CN109651758A - A kind of phenol-formaldehyde resin modified and preparation method thereof, phenol-formaldehyde resin modified plate - Google Patents
A kind of phenol-formaldehyde resin modified and preparation method thereof, phenol-formaldehyde resin modified plate Download PDFInfo
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- CN109651758A CN109651758A CN201811311842.3A CN201811311842A CN109651758A CN 109651758 A CN109651758 A CN 109651758A CN 201811311842 A CN201811311842 A CN 201811311842A CN 109651758 A CN109651758 A CN 109651758A
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- 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
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
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Abstract
The invention belongs to the technical fields of polymer modification, a kind of phenol-formaldehyde resin modified and preparation method thereof, phenol-formaldehyde resin modified plate are provided, phenol-formaldehyde resin modified use the raw material including following each component reaction be made: by the total weight of each component for 100wt% in terms of, 20~30wt% silicon molybdenum modifying agent, 70~80wt% nano montmorillonite-phenolic resin;The silicon molybdenum modifying agent uses each reaction raw materials including following weight percent to be prepared: by the total weight of each reaction raw materials for 100wt% in terms of, 10~15wt% phenyltrimethoxysila,e, 5~10wt% methyltrimethoxysilane, 0.5~1wt% basic catalyst potassium carbonate, 20~25wt% styrene solvent, 10~15wt% water, the compound of 35~50wt% molybdenum.The present invention can be obviously improved the heat resistance, corrosion resistance and mechanical property of phenolic resin, while keep biggish anti-friction coefficient.
Description
Technical field
The invention belongs to the technical field of polymer modification more particularly to a kind of phenol-formaldehyde resin modified and its preparation sides
Method, anti-acid corrosion-high temperature resistant abrasion phenol-formaldehyde resin modified plate.
Background technique
Using Zhungeer coal field " high alumina, rich gallium " advantage, smelting is extracted using circulating fluid bed coal ash " a step acid extracting "
The technology of golden grade aluminum oxide technique has had been reported that.In the operation stage of " a step acid extracting ", Part load condition is more harsh:
The liquid of such as high flow rate consolidates two-phase body operating condition (such as tank interior baffle), the liquid containing acid consolidates two-phase operating condition (such as precipitation separation tank
Body), the high temperature and high pressure condition (such as dissolve out pit) containing acid.These operating conditions not only contain mordant acidic materials while going back
With solid phase (SiO2, powdered coal cinder), liquid phase (liquor alumini chloridi), the multiphases such as gas phase (high-temperature vapor and volatility HCl) are situated between
The feature that matter coexists causes the equipment plate directly contacted with working condition and inside lining anti-corrosive material, will receive physics erosion, height
The phenomenon that warm chemical attack and abrasion, is obvious.
Currently, the plate and inside lining anti-corrosive material in pilot plant mostly use greatly the glass-reinforced plastic material of phenolic resin base.Phenol
Urea formaldehyde is due to having many advantages, such as that heat resistance is preferable, mechanical strength is high, hot property is stable, using than wide.A but " step
The working condition of acid extracting " harshness puts forward new requirements High Performance Phenolic Resins, e.g., the physics erosion under anti-higher temperature
And it denudes, the chemical attack etc. under higher temperature resistant.Phenolic resin plate how is set to be obviously improved its heat resistance, corrosion resistance
And mechanical property, biggish anti-friction coefficient is kept, there is far-reaching influence for the working condition requirement of satisfaction " a step acid extracting "
And meaning.
Summary of the invention
It is an object of the present invention to provide one kind aiming at the problem that existing phenolic resin plate property cannot be met the requirements
Phenol-formaldehyde resin modified and preparation method thereof, anti-acid corrosion-high temperature resistant abrasion phenol-formaldehyde resin modified plate, obtained modification phenol
Urea formaldehyde plate can be obviously improved the heat resistance, corrosion resistance and mechanical property of phenolic resin, while keep biggish anti-friction
Coefficient.
To achieve the goals above, the present invention provides a kind of phenol-formaldehyde resin modified, using the raw material including following each component
Reaction be made: by the total weight of each component for 100wt% in terms of,
Silicon molybdenum 20~30wt% of modifying agent,
Nano montmorillonite -70~80wt% of phenolic resin;
Wherein, the silicon molybdenum modifying agent uses each reaction raw materials including following weight percent to be prepared: with each anti-
Answer the total weight of raw material for 100wt% meter,
The phenol-formaldehyde resin modified provided according to the present invention, it is preferable that the compound of the molybdenum is selected from molybdenum sulfide and/or chlorination
Molybdenum.
It is highly preferred that powder of the compound of the molybdenum for partial size less than or equal to 70 μm, further preferably partial size 30~
70 μm of powder.
The phenol-formaldehyde resin modified provided according to the present invention, it is preferable that it includes such as that the nano montmorillonite-phenolic resin, which uses,
Each reaction raw materials of lower weight percent are prepared: by the total weight of each reaction raw materials for 100wt% in terms of,
30~60wt% of formaldehyde,
15~30wt% of phenol,
20~40wt% of nano montmorillonite.
It is a further object of the invention to provide a kind of preparation methods of phenol-formaldehyde resin modified as described above, including
Following steps:
1) in proportion by phenyltrimethoxysila,e, methyltrimethoxysilane, basic catalyst potassium carbonate and styrene
Solvent and water contact are reacted, then the compound of addition molybdenum is stirred to get silicon molybdenum modifying agent in the reaction system;
2) gained silicon molybdenum modifying agent and the nano montmorillonite-phenolic resin are stirred in proportion, then 140~
Solidify at a temperature of 160 DEG C, obtains the phenol-formaldehyde resin modified.
The preparation method provided according to the present invention, it is preferable that in step 2), the nano montmorillonite-phenolic resin is by wrapping
Each reaction raw materials for including following weight percent are prepared: by the total weight of each reaction raw materials for 100wt% in terms of,
30~60wt% of formaldehyde,
15~30wt% of phenol,
20~40wt% of nano montmorillonite;
The preparation process of the nano montmorillonite-phenolic resin includes: in proportion to stir formaldehyde, phenol and nano montmorillonite
Mixing is mixed, preferably mixing time is 0.5~1h;It is 7~8 by the pH value that ammonium hydroxide adjusts reaction system, is warming up to 80~95 DEG C
It is reacted, preferred reaction time is 1.5~2h;Nano montmorillonite-phenol resin solution is made after decompression dehydration again.
It is highly preferred that it is 75~80 DEG C that the process conditions of the decompression dehydration, which include: temperature, vacuum degree is 5~8Kpa.
The preparation method provided according to the present invention, it is preferable that in step 1), the reaction is performed under heating conditions, instead
Answer temperature be 75~90 DEG C, be heated to reflux the time be 12~for 24 hours;After the compound of molybdenum is added in the reaction system, it is stirred
Time is 1~2h.
Preferably, in step 2), the time being stirred is 0.5~1h, and the cured time is 2~3h.
It is another object of the present invention to also provide a kind of phenol-formaldehyde resin modified plate of anti-acid corrosion-high temperature resistant abrasion
Material is made using phenol-formaldehyde resin modified as former material by hot press forming technology;The phenol-formaldehyde resin modified is as described above changes
Property phenolic resin, or phenol-formaldehyde resin modified made from preparation method as described above.
The phenol-formaldehyde resin modified plate provided according to the present invention, it is preferable that the hot press forming technology includes hot pressing
And heat treatment process;
It is highly preferred that the temperature of the hot pressing is 150~160 DEG C, pressure is 20~25MPa, and the time is 15~20
Minute;
It is highly preferred that the temperature of the heat treatment process is 150~165 DEG C, the time is 3~4 hours.
Compared with prior art, the beneficial effect of technical solution of the present invention is:
(1) present invention increases the decomposition of main structure using the organosilicon containing methyl or phenyl as modifier component
Temperature, while increase the degree of cross linking after modified phenolic resin curing, this can be obviously improved the heat resistance, resistance to of phenolic resin
Corrosivity and mechanical property;
(2) present invention using the compound-material of molybdenum as modifier component, can make phenolic resin material erosion resistance and
The ability of abrasion improves, and keeps biggish anti-friction coefficient, while heat resistance with higher;
(3) for the present invention using the montmorillonite of the silicate plate of nano thickness, basic structural unit is by a piece of alumina eight
Face body is clipped between two panels oxygen-octahedron, and the layer structure formed by sharing oxygen atom;Phenol is polymerizeing instead with formaldehyde
It is seasonable that nano montmorillonite is added, make reaction that intercalation polymeric also have occurred while generating polymer, i.e. Phenol Monomer can enter
Between the silicate lamella of nano montmorillonite, to keep silicate lamella mutually compound with nanoscale with polymeric matrix, improve
The shock resistance of phenolic resin material, antifatigue, dimensional stability and liquid phase barrier property etc., so that playing enhances its comprehensive physical
Performance and the processing performance for improving its material.
Detailed description of the invention
The corresponding time plot for being bubbled failure of the phenolic resin plate that Fig. 1 is comparative example 1-3 and embodiment 1-3.
Fig. 2 is the scanned picture of the phenol-formaldehyde resin modified plate lacing film of embodiment 1 (before lacing film test).
Fig. 3 is the scanned picture of the phenol-formaldehyde resin modified plate lacing film of embodiment 1 (after lacing film test).
In above-mentioned Fig. 1:
Comparative example 1,2,3 and embodiment 1,2,3 respectively correspond the curve 1,2,3,4,5,6 in Fig. 1.
Specific embodiment
In order to technical characteristic and content of the invention is understood in detail, it is described in more detail below of the invention excellent
Select embodiment.Although describing the preferred embodiment of the present invention in embodiment, however, it is to be appreciated that can be in a variety of manners
Realize the present invention without that should be limited by the embodiments set forth herein.
In a kind of example of the invention, the phenol-formaldehyde resin modified uses the raw material including following each component to react system
: by the total weight of each component for 100wt% in terms of,
Silicon molybdenum 20~30wt% of modifying agent,
For example, 22wt%, 25wt%, 28wt%;
Nano montmorillonite -70~80wt% of phenolic resin;
For example, 72wt%, 75wt%, 78wt%;
Wherein, the silicon molybdenum modifying agent uses each reaction raw materials including following weight percent to be prepared: with each anti-
Answer the total weight of raw material for 100wt% meter,
10~15wt% of phenyltrimethoxysila,e,
For example, 12wt%, 13wt%, 14wt%;
5~10wt% of methyltrimethoxysilane,
For example, 6wt%, 7wt%, 8wt%;
Basic catalyst 0.5~1wt% of potassium carbonate,
For example, 0.6wt%, 0.7wt%, 0.8wt%;
20~25wt% of styrene solvent,
For example, 22wt%, 23wt%, 24wt%;
10~15wt% of water,
For example, 12wt%, 13wt%, 14wt%;
35~50wt% of compound of molybdenum;
For example, 38wt%, 40wt%, 42wt%, 45wt%, 48wt%.
The phenol-formaldehyde resin modified provided according to the present invention, it is preferable that the compound of the molybdenum is selected from molybdenum sulfide and/or chlorination
Molybdenum.
It is highly preferred that the compound of the molybdenum is the powder that partial size is less than or equal to 70;Further preferably 30~70 μm
Powder, for example, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm.The molybdenum compound for selecting the size, can fully change
Property phenolic resin, improves its wear-resisting, heat resistance.
The phenol-formaldehyde resin modified provided according to the present invention, it is preferable that it includes such as that the nano montmorillonite-phenolic resin, which uses,
Each reaction raw materials of lower weight percent are prepared: by the total weight of each reaction raw materials for 100wt% in terms of,
30~60wt% of formaldehyde,
For example, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%;
15~30wt% of phenol,
For example, 18wt%, 20wt%, 25wt%, 28wt%;
20~40wt% of nano montmorillonite,
For example, 25wt%, 30wt%, 35wt%.
In some examples of the invention, the preparation method of phenol-formaldehyde resin modified as described above, includes the following steps:
1) in proportion by phenyltrimethoxysila,e, methyltrimethoxysilane, basic catalyst potassium carbonate and styrene
Solvent and water contact is reacted, then in the reaction system be added molybdenum compound be stirred, preferably mixing time 1~
2h is to get silicon molybdenum modifying agent;In the preferred embodiment, phenyltrimethoxysila,e in step 1), methyltrimethoxysilane,
Basic catalyst potassium carbonate and styrene solvent and water contact and are performed under heating conditions reaction, and reaction temperature is 75~
90 DEG C, be heated to reflux the time be 12~for 24 hours.
2) gained silicon molybdenum modifying agent and the nano montmorillonite-phenolic resin are stirred in proportion, preferably stirring is mixed
0.5~1h of time of conjunction, then solidify at a temperature of 140~160 DEG C, the time of preferred consolidation is 2~3h, obtains the modification
Phenolic resin.
In some examples of the invention, the preparation process of the nano montmorillonite-phenolic resin includes: as described above
Ratio formaldehyde, phenol and nano montmorillonite are uniformly mixed, preferably mixing time be 0.5~1h;It is adjusted by ammonium hydroxide
The pH value of reaction system is 7~8, is warming up to 80~95 DEG C and is reacted, and preferred reaction time is 1.5~2h;Decompression dehydration again
Nano montmorillonite-phenol resin solution is made afterwards.It is highly preferred that the process conditions of the decompression dehydration include: temperature be 75~
80 DEG C, vacuum degree is 5~8Kpa.
A kind of phenol-formaldehyde resin modified plate of anti-acid corrosion-high temperature resistant abrasion, is with phenol-formaldehyde resin modified as described above
Or phenol-formaldehyde resin modified made from preparation method as described above is that former material is made by hot press forming technology.
In the preferred embodiment, the hot press forming technology includes hot pressing and heat treatment process.The hot pressing
Journey is that operation commonly used in the art can be realized;Preferably, the temperature of the hot pressing be 150~160 DEG C, pressure be 20~
25MPa, time are 15~20 minutes;The heat treatment process is that operation commonly used in the art can be realized;Preferably, the heat
The temperature for the treatment of process is 150~165 DEG C, and the time is 3~4h.
Raw material sources:
Phenyltrimethoxysila,e (Guangzhou Shuan Tao Fine Chemical Co., Ltd),
Methyltrimethoxysilane (Zhejiang Quzhou Zheng Bang organosilicon Co., Ltd),
Potassium carbonate (Changzhou Xian Zheng Chemical Co., Ltd.),
Styrene (Changzhou Wujin Linchuan Chemical Co., Ltd.),
Molybdenum sulfide (Tai'an Zhuo science, industry and trade Co., Ltd), molybdenum chloride (Hangzhou Pin Gao Chemical Co., Ltd.),
Formaldehyde (Shandong Xu Chen Chemical Industry Science Co., Ltd),
Phenol (Guangdong Guangyuan chemical plant),
Nano montmorillonite (Lingshou County Ao Tai mineral products processing factory),
Ammonium hydroxide (An Ye Chemical Co., Ltd., Taiyuan City),
Common phenolic sheet (Guangzhou healthy and free from worry Bei Te resin plate factory).
Embodiment 1
(1) preparation of silicon molybdenum modifying agent: at normal temperature 10 mass parts of phenyltrimethoxysila,e, methyl trimethoxy oxygroup silicon
10 mass parts of alkane, 1 mass parts of basic catalyst potassium carbonate and 20 mass parts of styrene solvent are uniformly mixed, and slowly add water
10 mass parts, water to be added finish, and are warming up to 80 DEG C, are heated to reflux 20h;To after completion of the reaction, standing is cooled to room temperature, add
Particle size is that 45 μm of 49 mass parts of molybdenum sulfide are stirred, and stirs 2h to get silicon molybdenum modifying agent.
(2) 40 mass parts of formaldehyde, 20 mass parts of phenol nano montmorillonite-phenol resin solution preparation: are added three mouthfuls
In bottle, 40 mass parts of nano montmorillonite are added and are stirred 1h;It is to be risen between 7~8 by the pH value that ammonium hydroxide adjusts reaction system
Temperature is reacted to 80 DEG C, after reacting 1.5h, decompression dehydration under being 8Kpa in 75 DEG C, vacuum degree;After amount to be drained off is stablized, it is made
Nano montmorillonite-phenol resin solution.
(3) by the resulting silicon molybdenum modifying agent of 20 mass parts and the resulting nano montmorillonite-phenol resin solution of 80 mass parts
It is stirred 1h, and solidifies 2.5h in 145 DEG C of baking oven to get the phenol-formaldehyde resin modified is arrived.
(4) hot-forming, heat pressing process is carried out using resulting phenol-formaldehyde resin modified as former material are as follows: 150 DEG C of hot pressing temperature,
Hot pressing pressure 25MPa, hot pressing time 15 minutes;Plate made of the compacting is heat-treated again, 165 DEG C of heat treatment temperature,
Heat treatment time 3 hours, obtain anti-acid corrosion-high temperature resistant abrasion phenol-formaldehyde resin modified plate.
Embodiment 2
(1) preparation of silicon molybdenum modifying agent: at normal temperature 15 mass parts of phenyltrimethoxysila,e, methyl trimethoxy oxygroup silicon
5 mass parts of alkane, 1 mass parts of basic catalyst potassium carbonate and 25 mass parts of styrene solvent are uniformly mixed, and slowly add water
15 mass parts, water to be added finish, and are warming up to 90 DEG C, are heated to reflux 15h;To after completion of the reaction, standing is cooled to room temperature, add
Particle size is 55 μm of 39 mass parts of molybdenum chloride, is stirred after 1.5h to get silicon molybdenum modifying agent.
(2) 50 mass parts of formaldehyde, 25 mass parts of phenol nano montmorillonite-phenol resin solution preparation: are added three mouthfuls
In bottles, 25 mass parts of nano montmorillonite are added and are stirred 0.5h, ammonium hydroxide is used to adjust the pH value of reaction system as between 7~8,
90 DEG C are warming up to be reacted;After reacting 1.5h, decompression dehydration under being 8Kpa in 80 DEG C, vacuum degree, after amount to be drained off is stablized, system
Nano montmorillonite-phenol resin solution out.
(3) by the resulting silicon molybdenum modifying agent of 30 mass parts and the resulting nano montmorillonite-phenol resin solution of 70 mass parts
It is stirred 1h, then solidifies 3h in 150 DEG C of baking oven to get the phenol-formaldehyde resin modified is arrived.
(4) hot-forming, heat pressing process is carried out using phenol-formaldehyde resin modified as former material are as follows: 160 DEG C of hot pressing temperature, hot pressing pressure
Power 20MPa, hot pressing time 15 minutes, then plate made of the compacting is heat-treated, 150 DEG C of heat treatment temperature, it is heat-treated
Time 3.5 hours, obtain anti-acid corrosion-high temperature resistant abrasion phenol-formaldehyde resin modified plate.
Embodiment 3
(1) preparation of silicon molybdenum modifying agent: at normal temperature 12 mass parts of phenyltrimethoxysila,e, methyl trimethoxy oxygroup silicon
8 mass parts of alkane, 0.5 mass parts of basic catalyst potassium carbonate and 20 mass parts of styrene solvent are uniformly mixed, and are slowly added
15 mass parts of water, water to be added finish, and are warming up to 75 DEG C, are heated to reflux for 24 hours;To after completion of the reaction, standing is cooled to room temperature, it is added
Mixture (molybdenum sulfide and molybdenum chloride respectively account for 50wt%) 44.5 mass parts for the molybdenum sulfide and molybdenum chloride that particle size is 60 μm, are stirred
1.5h is mixed to get silicon molybdenum modifying agent.
(2) 55 mass parts of formaldehyde, 25 mass parts of phenol nano montmorillonite-phenol resin solution preparation: are added three mouthfuls
In bottle, 20 mass parts of nano montmorillonite are added and are stirred 1h;Use ammonium hydroxide adjust reaction system pH value be 7~8 between, liter
Temperature is reacted to 85 DEG C, after reacting 2h, decompression dehydration under being 8Kpa in 80 DEG C, vacuum degree;After amount to be drained off is stablized, produces and receive
Rice montmorillonite-phenol resin solution.
(3) the resulting silicon molybdenum modifying agent of 25 mass parts and the resulting nano montmorillonite of 75 mass parts-phenolic resin are stirred
1h is mixed, then solidifies 2h in 160 DEG C of baking oven to get the phenol-formaldehyde resin modified is arrived.
(4) hot-forming, heat pressing process is carried out using gained phenol-formaldehyde resin modified as former material are as follows: 155 DEG C of hot pressing temperature, heat
Pressure pressure 25MPa, hot pressing time 15 minutes;Plate made of the compacting is heat-treated again, 160 DEG C of heat treatment temperature, heat
The processing time 3 hours obtains anti-acid corrosion-high temperature resistant abrasion phenol-formaldehyde resin modified plate.
Comparative example 1
50 mass parts of formaldehyde, 50 mass parts of phenol are added in there-necked flask and are stirred 0.5h, is adjusted and is reacted by ammonium hydroxide
The pH value of system is to be warming up to 90 DEG C between 7~8 and reacted;After reacting 1.5h, depressurized under being 8Kpa in 80 DEG C, vacuum degree
After amount to be drained off is stablized, phenol resin solution is made in dehydration;Gained phenol resin solution is solidified in 150 DEG C of baking oven again
3h to get arrive phenolic resin.
Hot-forming, heat pressing process is carried out using resulting phenolic resin as former material are as follows: 160 DEG C of hot pressing temperature, hot pressing pressure
Power 20MPa, hot pressing time 15 minutes;Plate made of the compacting is heat-treated again, 150 DEG C of heat treatment temperature, is heat-treated
Time 3.5 hours, obtain phenolic resin plate.
Comparative example 2 (it is modified not do silicon molybdenum)
40 mass parts of formaldehyde, 20 mass parts of phenol are added in there-necked flask, it is mixed that the stirring of 40 mass parts of nano montmorillonite is added
1h is closed, is to be warming up to 80 DEG C between 7~8 and reacted by the pH value that ammonium hydroxide adjusts reaction system;After reacting 1.5h, 75
DEG C, vacuum degree be decompression dehydration under 8Kpa, after amount to be drained off is stablized, nano montmorillonite-phenol resin solution is made;Again by gained
Nano montmorillonite-phenol resin solution solidifies 2.5h in 145 DEG C of baking oven to get nano montmorillonite-phenolic resin is arrived.
Hot-forming, heat pressing process is carried out using resulting nano montmorillonite-phenolic resin as former material are as follows: hot pressing temperature
150 DEG C, hot pressing pressure 25MPa, hot pressing time 15 minutes;Plate made of the compacting is heat-treated again, heat treatment temperature
165 DEG C, heat treatment time 3 hours, obtain phenolic resin plate.
Comparative example 3 (is not done nano montmorillonite modified)
(1) preparation of silicon molybdenum modifying agent: at normal temperature 10 mass parts of phenyltrimethoxysila,e, methyl trimethoxy oxygroup silicon
10 mass parts of alkane, 1 mass parts of basic catalyst potassium carbonate and 20 mass parts of styrene solvent are uniformly mixed, and slowly add water
10 mass parts;After water to be added, 80 DEG C are warming up to, 20h is heated to reflux;To after completion of the reaction, standing is cooled to room temperature, then plus
Enter 49 mass parts of molybdenum sulfide to be stirred, stirs 2h to get silicon molybdenum modifying agent.
(2) preparation of phenol resin solution: 67 mass parts of formaldehyde, 33 mass parts of phenol being added in there-necked flask and stir 1h,
It is to be warming up to 75 DEG C between 7~8 and reacted by the pH value that ammonium hydroxide adjusts reaction system;After reacting 2h, in 75 DEG C, vacuum
Degree is decompression dehydration under 8Kpa, and after amount to be drained off is stablized, phenol resin solution is made.
(3) resulting 20 mass parts of silicon molybdenum modifying agent and 80 mass parts of gained phenol resin solution are stirred 1h, and
Solidify 2.5h in 145 DEG C of baking oven to get phenol-formaldehyde resin modified is arrived.
(4) hot-forming, heat pressing process is carried out using resulting phenol-formaldehyde resin modified as former material are as follows: 150 DEG C of hot pressing temperature,
Hot pressing pressure 25MPa, hot pressing time 15 minutes;Plate made of the compacting is heat-treated again, 165 DEG C of heat treatment temperature,
Heat treatment time 3 hours, obtain phenol-formaldehyde resin modified plate.
<performance test>
High pressure, high temperature and the dynamic operation condition of corrosive wear are sealed to the phenolic resin plate of each embodiment and comparative example
Under gradient penetration experimental study.The research is by being bubbled the out-of-service time under multiphase flow medium and high-temperature and high-pressure conditions to plate
Test, the integrated performance indexs such as material high temperature resistant, shock resistance, wearability and liquid phase barrier property can be obtained as a result, test process
In lacing film used (being made by phenolic resin plate) experiment condition condition such as table 1.
The experiment condition condition of the test lacing film of table 1
After the phenolic resin plate of embodiment 1-3 and comparative example 1-3 is tested, infiltration cause plate be bubbled failure when
Half interval contour is shown in Fig. 1.As the result of Fig. 1 it is found that phenol-formaldehyde resin modified plate obtained by technical solution of the present invention is thick in different lacing films
The bubbling out-of-service time of degree is longer than comparative example 1-3, illustrate phenol-formaldehyde resin modified high temperature resistant, shock resistance obtained by the present invention,
The integrated performance indexs such as wearability and liquid phase barrier property are more excellent.
As shown in Figure 1, under the slurry physical abrasion operating condition of high temperature, high pressure and high sour, embodiment 1 (curve 4) is not
It is bubbled failure duration longest under stack pile size, shows its high temperature resistant, resistance to sour, erosion resistant and resistance to punching
It is optimal to hit comprehensive performance.
The surface topography map of 1 gained phenolic resin of embodiment experiment front and back is shown in Fig. 2, Fig. 3.By Fig. 2 and Fig. 3 it is found that from reality
The surface topography map comparison of the experiment of example 1 front and back is applied it is found that significant change does not occur for its surface textural, shows high temperature, high pressure
And high sour abrasion operating condition does not produce bigger effect its structure composition.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes are obvious for the those of ordinary skill in art field.
Claims (10)
1. a kind of phenol-formaldehyde resin modified, which is characterized in that use the raw material including following each component to react and be made: with each component
Total weight is 100wt% meter,
Silicon molybdenum 20~30wt% of modifying agent,
Nano montmorillonite -70~80wt% of phenolic resin;
Wherein, the silicon molybdenum modifying agent uses each reaction raw materials including following weight percent to be prepared: former with each reaction
The total weight of material is 100wt% meter,
2. phenol-formaldehyde resin modified according to claim 1, which is characterized in that the compound of the molybdenum be selected from molybdenum sulfide and/
Or molybdenum chloride.
3. phenol-formaldehyde resin modified according to claim 2, which is characterized in that the compound of the molybdenum is less than or equal to for partial size
70 μm of powder, preferably 30~70 μm of partial size of powder.
4. phenol-formaldehyde resin modified according to claim 1, which is characterized in that the nano montmorillonite-phenolic resin uses
Each reaction raw materials including following weight percent are prepared: by the total weight of each reaction raw materials for 100wt% in terms of,
30~60wt% of formaldehyde,
15~30wt% of phenol,
20~40wt% of nano montmorillonite.
5. a kind of preparation method of such as phenol-formaldehyde resin modified of any of claims 1-4, which is characterized in that including such as
Lower step:
1) in proportion by phenyltrimethoxysila,e, methyltrimethoxysilane, basic catalyst potassium carbonate and styrene solvent
And water contact is reacted, then the compound of addition molybdenum is stirred to get silicon molybdenum modifying agent in the reaction system;
2) gained silicon molybdenum modifying agent and the nano montmorillonite-phenolic resin are stirred in proportion, then at 140~160 DEG C
At a temperature of solidify, obtain the phenol-formaldehyde resin modified.
6. preparation method according to claim 5, which is characterized in that in step 2), the nano montmorillonite-phenolic resin
By include following weight percent each reaction raw materials be prepared: by the total weight of each reaction raw materials for 100wt% in terms of,
30~60wt% of formaldehyde,
15~30wt% of phenol,
20~40wt% of nano montmorillonite;
The preparation process of the nano montmorillonite-phenolic resin includes: to stir formaldehyde, phenol and nano montmorillonite to mix in proportion
It closes, preferably mixing time is 0.5~1h;It is 7~8 by the pH value that ammonium hydroxide adjusts reaction system, is warming up to 80~95 DEG C of progress
Reaction, preferred reaction time are 1.5~2h;Nano montmorillonite-phenol resin solution is made after decompression dehydration again.
7. preparation method according to claim 6, which is characterized in that the process conditions of the decompression dehydration include: temperature
It is 75~80 DEG C, vacuum degree is 5~8Kpa.
8. preparation method according to claim 5, which is characterized in that in step 1), it is described reaction in a heated condition into
Row, reaction temperature be 75~90 DEG C, be heated to reflux the time be 12~for 24 hours;After the compound of molybdenum is added in the reaction system, stirring
Incorporation time is 1~2h;
In step 2), the time being stirred is 0.5~1h, and the cured time is 2~3h.
9. a kind of anti-acid corrosion-the phenol-formaldehyde resin modified plate of high temperature resistant abrasion, which is characterized in that it with phenol-formaldehyde resin modified is original
Material is made by hot press forming technology;
The phenol-formaldehyde resin modified is such as phenol-formaldehyde resin modified of any of claims 1-4, or such as claim
Phenol-formaldehyde resin modified made from preparation method described in any one of 5-8.
10. phenol-formaldehyde resin modified plate according to claim 9, which is characterized in that the hot press forming technology includes heat
Press through journey and heat treatment process;
The temperature of the hot pressing is 150~160 DEG C, and pressure is 20~25MPa, and the time is 15~20 minutes;
The temperature of the heat treatment process is 150~165 DEG C, and the time is 3~4 hours.
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Cited By (1)
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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 |
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CN104292409A (en) * | 2014-09-29 | 2015-01-21 | 盐城工学院 | Modified phenolic resin and friction material containing same |
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