CN109749351A - A kind of phenol-formaldehyde resin modified, composite material and preparation method - Google Patents
A kind of phenol-formaldehyde resin modified, composite material and preparation method Download PDFInfo
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Abstract
The present invention proposes that a kind of phenol-formaldehyde resin modified, composite material and preparation method, including phenolic resin, chopped strand, cenosphere and heat reflection substance, cenosphere are made of phenolic aldehyde cenosphere and ceramic hollow microballon.The present invention is designed by special formulation, has taken into account non-ablative class surface emissivity, low-heat leads the advantage that heat absorption, quality injection are cracked with ablation class；Processing is blended with inorganic matter masterbatch by ceramic hollow microballon in the present invention, so that it is improved heat-proof quality and improves the capability of resistance to radiation on ablator surface.
Description
Technical field
The present invention relates to a kind of phenol-formaldehyde resin modifieds, composite material and preparation method, belong to technical field of composite materials.
Background technique
Hypersonic vehicle needs for a long time with high Mach flight, and surface needs to bear very high temperature and non-
Often big gas shock needs on its surface to ensure the normal work of element in aircraft body using thermal protection system.Heat
Guard system is that protection is on active service in high thermal environment aircraft from the key subsystem that burns or overheat.Existing thermal protection
System and material mainly include non-ablative class and ablation class.Non-ablative type thermally protective materials preventing principle: surface emissivity；Low-heat is led
Rate material hinders convective heat transfer, solid heat transfer etc..Ablative-type protective coating thermally protective materials preventing principle: the cracking heat absorption of Ablative resin；Carbon
Distillation heat absorption；The quality injection of cracked gas；The radiation effect of carburization zone.
Non-ablative class thermal protection is although reusable, but can not make accurately to the high heat-flux conditions or thermal environment of military service
Prediction, therefore can not determine moderate scheme.Ablating heat shield, solar heat protection is high-efficient, and adaptation flow field change ability is strong, and system knot
Structure is simple, more easy to the processing at the more severe position of thermal environment, need to only thicken part.But with more High Mach number
Flight demand, increase thickness simply is also not good act.
Phenolic resin mainly takes away heat by self-cleavage as common ablative-type protective coating material, in ablation process, phenol
Urea formaldehyde heat shield thickness has apparent reduction, serious to itself consumption.By adding thermal insulating filling (example in phenolic resin
Such as glass hollow microballoon) Lai Gaishan heat insulation, but the amount being added is very little, does not have obvious effect；The amount of addition is too many, again
It will affect moulding process and mechanical property.
Summary of the invention
It is an object of the invention to overcome the shortage of prior art, provide that one kind takes into account non-ablative class surface emissivity, low-heat is led
With ablation class cracking heat absorption, the phenol-formaldehyde resin modified of quality injection, composite material and preparation method.
Technical solution of the invention: a kind of phenol-formaldehyde resin modified, including phenolic resin, chopped strand, cenosphere,
Heat reflection substance and toughener, each component mass ratio are as follows:
The cenosphere is made of phenolic aldehyde cenosphere and ceramic hollow microballon, ceramic hollow microballon and phenolic aldehyde microballon
Mass ratio 1/2~2/1.
The ceramic hollow microballon by be blended with inorganic matter master batch processing after, make in ceramic hollow microballon and microballon it
Between air generate anion.
The inorganic matter master batch is tourmaline master batch or opal master batch, and but not limited to this, as long as ceramics can be excited
Air generates the inorganic matter of anion between cenosphere.
The inorganic matter master batch is that inorganic matter is made through broken, crushing, levigate, separation.
There are certain differences between the diameter of the ceramic hollow microballon and inorganic matter master batch, are convenient for ceramic hollow microballon
It is separated with the screening of inorganic matter master batch.
The cenosphere that the present invention uses is phenolic aldehyde cenosphere and ceramic hollow microballon.Phenolic composite material is due to phenol
Compatibility between the fabrics such as urea formaldehyde and quartz, high silicon oxygen, glass fibre is bad, along with phenolic resin brittleness itself compared with
Height, therefore the interlayer performance of composite material is poor.The present invention is hollow micro- by the way that suitable phenolic aldehyde is added in phenolic resin system
On the one hand pearl can significantly improve the toughness of resin matrix, on the other hand can be formed by phenolic aldehyde cenosphere excellent continuous
Phase improves the continuity of resin between composite material fabric layer and tissue layer, and then improves the interlayer of phenolic composite material
Energy.Therefore, the mass ratio of phenolic aldehyde cenosphere and phenolic resin is not less than 5:100, and otherwise improvement is unobvious.
In the case that cenosphere total amount is constant, the addition of ceramic hollow microballon has improvement to materials thermophysics performance, with
The increase of ceramic hollow microballon accounting, performance boost be more obvious；But ceramic hollow microballon accounting is more than comprehensive entirety after 1:1
Improvement declines instead, the mass ratio 1/2~2/1 of preferably ceramic cenosphere and phenolic aldehyde cenosphere, most preferably 1:1.
Under the same terms (ceramic hollow microballon accounting is identical), when early period increases with cenosphere total amount, composite material thermophysical property
It improves, after the arrival of cenosphere total amount and phenolic resin mass ratio 15:100 or so, cenosphere total amount is further added by, composite material
Thermophysical property raising is unobvious, but due to increasing microballon total amount accounting, larger to the Effect on Mechanical Properties of material.Therefore,
Cenosphere and phenolic resin mass ratio preferably 14~16:100.
The chopped strand can be 800 DEG C of heatproof or more, and thermal coefficient is lower than the chopped strand of 0.06W/ (mK),
As alumina silicate chopped strand, chopped carbon fiber, the quartz fibre that is chopped, ceramic chopped strand, basalt chopped fiber, the boron that is chopped are fine
Dimension etc., preferably alumina silicate chopped strand.
The addition of chopped strand can effectively improve composite material thermophysical property, but the amount being added will not play obviously very little
Effect, the amount of addition will affect the uniformity of resin again too much；It is preferred that the mass ratio of phenolic resin and alumina silicate chopped strand
For 100:5~20, optimum quality is than the mass ratio for phenolic resin and chopped strand in 100:9~11.
The present invention is used to improve the interface between fiber and phenolic resin using coupling agent, such as the silicon on alumina silicate fibre surface
There are strong hydrogen bonds for the hydroxyl of the siloxy group of acid groups and coupling agent generation bonding action, coupling agent amino and phenolic resin
Effect, thus the intensity of composite material can be significantly increased.For state of the art, specific coupling agent type and dosage can
It determines as the case may be, reference can be made to (foreign countries build for interface performance research that history Asia monarch writes silane coupling agent and Exploration of Mechanism [J]
Material science and technology, 2005,26 (4): 70-71).
The heat reflection substance be reflection coefficient > 80% inorganic filler, structure be spinelle or rutile-type, such as
TiO2, rutile type titanium white etc..
The addition of heat reflection substance can improve prepreg solidification after thermophysical property, but be added amount will not play very little it is bright
Aobvious effect, the amount of addition will affect the uniformity of resin again too much；It is preferred that the mass ratio of phenolic resin and heat reflection substance is
100:3~16, optimum quality ratio are 100:7~9.
Chopped strand, heat reflection substance and the ceramic hollow microballon for the lower thermal conductivity that the present invention uses all have lower lead
Hot coefficient, can effectively inhibit and radiation-screening heat and conduction are hot.It is in order to be further improved thermophysical property, ceramic hollow is micro-
Pearl carries out that processing is blended with inorganic matter masterbatch, and inorganic matter masterbatch can discharge the ion with identical charges, micro- in ceramic hollow in this way
It in pearl microballon and is no longer simple still air or vacuum between microballon and microballon, but there is largely have phase
With the ion of charge, the electromagnetism wave energy of the emission of ions with identical charges effectively shields the electromagnetic wave of thermal energy, more can be effective
The conduction for preventing thermal energy completely eliminates free air layer, reduces thermal coefficient resistance value, improves heat-proof quality and improves ablator
The capability of resistance to radiation on surface；Make voided layer on ceramic hollow microballon wall and microballon wall thickness uniform simultaneously, compressive resistance, expansion
Coefficient can be more uniform consistent.Therefore, the mass ratio of ceramic hollow microballon and phenolic resin is not less than 5:100, otherwise improves effect
Fruit is unobvious.
Toughener is state of the art, and specific type and dosage can determine as the case may be, general in engineering
It is the 0.5~1% of phenolic resin quality.The present invention is not particularly limited phenolic resin type, as long as being able to satisfy ablation material
The requirement of material.
A kind of phenolic resin composite is made by modification phenolic resin-based bluk recombination fabric, the modification phenol
Urea formaldehyde includes phenolic resin, chopped strand, cenosphere, heat reflection substance and toughener, and each component mass ratio is as follows:
The cenosphere is made of phenolic aldehyde cenosphere and ceramic hollow microballon, and ceramic hollow microballon is hollow with phenolic aldehyde
The mass ratio 1/2~2/1 of microballon.
The fabric is the composite fibre fabric for being added to spirality crimping phenolic fibre, the spiral shape volume
The quantity ratio that bent phenolic fibre accounts for composite fibre fabric is 1/3~1/2.
The composite fibre fabric can also be containing quartzy glass, aramid fiber, carbon fiber etc., and but not limited to this,
As long as temperature resistant grade, mechanical property etc. are able to satisfy ablator needs.
Fabric is woven to techniques well known, those skilled in the art can according to specific product to be prepared come
It determines.Spirality crimping phenolic fibre is prepared by the principle that generation turbulent flow, internal stress are irregular when polymer melt squeezes out and is formed
Fiber radial direction dissymmetrical structure and reach rolled efficiency, be techniques well known, specifically refer to Zhang Dongqing, Lei Shiwen, scape
The work such as benefit " melt-spun of hollow phenolic fibers is studied and performance characterization " (material engineering, 2007；Supplementary issue: 172-178), Cui Yan, king
Enable ox etc. write " design and application of melt-spun hollow fibre spinneret " (Zhengzhou Polytechnical Univ.'s journal, 1998；19:109—111),
Zhang Dongqing, Shi Jingli, Guo Quangui etc. write " influence of the spinneret pore structure to hollow phenolic fibers Cross Section Morphology in melt-spun " (aerospace material
Expect work, 2008,4,35-39) etc..
The present invention overcomes the smooth fibre commonly woven by increasing spirality crimping phenolic fibre in fabric
Not only intensity is low, but also can slide between fiber in the environment of high pressure, high gas flow, and the resin extruded defect gone, and makes multiple
Condensation material is tieed up shape effect in the environment of high pressure, high gas flow and is improved.
A kind of phenol-formaldehyde resin modified preparation method, is realized by following steps:
The first step, pre-treatment of raw material,
Pretreatment and ceramic hollow microballon pretreatment including chopped strand, the ceramic hollow microballon pretreatment is such as
Under:
A1.1, inorganic matter master batch is prepared,
Inorganic matter prepares inorganic matter master batch through broken, crushing, levigate, separation, drying；
A1.2, by the step A1.1 inorganic matter master batch being prepared and ceramic hollow microballon after mixing, then from mixing
Object sieve, which takes, isolates ceramic hollow microballon；
The pretreatment of chopped strand is techniques well known, specially dilutes coupling agent, configuration coupling with deionized water
Chopped strand is placed in coupling agent aqueous solution by agent aqueous solution, is impregnated to take out behind 30min~1 hour and is dried that (dip time cannot
It is too long, otherwise will affect fibre strength).
Second step prepares phenol-formaldehyde resin modified,
A2.1, weigh in proportion pretreated chopped strand and ceramic hollow microballon, phenolic resin, heat reflection substance,
Phenolic aldehyde cenosphere and toughener；
A2.2, weighed raw material are sequentially placed into order in the reaction kettle of pre- heating；
A2.3, raw material are stirred evenly in reaction kettle, obtains phenol-formaldehyde resin modified.
A kind of phenolic resin composite preparation method, is realized by following steps:
The first step, phenol-formaldehyde resin modified preparation,
A1.1, pre-treatment of raw material,
Pretreatment and ceramic hollow microballon pretreatment including chopped strand, the ceramic hollow microballon pretreatment is such as
Under:
A1.1.1, inorganic matter master batch is prepared,
Inorganic matter prepares inorganic matter master batch through broken, crushing, levigate, separation, drying；
A1.1.2, by the step A1.1.1 inorganic matter master batch being prepared and ceramic hollow microballon after mixing, then from
Mixture sieve, which takes, isolates ceramic hollow microballon；
A1.2, phenol-formaldehyde resin modified is prepared,
A1.2.1, pretreated chopped strand and ceramic hollow microballon, phenolic resin, heat reflection object are weighed in proportion
Matter, phenolic aldehyde cenosphere and toughener；
A1.2.2, weighed raw material are sequentially placed into order in the reaction kettle of pre- heating；
Raw material ordering in launching is as follows: resin is first added, phenolic resin preheating temperature is generally 50~70 DEG C；Again in resin
Middle addition toughener；Then chopped strand, heat reflection substance are added, phenolic aldehyde microballon, ceramic microbead is finally added, specifically adds suitable
Sequence is determined according to viscosity.
A1.2.3, raw material are stirred evenly in reaction kettle, obtains phenol-formaldehyde resin modified.
Second step prepares fabric,
The fabric is the composite fibre fabric for being added to spirality crimping phenolic fibre, the spiral shape volume
The quantity ratio that bent phenolic fibre accounts for composite fibre fabric is 1/3~1/2；
Third step, the preparation of prepreg；
Using the phenol-formaldehyde resin modified of first step preparation and the fabric of second step preparation, phenolic resin prepolymer is prepared
Leaching material；
Prepreg is the prior art, according to circumstances can choose preparation process.
4th step, prepreg solidification, obtains phenolic resin composite.
Curing process is determining according to the specific type of phenolic resin, techniques well known.
The present invention compared with prior art the utility model has the advantages that
(1) present invention is designed by special formulation, has taken into account non-ablative class surface emissivity, low-heat is led to crack with ablation class and be inhaled
Heat, the advantage of quality injection；
(2) by ceramic hollow microballon with inorganic matter masterbatch processing is blended in the present invention, keep microballon interior and microballon and microballon it
Between be no longer simple still air or vacuum, but there is a large amount of ions for having identical charges, have identical charges
The electromagnetism wave energy of emission of ions effectively shield the electromagnetic wave of thermal energy, more can effectively prevent the conduction of thermal energy, completely eliminate from
By air layer, thermal coefficient resistance value is reduced, improve heat-proof quality and improves the capability of resistance to radiation on ablator surface；
(3) present invention can be significantly improved by the way that suitable phenolic aldehyde cenosphere is added in phenolic resin system on the one hand
On the other hand the toughness of resin matrix can form excellent continuous phase by phenolic aldehyde cenosphere, improve composite material fabric
The continuity of resin between layer and tissue layer, and then improve the interlayer performance of phenolic composite material；
(4) present invention by fabric increase spirality crimping phenolic fibre, overcome commonly weave it is smooth
Not only intensity is low for fiber, but also can slide between fiber in the environment of high pressure, high gas flow, and the resin extruded defect gone,
Make composite material tie up shape effect in the environment of high pressure, high gas flow to be improved；
(5) preparation method of the present invention is simple, various raw material disposal modes are easy, without special equipment.
Specific embodiment
Below with reference to specific example, the present invention is described in detail.
Embodiment 1
Phenol-formaldehyde resin modified matches (mass ratio)
The preparation method is as follows:
1) ceramic hollow microballon blending is handled
Opal shale ore is produced into diameter in the opal master batch of 100um or so through broken, crushing, levigate, separation
(ceramic hollow microballon diameter is generally 10~30um), opal master batch is 2 hours dry at 120 DEG C, the albumen after drying
Stone master batch mixes in high-speed mixer with ceramic hollow microballon to be allowed to uniformly for 2 hours, after standing 30min cooling, from mixture
Sieve, which takes, isolates ceramic hollow microballon.
2) fabric prepares
Choose 85tex c-type quartz glass, spirality crimping phenolic fibre 20S/3, aramid fiber-tri- kinds of Kevlar K49
Fiber is that 1:1:1 weaves according to quantity ratio (radical ratio), knitting yarn weft density: 9/cm, surface density 150g/ ㎡.
3) prepared by phenol-formaldehyde resin modified
It weighs in the pre- reaction kettle for being warming up to 65 DEG C of 10kg phenolic resin addition and stirs 30min, the stirring of 50g toughener is added
10min is added 1kg alumina silicate chopped strand and stirs 10min, 800gTiO is added210min is stirred, it is total through step 1) that 750g is added
The ceramic hollow microballon of mixed processing stirs 10min, and 750g phenolic aldehyde tiny balloon is added and stirs 10min, to finally stir in reaction kettle
Can uniformly resin be taken out envelope freezing for use by mixing.
4) prepared by prepreg
The phenol-formaldehyde resin modified of step 3) and the fabric of step 2) are made into the prepreg that resin content is 40%.
Prepreg is prepared by test sample using mould pressing method, specific performance is shown in Table 1.
Embodiment 2
In addition to fabric, other are shown in Table 1 with embodiment 1, the test sample specific performance of this example with when step.
Fabric:
Bis- kinds of 85tex c-type quartz glass, spirality crimping phenolic fibre 20S/3 fibers are chosen according to quantity ratio (radical
Than) 5:4 carries out braiding braiding, knitting yarn weft density: 9/cm, surface density 150g/ ㎡.
Table 1
From table 1 it follows that using different fabrics, it is smaller on the influence of composite material thermophysical property, but in fabric
Aramid fiber, which is added, can improve the mechanical properties such as the tensile strength of composite material, and the addition of aramid fiber can also improve production well
The interlayer performance of product.
Embodiment 3,4
Heat reflection substance (TiO in embodiment 3,42) addition number is 3 and 16, other are with embodiment 1, obtained test examination
Sample specific performance is shown in Table 2.
Table 2
| Embodiment 3 | Embodiment 1 | Embodiment 4 | Comparative example 1 | |
| Thermal coefficient W/ (mK) | 0.14 | 0.1 | 0.15 | 0.2 |
| Linear ablative rate mm/s | 0.12 | 0.09 | 0.12 | 0.15 |
| Puffer ablation test mm/s | 0.23 | 0.18 | 0.25 | 0.3 |
| Tensile strength MPa | 230 | 237 | 232 | 235 |
| Compressive strength MPa | 165 | 173 | 169 | 170 |
From Table 2, it can be seen that the addition of heat reflection substance can effectively improve composite material thermophysical property, optimal phenolic aldehyde
The mass ratio of resin and heat reflection substance is near 100:8.
Embodiment 5,6
The addition number of alumina silicate chopped strand is respectively 5,20 in embodiment 5,6, other are with when preparation method with real
Example 1 is applied, obtained test sample specific performance is shown in Table 3.
Table 3
| Embodiment 5 | Embodiment 1 | Embodiment 6 | Comparative example 2 | |
| Thermal coefficient W/ (mK) | 0.15 | 0.1 | 0.17 | 0.28 |
| Linear ablative rate mm/s | 0.12 | 0.09 | 0.14 | 0.19 |
| Puffer ablation test mm/s | 0.23 | 0.18 | 0.25 | 0.32 |
| Tensile strength MPa | 243 | 237 | 235 | 230 |
| Compressive strength MPa | 168 | 173 | 170 | 172 |
From table 3 it is observed that the addition of alumina silicate chopped strand can effectively improve composite material thermophysical property, it is optimal
The mass ratio of phenolic resin and alumina silicate chopped strand is near 100:10.
Embodiment 7
Phenol-formaldehyde resin modified matches (mass ratio)
The preparation method is the same as that of Example 1, and obtained test sample specific performance is shown in Table 4.
Embodiment 8
Phenol-formaldehyde resin modified matches (mass ratio)
The preparation method is the same as that of Example 1, and obtained test sample specific performance is shown in Table 4.
Table 4
| Embodiment 7 | Embodiment 1 | Embodiment 8 | Comparative example 3 | |
| Thermal coefficient W/ (mK) | 0.16 | 0.1 | 0.15 | 0.26 |
| Linear ablative rate mm/s | 0.13 | 0.09 | 0.15 | 0.2 |
| Puffer ablation test mm/s | 0.24 | 0.18 | 0.23 | 0.3 |
| Tensile strength MPa | 240 | 237 | 239 | 235 |
| Compressive strength MPa | 175 | 173 | 172 | 170 |
From table 4, it can be seen that the addition of ceramic hollow microballon can effectively improve in the case where cenosphere total amount is constant
Composite material thermophysical property, with the increase of ceramic hollow microballon accounting, performance boost is more obvious；But ceramic hollow microballon accounts for
After reaching 1:1, then adds improvement and be declined slightly instead.
Embodiment 9
Phenol-formaldehyde resin modified matches (mass ratio)
The preparation method is the same as that of Example 1, and obtained test sample specific performance is shown in Table 5.
Embodiment 10
Phenol-formaldehyde resin modified matches (mass ratio)
The preparation method is the same as that of Example 1, and obtained test sample specific performance is shown in Table 5.
Table 5
| Embodiment 9 | Embodiment 1 | Embodiment 10 | |
| Thermal coefficient W/ (mK) | 0.16 | 0.1 | 0.09 |
| Linear ablative rate mm/s | 0.15 | 0.09 | 0.09 |
| Puffer ablation test mm/s | 0.24 | 0.18 | 0.17 |
| Tensile strength MPa | 238 | 237 | 165 |
| Compressive strength MPa | 170 | 173 | 122 |
As can be seen from Table 5, in the case that ceramic hollow microballon accounting is constant, early period increases with cenosphere total amount
When, composite material thermophysical property improves, hollow micro- after the arrival of cenosphere total amount and phenolic resin mass ratio 15:100 or so
Pearl total amount is further added by, and the raising of composite material thermophysical property is unobvious, but due to increasing microballon total amount accounting, to the power of material
Performance is learned to be affected.
Comparative example 1
Phenolic resin matches (mass ratio)
The preparation method is the same as that of Example 1 for other, and the test sample specific performance of this comparative example is shown in Table 2.
Comparative example 2
Phenolic resin matches (mass ratio)
The preparation method is the same as that of Example 1 for other, and the test sample specific performance of this comparative example is shown in Table 3.
Comparative example 3
Phenolic resin matches (mass ratio)
The preparation method is the same as that of Example 1 for other, and the test sample specific performance of this comparative example is shown in Table 4.
Unspecified part of the present invention is known to the skilled person technology.
Claims (10)
1. a kind of phenol-formaldehyde resin modified, it is characterised in that: including phenolic resin, chopped strand, cenosphere and heat reflection substance,
Each component mass ratio is as follows:
The cenosphere is made of phenolic aldehyde cenosphere and ceramic hollow microballon, the matter of ceramic hollow microballon and phenolic aldehyde microballon
Measure ratio 1/2~2/1.
2. a kind of phenol-formaldehyde resin modified according to claim 1, it is characterised in that: the ceramic hollow microballon by with
After inorganic matter master batch blending processing, the air in ceramic hollow microballon and between microballon is made to generate anion.
3. a kind of phenol-formaldehyde resin modified according to claim 1, it is characterised in that: the phenolic aldehyde cenosphere and phenolic aldehyde
The mass ratio of resin is not less than 5:100, and the mass ratio of the ceramic hollow microballon and phenolic resin is not less than 5:100.
4. a kind of phenol-formaldehyde resin modified according to claim 1, it is characterised in that: the phenol-formaldehyde resin modified each component
Mass ratio is as follows:
The mass ratio 1:1 of ceramic hollow microballon and phenolic aldehyde microballon.
5. a kind of phenolic resin composite using phenol-formaldehyde resin modified described in claim 1, it is characterised in that: by being modified
Phenolic resin as matrix resin composite fiber fabric is made, and after the ceramic hollow microballon is by the way that processing is blended with inorganic matter master batch, makes
Air in ceramic hollow microballon and between microballon generates anion.
6. a kind of phenolic resin composite according to claim 5, it is characterised in that: phenol-formaldehyde resin modified each component matter
It is as follows to measure ratio:
The mass ratio 1:1 of ceramic hollow microballon and phenolic aldehyde microballon.
7. a kind of phenolic resin composite according to claim 5, it is characterised in that: the fabric is addition
The composite fibre fabric of spirality crimping phenolic fibre, the spirality crimping phenolic fibre account for the number of composite fibre fabric
Amount is than being 1/3~1/2.
8. a kind of phenolic resin composite according to claim 5, it is characterised in that: the phenolic aldehyde cenosphere with
The mass ratio of phenolic resin is not less than 5:100, and the mass ratio of the ceramic hollow microballon and phenolic resin is not less than 5:100.
9. a kind of preparation method of phenol-formaldehyde resin modified described in claim 1, which is characterized in that realized by following steps:
The first step, pre-treatment of raw material, coupling agent pretreatment and ceramic hollow microballon pretreatment including chopped strand are described
Ceramic hollow microballon pretreatment is as follows:
A1.1, inorganic matter master batch is prepared,
Inorganic matter prepares inorganic matter master batch through broken, crushing, levigate, separation, drying；
A1.2, the step A1.1 inorganic matter master batch being prepared and ceramic hollow microballon after mixing, then from mixture are sieved
It takes and isolates ceramic hollow microballon；
Second step prepares phenol-formaldehyde resin modified,
A2.1, pretreated chopped strand and ceramic hollow microballon, phenolic resin, heat reflection substance and phenolic aldehyde are weighed in proportion
Cenosphere；
A2.2, weighed raw material are put into reaction kettle, stir evenly, obtains phenol-formaldehyde resin modified.
10. a kind of preparation method of phenolic resin composite as claimed in claim 6, which is characterized in that pass through following steps
It realizes:
The first step, phenol-formaldehyde resin modified preparation,
A1.1, pre-treatment of raw material,
Coupling agent pretreatment and ceramic hollow microballon pretreatment including chopped strand, the ceramic hollow microballon pretreatment is such as
Under:
A1.1.1, inorganic matter master batch is prepared,
Inorganic matter prepares inorganic matter master batch through broken, crushing, levigate, separation, drying；
A1.1.2, by the step A1.1.1 inorganic matter master batch being prepared and ceramic hollow microballon after mixing, then from mixing
Object sieve, which takes, isolates ceramic hollow microballon；
A1.2, phenol-formaldehyde resin modified is prepared,
A1.2.1, pretreated chopped strand and ceramic hollow microballon, phenolic resin, heat reflection substance and phenol are weighed in proportion
Aldehyde cenosphere；
A1.2.2, weighed raw material are put into reaction kettle, stir evenly, obtains phenol-formaldehyde resin modified；
Second step prepares fabric,
The fabric is the composite fibre fabric for being added to spirality crimping phenolic fibre, the spirality crimping phenol
The quantity ratio that aldehyde fiber accounts for composite fibre fabric is 1/3~1/2；
Third step, the preparation of prepreg；
Using the phenol-formaldehyde resin modified of first step preparation and the fabric of second step preparation, phenolic resin preimpregnation is prepared
Material；
4th step, prepreg solidification, obtains phenolic resin composite.
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| CN111100472A (en) * | 2020-01-03 | 2020-05-05 | 扬州市皇宙塑粉有限公司 | Composite plastic powder and preparation method thereof |
| CN112322049A (en) * | 2020-11-12 | 2021-02-05 | 株洲时代新材料科技股份有限公司 | Low-thermal-conductivity-coefficient organic silicon foam material and preparation method thereof |
| CN112574528A (en) * | 2020-11-20 | 2021-03-30 | 航天特种材料及工艺技术研究所 | Phenolic resin flaky reinforcing material and preparation method thereof |
| CN112574528B (en) * | 2020-11-20 | 2022-09-02 | 航天特种材料及工艺技术研究所 | Phenolic resin flaky reinforcing material and preparation method thereof |
| CN112223856A (en) * | 2020-12-17 | 2021-01-15 | 北京玻钢院复合材料有限公司 | Heat insulation layer structure of long tail nozzle of solid rocket engine and preparation method thereof |
| CN112223856B (en) * | 2020-12-17 | 2021-04-23 | 北京玻钢院复合材料有限公司 | Heat insulation layer structure of long tail nozzle of solid rocket engine and preparation method thereof |
| CN112920442A (en) * | 2021-01-29 | 2021-06-08 | 中国人民解放军国防科技大学 | Resin-based heat-proof composite material with surface coated with high-temperature infrared stealth coating and preparation method thereof |
| CN112920442B (en) * | 2021-01-29 | 2023-04-07 | 中国人民解放军国防科技大学 | Resin-based heat-proof composite material with surface coated with high-temperature infrared stealth coating and preparation method thereof |
| CN113845748A (en) * | 2021-09-30 | 2021-12-28 | 航天特种材料及工艺技术研究所 | Lightweight ablation-resistant anti-heat insulation material and preparation method thereof |
| CN115195254A (en) * | 2022-05-30 | 2022-10-18 | 航天特种材料及工艺技术研究所 | Heat insulation/ablation-resistant heat protection structure and preparation method thereof |
| CN115195254B (en) * | 2022-05-30 | 2024-04-02 | 航天特种材料及工艺技术研究所 | Heat insulation/ablation resistance heat protection structure and preparation method thereof |
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