CN112239526B - Preparation method of RTM type boron phenolic resin - Google Patents
Preparation method of RTM type boron phenolic resin Download PDFInfo
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Abstract
The invention relates to a preparation method of RTM type boron phenolic resin. The method comprises the steps of dissolving phenolic novolac resin and boric acid in an ethanol solution, adding the solution into a three-neck bottle, and dissolving the phenolic novolac resin and the boric acid in ethanol under the conditions of magnetic stirring and reflux to form a uniform mixed solution. Then the temperature is raised to the reaction temperature, and ethanol is removed by reduced pressure distillation. And finally, continuously stirring for reaction, cooling, and adding ethanol again to obtain the boron phenolic resin solution. Because the B-O bond energy is higher than that of the C-C bond, the addition of boron enables the cured product to contain a three-dimensional cross-linked network structure of boron, and the heat resistance of the phenolic resin is improved; the B-O bond has better flexibility and can reduce the brittleness of the phenolic resin; the method can synthesize the linear boron phenolic resin, and has high reaction degree and high boron composite content. The invention has the advantages of low cost, controllable process, low reaction condition, suitability for industrial production, suitability for RTM forming of reaction products and the like.
Description
Technical Field
The invention relates to a preparation method of RTM type boron phenolic resin, belonging to the technical field of phenolic resin materials and aircraft thermal protection.
Background
Ablative materials have found wide application in the aerospace industry, and almost all aerospace industry thermal protective materials have been applied to ablative materials. Phenolic resins are synthetic resins which are the earliest to realize industrial production in the world, are prepared by polycondensation of phenols (such as phenol and resorcinol) and aldehydes (such as formaldehyde and furfural) compounds, and have been used for over a century. The phenolic resin has excellent heat resistance, flame retardance and hot hardness, has higher strength at high temperature, and is widely applied to the field of aerospace ablative materials. However, with the higher demand of modern aerospace vehicles on speed, the requirements on the performance of the phenolic resin, particularly the ablation resistance, are more and more strict, and the development of heat-resistant and temperature-resistant materials is limited by the conditions of the phenolic resin due to the structure of the phenolic resin and the easily oxidized group of the phenolic resin. Therefore, heat resistance modification of phenolic resins has been a hot point of research.
Boron phenolic resins are one of the most successful phenolic resin modified varieties at present, and the research thereof starts in the united states of the 50 th century in 20 th century and is commercialized in the 60 th century. In China, in the 70 th 20 th century, the boron phenolic resin was successfully developed by the Beijing glass fiber reinforced plastic institute composite material Co-Ltd and the Hebei university together, and the mass production of the boron phenolic resin was realized. Because the B-O bond energy formed by substituting hydrogen in phenolic hydroxyl by boron is far greater than the C-C bond energy, free phenolic hydroxyl in the system is reduced, the polymerization degree is increased, small molecular gas generated at high temperature is less, and the ablation internal pressure is effectively controlled; meanwhile, the boron carbide honeycomb structure formed on the surface of the resin during high-temperature pyrolysis can prevent heat from diffusing inwards to protect an internal structure, so that the boron phenolic resin has excellent heat resistance.
Research on boride modified phenolic resin shows that boron has a remarkable effect on improving the heat resistance and the ablation resistance of the phenolic resin. No matter the inorganic boride or the organic boride is introduced into a molecular structure, the heat resistance and the carbon residue rate of the phenolic resin can be obviously improved, but the defects of the inorganic boride modified phenolic resin in the aspects of manufacturability and mechanical property are still obvious. The synthesis method of boron phenolic resin is mainly divided into three main types, namely a paraformaldehyde method, a salicyl alcohol method and a copolymerization blending method. At present, the paraformaldehyde method is mostly adopted in industrial production, but the method is difficult to produce the linear boron phenolic Resin suitable for RTM (Resin Transfer Molding) process.
Disclosure of Invention
Aiming at the ablation resistance requirement of the field of aerospace vehicles on phenolic thermal protection materials at present, the invention provides a preparation method of RTM type boron phenolic resin, which is used for successfully preparing the RTM type boron phenolic resin material by reacting boric acid with low molecular weight linear phenolic resin. By "RTM-type" is meant that the boron novolac resin is compatible with RTM molding processes.
The linear phenolic resin and the boric acid are dissolved in the ethanol, then the linear phenolic resin and the boric acid are added into a three-neck bottle, and the phenolic resin and the boric acid are dissolved in the ethanol under the conditions of magnetic stirring and reflux to form a uniform mixed solution. Then the temperature is raised to the reaction temperature, and the ethanol is removed by adopting a reduced pressure distillation mode. And finally, continuously stirring for reaction, cooling, and adding ethanol again to obtain the boron phenolic resin solution. Boron is introduced into the structure of the phenolic resin, and because the B-O bond energy is higher than that of a C-C bond, the addition of the boron enables the cured product to contain a three-dimensional cross-linked network structure of the boron, so that the heat resistance of the phenolic resin is improved; secondly, the B-O bond has better flexibility and can reduce the brittleness of the phenolic resin; finally, the method can synthesize the linear boron phenolic resin, and has high reaction degree and high boron composite content. The invention has the advantages of low cost, controllable process, low reaction condition, suitability for industrial production, suitability for RTM forming of reaction products and the like. The prepared boron phenolic resin has good manufacturability and low viscosity, can be cured to form a light aerogel structure, has excellent ablation resistance, can maintain the original shape and performance at high temperature, and is expected to be applied to the field of external thermal protection of high-speed aircrafts.
The purpose of the invention is realized by the following technical scheme.
A preparation method of RTM type boron phenolic resin comprises the following steps:
1) Dissolving phenolic resin and boric acid in ethanol to form a mixed solution;
2) Heating the mixed solution to a reaction temperature, and removing ethanol in the mixed solution by adopting a reduced pressure distillation mode;
3) And continuously stirring the solution from which the ethanol is removed at the reaction temperature, reacting for a certain time, cooling to a certain temperature, and adding the ethanol to obtain the boron phenolic resin solution.
Further, the phenolic resin in the step 1) is a linear phenolic resin, the number average molecular weight Mn is preferably in the range of 500-800, and the softening point is preferably 60-90 ℃.
Further, the adding amount of the boric acid in the step 1) is preferably between 1wt% and 10wt% of the content of the phenolic resin.
Further, the mass fraction of the phenolic resin and the boric acid in the mixed solution of step 1) is preferably between 20wt% and 70wt%, and more preferably 50wt%.
Preferably, in the step 1), a certain amount of phenolic resin powder, ethanol and boric acid accounting for 5wt% of the mass of the phenolic resin are added into a three-neck flask, and the phenolic resin and the boric acid are dissolved in the ethanol to form a uniform mixed solution with the mass fraction of 50% by stirring for 1-3 hours at 30-80 ℃ under the conditions of magnetic stirring and reflux.
Further, the temperature of the reduced pressure distillation in the step 2) is 90-130 ℃, and more preferably 110 ℃; the time of the reduced pressure distillation is 10-50min, and more preferably 30min. Namely, step 2) the mixed solution is preferably stirred and heated to 110 ℃ and distilled under reduced pressure for 30min to remove ethanol.
Further, the reaction temperature of the step 3) is 100-130 ℃, and is more preferably 110 ℃; the reaction time is 1-5h, and 4h is more preferable; the cooling to a certain temperature is to 60-80 deg.c, more preferably 80 deg.c. Namely, in the step 3), preferably, the mixture is continuously stirred and reacted for 4 hours at the reaction temperature of 110 ℃, and then the mixture is cooled to 80 ℃ and then added with ethanol to obtain the boron phenolic resin solution.
The invention also provides the RTM type boron phenolic resin prepared by the method.
The beneficial effects of the invention are:
(1) The invention designs a simple and effective reaction mode, and boric acid and linear phenolic resin are reacted to synthesize the boron phenolic resin. The controllable preparation of the linear boron phenolic resin is realized by regulating and controlling the boric acid content, the ethanol content, the reaction temperature and other conditions, the reaction condition is low, the boron recombination amount is high, the oxidation and ablation resistance is obviously improved, the process is simple and controllable, and the method is suitable for industrial production.
(2) According to the invention, boric acid is introduced into the phenolic resin to form a more stable three-dimensional cross-linked network structure, so that the thermal stability and the carbon residue rate of the phenolic resin are improved, and meanwhile, a boron carbide honeycomb structure formed on the surface of the resin during high-temperature pyrolysis can prevent heat from diffusing inwards to protect the internal structure, so that the boron phenolic resin has excellent ablation resistance.
(3) The boron element exists in the resin structure in the form of B-O bond, and transmits external force through single bond rotation and bond angle deformation, thereby making up the defects of large brittleness and difficult processing of common resin. Meanwhile, as the resin is converted from a dendritic structure to a three-dimensional structure, the formation of a polycarbon structure at high temperature is promoted, so that the heat resistance of the resin is increased. The oxidation resistance and the heat resistance of the boron modified phenolic resin are higher than those of the traditional phenolic resin. Therefore, the boron modified phenolic resin is more suitable to be used as matrix resin of an aerospace vehicle thermal protection material.
Drawings
FIG. 1 is an X-ray photoelectron spectrum of a RTM type boron-containing phenolic resin material prepared in example 1.
FIG. 2 is an X-ray diffraction pattern of the RTM-type boronovolac resin material prepared in example 1.
FIG. 3 is a thermogravimetric plot of the RTM-type boronovolac resin material prepared in example 1.
FIG. 4 is an X-ray diffraction pattern of the RTM-type boronovolac resin material prepared in example 2.
FIG. 5 is a thermogravimetric plot of the RTM-type boronovolac resin material prepared in example 2.
Detailed Description
For a better understanding of the present invention, reference is made to the following detailed description of the invention.
In the following examples:
x-ray photoelectron spectroscopy (XPS) instrument: model ESCA Lab 250xi, thermo Fisher Scientific;
x-ray diffraction (XRD) instrument: model PW-1710, philips; the X-ray source is Cu Ka, and the adopted wavelength is 0.154nm;
thermogravimetric (TG-DSC) analysis: the thermal gravimetric-differential thermal analysis instrument of the company Diamond TG/DTA of Perkin-Elmer in America is used for measuring, the heating rate is 20K/min under the nitrogen atmosphere, and the temperature scanning range is from room temperature to 800 ℃.
Example 1:
firstly, adding a certain amount of phenolic powder, ethanol and boric acid accounting for 5wt% of the mass of phenolic into a three-neck flask, and stirring for 1h at 80 ℃ under the conditions of magnetic stirring and reflux to dissolve phenolic resin and boric acid into ethanol to form a uniform mixed solution with the mass fraction of 50%. Subsequently, the temperature was raised to 110 ℃ with stirring, and ethanol was removed by distillation under reduced pressure for 30min. And finally, continuously stirring and reacting for 4 hours at the reaction temperature, cooling to 80 ℃, and adding ethanol to obtain the boron phenolic resin solution.
The X-ray photoelectron spectroscopy (picture 1) result shows that the molar content of the boron element is 5.61%, and the boric acid and the phenolic aerogel are successfully compounded. As can be seen from the X-ray diffraction in fig. 2, the prepared boron-phenolic aerogel has an amorphous peak at about 21 degrees, which corresponds to an amorphous structure of phenolic aldehyde and silicon oxide. The thermogravimetric curve (fig. 3) shows that the 800 ℃ residual weight of the boron-phenolic aerogel is 66%, the residual carbon rate of the phenolic aerogel is greatly improved, the temperature corresponding to the maximum thermal decomposition rate is increased, the thermal decomposition rate is reduced, and the thermal decomposition temperature area is widened. Boron is introduced into the structure of the phenolic resin, and because the B-O bond energy is higher than that of a C-C bond, the addition of the boron enables the cured product to contain a three-dimensional cross-linked network structure of the boron, so that the heat resistance of the phenolic resin is improved; secondly, the B-O bond has better flexibility, so that the brittleness of the phenolic resin can be reduced; finally, the method can synthesize the linear boron phenolic resin, and has high reaction degree and high boron composite content.
Example 2:
firstly, adding a certain amount of phenolic powder, ethanol and boric acid accounting for 10wt% of the mass of the phenolic into a three-neck flask, and stirring for 1h at 80 ℃ under the conditions of magnetic stirring and reflux to dissolve the phenolic resin and the boric acid into the ethanol to form a mixed solution with the uniform mass fraction of 50%. Subsequently, the mixture was stirred and heated to 110 ℃ and distilled under reduced pressure for 30min to remove ethanol. And finally, continuously stirring and reacting for 4 hours at the reaction temperature, cooling to 80 ℃, and adding ethanol to obtain the boron phenolic resin solution.
The X-ray photoelectron spectroscopy result shows that the molar content of the boron element is 9.79 percent, and the boric acid and the phenolic aerogel are successfully compounded. As can be seen from the X-ray diffraction in fig. 4, the prepared boron-phenolic aerogel has an amorphous peak at about 21 degrees, which corresponds to an amorphous structure of phenolic aldehyde and silicon oxide, and a tiny diffraction peak at 26 degrees, which corresponds to boric acid. The thermogravimetric curve (fig. 5) shows that the residual weight of the boron phenolic aerogel at 800 ℃ is 70%, the residual carbon rate of the phenolic aerogel is greatly improved, the temperature corresponding to the maximum thermal decomposition rate is increased, the thermal decomposition rate is reduced, and the thermal decomposition temperature area is widened. According to the invention, boric acid is introduced into the phenolic resin to form a more stable three-dimensional cross-linked network structure, so that the thermal stability and the carbon residue rate of the phenolic resin are improved, and meanwhile, a boron carbide honeycomb structure formed on the surface of the phenolic resin during high-temperature pyrolysis can prevent heat from diffusing inwards to protect the internal structure, so that the boron phenolic resin has excellent ablation resistance
Example 3:
firstly, adding a certain amount of phenolic powder, ethanol and boric acid accounting for 5wt% of the mass of the phenolic into a three-neck flask, and stirring for 1h at 80 ℃ under the conditions of magnetic stirring and reflux to dissolve the phenolic resin and the boric acid into the ethanol to form a mixed solution with the uniform mass fraction of 70%. Subsequently, the mixture was stirred and heated to 110 ℃ and distilled under reduced pressure for 30min to remove ethanol. And finally, continuously stirring and reacting for 4 hours at the reaction temperature, cooling to 80 ℃, and adding ethanol to obtain the boron phenolic resin solution.
The X-ray photoelectron spectroscopy result shows that the molar content of the boron element is 5.32 percent, and the boric acid and the phenolic aerogel are successfully compounded. As can be seen from X-ray diffraction, the prepared boron phenolic aerogel has an amorphous peak at about 21 ℃, corresponds to a phenolic aldehyde and silicon oxide amorphous structure, and has no boric acid diffraction peak. The thermogravimetric curve shows that the ablation-resistant boron-containing phenolic aerogel has a residual weight of 64% at 800 ℃, so that the residual carbon rate of the phenolic aerogel is greatly improved, the temperature corresponding to the maximum thermal decomposition rate is increased, the thermal decomposition rate is reduced, and the thermal decomposition temperature area is widened. The boron exists in the resin structure in the form of B-O bonds, and external force is transmitted through single bond rotation and bond angle deformation, so that the defects of high brittleness and difficult processing of common resin are overcome. Meanwhile, as the resin is converted from a dendritic structure to a three-dimensional structure, the formation of a polycarbon structure at high temperature is promoted, so that the heat resistance of the resin is increased. The oxidation resistance and the heat resistance of the boron modified phenolic resin are higher than those of the traditional phenolic resin.
Example 4:
firstly, adding a certain amount of phenolic powder, ethanol and boric acid accounting for 5wt% of the mass of phenolic into a three-neck flask, and stirring for 1h at 80 ℃ under the conditions of magnetic stirring and reflux to dissolve phenolic resin and boric acid into ethanol to form a uniform mixed solution with the mass fraction of 50%. Subsequently, the temperature was raised to 130 ℃ with stirring, and ethanol was removed by distillation under reduced pressure for 30min. And finally, continuously stirring and reacting for 4 hours at the reaction temperature, cooling to 80 ℃, and adding ethanol to obtain the boron phenolic resin solution.
The X-ray photoelectron spectroscopy result shows that the molar content of the boron element is 5.63 percent, and the boric acid and the phenolic aerogel are successfully compounded. As can be seen from X-ray diffraction, the prepared boron phenolic aerogel has an amorphous peak at about 21 ℃, and corresponds to a phenolic aldehyde and silicon oxide amorphous structure. The thermogravimetric curve shows that the ablation-resistant phenolic aerogel has the residual weight of 65% at 800 ℃, the residual carbon rate of the phenolic aerogel is greatly improved, the temperature corresponding to the maximum thermal decomposition rate is increased, the thermal decomposition rate is reduced, and the thermal decomposition temperature area is widened. Reacting boric acid with linear phenolic resin to synthesize boron phenolic resin. The controllable preparation of the linear boron phenolic resin is realized by regulating and controlling the boric acid content, the ethanol content, the reaction temperature and other conditions, the reaction condition is low, the boron recombination amount is high, the oxidation and ablation resistance is obviously improved, the process is simple and controllable, and the method is suitable for industrial production.
In summary, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation method of RTM type boron phenolic resin is characterized by comprising the following steps:
1) Dissolving phenolic resin and boric acid in ethanol to form a mixed solution;
2) Heating the mixed solution to a reaction temperature, and removing ethanol in the mixed solution by adopting a reduced pressure distillation mode;
3) Continuously stirring the solution without the ethanol at the reaction temperature, reacting for a certain time, cooling to a certain temperature, and adding the ethanol to obtain a boron phenolic resin solution suitable for an RTM (resin transfer molding) process; wherein, boron exists in the resin structure in the form of B-O bond, and transmits external force through single bond rotation and bond angle deformation;
wherein the phenolic resin in the step 1) is linear phenolic resin, and the number average molecular weight Mn is 500-800;
wherein, the adding amount of the boric acid in the step 1) is 1 to 10 weight percent of the content of the phenolic resin;
wherein, the reaction temperature in the step 3) is 100-130 ℃, and the reaction time is 1-5h; the cooling to a certain temperature is to be carried out to 60-80 ℃.
2. The method of claim 1, wherein the phenolic resin of step 1) has a softening point of 60 ℃ to 90 ℃.
3. The method according to claim 1, wherein the mass fraction of the phenolic resin and the boric acid in the mixed solution of step 1) is 20wt% to 70wt%.
4. The method according to claim 1, wherein the phenolic resin, the ethanol and the boric acid are added into the three-neck flask in the step 1), and the phenolic resin and the boric acid are dissolved in the ethanol to form a mixed solution by stirring for 1-3 hours at 30-80 ℃ under the conditions of magnetic stirring and reflux.
5. The method according to claim 1, wherein the temperature of the reduced pressure distillation in the step 2) is 90-130 ℃ and the time is 10-50min.
6. The method according to claim 5, wherein the reduced pressure distillation in step 2) is carried out at a temperature of 110 ℃ for a period of 30min.
7. The method according to claim 1, wherein the reaction temperature in step 3) is 110 ℃, and the reaction time is 4h; the cooling to a certain temperature is to 80 ℃.
8. An RTM type boron phenol formaldehyde resin prepared according to the process of any one of claims 1 to 7.
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| CN113651934A (en) * | 2021-08-31 | 2021-11-16 | 中国地质大学（北京） | Boride modified thermosetting phenolic resin and preparation and degradation method of composite material thereof |
| CN115403898B (en) * | 2022-09-30 | 2023-12-19 | 西安交通大学 | Phenolic resin suitable for RTM process and preparation method and application thereof |
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| US4663105A (en) * | 1985-01-23 | 1987-05-05 | Nissan Motor Co., Ltd. | Method of producing silicon carbide base sintered material containing boron as sintering assistant |
| JPS63156814A (en) * | 1986-12-22 | 1988-06-29 | Gunei Kagaku Kogyo Kk | Production of heat-resistant phenolic resin |
| CN102746479A (en) * | 2011-04-19 | 2012-10-24 | 襄樊学院 | Preparation method of boron-containing phenolic resin for friction materials |
| CN110746637A (en) * | 2019-11-04 | 2020-02-04 | 航天特种材料及工艺技术研究所 | Ceramic modified ablation-resistant phenolic aerogel and preparation method thereof |
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| US4663105A (en) * | 1985-01-23 | 1987-05-05 | Nissan Motor Co., Ltd. | Method of producing silicon carbide base sintered material containing boron as sintering assistant |
| JPS63156814A (en) * | 1986-12-22 | 1988-06-29 | Gunei Kagaku Kogyo Kk | Production of heat-resistant phenolic resin |
| CN102746479A (en) * | 2011-04-19 | 2012-10-24 | 襄樊学院 | Preparation method of boron-containing phenolic resin for friction materials |
| CN110746637A (en) * | 2019-11-04 | 2020-02-04 | 航天特种材料及工艺技术研究所 | Ceramic modified ablation-resistant phenolic aerogel and preparation method thereof |
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