CN105237808A - Intercalated composite material, preparation method thereof, and polymer nano-composite material - Google Patents
Intercalated composite material, preparation method thereof, and polymer nano-composite material Download PDFInfo
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- CN105237808A CN105237808A CN201510644334.7A CN201510644334A CN105237808A CN 105237808 A CN105237808 A CN 105237808A CN 201510644334 A CN201510644334 A CN 201510644334A CN 105237808 A CN105237808 A CN 105237808A
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Abstract
The invention provides an intercalated composite material, a preparation method thereof, and a polymer nano-composite material. The intercalated composite material comprises an inorganic layer board and interlayer ions; the interlayer ions and the inorganic layer board are different in charges; the interlayer ions are formed from an anion fluorocarbon surfactant or a cationic fluorocarbon surfactant; and the inorganic layer board is made of an inorganic layered material. Compared with the prior art, the preparation method adopting the fluorocarbon surfactants with high surface activity, hydrophobicity, chemical inertia and heat stability to form the interlayer ions makes the interlaced composite material have high heat resistance, chemical stability resistance and unique interface characteristics; the fluorocarbon surfactants can disperse nanometer lamellae in a polymer matrix in a high concentration manner, so high content nanometer hybridization of the polymer nanocomposite material is realized; and the fluorocarbon surfactants have high heatproof temperature, so improvement of the dielectric properties, the corona resistance and the breakdown resistance of the polymer nanocomposite material is facilitated.
Description
Technical field
The invention belongs to technical field of composite materials, particularly relate to intercalation composite material and preparation method thereof, polymer nanocomposites.
Background technology
Nano composite material refers to that dispersed phase size is the matrix material of nano level (1 ~ 100nm).Nanodispersed phase has the features such as unique surface effects, volume effect, quantum size effect and macro quanta tunnel effect, this makes polymer based nanocomposites present many characteristics being different from conventional composites materials, as synchronous toughen and intensify effect, high strength, high-modulus, Inverter fed motor, resistance toly to puncture, the characteristic such as opto-electronic conversion, efficient catalytic and barrier property.Thus, polymer based nanocomposites is an importance of nano composite material research field, causes the extensive concern of people.
Nanodispersed phase in nano composite material, can be divided into nanoparticle from pattern, nanometer rod and nanoscale twins.Nanoscale twins has the highest specific surface area, only need little filler, matrix material can be made to have quite high intensity, Young's modulus, toughness, excellent Inverter fed motor, resistance toly to puncture, thermostability, dimensional stability and barrier property, this is because nanoscale twins can planar orientation, play enhancement in the two-dimensional direction, therefore stratified material/polymer nanocomposites becomes one of focus studied in novel material and field of functional materials in recent years.
According to nanoscale twins charged state, two-dimensional layer material can be divided into positively charged ion and negatively charged ion and neutral stratified material.Cationic layered materials laminate is electronegative, and interlayer is balance cation, as polynite, saponite, titanate, niobate and laminated metal sulfide etc.Anion laminated material laminate is positively charged, and interlayer is balance anion, as layered double hydroxides such as hydrotalcites.The interlayer ion of cationic layered materials and anion laminated material is all easy to carry out intercalation permutoid reaction with organic ion, increase interlamellar spacing, simultaneously stratified material becomes lipophilicity from wetting ability, reduces the surface energy of stratified material, improves the consistency of itself and polymeric matrix and monomer.And organic ion can with various functional group, these functional groups can with interpolymer interaction, thus improve the cementability between inorganics and polymeric matrix.The stratified material modified of this organic intercalation is also peelable be the two-dimensional nano lamella of high-specific surface area, is scattered in polymeric matrix, structure nano composite material.The performance of stratified material/polymer composites depends on the stripping degree of scatter of nanoscale twins to a great extent.
Conventional organic ion intercalator is various tensio-active agents.The intercalator that cationic layered materials is conventional is cats product, as aliphatic alkyl amine salt, aliphatic alkyl (benzyl) quaternary ammonium salt etc.The intercalator that anion laminated material is conventional is anion surfactant, as aliphatic carboxylic acid (straight-chain dicarboxylic acid and monocarboxylic acid etc.), aromatic carboxylic acid and organic sulfonic acid or vitriol (sodium lauryl sulphate, Sodium dodecylbenzene sulfonate etc.).But these organic intercalation agent thermostabilitys are lower, easily decompose in the high temperature process and application process of nano composite material.
Heat-proof macromolecule material is a kind of special engineered material of heat-resisting, high-strength, high-ductility, low-k.It is widely applied in Aeronautics and Astronautics, microelectronics, photoelectron, information displaying and electric insulation etc.If stratified material and heat-proof macromolecule material high efficiency composition, not only can reduce the thermal expansivity of heat-proof macromolecule material, improve its moulding processability, its intensity, modulus, thermotolerance can also be significantly improved, improve dielectric properties, Inverter fed motor, resistance toly to puncture and water absorbability etc.
But at present in stratified material/polymer nanocomposites, the intercalator mainly hc-surfactant of stratified material.Intercalation stratified material prepared by this kind of hc-surfactant and heat-proof macromolecule material (as polyimide, aromatic polyamide, polyetherketone, polyethersulfone and polybenzimidazole etc.) compound tense, the subject matter existed is: (1) is at dipolar aprotic solvent (solvent N as conventional in polyimide, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, N-cyclohexyl pyrrolidone) in stripping dispersion concentration low, affect the dispersion situation of nanoscale twins in polymeric matrix, reduce the performance of matrix material; (2) when with polarity polymer melting high-temperature blending, easily degrade, easily reunite, be difficult to peel off dispersion; (3) thermotolerance is low, as the heat-stable material polyimide etc., the temperature of its processing and use is all more than 300 DEG C, hc-surfactant can decompose at such temperatures, between the interface being difficult to be deposited in polymkeric substance and nanoscale twins, affect the intercalation to stratified material and stripping dispersion, and then affect the performance of matrix material.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide good intercalation composite material of a kind of thermotolerance and preparation method thereof, polymer nanocomposites.
The invention provides a kind of intercalation composite material, comprise inorganic laminate and interlayer ion; Described interlayer ion is charge contrary with inorganic laminate; Described interlayer ion is formed by negatively charged ion fluorocarbon surfactant or cation fluorine carbon surface active agent; Described inorganic laminate is formed by inorganic lamellar material.
Preferably, the positive charge inorganic lamellar material in described inorganic lamellar material is double-metal hydroxide; Negative charge inorganic lamellar material in described inorganic lamellar material is silicate, titanate, niobate or metallic sulfide.
Preferably, described negatively charged ion fluorocarbon surfactant is one or more in fluoroalkyl carboxylic acids's salt, fluoroalkyl sulfonic acid salt, fluoroalkyl phosphate and fluoro-alkyl vitriol; Described cation fluorine carbon surface active agent is one or more in fluoro-alkyl amine, fluoro-alkyl imidazoles, fluoro-alkyl pyridine, fluoro-alkyl morpholine and fluoro-alkyl quaternary alkylphosphonium salt.
Preferably, described cation fluorine carbon surface active agent is selected from one or more in structure shown in formula (I) and formula (II):
Wherein, described R
1, R
2, R
3, R
4, R
5with R
6be methyl, ethyl, propyl group, butyl or sec.-propyl independently of one another; Described X is halogen atom; Described-R
7-be formula (1) and the one in formula (2) structure:
Wherein, described m
1with m
2be independently the integer of 1 ~ 3 separately;
Described R
fwith R
f' be one in formula (3) or formula (4) structure independently of one another:
-C
nF
2n+1(3)；
Wherein, described n and n ' is the integer of 1 ~ 20 independently of one another.
Preferably, described negatively charged ion fluorocarbon surfactant is selected from one or more in structure shown in formula (III) and formula (IV):
Wherein, described R
f1with R
f2be the one in formula (3) or formula (4) structure independently of one another:
-C
nF
2n+1(3)；
Wherein, described n and n ' is the integer of 1 ~ 20 independently of one another; Described M
1with M
2be metal that valency is monovalence or divalence independently of one another.
Present invention also offers a kind of preparation method of intercalation composite material, comprising:
Inorganic lamellar material and fluorocarbon surfactant are reacted in water, obtains intercalation composite material; Described fluorocarbon surfactant is negatively charged ion fluorocarbon surfactant or cation fluorine carbon surface active agent; Described inorganic lamellar material electrically charged charge contrary with fluorocarbon surfactant.
Preferably, the mass ratio of described inorganic lamellar material and fluorocarbon surfactant is 1:(0.5 ~ 20).
Preferably, the total mass of described inorganic lamellar material and fluorocarbon surfactant is 0.1% ~ 10% of quality.
Present invention also offers a kind of polymer nanocomposites, be composited by intercalation composite material and polymkeric substance.
Preferably, the mass ratio of described intercalation composite material and polymkeric substance is (0.1 ~ 50): 100.
The invention provides a kind of intercalation composite material and preparation method thereof, polymer nanocomposites, this intercalation composite material comprises inorganic laminate and interlayer ion; Described interlayer ion is charge contrary with inorganic laminate; Described interlayer ion is formed by negatively charged ion fluorocarbon surfactant or cation fluorine carbon surface active agent; Described inorganic laminate is formed by inorganic lamellar material.Compared with prior art, the present invention adopts fluorocarbon surfactant to form interlayer ion, fluorocarbon surfactant has higher surfactivity, hydrophobicity, unreactiveness and thermostability, makes intercalation composite material have the interfacial characteristics of higher thermotolerance, chemical-resistant stability and uniqueness; Fluorocarbon surfactant and dipolar aprotic solvent or polar polymer have good affinity, can the dispersing nanometer lamella of greater concn in polymeric matrix, thus make polymer nanocomposites realize the nano hybridization of high-content; Fluorocarbon surfactant has higher heat resisting temperature, all the time be present between nanoscale twins and polymer interface in the high temperature process and application process of polymkeric substance, " positive and negative charge to " between lamella and tensio-active agent contributes to improving the dielectric properties of polymer nanocomposites, Inverter fed motor and resistance to sparking energy.
Experimental result shows, the specific inductivity of polymer nanocomposites prepared by the present invention can reach 3.1, and dielectric loss can reach 0.01.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum of the fluorine carbon intercalation Mg-Al layered doubled hydroxide obtained in the embodiment of the present invention 1;
Fig. 2 is the X ray diffracting spectrum of the fluorine carbon intercalation Mg-Al layered doubled hydroxide obtained in the embodiment of the present invention 2;
Fig. 3 is the X ray diffracting spectrum of the fluorine carbon intercalated montmorillonite obtained in the embodiment of the present invention 3;
Fig. 4 is the X ray diffracting spectrum of the fluorine carbon intercalated montmorillonite obtained in the embodiment of the present invention 4.
Embodiment
Below in conjunction with the accompanying drawing of the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The invention provides a kind of intercalation composite material, comprise inorganic laminate and interlayer ion; Described interlayer ion is charge contrary with inorganic laminate; Described interlayer ion is formed by negatively charged ion fluorocarbon surfactant or cation fluorine carbon surface active agent; Described inorganic laminate is formed by inorganic lamellar material.
Wherein, described inorganic lamellar material is positive charge inorganic lamellar material or negative charge inorganic lamellar material; Positive charge inorganic lamellar material is positively charged inorganic lamellar material well known to those skilled in the art, and there is no special restriction, the present invention is preferably double-metal hydroxide, is more preferably Ripon; Described negative charge inorganic lamellar material is electronegative inorganic lamellar material well known to those skilled in the art, there is no special restriction, and the present invention is preferably silicate, titanate, niobate or metallic sulfide, is more preferably silicate.
Described negatively charged ion fluorocarbon surfactant is negatively charged ion fluorocarbon surfactant well known to those skilled in the art, there is no special restriction, the present invention be preferably in fluoroalkyl carboxylic acids's salt, fluoroalkyl sulfonic acid salt, fluoroalkyl phosphate and fluoro-alkyl vitriol one or more, be more preferably in structure shown in formula (III) and formula (IV) one or more, then be preferably formula (III) and the one in structure shown in formula (IV):
Wherein, described R
f1with R
f2be the one in formula (3) or formula (4) structure independently of one another:
-C
nF
2n+1(3)；
Wherein, described n and n ' is the integer of 1 ~ 20 independently of one another, is more preferably the integer of 2 ~ 10; Described M
1with M
2be the metal that valency is monovalence or divalence independently of one another, be more preferably sodium and/or potassium.
Described cation fluorine carbon surface active agent is cation fluorine carbon surface active agent well known to those skilled in the art, there is no special restriction, be preferably in fluoro-alkyl amine, fluoro-alkyl imidazoles, fluoro-alkyl pyridine, fluoro-alkyl morpholine and fluoro-alkyl quaternary alkylphosphonium salt in the present invention one or more, be more preferably in structure shown in formula (I) and formula (II) one or more, then be preferably formula (I) and the one in structure shown in formula (II):
Wherein, described R
1, R
2, R
3, R
4, R
5with R
6be the alkyl of C1 ~ C30 independently of one another, be preferably the alkyl of C1 ~ C20, be more preferably the alkyl of C1 ~ C10, then be preferably the alkyl of C1 ~ C5, most preferably be methyl, ethyl, propyl group, butyl or sec.-propyl; Described X is halogen atom, is preferably Cl, Br or I; Described-R
7-be formula (1) and the one in formula (2) structure:
Wherein, described m
1with m
2be independently the integer of 1 ~ 10 separately, be preferably the integer of 1 ~ 5, be more preferably the integer of 1 ~ 3;
Described R
fwith R
f' be one in formula (3) or formula (4) structure independently of one another:
-C
nF
2n+1(3)；
Wherein, described n and n ' is the integer of 1 ~ 20 independently of one another, is preferably the integer of 2 ~ 10.
The present invention adopts fluorocarbon surfactant to form interlayer ion, fluorocarbon surfactant has higher surfactivity, hydrophobicity, unreactiveness and thermostability, makes intercalation composite material have the interfacial characteristics of higher thermotolerance, chemical-resistant stability and uniqueness.
Present invention also offers a kind of preparation method of above-mentioned intercalation composite material, comprising: inorganic lamellar material and fluorocarbon surfactant are reacted in water, obtains intercalation composite material; Described inorganic lamellar material is positive charge stratified material or negative charge inorganic lamellar material; Described fluorocarbon surfactant is negatively charged ion fluorocarbon surfactant or cation fluorine carbon surface active agent.
Wherein, the restriction that the present invention is not special to the source of all raw materials, for commercially available.Described inorganic lamellar material and fluorocarbon surfactant are all same as above, do not repeat them here.
Inorganic lamellar material and fluorocarbon surfactant are reacted in water, the mass ratio of wherein said inorganic lamellar material and fluorocarbon surfactant is preferably 1:(0.5 ~ 20), be more preferably 1:(1 ~ 15), be more preferably 1:(1 ~ 10), be preferably 1:(1 ~ 5 again), most preferably be 1:(1 ~ 3); The total mass of described inorganic lamellar material and fluorocarbon surfactant is preferably 0.1% ~ 10% of quality, is more preferably 0.1% ~ 5%, then is preferably 0.1% ~ 3%, most preferably is 0.4% ~ 1%; The temperature of described reaction is preferably 10 DEG C ~ 100 DEG C, is more preferably 20 DEG C ~ 100 DEG C, then is preferably 30 DEG C ~ 90 DEG C, most preferably is 40 DEG C ~ 90 DEG C; The time of described reaction is preferably 5 ~ 48h, is more preferably 5 ~ 30h, then is preferably 8 ~ 30h, most preferably is 8 ~ 24h.
After reaction, preferably filter, dry, obtain intercalation composite material.The temperature of described drying is preferably 50 DEG C ~ 150 DEG C, is more preferably 50 DEG C ~ 100 DEG C, then is preferably 60 DEG C ~ 100 DEG C.
Present invention also offers a kind of polymer nanocomposites, be composited by above-mentioned intercalation composite material and polymkeric substance.
Wherein, the kind of described polymkeric substance is polymkeric substance well known to those skilled in the art, there is no special restriction, it can be aromatic ring polymkeric substance, one or more of heterocycle polymer and ladder polymer, polyphenyl is preferably in the present invention, polyphenylene ethyl, polyarylether, polyarylsulphone, polyaryletherketone, polyarylester, aromatic polyamide, polyimide, one or more in polybenzimidazole and poly quinoline, be more preferably polyphenyl, polyphenylene ethyl, polyarylether, polyarylsulphone, polyaryletherketone, polyarylester, aromatic polyamide, polyimide, one in polybenzimidazole and poly quinoline, be preferably polyimide again, polybenzimidazole or poly quinoline, most preferably be polyimide.
The mass ratio of described intercalation composite material and polymkeric substance is preferably (0.1 ~ 50): 100, is more preferably (0.4 ~ 20): 100, then be preferably (1 ~ 20): 100, most preferably be (1 ~ 10): 100.
In the present invention, the method for described compound is method well known to those skilled in the art, there is no special restriction, preferably adopts following methods to carry out compound in the present invention:
(1) in-situ polymerization: mixed with the polymerization single polymerization monomer of polymkeric substance by intercalation composite material, carries out polyreaction, in the polymerization of intercalation composite material interlayer, obtains polymer nanocomposites.
(2) solution intercalation: by intercalation composite material and polymer dispersed in solvent, polymkeric substance is inserted into the interlayer of intercalation composite material in the solution, obtains polymer nanocomposites after solvent evaporates.
(3) melt intercalation: by the polymer blending of intercalation composite material and molten state, obtain polymer nanocomposites.
The present invention for the first in-situ polymerization, polymkeric substance for polyimide, the process of synthetic polymer nano composite material is as follows: intercalation composite material, polymerization single polymerization monomer diamines are mixed with polymerization single polymerization monomer dianhydride, carry out polyreaction in a solvent, obtain polymer fluid; Then polymer fluid is carried out hot imidization process, obtain polymer nanocomposites.
Wherein, described polymerization single polymerization monomer diamines is the diamines that skilled person knows, and there is no special restriction, and the present invention's its structure preferred is as shown in formula V:
H
2N-R
8-NH
2(V)；
Wherein, described-R
8-be the one in following structure:
Described polymerization single polymerization monomer dianhydride is dianhydride well known to those skilled in the art, there is no special restriction, and the present invention is preferably its structure such as formula shown in (VI):
Wherein, described R
9one in following structure:
The quality of described polymerization single polymerization monomer diamines and polymerization single polymerization monomer dianhydride and be preferably 100:(0.1 ~ 50 with the mass ratio of intercalation composite material), be more preferably 100:(0.4 ~ 20), be preferably 100:(1 ~ 20 again), most preferably be 100:(1 ~ 10); Described polymerization single polymerization monomer dianhydride is 1:(0.95 ~ 1.05 with the ratio of the amount of substance of polymerization single polymerization monomer diamines).
Described solvent is organic solvent well known to those skilled in the art, there is no special restriction, is preferably one or more in N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide and dimethyl sulfoxide (DMSO) in the present invention.
Intercalation composite material, polymerization single polymerization monomer diamines are mixed with polymerization single polymerization monomer dianhydride, carries out polyreaction in a solvent, obtain polymer fluid; The temperature of described polyreaction is preferably 0 DEG C ~ 25 DEG C, is more preferably 5 DEG C ~ 20 DEG C, then is preferably 10 DEG C ~ 20 DEG C; The time of described polyreaction is preferably 2 ~ 24h, is more preferably 5 ~ 20h, then is preferably 5 ~ 15h.
Preferably polymer fluid is coated on substrate, carry out hot imidization process, obtain polymer nanocomposites.The temperature of described hot imidization process is preferably 50 DEG C ~ 450 DEG C, is more preferably 200 DEG C ~ 400 DEG C, then is preferably 300 DEG C ~ 400 DEG C; The time of described hot imidization process is preferably 1 ~ 15h, is more preferably 4 ~ 12h.
Fluorocarbon surfactant and dipolar aprotic solvent or polar polymer have good affinity, can the dispersing nanometer lamella of greater concn in polymeric matrix, thus make polymer nanocomposites realize the nano hybridization of high-content; Fluorocarbon surfactant has higher heat resisting temperature, all the time be present between nanoscale twins and polymer interface in the high temperature process and application process of polymkeric substance, " positive and negative charge to " between lamella and tensio-active agent contributes to improving the dielectric properties of polymer nanocomposites, Inverter fed motor and resistance to sparking energy.
In order to further illustrate the present invention, below in conjunction with embodiment, intercalation composite material provided by the invention and preparation method thereof, polymer nanocomposites are described in detail.
Reagent used in following examples is commercially available.
Embodiment 1
In reaction vessel, add 500g water successively, 1g Mg-Al layered doubled hydroxide and 3g fluorocarbon surfactant perfluoro octyl sulfonic acid potassium, 40 DEG C of reaction 24h, filter, 80 DEG C of vacuum dryings, obtain fluorine carbon intercalation Mg-Al layered doubled hydroxide.
Utilize X-ray diffraction to analyze the fluorine carbon intercalation Mg-Al layered doubled hydroxide obtained in embodiment 1, obtain its X ray diffracting spectrum, as shown in Figure 1.
Embodiment 2
In reaction vessel, add 500g water successively, 1g Mg-Al layered doubled hydroxide and 3g fluorocarbon surfactant perfluoro capryl carboxylic acid sodium, 40 DEG C of reaction 24h, filter, 80 DEG C of vacuum dryings, obtain fluorine carbon intercalation Mg-Al layered doubled hydroxide.
Utilize X-ray diffraction to analyze the fluorine carbon intercalation Mg-Al layered doubled hydroxide obtained in embodiment 2, obtain its X ray diffracting spectrum, as shown in Figure 2.
Embodiment 3
In reaction vessel, add 500g water successively, 1.0g layered silicate and 1.0g fluorocarbon surfactant perfluoro capryl trimethylammonium bromide, 90 DEG C of reaction 8h, filter, 80 DEG C of vacuum dryings, obtain fluorine carbon intercalated montmorillonite.
Utilize X-ray diffraction to analyze the fluorine carbon intercalated montmorillonite obtained in embodiment 3, obtain its X ray diffracting spectrum, as shown in Figure 3.
Embodiment 4
500g water is added successively, 1.0g layered silicate and 3.0g fluorocarbon surfactant N-(3-N, N in reaction vessel, the trimethylammonio propyl group of N-) perfluorinated octyl sulfuryl amine iodide, 90 DEG C of reaction 8h, filter, at 80 DEG C of vacuum dryings, obtain fluorine carbon intercalated montmorillonite.
Utilize X-ray diffraction to analyze the fluorine carbon intercalated montmorillonite obtained in embodiment 4, obtain its X ray diffracting spectrum, as shown in Figure 4.
Embodiment 5
42gN is added successively, N-N,N-DIMETHYLACETAMIDE, the fluorine carbon intercalation Mg-Al layered doubled hydroxide obtained in 0.042g embodiment 1 and 2.00g diaminodiphenyl oxide and 2.18g pyromellitic acid anhydride, 10 DEG C of reaction 10h in reaction vessel; Then applying being polymerized the thick liquid obtained on a glass, placing in an oven, heating, from room temperature to 350 DEG C, and keeping 1h at 350 DEG C, obtain polyimide nano-composite material.
Performance test is carried out to the polyimide nano-composite material obtained in embodiment 5, obtains the results are shown in Table 1.
Embodiment 6
42gN is added successively, the fluorine carbon intercalation Mg-Al layered doubled hydroxide obtained in dinethylformamide, 0.2g embodiment 2 and 1.08g Ursol D and 3.10g diphenyl ether tetraformic dianhydride, 10 DEG C of reaction 10h in reaction vessel; Applying being polymerized the thick liquid obtained on a glass, placing in an oven, heating, from room temperature to 400 DEG C, and keeping 1h at 400 DEG C, obtain polyimide nano-composite material.
Performance test is carried out to the polyimide nano-composite material obtained in embodiment 6, obtains the results are shown in Table 1.
Embodiment 7
The fluorine carbon intercalated montmorillonite, 1.98g diaminodiphenylmethane and the 3.22g benzophenone tetracarboxylic dianhydride that obtain in 42gN-methyl-2-pyrrolidone, 0.02g embodiment 3 is added successively, 10 DEG C of reaction 10h in reaction vessel; Applying being polymerized the thick liquid obtained on a glass, placing in an oven, heating, from room temperature to 350 DEG C, and keeping 1h at 350 DEG C, obtain polyimide nano-composite material.
Performance test is carried out to the polyimide nano-composite material obtained in embodiment 7, obtains the results are shown in Table 1.
Embodiment 8
42gN is added successively, the fluorine carbon intercalated montmorillonite, 2.92g triphen two ether diamine and the 2.18g biphenyl dianhydride that obtain in N-N,N-DIMETHYLACETAMIDE, 0.1g embodiment 4,10 DEG C of reaction 10h in reaction vessel; Applying being polymerized the thick liquid obtained on a glass, placing in an oven, heating, from room temperature to 350 DEG C, and keeping 1h at 350 DEG C, obtain polyimide nano-composite material.
Performance test is carried out to the polyimide nano-composite material obtained in embodiment 8, obtains the results are shown in Table 1.
Table 1 polyimide nano-composite material the performance test results
Claims (10)
1. an intercalation composite material, is characterized in that, comprises inorganic laminate and interlayer ion; Described interlayer ion is charge contrary with inorganic laminate; Described interlayer ion is formed by negatively charged ion fluorocarbon surfactant or cation fluorine carbon surface active agent; Described inorganic laminate is formed by inorganic lamellar material.
2. intercalation composite material according to claim 1, is characterized in that, the positive charge inorganic lamellar material in described inorganic lamellar material is double-metal hydroxide; Negative charge inorganic lamellar material in described inorganic lamellar material is silicate, titanate, niobate or metallic sulfide.
3. intercalation composite material according to claim 1, is characterized in that, described negatively charged ion fluorocarbon surfactant is one or more in fluoroalkyl carboxylic acids's salt, fluoroalkyl sulfonic acid salt, fluoroalkyl phosphate and fluoro-alkyl vitriol; Described cation fluorine carbon surface active agent is one or more in fluoro-alkyl amine, fluoro-alkyl imidazoles, fluoro-alkyl pyridine, fluoro-alkyl morpholine and fluoro-alkyl quaternary alkylphosphonium salt.
4. intercalation composite material according to claim 1, is characterized in that, described cation fluorine carbon surface active agent be selected from structure shown in formula (I) and formula (II) one or more:
Wherein, described R
1, R
2, R
3, R
4, R
5with R
6be methyl, ethyl, propyl group, butyl or sec.-propyl independently of one another; Described X is halogen atom; Described-R
7-be formula (1) and the one in formula (2) structure:
Wherein, described m
1with m
2be independently the integer of 1 ~ 3 separately;
Described R
fwith R
f' be one in formula (3) or formula (4) structure independently of one another:
-C
nF
2n+1(3)；
Wherein, described n and n ' is the integer of 1 ~ 20 independently of one another.
5. intercalation material according to claim 1, is characterized in that, described negatively charged ion fluorocarbon surfactant be selected from structure shown in formula (III) and formula (IV) one or more:
Wherein, described R
f1with R
f2be the one in formula (3) or formula (4) structure independently of one another:
-C
nF
2n+1(3)；
Wherein, described n and n ' is the integer of 1 ~ 20 independently of one another; Described M
1with M
2be metal that valency is monovalence or divalence independently of one another.
6. a preparation method for intercalation composite material, is characterized in that, comprising:
Inorganic lamellar material and fluorocarbon surfactant are reacted in water, obtains intercalation composite material; Described fluorocarbon surfactant is negatively charged ion fluorocarbon surfactant or cation fluorine carbon surface active agent; Described inorganic lamellar material electrically charged charge contrary with fluorocarbon surfactant.
7. preparation method according to claim 6, is characterized in that, the mass ratio of described inorganic lamellar material and fluorocarbon surfactant is 1:(0.5 ~ 20).
8. preparation method according to claim 6, is characterized in that, the total mass of described inorganic lamellar material and fluorocarbon surfactant is 0.1% ~ 10% of quality.
9. a polymer nanocomposites, is characterized in that, is composited by the intercalation composite material described in Claims 1 to 5 any one or the intercalation composite material prepared by claim 6 ~ 8 any one and polymkeric substance.
10. polymer nanocomposites according to claim 9, is characterized in that, the mass ratio of described intercalation composite material and polymkeric substance is (0.1 ~ 50): 100.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108676163A (en) * | 2018-06-07 | 2018-10-19 | 中国科学院长春应用化学研究所 | A kind of high-performance polyimide based composites and preparation method thereof |
| CN108752584A (en) * | 2018-06-07 | 2018-11-06 | 中国科学院长春应用化学研究所 | A kind of corona-resistant polyimide based composites and preparation method thereof |
| CN112599771A (en) * | 2020-12-15 | 2021-04-02 | 南京工业大学 | Metal-doped carbon tube/carbon sheet composite material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108676163A (en) * | 2018-06-07 | 2018-10-19 | 中国科学院长春应用化学研究所 | A kind of high-performance polyimide based composites and preparation method thereof |
| CN108752584A (en) * | 2018-06-07 | 2018-11-06 | 中国科学院长春应用化学研究所 | A kind of corona-resistant polyimide based composites and preparation method thereof |
| CN112599771A (en) * | 2020-12-15 | 2021-04-02 | 南京工业大学 | Metal-doped carbon tube/carbon sheet composite material and preparation method and application thereof |
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| CN105237808B (en) | 2018-06-01 |
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