the antimonous oxide, the kaolin and the talcum powder, and uniformly mixing by using the electric stirrer to obtain a mixture;
and S21c, coating the mixture in a mold, spreading glass fibers on the mixture, repeating the steps alternately for a plurality of times until the thickness reaches 2mm, finally solidifying the mixture for 2 hours at 170 ℃, 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 the fumed silica into the silicon modified phenolic resin, uniformly mixing by using an electric stirrer, sequentially adding the aluminum hydroxide, the bentonite and the talcum powder, and uniformly mixing by using the electric stirrer to obtain a mixture;
and S21d, coating the mixture in a mold, spreading glass fibers on the mixture, repeating the steps alternately for a plurality of times until the thickness reaches 2mm, finally solidifying the mixture for 2 hours at 170 ℃, 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 the fumed silica into the silicon modified phenolic resin, uniformly mixing by using an electric stirrer, sequentially adding the aluminum hydroxide, the kaolin and the talcum powder, and uniformly mixing by using the electric stirrer to obtain a mixture;
and S21e, coating the mixture in a mold, spreading glass fibers on the mixture, repeating the steps alternately for a plurality of times until the thickness reaches 2mm, finally solidifying the mixture for 2 hours at 170 ℃, 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;
and S21f, coating the mixture in a mold, spreading glass fibers on the mixture, repeating the steps alternately for a plurality of times until the thickness reaches 2mm, finally solidifying the mixture for 2 hours at 170 ℃, and cooling the mixture at room temperature to obtain the high-temperature flame-retardant glass fiber reinforced plastic.
Wherein the phenolic resin is 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;
and S21g, coating the mixture in a mold, spreading glass fibers on the mixture, repeating the steps alternately for a plurality of times until the thickness reaches 2mm, finally solidifying the mixture for 2 hours at 170 ℃, 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 were summarized in Table 1, and the data in Table 1 were all counted in terms of mass percent.
TABLE 1
Test group
The materials obtained in examples 1 to 7 and comparative examples 1 to 7 were subjected to a flexural strength test, an oxygen index test and a fire structural integrity test, and the results are shown in Table 2. The test method comprises the following steps:
1. bending strength test method:
using the three point bend test procedure, the test specimen should have a bending strength of 50000psi (344738 kPa) or more.
Sample size: 305mm x 478mm,
2. oxygen index test method:
according to GB/T8924-2005 oxygen index method of glass fiber reinforced plastics combustion performance test method.
3. Fire structural integrity testing method:
sample size: 203 mm.305 mm
Applying concentrated static load to the center of the unsupported span of the sample, keeping for 60min according to a heating curve, and recording the collapse time of the sample; if the sample does not collapse within 60 minutes, the sample is considered to conform to the primary structure fire integrity; if collapsed, it is considered to be level 0. The load was 88lbf (391N), and the contact surface with the sample was 0.09m 2 Is a square of (c).
Furnace temperature control curve: the temperature was raised to 927 ℃ for 60min according to astm e119-2018 temperature rise regime (see specifically fig. 2).
TABLE 2
(in the table, the oxygen content >60% means that the sample was not burned when the oxygen content reached 60%, and the test was not continued, and it was recorded that the oxygen index was greater than 60.)
As can be seen from Table 2, examples 1 to 7 all have higher normal temperature flexural strength, the oxygen index reaches more than 60%, and the structural integrity of the fire disaster reaches one level. Compared with the example 1, the example 4 and the example 5 respectively replace aluminum hydroxide completely or partially by magnesium hydroxide, still obtain higher normal-temperature bending strength, the oxygen index reaches more than 60%, and the structural integrity of fire disaster reaches one level. In example 4, since the compatibility of magnesium hydroxide with the resin matrix was slightly lower than that of aluminum hydroxide, the normal temperature bending strength was lower than that of example 1. Compared with the example 1, the example 6 and the example 7 respectively replace hexadecyl trimethoxy silane modified phenolic resin with amino propyl triethoxy silane modified phenolic resin and hexamethyldisiloxane modified phenolic resin, still obtain higher normal temperature bending strength, oxygen index is more than 60%, and fire structural integrity reaches a first level, which indicates that the silicon modified phenolic resin can improve high temperature resistance. Compared with the embodiment 1, the silicon modified phenolic resin is added in the comparative example 1, so that the surface of the glass fiber is not wrapped by enough resin, the prepared composite material has exposed glass fiber, local mechanical defect is caused, and the bending strength of the material is reduced; meanwhile, in the fire integrity test, the addition amount of the silicon modified phenolic resin is small, so that the carbon forming amount of a system after combustion is reduced, the heat release is increased, and the flame retardance is low finally. Compared with example 1, more silicon modified phenolic resin is added in comparative example 2, so that the brittleness of the obtained high-temperature flame-retardant glass fiber reinforced plastic is higher; meanwhile, the glass fiber serving as a framework has low addition amount, so that the obtained high-temperature flame-retardant glass fiber reinforced plastic has low normal-temperature bending strength and is extremely easy to collapse in fire structural integrity test. Compared with the example 1, the antimonous oxide is adopted to replace aluminum hydroxide in the comparative example 3, so that the curing time of the system is long and the curing degree is lower; meanwhile, the antimonous oxide cannot be decomposed to generate water vapor under the high-temperature condition, so that the hydration degree of kaolin is reduced, and a protective layer for preventing further degradation of resin cannot be further formed, so that the normal-temperature bending strength and the oxygen index are reduced. In comparative example 4, bentonite is used instead of kaolin, and because the thickening property of bentonite is obvious, the formed mixture has poor fluidity and insufficient infiltration with the surface of glass fiber, thereby affecting the normal-temperature bending strength. In comparative example 5, less kaolin was added than in example 1, which did not sufficiently form a protective layer on the resin surface, resulting in poor warm bending strength, oxygen index and fire structural integrity. Compared with the example 1, the ordinary phenolic resin is selected to replace the silicon modified phenolic resin in the comparative example 6, the silicon content in the system is obviously reduced, the oxygen index is reduced, the fire integrity level is reduced, the interface effect between the phenolic resin and the inorganic matters is poor, and the normal-temperature bending strength is reduced; in comparison with example 1, in comparative example 7, no fumed silica was used, and the dispersion uniformity of the inorganic matters in the resin matrix was poor, so that the flexural strength at room temperature was lowered, the high temperature resistance of fumed silica was not reflected, the oxygen index was lowered, and the fire structural integrity was 0 grade.
In summary, the invention adopts the silicon modified phenolic resin as the resin matrix of the glass fiber reinforced plastic, and adds the aluminum hydroxide, the magnesium hydroxide, the kaolin, the fumed silica and the talcum powder as the inorganic additive to fully exert the synergistic effect among the components, and the obtained high-temperature flame-retardant glass fiber reinforced plastic has higher normal-temperature bending strength, an oxygen index of more than 60 and primary fire structural integrity.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
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 according to claim 1, which comprises the following raw materials in percentage by weight:
3. the high temperature flame retardant glass fiber reinforced plastic of claim 1, wherein the glass fiber is a continuous alkali free glass fiber.
4. The high temperature flame retardant glass fiber reinforced plastic of claim 1, wherein the silicon modified phenolic resin is derived from the reaction of a silane with a phenolic resin.
5. The high temperature flame retardant glass fiber reinforced plastic of claim 4, wherein the silane is one or more of hexadecyltrimethoxysilane, aminopropyltriethoxysilane, propyltrimethoxysilane, hexamethyldisiloxane.
6. The high temperature flame retardant fiberglass reinforced plastic of claim 1, wherein the silicon modified phenolic resin is obtained by:
(1) Uniformly mixing a phenol solution, a formaldehyde solution and sodium hydroxide, heating to 70-90 ℃, preserving heat for 2-3 h, and then continuously reacting for 1-2 h under the conditions of vacuum and 70-80 ℃ to obtain a phenolic resin intermediate;
(2) Evenly mixing silane, water and methanol, regulating the pH value to 3-5, stirring for 3-5 h at 25-35 ℃, standing and layering, wherein the obtained oil phase is pretreated silane;
(3) Uniformly mixing the phenolic resin intermediate and the pretreated silane, heating to 70-80 ℃ to continue the reaction until the viscosity reaches 20 Pa.s, stopping the reaction, cooling to 35-45 ℃, adding absolute ethyl alcohol, and regulating the viscosity to 8-10 Pa.s to finally obtain the silicon modified phenolic resin.
7. The high temperature flame retardant glass fiber reinforced plastic according to claim 6, wherein the addition amount of the silane is 1 to 5% of the sum of the addition amount of the phenol solution and the formaldehyde solution.
8. The high temperature flame retardant glass fiber reinforced plastic of claim 1, wherein the kaolin has a particle size of 0.8 to 2 μm.
9. A method for preparing the high-temperature flame-retardant glass fiber reinforced plastic as claimed in any one of claims 1 to 8, 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 (3) paving the mixture and glass fibers in a mold in a layered overlapping mode, and finally curing to obtain the high-temperature flame-retardant glass fiber reinforced plastic.
10. The method for preparing high-temperature flame-retardant glass fiber reinforced plastic according to claim 9, wherein in the curing process, the curing temperature is 160-170 ℃ and the curing time is 2-3 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010390741.0A CN111518362B (en) | 2020-05-11 | 2020-05-11 | High-temperature flame-retardant glass fiber reinforced plastic and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010390741.0A CN111518362B (en) | 2020-05-11 | 2020-05-11 | High-temperature flame-retardant glass fiber reinforced plastic and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111518362A CN111518362A (en) | 2020-08-11 |
| CN111518362B true CN111518362B (en) | 2023-05-12 |
Family
ID=71908844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010390741.0A Active CN111518362B (en) | 2020-05-11 | 2020-05-11 | High-temperature flame-retardant glass fiber reinforced plastic and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111518362B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991011323A1 (en) * | 1990-01-29 | 1991-08-08 | Owens-Corning Fiberglas Corporation | Fire-resistant panel system |
| CN104292612A (en) * | 2014-05-27 | 2015-01-21 | 安徽宁国市高新管业有限公司 | High-strength wear resistant glass fiber reinforced plastic |
| CN104513453A (en) * | 2015-01-14 | 2015-04-15 | 苏州图纳新材料科技有限公司 | Thermoset phenolic resin composite material and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3179777B2 (en) * | 1989-11-27 | 2001-06-25 | 住友ベークライト株式会社 | Phenolic resin molding material |
| US9062202B2 (en) * | 2007-02-26 | 2015-06-23 | Hexion Inc. | Resin-polyester blend binder compositions, method of making same and articles made therefrom |
| CN103772904A (en) * | 2014-01-23 | 2014-05-07 | 南通美固复合材料有限公司 | Glass fiber unidirectional enhanced phenolic resin composite material cable holder and preparation method thereof |
| CN109517331A (en) * | 2018-11-30 | 2019-03-26 | 江苏中鹏新材料股份有限公司 | Without ammonia high intensity phenolaldehyde moulding compound and preparation method thereof |
| CN109735110A (en) * | 2019-01-15 | 2019-05-10 | 哈尔滨工业大学 | A kind of modified phenolic-organic siliconresin composite material and preparation method |
-
2020
- 2020-05-11 CN CN202010390741.0A patent/CN111518362B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991011323A1 (en) * | 1990-01-29 | 1991-08-08 | Owens-Corning Fiberglas Corporation | Fire-resistant panel system |
| CN104292612A (en) * | 2014-05-27 | 2015-01-21 | 安徽宁国市高新管业有限公司 | High-strength wear resistant glass fiber reinforced plastic |
| CN104513453A (en) * | 2015-01-14 | 2015-04-15 | 苏州图纳新材料科技有限公司 | Thermoset phenolic resin composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 玻纤增强酚醛注塑料的制备技术和性能;范宏，等;化工学报;第56卷(第10期);1993-1997 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111518362A (en) | 2020-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6617983B2 (en) | Ceramicized silicone resin composition, and prepreg and laminate using the same | |
| CN112961528B (en) | Environment-friendly fireproof coating and preparation method thereof | |
| CN109749463B (en) | High-molecular fireproof and moistureproof plugging agent and preparation method and application thereof | |
| CN109232850A (en) | A kind of fire-retardant low thermal conductivity rigid polyurethane foam of aeroge modified heat resistant and preparation method thereof | |
| CN109956726B (en) | Raw material composition and flexible heat-insulation board | |
| CN112831174A (en) | Preparation and application of ZnO @ MOF @ polyphosphazene flame retardant | |
| CN104804368A (en) | Phenolic resin and polyurethane prepolymer composite foam material and preparation method | |
| Gajiwala et al. | Hybridized resin matrix approach applied for development of carbon/carbon composites—I | |
| CN111518362B (en) | High-temperature flame-retardant glass fiber reinforced plastic and preparation method thereof | |
| CN113895103B (en) | High-toughness nano heat-insulating material and preparation method thereof | |
| CN114989756B (en) | High-temperature-resistant flame-retardant epoxy adhesive and preparation method thereof | |
| CN103602070A (en) | Silicone rubber composite material and preparation method thereof | |
| CN107501856B (en) | Preparation method of flame-retardant modified wood fiber composite phenolic foam | |
| CN106928648B (en) | Whisker reinforced toughened halogen-free flame-retardant phenolic foam plastic and preparation method thereof | |
| CN112898043B (en) | High-temperature-resistant energy-saving insulation board for industrial furnace and preparation method | |
| CN111807808B (en) | Preparation method of high-temperature-resistant heat-insulation composite material | |
| CN109868067A (en) | A kind of polystyrene thermal insulation plate material refractory adhesive | |
| CN115181499A (en) | Water-resistant, high-adhesion and flame-retardant magnesium oxychloride inorganic adhesive as well as preparation method and application thereof | |
| EP4177230A1 (en) | Composition for thermal insulation | |
| CN1848572A (en) | Light noninflammable anti corrosion high strength electric cable bridge trough box | |
| CN109694214B (en) | Novel bonding material for expanded perlite insulation board and preparation method and application thereof | |
| CN112680104A (en) | Environment-friendly steel structure fireproof coating and preparation method thereof | |
| CN111470841A (en) | Preparation method of floor heating material | |
| CN112552639B (en) | Non-combustible matrix resin and non-combustible glass fiber reinforced plastic prepared from same | |
| CN111196711A (en) | Waterproof building material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |