CN104722242B - Use of star/multi-arm block copolymers for producing mixtures containing nanoparticles - Google Patents
Use of star/multi-arm block copolymers for producing mixtures containing nanoparticles Download PDFInfo
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- CN104722242B CN104722242B CN201510041999.9A CN201510041999A CN104722242B CN 104722242 B CN104722242 B CN 104722242B CN 201510041999 A CN201510041999 A CN 201510041999A CN 104722242 B CN104722242 B CN 104722242B
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- nanoparticle
- block copolymer
- oxide
- independently
- sulfide
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Classifications
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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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
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Abstract
The invention provides a mixture containing nano particles prepared by utilizing a star-shaped block copolymer and a multi-arm block copolymer, and also provides a method for preparing the mixture containing the block copolymer and the nano particles and application thereof. The star-shaped block copolymer and the multi-arm block copolymer provided by the invention can effectively disperse the nanoparticles in the organic medium, and the formed dispersion system has high stability and can be stored for a long time without sedimentation.
Description
Technical field
The present invention relates to material science, concrete, relate to star/multi-arm block copolymer use in preparation contains the mixture of nanoparticle
On the way.
Background technology
Nano material has in the products such as lubricating oil, grease, electrocondution slurry, ink, printing glue, photoresist, coating, coating and binding agent
Extensively application.Improve nano material dispersibility in these media, be expected to significantly improve the stream of the tribological property of lube oil additive, coating
Levelling, the electrocondution slurry electric conductivity etc. in electric installation.
Nanoparticle granularity is little, and surface can be high, is susceptible to reunite between particle, and nano material dispersion in organic media and being stable into is limited
Make one of its wide variety of technical problem underlying.In actual application, often conventional surfactant improves the dispersing uniformity of nano-particle, stability.
Conventional low-molecular-weight surfactant has long-chain alkyl alcohol, chain alkyl amine, chain alkyl carboxylic acid etc..Conventional polymeric surfactant has poly-
Ether surfactant, poly-polysaccharide surfactant, Comblike polymers surfactant etc..
Existing polyether surfactant includes alkyl, polyether alcohol (Alkyl Polyether Alcohols), alkyl aryl polyether alcohol (Alkylaryl
Polyether Alcohols) and polyether block copolymer (Polyether Block Copolymers).In alkyl, polyether alcohol, with the ethoxy of alkyl chain end-blocking
Base/propoxylate (Alkyl PEG/PPG Ethers) is that such represents.In alkyl aryl polyether alcohol, with the ethyoxyl/propoxyl group of octyl phenol end-blocking
Compound (Octylphenol PEG/PPG Ethers) is that such represents.In polyether block copolymer, with Polyethylene Glycol, polypropylene glycol as construction unit
The block copolymer formed is representative, including Poloxamer, Hypermer, Zephrym linear polyethers block copolymer, the branched water of Tetronic
Dissolubility polyether block copolymer.
Existing research multiplex polyether surfactant dispersing nanoparticles in polarizable medium.But, in this type of application, existing polyethers
Class surfactant can only make the nanoparticle system holding of low concentration be uniformly dispersed stable at short notice.At time lengthening (usual week age)
Or under the conditions of high-concentration nanoparticles, existing polyether surfactant can not make nano-particle keep being uniformly dispersed stable, this not
Uniformly, unstability shows particularly evident in apolar medium.This of existing polyether surfactant makes nano-particle uneven, no
Stability property, limits its range of application, particularly limits its application in coating technology and ink technology.
Thus, the most to be improved to the dispersion technology of nano material.
Summary of the invention
It is contemplated that one of technical problem solved the most to a certain extent in correlative technology field.To this end, it is an object of the present invention to
Star block copolymer, multi-arm block copolymer new application in preparation contains the mixture of nanoparticle are proposed.
The present invention is following discovery based on inventor and completes:
Generally with hydroxyl, carboxyl or other polar functional groups, thus, there is ion between polymer and nanoparticle mutual in nanoparticle surface
Active force and Van der Waals force.Specifically, the chemical bond that ionic bond is anion and cation is formed by electrostatic interaction, ionic bond has
Feature unsaturated, direction-free.When contact liq medium, ionic dispersant is covered in nanometer by the adsorption to nanoparticle
Particle surface, so that nanoparticle surface repels each other with electric charge.Inventor finds, this strategy can be efficiently used for scatter table
Wear the nanoparticle of carboxyl plasma functional group.Model moral is there is between non-bonding atom in grafted moiety on dispersant and nanoparticle surface
Hua Li, the van der Waals interaction between low-molecular-weight dispersant and nanoparticle is little, but uses polymeric dispersant then effect entirely different.Poly-
In compound chain, the quantity of construction unit is the hugest, and each construction unit is all equivalent to a little molecule.Being not pointed towards property of Van der Waals force and
Will not be saturated, therefore the Van der Waals force between polymer chain and nanoparticle is sufficiently large and make polymer can be coated with nanoparticle surface at least
A part.Inventor finds, this strategy may be used for scatter table and wears the nanoparticle of nonionic functional group.
Thus, in a first aspect of the present invention, the invention provides block copolymer purposes in preparation contains the mixture of nanoparticle, institute
Stating block copolymer is at least one in star block copolymer and multi-arm block copolymer.Inventor finds, uses the present invention to provide
Nanoparticle can be effectively scattered in organic media by block copolymer, and the dispersion stability of formation is high, it is possible to long term storage and do not occur
Sedimentation.
According to the example of the present invention, the described mixture containing nanoparticle be selected from lubricating oil, grease, electrocondution slurry, ink, printing glue,
At least one in photoresist, coating, coating and binding agent.
According to the example of the present invention, gross mass based on the described mixture containing nanoparticle, the mass fraction of described nanoparticle is
0.001%～90%.
According to the example of the present invention, the mass ratio of described block copolymer and described nanoparticle is (0.0001-10): 1.
According to the example of the present invention, described block copolymer chemistry structure is made up of A segment and B segment two class segment.
According to the example of the present invention, the polyolefin that described A segment is blocked by strand skeleton one side is formed, end-blocking official's energy used by described A segment
Group is at least one in anhydride, carboxyl, amino, hydroxyl, epoxy radicals and NCO.
According to the example of the present invention, described B segment is formed by polyethers or polyester, and terminal functional group used by described B segment is anhydride, carboxyl, ammonia
At least one in base, hydroxyl, epoxy radicals and NCO.
According to the example of the present invention, the polyolefin of described strand skeleton one side end-blocking is the polyisobutylene selected from strand skeleton one side end-blocking, divides
At least one in the polybutene of subchain skeleton one side end-blocking and the polybutadiene of strand skeleton one side end-blocking.
According to the example of the present invention, the polyisobutylene of described strand skeleton one side end-blocking is at least one following:
Wherein, each n independently be the integer more than or equal to 5.
According to the example of the present invention, the polybutene of described strand skeleton one side end-blocking is at least one following:
Wherein, m1 and m2 is each independently the integer more than or equal to 0, and m1+m2 is the integer more than or equal to 5.
According to the example of the present invention, the polybutadiene of described strand skeleton one side end-blocking is at least one following:
Wherein, i+j+k=1, each n independently be the integer more than or equal to 5.
According to the example of the present invention, described polyethers is formed by least one in polyether polyol, polyether polyamine and polyethers glycidyl ether.
According to the example of the present invention, the construction unit of described polyethers is at least one following:
Wherein, each x independently be the integer more than or equal to 1.
According to the example of the present invention, described polyester is formed by least one in PEPA, polyester polyamine and polyester glycidyl ether.
According to the example of the present invention, the construction unit of described polyester is at least one following:
Wherein, each x independently be the integer more than or equal to 1,
Each r independently be the integer of 0-18,
Each t independently be the integer of 2-12,
R1For alkyl or oxyl.
According to the example of the present invention, what described polyethers was the most independent with the topological structure of described polyester is at least one in star, multi-arm shape.
According to the example of the present invention, described polyethers the most independent with the topological structure of described polyester at least one following:
Wherein, each A1,A2,A3,…,AnIndependently be described polyethers or the repetitive of described polyester,
R2For-H or-CH2-CH3,
Z is 0 or 2；
Each Y independently be terminal functional group, and described terminal functional group is in anhydride, carboxyl, amino, hydroxyl, epoxy radicals and NCO
At least one；
Each x1, x2, x3 ..., xn represents the quantity of repetitive；Each x1, x2, x3 ..., xn independently be the integer more than or equal to 0, and meets
x1+x2+x3+,…,+xn≥1。
According to the example of the present invention, star topology, the polyethers of multi-arm shape topological structure or polyester can be formed by least one following:
According to the example of the present invention, described nanoparticle be shaped as selected from spherical, lamellar, bar-shaped or linear at least one.
According to the example of the present invention, nano spherical particle, rod-like nano particle and linear nanoparticle are selected from metal oxide particle, metal sulfur
At least one in the metallic particles that chalcogenide particles, metallic particles, the metallic particles showing oxidation processes and surface sulfide process.
According to the example of the present invention, described metal oxide particle is selected from silicon dioxide, aluminium oxide, zinc oxide, copper oxide, nickel oxide, oxygen
Change at least one in cobalt, ferrum oxide, magnesium oxide, titanium oxide, zirconium oxide, tungsten oxide and molybdenum oxide.
According to the example of the present invention, metal sulfide grain is selected from zinc sulfide, cadmium sulfide, cinnabar, iron sulfide, cobalt sulfide, nickel sulfide,
At least one in tungsten sulfide and molybdenum sulfide.
According to the example of the present invention, described metallic particles is at least one in cobalt, ferrum, magnesium, aluminum, titanium, zirconium, silver, gold or its alloy.
According to the example of the present invention, flake nano is selected from layered double hydroxide, clay, layered metal phosphates, laminated metal tungsten
Hydrochlorate, laminated metal sulfide, graphite oxide, at least one in graphene oxide, and derivant.
In the second aspect of invention, the present invention provides the preparation method containing nanoparticle mixture.According to the example of the present invention, the method includes:
Block copolymer, nanoparticle and disperse medium are mixed, in order to obtain the described mixture containing nanoparticle.Inventor finds, utilizes this
The method of invention can fast and effeciently prepare the mixture containing nanoparticle that dispersion stabilization is good, and simple to operate, convenient and swift,
With low cost, it is easy to accomplish large-scale production.
In the third aspect of invention, the invention provides the mixture containing nanoparticle.According to the example of the present invention, described containing nanoparticle
Mixture utilize foregoing method to prepare.Inventor finds, the mixture dispersion stabilization containing nanoparticle of the present invention is preferable,
Long period can store and sedimentation phenomenon not occur.
Accompanying drawing explanation
Fig. 1 shows the example according to the present invention, utilizes the mechanism schematic diagram of block copolymer dispersing nanoparticles, and nanoparticle is with spheroidal particle
For representing, wherein:
Fig. 1 (A) shows the example according to the present invention, utilizes star or the mechanism schematic diagram of multi-arm block copolymer dispersing nanoparticles；Fig. 1 (B)
Show the example according to the present invention, utilize the mechanism schematic diagram of shape block copolymer dispersing nanoparticles；
Fig. 2 shows according to embodiments of the invention 5, utilizes three arm block copolymer dispersion ZrO2And TiO2Actual effect schematic diagram, wherein:
" a1 ", " a2 ", " a3 ", " a4 ", " a5 ", " a6 " and " a7 " represents ZrO respectively2Nanoparticle mass fraction is respectively 0.01%, 0.05%, 0.1%,
0.2%, the mixture of 0.3%, 0.4% and 1%；" b1 ", " b2 ", " b3 ", " b4 ", " b5 ", " b6 " and " b7 " represents TiO respectively2Nanoparticle
The mass fraction of son is respectively the mixture of 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4% and 1%, and each subgraph implication of Fig. 2 is such as
Under:
Fig. 2 (A) shows according to embodiments of the invention 5, and nanoparticle is just by the design sketch after ultrasonic disperse；
Fig. 2 (B) display according to the present invention according to this, nanoparticle is by the actual effect figure after disperseing a day；
Fig. 2 (C) display is according to embodiments of the invention 5, and nanoparticle is by the actual effect figure after disperseing four days；
Fig. 2 (D) display is according to embodiments of the invention 5, and nanoparticle is by the actual effect figure after disperseing 12 days；
Fig. 2 (E) display is according to embodiments of the invention 5, and nanoparticle is by the actual effect figure after disperseing 25 days；
Fig. 2 (F) display is according to embodiments of the invention 5, and nanoparticle is by the actual effect figure after disperseing 55 days；
Fig. 2 (G) display is according to embodiments of the invention 5, and nanoparticle is by the actual effect figure after disperseing 65 days；
Fig. 3 shows according to embodiments of the invention 6, utilizes four arm block copolymer dispersion ZrO2And TiO2Actual effect schematic diagram, wherein:
" a " represents ZrO2Nanoparticle, " b " represents TiO2Nanoparticle；
Fig. 4 shows according to embodiments of the invention 7, utilizes shape block copolymer to disperse ZrO2And TiO2Actual effect schematic diagram, wherein:
" a " represents ZrO2Nanoparticle, " b " represents TiO2Nanoparticle；
Fig. 5 shows according to embodiments of the invention 8, utilizes the actual effect of three arm block copolymers, star block copolymer dispersion nano copper particle
Really schematic diagram, wherein: " a " represents and utilize three arm block copolymer dispersion nano copper particles, and " b " represents and utilize star block copolymer to disperse nanometer
Copper granule；
Fig. 6 shows according to embodiments of the invention 9, utilizes oleic acid to disperse ZrO2And TiO2Actual effect schematic diagram, wherein: " a " represents ZrO2
Nanoparticle, " b " represents TiO2Nanoparticle；And
Fig. 7 shows according to embodiments of the invention, the synthetic route chart of block copolymer, wherein,
Fig. 7 (A) is star or the synthetic route chart of multi-arm shape block copolymer,
Fig. 7 (B) is the synthetic route chart of shape block copolymer.
Detailed description of the invention
Embodiments of the invention are described below in detail.The embodiments described below is exemplary, be only used for explain the present invention, and it is not intended that
Limitation of the present invention.Unreceipted concrete technology or condition in embodiment, according to technology or the condition described by the document in this area or press
Carry out according to product description.Agents useful for same or instrument unreceipted production firm person, be can by city available from conventional products.
In a first aspect of the present invention, the invention provides based block copolymer purposes in preparation contains the mixture of nanoparticle, used
Block copolymer type includes star block copolymer, multi-arm block copolymer and shape block copolymer.Inventor finds, uses the present invention to carry
Nanoparticle can be effectively scattered in organic media by the block copolymer of confession, and the dispersion stability of formation is high, it is possible to long term storage and not
Settle.According to a particular embodiment of the invention, the mixture containing nanoparticle that block copolymer dispersion obtains is utilized at ambient temperature
At least can be with stable existence two months.
According to the example of the present invention, between functional group and the block copolymer of nanoparticle surface, there is ionic interaction power or Van der Waals force, by
This, block copolymer can be adsorbed in nanoparticle surface, after absorption block copolymer, mutually exclusive between nanoparticle, thus, it is possible to surely
Fixed is scattered in disperse medium, and Fig. 1 (A) and Fig. 1 (B) is shown in by dispersion mechanism schematic diagram.
According to the example of the present invention, the described mixture containing nanoparticle be selected from lubricating oil, grease, electrocondution slurry, ink, printing glue,
At least one in photoresist, coating, coating and binding agent.Thereby, it is possible to utilize block copolymer that nanoparticle is stably scattered in lubrication
In oil, grease, electrocondution slurry, ink, printing glue, photoresist, coating, coating and binding agent, solve nano material in organic media
Dispersion and the problem of poor stability, and then be effectively improved the tribological property of lube oil additive, the levelability of coating, electrocondution slurry conduction
Electric conductivity etc. in device.
According to the example of the present invention, gross mass based on the described mixture containing nanoparticle, the mass fraction of described nanoparticle is
0.001%～90%.Thus, dispersion and the stabilizing effect of nanoparticle are preferable.
According to the example of the present invention, the mass ratio of described block copolymer and described nanoparticle is 0.0001-10.Thus, be conducive to improving nanometer
The dispersion of particle and stability, and this ratio has dispersion effect and the stability being significantly better than other ratios.
According to the example of the present invention, described block copolymer shape includes star block copolymer, multi-arm block copolymer and shape block copolymer,
Preferably star block copolymer or multi-arm block copolymer.Thus, be conducive to improving dispersion effect and the stability of nanoparticle.
According to the example of the present invention, described block copolymer chemistry structure is made up of A segment and B segment two class segment, and described block copolymer can
To be prepared by the synthetic route shown in Fig. 7, wherein, Fig. 7 (A) is the synthetic route chart of multi-arm or star block copolymer, Fig. 7 (B)
Synthetic route chart for shape block copolymer.
According to the example of the present invention, the polyolefin that the A segment of described block copolymer is blocked by strand skeleton one side is formed.
According to the example of the present invention, the polyolefin of strand skeleton one side end-blocking is the raw material forming A segment, and wherein, terminal functionality can be
At least one in anhydride, carboxyl, amino, hydroxyl, epoxy radicals and NCO.
According to the example of the present invention, the B segment of described block copolymer is formed by polyethers or polyester, terminal functional group used by B segment be anhydride,
At least one in carboxyl, amino, hydroxyl, epoxy radicals and NCO.
According to the example of the present invention, forming the polyolefin of strand skeleton one side end-blocking used by A segment is preferably to be selected from strand skeleton one side end-blocking
At least one in the polybutadiene of polyisobutylene, the polybutene of strand skeleton one side end-blocking and strand skeleton one side end-blocking.
According to the example of the present invention, the polyisobutylene of described strand skeleton one side end-blocking is at least one following:
Wherein, each n independently be as the integer more than or equal to 5.
It should be noted that unless otherwise explicitly pointed out, the describing mode " each ... to independently be " used in the present invention with " ... each
Independently be " and " ... independently be " can exchange, all should be interpreted broadly, it both may refer in different chemical structures, same-sign it
Do not affect mutually between concrete option expressed by between, it is also possible to represent in identical chemical constitution, concrete choosing expressed between same-sign
Do not affect mutually between Xiang.
According to the example of the present invention, the polybutene of described strand skeleton one side end-blocking is at least one following:
Wherein, each m1 and m2 is each independently the integer more than or equal to 0, and in each structural formula, m1+m2 is more than or equal to 5
Integer.
According to the example of the present invention, the polybutadiene of described strand skeleton one side end-blocking is at least one following:
Wherein, in each structural formula, i+j+k=1, each n independently be the integer more than or equal to 5.
According to the example of the present invention, forming polyethers used by B segment can be polyether polyol, polyether polyamine or polyethers glycidyl ether.Binary
Alcohol, epoxide, siloxanes or derivatives thereof form the basic structural unit of polyethers chemical constitution, and the repetition of preferred, polyethers chemical constitution
Unit is flexible.Wherein, dihydroxylic alcohols can be selected from ethylene glycol, 1,2-PD, 1, in 2-butanediol, 1,3 butylene glycol and BDO
At least one；Epoxide can be at least one in oxirane, expoxy propane, 1,2-epoxy butane and oxolane；Silicon
Oxygen alkane can be at least one in dimethyl siloxane or di-ethyl siloxane.Thus, the dispersion stabilization of nanoparticle is preferable.
When the carbon number of the repetitive of polyethers is more than 2, repetitive is hydrophobic, otherwise is then hydrophilic.
According to the example of the present invention, the construction unit of described polyethers is at least one following:
Wherein, each x independently be the integer more than or equal to 1.Thus, the dispersion stabilization of nanoparticle is preferable.
According to the example of the present invention, another presoma forming B segment is made up of polyester construction.Polyester can be PEPA, polyester
Polyamines or polyester glycidyl ether.
Dihydroxylic alcohols, siloxanes or derivatives thereof, alkyd/dicarboxylic acids/lactone or derivatives thereof forms the basic structural unit of polyester, and the most poly-
The construction unit of ester is flexible.According to some examples of the present invention, dihydroxylic alcohols can be selected from ethylene glycol, 1,2-PD, 1,2-butanediol,
At least one in 1,3 butylene glycol and 1,4-butanediol；Siloxanes can be at least in dimethyl siloxane or di-ethyl siloxane
Kind；Alkyd/dicarboxylic acids/lactone or derivatives thereof can be the substituted gamma-butyrolacton of alkyl, the substituted δ-valerolactone of alkyl, the substituted ε of alkyl-own
At least one in lactone, gamma-butyrolacton, δ-valerolactone, 6-caprolactone and fatty acid.Thus, the dispersion stabilization of nanoparticle is preferable.
When in the constitutional repeating unit of polyester without polyether structure unit, and when carbon number is more than 6, then repetitive is hydrophobic,
Otherwise it is then hydrophilic.
According to the example of the present invention, the construction unit of described polyester is at least one following:
Wherein, each x independently be the integer more than or equal to 1, and each r independently be the integer of 0-18, and each t independently be the integer of 2-12.
R1For alkyl or oxyl, alkyl is preferably smaller than equal to the alkyl of eight carbon atoms, and oxyl is preferably smaller than equal to the alkoxyl of eight carbon atoms.
Thus, nanoparticle dispersion effect is preferable, and stability is preferable, it is possible to preserve for a long time and sedimentation phenomenon does not occur.
According to the example of the present invention, formed the topological structure of polyethers or polyester used by B segment the most independent for selected from star, multi-arm shape and line
At least one in shape, preferably star or multi-arm shape.Thus, be conducive to improving dispersion effect and the stability of nanoparticle.
According to the example of the present invention, the topological structure of described polyethers and described polyester the most independent at least one following:
Wherein, each A1,A2,A3,…,AnIndependently be described polyethers or the repetitive of described polyester, R2For-H or-CH2-CH3, z is 0
Or 2；Each Y independently be terminal functional group, at least one in anhydride, carboxyl, amino, hydroxyl, epoxy radicals and NCO；Respectively
X1, x2, x3 ..., xn represents the quantity of repetitive；Each x1, x2, x3 ..., xn independently be the integer more than or equal to 0, and meets
x1+x2+x3+,…,+xn≥1。
According to the example of the present invention, in star topology, multi-arm shape topological structure, common formation star structure unit, multi-arm shape structure
The raw material of unit is glycerol, trimethylolpropane, tetramethylolmethane, dipentaerythritol and Pehanorm.Preferably, formed star structure,
The raw material of multi-arm shape construction unit is at least one following:
According to the example of the present invention, the macromolecular chemistry reaction involved by synthetic segmented copolymer can be one of these reactions: carboxyl and hydroxyl
Condensation, carboxyl form ester bond, anhydride in alcoholic extract hydroxyl group environment form amido link, hydroxyl and Carbimide. in amino environment with amino condensation, anhydride
Ester generation additive reaction, amino make epoxide group generation ring-opening reaction, amino make epoxide group send out with isocyanates generation additive reaction, alcoholic extract hydroxyl group
Raw ring-opening reaction.
In brief, the block copolymer of of the present invention example can be synthesized by one of above-mentioned macromolecular chemistry.Described block copolymer
It is prepared by the general synthetic routes shown in Fig. 7.
According to another concrete example of the present invention, three arm block copolymers can be prepared according to synthetic route as follows:
According to another concrete example of the present invention, four arm block copolymers can be prepared according to synthetic route as follows:
According to another concrete example of the present invention, star block copolymer can be prepared according to synthetic route as follows:
A concrete example according to the present invention, can prepare shape block copolymer according to synthetic route as follows:
According to another concrete example of the present invention, three arm block copolymers can be prepared according to synthetic route as follows:
According to another concrete example of the present invention, four arm block copolymers can be prepared according to synthetic route as follows:
According to another concrete example of the present invention, star block copolymer can be prepared according to synthetic route as follows:
According to another concrete example of the present invention, shape block copolymer can be prepared according to synthetic route as follows:
According to the example of the present invention, described nanoparticle be shaped as selected from spherical, lamellar, bar-shaped or linear at least one.Thus, receive
The dispersion effect of rice corpuscles and having good stability.
According to the example of the present invention, nano spherical particle, rod-like nano particle and linear nanoparticle are selected from metal oxide particle, metal sulfur
At least one in the metallic particles that chalcogenide particles, metallic particles, the metallic particles showing oxidation processes and surface sulfide process.Thus, favorably
In the dispersion effect and the stability that improve nanoparticle.
According to the example of the present invention, described metal oxide particle is selected from silicon dioxide, aluminium oxide, zinc oxide, copper oxide, nickel oxide, oxygen
Change at least one in cobalt, ferrum oxide, magnesium oxide, titanium oxide, zirconium oxide, tungsten oxide and molybdenum oxide.Thus, be conducive to improving nanoparticle
Dispersion effect and stability.
According to the example of the present invention, metal sulfide grain is selected from zinc sulfide, cadmium sulfide, cinnabar, iron sulfide, cobalt sulfide, nickel sulfide,
At least one in tungsten sulfide and molybdenum sulfide.Thus, be conducive to improving dispersion effect and the stability of nanoparticle.
According to the example of the present invention, described metallic particles is at least one in cobalt, ferrum, magnesium, aluminum, titanium, zirconium, silver, gold or its alloy.
Thus, be conducive to improving dispersion effect and the stability of nanoparticle.
According to the example of the present invention, flake nano is selected from layered double hydroxide, clay, layered metal phosphates, laminated metal tungsten
Hydrochlorate, laminated metal sulfide, graphite oxide, at least one in graphene oxide, and derivant.Thus, be conducive to improving nanometer
The dispersion effect of particle and stability.
According to the example of the present invention, no matter the B segment that polyethers or polyester are formed is the most hydrophilic, the block copolymer prepared all can be by nanoparticle
Son is stably dispersed in suitable solvent.Under preferable case, for more preferable dispersing hydrophobic nanoparticle, the B segment in block copolymer is excellent
Elect as hydrophobic；For more preferable dispersed hydrophilic nano-particle, preferably B segment is hydrophilic.Thus, the dispersion effect of nanoparticle
All preferable with stability, the mixture containing nanoparticle of formation can long term storage, be not susceptible to sedimentation.
In the second aspect of invention, the present invention provides the preparation method containing block copolymer with nanoparticle mixture；Block copolymerization species used
Type includes star block copolymer, multi-arm block copolymer and shape block copolymer.According to the example of the present invention, the method includes: by block
Copolymer, nanoparticle and disperse medium mixing, in order to obtain the described mixture containing nanoparticle.Inventor finds, utilizes the present invention's
Method can fast and effeciently prepare the mixture containing nanoparticle that dispersion stabilization is good, and simple to operate, convenient and swift, cost
Cheap, it is easy to accomplish large-scale production.
It should be noted that block copolymer described in the method for the present invention and nanoparticle have foregoing block copolymer with
All feature and advantage of nanoparticle, this is no longer going to repeat them.
In the third aspect of invention, the invention provides the mixture containing block copolymer Yu nanoparticle, block copolymer type used includes
Star block copolymer, multi-arm block copolymer and shape block copolymer.According to the example of the present invention, the described mixture containing nanoparticle
Foregoing method is utilized to prepare.Inventor finds, the mixture dispersion stabilization containing nanoparticle of the present invention is preferable, it is possible to relatively
Long-time storage and be not susceptible to sedimentation phenomenon.
According to the example of the present invention, described block copolymer and nanoparticle have all spies of block copolymer described above and nanoparticle
Levying and advantage, this is no longer going to repeat them.
Embodiment 1: the synthesis of isobutene .-propylene glycol-isobutene. three arm block copolymer
173.25g (excess 5%) polyisobutylene butanedioic anhydride (PIBSA) (molecular weight is 1100g/mol) and 200ml normal hexane are dissolved in 500ml
There-necked flask in, then in nitrogen atmosphere, continuously stirred under the conditions of, there-necked flask is placed in 60 DEG C of oil baths, utilizes the constant pressure addition of 150ml
By 22.0g polyetheramine T-403, (molecular weight is 440g/mol to funnel, three arm polymer, one amino of the molecule chain end band of each arm.) molten
In 100ml acetone, when the temperature stabilization of the solution in there-necked flask is at 60 DEG C, polyetheramine T-403 solution is added dropwise in there-necked flask,
Obtained solution stirs at least 8 hours at 60 DEG C, becomes yellow-white emulsion to solution, and rotary evaporation in vacuo removes solvent, obtains viscosity
Weak yellow liquid shape product, be target product.
Embodiment 2: the synthesis of isobutene .-tetramethylolmethane propoxylate-isobutene. four arm block copolymer
By 115.5g (excess 5%) polyisobutylene butanedioic anhydride (PIBSA) (molecular weight is 1100g/mol) and 200ml DMF
Be dissolved in the there-necked flask of 500ml, then in nitrogen atmosphere, continuously stirred under the conditions of, there-necked flask is placed in 100 DEG C of oil baths, utilizes 150ml
Constant pressure funnel by 10.65g polypentaerythritol propoxylate (molecular weight 426g/mol, No. CAS: 9051-49-4, four arm polymer,
One hydroxyl of the molecule chain end band of each arm.) be dissolved in 80ml DMF, when the temperature of the solution in there-necked flask is steady
When being scheduled on 100 DEG C, being added dropwise in there-necked flask by polypentaerythritol propoxylate solution, obtained solution stirs at least 24 at 100 DEG C
Hour, becoming yellow-white emulsion to solution, rotary evaporation in vacuo removes solvent, obtains the weak yellow liquid shape product of viscosity, is target product.
Embodiment 3: the synthesis of isobutene .-tetramethylolmethane propoxylate-isobutene. star block copolymer
By 115.5g (excess 5%) polyisobutylene butanedioic anhydride (PIBSA) (molecular weight is 1100g/mol) and 200ml DMF
Be dissolved in the there-necked flask of 500ml, then in nitrogen atmosphere, continuously stirred under the conditions of, there-necked flask is placed in 100 DEG C of oil baths, utilizes 150ml
Constant pressure funnel by 7.86g polypentaerythritol propoxylate (molecular weight 629g/mol, No. CAS: 9051-49-4, star polymer,
Containing eight strand branches, one hydroxyl of the end strips of each strand branch.) be dissolved in 80ml DMF, when three
Polypentaerythritol propoxylate solution, when 100 DEG C, is added dropwise in there-necked flask, obtained solution by the temperature stabilization of the solution in mouth bottle
Stirring at 100 DEG C at least 24 hours, become yellow-white emulsion to solution, rotary evaporation in vacuo removes solvent, obtains the light yellow liquid of viscosity
Body shape product, is target product.
Embodiment 4: the synthesis of isobutene .-propylene glycol-isobutene. shape block copolymer
115.5g (excess 5%) polyisobutylene butanedioic anhydride (PIBSA) (molecular weight is 1100g/mol) and 200ml normal hexane are dissolved in 500ml's
In there-necked flask, then in nitrogen atmosphere, continuously stirred under the conditions of, there-necked flask is placed in 60 DEG C of oil baths, utilizes the constant pressure addition of 150ml to leak
By 11.5g PEG two (2-aminopropyl ether) D230, (molecular weight is 230g/mol to bucket, line polymer, two ends of strand
Hold one amino of each band.) be dissolved in 80ml acetone, when the temperature stabilization of the solution in there-necked flask is at 60 DEG C, by PEG two (2
-aminopropyl ether) D230 solution is added dropwise in there-necked flask, and obtained solution stirs at least 8 hours at 60 DEG C, becomes HUANGBAI(sic) to solution
Color emulsion, after rotary evaporation in vacuo removes solvent, obtains the weak yellow liquid shape product of viscosity, is target product.
Embodiment 5: utilize three arm block copolymer dispersion ZrO2And TiO2
By isobutene .-glycerol-isobutene. three arm block copolymer of preparation, ZrO in embodiment 12Nanoparticle (particle diameter 50 ± 5nm, high temperature sintering
Granule), TiO2Nanoparticle (particle diameter 25 ± 5nm, hydrophilic particle) and liquid paraffin mixing, prepare isobutene .-glycerol-isobutene. three arm block
The mass fraction of copolymer is 5%, ZrO2Nanoparticle and TiO2The mass fraction of nanoparticle is respectively 0.01%, and 0.05%, 0.1%, 0.2%,
The mixture of 0.3%, 0.4% and 1%.Dispersion effect is shown in Fig. 2 (A) to Fig. 2 (G), and as seen from the figure, three arm block copolymers of preparation are not to
It is respectively provided with extraordinary dispersion stabilization with the nanoparticle of concentration.Experimental result shows, the nanoparticle after dispersion can the most stably stand
Place two months.Further, experimental result shows: in the range of longer time scale, uses the three arm block copolymer dispersing nanoparticles prepared,
When, after nanoparticle settlement polar small part, nanoparticle no longer settles, whole dispersion reaches balance.
Embodiment 6: utilize four arm block copolymer dispersion ZrO2And TiO2
By the isobutene .-tetramethylolmethane propoxylate-isobutene. four arm block copolymer of preparation, ZrO in embodiment 22Nanoparticle (particle diameter
50 ± 5nm, high temperature sintering granule), TiO2Nanoparticle (particle diameter 25 ± 5nm, hydrophilic particle) and liquid paraffin mixing, prepare isobutene .-Ji Wusi
The mass fraction of alcohol propoxylate-isobutene. four arm block copolymer is 5%, ZrO2Nanoparticle and TiO2Nanoparticle is the mixing of 1%
Thing.Dispersion effect is shown in Fig. 3, and as seen from Figure 3, four arm block copolymers of preparation have extraordinary dispersion stabilization to nanoparticle.
Experimental result shows, the nanoparticle after dispersion can the most stably stand placement two months.Further, experimental result shows: when longer
Between in range scale, with the four arm block copolymer dispersing nanoparticles prepared, when, after nanoparticle settlement polar small part, nanoparticle is the most heavy
Fall, whole dispersion reaches balance.
Embodiment 7: utilize shape block copolymer to disperse ZrO2And TiO2
By the isobutene .-glycerol-isobutene. shape block copolymer of preparation, ZrO in embodiment 42Nanoparticle (particle diameter 50 ± 5nm, high temperature sintering
Granule), TiO2Nanoparticle (particle diameter 25 ± 5nm, hydrophilic particle) and liquid paraffin mixing, prepare isobutene .-glycerol-isobutene. Linear block
The mass fraction of copolymer is 5%, ZrO2Nanoparticle and TiO2Nanoparticle is the mixture of 1%.Dispersion effect is shown in Fig. 4, by Fig. 4
It can be seen that the shape block copolymer of preparation has extraordinary dispersion stabilization to nanoparticle.Experimental result shows, the nanometer after dispersion
Particle can the most stably stand placement two months.Further, experimental result shows: in the range of longer time scale, linear with prepare
Block copolymer dispersing nanoparticles, after nanoparticle sedimentation is a small amount of, nanoparticle no longer settles, and whole dispersion reaches balance.
Embodiment 8: utilize three arm block copolymers, star block copolymer to disperse nano copper particle
By the isobutene .-tetramethylolmethane propoxylate-isobutene. star of preparation in three arm block copolymers of preparation, embodiment 3 in embodiment 1
Block copolymer, mixes with copper nano-particle (particle diameter 80～100nm) and liquid paraffin respectively, configures three arm block copolymers, starblock copolymerization
The mass fraction of thing is respectively 5%, and the mass fraction of copper nano-particle is the mixture of 1%.Dispersion effect is shown in Fig. 5, as seen from Figure 5,
Three arm block copolymers of preparation, star block copolymer have preferable dispersion stabilization to nanoparticle.Experimental result shows, after dispersion
Nanoparticle can the most stably stand placement two months.Further, experimental result shows: in the range of longer time scale, with prepare
Three arm block copolymers, star block copolymer dispersing nanoparticles, after nanoparticle sedimentation small part, nanoparticle no longer settles, whole point
Prose style free from parallelism system reaches balance.
Embodiment 9 utilizes oleic acid to disperse ZrO2And TiO2
By oleic acid, ZrO2Nanoparticle (particle diameter 50 ± 5nm, high temperature sintering granule), TiO2Nanoparticle (particle diameter 25 ± 5nm, hydrophilic particle) and liquid
Paraffin body mixes, and the mass fraction of configuration oleic acid is 5%, ZrO2Nanoparticle and TiO2The mass fraction of nanoparticle is the mixture of 1%.
Dispersion effect is shown in Fig. 6, and oleic acid Small molecular surfactant is very poor to the dispersion effect of nanoparticle, and about two day time, nanoparticle is the most complete
Portion settles.
In the description of this specification, reference term " embodiment ", " some embodiments ", " example ", " concrete example " or " some show
Example " etc. description means to combine this embodiment or example describes specific features, structure, material or feature be contained at least one of the present invention
In embodiment or example.In this manual, the schematic representation of above-mentioned term is necessarily directed to identical embodiment or example.And,
The specific features, structure, material or the feature that describe can be to combine in one or more embodiments in office or example in an appropriate manner.Additionally,
In the case of the most conflicting, those skilled in the art can be by the different embodiments described in this specification or example and different embodiment
Or the feature of example is combined and combines.
Although above it has been shown and described that embodiments of the invention, it is to be understood that above-described embodiment is exemplary, it is impossible to be interpreted as
Limitation of the present invention, above-described embodiment can be changed by those of ordinary skill in the art within the scope of the invention, revise, replace and
Modification.
Claims (10)
1. block copolymer preparation containing nanoparticle mixture in purposes, described block copolymer be selected from star block copolymer with
At least one in multi-arm block copolymer,
Wherein, described block copolymer chemistry structure is made up of A segment and B segment two class segment；
The polyolefin that described A segment is blocked by strand skeleton one side is formed, and terminal functional group used by described A segment is anhydride, carboxyl, ammonia
At least one in base, hydroxyl, epoxy radicals and NCO；
Described B segment is formed by polyethers or polyester, terminal functional group used by described B segment be anhydride, carboxyl, amino, hydroxyl, epoxy radicals and
At least one in NCO,
Gross mass based on the described mixture containing nanoparticle, the mass fraction of described nanoparticle is 0.001%～90%,
The mass ratio of described block copolymer and described nanoparticle is (0.0001-10): 1.
Purposes the most according to claim 1, it is characterised in that the described mixture containing nanoparticle be selected from lubricating oil, grease,
At least one in electrocondution slurry, ink, printing glue, photoresist, coating, coating and binding agent.
Purposes the most according to claim 1, it is characterised in that the polyolefin of described strand skeleton one side end-blocking is selected from strand bone
In the polybutadiene of the polyisobutylene of frame one side end-blocking, the polybutene of strand skeleton one side end-blocking and strand skeleton one side end-blocking at least one
Kind,
The polyisobutylene of described strand skeleton one side end-blocking is at least one following:
Wherein, each n independently be the integer more than or equal to 5,
The polybutene of described strand skeleton one side end-blocking is at least one following:
Wherein, m1 and m2 is each independently the integer more than or equal to 0, and m1+m2 is the integer more than or equal to 5,
The polybutadiene of described strand skeleton one side end-blocking is at least one following:
Wherein, i+j+k=1, each n independently be the integer more than or equal to 5.
Purposes the most according to claim 1, it is characterised in that described polyethers is shunk by selected from polyether polyol, polyether polyamine and polyethers
At least one in glycerin ether is formed,
The construction unit of described polyethers is at least one following:
Wherein, each x independently be the integer more than or equal to 1.
Purposes the most according to claim 1, it is characterised in that described polyester is shunk by selected from PEPA, polyester polyamine and polyester
At least one in glycerin ether is formed,
The construction unit of described polyester is at least one following:
Wherein, each x independently be the integer more than or equal to 1,
Each r is the integer of 0-18 independently,
Each t is the integer of 2-12 independently,
R1For alkyl or oxyl.
Purposes the most according to claim 1, it is characterised in that described polyethers the most independent with the topological structure of described polyester for being selected from
At least one in star, multi-arm shape,
The topological structure of described polyethers and described polyester the most independent at least one following:
Wherein, each A1,A2,A3,…,AnIndependently be described polyethers or the repetitive of described polyester,
R2For-H or-CH2-CH3,
Z is 0 or 2；
Each Y independently be terminal functional group, and described terminal functional group is in anhydride, carboxyl, amino, hydroxyl, epoxy radicals and NCO
At least one；
Each x1, x2, x3 ..., xn represents the quantity of repetitive；Each x1, x2, x3 ..., xn independently be the integer more than or equal to 0, and meets
X1+x2+x3+ ... ,+xn >=1,
Star topology, the polyethers of multi-arm topological structure or polyester are formed by least one following:
Purposes the most according to claim 1, it is characterised in that being shaped as selected from spherical, lamellar, bar-shaped or line of described nanoparticle
At least one in shape,
Described nano spherical particle, rod-like nano particle and linear nanoparticle are selected from metal oxide particle, metal sulfide grain, metal
At least one in the metallic particles that granule, the metallic particles of surface oxidation treatment and surface sulfide process,
Described metal oxide particle is selected from silicon dioxide, aluminium oxide, zinc oxide, copper oxide, nickel oxide, cobalt oxide, ferrum oxide, oxidation
At least one in magnesium, titanium oxide, zirconium oxide, tungsten oxide and molybdenum oxide,
Described metal sulfide grain is selected from zinc sulfide, cadmium sulfide, cinnabar, iron sulfide, cobalt sulfide, nickel sulfide, tungsten sulfide and molybdenum sulfide
In at least one,
Described metallic particles is at least one in cobalt, ferrum, magnesium, aluminum, titanium, zirconium, silver, gold or its alloy,
Described flake nano is selected from layered double hydroxide, clay, layered metal phosphates, laminated metal tungstates, laminated metal
Sulfide, graphite oxide, at least one in graphene oxide, and derivant.
8. the method preparing the mixture containing nanoparticle, it is characterised in that including:
Block copolymer, nanoparticle and disperse medium are mixed, in order to obtain the described mixture containing nanoparticle；
Wherein, described block copolymer is the block copolymer according to any one of claim 1-7,
Described disperse medium is apolar medium.
Method the most according to claim 8, it is characterised in that described apolar medium is hydrocarbon medium.
10. the mixture containing nanoparticle, it is characterised in that be to utilize the method described in claim 8 or 9 to prepare.
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| CN106832844B (en) * | 2017-02-10 | 2018-11-20 | 四川大学 | Four arm PEG-PCL of one kind, graphene oxide composite material and preparation method thereof |
| CN108384438A (en) * | 2018-03-14 | 2018-08-10 | 湖南宏泰新材料有限公司 | A kind of resistance to steel wool anti-fingerprint nanometer UV coating of anodic oxidation |
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| WO2007096056A1 (en) * | 2006-02-23 | 2007-08-30 | Sustech Gmbh & Co. Kg | Multifunctional star-shaped prepolymers, their preparation and use |
| WO2009097529A1 (en) * | 2008-01-30 | 2009-08-06 | Dow Global Technologies Inc. | PROPYLENE/α-OLEFIN BLOCK INTERPOLYMERS |
| CN102206313A (en) * | 2005-09-07 | 2011-10-05 | 日本曹达株式会社 | Star polymer and process for production thereof |
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| US8153729B2 (en) * | 2008-05-29 | 2012-04-10 | The Regents Of The University Of California | Highly efficient agents for dispersion of nanoparticles in matrix materials |
| KR101685646B1 (en) * | 2010-12-29 | 2016-12-13 | 한화케미칼 주식회사 | Biocompatible Agent for Dispersing Nanoparticles into Aqueous Solution using Mussel Adhesive Protein Mimic polymer |
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| CN102206313A (en) * | 2005-09-07 | 2011-10-05 | 日本曹达株式会社 | Star polymer and process for production thereof |
| WO2007096056A1 (en) * | 2006-02-23 | 2007-08-30 | Sustech Gmbh & Co. Kg | Multifunctional star-shaped prepolymers, their preparation and use |
| WO2009097529A1 (en) * | 2008-01-30 | 2009-08-06 | Dow Global Technologies Inc. | PROPYLENE/α-OLEFIN BLOCK INTERPOLYMERS |
| CN103224598A (en) * | 2013-04-26 | 2013-07-31 | 广东药学院 | Preparation methods of cyclodextrin-based star-block polymer and cyclodextrin-based star-block polymer/gold nano-rod composite material |
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