CN109651758B - Modified phenolic resin, preparation method thereof and modified phenolic resin plate - Google Patents
Modified phenolic resin, preparation method thereof and modified phenolic resin plate Download PDFInfo
- Publication number
- CN109651758B CN109651758B CN201811311842.3A CN201811311842A CN109651758B CN 109651758 B CN109651758 B CN 109651758B CN 201811311842 A CN201811311842 A CN 201811311842A CN 109651758 B CN109651758 B CN 109651758B
- Authority
- CN
- China
- Prior art keywords
- phenolic resin
- molybdenum
- modified phenolic
- raw materials
- nano montmorillonite
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention belongs to the technical field of modification of high polymer materials, and provides a modified phenolic resin, a preparation method thereof and a modified phenolic resin plate, wherein the modified phenolic resin is prepared by reacting the following raw materials: taking the total weight of all the components as 100 wt%, 20-30 wt% of a silicon-molybdenum modifier and 70-80 wt% of nano montmorillonite-phenolic resin; the silicon-molybdenum modifier is prepared from the following reaction raw materials in percentage by weight: the total weight of all reaction raw materials is 100 wt%, and the reaction raw materials comprise 10-15 wt% of phenyl trimethoxy silane, 5-10 wt% of methyl trimethoxy silane, 0.5-1 wt% of a basic catalyst potassium carbonate, 20-25 wt% of a styrene solvent, 10-15 wt% of water and 35-50 wt% of a molybdenum compound. The invention can obviously improve the heat resistance, corrosion resistance and mechanical property of the phenolic resin, and simultaneously keep larger friction coefficient.
Description
Technical Field
The invention belongs to the technical field of modification of high polymer materials, and particularly relates to a modified phenolic resin, a preparation method thereof and an acid corrosion-resistant high-temperature abrasion-resistant modified phenolic resin plate.
Background
The technology of extracting metallurgical-grade aluminum oxide by using the advantages of high aluminum and rich gallium in the quasi-Gelle coal field and adopting the one-step acid dissolution method of circulating fluidized bed fly ash has been reported. In the process stage of the one-step acid dissolution method, the conditions of part of working conditions are harsh: such as high-flow-rate liquid-solid two-phase working conditions (such as a baffle inside the tank body), acid-containing liquid-solid two-phase working conditions (such as a settling separation tank body), acid-containing high-temperature high-pressure working conditions (such as a tank after dissolution), and the like. These operating modes contain not only corrosive acidic substances but also solid phases (SiO)2The coexistence of multi-phase media such as pulverized coal ash, liquid phase (aluminum chloride solution), gas phase (high-temperature steam and volatile HCl) and the like causes the phenomena of physical erosion, high-temperature chemical corrosion and abrasion of equipment plates and lining anti-corrosion materials which are directly contacted with working conditions to be obvious.
At present, most of the plates and lining anti-corrosion materials in the pilot plant equipment adopt phenolic resin-based glass fiber reinforced plastic materials. The phenolic resin has the advantages of good heat resistance, high mechanical strength, stable thermal performance and the like, and is widely applied. However, the harsh working conditions of the one-step acid dissolution method impose new requirements on the high-performance phenolic resin, such as physical erosion and abrasion resistance at higher temperature, chemical erosion resistance at higher temperature and the like. How to enable the phenolic resin plate to obviously improve the heat resistance, the corrosion resistance and the mechanical property, keep larger friction resistance coefficient and have profound influence and significance on meeting the working condition requirement of a one-step acid dissolution method.
Disclosure of Invention
The invention aims to provide a modified phenolic resin, a preparation method thereof and an acid corrosion-resistant high-temperature abrasion-resistant modified phenolic resin plate aiming at the problem that the performance of the existing phenolic resin plate cannot meet the requirements.
In order to achieve the purpose, the invention provides a modified phenolic resin which is prepared by reacting the following raw materials: based on the total weight of all the components as 100wt percent,
20-30 wt% of silicon-molybdenum modifier,
70-80 wt% of nano montmorillonite-phenolic resin;
the silicon-molybdenum modifier is prepared from the following reaction raw materials in percentage by weight: based on the total weight of all reaction raw materials as 100 wt%,
according to the modified phenolic resin provided by the invention, preferably, the molybdenum compound is selected from molybdenum sulfide and/or molybdenum chloride.
More preferably, the molybdenum compound is a powder having a particle size of 70 μm or less, and still more preferably a powder having a particle size of 30 to 70 μm.
According to the modified phenolic resin provided by the invention, preferably, the nano montmorillonite-phenolic resin is prepared by adopting the following reaction raw materials in percentage by weight: based on the total weight of all reaction raw materials as 100 wt%,
30-60 wt% of formaldehyde,
15-30 wt% of phenol,
20-40 wt% of nano montmorillonite.
Another object of the present invention is to provide a method for preparing the above modified phenolic resin, comprising the following steps:
1) according to a certain proportion, phenyl trimethoxy silane, methyl trimethoxy silane, an alkaline catalyst potassium carbonate, a styrene solvent and water are contacted to react, and then a molybdenum compound is added into a reaction system to be stirred and mixed, so that a silicon-molybdenum modifier is obtained;
2) and stirring and mixing the obtained silicon-molybdenum modifier and the nano montmorillonite-phenolic resin according to the proportion, and curing at the temperature of 140-160 ℃ to obtain the modified phenolic resin.
According to the preparation method provided by the invention, preferably, in the step 2), the nano montmorillonite-phenolic resin is prepared from the following reaction raw materials in percentage by weight: based on the total weight of all reaction raw materials as 100 wt%,
30-60 wt% of formaldehyde,
15-30 wt% of phenol,
20-40 wt% of nano montmorillonite;
the preparation process of the nano montmorillonite-phenolic resin comprises the following steps: stirring and mixing formaldehyde, phenol and nano montmorillonite in proportion, wherein the preferable stirring time is 0.5-1 h; adjusting the pH value of the reaction system to 7-8 by ammonia water, heating to 80-95 ℃ for reaction, and preferably selecting the reaction time to be 1.5-2 h; then the nano montmorillonite-phenolic resin solution is prepared after decompression and dehydration.
More preferably, the process conditions for the reduced pressure dehydration include: the temperature is 75-80 ℃, and the vacuum degree is 5-8 Kpa.
According to the preparation method provided by the invention, preferably, in the step 1), the reaction is carried out under a heating condition, the reaction temperature is 75-90 ℃, and the heating reflux time is 12-24 hours; and after adding a molybdenum compound into the reaction system, stirring and mixing for 1-2 h.
Preferably, in the step 2), the stirring and mixing time is 0.5-1 h, and the curing time is 2-3 h.
The invention also provides a modified phenolic resin plate with acid corrosion resistance and high temperature abrasion resistance, which is prepared by taking the modified phenolic resin as a raw material and performing a hot press molding process; the modified phenolic resin is the modified phenolic resin or the modified phenolic resin prepared by the preparation method.
According to the modified phenolic resin plate provided by the invention, preferably, the hot press forming process comprises a hot press process and a heat treatment process;
more preferably, the temperature in the hot pressing process is 150-160 ℃, the pressure is 20-25 MPa, and the time is 15-20 minutes;
more preferably, the temperature of the heat treatment process is 150-165 ℃ and the time is 3-4 hours.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
(1) the organic silicon containing methyl or phenyl is used as a modifier component, so that the decomposition temperature of the main body structure is increased, and the crosslinking degree of the modified phenolic resin after curing is increased, so that the heat resistance, the corrosion resistance and the mechanical property of the phenolic resin can be obviously improved;
(2) according to the invention, a molybdenum compound material is used as a modifier component, so that the erosion resistance and abrasion resistance of the phenolic resin material are improved, a larger friction coefficient is kept, and meanwhile, the phenolic resin material has higher heat resistance;
(3) the invention adopts the montmorillonite of the silicate sheet with nanometer thickness, the basic structure unit of the montmorillonite is a layer structure formed by sandwiching a sheet of aluminum octahedron between two sheets of silicon-oxygen tetrahedrons and sharing oxygen atoms; the nano montmorillonite is added in the polymerization reaction of phenol and formaldehyde, so that the intercalation polymerization is also carried out while the polymer is generated by the reaction, namely, the phenol monomer can enter between the silicate sheets of the nano montmorillonite, so that the silicate sheets and the polymer matrix are compounded in a nano scale, the impact resistance, fatigue resistance, size stability, liquid phase barrier property and the like of the phenolic resin material are improved, and the comprehensive physical properties and the processing property of the material are enhanced.
Drawings
FIG. 1 is a graph of the time to blister failure for the phenolic resin boards of comparative examples 1-3 and examples 1-3.
FIG. 2 is a scanned image of the modified phenolic resin board coupon of example 1 (before coupon testing).
FIG. 3 is a scanned picture of a coupon for the modified phenolic resin board of example 1 (after the coupon test).
In the above fig. 1:
comparative examples 1, 2, 3 and examples 1, 2, 3 correspond to curves 1, 2, 3, 4, 5, 6, respectively, in fig. 1.
Detailed Description
In order that the technical features and contents of the present invention can be understood in detail, preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
In one example of the present invention, the modified phenolic resin is prepared by reacting raw materials comprising the following components: based on the total weight of all the components as 100wt percent,
20-30 wt% of silicon-molybdenum modifier,
for example, 22 wt%, 25 wt%, 28 wt%;
70-80 wt% of nano montmorillonite-phenolic resin;
for example, 72 wt%, 75 wt%, 78 wt%;
the silicon-molybdenum modifier is prepared from the following reaction raw materials in percentage by weight: based on the total weight of all reaction raw materials as 100 wt%,
10-15 wt% of phenyl trimethoxy silane,
for example, 12 wt%, 13 wt%, 14 wt%;
5-10 wt% of methyltrimethoxysilane,
for example, 6 wt%, 7 wt%, 8 wt%;
0.5-1 wt% of alkaline catalyst potassium carbonate,
for example, 0.6 wt%, 0.7 wt%, 0.8 wt%;
20-25 wt% of styrene solvent,
for example, 22 wt%, 23 wt%, 24 wt%;
10-15 wt% of water,
for example, 12 wt%, 13 wt%, 14 wt%;
35-50 wt% of a molybdenum compound;
for example, 38 wt%, 40 wt%, 42 wt%, 45 wt%, 48 wt%.
According to the modified phenolic resin provided by the invention, preferably, the molybdenum compound is selected from molybdenum sulfide and/or molybdenum chloride.
More preferably, the molybdenum compound is a powder having a particle size of 70 or less; more preferably 30 to 70 μm, for example, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm. The molybdenum compound with the size can be selected to fully modify the phenolic resin and improve the wear resistance and the heat resistance of the phenolic resin.
According to the modified phenolic resin provided by the invention, preferably, the nano montmorillonite-phenolic resin is prepared by adopting the following reaction raw materials in percentage by weight: based on the total weight of all reaction raw materials as 100 wt%,
30-60 wt% of formaldehyde,
for example, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%;
15-30 wt% of phenol,
for example, 18 wt%, 20 wt%, 25 wt%, 28 wt%;
20-40 wt% of nano montmorillonite,
for example, 25 wt%, 30 wt%, 35 wt%.
In some examples of the present invention, the method for preparing the modified phenolic resin comprises the following steps:
1) according to the proportion, phenyl trimethoxy silane, methyl trimethoxy silane, an alkaline catalyst potassium carbonate, a styrene solvent and water are contacted to react, a molybdenum compound is added into a reaction system, and the mixture is stirred and mixed, preferably for 1-2 h, so that a silicon-molybdenum modifier is obtained; in a preferred embodiment, in the step 1), phenyltrimethoxysilane, methyltrimethoxysilane, a basic catalyst potassium carbonate, a styrene solvent and water are contacted and reacted under the heating condition, wherein the reaction temperature is 75-90 ℃, and the heating reflux time is 12-24 h.
2) And stirring and mixing the obtained silicon-molybdenum modifier and the nano montmorillonite-phenolic resin according to the proportion, preferably stirring and mixing for 0.5-1 h, and curing at the temperature of 140-160 ℃, preferably curing for 2-3 h to obtain the modified phenolic resin.
In some examples of the present invention, the preparation process of the nanomontmorillonite-phenolic resin comprises: uniformly stirring and mixing the formaldehyde, the phenol and the nano montmorillonite according to the proportion, and preferably stirring for 0.5-1 h; adjusting the pH value of the reaction system to 7-8 by ammonia water, heating to 80-95 ℃ for reaction, and preferably selecting the reaction time to be 1.5-2 h; then the nano montmorillonite-phenolic resin solution is prepared after decompression and dehydration. More preferably, the process conditions for the reduced pressure dehydration include: the temperature is 75-80 ℃, and the vacuum degree is 5-8 Kpa.
The acid corrosion-resistant and high-temperature abrasion-resistant modified phenolic resin plate is prepared by taking the modified phenolic resin or the modified phenolic resin prepared by the preparation method as a raw material and performing hot press molding.
In a preferred embodiment, the hot press forming process includes a hot press process and a heat treatment process. The hot pressing process can be realized by the operation commonly used in the field; preferably, the temperature in the hot pressing process is 150-160 ℃, the pressure is 20-25 MPa, and the time is 15-20 minutes; the heat treatment process can be realized by the operation commonly used in the field; preferably, the temperature in the heat treatment process is 150-165 ℃ and the time is 3-4 h.
The raw material sources are as follows:
phenyltrimethoxysilane (Guangzhou Shuangtao Fine chemical Co., Ltd.),
methyltrimethoxysilane (Zhejiang Quzhou Zhengbang organosilicon Co., Ltd.),
potassium carbonate (orthodox chemical industry limited, Changzhou city),
styrene (Wu Chin Linchuan chemical Co., Ltd., Changzhou city),
molybdenum sulfide (Takara Industrial & trade Co., Ltd.), molybdenum chloride (Hangzhou high chemical Co., Ltd.),
formaldehyde (Shandong Xun chemical science and technology Co., Ltd.),
phenol (Guangdong chemical plant in Guangdong province),
nanometer montmorillonite (Orotae processing factory in Lingshu county),
ammonia (Taiyuan city Anye chemical Co., Ltd.),
common phenolic boards (guangzhou kangning fibrate resin board factory).
Example 1
(1) Preparing a silicon-molybdenum modifier: stirring and mixing 10 parts by mass of phenyltrimethoxysilane, 10 parts by mass of methyltrimethoxysilane, 1 part by mass of alkaline catalyst potassium carbonate and 20 parts by mass of styrene solvent uniformly at normal temperature, slowly adding 10 parts by mass of water, heating to 80 ℃ after the water is added, and heating and refluxing for 20 hours; and after the reaction is finished, standing and cooling to room temperature, adding 49 parts by mass of molybdenum sulfide with the particle size of 45 mu m, stirring and mixing, and stirring for 2 hours to obtain the silicon-molybdenum modifier.
(2) Preparing nano montmorillonite-phenolic resin solution: adding 40 parts by mass of formaldehyde and 20 parts by mass of phenol into a three-necked bottle, adding 40 parts by mass of nano montmorillonite, and stirring and mixing for 1 h; adjusting the pH value of a reaction system to be 7-8 by ammonia water, heating to 80 ℃ for reaction, and after reacting for 1.5h, performing reduced pressure dehydration at 75 ℃ and under the vacuum degree of 8 Kpa; after the dehydration amount is stable, the nano montmorillonite-phenolic resin solution is prepared.
(3) And stirring and mixing 20 parts by mass of the obtained silicon-molybdenum modifier and 80 parts by mass of the obtained nano montmorillonite-phenolic resin solution for 1 hour, and curing in an oven at 145 ℃ for 2.5 hours to obtain the modified phenolic resin.
(4) The obtained modified phenolic resin is used as a raw material to be hot-pressed and formed, and the hot-pressing process comprises the following steps: the hot pressing temperature is 150 ℃, the hot pressing pressure is 25MPa, and the hot pressing time is 15 minutes; and then carrying out heat treatment on the pressed board at 165 ℃ for 3 hours to obtain the acid corrosion-resistant high-temperature-resistant abrasion-resistant modified phenolic resin board.
Example 2
(1) Preparing a silicon-molybdenum modifier: stirring and mixing 15 parts by mass of phenyltrimethoxysilane, 5 parts by mass of methyltrimethoxysilane, 1 part by mass of alkaline catalyst potassium carbonate and 25 parts by mass of styrene solvent uniformly at normal temperature, slowly adding 15 parts by mass of water, heating to 90 ℃ after the water is added, and heating and refluxing for 15 hours; and after the reaction is finished, standing and cooling to room temperature, adding 39 parts by mass of molybdenum chloride with the particle size of 55 mu m, and stirring and mixing for 1.5h to obtain the silicon-molybdenum modifier.
(2) Preparing nano montmorillonite-phenolic resin solution: adding 50 parts by mass of formaldehyde and 25 parts by mass of phenol into a three-necked bottle, adding 25 parts by mass of nano montmorillonite, stirring and mixing for 0.5h, adjusting the pH value of a reaction system to 7-8 by adopting ammonia water, and heating to 90 ℃ for reaction; after reacting for 1.5h, decompressing and dehydrating at 80 ℃ and under the vacuum degree of 8Kpa, and preparing the nano montmorillonite-phenolic resin solution after the dehydration amount is stable.
(3) And stirring and mixing 30 parts by mass of the obtained silicon-molybdenum modifier and 70 parts by mass of the obtained nano montmorillonite-phenolic resin solution for 1 hour, and curing in an oven at 150 ℃ for 3 hours to obtain the modified phenolic resin.
(4) The modified phenolic resin is used as a raw material to carry out hot press molding, and the hot press process comprises the following steps: hot pressing temperature is 160 ℃, hot pressing pressure is 20MPa, hot pressing time is 15 minutes, then the pressed board is subjected to heat treatment, the heat treatment temperature is 150 ℃, and the heat treatment time is 3.5 hours, so that the acid corrosion resistant-high temperature abrasion resistant modified phenolic resin board is obtained.
Example 3
(1) Preparing a silicon-molybdenum modifier: stirring and mixing 12 parts by mass of phenyltrimethoxysilane, 8 parts by mass of methyltrimethoxysilane, 0.5 part by mass of alkaline catalyst potassium carbonate and 20 parts by mass of styrene solvent uniformly at normal temperature, slowly adding 15 parts by mass of water, heating to 75 ℃ after the water is added, and heating and refluxing for 24 hours; after the reaction is finished, standing and cooling to room temperature, adding 44.5 parts by mass of a mixture of molybdenum sulfide and molybdenum chloride with the particle size of 60 mu m (the molybdenum sulfide and the molybdenum chloride respectively account for 50 wt%), and stirring for 1.5h to obtain the silicon-molybdenum modifier.
(2) Preparing nano montmorillonite-phenolic resin solution: adding 55 parts by mass of formaldehyde and 25 parts by mass of phenol into a three-necked bottle, adding 20 parts by mass of nano montmorillonite, and stirring and mixing for 1 h; adjusting the pH value of a reaction system to be 7-8 by adopting ammonia water, heating to 85 ℃ for reaction, and performing reduced pressure dehydration at 80 ℃ and a vacuum degree of 8Kpa after reacting for 2 hours; after the dehydration amount is stable, the nano montmorillonite-phenolic resin solution is prepared.
(3) And stirring and mixing 25 parts by mass of the obtained silicon-molybdenum modifier and 75 parts by mass of the obtained nano montmorillonite-phenolic resin for 1 hour, and curing in a drying oven at 160 ℃ for 2 hours to obtain the modified phenolic resin.
(4) The obtained modified phenolic resin is used as a raw material to be hot-pressed and formed, and the hot-pressing process comprises the following steps: hot pressing temperature is 155 ℃, hot pressing pressure is 25MPa, and hot pressing time is 15 minutes; and then carrying out heat treatment on the pressed board at the heat treatment temperature of 160 ℃ for 3 hours to obtain the acid corrosion-resistant high-temperature-resistant abrasion-resistant modified phenolic resin board.
Comparative example 1
Adding 50 parts by mass of formaldehyde and 50 parts by mass of phenol into a three-necked bottle, stirring and mixing for 0.5h, adjusting the pH value of a reaction system to 7-8 by ammonia water, and heating to 90 ℃ for reaction; after reacting for 1.5h, carrying out reduced pressure dehydration at 80 ℃ and under the vacuum degree of 8Kpa, and obtaining a phenolic resin solution after the dehydration amount is stable; and curing the obtained phenolic resin solution in an oven at 150 ℃ for 3 hours to obtain the phenolic resin.
The obtained phenolic resin is used as a raw material to be hot-pressed and formed, and the hot-pressing process comprises the following steps: the hot pressing temperature is 160 ℃, the hot pressing pressure is 20MPa, and the hot pressing time is 15 minutes; and then carrying out heat treatment on the pressed plate, wherein the heat treatment temperature is 150 ℃, and the heat treatment time is 3.5 hours, so as to obtain the phenolic resin plate.
COMPARATIVE EXAMPLE 2 (without Si-Mo modification)
Adding 40 parts by mass of formaldehyde and 20 parts by mass of phenol into a three-necked bottle, adding 40 parts by mass of nano montmorillonite, stirring and mixing for 1h, adjusting the pH value of a reaction system to be 7-8 by ammonia water, and heating to 80 ℃ for reaction; after reacting for 1.5h, carrying out reduced pressure dehydration at 75 ℃ and under the vacuum degree of 8Kpa, and preparing a nano montmorillonite-phenolic resin solution after the dehydration amount is stable; and curing the obtained nano montmorillonite-phenolic resin solution in an oven at 145 ℃ for 2.5 hours to obtain the nano montmorillonite-phenolic resin.
The obtained nano montmorillonite-phenolic resin is used as a raw material to be hot-pressed and formed, and the hot-pressing process comprises the following steps: the hot pressing temperature is 150 ℃, the hot pressing pressure is 25MPa, and the hot pressing time is 15 minutes; and then carrying out heat treatment on the pressed plate, wherein the heat treatment temperature is 165 ℃, and the heat treatment time is 3 hours, so as to obtain the phenolic resin plate.
Comparative example 3 (modified with nano montmorillonite)
(1) Preparing a silicon-molybdenum modifier: stirring and uniformly mixing 10 parts by mass of phenyltrimethoxysilane, 10 parts by mass of methyltrimethoxysilane, 1 part by mass of alkaline catalyst potassium carbonate and 20 parts by mass of styrene solvent at normal temperature, and slowly adding 10 parts by mass of water; after the water is added, the temperature is raised to 80 ℃, and the heating reflux is carried out for 20 hours; and after the reaction is finished, standing and cooling to room temperature, adding 49 parts by mass of molybdenum sulfide, stirring and mixing, and stirring for 2 hours to obtain the silicon-molybdenum modifier.
(2) Preparation of phenolic resin solution: adding 67 parts by mass of formaldehyde and 33 parts by mass of phenol into a three-necked bottle, stirring for 1h, adjusting the pH value of a reaction system to 7-8 by ammonia water, and heating to 75 ℃ for reaction; after reacting for 2h, dehydrating under reduced pressure at 75 ℃ and the vacuum degree of 8Kpa, and obtaining the phenolic resin solution after the dehydration amount is stable.
(3) And stirring and mixing 20 parts by mass of the obtained silicon-molybdenum modifier and 80 parts by mass of the obtained phenolic resin solution for 1 hour, and curing in an oven at the temperature of 145 ℃ for 2.5 hours to obtain the modified phenolic resin.
(4) The obtained modified phenolic resin is used as a raw material to be hot-pressed and formed, and the hot-pressing process comprises the following steps: the hot pressing temperature is 150 ℃, the hot pressing pressure is 25MPa, and the hot pressing time is 15 minutes; and then carrying out heat treatment on the pressed plate at 165 ℃ for 3 hours to obtain the modified phenolic resin plate.
< Performance test >
The phenolic resin plates of the examples and the comparative examples are subjected to gradient penetration experimental study under dynamic working conditions of sealing high pressure, high temperature and corrosive wear. The research can obtain the comprehensive performance index results of the material such as high temperature resistance, impact resistance, wear resistance, liquid phase barrier property and the like by testing the bubbling failure time of the plate under the conditions of a multiphase flow medium and high temperature and high pressure, and the experimental working condition of the hanging piece (prepared by the phenolic resin plate) used in the testing process is shown in table 1.
Table 1 experimental conditions for testing coupon
The time profile of permeation leading to blister failure of the phenolic resin boards of examples 1-3 and comparative examples 1-3 after testing is shown in figure 1. The results in fig. 1 show that the bubble failure time of the modified phenolic resin board obtained by the technical scheme of the invention at different hanger thicknesses is longer than that of the board obtained by the comparative examples 1-3, which indicates that the modified phenolic resin obtained by the invention has excellent comprehensive performance indexes such as high temperature resistance, impact resistance, wear resistance and liquid phase barrier property.
As can be seen from fig. 1, under the physical erosion conditions of slurry with high temperature, high pressure and high acid corrosion, the bubbling failure of example 1 (curve 4) lasts the longest time under different thickness dimensions, indicating that the slurry has the best combination of high temperature resistance, acid corrosion resistance, abrasion resistance and impact resistance.
The surface topography of the phenolic resin obtained in example 1 before and after the experiment is shown in fig. 2 and 3. As can be seen from fig. 2 and 3, the comparison of the surface topography before and after the experiment in example 1 shows that the surface structure does not change significantly, indicating that the working conditions of high temperature, high pressure and high acid corrosion do not have a great influence on the structure composition.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (8)
1. The modified phenolic resin is characterized by being prepared by reacting the following raw materials: based on the total weight of all the components as 100wt percent,
20-30 wt% of silicon-molybdenum modifier,
70-80 wt% of nano montmorillonite-phenolic resin;
the nano montmorillonite-phenolic resin is prepared from the following reaction raw materials in percentage by weight: based on the total weight of all reaction raw materials as 100 wt%,
30-60 wt% of formaldehyde,
15-30 wt% of phenol,
20-40 wt% of nano montmorillonite;
the silicon-molybdenum modifier is prepared from the following reaction raw materials in percentage by weight: based on the total weight of all reaction raw materials as 100 wt%,
the compound of molybdenum is selected from molybdenum sulfide and/or molybdenum chloride;
the molybdenum compound is powder with the particle size of less than or equal to 70 mu m.
2. The modified phenolic resin of claim 1, wherein the molybdenum compound is a powder having a particle size of 30 to 70 μm.
3. A process for the preparation of a modified phenolic resin according to any one of claims 1 to 2, comprising the steps of:
1) according to a certain proportion, phenyl trimethoxy silane, methyl trimethoxy silane, an alkaline catalyst potassium carbonate, a styrene solvent and water are contacted to react, and then a molybdenum compound is added into a reaction system to be stirred and mixed, so that a silicon-molybdenum modifier is obtained;
2) and stirring and mixing the obtained silicon-molybdenum modifier and the nano montmorillonite-phenolic resin according to the proportion, and curing at the temperature of 140-160 ℃ to obtain the modified phenolic resin.
4. The preparation method of claim 3, wherein in the step 2), the nano montmorillonite-phenolic resin is prepared from the following reaction raw materials in percentage by weight: based on the total weight of all reaction raw materials as 100 wt%,
30-60 wt% of formaldehyde,
15-30 wt% of phenol,
20-40 wt% of nano montmorillonite;
the preparation process of the nano montmorillonite-phenolic resin comprises the following steps: stirring and mixing formaldehyde, phenol and nano montmorillonite in proportion for 0.5-1 h; adjusting the pH value of the reaction system to 7-8 by ammonia water, heating to 80-95 ℃ for reaction, wherein the reaction time is 1.5-2 h; then the nano montmorillonite-phenolic resin solution is prepared after decompression and dehydration.
5. The preparation method according to claim 4, wherein the process conditions of the reduced pressure dehydration comprise: the temperature is 75-80 ℃, and the vacuum degree is 5-8 KPa.
6. The preparation method according to claim 3, wherein in the step 1), the reaction is carried out under heating, the reaction temperature is 75-90 ℃, and the heating reflux time is 12-24 h; adding a molybdenum compound into a reaction system, and stirring and mixing for 1-2 h;
in the step 2), the stirring and mixing time is 0.5-1 h, and the curing time is 2-3 h.
7. The acid corrosion-resistant and high-temperature abrasion-resistant modified phenolic resin plate is characterized in that the modified phenolic resin is used as a raw material and is prepared by a hot-press molding process;
the modified phenolic resin is the modified phenolic resin as defined in any one of claims 1-2 or the modified phenolic resin prepared by the preparation method as defined in any one of claims 3-6.
8. The modified phenolic resin plate according to claim 7, wherein the hot press forming process comprises a hot press process and a heat treatment process;
the temperature in the hot pressing process is 150-160 ℃, the pressure is 20-25 MPa, and the time is 15-20 minutes;
the temperature of the heat treatment process is 150-165 ℃, and the time is 3-4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811311842.3A CN109651758B (en) | 2018-11-06 | 2018-11-06 | Modified phenolic resin, preparation method thereof and modified phenolic resin plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811311842.3A CN109651758B (en) | 2018-11-06 | 2018-11-06 | Modified phenolic resin, preparation method thereof and modified phenolic resin plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109651758A CN109651758A (en) | 2019-04-19 |
| CN109651758B true CN109651758B (en) | 2021-11-30 |
Family
ID=66110173
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811311842.3A Active CN109651758B (en) | 2018-11-06 | 2018-11-06 | Modified phenolic resin, preparation method thereof and modified phenolic resin plate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109651758B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112339385A (en) * | 2020-10-16 | 2021-02-09 | 广东中晨电子科技有限公司 | Lubricating cover plate and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1403524A (en) * | 2001-09-07 | 2003-03-19 | 中国科学院化学研究所 | Modified nano phenolic resin binder and its prepn and use |
| CN104292409A (en) * | 2014-09-29 | 2015-01-21 | 盐城工学院 | Modified phenolic resin and friction material containing same |
| CN104974464A (en) * | 2014-04-04 | 2015-10-14 | 湖北文理学院 | Methods for preparing molybdenum modified phenolic resin and preparing friction material from molybdenum modified phenolic resin |
| CN105273359A (en) * | 2015-09-11 | 2016-01-27 | 苏州兴业材料科技股份有限公司 | High-residual-carbon silica-containing molybdenum phenolic resin and preparation method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06306186A (en) * | 1993-04-27 | 1994-11-01 | Aisin Chem Co Ltd | Friction material |
-
2018
- 2018-11-06 CN CN201811311842.3A patent/CN109651758B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1403524A (en) * | 2001-09-07 | 2003-03-19 | 中国科学院化学研究所 | Modified nano phenolic resin binder and its prepn and use |
| CN104974464A (en) * | 2014-04-04 | 2015-10-14 | 湖北文理学院 | Methods for preparing molybdenum modified phenolic resin and preparing friction material from molybdenum modified phenolic resin |
| CN104292409A (en) * | 2014-09-29 | 2015-01-21 | 盐城工学院 | Modified phenolic resin and friction material containing same |
| CN105273359A (en) * | 2015-09-11 | 2016-01-27 | 苏州兴业材料科技股份有限公司 | High-residual-carbon silica-containing molybdenum phenolic resin and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109651758A (en) | 2019-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5307804B2 (en) | Silicone resin composite for high temperature resistant elastic composite applications and method of manufacturing the same | |
| CN104017364B (en) | One kind graphite type carbon nitride/composite polyimide material and preparation method thereof | |
| US20070093587A1 (en) | Silicon carbide precursors and uses thereof | |
| CN108516849B (en) | Zirconium mullite brick for cement kiln and preparation method thereof | |
| US9382429B2 (en) | Preparation method of carbon modified filler | |
| CN111848172B (en) | Molybdenum disilicide/silicon carbide three-dimensional polymer precursor ceramic and preparation method thereof | |
| CN109651758B (en) | Modified phenolic resin, preparation method thereof and modified phenolic resin plate | |
| CN113087534B (en) | High-temperature-resistant alkali-activated aluminosilicate binder and preparation method thereof | |
| CN108774462B (en) | Room-temperature-curing high-temperature-resistant anticorrosive coating and preparation method thereof | |
| CN115181393B (en) | Modified resin matrix composite material for heat insulation and preparation method thereof | |
| CN106631026A (en) | Al<4>SiC<4>-Al<4>O<4>C compound materials and preparation method thereof | |
| CN112851291A (en) | Silicon carbide slurry utilizing waste silicon carbide shed plates and preparation method thereof | |
| CN113461410B (en) | Al-Al added with titanium nitride coated mullite 2 O 3 Sliding plate brick and production method thereof | |
| Zhang et al. | Effects of graphene addition on the microstructure and anti-ablation properties of C/C–SiC composites prepared by precursor impregnation and pyrolysis | |
| Lu et al. | Sol–gel synthesis of nanosilica-coated para-aramid fibers and their application in the preparation of paper-based friction materials | |
| CN104261840B (en) | A kind of phosphate combines low aluminum silicon not brick and preparation method thereof | |
| CN101028978A (en) | Composite carbon brick and its production | |
| JP2008255133A (en) | Method for synthesizing organic friction-regulator by utilizing superheated steam | |
| CN1724472A (en) | Compound phose material of beta cellulose and alpha cellulose and its preparation technology | |
| CN101705074A (en) | High temperature screw thread fastening glue and production method thereof | |
| CN1165255A (en) | Brake plate | |
| CN112442328B (en) | Adhesive, preparation method and application thereof | |
| CN114853443A (en) | Plastic bonding agent for repairing material and preparation method thereof | |
| CN1019968C (en) | Producing method of carbon complex moulding for inlaying mineral fibre | |
| CN1260179C (en) | Process for synthesizing high purity sialon material by coal-series kaolin |
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 |