CN108641356A - Graphene/class graphene WS of three phosphonitrilic polymer of ring modification2/ Bismaleimide composites and preparation method - Google Patents
Graphene/class graphene WS of three phosphonitrilic polymer of ring modification2/ Bismaleimide composites and preparation method Download PDFInfo
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Abstract
The present invention relates to a kind of graphene/class graphene WS of three phosphonitrilic polymer of ring modification2/ Bismaleimide composites and preparation method, first with the method for low energy ball milling and ultrasound by WS2Remove into class graphene WS2, then with graphite oxide is dilute is added in high-temperature high-pressure reaction kettle together, and appropriate hydrazine hydrate is added, one pot of hydro-thermal method carries out reaction and prepares graphene/class graphene WS2.Then using itself and hexachlorocyclotriph,sphazene, branched polyethyleneimine as raw material, using triethylamine as acid binding agent, graphene/class graphene WS of three phosphonitrilic polymer of ring modification is prepared using template in situ2.Composite material is finally mixed with certain proportion and diphenyl-methane type bismaleimide and diallyl bisphenol.Prepared composite material has good interface bond strength, excellent mechanical property and tribological property.
Description
Technical field
The invention belongs to advanced compound materials science domains, are related to a kind of graphite of three phosphonitrilic polymer of ring modification
Alkene/class graphene WS2/ Bismaleimide composites and preparation method.
Background technology
Graphene is a kind of New Two Dimensional stratified material, since it is with excellent tensile strength, high flexibility, good
Good thermal conductivity, mechanical property and good electronic transmission performance, therefore as the hot spot of Recent study.Graphene is as solid
Body lubricant, can the larger frictional behaviour for improving composite material.For example, Wang Han et al. [Compos.Part
A.Appl.S 67 (2014) 268-273] it multi-layer graphene is added to as filler in polyvinyl chloride prepares composite material, it sends out
The presence of existing multi-layer graphene can be substantially reduced the friction coefficient and wear rate of composite material.For another example, hyperbranched silane is utilized
Coupling agent KH-560 and polyetheramine are prepared for a kind of solvent-free graphene nanobelt colloid, are then added in epoxy resin and make
Standby composite material finds that prepared composite material has excellent mechanical performance, frictional behaviour.Therefore, graphene or modification
Graphene can be used for kollag to improve the frictional behaviour of polymeric matrix.
However, graphene causes to prevent it from a solvent stablizing since piece interlayer mutually has very strong Van der Waals force
Dispersion, and it is poor with the compatibility of other materials, seriously constrain the application of graphene.With the rise of graphene, transition
Metal sulfide also begins to the extensive concern for causing people, because it can remove into the layer structure similar to graphene.Two
Tungsten sulfide is Typical Representative therein, it is analogous to the hexagonal system structure compound of two-dimensional layer compound.WS2With W originals
The interlayer structure that sublayer and two S atom layers are formed all is connected with S-W-S covalent bonds between every layer, between layers
There is weaker Van der Waals force, interlamellar spacing 0.62nm.WS2Key effect in layer is stronger, however key between layers
Effect is weaker, and this special structure makes it be had a wide range of applications in terms of lubrication.For example, Xu Shusheng et al.
[Materials&Design,2016,93:494-502] by Sb2O3And WS2It has been collectively incorporated on Cu substrate composite coatings and has prepared
It is a kind of that there are excellent low-friction coefficient and wear-resisting plural layers, the results showed that WS2-Sb2O3The wear-out life of/Cu multilayer films
1.1 × 10 can be up to6Period.Additionally, it has been found that class graphene WS2It can act synergistically between graphene, and
And the WS of stripping2Since the number of plies can greatly reduce, and there is the pattern and layer structure similar with graphene, the two is compound
Afterwards, its friction coefficient can be made lower.Therefore, patent of the present invention prepares graphene/class graphene WS first2Compound particle makes
Material not only there is excellent antifriction quality also to possess good wearability.In addition to this, it is contemplated that by prepared nano-particle
It is added in bimaleimide resin base body and prepares composite material, therefore the interface cohesion between nano-particle and resin matrix
Property is a prodigious problem.
Invention content
Technical problems to be solved
In order to avoid the shortcomings of the prior art, the present invention propose the graphene of three phosphonitrilic polymer of ring modification a kind of/
Class graphene WS2/ Bismaleimide composites and preparation method solve graphene composite material and disperse in the polymer not
The problem of uniformly and with bimaleimide resin poor compatibility.
Technical solution
A kind of graphene/class graphene WS of three phosphonitrilic polymer of ring modification2/ Bismaleimide composites, it is special
Sign is that component is graphene/class graphene WS of 0.1~20 part of three phosphonitrilic polymer of ring modification2Nano-complex particle, 100 parts
Diphenyl-methane type bismaleimide and 10~100 parts of diallyl bisphenols.
Graphene/class graphene WS of three phosphonitrilic polymer of ring modification2Nano-complex particle is using template in situ
Method prepares graphene/class graphene WS of three phosphonitrile of ring modification2Nano-complex particle, wherein：Graphene and class graphene WS2's
Mass ratio is 1:(0.1~10), three phosphonitrilic polymer grafting rate of ring are 0.1~50%；Three phosphonitrilic polymer of the ring is with six
Three phosphonitrile of chlorine ring and branched polyethyleneimine polycondensation form.
A kind of graphene/class graphene WS for preparing three phosphonitrilic polymer of ring described in claims 1 or 2 and modifying2/ span comes
The method of acid imide composite material, it is characterised in that steps are as follows：
Step 1：By WS2With NaCl dry blends with 1:10 ratio mechanochemistry in ball mill agate grinding bowl handles 2h
The product of nanostructure is obtained, is dried using the product of water washing nanostructure, and at 100 DEG C, then ultrasound 30min systems
Standby class graphene WS2；
Step 2：By graphene oxide and class graphene WS2It is 1 in mass ratio:(0.1~10) be mixed to join 100~
In 500mL ethyl alcohol, it is transferred in high temperature and pressure hydro-thermal reaction kettle after ultrasound 30min at 180W, adds 1~5mL hydrazine hydrates,
Sealing is reacted for 24 hours at 220 DEG C；It carries out filtering and being washed for several times with deionized water and ethyl alcohol after it is cooled to room temperature, in 60
It DEG C is dried in vacuum overnight to get graphene/class graphene WS2Nano-complex particle rGO/GL-WS2；
Step 3：By rGO/GL-WS2, hexachlorocyclotriph,sphazene, branched polyethyleneimine is according to 1:(0.5~3):(1~4)
It is mixed, adds 100~500mL tetrahydrofurans, 1~8mL triethylamines, 4~10h is reacted at 25~60 DEG C；Then filter,
For several times through tetrahydrofuran washing, it is dried in vacuum overnight at 60 DEG C to get the rGO/GL-WS modified to three phosphonitrilic polymer of ring2For
PHbP/rGO/GL-WS2；
Step 4：By 0.1~20 part of PHbP/rGO/GL-WS2, 100 parts of diphenyl-methane type bismaleimide and 10~
100 parts of diallyl bisphenols after 10~80min of ultrasonic disperse, heat molten under the power of 120~300W at 130~150 DEG C
Melt, 15~80min of pre-polymerization is poured into the mold of preheating, is put into 130~150 DEG C of vacuum tank, is vacuumized removing bubble, is put
Enter air dry oven and carry out step-up temperature solidification, curing process is 150 DEG C/2h+180 DEG C/2h+220 DEG C/4h+250 DEG C/4h, so
Natural cooling afterwards demoulds up to PHbP/rGO/GL-WS2/ Bismaleimide composites.
Above-mentioned is to prepare portion PHbP/rGO/GL-WS2The proportioning of/Bismaleimide composites.
Reaction mixture when step 1 grinding:Ball is again than being 1:7.
Advantageous effect
A kind of graphene/class graphene WS of three phosphonitrilic polymer of ring modification proposed by the present invention2/ bismaleimide is multiple
Condensation material and preparation method, polyphosphazene modify the WS of preparation2The dispersibility of graphene had both can be improved in/graphene composite particle,
The interface bond strength of graphene and resin can be improved again.
Polyphosphazene is that with N, P atom, alternately single double bond arranges on a kind of main chain, and side group is made of organic group
Line style or cricoid inorganic organic polymer have excellent performance and are widely applied.In recent years, researcher utilizes poly- phosphorus
Nitrile carries out surface functionalization to conventional filler, and carrys out the interfacial bonding property that modified resin improves composite material with this.For example,
Zhang Xiaoqing[RSC Advances,2014,4(24):12198-12205] poly phosphazene with active amino is grafted
There is strong interface between carbon fiber surface (CF-ACP), and polypropylene PP (M-PP) composite material of maleic anhydride grafting
Interaction, compared with unmodified CF/M-PP composite materials, the interface shear strength of CF-ACP/M-PP composite materials increases
223.0%.Therefore, this method makes prepared composite material other than with good mechanical property, also has excellent
Frictional behaviour, can be used as space flight, aero-engine sealing material etc..Not only the dispersibility of graphene can be improved, but also stone can be improved
The interface bond strength of black alkene and resin, in addition, make prepared material also have anti-friction wear-resistant, high temperature resistant, super abrasive, from
The features such as lubrication.
The present invention compared with the existing technology, has the advantage that：
The present invention first prepares rGO/GL-WS2, class graphene WS2It can act synergistically between graphene, graphene
Incorporation can inhibit class graphene WS2Stacking between layers, and class graphene WS2Presence can prevent graphene
Reunite, improves the dispersibility of nano-particle in organic solvent；Then polymer is modified by rGO/GL-WS with three phosphonitrile of ring2
And be added in bimaleimide resin as solid lubrication additive and prepare composite material, such nanoparticle surface will
With a large amount of active aminos, Michael addition reaction can be carried out with bimaleimide resin base body, improve nano-particle and
The interfacial bonding property of resin matrix, so that it may obtain the graphite that a kind of super abrasive low friction, adhesion strength are high and processing technology is excellent
Alkenyl two-dimensional nano composite material.
Description of the drawings
Fig. 1：Graphene/class graphene WS of three phosphonitrilic polymer of ring modification2(PHbP/rGO/GL-WS2) reaction process
Schematic diagram
Fig. 2：Diphenyl-methane type bismaleimide structure formula
Fig. 3：Diallyl bisphenol structural formula
Specific implementation mode
In conjunction with embodiment, attached drawing, the invention will be further described：
Since the dispersibility of graphene in a solvent is poor, consider and class graphene WS2It carries out compound preparing graphite
Alkene/class graphene WS2Nano-complex particle, makes to act synergistically between the two, and can both enhance anti-friction wear-resistant can be with
Improve its dispersibility in organic solvent.But there is also the problems poor with the compatibility of resin matrix, therefore utilize
Three phosphonitrilic polymer of ring carries out it rGO/GL-WS that modification prepares the modification of three phosphonitrile of ring2, such nanoparticle surface is just
A large amount of active aminos can be carried, Michael addition reaction can be carried out with bimaleimide resin base body, can thus be carried
The interfacial bonding property of high nano-particle and resin matrix.The present invention prepares class graphite by low energy ball milling and the method for ultrasound first
Alkene WS2, then itself and graphene oxide, hydrazine hydrate are added in high-temperature high-pressure reaction kettle together, utilize one pot of hydro-thermal legal system
Standby graphene/class graphene WS2Nano-complex particle.Then with gained nano-particle and hexachlorocyclotriph,sphazene, branched poly- second
Alkene imines is raw material, and using triethylamine as acid binding agent, graphene/class graphene of polyphosphazene modification is prepared using template in situ
WS2.It is double with certain proportion and diphenyl-methane type bismaleimide and diallyl using nano-particle as solid lubrication additive
Phenol A mixing prepares composite material using casting method curing molding.
The technical solution adopted by the present invention is：
Graphene/class graphene WS of 0.1~20 part of three phosphonitrilic polymer of ring modification2, 100 parts of diphenyl-methane type spans
Carry out acid imide and 10~100 parts of diallyl bisphenols are prepared with casting moulding.
Preparation method includes the following steps：
The first step prepares class graphite WS by low energy ball milling and ultrasonic method2(GL-WS2)；Pass through modified Hummer ' s methods
Prepare graphene oxide (GO).
Second step, by the GO and class graphene WS prepared by upper step2It is dissolved in deionized water, ultrasonic disperse simultaneously stirs
30min.Appropriate hydrazine hydrate is transferred it in high-temperature high-pressure reaction kettle and is added, high-temperature high-voltage reaction is for 24 hours.Finally, it waits for
It is cooled to room temperature, and filters and is washed with deionized for several times, dries to get graphene/class graphene WS2Nano-complex particle
(rGO/GL-WS2)。
Third walks, by graphene/class graphene WS2Nano-complex particle is dissolved in ultrasonic disperse half an hour in tetrahydrofuran,
Under stiring, hexachlorocyclotriph,sphazene (HCCP) and branched polyethyleneimine (bPEI) are added in above-mentioned reaction solution, then
Appropriate triethylamine is added as acid binding agent, heating reaction 5 hours, you can obtain graphene/class of three phosphonitrilic polymer of ring modification
Graphene WS2(PHbP/rGO/GL-WS2).Its reaction process is as shown in Figure 1.
4th step, with certain proportion by PHbP/rGO/GL-WS2, diphenyl-methane type bismaleimide and diallyl it is double
Phenol A mixing, heats pre-polymerization, vacuumizes to be poured into be put into baking oven in preheated mold after bubble removing and is cured.
The specific method is as follows：
Step 1：By WS2With NaCl dry blends with 1:10 ratio mechanochemistry in ball mill agate grinding bowl handles 2h
(reaction mixture:Ball is again than being 1:7) the product water for, obtaining nanostructure is thoroughly washed and (is desalted to remove), and at 100 DEG C
It is dried, then ultrasound 30min prepares class graphene WS2。
Step 2：By graphene oxide and class graphene WS2It is 1 in mass ratio:(0.5~3) be mixed to join 100~
In 500mL ethyl alcohol, the ultrasound 30min at 180W is transferred in high temperature and pressure hydro-thermal reaction kettle, and 1~5mL hydrazine hydrates are added,
Sealing is reacted for 24 hours at 220 DEG C.Then it carries out filtering and being washed for several times with deionized water and ethyl alcohol after it is cooled to room temperature,
Product is dried in vacuum overnight in 60 DEG C to get graphene/class graphene WS2Nano-complex particle (rGO/GL-WS2)。
Step 3：By rGO/GL-WS obtained2, hexachlorocyclotriph,sphazene, branched polyethyleneimine is according to 1:(0.5~3):
(1~4) be added three-necked flask in, add 100~500mL tetrahydrofurans, 1~8mL triethylamines, at 25~60 DEG C react 4~
10h.Then it filters, washed for several times through tetrahydrofuran, is dried in vacuum overnight at 60 DEG C, you can obtain the modification of three phosphonitrilic polymer of ring
RGO/GL-WS2(PHbP/rGO/GL-WS2)。
Step 4：By 0.1~20 part of PHbP/rGO/GL-WS2, 100 parts of diphenyl-methane type bismaleimide and 10~
100 parts of diallyl bisphenols after 10~80min of ultrasonic disperse, heat molten under the power of 120~300W at 130~150 DEG C
Melt, 15~80min of pre-polymerization is poured into the mold of preheating, is put into 130~150 DEG C of vacuum tank, is vacuumized removing bubble, is put
Enter air dry oven and carry out step-up temperature solidification, curing process is 150 DEG C/2h+180 DEG C/2h+220 DEG C/4h+250 DEG C/4h, so
Natural cooling afterwards demoulds up to PHbP/rGO/GL-WS2/ Bismaleimide composites.
Embodiment 1：
Step 1：By WS2With NaCl dry blends with 1:10 ratio mechanochemistry in ball mill agate grinding bowl handles 2h
(reaction mixture:Ball is again than being 1:7) product for, obtaining nanostructure is thoroughly washed with water, and is dried at 100 DEG C, so
Ultrasound 30min prepares class graphene WS afterwards2。
Step 2：By graphene oxide and class graphene WS2It is 1 in mass ratio:0.5 is mixed to join in 100mL ethyl alcohol,
The ultrasound 30min at 180W, is transferred in high temperature and pressure hydro-thermal reaction kettle, and 5mL hydrazine hydrates are added, and is sealed at 220 DEG C anti-
It should for 24 hours.Then it carries out filtering after it is cooled to room temperature and be washed for several times with deionized water and ethyl alcohol, by product in 60 DEG C of progress
It is dried in vacuum overnight to get graphene/class graphene WS2Nano-complex particle (rGO/GL-WS2)。
Step 3：By rGO/GL-WS obtained2, hexachlorocyclotriph,sphazene, branched polyethyleneimine is according to 1:0.5:1 is added
Into three-necked flask, 100mL tetrahydrofurans, 1mL triethylamines are added, 4h is reacted at 25 DEG C.Then it filters, washed through tetrahydrofuran
It washs for several times, is dried in vacuum overnight at 60 DEG C, you can obtain the rGO/GL-WS of three phosphonitrilic polymer of ring modification2(PHbP/rGO/GL-
WS2)。
Step 4：By 0.1 part of PHbP/rGO/GL-WS2, 100 parts of diphenyl-methane type bismaleimide and 10 parts of diene
Propyl bisphenol-A after ultrasonic disperse 10min, heats melting under the power of 120W at 130 DEG C, and pre-polymerization 15min pours into preheating
It in mold, is put into 130 DEG C of vacuum tank, vacuumizes removing bubble, be put into air dry oven and carry out step-up temperature solidification, solidification
Technique is 150 DEG C/2h+180 DEG C/2h+220 DEG C/4h+250 DEG C/4h, then natural cooling, is demoulded up to PHbP/rGO/GL-
WS2/ Bismaleimide composites.
Embodiment 2：
Step 1：By WS2With NaCl dry blends with 1:10 ratio mechanochemistry in ball mill agate grinding bowl handles 2h
(reaction mixture:Ball is again than being 1:7) product for, obtaining nanostructure is thoroughly washed with water, and is dried at 100 DEG C, so
Ultrasound 30min prepares class graphene WS afterwards2。
Step 2：By graphene oxide and class graphene WS2It is 1 in mass ratio:1 is mixed to join in 200mL ethyl alcohol,
Ultrasound 30min under 180W, is transferred in high temperature and pressure hydro-thermal reaction kettle, and 3mL hydrazine hydrates are added, and reaction is sealed at 220 DEG C
24h.Then it carries out filtering after it is cooled to room temperature and be washed for several times with deionized water and ethyl alcohol, product is carried out very in 60 DEG C
Sky is dried overnight to get graphene/class graphene WS2Nano-complex particle (rGO/GL-WS2)。
Step 3：By rGO/GL-WS obtained2, hexachlorocyclotriph,sphazene, branched polyethyleneimine is according to 1:1:1.5 being added
Into three-necked flask, 200mL tetrahydrofurans, 3mL triethylamines are added, 6h is reacted at 40 DEG C.Then it filters, washed through tetrahydrofuran
It washs for several times, is dried in vacuum overnight at 60 DEG C, you can obtain the rGO/GL-WS of three phosphonitrilic polymer of ring modification2(PHbP/rGO/GL-
WS2)。
Step 4：By 2 parts of PHbP/rGO/GL-WS2, 100 parts of diphenyl-methane type bismaleimide and 50 part of two allyl
Base bisphenol-A after ultrasonic disperse 30min, heats melting under the power of 180W at 135 DEG C, and pre-polymerization 30min pours into the mould of preheating
It in tool, is put into 135 DEG C of vacuum tank, vacuumizes removing bubble, be put into air dry oven and carry out step-up temperature solidification, cure work
Skill is 150 DEG C/2h+180 DEG C/2h+220 DEG C/4h+250 DEG C/4h, then natural cooling, is demoulded up to PHbP/rGO/GL-WS2/
Bismaleimide composites.
Embodiment 3：
Step 1：By WS2With NaCl dry blends with 1:10 ratio mechanochemistry in ball mill agate grinding bowl handles 2h
(reaction mixture:Ball is again than being 1:7) product for, obtaining nanostructure is thoroughly washed with water, and is dried at 100 DEG C, so
Ultrasound 30min prepares class graphene WS afterwards2。
Step 2：By graphene oxide and class graphene WS2It is 1 in mass ratio:2 are mixed to join in 300mL ethyl alcohol,
Ultrasound 30min under 180W, is transferred in high temperature and pressure hydro-thermal reaction kettle, and 2mL hydrazine hydrates are added, and reaction is sealed at 220 DEG C
24h.Then it carries out filtering after it is cooled to room temperature and be washed for several times with deionized water and ethyl alcohol, product is carried out very in 60 DEG C
Sky is dried overnight to get graphene/class graphene WS2Nano-complex particle (rGO/GL-WS2)。
Step 3：By rGO/GL-WS obtained2, hexachlorocyclotriph,sphazene, branched polyethyleneimine is according to 1:2:3 are added to
In three-necked flask, 300mL tetrahydrofurans, 5mL triethylamines are added, 8h is reacted at 50 DEG C.Then it filters, washed through tetrahydrofuran
For several times, it is dried in vacuum overnight at 60 DEG C, you can obtain the rGO/GL-WS of three phosphonitrilic polymer of ring modification2(PHbP/rGO/GL-
WS2)。
Step 4：By 8 parts of PHbP/rGO/GL-WS2, 100 parts of diphenyl-methane type bismaleimide and 80 part of two allyl
Base bisphenol-A after ultrasonic disperse 60min, heats melting under the power of 240W at 140 DEG C, and pre-polymerization 60min pours into the mould of preheating
It in tool, is put into 140 DEG C of vacuum tank, vacuumizes removing bubble, be put into air dry oven and carry out step-up temperature solidification, cure work
Skill is 150 DEG C/2h+180 DEG C/2h+220 DEG C/4h+250 DEG C/4h, then natural cooling, is demoulded up to PHbP/rGO/GL-WS2/
Bismaleimide composites.
Implement example 4：
Step 1：By WS2 and NaCl dry blends with 1:10 ratio mechanochemistry in ball mill agate grinding bowl handles 2h
(reaction mixture:Ball is again than being 1:7) product for, obtaining nanostructure is thoroughly washed with water, and is dried at 100 DEG C, so
Ultrasound 30min prepares class graphene WS2 afterwards.
Step 2：By graphene oxide and class graphene WS2It is 1 in mass ratio:3 are mixed to join in 500mL ethyl alcohol,
Ultrasound 30min under 180W, is transferred in high temperature and pressure hydro-thermal reaction kettle, and 1mL hydrazine hydrates are added, and reaction is sealed at 220 DEG C
24h.Then it carries out filtering after it is cooled to room temperature and be washed for several times with deionized water and ethyl alcohol, product is carried out very in 60 DEG C
Sky is dried overnight to get graphene/class graphene WS2Nano-complex particle (rGO/GL-WS2)。
Step 3：By rGO/GL-WS obtained2, hexachlorocyclotriph,sphazene, branched polyethyleneimine is according to 1:3:4 are added to
In three-necked flask, 500mL tetrahydrofurans, 8mL triethylamines are added, 10h is reacted at 60 DEG C.Then it filters, washed through tetrahydrofuran
It washs for several times, is dried in vacuum overnight at 60 DEG C, you can obtain the rGO/GL-WS of three phosphonitrilic polymer of ring modification2(PHbP/rGO/GL-
WS2)。
Step 4：By 10 parts of PHbP/rGO/GL-WS2, 100 parts of diphenyl-methane type bismaleimide and 100 parts of diene
Propyl bisphenol-A after ultrasonic disperse 80min, heats melting under the power of 300W at 150 DEG C, and pre-polymerization 80min pours into preheating
It in mold, is put into 150 DEG C of vacuum tank, vacuumizes removing bubble, be put into air dry oven and carry out step-up temperature solidification, solidification
Technique is 150 DEG C/2h+180 DEG C/2h+220 DEG C/4h+250 DEG C/4h, then natural cooling, is demoulded up to PHbP/rGO/GL-
WS2/ Bismaleimide composites.
Claims (4)
1. a kind of graphene/class graphene WS of three phosphonitrilic polymer of ring modification2/ Bismaleimide composites, feature exist
In graphene/class graphene WS that component is the modification of 0.1~20 part of three phosphonitrilic polymer of ring2Nano-complex particle, 100 parts of hexichol
Methane type bismaleimide and 10~100 parts of diallyl bisphenols.
2. graphene/class graphene WS of three phosphonitrilic polymer of ring modification according to claim 12/ bismaleimide is compound
Material, it is characterised in that：Graphene/class graphene WS of three phosphonitrilic polymer of ring modification2Nano-complex particle is to use
Template in situ prepares graphene/class graphene WS of three phosphonitrile of ring modification2Nano-complex particle, wherein：Graphene and class stone
Black alkene WS2Mass ratio be 1:(0.1~10), three phosphonitrilic polymer grafting rate of ring are 0.1~50%；Three phosphonitrile of the ring polymerize
Object is formed with hexachlorocyclotriph,sphazene and branched polyethyleneimine polycondensation.
3. a kind of graphene/class graphene WS for preparing three phosphonitrilic polymer of ring described in claims 1 or 2 and modifying2/ span carrys out acyl
The method of imines composite material, it is characterised in that steps are as follows：
Step 1：By WS2With NaCl dry blends with 1:10 ratio mechanochemistry processing 2h in ball mill agate grinding bowl is obtained
The product of nanostructure is dried using the product of water washing nanostructure, and at 100 DEG C, and then ultrasound 30min prepares class
Graphene WS2；
Step 2：By graphene oxide and class graphene WS2It is 1 in mass ratio:(0.1~10) is mixed to join 100~500mL second
In alcohol, it is transferred in high temperature and pressure hydro-thermal reaction kettle after ultrasound 30min at 180W, 1~5mL hydrazine hydrates is added, at 220 DEG C
Lower sealing reaction is for 24 hours；It carries out filtering after it is cooled to room temperature and be washed for several times with deionized water and ethyl alcohol, carried out in 60 DEG C true
Sky is dried overnight to get graphene/class graphene WS2Nano-complex particle rGO/GL-WS2；
Step 3：By rGO/GL-WS2, hexachlorocyclotriph,sphazene, branched polyethyleneimine is according to 1:(0.5~3):(1~4) it carries out
Mixing, adds 100~500mL tetrahydrofurans, 1~8mL triethylamines, and 4~10h is reacted at 25~60 DEG C；Then it filters, through four
Hydrogen furans washs for several times, is dried in vacuum overnight at 60 DEG C to get the rGO/GL-WS modified to three phosphonitrilic polymer of ring2For PHbP/
rGO/GL-WS2；
Step 4：By 0.1~20 part of PHbP/rGO/GL-WS2, 100 parts of diphenyl-methane type bismaleimide and 10~100 parts
Diallyl bisphenol after 10~80min of ultrasonic disperse, heats melting, in advance under the power of 120~300W at 130~150 DEG C
Poly- 15~80min is poured into the mold of preheating, is put into 130~150 DEG C of vacuum tank, is vacuumized removing bubble, is put into air blast
Drying box carries out step-up temperature solidification, and curing process is 150 DEG C/2h+180 DEG C/2h+220 DEG C/4h+250 DEG C/4h, then natural
It is cooling, it demoulds up to PHbP/rGO/GL-WS2/ Bismaleimide composites；
Above-mentioned is to prepare portion PHbP/rGO/GL-WS2The proportioning of/Bismaleimide composites.
4. method according to claim 3, it is characterised in that：Reaction mixture when step 1 grinding:Ball is again than being 1:7.
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| CN111349244A (en) * | 2020-01-17 | 2020-06-30 | 北京理工大学 | Preparation method of environment-friendly type cross-linked polyphosphazene |
| CN113957728A (en) * | 2021-11-29 | 2022-01-21 | 广东昊天服装实业有限公司 | Preparation method and application of nanogel composite dyeing flame retardant |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400956A (en) * | 2018-10-24 | 2019-03-01 | 中国科学技术大学 | A kind of preparation method and applications of the modified black phosphorus alkene of polyphosphazene |
| CN109400956B (en) * | 2018-10-24 | 2020-01-03 | 中国科学技术大学 | Preparation method and application of polyphosphazene modified black phosphorus alkene |
| CN109912845A (en) * | 2019-02-22 | 2019-06-21 | 四川大学 | A kind of graphene oxide and its epoxy nano composite material that epoxy radicals end-blocking is modified |
| CN111349244A (en) * | 2020-01-17 | 2020-06-30 | 北京理工大学 | Preparation method of environment-friendly type cross-linked polyphosphazene |
| CN111349244B (en) * | 2020-01-17 | 2021-03-19 | 北京理工大学 | Preparation method of environment-friendly type cross-linked polyphosphazene |
| CN113957728A (en) * | 2021-11-29 | 2022-01-21 | 广东昊天服装实业有限公司 | Preparation method and application of nanogel composite dyeing flame retardant |
| CN113957728B (en) * | 2021-11-29 | 2024-03-26 | 广东昊天服装实业有限公司 | Preparation method and application of nanogel composite dyeing flame retardant |
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