CN110003636A - Expanded graphite-epoxy resin-polyurethane resin pressure resistance composite material and preparation method thereof - Google Patents
Expanded graphite-epoxy resin-polyurethane resin pressure resistance composite material and preparation method thereof Download PDFInfo
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- CN110003636A CN110003636A CN201910284985.8A CN201910284985A CN110003636A CN 110003636 A CN110003636 A CN 110003636A CN 201910284985 A CN201910284985 A CN 201910284985A CN 110003636 A CN110003636 A CN 110003636A
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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Abstract
Expanded graphite-epoxy resin-polyurethane resin pressure resistance composite material and preparation method thereof, the invention belongs to pressure-resistant seal material manufacturing fields, the present invention in order to solve the problems, such as in the prior art comprising expanded graphite pressure-resistant seal material under compression intensity, elasticity and toughness show it is poor, preparation method proposed by the present invention mainly includes step 1: preparing expanded graphite, and carries out surface modification treatment to the expanded graphite prepared；Step 2: the preparation of modified epoxy；Step 3: expanded graphite-epoxy resin-polyurethane resin pressure resistance composite material preparation.Present invention is mainly used for the preparations of expanded graphite-epoxy resin-polyurethane resin pressure resistance composite material.
Description
Technical field
The invention belongs to pressure-resistant seal material manufacturing fields, more particularly to expanded graphite-epoxy resin-polyurethane resin
Pressure-resistant composite material and preparation method thereof.
Background technique
With the fast development of petrochemical industry and Nuclear Power Industry, the requirement for sealing material is also increasingly harsher.It is swollen
Swollen graphite relies on its excellent performance, becomes novel sealing material instead of asbestos already.Expanded graphite inherits natural stone
The excellent performance of Miboin body many, such as heat-resisting quantity, corrosion resistance and radiation resistance.Due to special processing technology, day is caused
Right graphite microstructure changes, and so that expanded graphite is obtained loose porous structure, causes its compression performance preferable, is a kind of
Excellent sealing material is widely used in various sealed environments.But there is also some obvious disadvantages for expanded graphite, such as
Mechanical strength is low, plastic deformation and wear-resisting property are poor, will appear conquassation when serving as sealing material, situations such as falling apart, makes it
Using being limited by very large.
Resin-based materials can fill the hole of expanded graphite, improve what expanded graphite leaked during static seal
Situation, and resin-based materials have excellent mechanical performance, can improve the elasticity and toughness of expanded graphite, by by resin
Sill is compound with expanded graphite, can play the synergistic effect of resin-based materials and expanded graphite, so that it is excellent to prepare performance
Different pressure-resistant composite material.
In conclusion the pressure-resistant seal material in currently available technology comprising expanded graphite leaks in use, bullet
Property and toughness show it is poor, therefore provide it is a kind of comprising expanded graphite, epoxy resin, polyurethane resin pressure-resistant seal material
Preparation method correspond to actual needs very much.
Summary of the invention
The present invention is to solve the intensity, elasticity and tough under compression of the pressure-resistant seal material comprising expanded graphite in the prior art
Property shows poor problem.And then propose expanded graphite-epoxy resin-polyurethane resin pressure resistance composite material and preparation method thereof.
Expanded graphite of the invention-epoxy resin-polyurethane resin pressure resistance composite material and preparation method thereof, mainly takes
The preparation method is as follows:
Step 1: expanded graphite is prepared, and surface modification treatment is carried out to the expanded graphite prepared；
Step 1 one: 80-120ml glacial acetic acid addition 400-600ml perchloric acid is taken to be configured to glacial acetic acid-perchloric acid mixing molten
Liquid I；
Step 1 two: taking 100 mesh crystalline flake graphite 8-10g to be put into there-necked flask, and glacial acetic acid-perchloric acid mixed solution is added
I20-40ml, ice-water bath stirring 10-30min, which is uniformly mixed, obtains mixed solution I I；
Step 1 three: 1-5g potassium permanganate point n times equivalent is added in glacial acetic acid-perchloric acid mixed solution I I, to height
After all glacial acetic acid-perchloric acid mixed solution I I is added in potassium manganate, obtained after bath temperature is increased to 30-40 DEG C of reaction 1-3h
Mixture I, N are positive integer；
Step 1 four: after mixture I is washed to neutrality, in placement surface ware I, system is dried in the environment of 40-80 DEG C
Obtain expansible graphite；
Step 1 five: expansible graphite being placed in 1000 DEG C of Muffle furnaces and carries out extruding, and expanded graphite is made；
Step 1 six: the silane coupling agent of 1-3g is dissolved in 80-100g dehydrated alcohol and is configured to surface treating agent；
Step 1 seven: surface treating agent configured in step 1 six is added in bottle,suction, takes expansion stone obtained
Black 3-5g is dispersed in surface treating agent, and bottle,suction is evacuated under conditions of -0.1MPa and carries out magnetic agitation 1-3h, obtains product
I；
Step 1 eight: after the product I that step 1 seven obtains is filtered and washed, in placement surface ware II, at 30-50 DEG C
12-24h is dried under environment, obtains the modified expanded graphite in surface；
Step 2: the preparation of modified epoxy；
Step 2 one: 100-120g epoxy resin is placed into 500ml there-necked flask, and in the environment of inert gas shielding
Under be heated to 30-50 DEG C；
Step 2 two: 10-150g polyurethane resin is added in the epoxy resin after heating, and stirs 1-2h, is obtained
Product II；
Step 2 three: modified epoxy will be formed after the cooling of product II obtained in step 2 two；
Step 3: expanded graphite-epoxy resin-polyurethane resin pressure resistance composite material preparation；
Step 3 one: the expanded graphite for taking the surface 0.1-0.5g modified is added in 10g modified epoxy, is mixed
Uniformly；
Step 3 two: according to the content of epoxy resin in modified epoxy, according to quality than epoxy resin: fatty amine is solid
Fatty amine curing agent is added in agent=2:1 ratio, is mixed evenly, obtains expanded graphite-epoxy resin-polyurethane resin
Pressure-resistant composite material；
Step 3 three: expanded graphite obtained in step 3 two-epoxy resin-polyurethane resin pressure resistance composite material is put
Enter in molding die, be heating and curing 4-12h in the environment of 30-50 DEG C, obtains the pressure-resistant gasket of required shape；
Preferably, in the step 1 three by 1-5g potassium permanganate point n times equivalent be added to glacial acetic acid-perchloric acid mix it is molten
In liquid II, the value range of N is 8-12 times；
Preferably, the surface plate I in the step 1 four is glass surface ware；
Preferably, the silane coupling agent in the step 1 six is KH-560 type silane coupling agent；
Preferably, epoxy resin is E-51 type epoxy resin in the step 2 one；
Preferably, be heating and curing in the environment of 30-50 DEG C 4-12h in the step 3 three, could alternatively be in room temperature
Middle solidification 3-7 days.
The present invention compared with the existing technology the utility model has the advantages that
Expanded graphite prepared by the present invention-epoxy resin-polyurethane resin pressure resistance composite material has excellent draftability
Energy and compression performance can enhance infiltration of the expanded graphite in modified resin by the expanded graphite that silane coupling agent is handled
Property, make its dispersion more uniformly, the stress that not will cause material is concentrated and destroys material in use；Modified epoxy tree
The addition of rouge makes composite material have excellent mechanical performance, is filled with the hole of expanded graphite, enhances the close of composite material
Sealing property.Furthermore composite material is conducive to the operation of material upon mixing at paste, operate it can arbitrarily before the forming,
It is satisfied with special operation condition and particular surroundings, keeps the application range of pressure-resistant composite material more extensive, expanded graphite-epoxy resin-is poly-
Urethane resin pressure resistance composite material both can directly be made into pressure-resistant plate, and creamy material can also be coated, be filled out by washer, gasket
Gap plays the role of pressure-resistant after solidification.
Detailed description of the invention
Fig. 1 is polyurethane resin content and pressure-resistant composite material rebound degree relational graph；
Fig. 2 is polyurethane resin content and pressure-resistant composite material tensile strength relational graph；
Fig. 3 is polyurethane resin content and pressure-resistant composite material compressive strength relational graph.
Abscissa is the content of polyurethane resin in Fig. 1, and unit g, ordinate is pressure-resistant composite material rebound degree, unit
It is 1%；
Abscissa is the content of polyurethane resin in Fig. 2, and unit g, ordinate is pressure-resistant composite material tensile strength, single
Position is Mpa；
Abscissa is the content of polyurethane resin in Fig. 3, and unit g, ordinate is pressure-resistant composite material compressive strength, single
Position is Mpa.
Specific embodiment
Specific embodiment 1: expanded graphite described in present embodiment-epoxy resin-polyurethane resin pressure resistance composite wood
Preparation method for material, it is specific to operate are as follows:
Step 1: expanded graphite is prepared, and surface modification treatment is carried out to the expanded graphite prepared；
Step 1 one: 80-120ml glacial acetic acid addition 400-600ml perchloric acid is taken to be configured to glacial acetic acid-perchloric acid mixing molten
Liquid I；
Step 1 two: taking 100 mesh crystalline flake graphite 8-10g to be put into there-necked flask, and glacial acetic acid-perchloric acid mixed solution is added
I20-40ml, ice-water bath stirring 10-30min, which is uniformly mixed, obtains glacial acetic acid-perchloric acid mixed solution I I；
Step 1 three: 1-5g potassium permanganate point n times equivalent is added in glacial acetic acid-perchloric acid mixed solution I I, to height
After all glacial acetic acid-perchloric acid mixed solution I I is added in potassium manganate, obtained after bath temperature is increased to 30-40 DEG C of reaction 1-3h
Mixture I, N are positive integer；
Step 1 four: after mixture I is washed to neutrality, in placement surface ware I, system is dried in the environment of 40-80 DEG C
Obtain expansible graphite；
Step 1 five: expansible graphite being placed in 1000 DEG C of Muffle furnaces and carries out extruding, and expanded graphite is made；
Step 1 six: the silane coupling agent of 1-3g is dissolved in 80-100g dehydrated alcohol and is configured to surface treating agent；
Step 1 seven: surface treating agent configured in step 1 six is added in bottle,suction, takes expansion stone obtained
Black 3-5g is dispersed in surface treating agent, and bottle,suction is evacuated under conditions of -0.1MPa and carries out magnetic agitation 1-3h, obtains product
I；
Step 1 eight: after the product I that step 1 seven obtains is filtered and washed, in placement surface ware II, at 30-50 DEG C
12-24h is dried under environment, obtains the modified expanded graphite in surface；
Step 2: the preparation of modified epoxy；
Step 2 one: 100-120g epoxy resin is placed into 500ml there-necked flask, and in the environment of inert gas shielding
Under be heated to 30-50 DEG C；
Step 2 two: 10-150g polyurethane resin is added in the epoxy resin after heating, and stirs 1-2h, is obtained
Product II；
Step 2 three: modified epoxy will be formed after the cooling of product II obtained in step 2 two；
Step 3: expanded graphite-epoxy resin-polyurethane resin pressure resistance composite material preparation；
Step 3 one: the expanded graphite for taking the surface 0.1-0.5g modified is added in 10g modified epoxy, is mixed
Uniformly；
Step 3 two: according in step 3 one in modified epoxy epoxy resin content, compare asphalt mixtures modified by epoxy resin according to quality
Rouge: fatty amine curing agent is added in fatty amine curing agent=2:1 ratio, is mixed evenly, obtains expanded graphite-asphalt mixtures modified by epoxy resin
Rouge-polyurethane resin pressure resistance composite material；
Step 3 three: expanded graphite obtained in step 3 two-epoxy resin-polyurethane resin pressure resistance composite material is put
Enter in molding die, be heating and curing 4-12h in the environment of 30-50 DEG C, obtains the pressure-resistant gasket of required shape；
Step 3 two described in present embodiment: according in step 3 one in modified epoxy epoxy resin content,
According to quality than epoxy resin: fatty amine curing agent is added in fatty amine curing agent=2:1 ratio, wherein the content of epoxy resin
Specifically according to the constituent content decision of epoxy resin when modified epoxy obtained in step 2, such as: in step 2
The component ratio of epoxy resin and polyurethane resin is 4:1 in modified epoxy obtained, then records in step 3 two according to step
The content of epoxy resin is 10g × [4/ (4+1)]=8g in modified epoxy in rapid 31, according to quality than epoxy resin:
Fatty amine curing agent is added in fatty amine curing agent=2:1 ratio, and addition fatty amine curing agent is 4g, and in the present embodiment
The heating, drying equipment being related to is the DHG-9240A type electric heating constant temperature forced air drying of Shanghai Yiheng Scientific Instruments Co., Ltd's production
Case uses the electric hot plate of model IKARH-1 when only heating to there-necked flask.
Specific embodiment 2: dividing n times equivalent to be added in 1-5g potassium permanganate in step 1 three described in present embodiment
Into glacial acetic acid-perchloric acid mixed solution I I, the value range of N is 8-12 times.Other undisclosed technologies and step and specific reality
It is identical to apply mode one.
So set, be primarily due to once by potassium permanganate all be added can cause system temperature suddenly increases generation it is quick-fried
It is fried, therefore divide and be added several times.A small amount of potassium permanganate is added every time can be such that temperature of reaction system slightly increases, and system temperatures is waited to reduce
Again plus next time potassium permanganate afterwards, general point 10 times or so, every minor tick 1-2 minutes, although will not strictly quantify every time,
Generally for the equilibrium of the safety of operation and reaction efficiency, each additional amount is essentially identical.
Specific embodiment 3: the surface plate I in step 1 four described in present embodiment is glass surface ware.Other are not
Public technology and step are same as the specific embodiment one.
So set, not having to canister, because there is perchloric acid in reaction process, Ke Nengzao as far as possible with glass surface ware
At metal erosion contaminated samples, eventually on after experiment material parameter and performance influenced.
Specific embodiment 4: the silane coupling agent in step 1 six described in present embodiment is that KH-560 type silane is even
Join agent.Other undisclosed technologies and step are same as the specific embodiment one.
So set, expanded graphite and epoxy resin itself are different substance, there can be interface during mixing,
This interface is often the position for leading to material cracks, destruction, handles expanded graphite with KH-560, purpose also mainly weakens boundary
In face of the influence of material.So KH-560 is actually an optimal selection, KH-550, KH-570 also can handle interface, but
Be that effect does not have that KH-560 is good, even and if expanded graphite is not surface-treated, composite material can also be prepared, only without
Method obtains excellent effect.
Specific embodiment 5: epoxy resin is E-51 type epoxy resin in step 2 one described in present embodiment.Its
Technology is not disclosed in he and step is same as the specific embodiment one.
Specific embodiment 6: the inert gas in step 2 one described in step 2 one described in present embodiment is nitrogen
Gas.Other undisclosed technologies and step are same as the specific embodiment one.
So set, the polyurethane for needing to be added in the next steps needs environment to shift to an earlier date starvation, so in epoxy
Resin heating process uses inert gas shielding, and the main reason for preventing polyurethane from reacting with oxygen, and selecting nitrogen is
The price of nitrogen itself is lower, and nitrogen, which is added, relative to other inert gases equally has good protecting effect, chooses nitrogen
Have better economy.
Specific embodiment seven, be heating and curing in step 3 two described in present embodiment 4- in the environment of 30-50 DEG C
12h could alternatively be and solidify 3-7 days at room temperature.Other undisclosed technologies and step are same as the specific embodiment one.
So set, polyurethane system belongs to moisture-curable in modified resin, for temperature no more than 50 DEG C, temperature is too high
Words polyurethane, which can decompose to give off gas, destroys material in forming process, and curing time can be reduced by being heating and curing, but
Effect in service performance not as good as room temperature curing is good.
Embodiment
Embodiment one:
The present embodiment provides expanded graphite-epoxy resin-polyurethane resin pressure resistance composite material and preparation method thereofs, specifically press
It is carried out according to following steps:
Step 1: expanded graphite is prepared, and surface modification treatment is carried out to the expanded graphite prepared；
Step 1 one: it takes 100ml glacial acetic acid that 500ml perchloric acid is added and is configured to glacial acetic acid-perchloric acid mixed solution I；
Step 1 two: taking 100 mesh crystalline flake graphite 9g to be put into there-necked flask, and glacial acetic acid-perchloric acid mixed solution is added
I30ml, ice-water bath stirring 20min, which is uniformly mixed, obtains glacial acetic acid-perchloric acid mixed solution I I；
Step 1 three: 10 equivalent of 3g potassium permanganate point are added in glacial acetic acid-perchloric acid mixed solution I I, to Gao Meng
After all glacial acetic acid-perchloric acid mixed solution I I is added in sour potassium, mixture is obtained after bath temperature is increased to 35 DEG C of reaction 2h
I；
Step 1 four: after mixture I is washed to neutrality, in placement surface ware I, drying is obtained in the environment of 60 DEG C can
Expanded graphite；
Step 1 five: expansible graphite being placed in 1000 DEG C of Muffle furnaces and carries out extruding, and expanded graphite is made；
Step 1 six: the silane coupling agent of 2g is dissolved in 100g dehydrated alcohol and is configured to surface treating agent；
Step 1 seven: surface treating agent configured in step 1 six is added in bottle,suction, takes expansion stone obtained
Black 4g is dispersed in surface treating agent, and bottle,suction is evacuated under conditions of -0.1MPa and carries out magnetic agitation 2h, obtains product I；
Step 1 eight: after the product I that step 1 seven obtains is filtered and washed, in placement surface ware II, in 40 DEG C of ring
18h is dried under border, obtains the modified expanded graphite in surface；
Step 2: the preparation of modified epoxy；
Step 2 one: 100g epoxy resin is placed into 500ml there-necked flask, and is heated in the environment of nitrogen protection
50℃；
Step 2 two: 150g polyurethane resin is added in the epoxy resin after heating, and stirs 1h, obtains product
II；
Step 2 three: modified epoxy A will be formed after the cooling of product II obtained in step 2 two；
Step 3: expanded graphite-epoxy resin-polyurethane resin pressure resistance composite material preparation；
Step 3 one: the expanded graphite for taking the surface 0.5g modified is added in 10g modified epoxy A, is mixed equal
It is even；
Step 3 two: according to the content of epoxy resin in modified epoxy, according to quality than epoxy resin: fatty amine is solid
Fatty amine curing agent is added in agent=2:1 ratio, is mixed evenly, obtains expanded graphite-epoxy resin-polyurethane resin
Pressure-resistant composite material；
Step 3 three: expanded graphite obtained in step 3 two-epoxy resin-polyurethane resin pressure resistance composite material is put
Enter in molding die, solidifies 3 days under room temperature environment, obtain the pressure-resistant gasket of required shape.
Expanded graphite manufactured in the present embodiment-epoxy resin-polyurethane resin pressure resistance composite material, tensile strength are reachable
0.676MPa, compressive strength can achieve effect pressure-resistant after sealing up to 3.747MPa, rebound degree 98%.
Embodiment two:
The present embodiment provides expanded graphite-epoxy resin-polyurethane resin pressure resistance composite material and preparation method thereofs, specifically press
It is carried out according to following steps:
Step 1: expanded graphite is prepared, and surface modification treatment is carried out to the expanded graphite prepared；
Step 1 one: it takes 100ml glacial acetic acid that 500ml perchloric acid is added and is configured to glacial acetic acid-perchloric acid mixed solution I；
Step 1 two: taking 100 mesh crystalline flake graphite 9g to be put into there-necked flask, and glacial acetic acid-perchloric acid mixed solution is added
I30ml, ice-water bath stirring 20min, which is uniformly mixed, obtains glacial acetic acid-perchloric acid mixed solution I I；
Step 1 three: 10 equivalent of 3g potassium permanganate point are added in glacial acetic acid-perchloric acid mixed solution I I, to Gao Meng
After all glacial acetic acid-perchloric acid mixed solution I I is added in sour potassium, mixture is obtained after bath temperature is increased to 35 DEG C of reaction 2h
I；
Step 1 four: after mixture I is washed to neutrality, in placement surface ware I, drying is obtained in the environment of 60 DEG C can
Expanded graphite；
Step 1 five: expansible graphite being placed in 1000 DEG C of Muffle furnaces and carries out extruding, and expanded graphite is made；
Step 1 six: the silane coupling agent of 2g is dissolved in 100g dehydrated alcohol and is configured to surface treating agent；
Step 1 seven: surface treating agent configured in step 1 six is added in bottle,suction, takes expansion stone obtained
Black 4g is dispersed in surface treating agent, and bottle,suction is evacuated under conditions of -0.1MPa and carries out magnetic agitation 2h, obtains product I；
Step 1 eight: after the product I that step 1 seven obtains is filtered and washed, in placement surface ware II, in 40 DEG C of ring
18h is dried under border, obtains the modified expanded graphite in surface；
Step 2: the preparation of modified epoxy；
Step 2 one: 100g epoxy resin is placed into 500ml there-necked flask, and is heated in the environment of nitrogen protection
50℃；
Step 2 two: 150g polyurethane resin is added in the epoxy resin after heating, and stirs 1h, obtains product
II；
Step 2 three: modified epoxy A will be formed after the cooling of product II obtained in step 2 two；
Step 3: expanded graphite-epoxy resin-polyurethane resin pressure resistance composite material preparation；
Step 3 one: the expanded graphite for taking the surface 0.25g modified is added in 10g modified epoxy A, is mixed equal
It is even；
Step 3 two: according to the content of epoxy resin in modified epoxy, according to quality than epoxy resin: fatty amine is solid
Fatty amine curing agent is added in agent=2:1 ratio, is mixed evenly, obtains expanded graphite-epoxy resin-polyurethane resin
Pressure-resistant composite material；
Step 3 three: expanded graphite obtained in step 3 two-epoxy resin-polyurethane resin pressure resistance composite material is put
Enter in molding die, solidifies 3 days under room temperature environment, obtain the pressure-resistant gasket of required shape.
Expanded graphite manufactured in the present embodiment-epoxy resin-polyurethane resin pressure resistance composite material, tensile strength are reachable
1.549MPa, compressive strength can achieve effect pressure-resistant after sealing up to 5.641MPa, rebound degree 95%.
Embodiment three:
The present embodiment provides expanded graphite-epoxy resin-polyurethane resin pressure resistance composite material and preparation method thereofs, specifically press
It is carried out according to following steps:
Step 1: expanded graphite is prepared, and surface modification treatment is carried out to the expanded graphite prepared；
Step 1 one: it takes 100ml glacial acetic acid that 500ml perchloric acid is added and is configured to glacial acetic acid-perchloric acid mixed solution I；
Step 1 two: taking 100 mesh crystalline flake graphite 9g to be put into there-necked flask, and glacial acetic acid-perchloric acid mixed solution is added
I30ml, ice-water bath stirring 20min, which is uniformly mixed, obtains glacial acetic acid-perchloric acid mixed solution I I；
Step 1 three: 10 equivalent of 3g potassium permanganate point are added in glacial acetic acid-perchloric acid mixed solution I I, to Gao Meng
After all glacial acetic acid-perchloric acid mixed solution I I is added in sour potassium, mixture is obtained after bath temperature is increased to 35 DEG C of reaction 2h
I；
Step 1 four: after mixture I is washed to neutrality, in placement surface ware I, drying is obtained in the environment of 60 DEG C can
Expanded graphite；
Step 1 five: expansible graphite being placed in 1000 DEG C of Muffle furnaces and carries out extruding, and expanded graphite is made；
Step 1 six: the silane coupling agent of 2g is dissolved in 100g dehydrated alcohol and is configured to surface treating agent；
Step 1 seven: surface treating agent configured in step 1 six is added in bottle,suction, takes expansion stone obtained
Black 4g is dispersed in surface treating agent, and bottle,suction is evacuated under conditions of -0.1MPa and carries out magnetic agitation 2h, obtains product I；
Step 1 eight: after the product I that step 1 seven obtains is filtered and washed, in placement surface ware II, in 40 DEG C of ring
18h is dried under border, obtains the modified expanded graphite in surface；
Step 2: the preparation of modified epoxy；
Step 2 one: 100g epoxy resin is placed into 500ml there-necked flask, and is heated in the environment of nitrogen protection
50℃；
Step 2 two: 75g polyurethane resin is added in the epoxy resin after heating, and stirs 1h, obtains product II；
Step 2 three: modified epoxy A will be formed after the cooling of product II obtained in step 2 two；
Step 3: expanded graphite-epoxy resin-polyurethane resin pressure resistance composite material preparation；
Step 3 one: the expanded graphite for taking the surface 0.5g modified is added in 10g modified epoxy A, is mixed equal
It is even；
Step 3 two: according to the content of epoxy resin in modified epoxy, according to quality than epoxy resin: fatty amine is solid
Fatty amine curing agent is added in agent=2:1 ratio, is mixed evenly, obtains expanded graphite-epoxy resin-polyurethane resin
Pressure-resistant composite material；
Step 3 three: expanded graphite obtained in step 3 two-epoxy resin-polyurethane resin pressure resistance composite material is put
Enter in molding die, solidifies 3 days under room temperature environment, obtain the pressure-resistant gasket of required shape.
Expanded graphite manufactured in the present embodiment-epoxy resin-polyurethane resin pressure resistance composite material, tensile strength are reachable
2.435MPa, compressive strength can achieve effect pressure-resistant after sealing up to 14.901MPa, rebound degree 92%.
Example IV:
The present embodiment provides expanded graphite-epoxy resin-polyurethane resin pressure resistance composite material and preparation method thereofs, specifically press
It is carried out according to following steps:
Step 1: expanded graphite is prepared, and surface modification treatment is carried out to the expanded graphite prepared；
Step 1 one: it takes 100ml glacial acetic acid that 500ml perchloric acid is added and is configured to glacial acetic acid-perchloric acid mixed solution I；
Step 1 two: taking 100 mesh crystalline flake graphite 9g to be put into there-necked flask, and glacial acetic acid-perchloric acid mixed solution is added
I30ml, ice-water bath stirring 20min, which is uniformly mixed, obtains glacial acetic acid-perchloric acid mixed solution I I；
Step 1 three: 10 equivalent of 3g potassium permanganate point are added in glacial acetic acid-perchloric acid mixed solution I I, to Gao Meng
After all glacial acetic acid-perchloric acid mixed solution I I is added in sour potassium, mixture is obtained after bath temperature is increased to 35 DEG C of reaction 2h
I；
Step 1 four: after mixture I is washed to neutrality, in placement surface ware I, drying is obtained in the environment of 60 DEG C can
Expanded graphite；
Step 1 five: expansible graphite being placed in 1000 DEG C of Muffle furnaces and carries out extruding, and expanded graphite is made；
Step 1 six: the silane coupling agent of 2g is dissolved in 100g dehydrated alcohol and is configured to surface treating agent；
Step 1 seven: surface treating agent configured in step 1 six is added in bottle,suction, takes expansion stone obtained
Black 4g is dispersed in surface treating agent, and bottle,suction is evacuated under conditions of -0.1MPa and carries out magnetic agitation 2h, obtains product I；
Step 1 eight: after the product I that step 1 seven obtains is filtered and washed, in placement surface ware II, in 40 DEG C of ring
18h is dried under border, obtains the modified expanded graphite in surface；
Step 2: the preparation of modified epoxy；
Step 2 one: 100g epoxy resin is placed into 500ml there-necked flask, and is heated in the environment of nitrogen protection
50℃；
Step 2 two: 75g polyurethane resin is added in the epoxy resin after heating, and stirs 1h, obtains product II；
Step 2 three: modified epoxy A will be formed after the cooling of product II obtained in step 2 two；
Step 3: expanded graphite-epoxy resin-polyurethane resin pressure resistance composite material preparation；
Step 3 one: the expanded graphite for taking the surface 0.25g modified is added in 10g modified epoxy A, is mixed equal
It is even；
Step 3 two: according to the content of epoxy resin in modified epoxy, according to quality than epoxy resin: fatty amine is solid
Fatty amine curing agent is added in agent=2:1 ratio, is mixed evenly, obtains expanded graphite-epoxy resin-polyurethane resin
Pressure-resistant composite material；
Step 3 three: expanded graphite obtained in step 3 two-epoxy resin-polyurethane resin pressure resistance composite material is put
Enter in molding die, solidifies 3 days under room temperature environment, obtain the pressure-resistant gasket of required shape.
Expanded graphite manufactured in the present embodiment-epoxy resin-polyurethane resin pressure resistance composite material, tensile strength are reachable
4.087MPa, compressive strength can achieve effect pressure-resistant after sealing up to 17.482MPa, rebound degree 88%.
Embodiment five:
The present embodiment provides expanded graphite-epoxy resin-polyurethane resin pressure resistance composite material and preparation method thereofs, specifically press
It is carried out according to following steps:
Step 1: expanded graphite is prepared, and surface modification treatment is carried out to the expanded graphite prepared；
Step 1 one: it takes 100ml glacial acetic acid that 500ml perchloric acid is added and is configured to glacial acetic acid-perchloric acid mixed solution I；
Step 1 two: taking 100 mesh crystalline flake graphite 9g to be put into there-necked flask, and glacial acetic acid-perchloric acid mixed solution is added
I30ml, ice-water bath stirring 20min, which is uniformly mixed, obtains glacial acetic acid-perchloric acid mixed solution I I；
Step 1 three: 10 equivalent of 3g potassium permanganate point are added in glacial acetic acid-perchloric acid mixed solution I I, to Gao Meng
After all glacial acetic acid-perchloric acid mixed solution I I is added in sour potassium, mixture is obtained after bath temperature is increased to 35 DEG C of reaction 2h
I；
Step 1 four: after mixture I is washed to neutrality, in placement surface ware I, drying is obtained in the environment of 60 DEG C can
Expanded graphite；
Step 1 five: expansible graphite being placed in 1000 DEG C of Muffle furnaces and carries out extruding, and expanded graphite is made；
Step 1 six: the silane coupling agent of 2g is dissolved in 100g dehydrated alcohol and is configured to surface treating agent；
Step 1 seven: surface treating agent configured in step 1 six is added in bottle,suction, takes expansion stone obtained
Black 4g is dispersed in surface treating agent, and bottle,suction is evacuated under conditions of -0.1MPa and carries out magnetic agitation 2h, obtains product I；
Step 1 eight: after the product I that step 1 seven obtains is filtered and washed, in placement surface ware II, in 40 DEG C of ring
18h is dried under border, obtains the modified expanded graphite in surface；
Step 2: the preparation of modified epoxy；
Step 2 one: 100g epoxy resin is placed into 500ml there-necked flask, and is heated in the environment of nitrogen protection
50℃；
Step 2 two: 20g polyurethane resin is added in the epoxy resin after heating, and stirs 1h, obtains product II；
Step 2 three: modified epoxy A will be formed after the cooling of product II obtained in step 2 two；
Step 3: expanded graphite-epoxy resin-polyurethane resin pressure resistance composite material preparation；
Step 3 one: the expanded graphite for taking the surface 0.5g modified is added in 10g modified epoxy A, is mixed equal
It is even；
Step 3 two: according to the content of epoxy resin in modified epoxy, according to quality than epoxy resin: fatty amine is solid
Fatty amine curing agent is added in agent=2:1 ratio, is mixed evenly, obtains expanded graphite-epoxy resin-polyurethane resin
Pressure-resistant composite material；
Step 3 three: expanded graphite obtained in step 3 two-epoxy resin-polyurethane resin pressure resistance composite material is put
Enter in molding die, 50 DEG C of solidification 6h obtain the pressure-resistant gasket of required shape.
Expanded graphite manufactured in the present embodiment-epoxy resin-polyurethane resin pressure resistance composite material, tensile strength are reachable
7.998MPa, compressive strength can achieve effect pressure-resistant after sealing up to 26.669MPa, rebound degree 83%.
Embodiment six:
The present embodiment provides expanded graphite-epoxy resin-polyurethane resin pressure resistance composite material and preparation method thereofs, specifically press
It is carried out according to following steps:
Step 1: expanded graphite is prepared, and surface modification treatment is carried out to the expanded graphite prepared；
Step 1 one: it takes 100ml glacial acetic acid that 500ml perchloric acid is added and is configured to glacial acetic acid-perchloric acid mixed solution I；
Step 1 two: taking 100 mesh crystalline flake graphite 9g to be put into there-necked flask, and glacial acetic acid-perchloric acid mixed solution is added
I30ml, ice-water bath stirring 20min, which is uniformly mixed, obtains glacial acetic acid-perchloric acid mixed solution I I；
Step 1 three: 10 equivalent of 3g potassium permanganate point are added in glacial acetic acid-perchloric acid mixed solution I I, to Gao Meng
After all glacial acetic acid-perchloric acid mixed solution I I is added in sour potassium, mixture is obtained after bath temperature is increased to 35 DEG C of reaction 2h
I；
Step 1 four: after mixture I is washed to neutrality, in placement surface ware I, drying is obtained in the environment of 60 DEG C can
Expanded graphite；
Step 1 five: expansible graphite being placed in 1000 DEG C of Muffle furnaces and carries out extruding, and expanded graphite is made；
Step 1 six: the silane coupling agent of 2g is dissolved in 100g dehydrated alcohol and is configured to surface treating agent；
Step 1 seven: surface treating agent configured in step 1 six is added in bottle,suction, takes expansion stone obtained
Black 4g is dispersed in surface treating agent, and bottle,suction is evacuated under conditions of -0.1MPa and carries out magnetic agitation 2h, obtains product I；
Step 1 eight: after the product I that step 1 seven obtains is filtered and washed, in placement surface ware II, in 40 DEG C of ring
18h is dried under border, obtains the modified expanded graphite in surface；
Step 2: the preparation of modified epoxy；
Step 2 one: 100g epoxy resin is placed into 500ml there-necked flask, and is heated in the environment of nitrogen protection
50℃；
Step 2 two: 20g polyurethane resin is added in the epoxy resin after heating, and stirs 1h, obtains product II；
Step 2 three: modified epoxy A will be formed after the cooling of product II obtained in step 2 two；
Step 3: expanded graphite-epoxy resin-polyurethane resin pressure resistance composite material preparation；
Step 3 one: the expanded graphite for taking the surface 0.25g modified is added in 10g modified epoxy A, is mixed equal
It is even；
Step 3 two: according to the content of epoxy resin in modified epoxy, according to quality than epoxy resin: fatty amine is solid
Fatty amine curing agent is added in agent=2:1 ratio, is mixed evenly, obtains expanded graphite-epoxy resin-polyurethane resin
Pressure-resistant composite material；
Step 3 three: expanded graphite obtained in step 3 two-epoxy resin-polyurethane resin pressure resistance composite material is put
Enter in molding die, 50 DEG C of solidification 6h obtain the pressure-resistant gasket of required shape.
Expanded graphite manufactured in the present embodiment-epoxy resin-polyurethane resin pressure resistance composite material, tensile strength are reachable
9.384MPa, compressive strength can achieve effect pressure-resistant after sealing up to 34.128MPa, rebound degree 80%.
Passing through the comparison of above six embodiments, it can be seen that tensile strength, compressive strength and rebound degree are in inverse ratio, with
The increase of tensile strength and compressive strength, rebound degree opposite can reduce, in practical applications, user can pass through actual rings
The demand in border go to be properly adjusted in prepare the dosage of polyurethane resin in modified epoxy, the additional amount of modified expanded graphite and
Curing mode goes to change required performance in expanded graphite-epoxy resin-polyurethane resin pressure resistance composite material preparation process
Parameter, to meet the demand of the sealing pressure resistance under a variety of varying environments.
The present invention is disclosed as above with preferable case study on implementation, and however, it is not intended to limit the invention, any to be familiar with this profession
Technical staff, without departing from the scope of the present invention, when the structure and technology contents that can use the disclosure above are done
A little change or it is modified to the equivalence enforcement case of equivalent variations out, but it is all without departing from technical solution of the present invention
Hold, any simple modification, equivalent change and modification done according to the technical essence of the invention to the above case study on implementation still belong to
Technical solution of the present invention range.
Claims (7)
1. expanded graphite-epoxy resin-polyurethane resin pressure resistance composite material and preparation method thereof, it is characterised in that:
Step 1: expanded graphite is prepared, and surface modification treatment is carried out to the expanded graphite prepared；
Step 1 one: it takes 80-120ml glacial acetic acid that 400-600ml perchloric acid is added and is configured to glacial acetic acid-perchloric acid mixed solution I；
Step 1 two: taking 100 mesh crystalline flake graphite 8-10g to be put into there-necked flask, and glacial acetic acid-perchloric acid mixed solution I 20- is added
40ml, ice-water bath stirring 10-30min, which is uniformly mixed, obtains glacial acetic acid-perchloric acid mixed solution I I；
Step 1 three: 1-5g potassium permanganate point n times equivalent is added in glacial acetic acid-perchloric acid mixed solution I I, to permanganic acid
After all glacial acetic acid-perchloric acid mixed solution I I is added in potassium, mixed after bath temperature is increased to 30-40 DEG C of reaction 1-3h
Object I, N are positive integer；
Step 1 four: after mixture I is washed to neutrality, in placement surface ware I, drying is obtained in the environment of 40-80 DEG C can
Expanded graphite；
Step 1 five: expansible graphite being placed in 1000 DEG C of Muffle furnaces and carries out extruding, and expanded graphite is made；
Step 1 six: the silane coupling agent of 1-3g is dissolved in 80-100g dehydrated alcohol and is configured to surface treating agent；
Step 1 seven: surface treating agent configured in step 1 six is added in bottle,suction, takes expanded graphite 3- obtained
5g is dispersed in surface treating agent, and bottle,suction is evacuated under conditions of -0.1MPa and carries out magnetic agitation 1-3h, obtains product I；
Step 1 eight: after the product I that step 1 seven obtains is filtered and washed, in placement surface ware II, in 30-50 DEG C of environment
Lower drying 12-24h obtains the modified expanded graphite in surface；
Step 2: the preparation of modified epoxy；
Step 2 one: 100-120g epoxy resin is placed into 500ml there-necked flask, and is added in the environment of inert gas shielding
Heat arrives 30-50 DEG C；
Step 2 two: 10-150g polyurethane resin is added in the epoxy resin after heating, and stirs 1-2h, obtains product
II；
Step 2 three: modified epoxy will be formed after the cooling of product II obtained in step 2 two；
Step 3: expanded graphite-epoxy resin-polyurethane resin pressure resistance composite material preparation；
Step 3 one: the expanded graphite for taking the surface 0.1-0.5g modified is added in 10g modified epoxy, is mixed equal
It is even；
Step 3 two: according to the content of epoxy resin in modified epoxy, according to quality than epoxy resin: fatty amine curing agent
Fatty amine curing agent is added in the ratio of=2:1, is mixed evenly, and obtains expanded graphite-epoxy resin-polyurethane resin pressure resistance
Composite material；
Step 3 three: expanded graphite obtained in step 3 two-epoxy resin-polyurethane resin pressure resistance composite material is put into
In pattern tool, be heating and curing 4-12h in the environment of 30-50 DEG C, obtains the pressure-resistant gasket of required shape.
2. expanded graphite according to claim 1-epoxy resin-polyurethane resin pressure resistance composite material and preparation method thereof,
It is characterized by: 1-5g potassium permanganate point n times equivalent is added to glacial acetic acid-perchloric acid mixed solution I I in the step 1 three
In, the value range of N is 8-12 times.
3. expanded graphite according to claim 2-epoxy resin-polyurethane resin pressure resistance composite material and preparation method thereof,
It is characterized by: the surface plate I in the step 1 four is glass surface ware.
4. expanded graphite according to claim 3-epoxy resin-polyurethane resin pressure resistance composite material and preparation method thereof,
It is characterized by: the silane coupling agent in the step 1 six is KH-560 type silane coupling agent.
5. expanded graphite according to claim 4-epoxy resin-polyurethane resin pressure resistance composite material and preparation method thereof,
It is characterized by: epoxy resin is E-51 type epoxy resin in the step 2 one.
6. expanded graphite according to claim 5-epoxy resin-polyurethane resin pressure resistance composite material and preparation method thereof,
It is characterized by: the inert gas in the step 2 one is nitrogen.
7. expanded graphite according to claim 6-epoxy resin-polyurethane resin pressure resistance composite material and preparation method thereof,
It is characterized by: the 4-12h that is heating and curing in the environment of 30-50 DEG C in the step 3 three, could alternatively be solid at room temperature
Change 3-7d.
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