CN105524299B - Functionalization graphene and preparation method and with its fire-retardant cross-linked type polyurethane rigid foam - Google Patents
Functionalization graphene and preparation method and with its fire-retardant cross-linked type polyurethane rigid foam Download PDFInfo
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/0058—≥50 and <150kg/m3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0075—Foam properties prepared with an isocyanate index of 60 or lower
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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Abstract
The general structure of functionalization graphene disclosed by the invention is as follows:X is epoxies group in formula, and Y is graphene, Z C1‑C6Any one of alkyl, be the product grafted graphene oxide reacted under water-less environment by phosphorus chlorine compound, monomer containing epoxy construction, phenolic monomers and obtain.After hard polyurethane foam is added in the functionalization graphene by the present invention, because of its good dispersion, its effect as essential type fire retardant can preferably be played, its anti-flammability and compressibility is substantially improved, its density, heat-insulating property again can be suitable with conventional polyurethanes hard bubble, and the technology of preparing of functionalization graphene and hard polyurethane foam is simple and easy, it is convenient to carry out large-scale promotion application.
Description
Technical field
The invention belongs to graphene and its preparation and with its fire-retardant hard polyurethane foam technical field, in particular to one
Kind there is functionalization graphene and preparation method thereof of high fire-retardance efficiency and with its fire-retardant cross-linked type polyurethane rigid foam.
Background technique
Hard polyurethane foam is due to extremely low thermal coefficient, low-density, high specific strength value and good cementability
The advantages that energy, by the welcome for requiring heat-insulating property stringent refrigeration equipment and construction industry, demand increases year by year and it
Application field is also constantly expanding.But hard polyurethane foam still faces following problem in practical applications and needs to solve:
The high resistant burning problem of hard polyurethane foam.For polyurethane because being influenced by structural factor, decomposition temperature is lower, fire-retardant
Performance is poor, and the oxygen index (OI) of non-modified hard polyurethane foam generally only has 19% or so, meets fire and easily burns.At present to poly-
It is using additive flame retardant or design flame retardant polyol that urethane hard bubble, which carries out fire-retardant used conventional method,.But it wherein hinders
The flame retarding efficiency of combustion type polyalcohol it is then relatively low and on the mechanical performances such as the compression performance of foam, dimensional stability influence compared with
Greatly, existing additive flame retardant majority is halogen containing flame-retardant, and when burning can generate a large amount of cigarette and toxic corrosivity gas
Body will cause huge primary injury to human body in the scene of a fire, serious to interfere fire fighting and evacuating personnel, corrosion instrument and equipment.This
Outside, the problem of most halogen containing flame-retardants are migrated there is also elongated at any time.In additive flame retardant, expanded graphite is
A kind of common expansion type flame retardant, since its expansion ratio is high, expansion effect is obvious and environmental-friendly and have larger application prospect,
Make if CN 101265358B is in " hard polyurethane foams, preparation method and application " to using only expanded graphite
It is reported for fire retardant hard polyurethane foam, and illustrates the hard polyurethane foam table after combustion for adding expanded graphite
Face has the layer of charcoal of expanded graphite formation.But because the mechanism of intumescence of expanded graphite is physical expansion, though expansion ratio is unable to greatly shape
At the layer of charcoal of enough densifications to protect substrate, large specific surface area for polyurethane foam resilience in comparison body and plastics etc., so that swollen
The drawback of swollen graphite seems more prominent.Further, since expanded graphite wick effect in polyurethane foam is obvious, thus it is general
Expanded graphite is seldom used for polyurethane foam separately as fire retardant, and made using the method for compounding or cladding mostly
With " a kind of composite flame retardant with core-shell structure and preparation method thereof " and CN 101503567 as disclosed in 102140184 A of CN
Melamino-formaldehyde is just respectively adopted in " a kind of nano composite expansion flame-retardant polyurethane foam plastic and preparation method thereof " disclosed in A
Resin cladding expanded graphite and non-halogen phosphoric acid ester compounding expanded graphite carry out resistance combustion polyurethane foam, but due to expanded graphite interlayer
Away from smaller, cause the dispersibility for after coating or compounding in polyurethane foam substrate can be worse, thus to the machine of polyurethane foam
The generation of tool performance seriously affects, though the influence can be reduced by reducing the partial size of expanded graphite, with expanded graphite partial size
Reduction, flame retarding efficiency again therewith rapidly decline.
The non-halogen problem of hard polyurethane foam foaming agent.Up to now, HCFC-141b, pentane and water are that hard is poly-
The common foaming of urethane foam.Although HCFC-141b ozone-depleting is dived, value is existing compared to fluorochlorohydrocarbon class foaming agent significantly drops
It is low, but it cannot still ignore the destruction of atmospheric ozone layer.Pentane is due to highly volatile and burning, using it as hair
The flame retardant property of polyurethane foam can be then greatly reduced in infusion.Use water as foaming agent merely, if not to polyurethane foam into
Row is modified, and foam performance and dimensional stability will receive larger impact, and may exist when industrialized production due to part
Temperature is excessively high and the phenomenon that burning core.
The low-density of hard polyurethane foam and the contradictory problems of dimensional stability.It is well known that foamed plastics is low close
The purpose of degreeization is to realize that raw material usage amount is cut down, transportation cost reduces and lightweight bring construction cost reduces
Advantage, but low-density not only results in the decline of foamed plastics intensity, and moulds by the hard polyurethane foam of representative of plate
Material is also also easy to produce the decline of dimensional stability.
Summary of the invention
In order to solve the problems in the prior art, the purpose of the present invention is to provide that a kind of flame retarding efficiency is high, fire retardation first
Lasting functionalization graphene, the graphene can not only be used for into carbon flame-proof catalyst, increase the degree of cross linking but also as crosslinking center
To improve layer of charcoal density, while it can also be dispersed in polyurethane foam substrate and increase the dimensionally stable of hard polyurethane foam
Property.
It is a further object of the present invention to provide a kind of preparation methods of above-mentioned functionalization graphene.
Another object of the present invention, which is to provide, a kind of to be used above-mentioned functionalization graphene as high-efficient and lasting and can improve substrate
The flame retardant cross-linked type polyurethane rigid foam of stability.
A kind of functionalization graphene provided by the invention, the general structure of the graphene are as follows:
X is epoxies group in formula, and Y is graphene, Z C1-C6Any one of alkyl.
Epoxies group described in the above graphene-structured be glycidyl, epoxybutyl, epoxypentyl or epoxy oneself
Any one of base.
The preparation method of above-mentioned functionalization graphene provided by the invention, the specific process step and condition of the preparation method
It is as follows:
1) three-functionality-degree phosphoryl chloride phosphorus oxychloride or pyrophosphoryl chloride are dissolved in organic solvent, instill identical work as under ice-water bath stirs
Measure C1-C6Alcohols material, react 3~5h after heating remove organic solvent, be continuously heating to solution 3~8h of slightly boiled lower reaction, subtract
Pressure distillation collects 160~240 DEG C of fraction, then fraction is carried out air-distillation, collects 240~280 DEG C of fraction to get list
Replace phosphoryl chloride phosphorus oxychloride；
2) the monosubstituted phosphoryl chloride phosphorus oxychloride of gained or two commercially available degree of functionality phosphoryl chloride phosphorus oxychlorides are added in organic solvent and are stirred evenly, then
The epoxy types for the equimolar amounts being dissolved in organic solvent are finished in being slowly added dropwise in 1~2h, continue slowly heating simultaneously
Epoxy group phosphinylidyne solutions of chlorine is made in 2~5h of back flow reaction；
3) graphene is uniformly dispersed in dispersing agent, is then slowly dropped at room temperature in epoxy group phosphinylidyne solutions of chlorine,
Dispersing agent is distilled off after reacting 3~5h in temperature rising reflux, is further continued for heating and steams other unreacted substances, is cooled to 80~90
DEG C, C is slowly added into reaction system1-C6Hydroxyl substance, additional amount are at least 1 times of hydroxyl/chlorine atom molar amount, after
1~2h of continuous reaction, products therefrom is finally successively washed with acetone and boiling water to filtrate pH be in neutrality, dry, middle ring
The additive amount of oxygroup phosphoryl chloride phosphorus oxychloride is 1~2mol/25g graphene.
Epoxy types used in above method are appointing in epoxy prapanol, epoxy butanol, epoxy amylalcohol or epoxy hexanol
It is a kind of；Phosphoryl chloride phosphorus oxychloride is phosphorus oxychloride, phosphorus thiochloride, pyrophosphoric acid chlorine, dichlorophenyl chlorine phosphate, diphenylphosphoryl dichloro, 2- chlorobenzene
Any one of base-phenyl phosphate ester, methyl acid phosphate dichloro methyl esters, chloromethyl-methyl-phosphoryl chloride phosphorus oxychloride, 2- rubigan phosphate.
Graphene used in above method obtains in the following manner: 1) by graphite according to Journal of the
American Chemical Society, Year 1958, Volume 80, Issue 6, Page 1339 and Advanced
The method preparation that Materials, Year 2010, Volume 22, Issue 35, Page 3906-24 are reported；2) by expanding
The expanded graphite that temperature is 180~220 DEG C is made through accepted methods such as oxidation-reduction method, electrochemical process, mechanical stripping methods, wherein
It is preferred that graphene prepared by oxidation-reduction method；3) commercially available graphene also can, wherein it is preferred that graphene prepared by oxidation-reduction method.
C used in above method1-C6Alcohols material be methanol, ethyl alcohol, 1- propyl alcohol, 2- propyl alcohol, 2- methyl-1-the third
Alcohol, 2- methyl-2-propanol, n-butyl alcohol, 2- butanol, 2,2- dimethyl propyl alcohol, 1- amylalcohol, 2- amylalcohol, 3- amylalcohol, 2- methyl-1-
Butanol, 2- methyl -2- butanol, 3- methyl -2- butanol, 3- methyl-1-butanol, 2,2- dimethyl -1- propyl alcohol, 1- hexanol, 2- oneself
Alcohol, 3- hexanol, 2- methyl-1-pentene alcohol, 2- methyl -2- amylalcohol, 2- methyl -3- amylalcohol, 4- methyl -2- amylalcohol, 4- methyl-1-pentene
Alcohol, 3- methyl-1-pentene alcohol, 3- methyl -2- amylalcohol, 3- methyl -3- amylalcohol, 2- ethyl-n-butyl alcohol, 2,2- dimethyl-1-butanol,
Any one of 3,3- dimethyl -2- butanol, 3,3- dimethyl-1-butanol, cyclopentanol or cyclohexanol, preferably methanol, ethyl alcohol, third
Alcohol.
Commercially available two degrees of functionality phosphoryl chloride phosphorus oxychloride used in above method be diphenylphosphoryl dichloro, 2- chlorphenyl-phenyl phosphate ester,
Any one of methyl acid phosphate dichloro methyl esters, chloromethyl-methyl-phosphoryl chloride phosphorus oxychloride or 2- rubigan phosphoryl chloride phosphorus oxychloride.
C used in above method1-C6Hydroxyl substance be methanol, ethyl alcohol, 1- propyl alcohol, 2- propyl alcohol, 2- methyl-1-propyl alcohol,
2- methyl-2-propanol, n-butyl alcohol, 2- butanol, 2,2- dimethyl propyl alcohol, 1- amylalcohol, 2- amylalcohol, 3- amylalcohol, 2-methyl-1-butene
Alcohol, 2- methyl -2- butanol, 3- methyl -2- butanol, 3- methyl-1-butanol, 2,2- dimethyl -1- propyl alcohol, 1- hexanol, 2- hexanol,
3- hexanol, 2- methyl-1-pentene alcohol, 2- methyl -2- amylalcohol, 2- methyl -3- amylalcohol, 4- methyl -2- amylalcohol, 4- methyl-1-pentene alcohol,
3- methyl-1-pentene alcohol, 3- methyl -2- amylalcohol, 3- methyl -3- amylalcohol, 2- ethyl-n-butyl alcohol, 2,2- dimethyl-1-butanol, 3,
3- dimethyl -2- butanol, 3,3- dimethyl-1-butanol, cyclopentanol, cyclohexanol, ethylene glycol, propylene glycol, 1,3 butylene glycol, 1,4-
Any one of butanediol, neopentyl glycol or glycerine, preferably methanol or ethyl alcohol；And its additional amount is preferably hydroxyl/chlorine atom
1~1.5 times of molar amount.
Organic solvent used in above method is acetone, chloroform, acetonitrile, nitromethane, 2- butanone, tetrahydrofuran, methyl
Isobutyl ketone, benzene,toluene,xylene, propyl ether, carbon tetrachloride, trichloro ethylene, hexamethylene, trimethylpentane, isooctane or n-hexane
Any one of.
Dispersing agent used in above method is that acetone, chloroform, acetonitrile, nitromethane, 2- butanone, tetrahydrofuran, methyl are different
In butanone, benzene,toluene,xylene, propyl ether, carbon tetrachloride, trichloro ethylene, hexamethylene, trimethylpentane, isooctane or n-hexane
It is any.
The fire retardant provided by the invention for using above-mentioned functionalization graphene as high-efficient and lasting and substrate stability can be improved
Fire-retardant cross-linked type polyurethane rigid foam, the cross-linked type polyurethane rigid foam are by polyisocyanates, polyalcohol, catalysis
Agent, foaming agent are made according to conventional proportions of conventional one step of mixing foaming, it is characterised in that isocyanate index is
1.5~2.5, in terms of polyol quality part, the additive amount of functionalization graphene fire retardant is 10~160 parts, gained foam density
For 36-55Kg/m3, compressive strength 1232-1730kPa, rate of closed hole 84-91%, vertical combustion (UL-94) grade is V-
0 grade, limit oxygen index 23.4-34.5%, thermal coefficient is 0.028-0.035W/ (mK).
In the above hard polyurethane foam, isocyanate index is 2.0~2.5, in terms of polyol quality part, functionalization
The additive amount of Graphene fire retardant is 40~160 parts, and gained foam density is 36-55kg/m3, compressive strength 1302-
1730kPa, rate of closed hole 84-91%, vertical combustion (UL-94) grade are V-0 grades, and limit oxygen index 25.4-34.5% is led
Hot coefficient is 0.028-0.035W/ (mK).
In the above hard polyurethane foam, isocyanate index is 2.0~2.5, in terms of polyol quality part, functionalization
The additive amount of Graphene fire retardant is 80~160 parts, and gained foam density is 44-55Kg/m3, compressive strength 1487-
1730kPa, rate of closed hole 84-91%, vertical combustion (UL-94) grade are V-0 grades, and limit oxygen index 30.2-34.5% is led
Hot coefficient is 0.028-0.035W/ (mK).
Compared with the prior art, the invention has the following advantages:
1. since functionalization graphene provided by the invention is to be changed the surface of graphene made of expanded graphite
Property processing, so that piece interlamellar spacing is become larger, keep the dispersion of fire retardant in the substrate more uniform, and the hydroxyl on surface, epoxy
Base can be reacted with isocyanates, enable fire retardant and substrate by chemical bond linkage, thus the functionalization graphene is in polyurethane
Dispersibility in foam can be permanently well dispersed in polyurethane foam substrate far more than conventional expanded graphite, can be preferably
Its effect as essential type fire retardant is played, and the dimensional stability of hard polyurethane foam can be increased, it will not be to polyurethane foam
Foam substrate has a negative impact.
2. due to graphene, P elements, polyisocyanates and function in functionalization graphene fire retardant provided by the invention
Poly- isocyanuric acid made of oxazolidone ring and polyisocyanates itself trimerization that epoxy group in energy graphite alkene generates
A variety of ignition-proof elements such as ester ring, both can using the poly-isocyanurate ring generated, high-crosslinking-degree caused by oxazolidone ring come
The chemically expansible for improving the decomposition temperature of hard polyurethane foam, and the physical expansion of raw material expanded graphite and P elements capable of being made to be catalyzed
The wick effect and layer of charcoal for combining to solve the problems, such as single expanded graphite are loose, and compensate for the expansion multiplying power of chemically expansible
Low deficiency, the graphene is alternatively arranged as the crosslinking center increase degree of cross linking to improve layer of charcoal density in addition, thus flame retarding efficiency is high,
Enable obtained hard polyurethane foams that there is good flame-retardance.
3. the hydroxyl and epoxy group due to the modified rear surface of graphene provided by the invention can also be reacted with isocyanates, energy
It is enough to be permanently well dispersed in polyurethane foam substrate, because of anti-flammability caused by being migrated without elongated generation at any time
Phenomenon can be reduced.
4. gathering since hard polyurethane foams provided by the invention generate in foaming process with polyisocyanates trimerization
Isocyanurate ring, polyisocyanates and epoxy group generate oxazolidone, polyisocyanates and carbamate and generate substituted urea
The raising degree of cross linking is carried out etc. a variety of reactions, thus keeps obtained hard polyurethane foam crosslinking degree higher, dimensional stability
It is good, and high temperature resistance and weather resistance are more preferable compared to existing hard polyurethane foam.
5. since hard polyurethane foams provided by the invention are not on the one hand using the organic alkane that can influence flame retardant effect
Class foaming agent, but carbon dioxide can be generated and the water that foams is as foaming agent so that institute's filling gas is complete in abscess by all using
Portion is carbon dioxide, and foaming agent used in another aspect and fire retardant are Halogen compound, will not to ozone layer generate destroy or
Potential impact, thus the full water foamed cross-linked type polyurethane hard bubble for keeping obtained function graphite fire-retardant both had it is good fire-retardant
Performance, i.e., when functionalization expanded graphite additive amount is no more than 5% (mass fraction), vertical combustion can reach UL-94V-0
Grade, limit oxygen index can reach 30~35%, also reduce exclusive use water as foaming agent and stablize to foaming and foam size
The influence of property, at the same it is environmentally friendly.
6. not only raw material is easy to get functionalization graphene fire retardant provided by the invention, production process is routine operation, just
In factory's expanded production, and the hard polyurethane foam production technology used is similar with existing hard polyurethane foam production technology,
Large-scale promotion utilization can be carried out without replacement production equipment.
Detailed description of the invention
Fig. 1 is the reaction route schematic diagram provided according to technical solution of the present invention, wherein functionalization graphene structural formula
X, Z is by taking epoxy prapanol, methanol as an example respectively, and phosphoryl chloride phosphorus oxychloride is by taking phosphorus oxychloride as an example, and polyisocyanates is with polymethylene two
For phenyl diisocyanate.
Fig. 2 is thermogravimetric in nitrogen of raw material expanded graphite and modified graphene prepared by embodiment 1 and its once micro-
Divide (TG/DTG) curve.In comparison with expanded graphite, the maximum decomposition temperature of modified graphene increases.Since chemically expansible is made
With residual mass has increase in 200~540 DEG C, and after 550 DEG C, due to the decomposition of graft, modified graphene is decomposed
Accelerate, residual mass is less than expanded graphite.
Table 1 is the constituent content test result of modified graphene prepared by raw material expanded graphite and embodiment 1.EDX result
It has been shown that, the P element content of modified graphene surface grafting reach 2.56%.ICP-AES test surfaces, P element is total modifies
Mass fraction in graphene has reached 2.95%.
Fig. 3 is that the scanning electron microscope of anti-inflaming polyurethane hard foam prepared by hard polyurethane foam prepared by comparative example and embodiment 1 is shone
Piece.It can be seen that the addition of modified graphene can reduce the anisotropy of foam, thus make abscess is more regular, hole wall more
It is thick.In addition, scheming marked modified graphene part from f can be seen that the compatibility of modified graphene and foam has obtained greatly
It is promoted.
After Fig. 4 is the fire-retardant full water foamed cross-linked type polyurethane hard bubble vertical combustion of functionalization graphene produced by the present invention
The appearance of a sample after sample and alcohol blast burner sustained combustion test.Vertical combustion is lighted a fire for the first time to be put out from fire, fire endurance period burning
Time is 0s, and second of igniting cannot light.Alcohol blast burner sustained combustion 3min, middle part sustained combustion partial ablation depth about 4
~5mm, description of test functionalization graphene have good inhibiting effect to the Actual combustion process of material.
Fig. 5 be hard polyurethane foam prepared by hard polyurethane foam and comparative example prepared by the embodiment of the present invention 1 in air
Thermogravimetric curve, functionalization graphene additive amount be 4.0wt% when hard polyurethane foam decomposition temperature compare conventional polyurethanes
Hard bubble is obviously improved, and can just be decomposed at relatively high temperatures, and the residual mass at 700 DEG C is 29.0%, and common
Hard polyurethane foam has been decomposed at 700 DEG C completely without any residual, and comparison knows functionalization graphene prepared by the present invention
The thermal stability that hard polyurethane foam can be significantly improved promotes quality residual of the polyurethane foamed material at 700 DEG C by 0
To 24%.
Specific embodiment
Embodiment is given below so that the invention will be further described.It is necessarily pointed out that following embodiment is not
It can be interpreted as limiting the scope of the invention, if the person skilled in the art in the field is according to aforementioned present invention content to this
Some nonessential modifications and adaptations are made in invention, still fall within the scope of the present invention.
In addition, it is worth noting that:
Following embodiment and the correlated performance test data of the foam of comparative example preparation are carried out according to following standard: bubble
The testing standard of foam density is GB/T 6343-1995；The testing standard of compressive strength is GB/T 8813-2008；Vertical combustion
Testing standard be UL-94-2010；The testing standard of limit oxygen index is GB/T 2406.2-2009；The test of thermal coefficient
Standard is GB/T 10294-2008.
Embodiment 1
(1) Hummer method prepares graphene
By 10g expanded graphite and 5g nitric acid and 230ml sulfuric acid as in there-necked flask, it is slowly added under ice bath mechanical stirring
30g potassium permanganate keeps temperature to be no more than 9 DEG C, removes water-bath, reacts 4h at 35 DEG C, and reactant is slowly dilute with 460ml water
It releases, temperature rises to about 98 DEG C, keeps 1h.After continuing dilution with 1400ml water, with 3% dioxygen water process reactant to bright orange
Color filters, washing, with 50ml hydrazine hydrate reduction, filters, washing, drying.
(2) graft is prepared
By 30.6g phosphorus oxychloride as being slowly dropped into 6.4g methanol in there-necked flask, in 30min.50 DEG C are to slowly warm up to, instead
Chloroform is steamed after answering 4h.It is slightly boiled to be warming up to solution, steams unreacted reactant after the reaction was continued 6h.Product is added in 100ml acetone
It stirs evenly.By 14.8g epoxy prapanol with acetone dilute dissolution after in be slowly added dropwise in 1h into, be added dropwise to complete after slowly heat up back
Stream reaction 4h.
(3) graft is grafted on into graphene
5.0g graphene dispersion is slowly dropped into graft/acetone soln at room temperature after 200ml acetone, flow back 4h
After steam acetone, continue heating and keep that solution is slightly boiled steams other unreacted substances.End of reaction is cooled to 80 DEG C, to reaction
9.2g ethyl alcohol is slowly added in system, the reaction was continued 1h.Products therefrom is finally used into boiling water and ethanol washing respectively.
(4) hard polyurethane foam is prepared using functionalization graphene:
By 10.0g functionalization graphene, 25.0g polyether polyol, 20.0g PEG-400,3.0g deionized water and 2.0g
Silicone oil stirs for 24 hours at room temperature, and 1.0gDMP-30,0.1g stannous octoate, high-speed stirred 5min are added after the completion of stirring.It is added
High-speed stirred 10s after 142.0gMDI, mixed liquor is poured into chunk and is foamed.After the completion of foaming, respectively at 80 DEG C and
Solidify 4h at 120 DEG C.Sampling and testing after for 24 hours.
Gained foam density is 36Kg/m3, compressive strength 1302kPa, rate of closed hole 91%.Vertical combustion grade is
V-0 grades (UL-94), limit oxygen index 25.4%, thermal coefficient is 0.029W/ (mK).
In order to investigate whether functionalization graphene preparation succeeds, the present invention is to the resulting functionalization graphene of the present embodiment
(FGN) with raw materials used expanded graphite (EG) surface-element and inside P elements content pass through respectively X-ray energy spectrum (EDX) and
Atomic emission spectrum (ICP-AES) is tested, and as a result see the table below.From following table result as it can be seen that expanded graphite surface only detects
Carbon has been arrived, and functionalization graphene surface has then been detected also containing 21.49% oxygen element and 2.56% P elements；
The content of internal P elements, functionalization graphene are much higher than expanded graphite.This sufficiently shows the successful system of functionalization graphene
It is standby.
Table
Embodiment 2
(1) Hummer method prepares graphene
By 10g expanded graphite and 5g nitric acid and 230ml sulfuric acid as in there-necked flask, it is slowly added under ice bath mechanical stirring
30g potassium permanganate keeps temperature to be no more than 9 DEG C, removes water-bath, reacts 4h at 35 DEG C, and reactant is slowly dilute with 460ml water
It releases, temperature rises to about 98 DEG C, keeps 1h.After continuing dilution with 1400ml water, with 3% dioxygen water process reactant to bright orange
Color filters, washing, with 50ml hydrazine hydrate reduction, filters, washing, drying.
(2) graft is prepared
By 19.4g diphenylphosphoryl dichloro as in there-necked flask, 7.4g epoxy prapanol 150ml acetone is diluted under ice bath
It is slowly added dropwise in 2h after dissolution into slowly temperature rising reflux reacts 3h after being added dropwise to complete.
(3) graft is grafted on into graphene
5.0g graphene dispersion is slowly dropped into graft/acetone soln at room temperature after 200ml acetone, flow back 3h
After steam acetone, continue heating and keep that solution is slightly boiled steams other unreacted substances.End of reaction is cooled to 80 DEG C, to reaction
4.6g ethyl alcohol is slowly added in system, the reaction was continued 1h.Products therefrom is finally used into boiling water and ethanol washing respectively.
(4) hard polyurethane foam is prepared using functionalization graphene
By 40.0g functionalization graphene, 25.0g polyether polyol, 20.0g PEG-400,3.0g deionized water and 2.0g
Silicone oil stirs for 24 hours at room temperature, and 1.0gDMP-30,0.1g stannous octoate, high-speed stirred 5min are added after the completion of stirring.It is added
High-speed stirred 10s after 142.0gMDI, mixed liquor is poured into chunk and is foamed.After the completion of foaming, respectively at 80 DEG C and
Solidify 4h at 120 DEG C.Sampling and testing after for 24 hours.
Gained foam density is 46Kg/m3, compressive strength 1730kPa, rate of closed hole 88%.Vertical combustion grade is
V-0 grades (UL-94), limit oxygen index 34.0%, thermal coefficient is 0.035W/ (mK).
Embodiment 3
(1) Hummer method prepares graphene
By 10g expanded graphite and 5g nitric acid and 230ml sulfuric acid as in there-necked flask, it is slowly added under ice bath mechanical stirring
30g potassium permanganate keeps temperature to be no more than 9 DEG C, removes water-bath, reacts 4h at 35 DEG C, and reactant is slowly dilute with 460ml water
It releases, temperature rises to about 98 DEG C, keeps 1h.After continuing dilution with 1400ml water, with 3% dioxygen water process reactant to bright orange
Color filters, washing, with 50ml hydrazine hydrate reduction, filters, washing, drying.
(2) graft is prepared
By 25.0g pyrophosphoric acid chlorine as in there-necked flask, 7.4g epoxy prapanol 150ml acetone is diluted after dissolving in ice water
It is slowly added dropwise in 2h under bath into slowly heat up simultaneously back flow reaction 5h after being added dropwise to complete.
(3) graft is grafted on into graphene
5.0g graphene dispersion is slowly dropped into graft/acetone soln at room temperature after acetone, is steamed after the 5h that flows back
Acetone out continues heating and keeps that solution is slightly boiled steams other unreacted substances.End of reaction is cooled to 80 DEG C, to reaction system
In be slowly added to 6.9g ethyl alcohol, the reaction was continued 2h.Products therefrom is finally used into boiling water and ethanol washing respectively.
(4) hard polyurethane foam is prepared using functionalization graphene
By 20.0g functionalization graphene, 25.0g polyether polyol, 20.0g PEG-400,3.0g deionized water and 2.0g
Silicone oil stirs for 24 hours at room temperature, and 1.0gDMP-30,0.1g stannous octoate, high-speed stirred 5min are added after the completion of stirring.It is added
High-speed stirred 10s after 177.0gMDI, mixed liquor is poured into chunk and is foamed.After the completion of foaming, respectively at 80 DEG C and
Solidify 4h at 120 DEG C.Sampling and testing after for 24 hours.
Gained foam density is 44Kg/m3, compressive strength 1698kPa, rate of closed hole 84%.Vertical combustion grade is
V-0 grades (UL-94), limit oxygen index 30.2%, thermal coefficient is 0.032W/ (mK).
Embodiment 4
(1) Hummer method prepares graphene
By 10g expanded graphite and 5g nitric acid and 230ml sulfuric acid as in there-necked flask, it is slowly added under ice bath mechanical stirring
30g potassium permanganate keeps temperature to be no more than 9 DEG C, removes water-bath, reacts 4h at 35 DEG C, and reactant is slowly dilute with 460ml water
It releases, temperature rises to about 98 DEG C, keeps 1h.After continuing dilution with 1400ml water, with 3% dioxygen water process reactant to bright orange
Color filters, washing, with 50ml hydrazine hydrate reduction, filters, washing, drying.
(2) graft is prepared
By 14.8g methyl acid phosphate dichloro methyl esters as in there-necked flask, by 7.4g epoxy prapanol acetone dilute after dissolution
It is slowly added dropwise in 2h into slowly heat up simultaneously back flow reaction 2h after being added dropwise to complete.
(3) graft is grafted on into graphene
5.0g graphene dispersion is slowly dropped into graft/acetone soln at room temperature after 200ml acetone, flow back 4h
Acetone is steamed afterwards, is continuously heating to that solution is slightly boiled to steam other unreacted substances.End of reaction is cooled to 80 DEG C, to anti-
It answers and is slowly added to 4.6g ethyl alcohol in system, the reaction was continued 1h.Products therefrom is finally used into boiling water and ethanol washing respectively.
(4) hard polyurethane foam is prepared using functionalization graphene
By 5.0g functionalization graphene, 25.0g polyether polyol, 20.0g PEG-400,3.0g deionized water and 2.0g silicon
Oil stirs for 24 hours at room temperature, and 1.0gDMP-30,0.1g stannous octoate, high-speed stirred 5min are added after the completion of stirring.It is added
High-speed stirred 10s after 142.0gMDI, mixed liquor is poured into chunk and is foamed.After the completion of foaming, respectively at 80 DEG C and
Solidify 4h at 120 DEG C.Sampling and testing after for 24 hours.
Gained foam density is 36Kg/m3, compressive strength 1288kPa, rate of closed hole 90%.Vertical combustion grade is
V-0 grades (UL-94), limit oxygen index 24.0%, thermal coefficient is 0.028W/ (mK).
Embodiment 5
(1) Hummer method prepares graphene
By 10g expanded graphite and 5g nitric acid and 230ml sulfuric acid as in there-necked flask, it is slowly added under ice bath mechanical stirring
30g potassium permanganate keeps temperature to be no more than 9 DEG C, removes water-bath, reacts 4h at 35 DEG C, and reactant is slowly dilute with 460ml water
It releases, temperature rises to about 98 DEG C, keeps 1h.After continuing dilution with 1400ml water, with 3% dioxygen water process reactant to bright orange
Color filters, washing, with 50ml hydrazine hydrate reduction, filters, washing, drying.
(2) graft is prepared
By 14.6g chloromethyl-methyl-phosphoryl chloride phosphorus oxychloride as in there-necked flask, 7.4g epoxy prapanol acetone is diluted after dissolving
It is slowly added dropwise in 2h into slowly heat up simultaneously back flow reaction 4h after being added dropwise to complete.
(3) graft is grafted on into graphene
5.0g graphene dispersion is slowly dropped into graft/acetone soln at room temperature after 200ml acetone, flow back 4h
Acetone is steamed afterwards, is continuously heating to that solution is slightly boiled to steam other unreacted substances.End of reaction is cooled to 80 DEG C, to anti-
It answers and is slowly added to 5.8g ethyl alcohol in system, the reaction was continued 1h.Products therefrom is finally used into boiling water and ethanol washing respectively.
(4) hard polyurethane foam is prepared using functionalization graphene
By 2.5g functionalization graphene, 25.0g polyether polyol, 20.0g PEG-400,3.0g deionized water and 2.0g silicon
Oil stirs for 24 hours at room temperature, and 1.0gDMP-30,0.1g stannous octoate, high-speed stirred 5min are added after the completion of stirring.It is added
High-speed stirred 10s after 142.0gMDI, mixed liquor is poured into chunk and is foamed.After the completion of foaming, respectively at 80 DEG C and
Solidify 4h at 120 DEG C.Sampling and testing after for 24 hours.
Gained foam density is 37Kg/m3, compressive strength 1232Pa, rate of closed hole 88%.Vertical combustion grade is
V-0 grades (UL-94), limit oxygen index 23.4%, thermal coefficient is 0.028W/ (mK).
Embodiment 6
(1) Hummer method prepares graphene
By 10g expanded graphite and 5g nitric acid and 230ml sulfuric acid as in there-necked flask, it is slowly added under ice bath mechanical stirring
30g potassium permanganate keeps temperature to be no more than 9 DEG C, removes water-bath, reacts 4h at 35 DEG C, and reactant is slowly dilute with 460ml water
It releases, temperature rises to about 98 DEG C, keeps 1h.After continuing dilution with 1400ml water, with 3% dioxygen water process reactant to bright orange
Color filters, washing, with 50ml hydrazine hydrate reduction, filters, washing, drying.
(2) graft is prepared
By 15.3g phosphorus oxychloride as being slowly dropped into 10.2g 3- methyl -2- amylalcohol in there-necked flask, in 30min.It is warming up to
Solution is slightly boiled, steams solvent toluene after the reaction was continued 4h, the reaction was continued 8h, and unreacted reactant is steamed.100ml bis- is added in product
It is stirred evenly in toluene.By 8.8g epoxy butanol with hexamethylene dilute dissolution after in be slowly added dropwise in 2h into, after being added dropwise to complete delay
Slow temperature rising reflux reacts 5h.
(3) graft is grafted on into graphene
5.0g graphene dispersion is slowly dropped into graft/acetone soln at room temperature after 200ml dimethylbenzene, is flowed back
Hexamethylene is steamed after 5h, is continued heating and is kept that solution is slightly boiled steams other unreacted substances.End of reaction is cooled to 80 DEG C, to
3.9g ethylene glycol is slowly added in reaction system, the reaction was continued 2h.Products therefrom is finally used into boiling water and ethanol washing respectively.
(4) hard polyurethane foam is prepared with functionalization graphene
By 40.0g functionalization graphene, 25.0g polyether polyol, 20.0g PEG-400,3.0g deionized water and 2.0g
Silicone oil stirs for 24 hours at room temperature, and 1.0gDMP-30,0.1g stannous octoate, high-speed stirred 5min are added after the completion of stirring.It is added
High-speed stirred 10s after 177.0gMDI, mixed liquor is poured into chunk and is foamed.After the completion of foaming, respectively at 80 DEG C and
Solidify 4h at 120 DEG C.Sampling and testing after for 24 hours.
Gained foam density is 55Kg/m3, compressive strength 1687kPa, rate of closed hole 85%.Vertical combustion grade is
V-0 grades (UL-94), limit oxygen index 34.5%, thermal coefficient is 0.032W/ (mK).
Embodiment 7
(1) graft is prepared
By 30.6g phosphorus oxychloride as being slowly dropped into 6.4g methanol in there-necked flask, in 30min.It is slightly boiled to be warming up to solution, after
Solvent chloroform is steamed after continuous reaction 4h, the reaction was continued 3h steams unreacted reactant.It is equal that stirring in 100ml acetone is added in product
It is even.By 14.8g epoxy prapanol with acetone dilute dissolution after in be slowly added dropwise in 1h into, be added dropwise to complete after slowly temperature rising reflux reaction
4h。
(2) graft is grafted on into commercially available graphene
The commercially available graphene dispersion of 5.0g is slowly dropped into graft/acetone soln at room temperature after 200ml acetone, is returned
Acetone is steamed after stream 4h, continues heating and keeps that solution is slightly boiled steams other unreacted substances.End of reaction is cooled to 80 DEG C, to
9.2g ethyl alcohol is slowly added in reaction system, the reaction was continued 1h.Products therefrom is finally used into boiling water and ethanol washing respectively.
(3) hard polyurethane foam is prepared with functionalization graphene:
By 20.0g functionalization graphene, 25.0g polyether polyol, 20.0g PEG-400,3.0g deionized water and 2.0g
Silicone oil stirs for 24 hours at room temperature, and 1.0gDMP-30,0.1g stannous octoate, high-speed stirred 5min are added after the completion of stirring.It is added
High-speed stirred 10s after 142.0gMDI, mixed liquor is poured into chunk and is foamed.After the completion of foaming, respectively at 80 DEG C and
Solidify 4h at 120 DEG C.Sampling and testing after for 24 hours.
Gained foam density is 44Kg/m3, compressive strength 1544kPa, rate of closed hole 91%.Vertical combustion grade is
V-0 grades (UL-94), limit oxygen index 32.0%, thermal coefficient is 0.030W/ (mK).
Embodiment 8
(1) Hummer method prepares graphene
By 10g expanded graphite and 5g nitric acid and 230ml sulfuric acid as in there-necked flask, it is slowly added under ice bath mechanical stirring
30g potassium permanganate keeps temperature to be no more than 9 DEG C, removes water-bath, reacts 4h at 35 DEG C, and reactant is slowly dilute with 460ml water
It releases, temperature rises to about 98 DEG C, keeps 1h.After continuing dilution with 1400ml water, with 3% dioxygen water process reactant to bright orange
Color filters, washing, with 50ml hydrazine hydrate reduction, filters, washing, drying.
(2) graft is prepared
By 30.6g phosphorus oxychloride as being slowly dropped into 6.4g methanol in there-necked flask, in 30min.It is slightly boiled to be warming up to solution, after
Solvent acetonitrile is steamed after continuous reaction 4h, the reaction was continued 4h steams unreacted reactant.It is equal that stirring in 100ml toluene is added in product
It is even.After 14.8g epoxy prapanol is dissolved with dilution with toluene in be slowly added dropwise in 1.5h into, be added dropwise to complete after slowly temperature rising reflux it is anti-
Answer 2.5h.
(3) graft is grafted on into graphene
5.0g graphene dispersion is slowly dropped into graft/acetone soln at room temperature after 200ml toluene, is flowed back
Toluene is steamed after 3.5h, is continued heating and is kept that solution is slightly boiled steams other unreacted substances.End of reaction is cooled to 80 DEG C, to
9.6g methanol is slowly added in reaction system, the reaction was continued 1.5h.Products therefrom is finally used into boiling water and ethanol washing respectively.
(4) hard polyurethane foam is prepared with functionalization graphene:
By 15.0g functionalization graphene, 25.0g polyether polyol, 20.0g PEG-400,3.0g deionized water and 2.0g
Silicone oil stirs for 24 hours at room temperature, and 1.0gDMP-30,0.1g stannous octoate, high-speed stirred 5min are added after the completion of stirring.It is added
High-speed stirred 10s after 142.0gMDI, mixed liquor is poured into chunk and is foamed.After the completion of foaming, respectively at 80 DEG C and
Solidify 4h at 120 DEG C.Sampling and testing after for 24 hours.
Gained foam density is 41Kg/m3, compressive strength 1355kPa, rate of closed hole 90%.Vertical combustion grade is
V-0 grades (UL-94), limit oxygen index 28.5%, thermal coefficient is 0.031W/ (mK).
Embodiment 9
(1) Hummer method prepares graphene
By 10g expanded graphite and 5g nitric acid and 230ml sulfuric acid as in there-necked flask, it is slowly added under ice bath mechanical stirring
30g potassium permanganate keeps temperature to be no more than 9 DEG C, removes water-bath, reacts 4h at 35 DEG C, and reactant is slowly dilute with 460ml water
It releases, temperature rises to about 98 DEG C, keeps 1h.After continuing dilution with 1400ml water, with 3% dioxygen water process reactant to bright orange
Color filters, washing, with 50ml hydrazine hydrate reduction, filters, washing, drying.
(2) graft is prepared
By 30.6g phosphorus oxychloride as being slowly dropped into 20g cyclohexanol in there-necked flask, in 30min.It is slightly boiled to be warming up to solution,
Solvent acetonitrile is steamed after the reaction was continued 4.5h, the reaction was continued 5h steams unreacted reactant.Product is added in 100ml toluene and is stirred
It mixes uniformly.In being slowly added dropwise in 2h into being added dropwise to complete rear slow temperature rising reflux after 14.8g epoxy prapanol is dissolved with dilution with toluene
React 3h.
(3) graft is grafted on into graphene
5.0g graphene dispersion is slowly dropped into graft/acetone soln at room temperature after 200ml toluene, flow back 4h
After steam toluene, continue heating and keep that solution is slightly boiled steams other unreacted substances.End of reaction is cooled to 80 DEG C, to reaction
13.5g 1,4-butanediol is slowly added in system, the reaction was continued 2h.Products therefrom is finally used into boiling water and ethanol washing respectively.
(4) hard polyurethane foam is prepared with functionalization graphene:
By 20.0g functionalization graphene, 25.0g polyether polyol, 20.0g PEG-400,3.0g deionized water and 2.0g
Silicone oil stirs for 24 hours at room temperature, and 1.0gDMP-30,0.1g stannous octoate, high-speed stirred 5min are added after the completion of stirring.It is added
High-speed stirred 10s after 142.0gMDI, mixed liquor is poured into chunk and is foamed.After the completion of foaming, respectively at 80 DEG C and
Solidify 4h at 120 DEG C.Sampling and testing after for 24 hours.
Gained foam density is 45Kg/m3, compressive strength 1487kPa, rate of closed hole 89%.Vertical combustion grade is
V-0 grades (UL-94), limit oxygen index 30.2%, thermal coefficient is 0.033W/ (mK).
Embodiment 10
(1) Hummer method prepares graphene
By 10g expanded graphite and 5g nitric acid and 230ml sulfuric acid as in there-necked flask, it is slowly added under ice bath mechanical stirring
30g potassium permanganate keeps temperature to be no more than 9 DEG C, removes water-bath, reacts 4h at 35 DEG C, and reactant is slowly dilute with 460ml water
It releases, temperature rises to about 98 DEG C, keeps 1h.After continuing dilution with 1400ml water, with 3% dioxygen water process reactant to bright orange
Color filters, washing, with 50ml hydrazine hydrate reduction, filters, washing, drying.
(2) graft is prepared
By 30.6g phosphorus oxychloride as being slowly dropped into 17.6g 1- amylalcohol in there-necked flask, in 30min.It is micro- to be warming up to solution
Boiling steams solvent acetonitrile after the reaction was continued 5h, the reaction was continued 6h, and unreacted reactant is steamed.Product is added in 100ml hexamethylene
It stirs evenly.By 14.8g epoxy prapanol with hexamethylene dilute dissolution after in be slowly added dropwise in 2h into, be added dropwise to complete after slowly heating
Back flow reaction 4h.
(3) graft is grafted on into graphene
5.0g graphene dispersion is slowly dropped into graft/acetone soln at room temperature after 200ml hexamethylene, is flowed back
Hexamethylene is steamed after 3h, is continued heating and is kept that solution is slightly boiled steams other unreacted substances.End of reaction is cooled to 80 DEG C, to
10.4g neopentyl glycol is slowly added in reaction system, the reaction was continued 1.5h.Finally products therefrom is washed with boiling water and ethyl alcohol respectively
It washs.
(4) hard polyurethane foam is prepared with functionalization graphene:
By 25.0g functionalization graphene, 25.0g polyether polyol, 20.0g PEG-400,3.0g deionized water and 2.0g
Silicone oil stirs for 24 hours at room temperature, and 1.0gDMP-30,0.1g stannous octoate, high-speed stirred 5min are added after the completion of stirring.It is added
High-speed stirred 10s after 142.0gMDI, mixed liquor is poured into chunk and is foamed.After the completion of foaming, respectively at 80 DEG C and
Solidify 4h at 120 DEG C.Sampling and testing after for 24 hours.
Gained foam density is 49Kg/m3, compressive strength 1609kPa, rate of closed hole 87%.Vertical combustion grade is
V-0 grades (UL-94), limit oxygen index 30.8%, thermal coefficient is 0.034W/ (mK).
Embodiment 11
(1) Hummer method prepares graphene
By 10g expanded graphite and 5g nitric acid and 230ml sulfuric acid as in there-necked flask, it is slowly added under ice bath mechanical stirring
30g potassium permanganate keeps temperature to be no more than 9 DEG C, removes water-bath, reacts 4h at 35 DEG C, and reactant is slowly dilute with 460ml water
It releases, temperature rises to about 98 DEG C, keeps 1h.After continuing dilution with 1400ml water, with 3% dioxygen water process reactant to bright orange
Color filters, washing, with 50ml hydrazine hydrate reduction, filters, washing, drying.
(2) graft is prepared
By 30.6g phosphorus oxychloride as being slowly dropped into 17.6g 1- amylalcohol in there-necked flask, in 30min.It is micro- to be warming up to solution
Boiling steams solvent acetonitrile after the reaction was continued 5h, the reaction was continued 7h, and unreacted reactant is steamed.Product is added in 100ml hexamethylene
It stirs evenly.By 14.8g epoxy prapanol with hexamethylene dilute dissolution after in be slowly added dropwise in 2h into, be added dropwise to complete after slowly heating
Back flow reaction 4h.
(3) graft is grafted on into graphene
5.0g graphene dispersion is slowly dropped into graft/acetone soln at room temperature after 200ml hexamethylene, is flowed back
Hexamethylene is steamed after 3h, is continued heating and is kept that solution is slightly boiled steams other unreacted substances.End of reaction is cooled to 80 DEG C, to
6.2g glycerine is slowly added in reaction system, the reaction was continued 1.5h.Products therefrom is finally used into boiling water and ethanol washing respectively.
(4) hard polyurethane foam is prepared with functionalization graphene:
By 30.0g functionalization graphene, 25.0g polyether polyol, 20.0g PEG-400,3.0g deionized water and 2.0g
Silicone oil stirs for 24 hours at room temperature, and 1.0gDMP-30,0.1g stannous octoate, high-speed stirred 5min are added after the completion of stirring.It is added
High-speed stirred 10s after 177.0gMDI, mixed liquor is poured into chunk and is foamed.After the completion of foaming, respectively at 80 DEG C and
Solidify 4h at 120 DEG C.Sampling and testing after for 24 hours.
Gained foam density is 48Kg/m3, compressive strength 1671kPa, rate of closed hole 88%.Vertical combustion grade is
V-0 grades (UL-94), limit oxygen index 31.6%, thermal coefficient is 0.032W/ (mK).
Embodiment 12
(1) Hummer method prepares graphene
By 10g expanded graphite and 5g nitric acid and 230ml sulfuric acid as in there-necked flask, it is slowly added under ice bath mechanical stirring
30g potassium permanganate keeps temperature to be no more than 9 DEG C, removes water-bath, reacts 4h at 35 DEG C, and reactant is slowly dilute with 460ml water
It releases, temperature rises to about 98 DEG C, keeps 1h.After continuing dilution with 1400ml water, with 3% dioxygen water process reactant to bright orange
Color filters, washing, with 50ml hydrazine hydrate reduction, filters, washing, drying.
(2) graft is prepared
By 30.6g phosphorus oxychloride as being slowly dropped into 17.2g cyclopentanol in there-necked flask, in 30min.It is micro- to be warming up to solution
Boiling steams solvent hexamethylene after the reaction was continued 3.5h, the reaction was continued 8h, and unreacted reactant is steamed.100ml hexamethylene is added in product
It is stirred evenly in alkane.By 14.8g epoxy prapanol with hexamethylene dilute dissolution after in be slowly added dropwise in 2h into, be added dropwise to complete after slowly
Temperature rising reflux reacts 5h.
(3) graft is grafted on into graphene
5.0g graphene dispersion is slowly dropped into graft/acetone soln at room temperature after 200ml hexamethylene, is flowed back
Hexamethylene is steamed after 4.5h, is continued heating and is kept that solution is slightly boiled steams other unreacted substances.End of reaction is cooled to 80 DEG C,
3.9g ethylene glycol is slowly added into reaction system, the reaction was continued 2h.Products therefrom is finally used into boiling water and ethanol washing respectively.
(4) hard polyurethane foam is prepared with functionalization graphene:
By 35.0g functionalization graphene, 25.0g polyether polyol, 20.0g PEG-400,3.0g deionized water and 2.0g
Silicone oil stirs for 24 hours at room temperature, and 1.0gDMP-30,0.1g stannous octoate, high-speed stirred 5min are added after the completion of stirring.It is added
High-speed stirred 10s after 177.0gMDI, mixed liquor is poured into chunk and is foamed.After the completion of foaming, respectively at 80 DEG C and
Solidify 4h at 120 DEG C.Sampling and testing after for 24 hours.
Gained foam density is 55Kg/m3, compressive strength 1675kPa, rate of closed hole 84%.Vertical combustion grade is
V-0 grades (UL-94), limit oxygen index 34.0%, thermal coefficient is 0.028W/ (mK).
Embodiment 13
(1) Hummer method prepares graphene
By 10g expanded graphite and 5g nitric acid and 230ml sulfuric acid as in there-necked flask, it is slowly added under ice bath mechanical stirring
30g potassium permanganate keeps temperature to be no more than 9 DEG C, removes water-bath, reacts 4h at 35 DEG C, and reactant is slowly dilute with 460ml water
It releases, temperature rises to about 98 DEG C, keeps 1h.After continuing dilution with 1400ml water, with 3% dioxygen water process reactant to bright orange
Color filters, washing, with 50ml hydrazine hydrate reduction, filters, washing, drying.
(2) graft is prepared
By 15.3g phosphorus oxychloride as being slowly dropped into 10.2g 3- methyl -2- amylalcohol in there-necked flask, in 30min.It is warming up to
Solution is slightly boiled, steams solvent toluene after the reaction was continued 4h, the reaction was continued 8h, and unreacted reactant is steamed.100ml bis- is added in product
It is stirred evenly in toluene.By 7.4g epoxy prapanol with dimethylbenzene dilute dissolution after in be slowly added dropwise in 2h into, after being added dropwise to complete delay
Slow temperature rising reflux reacts 5h.
(3) graft is grafted on into graphene
3.4g graphene dispersion is slowly dropped into graft/xylene solution at room temperature after 200ml dimethylbenzene, is returned
Dimethylbenzene is steamed after stream 5h, continues heating and keeps that solution is slightly boiled steams other unreacted substances.End of reaction is cooled to 80 DEG C,
3.9g ethylene glycol is slowly added into reaction system, the reaction was continued 2h.Products therefrom is finally used into boiling water and ethanol washing respectively.
(4) hard polyurethane foam is prepared using functionalization graphene:
By 40.0g functionalization graphene, 25.0g polyether polyol, 20.0g PEG-400,3.0g deionized water and 2.0g
Silicone oil stirs for 24 hours at room temperature, and 1.0gDMP-30,0.1g stannous octoate, high-speed stirred 5min are added after the completion of stirring.It is added
High-speed stirred 10s after 177.0gMDI, mixed liquor is poured into chunk and is foamed.After the completion of foaming, respectively at 80 DEG C and
Solidify 4h at 120 DEG C.Sampling and testing after for 24 hours.
Gained foam density is 53Kg/m3, compressive strength 1730kPa, rate of closed hole 86%.Vertical combustion grade is
V-0 grades (UL-94), limit oxygen index 34.0%, thermal coefficient is 0.030W/ (mK).
Embodiment 14
(1) Hummer method prepares graphene
By 10g expanded graphite and 5g nitric acid and 230ml sulfuric acid as in there-necked flask, it is slowly added under ice bath mechanical stirring
30g potassium permanganate keeps temperature to be no more than 9 DEG C, removes water-bath, reacts 4h at 35 DEG C, and reactant is slowly dilute with 460ml water
It releases, temperature rises to about 98 DEG C, keeps 1h.After continuing dilution with 1400ml water, with 3% dioxygen water process reactant to bright orange
Color filters, washing, with 50ml hydrazine hydrate reduction, filters, washing, drying.
(2) graft is prepared
By 15.3g phosphorus oxychloride as being slowly dropped into 10.2g 3- methyl -2- amylalcohol in there-necked flask, in 30min.It is warming up to
Solution is slightly boiled, steams solvent toluene after the reaction was continued 4h, the reaction was continued 8h, and unreacted reactant is steamed.100ml bis- is added in product
It is stirred evenly in toluene.By 10.2g epoxy amylalcohol with dimethylbenzene dilute dissolution after in be slowly added dropwise in 2h into, after being added dropwise to complete delay
Slow temperature rising reflux reacts 5h.
(3) graft is grafted on into graphene
5.0g graphene dispersion is slowly dropped into graft/xylene solution at room temperature after 200ml dimethylbenzene, is returned
Dimethylbenzene is steamed after stream 5h, continues heating and keeps that solution is slightly boiled steams other unreacted substances.End of reaction is cooled to 80 DEG C,
3.9g ethylene glycol is slowly added into reaction system, the reaction was continued 2h.Products therefrom is finally used into boiling water and ethanol washing respectively.
(4) hard polyurethane foam is prepared using functionalization graphene:
By 40.0g functionalization graphene, 25.0g polyether polyol, 20.0g PEG-400,3.0g deionized water and 2.0g
Silicone oil stirs for 24 hours at room temperature, and 1.0gDMP-30,0.1g stannous octoate, high-speed stirred 5min are added after the completion of stirring.It is added
High-speed stirred 10s after 177.0gMDI, mixed liquor is poured into chunk and is foamed.After the completion of foaming, respectively at 80 DEG C and
Solidify 4h at 120 DEG C.Sampling and testing after for 24 hours.
Gained foam density is 53Kg/m3, compressive strength 1730kPa, rate of closed hole 86%.Vertical combustion grade is
V-0 grades (UL-94), limit oxygen index 34.0%, thermal coefficient is 0.030W/ (mK).
Embodiment 15
(1) graft is prepared
By 33.8g phosphorus thiochloride as being slowly dropped into 6.4g methanol in there-necked flask, in 30min.It is slightly boiled to be warming up to solution, after
Solvent chloroform is steamed after continuous reaction 4h, the reaction was continued 3h steams unreacted reactant.It is equal that stirring in 100ml acetone is added in product
It is even.By 14.8g epoxy prapanol with acetone dilute dissolution after in be slowly added dropwise in 1h into, be added dropwise to complete after slowly temperature rising reflux reaction
4h。
(2) graft is grafted on into commercially available graphene
5.0g graphene dispersion is slowly dropped into graft/acetone soln at room temperature after 200ml acetone, flow back 4h
After steam acetone, continue heating and keep that solution is slightly boiled steams other unreacted substances.End of reaction is cooled to 80 DEG C, to reaction
9.2g ethyl alcohol is slowly added in system, the reaction was continued 1h.Products therefrom is finally used into boiling water and ethanol washing respectively.
(3) hard polyurethane foam is prepared with functionalization graphene:
By 20.0g functionalization graphene, 25.0g polyether polyol, 20.0g PEG-400,3.0g deionized water and 2.0g
Silicone oil stirs for 24 hours at room temperature, and 1.0gDMP-30,0.1g stannous octoate, high-speed stirred 5min are added after the completion of stirring.It is added
High-speed stirred 10s after 142.0gMDI, mixed liquor is poured into chunk and is foamed.After the completion of foaming, respectively at 80 DEG C and
Solidify 4h at 120 DEG C.Sampling and testing after for 24 hours.
Gained foam density is 44Kg/m3, compressive strength 1530kPa, rate of closed hole 88%.Vertical combustion grade is
V-0 grades (UL-94), limit oxygen index 31.0%, thermal coefficient is 0.030W/ (mK).
Comparative example 1
25.0g polyether polyol, 20.0g PEG-400,3.0g deionized water and 2.0g silicone oil are stirred at room temperature
For 24 hours, 1.0gDMP-30,0.1g stannous octoate, high-speed stirred 5min are added after the completion of stirring.High-speed stirring after addition 106.5gMDI
10s is mixed, mixed liquor is poured into chunk and is foamed.After the completion of foaming, solidify 4h at 80 DEG C and 120 DEG C respectively.24h
Sampling and testing afterwards.
Gained foam density is 37Kg/m3, compressive strength 526kPa, rate of closed hole 91%.In vertical burn test
Flame combustion to fixture, stepless, limit oxygen index 19.2%, thermal coefficient is 0.026W/ (mK).
Comparative example 2
25.0g polyether polyol, 20.0g PEG-400,3.0g deionized water and 2.0g silicone oil are stirred at room temperature
For 24 hours, 1.0gDMP-30,0.1g stannous octoate, high-speed stirred 5min are added after the completion of stirring.High-speed stirring after addition 142.0gMDI
10s is mixed, mixed liquor is poured into chunk and is foamed.After the completion of foaming, solidify 4h at 80 DEG C and 120 DEG C respectively.24h
Sampling and testing afterwards.
Gained foam density is 40Kg/m3, compressive strength 588kPa, rate of closed hole 90%.In vertical burn test
Flame combustion to fixture, stepless, limit oxygen index 19.4%, thermal coefficient is 0.028W/ (mK).
Comparative example 3
25.0g polyether polyol, 20.0g PEG-400,3.0g deionized water and 2.0g silicone oil are stirred at room temperature
For 24 hours, 1.0gDMP-30,0.1g stannous octoate, high-speed stirred 5min are added after the completion of stirring.High-speed stirring after addition 177.0gMDI
10s is mixed, mixed liquor is poured into chunk and is foamed.After the completion of foaming, solidify 4h at 80 DEG C and 120 DEG C respectively.24h
Sampling and testing afterwards.
Gained foam density is 44Kg/m3, compressive strength 653kPa, rate of closed hole 90%.In vertical burn test
Flame combustion to fixture, stepless, limit oxygen index 19.4%, thermal coefficient is 0.028W/ (mK).
It can be found by comparison, the fire-retardant full water foamed cross-linked type polyurethane hard bubble of the functionalization graphene of embodiment preparation
Compared with the conventional polyurethanes hard bubble of comparative example preparation, the flame retardant properties such as vertical combustion, limit oxygen index and high-temperature residual quality
Have and is obviously improved, and in the case where variable density is little, compressive strength is also promoted obviously.Thermal constant test shows to change
The heat insulation-type of hard polyurethane foam remains to be maintained in same level with unmodified hard polyurethane foam after property.
Claims (8)
1. a kind of functionalization graphene, it is characterised in that the general structure of the graphene is as follows:
X is epoxies group in formula, and Y is graphene, Z C1-C6Any one of alkyl.
2. functionalization graphene according to claim 1, it is characterised in that epoxies base described in the graphene-structured
Group is any one of glycidyl, epoxybutyl, epoxypentyl or epoxyhexyl.
3. a kind of method for preparing functionalization graphene described in claim 1, the specific process step and condition of the preparation method
It is as follows:
1) three-functionality-degree phosphoryl chloride phosphorus oxychloride or pyrophosphoryl chloride are dissolved in organic solvent, stir the identical equivalent C of lower instillation in ice-water bath1-
C6Alcohols material, heating removes organic solvent after reacting 3~5h, is continuously heating to solution 3~8h of slightly boiled lower reaction, decompression steaming
It evaporates, collects monosubstituted phosphoryl chloride phosphorus oxychloride fraction or pyrophosphoryl chloride substituent fraction；
2) the monosubstituted phosphoryl chloride phosphorus oxychloride of gained or two commercially available degree of functionality phosphoryl chloride phosphorus oxychlorides are added in organic solvent and are stirred evenly, it then will be molten
The epoxy types of the equimolar amounts of solution in organic solvent, which are slowly added dropwise, to be finished, and slowly heating and 2~5h of back flow reaction are continued,
Epoxy group phosphinylidyne solutions of chlorine is made；
3) graphene is uniformly dispersed in dispersing agent and is slowly dropped into epoxy group phosphinylidyne solutions of chlorine, epoxy group phosphoryl chloride phosphorus oxychloride
Additive amount is 1~2mol/25g graphene.Dispersing agent is evaporated off after reacting 3~5h in temperature rising reflux, 80~90 DEG C is cooled to, to reaction
C is slowly added in system1-C6Hydroxyl substance, additional amount are at least 1 times of hydroxyl/chlorine atom molar amount, the reaction was continued 1~
Products therefrom is finally washed, is dry by 2h,
Epoxy types used in it are any one of epoxy prapanol, epoxy butanol, epoxy amylalcohol or epoxy hexanol.
4. the method according to claim 3 for preparing functionalization graphene, three-functionality-degree phosphorus used in the preparation method
Acyl chlorides is phosphorus oxychloride or phosphorus thiochloride.
5. the method according to claim 3 or 4 for preparing functionalization graphene, in the preparation method into reaction system plus
The C entered1-C6Hydroxyl substance is by 1~1.5 times of equivalent of chlorine atom molar amount.
6. a kind of flame retardant cross-linked type polyurethane rigid foam of functionalization graphene described in claim 1, the friendship
Connection type polyurethane rigid foam is by polyisocyanates, polyalcohol, catalyst, foaming agent according to conventional proportions, using routine
Step foaming is mixed to be made, it is characterised in that isocyanate index used is 1.5~2.5, in terms of polyol quality part, function
The additive amount of energy graphite alkene fire retardant is 10~160 parts, and gained foam density is 36-55kg/m3, compressive strength is
1232-1730kPa, rate of closed hole 84-92%, vertical combustion grade is V-0 grades, limit oxygen index 23.4-34.5%, thermally conductive
Coefficient is 0.028-0.035W/ (mK).
7. the flame retardant cross-linked type polyurethane rigid foam of functionalization graphene according to claim 6, feature
It is in the cross-linked type polyurethane rigid foam, isocyanate index is 2.0~2.5, in terms of polyol quality part, function fossil
The additive amount of black alkene fire retardant is 40~160 parts, and gained foam density is 36-55kg/m3, compressive strength 1302-
1730kPa, rate of closed hole 84-92%, vertical combustion (UL-94) grade are V-0 grades, and limit oxygen index 25.4-34.5% is led
Hot coefficient is 0.028-0.035W/ (mK).
8. the flame retardant cross-linked type polyurethane rigid foam of functionalization graphene according to claim 6, feature
The isocyanate index for being the cross-linked type polyurethane rigid foam is 2.0~2.5, in terms of polyol quality part, function fossil
The additive amount of black alkene fire retardant is 80~160 parts, and gained foam density is 44-55kg/m3, compressive strength 1487-
1730kPa, rate of closed hole 84-91%, vertical combustion (UL-94) grade are V-0 grades, and limit oxygen index 30.2-34.5% is led
Hot coefficient is 0.028-0.035W/ (mK).
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| CN106823229B (en) * | 2017-01-13 | 2019-08-16 | 东莞市安绿美新材料科技有限公司 | Efficient and environment-friendly type fire retardant extinguisher and preparation method thereof |
| CN106832189A (en) * | 2017-01-24 | 2017-06-13 | 南京科孚纳米技术有限公司 | A kind of preparation method of Graphene compound polyurethane material |
| CN107298742A (en) * | 2017-06-27 | 2017-10-27 | 烟台市烯能新材料股份有限公司 | A kind of preparation method of graphene polyurethane foam cotton |
| CN110229304B (en) * | 2019-07-09 | 2021-09-21 | 兰州大学 | Flame-retardant graphene polyurethane composite foam material and preparation method thereof |
| CN112778368B (en) * | 2021-01-05 | 2022-08-23 | 江苏利思德新材料有限公司 | Dialkyl phosphinate containing active epoxy group and preparation and application thereof |
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