CN105524299A - Functionalized graphene, preparation method and cross-linking type rigid polyurethane foam adopting functionalized graphene for flame retardancy - Google Patents
Functionalized graphene, preparation method and cross-linking type rigid polyurethane foam adopting functionalized graphene for flame retardancy 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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- 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
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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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
- C08G2110/0025—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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- 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
- C08G2110/0058—≥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
Abstract
The invention discloses functionalized graphene. A general structural formula of the functionalized graphene is represented in the specification, wherein X is an epoxy group, Y is graphene, Z is any one of alkyl groups of C1-C6, and the functionalized graphene is prepared by grafting graphene oxide onto a product obtained through reaction of a phosphorus and chlorine compound, epoxy structure containing monomers and phenol monomers in an environment without water. After the functionalized graphene is added to rigid polyurethane foam, the functionalized graphene as an intrinsic type flame retardant can better perform functions on the basis of good dispersibility, flame retardancy and compressibility of the rigid polyurethane foam are greatly improved, the density and the heat insulating performance of the rigid polyurethane foam can be equivalent to those of common rigid polyurethane foam, besides, a preparation technology of the functionalized graphene and the rigid polyurethane foam is simple and easy, and large-scale popularization and application can be performed conveniently.
Description
Technical field
The invention belongs to Graphene and preparation thereof and by its fire-retardant hard polyurethane foam technical field, particularly a kind of have functionalization graphene of high flame retardant efficiency and preparation method thereof and with its fire-retardant cross-linked type polyurethane rigid foam.
Background technology
Hard polyurethane foam is owing to having the advantages such as extremely low thermal conductivity, low density, high specific strength value and good adhesiveproperties, be subject to requiring strict refrigeration equipment and the welcome of construction industry to heat-insulating property, its demand increase year by year and its Application Areas also in continuous expansion.But hard polyurethane foam still faces following problem in actual applications to be needed to solve:
The high resistant burning problem of hard polyurethane foam.Urethane is because affecting by textural factor, and decomposition temperature is lower, and flame retardant properties is poor, and the oxygen index of the hard polyurethane foam of non-modified generally only has about 19%, meets fire and very easily burns.At present fire-retardant adopted ordinary method is carried out for using additive flame retardant or design flame retardant polyol to hard polyurethane foam.But wherein the flame retarding efficiency of flame retardant polyol is then relatively low and larger to the mechanical impact such as compression performance, dimensional stability of foam, and existing additive flame retardant majority is halogen containing flame-retardant, a large amount of cigarettes and poisonous corrosive gases can be produced during burning, to cause huge once injury to human body in the scene of a fire, serious obstruction is put out a fire and evacuating personnel, corrosion instrument and equipment.In addition, most halogen containing flame-retardant also exist elongated in time and migration problem.In additive flame retardant, expanded graphite is a kind of conventional expansion type flame retardant, because its ratio of expansion is high, expansion effect obviously and environmental friendliness and have larger application prospect, as CN101265358B in " hard polyurethane foams, its preparation method and application " just to utilizing separately expanded graphite to report as fire retardant hard polyurethane foam, and illustrate add expanded graphite hard polyurethane foam after combustion surface have expanded graphite formed layer of charcoal.But the mechanism of intumescence because of expanded graphite is physical expansion, though ratio of expansion can not form greatly enough fine and close layer of charcoal to protect base material, the specific surface areas such as polyurethane foam resilience in comparison body and plastics are large, make this drawback of expanded graphite seem more outstanding.In addition, because expanded graphite wick effect in polyurethane foam is obvious, therefore generally little expanded graphite is used for polyurethane foam as fire retardant separately, and be adopt composite or coated method to use mostly, disclosed in CN102140184A, " a kind of composite flame retardant with core-shell structure and preparation method thereof " and CN101503567A disclosed " a kind of nano composite expansion flame-retardant polyurethane foam plastic and preparation method thereof " just adopt Melamino-formaldehyde resin encapsulated expanded graphite and the composite expanded graphite of non-halogen phosphoric acid ester to carry out resistance combustion polyurethane foam respectively, but because expanded graphite interlamellar spacing is less, cause coated or composite after dispersiveness in polyurethane foam base material can be poorer, thus the mechanical property generation of polyurethane foam is had a strong impact on, though this impact reduces by the particle diameter reducing expanded graphite, but along with the reduction of expanded graphite particle diameter, its flame retarding efficiency declines rapidly again thereupon.
The non-halogen problem of hard polyurethane foam whipping agent.Up to now, HCFC-141b, pentane and water are the common foamings of hard polyurethane foams.Although HCFC-141b ozone-depleting is dived, value compares that fluorochlorohydrocarbon class whipping agent is existing significantly to be reduced, and it still can not be ignored the destruction of atmospheric ozone layer.Pentane, due to highly volatile and burning, adopts it then significantly can reduce the flame retardant properties of polyurethane foam as whipping agent.Simple use water is as whipping agent, if do not carry out modification to polyurethane foam, its foam performance and dimensional stability can be a greater impact, and may exist during suitability for industrialized production because local temperature is too high and burn the phenomenon of core.
The low densityization of hard polyurethane foam and the contradictory problems of dimensional stability.As everyone knows, the object of porous plastics low density is the advantage in order to realize the construction cost reduction that raw material usage quantity is cut down, transportation cost reduces and lightweight brings, but low densityization not only can cause the decline of porous plastics intensity, and take sheet material as the decline that the polyurethane rigid foam plastic of representative also easily produces dimensional stability.
Summary of the invention
The object of the invention is for prior art Problems existing, first the functionalization graphene that a kind of flame retarding efficiency is high, fire retardation is lasting is provided, this Graphene both can be used as into carbon flame-proof catalyzer, can be used as again crosslinked center and increase degree of crosslinking to improve layer of charcoal density, the dimensional stability increasing hard polyurethane foam in polyurethane foam base material can also be dispersed in simultaneously.
Another object of the present invention is to provide a kind of preparation method of above-mentioned functions functionalized graphene.
Another object of the present invention is to provide a kind of above-mentioned functionalization graphene as high-efficient and lasting and can improves the flame retardant cross-linked type polyurethane rigid foam of substrate stability.
A kind of functionalization graphene provided by the invention, the general structure of this Graphene is as follows:
In formula, X is epoxies group, and Y is Graphene, and Z is C
1-C
6alkyl in any one.
Epoxies group described in above graphene-structured is any one in epoxypropyl, epoxybutyl, epoxypentyl or epoxyhexyl.
The preparation method of above-mentioned functions functionalized graphene provided by the invention, the concrete technology step of this preparation method and condition as follows:
1) three-functionality-degree phosphoryl chloride or pyrophosphoryl chloride are dissolved in organic solvent, stir the identical equivalent C of lower instillation in ice-water bath
1-C
6alcohols material, reaction 3 ~ 5h after heat up removing organic solvent, continue to be warming up to the micro-lower reaction 3 ~ 8h that boils of solution, underpressure distillation, collects the cut of 160 ~ 240 DEG C, then cut is carried out air distillation, collects the cut of 240 ~ 280 DEG C, obtains monosubstituted phosphoryl chloride;
2) monosubstituted for gained phosphoryl chloride or two commercial functionality phosphoryl chlorides are added in organic solvent stir, then the epoxy types of the equimolar amount dissolved in organic solvent is slowly dropwised in 1 ~ 2h, continue slowly to heat up and back flow reaction 2 ~ 5h, obtained epoxy group(ing) phosphoryl chloride solution;
3) Graphene is uniformly dispersed in dispersion agent, then under room temperature slowly in instillation epoxy group(ing) phosphoryl chloride solution, distillation removing dispersion agent after temperature rising reflux reaction 3 ~ 5h, then continue intensification and steam other materials unreacted, be cooled to 80 ~ 90 DEG C, in reaction system, slowly add C
1-C
6hydroxy kind material, its add-on is hydroxyl/chlorine atomic molar gauge at least 1 times, continues reaction 1 ~ 2h, is finally washed to filtrate pH in neutral with acetone and boiling water successively by products therefrom, dry, the addition of its epoxy group phosphoryl chloride is 1 ~ 2mol/25g Graphene.
Above method epoxy types used is any one in R-GLYCIDOL, epoxy butanols, epoxy amylalcohol or epoxy hexanol; Phosphoryl chloride is any one in phosphorus oxychloride, phosphorus thiochloride, tetra-sodium chlorine, dichlorophenyl chlorine phosphoric acid ester, diphenylphosphoryl dichloro, 2-chloro-phenyl--phenyl phosphate ester, methyl acid phosphate dichloro methyl esters, chloromethyl-methyl-phosphoryl chloride, 2-rubigan phosphoric acid ester.
Above method Graphene used obtains in the following manner: 1) by graphite according to JournaloftheAmericanChemicalSociety, Year1958, Volume80, Issue6, Page1339 and AdvancedMaterials, Year2010, Volume22, the method preparation that Issue35, Page3906-24 report; 2) be that the expanded graphite of 180 ~ 220 DEG C obtains through accepted method such as oxidation reduction process, electrochemical process, mechanically peel methods by expansion temperature, wherein Graphene prepared by preferential oxidation reduction method; 3) commercially available Graphene also can, the Graphene wherein prepared by preferential oxidation reduction method.
C used in above method
1-C
6alcohols material be methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 2-methyl isophthalic acid-propyl alcohol, 2-methyl-2-propanol, n-butyl alcohol, 2-butanols, 2, 2-dimethyl propyl alcohol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 2-methyl-1-butene alcohol, 2-methyl-2-butanols, 3-methyl-2-butanols, 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-butanols, 3, 3-dimethyl-1-butanol, any one in cyclopentanol or hexalin, particular methanol, ethanol, propyl alcohol.
Commercial two functionality phosphoryl chlorides used in above method are any one in diphenylphosphoryl dichloro, 2-chloro-phenyl--phenyl phosphate ester, methyl acid phosphate dichloro methyl esters, chloromethyl-methyl-phosphoryl chloride or 2-rubigan phosphoryl chloride.
The C that above method is used
1-C
6hydroxy kind material is methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 2-methyl isophthalic acid-propyl alcohol, 2-methyl-2-propanol, n-butyl alcohol, 2-butanols, 2, 2-dimethyl propyl alcohol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 2-methyl-1-butene alcohol, 2-methyl-2-butanols, 3-methyl-2-butanols, 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-butanols, 3, 3-dimethyl-1-butanol, cyclopentanol, hexalin, ethylene glycol, propylene glycol, 1, 3-butyleneglycol, 1, 4-butyleneglycol, any one in neopentyl glycol or glycerol, particular methanol or ethanol, and its add-on is preferably hydroxyl/chlorine atomic molar gauge 1 ~ 1.5 times.
Above method organic solvent used is any one in acetone, chloroform, acetonitrile, Nitromethane 99Min., 2-butanone, tetrahydrofuran (THF), mibk, benzene,toluene,xylene, propyl ether, tetracol phenixin, trieline, hexanaphthene, trimethylpentane, octane-iso or normal hexane.
Above method dispersion agent used is any one in acetone, chloroform, acetonitrile, Nitromethane 99Min., 2-butanone, tetrahydrofuran (THF), mibk, benzene,toluene,xylene, propyl ether, tetracol phenixin, trieline, hexanaphthene, trimethylpentane, octane-iso or normal hexane.
Provided by the inventionly can improve the flame retardant cross-linked type polyurethane rigid foam of substrate stability with above-mentioned functionalization graphene as high-efficient and lasting, this cross-linked type polyurethane rigid foam is by polyisocyanates, polyvalent alcohol, catalyzer, whipping agent conveniently proportioning, conventional mix and blend one step foaming is adopted to make, it is characterized in that isocyanate index is 1.5 ~ 2.5, in polyol quality part, the addition of functionalization graphene fire retardant is 10 ~ 160 parts, and gained foam density is 36-55Kg/m
3, its compressive strength is 1232-1730kPa, and rate of closed hole is 84-91%, and vertical combustion (UL-94) grade is V-0 level, and limiting oxygen index(LOI) is 23.4-34.5%, and thermal conductivity is 0.028-0.035W/ (mK).
When in above hard polyurethane foam, isocyanate index is 2.0 ~ 2.5, and in polyol quality part, the addition of functionalization graphene fire retardant is 40 ~ 160 parts, and gained foam density is 36-55kg/m
3, its compressive strength is 1302-1730kPa, and rate of closed hole is 84-91%, and vertical combustion (UL-94) grade is V-0 level, and limiting oxygen index(LOI) is 25.4-34.5%, and thermal conductivity is 0.028-0.035W/ (mK).
When in above hard polyurethane foam, isocyanate index is 2.0 ~ 2.5, and in polyol quality part, the addition of functionalization graphene fire retardant is 80 ~ 160 parts, and gained foam density is 44-55Kg/m
3, its compressive strength is 1487-1730kPa, and rate of closed hole is 84-91%, and vertical combustion (UL-94) grade is V-0 level, and limiting oxygen index(LOI) is 30.2-34.5%, and thermal conductivity is 0.028-0.035W/ (mK).
Compared with prior art, tool has the following advantages in the present invention:
1. modification has been carried out on the surface being the Graphene made by expanded graphite due to functionalization graphene provided by the invention, sheet interlayer spacing is not only made to become large, make fire retardant dispersion in the substrate more even, and the hydroxyl on surface, epoxy group(ing) energy and isocyanate reaction, make fire retardant and base material by chemical bond linkage, thus the dispersiveness of this functionalization graphene in polyurethane foam far exceedes conventional expanded graphite, can forever be well dispersed in polyurethane foam base material, its effect as essential type fire retardant can be played better, the dimensional stability of hard polyurethane foam can be increased again, can not have a negative impact to polyurethane foam base material.
2. due to the Graphene in functionalization graphene fire retardant provided by the invention, phosphoric, epoxide group in polyisocyanates and functionalization graphene generates the multiple ignition-proof elements such as the poly-isocyanurate ring of oxazolidone ring and polyisocyanates self trimerization, both the poly-isocyanurate ring of generation can have been utilized, the high-crosslinking-degree that oxazolidone ring produces is to improve the decomposition temperature of hard polyurethane foam, the wick effect that the physical expansion of raw material expanded graphite can be made again to combine with the chemically expansible of phosphoric institute catalysis solve single expanded graphite and the loose problem of layer of charcoal, and the deficiency that the expansion multiplying power that compensate for chemically expansible is low, in addition this Graphene also can be used as crosslinked center increases degree of crosslinking to improve layer of charcoal density, thus flame retarding efficiency is high, obtained hard polyurethane foams is made to have good flame-retardance energy.
3. due to the hydroxyl on the modified surface of Graphene provided by the invention and epoxy group(ing) also can with isocyanate reaction, forever can be well dispersed in polyurethane foam base material, thus there will not be and elongatedly in time produce migration and the flame retardant properties that causes reduces phenomenon.
4. to Cheng the carrying out that oxazolidone, polyisocyanates and carbamate generate the multiple reactions such as substituted urea with epoxy group(ing) Sheng improve degree of crosslinking because hard polyurethane foams provided by the invention generates poly-isocyanurate ring, polyisocyanates with polyisocyanates trimerization in foaming process, thus make obtained hard polyurethane foam crosslinking degree higher, good stability of the dimension, and resistance to elevated temperatures and weather resistance to compare existing hard polyurethane foam better.
5. because hard polyurethane foams provided by the invention does not adopt the organic alkane class whipping agent that can affect flame retardant effect on the one hand, but all use can produce carbonic acid gas and the water that foams as whipping agent to make in abscess institute's blanketing gas all for carbonic acid gas, whipping agent used and fire retardant are non-halogen compound on the other hand, can not produce ozonosphere and destroy or potential impact, thus make the fire-retardant full water foamed cross-linked type polyurethane of obtained functionalization graphite hard bubble and both there is good flame-retardance energy, namely when functionalization expanded graphite addition is no more than 5% (massfraction), its vertical combustion all can reach UL-94V-0 level, limiting oxygen index(LOI) can reach 30 ~ 35%, also reduce and be used alone water as whipping agent to foaming and the impact of foam size stability, simultaneously environmentally friendly.
6. functionalization graphene fire retardant provided by the invention not only raw material be easy to get, production process is routine operation, be convenient to factory's extension produce, and adopt hard polyurethane foam production technique and existing hard polyurethane foam production technique similar, also can carry out large-scale promotion utilization without the need to changing production unit.
Accompanying drawing explanation
Fig. 1 is the reaction scheme schematic diagram provided according to technical solution of the present invention, wherein X, Z of functionalization graphene structural formula are for R-GLYCIDOL, methyl alcohol respectively, phosphoryl chloride is for phosphorus oxychloride, and polyisocyanates is for polymethylene diphenyl diisocyanate.
The thermogravimetric of the modified graphene of Fig. 2 prepared by raw material expanded graphite and embodiment 1 in nitrogen and once differentiation (TG/DTG) curve thereof.With expanded graphite Comparatively speaking, the maximum decomposition temperature of modified graphene increases.Due to chemically expansible effect, in 200 ~ 540 DEG C, residual mass all has increase, and after 550 DEG C, due to the decomposition of grafts, modified graphene decomposes to be accelerated, and residual mass is less than expanded graphite.
The constituent content test result of table 1 modified graphene prepared by raw material expanded graphite and embodiment 1.EDX result shows, and the P element content of modified graphene surface grafting reaches 2.56%.ICP-AES test surfaces, the massfraction of P element in overall modified graphene reaches 2.95%.
The stereoscan photograph of Fig. 3 anti-inflaming polyurethane hard foam prepared by hard polyurethane foam and embodiment 1 prepared by comparative example.As seen from the figure, modified graphene add the anisotropy that can reduce foam, thus make that abscess is more regular, hole wall is thicker.In addition, the modified graphene part scheming to mark from f can be found out, the consistency of modified graphene and foam obtains significant increase.
Fig. 4 is that the fire-retardant full water foamed cross-linked type polyurethane of functionalization graphene that the present invention obtains to hard bubble after vertical combustion sample outward appearance after sample and alcohol blast burner sustained combustion test.Namely vertical combustion first time igniting puts out from fire, and fire endurance period combustion time is 0s, and refire time can not be lighted.Alcohol blast burner sustained combustion 3min, the middle part sustained combustion partial ablation degree of depth about 4 ~ 5mm, the Actual combustion process of description of test functionalization graphene to material has good restraining effect.
The aerial thermogravimetric curve of hard polyurethane foam prepared by the hard polyurethane foam of Fig. 5 prepared by the embodiment of the present invention 1 and comparative example, when functionalization graphene addition is 4.0wt%, hard polyurethane foam decomposition temperature is compared conventional polyurethanes and have been hard bubbled obvious lifting, just can decompose at relatively high temperatures, and the residual mass at 700 DEG C is 29.0%, and conventional polyurethanes to be hard bubbled 700 DEG C time and to be decomposed completely and without any residual, the functionalization graphene contrasted prepared by known the present invention can significantly improve the thermostability of hard polyurethane foam, the quality of polyurethane foamed material at 700 DEG C is remained and is promoted to 24% by 0.
Embodiment
Provide embodiment below so that the invention will be further described.What be necessary to herein means out is; following examples can not be interpreted as limiting the scope of the invention; if the person skilled in the art in this field makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belong to scope.
In addition, what deserves to be explained is:
The correlated performance test data of foam prepared by following examples and comparative example is carried out according to following standard: the testing standard of foam density is GB/T6343-1995; The testing standard of compressive strength is GB/T8813-2008; The testing standard of vertical combustion is UL-94-2010; The testing standard of limiting oxygen index(LOI) is GB/T2406.2-2009; The testing standard of thermal conductivity is GB/T10294-2008.
Embodiment 1
(1) Hummer legal system is for Graphene
By 10g expanded graphite and 5g nitric acid and 230ml sulfuric acid as in there-necked flask, slowly add 30g potassium permanganate under ice bath mechanical stirring, keep temperature to be no more than 9 DEG C, remove water-bath, react 4h at 35 DEG C, reactant 460ml water is slowly diluted, temperature rises to about 98 DEG C, keeps 1h.After continuing dilution with 1400ml water, with 3% hydrogen peroxide processing reaction thing to glassy yellow, suction filtration, washing, use 50ml hydrazine hydrate reduction, suction filtration, washing, drying.
(2) grafts is prepared
By 30.6g phosphorus oxychloride as in there-necked flask, in 30min, slowly instill 6.4g methyl alcohol.Slowly be warming up to 50 DEG C, after reaction 4h, steam chloroform.Be warming up to that solution is micro-to boil, after continuing reaction 6h, steam unreacted reactant.Product is added in 100ml acetone and stir.Slowly be added dropwise in 1h after 14.8g R-GLYCIDOL acetone diluted is dissolved, be added dropwise to complete rear slow temperature rising reflux reaction 4h.
(3) grafts is grafted on Graphene
5.0g graphene dispersion slowly instilled under room temperature in grafts/acetone soln after 200ml acetone, steam acetone after backflow 4h, continuing to heat up keeps micro-the boiling of solution to steam other materials unreacted.React complete and be cooled to 80 DEG C, in reaction system, slowly add 9.2g ethanol, continue reaction 1h.Finally products therefrom is used boiling water and washing with alcohol respectively.
(4) functionalization graphene is utilized to prepare hard polyurethane foam:
By 10.0g functionalization graphene, 25.0g polyether glycol, 20.0gPEG-400,3.0g deionized water and 2.0g silicone oil in stirred at ambient temperature 24h, add 1.0gDMP-30,0.1g stannous octoate after having stirred, high-speed stirring 5min.Add high-speed stirring 10s after 142.0gMDI, mixed solution is poured in chunk and foams.After having foamed, at 80 DEG C and 120 DEG C, solidify 4h respectively.Sampling and testing after 24h.
Gained foam density is 36Kg/m
3, its compressive strength is 1302kPa, and rate of closed hole is 91%.Vertical combustion grade is V-0 level (UL-94), and limiting oxygen index(LOI) is 25.4%, and thermal conductivity is 0.029W/ (mK).
Whether successful in order to investigate functionalization graphene preparation, the present invention tests respectively by X-ray energy spectrum (EDX) and atomic emission spectrum (ICP-AES) the content of the functionalization graphene (FGN) of the present embodiment gained with raw materials used expanded graphite (EG) surface-element and inner phosphoric, the results are shown in following table.From following table result, carbon has only been detected on expanded graphite surface, and functionalization graphene surface has then been detected and also contained the oxygen element of 21.49% and the phosphoric of 2.56%; The content of inner phosphoric, functionalization graphene is far above expanded graphite.This fully indicates the successful preparation of functionalization graphene.
Table
Embodiment 2
(1) Hummer legal system is for Graphene
By 10g expanded graphite and 5g nitric acid and 230ml sulfuric acid as in there-necked flask, slowly add 30g potassium permanganate under ice bath mechanical stirring, keep temperature to be no more than 9 DEG C, remove water-bath, react 4h at 35 DEG C, reactant 460ml water is slowly diluted, temperature rises to about 98 DEG C, keeps 1h.After continuing dilution with 1400ml water, with 3% hydrogen peroxide processing reaction thing to glassy yellow, suction filtration, washing, use 50ml hydrazine hydrate reduction, suction filtration, washing, drying.
(2) grafts is prepared
By 19.4g diphenylphosphoryl dichloro as in there-necked flask, be slowly added dropwise in 2h after 7.4g R-GLYCIDOL 150ml acetone diluted being dissolved under ice bath, be added dropwise to complete rear slow temperature rising reflux reaction 3h.
(3) grafts is grafted on Graphene
5.0g graphene dispersion slowly instilled under room temperature in grafts/acetone soln after 200ml acetone, steam acetone after backflow 3h, continuing to heat up keeps micro-the boiling of solution to steam other materials unreacted.React complete and be cooled to 80 DEG C, in reaction system, slowly add 4.6g ethanol, continue reaction 1h.Finally products therefrom is used boiling water and washing with alcohol respectively.
(4) functionalization graphene is utilized to prepare hard polyurethane foam
By 40.0g functionalization graphene, 25.0g polyether glycol, 20.0gPEG-400,3.0g deionized water and 2.0g silicone oil in stirred at ambient temperature 24h, add 1.0gDMP-30,0.1g stannous octoate after having stirred, high-speed stirring 5min.Add high-speed stirring 10s after 142.0gMDI, mixed solution is poured in chunk and foams.After having foamed, at 80 DEG C and 120 DEG C, solidify 4h respectively.Sampling and testing after 24h.
Gained foam density is 46Kg/m
3, its compressive strength is 1730kPa, and rate of closed hole is 88%.Vertical combustion grade is V-0 level (UL-94), and limiting oxygen index(LOI) is 34.0%, and thermal conductivity is 0.035W/ (mK).
Embodiment 3
(1) Hummer legal system is for Graphene
By 10g expanded graphite and 5g nitric acid and 230ml sulfuric acid as in there-necked flask, slowly add 30g potassium permanganate under ice bath mechanical stirring, keep temperature to be no more than 9 DEG C, remove water-bath, react 4h at 35 DEG C, reactant 460ml water is slowly diluted, temperature rises to about 98 DEG C, keeps 1h.After continuing dilution with 1400ml water, with 3% hydrogen peroxide processing reaction thing to glassy yellow, suction filtration, washing, use 50ml hydrazine hydrate reduction, suction filtration, washing, drying.
(2) grafts is prepared
By 25.0g tetra-sodium chlorine as in there-necked flask, be slowly added dropwise in 2h under ice-water bath after 7.4g R-GLYCIDOL 150ml acetone diluted is dissolved, be added dropwise to complete rear slow intensification and back flow reaction 5h.
(3) grafts is grafted on Graphene
5.0g graphene dispersion slowly instilled under room temperature in grafts/acetone soln after acetone, steam acetone after backflow 5h, continuing to heat up keeps micro-the boiling of solution to steam other materials unreacted.React complete and be cooled to 80 DEG C, in reaction system, slowly add 6.9g ethanol, continue reaction 2h.Finally products therefrom is used boiling water and washing with alcohol respectively.
(4) functionalization graphene is utilized to prepare hard polyurethane foam
By 20.0g functionalization graphene, 25.0g polyether glycol, 20.0gPEG-400,3.0g deionized water and 2.0g silicone oil in stirred at ambient temperature 24h, add 1.0gDMP-30,0.1g stannous octoate after having stirred, high-speed stirring 5min.Add high-speed stirring 10s after 177.0gMDI, mixed solution is poured in chunk and foams.After having foamed, at 80 DEG C and 120 DEG C, solidify 4h respectively.Sampling and testing after 24h.
Gained foam density is 44Kg/m
3, its compressive strength is 1698kPa, and rate of closed hole is 84%.Vertical combustion grade is V-0 level (UL-94), and limiting oxygen index(LOI) is 30.2%, and thermal conductivity is 0.032W/ (mK).
Embodiment 4
(1) Hummer legal system is for Graphene
By 10g expanded graphite and 5g nitric acid and 230ml sulfuric acid as in there-necked flask, slowly add 30g potassium permanganate under ice bath mechanical stirring, keep temperature to be no more than 9 DEG C, remove water-bath, react 4h at 35 DEG C, reactant 460ml water is slowly diluted, temperature rises to about 98 DEG C, keeps 1h.After continuing dilution with 1400ml water, with 3% hydrogen peroxide processing reaction thing to glassy yellow, suction filtration, washing, use 50ml hydrazine hydrate reduction, suction filtration, washing, drying.
(2) grafts is prepared
By 14.8g methyl acid phosphate dichloro methyl esters as in there-necked flask, be slowly added dropwise in 2h after 7.4g R-GLYCIDOL acetone diluted is dissolved, be added dropwise to complete rear slow intensification and back flow reaction 2h.
(3) grafts is grafted on Graphene
5.0g graphene dispersion is slowly instilled in grafts/acetone soln after 200ml acetone under room temperature, steams acetone after backflow 4h, continue to be warming up to micro-the boiling of solution and steam other materials unreacted.React complete and be cooled to 80 DEG C, in reaction system, slowly add 4.6g ethanol, continue reaction 1h.Finally products therefrom is used boiling water and washing with alcohol respectively.
(4) functionalization graphene is utilized to prepare hard polyurethane foam
By 5.0g functionalization graphene, 25.0g polyether glycol, 20.0gPEG-400,3.0g deionized water and 2.0g silicone oil in stirred at ambient temperature 24h, add 1.0gDMP-30,0.1g stannous octoate after having stirred, high-speed stirring 5min.Add high-speed stirring 10s after 142.0gMDI, mixed solution is poured in chunk and foams.After having foamed, at 80 DEG C and 120 DEG C, solidify 4h respectively.Sampling and testing after 24h.
Gained foam density is 36Kg/m
3, its compressive strength is 1288kPa, and rate of closed hole is 90%.Vertical combustion grade is V-0 level (UL-94), and limiting oxygen index(LOI) is 24.0%, and thermal conductivity is 0.028W/ (mK).
Embodiment 5
(1) Hummer legal system is for Graphene
By 10g expanded graphite and 5g nitric acid and 230ml sulfuric acid as in there-necked flask, slowly add 30g potassium permanganate under ice bath mechanical stirring, keep temperature to be no more than 9 DEG C, remove water-bath, react 4h at 35 DEG C, reactant 460ml water is slowly diluted, temperature rises to about 98 DEG C, keeps 1h.After continuing dilution with 1400ml water, with 3% hydrogen peroxide processing reaction thing to glassy yellow, suction filtration, washing, use 50ml hydrazine hydrate reduction, suction filtration, washing, drying.
(2) grafts is prepared
By 14.6g chloromethyl-methyl-phosphoryl chloride as in there-necked flask, be slowly added dropwise in 2h after 7.4g R-GLYCIDOL acetone diluted is dissolved, be added dropwise to complete rear slow intensification and back flow reaction 4h.
(3) grafts is grafted on Graphene
5.0g graphene dispersion is slowly instilled in grafts/acetone soln after 200ml acetone under room temperature, steams acetone after backflow 4h, continue to be warming up to micro-the boiling of solution and steam other materials unreacted.React complete and be cooled to 80 DEG C, in reaction system, slowly add 5.8g ethanol, continue reaction 1h.Finally products therefrom is used boiling water and washing with alcohol respectively.
(4) functionalization graphene is utilized to prepare hard polyurethane foam
By 2.5g functionalization graphene, 25.0g polyether glycol, 20.0gPEG-400,3.0g deionized water and 2.0g silicone oil in stirred at ambient temperature 24h, add 1.0gDMP-30,0.1g stannous octoate after having stirred, high-speed stirring 5min.Add high-speed stirring 10s after 142.0gMDI, mixed solution is poured in chunk and foams.After having foamed, at 80 DEG C and 120 DEG C, solidify 4h respectively.Sampling and testing after 24h.
Gained foam density is 37Kg/m
3, its compressive strength is 1232Pa, and rate of closed hole is 88%.Vertical combustion grade is V-0 level (UL-94), and limiting oxygen index(LOI) is 23.4%, and thermal conductivity is 0.028W/ (mK).
Embodiment 6
(1) Hummer legal system is for Graphene
By 10g expanded graphite and 5g nitric acid and 230ml sulfuric acid as in there-necked flask, slowly add 30g potassium permanganate under ice bath mechanical stirring, keep temperature to be no more than 9 DEG C, remove water-bath, react 4h at 35 DEG C, reactant 460ml water is slowly diluted, temperature rises to about 98 DEG C, keeps 1h.After continuing dilution with 1400ml water, with 3% hydrogen peroxide processing reaction thing to glassy yellow, suction filtration, washing, use 50ml hydrazine hydrate reduction, suction filtration, washing, drying.
(2) grafts is prepared
By 15.3g phosphorus oxychloride as in there-necked flask, in 30min, slowly instill 10.2g3-methyl-2-amylalcohol.Be warming up to that solution is micro-to boil, after continuing reaction 4h, steam solvent toluene, continue reaction 8h, unreacted reactant is steamed.Product is added in 100ml dimethylbenzene and stir.Slowly be added dropwise in 2h after the dilution of 8.8g epoxy butanols hexanaphthene is dissolved, be added dropwise to complete rear slow temperature rising reflux reaction 5h.
(3) grafts is grafted on Graphene
5.0g graphene dispersion slowly instilled under room temperature in grafts/acetone soln after 200ml dimethylbenzene, steam hexanaphthene after backflow 5h, continuing to heat up keeps micro-the boiling of solution to steam other materials unreacted.React complete and be cooled to 80 DEG C, in reaction system, slowly add 3.9g ethylene glycol, continue reaction 2h.Finally products therefrom is used boiling water and washing with alcohol respectively.
(4) hard polyurethane foam is prepared with functionalization graphene
By 40.0g functionalization graphene, 25.0g polyether glycol, 20.0gPEG-400,3.0g deionized water and 2.0g silicone oil in stirred at ambient temperature 24h, add 1.0gDMP-30,0.1g stannous octoate after having stirred, high-speed stirring 5min.Add high-speed stirring 10s after 177.0gMDI, mixed solution is poured in chunk and foams.After having foamed, at 80 DEG C and 120 DEG C, solidify 4h respectively.Sampling and testing after 24h.
Gained foam density is 55Kg/m
3, its compressive strength is 1687kPa, and rate of closed hole is 85%.Vertical combustion grade is V-0 level (UL-94), and limiting oxygen index(LOI) is 34.5%, and thermal conductivity is 0.032W/ (mK).
Embodiment 7
(1) grafts is prepared
By 30.6g phosphorus oxychloride as in there-necked flask, in 30min, slowly instill 6.4g methyl alcohol.Be warming up to that solution is micro-to boil, after continuing reaction 4h, steam solvent chloroform, continue reaction 3h, unreacted reactant is steamed.Product is added in 100ml acetone and stir.Slowly be added dropwise in 1h after 14.8g R-GLYCIDOL acetone diluted is dissolved, be added dropwise to complete rear slow temperature rising reflux reaction 4h.
(2) grafts is grafted on commercially available Graphene
Commercially available for 5.0g graphene dispersion slowly instilled under room temperature in grafts/acetone soln after 200ml acetone, steam acetone after backflow 4h, continuing to heat up keeps micro-the boiling of solution to steam other materials unreacted.React complete and be cooled to 80 DEG C, in reaction system, slowly add 9.2g ethanol, continue reaction 1h.Finally products therefrom is used boiling water and washing with alcohol respectively.
(3) hard polyurethane foam is prepared with functionalization graphene:
By 20.0g functionalization graphene, 25.0g polyether glycol, 20.0gPEG-400,3.0g deionized water and 2.0g silicone oil in stirred at ambient temperature 24h, add 1.0gDMP-30,0.1g stannous octoate after having stirred, high-speed stirring 5min.Add high-speed stirring 10s after 142.0gMDI, mixed solution is poured in chunk and foams.After having foamed, at 80 DEG C and 120 DEG C, solidify 4h respectively.Sampling and testing after 24h.
Gained foam density is 44Kg/m
3, its compressive strength is 1544kPa, and rate of closed hole is 91%.Vertical combustion grade is V-0 level (UL-94), and limiting oxygen index(LOI) is 32.0%, and thermal conductivity is 0.030W/ (mK).
Embodiment 8
(1) Hummer legal system is for Graphene
By 10g expanded graphite and 5g nitric acid and 230ml sulfuric acid as in there-necked flask, slowly add 30g potassium permanganate under ice bath mechanical stirring, keep temperature to be no more than 9 DEG C, remove water-bath, react 4h at 35 DEG C, reactant 460ml water is slowly diluted, temperature rises to about 98 DEG C, keeps 1h.After continuing dilution with 1400ml water, with 3% hydrogen peroxide processing reaction thing to glassy yellow, suction filtration, washing, use 50ml hydrazine hydrate reduction, suction filtration, washing, drying.
(2) grafts is prepared
By 30.6g phosphorus oxychloride as in there-necked flask, in 30min, slowly instill 6.4g methyl alcohol.Be warming up to that solution is micro-to boil, after continuing reaction 4h, steam solvent acetonitrile, continue reaction 4h, unreacted reactant is steamed.Product is added in 100ml toluene and stir.Slowly be added dropwise in 1.5h after 14.8g R-GLYCIDOL dilution with toluene is dissolved, be added dropwise to complete rear slow temperature rising reflux reaction 2.5h.
(3) grafts is grafted on Graphene
5.0g graphene dispersion slowly instilled under room temperature in grafts/acetone soln after 200ml toluene, steam toluene after backflow 3.5h, continuing to heat up keeps micro-the boiling of solution to steam other materials unreacted.React complete and be cooled to 80 DEG C, in reaction system, slowly add 9.6g methyl alcohol, continue reaction 1.5h.Finally products therefrom is used boiling water and washing with alcohol respectively.
(4) hard polyurethane foam is prepared with functionalization graphene:
By 15.0g functionalization graphene, 25.0g polyether glycol, 20.0gPEG-400,3.0g deionized water and 2.0g silicone oil in stirred at ambient temperature 24h, add 1.0gDMP-30,0.1g stannous octoate after having stirred, high-speed stirring 5min.Add high-speed stirring 10s after 142.0gMDI, mixed solution is poured in chunk and foams.After having foamed, at 80 DEG C and 120 DEG C, solidify 4h respectively.Sampling and testing after 24h.
Gained foam density is 41Kg/m
3, its compressive strength is 1355kPa, and rate of closed hole is 90%.Vertical combustion grade is V-0 level (UL-94), and limiting oxygen index(LOI) is 28.5%, and thermal conductivity is 0.031W/ (mK).
Embodiment 9
(1) Hummer legal system is for Graphene
By 10g expanded graphite and 5g nitric acid and 230ml sulfuric acid as in there-necked flask, slowly add 30g potassium permanganate under ice bath mechanical stirring, keep temperature to be no more than 9 DEG C, remove water-bath, react 4h at 35 DEG C, reactant 460ml water is slowly diluted, temperature rises to about 98 DEG C, keeps 1h.After continuing dilution with 1400ml water, with 3% hydrogen peroxide processing reaction thing to glassy yellow, suction filtration, washing, use 50ml hydrazine hydrate reduction, suction filtration, washing, drying.
(2) grafts is prepared
By 30.6g phosphorus oxychloride as in there-necked flask, in 30min, slowly instill 20g hexalin.Be warming up to that solution is micro-to boil, after continuing reaction 4.5h, steam solvent acetonitrile, continue reaction 5h, unreacted reactant is steamed.Product is added in 100ml toluene and stir.Slowly be added dropwise in 2h after 14.8g R-GLYCIDOL dilution with toluene is dissolved, be added dropwise to complete rear slow temperature rising reflux reaction 3h.
(3) grafts is grafted on Graphene
5.0g graphene dispersion slowly instilled under room temperature in grafts/acetone soln after 200ml toluene, steam toluene after backflow 4h, continuing to heat up keeps micro-the boiling of solution to steam other materials unreacted.React complete and be cooled to 80 DEG C, in reaction system, slowly add 13.5g1,4-butyleneglycol, continue reaction 2h.Finally products therefrom is used boiling water and washing with alcohol respectively.
(4) hard polyurethane foam is prepared with functionalization graphene:
By 20.0g functionalization graphene, 25.0g polyether glycol, 20.0gPEG-400,3.0g deionized water and 2.0g silicone oil in stirred at ambient temperature 24h, add 1.0gDMP-30,0.1g stannous octoate after having stirred, high-speed stirring 5min.Add high-speed stirring 10s after 142.0gMDI, mixed solution is poured in chunk and foams.After having foamed, at 80 DEG C and 120 DEG C, solidify 4h respectively.Sampling and testing after 24h.
Gained foam density is 45Kg/m
3, its compressive strength is 1487kPa, and rate of closed hole is 89%.Vertical combustion grade is V-0 level (UL-94), and limiting oxygen index(LOI) is 30.2%, and thermal conductivity is 0.033W/ (mK).
Embodiment 10
(1) Hummer legal system is for Graphene
By 10g expanded graphite and 5g nitric acid and 230ml sulfuric acid as in there-necked flask, slowly add 30g potassium permanganate under ice bath mechanical stirring, keep temperature to be no more than 9 DEG C, remove water-bath, react 4h at 35 DEG C, reactant 460ml water is slowly diluted, temperature rises to about 98 DEG C, keeps 1h.After continuing dilution with 1400ml water, with 3% hydrogen peroxide processing reaction thing to glassy yellow, suction filtration, washing, use 50ml hydrazine hydrate reduction, suction filtration, washing, drying.
(2) grafts is prepared
By 30.6g phosphorus oxychloride as in there-necked flask, in 30min, slowly instill 17.6g1-amylalcohol.Be warming up to that solution is micro-to boil, after continuing reaction 5h, steam solvent acetonitrile, continue reaction 6h, unreacted reactant is steamed.Product is added in 100ml hexanaphthene and stir.Slowly be added dropwise in 2h after the dilution of 14.8g R-GLYCIDOL hexanaphthene is dissolved, be added dropwise to complete rear slow temperature rising reflux reaction 4h.
(3) grafts is grafted on Graphene
5.0g graphene dispersion slowly instilled under room temperature in grafts/acetone soln after 200ml hexanaphthene, steam hexanaphthene after backflow 3h, continuing to heat up keeps micro-the boiling of solution to steam other materials unreacted.React complete and be cooled to 80 DEG C, in reaction system, slowly add 10.4g neopentyl glycol, continue reaction 1.5h.Finally products therefrom is used boiling water and washing with alcohol respectively.
(4) hard polyurethane foam is prepared with functionalization graphene:
By 25.0g functionalization graphene, 25.0g polyether glycol, 20.0gPEG-400,3.0g deionized water and 2.0g silicone oil in stirred at ambient temperature 24h, add 1.0gDMP-30,0.1g stannous octoate after having stirred, high-speed stirring 5min.Add high-speed stirring 10s after 142.0gMDI, mixed solution is poured in chunk and foams.After having foamed, at 80 DEG C and 120 DEG C, solidify 4h respectively.Sampling and testing after 24h.
Gained foam density is 49Kg/m
3, its compressive strength is 1609kPa, and rate of closed hole is 87%.Vertical combustion grade is V-0 level (UL-94), and limiting oxygen index(LOI) is 30.8%, and thermal conductivity is 0.034W/ (mK).
Embodiment 11
(1) Hummer legal system is for Graphene
By 10g expanded graphite and 5g nitric acid and 230ml sulfuric acid as in there-necked flask, slowly add 30g potassium permanganate under ice bath mechanical stirring, keep temperature to be no more than 9 DEG C, remove water-bath, react 4h at 35 DEG C, reactant 460ml water is slowly diluted, temperature rises to about 98 DEG C, keeps 1h.After continuing dilution with 1400ml water, with 3% hydrogen peroxide processing reaction thing to glassy yellow, suction filtration, washing, use 50ml hydrazine hydrate reduction, suction filtration, washing, drying.
(2) grafts is prepared
By 30.6g phosphorus oxychloride as in there-necked flask, in 30min, slowly instill 17.6g1-amylalcohol.Be warming up to that solution is micro-to boil, after continuing reaction 5h, steam solvent acetonitrile, continue reaction 7h, unreacted reactant is steamed.Product is added in 100ml hexanaphthene and stir.Slowly be added dropwise in 2h after the dilution of 14.8g R-GLYCIDOL hexanaphthene is dissolved, be added dropwise to complete rear slow temperature rising reflux reaction 4h.
(3) grafts is grafted on Graphene
5.0g graphene dispersion slowly instilled under room temperature in grafts/acetone soln after 200ml hexanaphthene, steam hexanaphthene after backflow 3h, continuing to heat up keeps micro-the boiling of solution to steam other materials unreacted.React complete and be cooled to 80 DEG C, in reaction system, slowly add 6.2g glycerol, continue reaction 1.5h.Finally products therefrom is used boiling water and washing with alcohol respectively.
(4) hard polyurethane foam is prepared with functionalization graphene:
By 30.0g functionalization graphene, 25.0g polyether glycol, 20.0gPEG-400,3.0g deionized water and 2.0g silicone oil in stirred at ambient temperature 24h, add 1.0gDMP-30,0.1g stannous octoate after having stirred, high-speed stirring 5min.Add high-speed stirring 10s after 177.0gMDI, mixed solution is poured in chunk and foams.After having foamed, at 80 DEG C and 120 DEG C, solidify 4h respectively.Sampling and testing after 24h.
Gained foam density is 48Kg/m
3, its compressive strength is 1671kPa, and rate of closed hole is 88%.Vertical combustion grade is V-0 level (UL-94), and limiting oxygen index(LOI) is 31.6%, and thermal conductivity is 0.032W/ (mK).
Embodiment 12
(1) Hummer legal system is for Graphene
By 10g expanded graphite and 5g nitric acid and 230ml sulfuric acid as in there-necked flask, slowly add 30g potassium permanganate under ice bath mechanical stirring, keep temperature to be no more than 9 DEG C, remove water-bath, react 4h at 35 DEG C, reactant 460ml water is slowly diluted, temperature rises to about 98 DEG C, keeps 1h.After continuing dilution with 1400ml water, with 3% hydrogen peroxide processing reaction thing to glassy yellow, suction filtration, washing, use 50ml hydrazine hydrate reduction, suction filtration, washing, drying.
(2) grafts is prepared
By 30.6g phosphorus oxychloride as in there-necked flask, in 30min, slowly instill 17.2g cyclopentanol.Be warming up to that solution is micro-to boil, after continuing reaction 3.5h, steam solvent hexanaphthene, continue reaction 8h, unreacted reactant is steamed.Product is added in 100ml hexanaphthene and stir.Slowly be added dropwise in 2h after the dilution of 14.8g R-GLYCIDOL hexanaphthene is dissolved, be added dropwise to complete rear slow temperature rising reflux reaction 5h.
(3) grafts is grafted on Graphene
5.0g graphene dispersion slowly instilled under room temperature in grafts/acetone soln after 200ml hexanaphthene, steam hexanaphthene after backflow 4.5h, continuing to heat up keeps micro-the boiling of solution to steam other materials unreacted.React complete and be cooled to 80 DEG C, in reaction system, slowly add 3.9g ethylene glycol, continue reaction 2h.Finally products therefrom is used boiling water and washing with alcohol respectively.
(4) hard polyurethane foam is prepared with functionalization graphene:
By 35.0g functionalization graphene, 25.0g polyether glycol, 20.0gPEG-400,3.0g deionized water and 2.0g silicone oil in stirred at ambient temperature 24h, add 1.0gDMP-30,0.1g stannous octoate after having stirred, high-speed stirring 5min.Add high-speed stirring 10s after 177.0gMDI, mixed solution is poured in chunk and foams.After having foamed, at 80 DEG C and 120 DEG C, solidify 4h respectively.Sampling and testing after 24h.
Gained foam density is 55Kg/m
3, its compressive strength is 1675kPa, and rate of closed hole is 84%.Vertical combustion grade is V-0 level (UL-94), and limiting oxygen index(LOI) is 34.0%, and thermal conductivity is 0.028W/ (mK).
Embodiment 13
(1) Hummer legal system is for Graphene
By 10g expanded graphite and 5g nitric acid and 230ml sulfuric acid as in there-necked flask, slowly add 30g potassium permanganate under ice bath mechanical stirring, keep temperature to be no more than 9 DEG C, remove water-bath, react 4h at 35 DEG C, reactant 460ml water is slowly diluted, temperature rises to about 98 DEG C, keeps 1h.After continuing dilution with 1400ml water, with 3% hydrogen peroxide processing reaction thing to glassy yellow, suction filtration, washing, use 50ml hydrazine hydrate reduction, suction filtration, washing, drying.
(2) grafts is prepared
By 15.3g phosphorus oxychloride as in there-necked flask, in 30min, slowly instill 10.2g3-methyl-2-amylalcohol.Be warming up to that solution is micro-to boil, after continuing reaction 4h, steam solvent toluene, continue reaction 8h, unreacted reactant is steamed.Product is added in 100ml dimethylbenzene and stir.Slowly be added dropwise in 2h after the dilution of 7.4g R-GLYCIDOL dimethylbenzene is dissolved, be added dropwise to complete rear slow temperature rising reflux reaction 5h.
(3) grafts is grafted on Graphene
3.4g graphene dispersion slowly instilled under room temperature in grafts/xylene solution after 200ml dimethylbenzene, steam dimethylbenzene after backflow 5h, continuing to heat up keeps micro-the boiling of solution to steam other materials unreacted.React complete and be cooled to 80 DEG C, in reaction system, slowly add 3.9g ethylene glycol, continue reaction 2h.Finally products therefrom is used boiling water and washing with alcohol respectively.
(4) functionalization graphene is utilized to prepare hard polyurethane foam:
By 40.0g functionalization graphene, 25.0g polyether glycol, 20.0gPEG-400,3.0g deionized water and 2.0g silicone oil in stirred at ambient temperature 24h, add 1.0gDMP-30,0.1g stannous octoate after having stirred, high-speed stirring 5min.Add high-speed stirring 10s after 177.0gMDI, mixed solution is poured in chunk and foams.After having foamed, at 80 DEG C and 120 DEG C, solidify 4h respectively.Sampling and testing after 24h.
Gained foam density is 53Kg/m
3, its compressive strength is 1730kPa, and rate of closed hole is 86%.Vertical combustion grade is V-0 level (UL-94), and limiting oxygen index(LOI) is 34.0%, and thermal conductivity is 0.030W/ (mK).
Embodiment 14
(1) Hummer legal system is for Graphene
By 10g expanded graphite and 5g nitric acid and 230ml sulfuric acid as in there-necked flask, slowly add 30g potassium permanganate under ice bath mechanical stirring, keep temperature to be no more than 9 DEG C, remove water-bath, react 4h at 35 DEG C, reactant 460ml water is slowly diluted, temperature rises to about 98 DEG C, keeps 1h.After continuing dilution with 1400ml water, with 3% hydrogen peroxide processing reaction thing to glassy yellow, suction filtration, washing, use 50ml hydrazine hydrate reduction, suction filtration, washing, drying.
(2) grafts is prepared
By 15.3g phosphorus oxychloride as in there-necked flask, in 30min, slowly instill 10.2g3-methyl-2-amylalcohol.Be warming up to that solution is micro-to boil, after continuing reaction 4h, steam solvent toluene, continue reaction 8h, unreacted reactant is steamed.Product is added in 100ml dimethylbenzene and stir.Slowly be added dropwise in 2h after the dilution of 10.2g epoxy amylalcohol dimethylbenzene is dissolved, be added dropwise to complete rear slow temperature rising reflux reaction 5h.
(3) grafts is grafted on Graphene
5.0g graphene dispersion slowly instilled under room temperature in grafts/xylene solution after 200ml dimethylbenzene, steam dimethylbenzene after backflow 5h, continuing to heat up keeps micro-the boiling of solution to steam other materials unreacted.React complete and be cooled to 80 DEG C, in reaction system, slowly add 3.9g ethylene glycol, continue reaction 2h.Finally products therefrom is used boiling water and washing with alcohol respectively.
(4) functionalization graphene is utilized to prepare hard polyurethane foam:
By 40.0g functionalization graphene, 25.0g polyether glycol, 20.0gPEG-400,3.0g deionized water and 2.0g silicone oil in stirred at ambient temperature 24h, add 1.0gDMP-30,0.1g stannous octoate after having stirred, high-speed stirring 5min.Add high-speed stirring 10s after 177.0gMDI, mixed solution is poured in chunk and foams.After having foamed, at 80 DEG C and 120 DEG C, solidify 4h respectively.Sampling and testing after 24h.
Gained foam density is 53Kg/m
3, its compressive strength is 1730kPa, and rate of closed hole is 86%.Vertical combustion grade is V-0 level (UL-94), and limiting oxygen index(LOI) is 34.0%, and thermal conductivity is 0.030W/ (mK).
Embodiment 15
(1) grafts is prepared
By 33.8g phosphorus thiochloride as in there-necked flask, in 30min, slowly instill 6.4g methyl alcohol.Be warming up to that solution is micro-to boil, after continuing reaction 4h, steam solvent chloroform, continue reaction 3h, unreacted reactant is steamed.Product is added in 100ml acetone and stir.Slowly be added dropwise in 1h after 14.8g R-GLYCIDOL acetone diluted is dissolved, be added dropwise to complete rear slow temperature rising reflux reaction 4h.
(2) grafts is grafted on commercially available Graphene
5.0g graphene dispersion slowly instilled under room temperature in grafts/acetone soln after 200ml acetone, steam acetone after backflow 4h, continuing to heat up keeps micro-the boiling of solution to steam other materials unreacted.React complete and be cooled to 80 DEG C, in reaction system, slowly add 9.2g ethanol, continue reaction 1h.Finally products therefrom is used boiling water and washing with alcohol respectively.
(3) hard polyurethane foam is prepared with functionalization graphene:
By 20.0g functionalization graphene, 25.0g polyether glycol, 20.0gPEG-400,3.0g deionized water and 2.0g silicone oil in stirred at ambient temperature 24h, add 1.0gDMP-30,0.1g stannous octoate after having stirred, high-speed stirring 5min.Add high-speed stirring 10s after 142.0gMDI, mixed solution is poured in chunk and foams.After having foamed, at 80 DEG C and 120 DEG C, solidify 4h respectively.Sampling and testing after 24h.
Gained foam density is 44Kg/m
3, its compressive strength is 1530kPa, and rate of closed hole is 88%.Vertical combustion grade is V-0 level (UL-94), and limiting oxygen index(LOI) is 31.0%, and thermal conductivity is 0.030W/ (mK).
Comparative example 1
By 25.0g polyether glycol, 20.0gPEG-400,3.0g deionized water and 2.0g silicone oil in stirred at ambient temperature 24h, add 1.0gDMP-30,0.1g stannous octoate after having stirred, high-speed stirring 5min.Add high-speed stirring 10s after 106.5gMDI, mixed solution is poured in chunk and foams.After having foamed, at 80 DEG C and 120 DEG C, solidify 4h respectively.Sampling and testing after 24h.
Gained foam density is 37Kg/m
3, its compressive strength is 526kPa, and rate of closed hole is 91%.The burning of vertical combustion test Flame is to fixture, and stepless, limiting oxygen index(LOI) is 19.2%, and thermal conductivity is 0.026W/ (mK).
Comparative example 2
By 25.0g polyether glycol, 20.0gPEG-400,3.0g deionized water and 2.0g silicone oil in stirred at ambient temperature 24h, add 1.0gDMP-30,0.1g stannous octoate after having stirred, high-speed stirring 5min.Add high-speed stirring 10s after 142.0gMDI, mixed solution is poured in chunk and foams.After having foamed, at 80 DEG C and 120 DEG C, solidify 4h respectively.Sampling and testing after 24h.
Gained foam density is 40Kg/m
3, its compressive strength is 588kPa, and rate of closed hole is 90%.The burning of vertical combustion test Flame is to fixture, and stepless, limiting oxygen index(LOI) is 19.4%, and thermal conductivity is 0.028W/ (mK).
Comparative example 3
By 25.0g polyether glycol, 20.0gPEG-400,3.0g deionized water and 2.0g silicone oil in stirred at ambient temperature 24h, add 1.0gDMP-30,0.1g stannous octoate after having stirred, high-speed stirring 5min.Add high-speed stirring 10s after 177.0gMDI, mixed solution is poured in chunk and foams.After having foamed, at 80 DEG C and 120 DEG C, solidify 4h respectively.Sampling and testing after 24h.
Gained foam density is 44Kg/m
3, its compressive strength is 653kPa, and rate of closed hole is 90%.The burning of vertical combustion test Flame is to fixture, and stepless, limiting oxygen index(LOI) is 19.4%, and thermal conductivity is 0.028W/ (mK).
Can be found by contrast, the fire-retardant full water foamed cross-linked type polyurethane of the functionalization graphene prepared of embodiment hard bubbles compared with the conventional polyurethanes prepared with comparative example hard bubbles, the flame retardant propertiess such as vertical combustion, limiting oxygen index(LOI) and high-temperature residual quality have all had remarkable lifting, and when variable density is little, compressive strength also promotes obviously.Thermal constant test shows, the heat insulation-type of modified hard polyurethane foam still can remain in same level with unmodified hard polyurethane foam.
Claims (10)
1. a functionalization graphene, is characterized in that the general structure of this Graphene is as follows:
In formula, X is epoxies group, and Y is Graphene, and Z is C
1-C
6alkyl in any one.
2. functionalization graphene according to claim 1, is characterized in that the epoxies group described in this graphene-structured is any one in epoxypropyl, epoxybutyl, epoxypentyl or epoxyhexyl.
3. prepare a method for functionalization graphene described in claim 1, the concrete technology step of this preparation method and condition as follows:
1) three-functionality-degree phosphoryl chloride or pyrophosphoryl chloride are dissolved in organic solvent, stir the identical equivalent C of lower instillation in ice-water bath
1-C
6alcohols material, reaction 3 ~ 5h after heat up removing organic solvent, continue to be warming up to the micro-lower reaction 3 ~ 8h that boils of solution, underpressure distillation, collects monosubstituted phosphoryl chloride cut.
2) monosubstituted for gained phosphoryl chloride or two commercial functionality phosphoryl chlorides are added in organic solvent stir, then the epoxy types of the equimolar amount dissolved in organic solvent is slowly dropwised, continue slowly to heat up and back flow reaction 2 ~ 5h, obtained epoxy group(ing) phosphoryl chloride solution;
3) be uniformly dispersed in dispersion agent by Graphene and slowly instill in epoxy group(ing) phosphoryl chloride solution, the addition of its epoxy group phosphoryl chloride is 1 ~ 2mol/25g Graphene.Steam except dispersion agent after temperature rising reflux reaction 3 ~ 5h, be cooled to 80 ~ 90 DEG C, in reaction system, slowly add C
1-C
6hydroxy kind material, its add-on is hydroxyl/chlorine atomic molar gauge at least 1 times, continues reaction 1 ~ 2h, finally by products therefrom washing, drying.
4. the method preparing functionalization graphene according to claim 3, epoxy types used in this preparation method is any one in R-GLYCIDOL, epoxy butanols, epoxy amylalcohol or epoxy hexanol.
5. the method preparing functionalization graphene according to claim 3 or 4, three-functionality-degree phosphoryl chloride used in this preparation method is phosphorus oxychloride or phosphorus thiochloride; In this preparation method, commercial two functionality phosphoryl chlorides used are any one in diphenylphosphoryl dichloro, methyl acid phosphate dichloro methyl esters, chloromethyl-methyl-phosphoryl chloride, 2-rubigan phosphoric acid ester.
6. the method preparing functionalization graphene according to claim 3 or 4, the C added in reaction system in this preparation method
1-C
6hydroxy kind material is for press chlorine atomic molar gauge 1 ~ 1.5 times of equivalent.
7. the method preparing functionalization graphene according to claim 5, the C added in reaction system in this preparation method
1-C
6hydroxy kind material is for press chlorine atomic molar gauge 1 ~ 1.5 times of equivalent.
8. one kind with the flame retardant cross-linked type polyurethane rigid foam of functionalization graphene according to claim 1, this cross-linked type polyurethane rigid foam is by polyisocyanates, polyvalent alcohol, catalyzer, whipping agent conveniently proportioning, conventional mix and blend one step foaming is adopted to make, it is characterized in that isocyanate index used is 1.5 ~ 2.5, in polyol quality part, the addition of functionalization graphene fire retardant is 10 ~ 160 parts, and gained foam density is 36-55kg/m
3, its compressive strength is 1232-1730kPa, and rate of closed hole is 84-92%, and vertical combustion grade is V-0 level, and limiting oxygen index(LOI) is 23.4-34.5%, and thermal conductivity is 0.028-0.035W/ (mK).
9. the flame retardant cross-linked type polyurethane rigid foam of functionalization graphene according to claim 8, it is characterized in that this cross-linking type is when in above hard polyurethane foam, isocyanate index is 2.0 ~ 2.5, in polyol quality part, the addition of functionalization graphene fire retardant is 40 ~ 160 parts, and gained foam density is 36-55kg/m
3, its compressive strength is 1302-1730kPa, and rate of closed hole is 84-92%, and vertical combustion (UL-94) grade is V-0 level, and limiting oxygen index(LOI) is 25.4-34.5%, and thermal conductivity is 0.028-0.035W/ (mK).
10. the flame retardant cross-linked type polyurethane rigid foam of functionalization graphene according to claim 8, it is characterized in that the isocyanate index of this cross-linked type polyurethane rigid foam is 2.0 ~ 2.5, in polyol quality part, the addition of functionalization graphene fire retardant is 80 ~ 160 parts, and gained foam density is 44-55kg/m
3, its compressive strength is 1487-1730kPa, and rate of closed hole is 84-91%, and vertical combustion (UL-94) grade is V-0 level, and limiting oxygen index(LOI) is 30.2-34.5%, and thermal conductivity is 0.028-0.035W/ (mK).
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