CN112094478A - Fast-curing phenolic resin-based thermal protection material and preparation method thereof - Google Patents
Fast-curing phenolic resin-based thermal protection material and preparation method thereof Download PDFInfo
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- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 51
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 48
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000835 fiber Substances 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 11
- 238000003825 pressing Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 7
- 239000005642 Oleic acid Substances 0.000 claims description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical group [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 229920002866 paraformaldehyde Polymers 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 230000007480 spreading Effects 0.000 claims description 3
- 238000003892 spreading Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 17
- 230000008901 benefit Effects 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 230000003335 steric effect Effects 0.000 abstract description 2
- 238000002679 ablation Methods 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- -1 phenolic aldehyde Chemical class 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- QFXZANXYUCUTQH-UHFFFAOYSA-N ethynol Chemical group OC#C QFXZANXYUCUTQH-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
-
- 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
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
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- 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
- C08K7/10—Silicon-containing compounds
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention discloses a preparation method of a fast curing phenolic resin-based thermal protection material, and relates to the technical field of thermal protection composite materials. Compared with the common phenolic resin, the high-ortho phenolic resin has the advantages that in the curing process, due to the low steric effect of unreacted hydrogen on the para position of phenolic hydroxyl, the curing efficiency is high, the cured crosslinking density is high, the high-temperature carbon residue rate is excellent, and the high-ortho phenolic resin has more excellent heat resistance and mechanical properties after being compounded with high-silica fiber with high specific strength by mould pressing.
Description
The technical field is as follows:
the invention relates to the technical field of heat-proof composite materials, in particular to a fast-curing phenolic resin-based thermal protection material and a preparation method thereof.
Background art:
with the rapid development of the aerospace and military industries, thermal protective materials are also exposed to harsh environments. Such as high temperature, high pressure, high heat flux, etc. The jet pipe is one of the important parts of the solid propellant rocket engine and mainly used for converting the internal energy of the propellant in the combustion chamber into kinetic energy to push the rocket to fly. During operation, the entire nozzle interior is filled with a large volume of high temperature, high pressure, high velocity gas stream with solid particles. All parts of the nozzle are subjected to strong thermal shock and mechanical shock. In order to prevent the heat in the jet pipe from being rapidly transferred to the rocket shell to cause the rocket shell to lose efficacy, a material with good heat insulation performance and strong instant ablation resistance is selected as a lining material of the rocket engine.
The high silica/phenolic composite material uses phenolic resin as a matrix and is reinforced by high silica fibers. The material is widely applied to the lining material of the nozzle of the medium and small-caliber rocket engine because of the ablation performance of low density, low thermal conductivity, high strength and high reliability. In the ablation process, the high-silica/phenolic aldehyde composite material can not only generate penetrating pyrolysis gas to bring partial heat into the atmosphere, but also form a thicker carbonized layer. The carbonization zone prevents heat from being transferred to the inside by radiating the effective heat that gives off of effect. In addition, the high silica fibers at high temperature melt to absorb part of the heat and form SiO2And the liquid film is covered on the surface of the ablation material and plays a role in resisting high-speed high-temperature air flow scouring. At present, the composite spray pipe of the common phenolic resin and the high silica fiber is prepared by adopting a compression molding process, and has the characteristics of high designability of material shape and structure, good process repeatability and the like. But also has the defects of slow curing process, long preparation period and the like, and increases the processing cost. And limits the wide application of the traditional Chinese medicine to a certain extent. And the high silica/phenolic aldehyde based composite material prepared in a short period can cause the thermal property and the mechanical property to be reduced to different degrees. Therefore, how to ensure the high mechanical property and ablation resistance of the composite material on the premise of shortening the period and reducing the costPerformance is the focus of current research.
The invention content is as follows:
the technical problem to be solved by the invention is to provide a fast curing phenolic resin-based thermal protection material and a preparation method thereof, and the prepared composite material has good heat resistance and high strength and can meet the requirement of long-time ablation thermal insulation. More importantly, the high-ortho phenolic resin is used as matrix resin, the high reactivity of the high-ortho phenolic resin effectively reduces the curing time in the mould pressing process, shortens the preparation period, and is an ablation heat-proof and heat-insulating integrated composite material.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
a preparation method of a fast curing phenolic resin-based thermal protection material comprises the following preparation steps:
a) adding high-ortho phenolic resin and ethanol into a mixing container, stirring, adding an internal release agent, talcum powder and a silane coupling agent, and uniformly mixing to obtain a high-ortho phenolic resin solution;
b) adding the chopped high-silica fiber filaments into the product obtained in the step a), uniformly stirring to obtain a premix, spreading the premix in an oven for drying, and sealing and storing for later use;
c) uniformly spraying an external release agent in a clean die, preheating the die, putting the premix dried to constant weight in the step b) into the die, closing the die, applying pressure for prepressing, heating and curing, preserving heat and pressure in the curing process, cooling and demolding to obtain the rapidly-cured phenolic resin-based thermal protection material.
The preparation method of the high ortho phenolic resin comprises the following steps: putting phenol and paraformaldehyde into a reaction kettle, stirring and mixing, adding a catalyst, adjusting the pH value to 4-6 by glacial acetic acid, heating to a reflux temperature for reaction, performing vacuum dehydration after reacting for a certain time, maintaining the dehydration temperature for a period of time after the dehydration temperature is increased to 90-100 ℃, measuring the viscosity and the gel time of the resin, stopping vacuumizing after meeting the requirement, adding industrial alcohol, continuously stirring, cooling, and discharging to obtain the high-ortho phenolic resin.
The molar ratio of the phenol to the formaldehyde in the step is 1: 1.5-2; the catalyst is magnesium oxide, and the addition amount of the magnesium oxide is 2-4% of the mass of the phenol; after the temperature is raised to the reflux temperature, keeping for 1-3 h; the purity of the industrial alcohol is 95 percent; the gel time is 70-120S/150 ℃.
The mass ratio of the high ortho phenolic resin to the ethanol is 1: 0.67-0.75.
The length of the chopped high silica fiber filaments is 15-30 mm.
The drying temperature is 80-100 ℃, and the drying time is 30-60 min.
The premix dried to constant weight in the step b) comprises the following components: 30-40% of high-ortho phenolic resin liquid, 1-2% of oleic acid, 0.7-1% of talcum powder, 1-2% of silane coupling agent and 50-60% of high-silica fiber in percentage by mass.
The internal release agent is oleic acid, and the external release agent is 19 wrelsee.
When the die is preheated, the temperature of the die is increased to 90-130 ℃ at the temperature increasing rate of 5 ℃/min, and the preheating time is 10-15 min.
The curing pressure is 5MPa, the curing temperature is 170-180 ℃, and the curing time is 1-1.5 min/mm. If the pressure is reduced, the pressure is supplemented.
The technical indexes of the premix prepared by the invention are as follows:
| appearance of the product | Volatile fraction/%) | Gel content/% | Insoluble resin content/%) |
| Light yellow | 1-5 | 40-45 | 5-10 |
The invention has the beneficial effects that:
(1) the rapid curing phenolic resin-based thermal protection material prepared by the invention meets the requirements of GJB1595-93 technical indexes and the like, and simultaneously overcomes the problems of slow curing process, long preparation period and the like of the common phenolic resin-based thermal protection composite material.
(2) Compared with the common phenolic resin, the high-ortho phenolic resin has the advantages that in the curing process, due to the low steric effect of unreacted hydrogen on the para position of phenolic hydroxyl, the curing efficiency is high, the cured crosslinking density is high, the high-temperature carbon residue rate is excellent, and the high-ortho phenolic resin has more excellent heat resistance and mechanical property after being compounded with high-silica fiber with high specific strength through mould pressing;
(3) the ablation heat protection mechanism of the fast curing high silica/phenolic composite material prepared by the invention can be explained by three aspects:
a. the high specific heat capacity of the composite material can absorb part of heat transferred into the interior in the high-temperature ablation process;
b. the generated pyrolysis gas escapes and forms a thermal blocking effect to prevent the heat from further corroding the substrate;
c. the C-Si reaction between the pyrolytic carbon residue generated by the resin and the high-silica fiber is an endothermic reaction, and the high-silica fiber at high temperature is melted to absorb partial heat and form SiO2And the liquid film covers the surface of the ablation material.
In addition, the curing agent has the advantages of high curing speed, good processing performance and the like, greatly reduces the production cost, has low density, and can meet the strict requirements of the rocket engine on the improvement of the heat insulation performance and the weight reduction of the heat-proof material.
Description of the drawings:
FIG. 1 is a DSC curve of a high ortho phenolic resin in example 1 of the present invention;
FIG. 2 is a DSC curve of an ammonia phenolic resin in a comparative example.
The specific implementation mode is as follows:
in order to make the technical means, the original characteristics, the achieved purposes and the effects of the invention easy to understand, the invention is further explained by combining the specific embodiments and the drawings.
Example 1
Preparing high ortho phenolic resin: putting 300g of phenol and 154g of paraformaldehyde into a reaction kettle, stirring and mixing, adding 9g of magnesium oxide, adjusting the pH value to 5 with glacial acetic acid, heating to a reflux temperature for condensation reaction, performing vacuum dehydration after reacting for 1h, maintaining the dehydration temperature at 90 ℃ for a period of time, measuring the viscosity and the gelation time of the resin, stopping vacuumizing when the gelation time is 80s/150 ℃, adding 200g of 95% industrial alcohol, continuously stirring, cooling to 60 ℃, and discharging to obtain the high-ortho phenolic resin.
a) Adding the high-ortho phenolic resin and absolute ethyl alcohol into a reaction container according to the mass ratio of 1: 0.68. Mechanically stirring to uniformly disperse the mixture; and sequentially adding an internal release agent oleic acid, talcum powder and a silane coupling agent, and uniformly mixing to obtain the high-ortho phenolic resin solution.
b) Adding high-silica chopped fiber filaments with the length of 20mm into the product obtained in the step a), uniformly stirring in a reaction kettle at the rotating speed of 20rpm, finally spreading the premix in an oven, and drying at 80 ℃ for 12 h. After the premix is dried to constant weight, sealing and storing for later use; wherein the components are as follows (by mass percent): 40% of high-ortho phenolic resin, 1% of oleic acid, 0.9% of talcum powder, 1.1% of silane coupling agent and 57% of high-silica fiber.
c) The 19 wreseal external mold release was sprayed uniformly into the cleaned mold. The premix dried to constant weight in step b) is then placed in a mold, pressure is applied and the surface is smoothed. The temperature of the die is increased to 115 ℃ at the temperature increasing rate of 5 ℃/min, and the preheating time is 10 min. And (5) after the temperature is constant, filling the dried premix into a mold, and closing the mold. After 20s, the pressure is increased to 5 MPa. The curing temperature is 170 ℃ and the curing time is 1.5 min/mm. If the pressure is reduced, the pressure is supplemented. After the post-curing is finished, the film is removed after the temperature is reduced to 120 ℃.
The fast curing high silica/phenolic composite obtained in this example was tested for properties, the results of which are shown in table 1.
Comparative example 1
The preparation method is basically the same as that of the example, except that: mixing commercially available ammonia phenolic resin with solid content of 60%, specific gravity of 1.06, free phenol of more than 15% and polymerization speed of 80s/150 ℃ and absolute ethyl alcohol according to the ratio of 1: a ratio of 0.68 was added to the reaction vessel. And mechanically stirring and mixing the high silica short-cut fiber with the length of 20mm, and then drying the mixture to prepare the high silica/phenolic aldehyde composite material according to the steps of the embodiment. Wherein the components are as follows (by mass percent): 40% of ammonia phenolic resin, 1% of oleic acid, 0.9% of talcum powder, 1.1% of silane coupling agent and 57% of high silica fiber.
The curing reaction temperature and reaction heat of the high ortho phenolic resin in example 1 and the amino phenolic resin in comparative example 1 were tested by Differential Scanning Calorimetry (DSC) and the results are shown in figures 1 and 2.
As can be seen from fig. 1 and 2, the curing reaction initiation, peak and termination temperatures of the high ortho phenolic resin are advanced and the heat of reaction is reduced compared to the conventional ammonia phenolic resin. The resin polymerization rate was tested according to GJB 1059.4-90. The polymerization speed test result shows that the gel time of the high ortho phenolic resin is obviously lower than that of the common ammonia phenolic resin.
The rapid curing high silica/phenolic aldehyde composite material obtained in the comparative example and the embodiment is subjected to physical and chemical performance tests and is compared with GJB1595-93 Standard of high silica chopped fiber reinforced phenolic plastic molded end caps and end bodies; measuring density according to GB/T1463-2005 standard, measuring tensile property according to GB/T1447-2005 standard, measuring bending property according to GB/T1449-2005 standard, measuring thermal conductivity according to GB/T3139-2005 test standard, carrying out oxy-acetylene ablation test according to GJB323A-96 standard, and averaging average specific heat capacity according to GB/T3140-2005 standard. The test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, all indexes of the fast-curing high-silica/phenolic resin-based heat-proof composite material prepared by the invention meet the technical requirements of military standard GJB1595-93 in the aerospace industry. And the parameters such as the thermal conductivity coefficient, the specific heat, the line ablation rate and the like are higher than those of the common high silica/phenolic aldehyde composite material of the same type. More importantly, the pressing time is obviously shortened, the production efficiency is improved, and the labor and time cost are saved.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A preparation method of a fast curing phenolic resin-based thermal protection material is characterized by comprising the following steps: the preparation method comprises the following preparation steps:
a) adding high-ortho phenolic resin and ethanol into a mixing container, stirring, adding an internal release agent, talcum powder and a silane coupling agent, and uniformly mixing to obtain a high-ortho phenolic resin solution;
b) adding the chopped high-silica fiber filaments into the product obtained in the step a), uniformly stirring to obtain a premix, spreading the premix in an oven for drying, and sealing and storing for later use;
c) uniformly spraying an external release agent in a clean die, preheating the die, putting the premix dried to constant weight in the step b) into the die, closing the die, applying pressure for prepressing, heating and curing, preserving heat and pressure in the curing process, cooling and demolding to obtain the rapidly-cured phenolic resin-based thermal protection material.
2. The method of claim 1, wherein: the preparation method of the high ortho phenolic resin comprises the following steps: putting phenol and paraformaldehyde into a reaction kettle, stirring and mixing, adding a catalyst, adjusting the pH value to 4-6 by glacial acetic acid, heating to a reflux temperature for reaction, performing vacuum dehydration after reacting for a certain time, maintaining for a period of time after the dehydration temperature is increased to 90-100 ℃, determining the viscosity and the gel time of resin, stopping vacuumizing after meeting the requirement, adding industrial alcohol, continuously stirring, cooling, and discharging.
3. The method of claim 2, wherein: the molar ratio of the phenol to the formaldehyde in the step is 1: 1.5-2; the catalyst is magnesium oxide, and the addition amount of the magnesium oxide is 2-4% of the mass of the phenol; after the temperature is raised to the reflux temperature, keeping for 1-3 h; the purity of the industrial alcohol is 95 percent; the gel time is 70-120S/150 ℃.
4. The method of claim 1, wherein: the mass ratio of the high ortho phenolic resin to the ethanol is 1: 0.67-0.75.
5. The method of claim 1, wherein: the length of the chopped high silica fiber filaments is 15-30 mm.
6. The method of claim 1, wherein: the drying temperature is 80-100 ℃, and the drying time is 30-60 min.
7. The method of claim 1, wherein: the premix dried to constant weight in the step b) comprises the following components: 30-40% of high-ortho phenolic resin liquid, 1-2% of oleic acid, 0.7-1% of talcum powder, 1-2% of silane coupling agent and 50-60% of high-silica fiber in percentage by mass.
8. The method of claim 1, wherein: the internal release agent is oleic acid, and the external release agent is 19 wrelsee.
9. The method of claim 1, wherein: when the die is preheated, the temperature of the die is increased to 90-130 ℃ at the temperature increasing rate of 5 ℃/min, and the preheating time is 10-15 min.
10. The method of claim 1, wherein: the curing pressure is 5MPa, the curing temperature is 170-180 ℃, and the curing time is 1-1.5 min/mm. If the pressure is reduced, the pressure is supplemented.
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| CN116376216A (en) * | 2023-03-27 | 2023-07-04 | 宁波安力电子材料有限公司 | Preparation method of phenolic resin molding material for commutator |
| CN117209844A (en) * | 2023-08-28 | 2023-12-12 | 蚌埠市天宇高温树脂材料有限公司 | Layered graphite carbon nitride nano-sheet containing zirconium and titanium, and preparation method and application thereof |
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| CN116376216B (en) * | 2023-03-27 | 2023-11-28 | 宁波安力电子材料有限公司 | Preparation method of phenolic resin molding material for commutator |
| CN117209844A (en) * | 2023-08-28 | 2023-12-12 | 蚌埠市天宇高温树脂材料有限公司 | Layered graphite carbon nitride nano-sheet containing zirconium and titanium, and preparation method and application thereof |
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Application publication date: 20201218 |