WO2016119290A1 - Use of star-shaped/multi-arm block copolymer in preparation of mixture containing nano-particles - Google Patents

Use of star-shaped/multi-arm block copolymer in preparation of mixture containing nano-particles Download PDF

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WO2016119290A1
WO2016119290A1 PCT/CN2015/074326 CN2015074326W WO2016119290A1 WO 2016119290 A1 WO2016119290 A1 WO 2016119290A1 CN 2015074326 W CN2015074326 W CN 2015074326W WO 2016119290 A1 WO2016119290 A1 WO 2016119290A1
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nanoparticles
use according
block copolymer
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French (fr)
Chinese (zh)
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孙大陟
雍怀松
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南方科技大学
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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

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  • This invention relates to the field of materials science and, in particular, to the use of star/multiarm block copolymers in the preparation of mixtures containing nanoparticles.
  • Nanomaterials are widely used in lubricants, greases, conductive pastes, inks, printing pastes, photoresists, coatings, coatings and adhesives. Improving the dispersibility of nanomaterials in these media is expected to significantly improve the tribological properties of the lubricant additive, the leveling of the coating, and the conductivity of the conductive paste in the conductive device.
  • Nanoparticles have small particle size, high surface energy, and easy agglomeration between particles.
  • the dispersion and stabilization of nanomaterials in organic media has become one of the main technical problems that limit its wide application.
  • surfactants are often used to improve the dispersion uniformity and stability of the nanoparticles.
  • Commonly used low molecular surfactants are long chain alkyl alcohols, long chain alkyl amines, long chain alkyl carboxylic acids and the like.
  • Commonly used polymer surfactants are polyether surfactants, polysaccharide surfactants, comb polymer surfactants, and the like.
  • Existing polyether surfactants include Alkyl Polyether Alcohols, Alkylaryl Polyether Alcohols, and Polyether Block Copolymers.
  • alkyl polyether alcohols an alkyl group-terminated ethoxy/propoxylate (Alkyl PEG/PPG Ethers) is representative of this class.
  • alkylaryl polyether alcohols octylphenol-terminated ethoxy/propoxylate (Octylphenol PEG/PPG Ethers) is representative of this class.
  • block copolymers formed by using polyethylene glycol and polypropylene glycol as structural units are representative, including Poloxamer, Hypermer, Zephrym linear polyether block copolymer, and Tetronic branched water-soluble polyether embedded. Segment copolymer.
  • the present invention aims to solve at least one of the technical problems in the related art at least to some extent.
  • the invention One purpose is to propose a new use of star block copolymers, multi-arm block copolymers in the preparation of mixtures containing nanoparticles.
  • the surface of the nanoparticles typically carries hydroxyl, carboxyl or other polar functional groups, whereby ionic interaction forces and van der Waals forces are present between the polymer and the nanoparticles.
  • the ionic bond is a chemical bond formed by an electrostatic interaction between an anion and a cation, and the ionic bond is characterized by being unsaturated and non-directional.
  • the ionic dispersant covers the surface of the nanoparticles by adsorbing the nanoparticles, so that the surfaces of the nanoparticles are charged with one another and repel each other. The inventors have found that this strategy can be effectively used to disperse nanoparticles having carboxyl-plasma functional groups on the surface.
  • Van der Waals force between the dispersant and the unbonded atoms in the graft group on the surface of the nanoparticles There is a van der Waals force between the dispersant and the unbonded atoms in the graft group on the surface of the nanoparticles.
  • the van der Waals force between the low molecular weight dispersant and the nanoparticles has little effect, but the effect is completely different with the polymer dispersant.
  • the number of structural units in a polymer chain is very large, and each structural unit is equivalent to a small molecule.
  • Van der Waals forces are not directional and do not saturate, so the van der Waals forces between the polymer chains and the nanoparticles are large enough to allow the polymer to coat at least a portion of the surface of the nanoparticles.
  • This strategy can be used to disperse nanoparticles with nonionic functional groups on the surface.
  • the invention provides the use of a block copolymer in the preparation of a mixture comprising nanoparticles selected from the group consisting of a star block copolymer and a multi-arm block copolymer At least one of the substances.
  • the inventors have found that the use of the block copolymer provided by the present invention can effectively disperse nanoparticles in an organic medium, and the resulting dispersion has high stability and can be stored for a long period of time without sedimentation.
  • the nanoparticle-containing mixture is at least one selected from the group consisting of lubricating oils, greases, conductive pastes, inks, printing pastes, photoresists, coatings, coatings, and binders.
  • the mass fraction of the nanoparticles is 0.001% to 90% based on the total mass of the nanoparticle-containing mixture.
  • the mass ratio of the block copolymer to the nanoparticles is (0.0001-10):1.
  • the block copolymer chemical structure is composed of two types of segments, an A segment and a B segment.
  • the A segment is formed of a polyolefin terminated on one side by a molecular chain skeleton, and the blocked functional group used in the A segment is at least at least an acid anhydride, a carboxyl group, an amino group, a hydroxyl group, an epoxy group, and an isocyanate group.
  • the blocked functional group used in the A segment is at least at least an acid anhydride, a carboxyl group, an amino group, a hydroxyl group, an epoxy group, and an isocyanate group.
  • the B segment is formed of a polyether or a polyester, and the blocked functional group used for the B segment is at least one of an acid anhydride, a carboxyl group, an amino group, a hydroxyl group, an epoxy group, and an isocyanate group.
  • the single-side terminated polyolefin of the molecular chain skeleton is a polyisobutylene which is one-side terminated from a molecular chain skeleton, a polybutene which is unilaterally terminated by a molecular chain skeleton, and a polybutene which is unilaterally terminated by a molecular chain skeleton. At least one of the dienes.
  • the molecularly oriented single-side terminated polyisobutylene is at least one of the following:
  • n is independently an integer greater than or equal to 5.
  • the single-side terminated polybutene of the molecular chain skeleton is at least one of the following:
  • the molecular chain backbone unilaterally capped polybutadiene is at least one of the following:
  • each n is independently an integer greater than or equal to 5.
  • the polyether is formed from at least one selected from the group consisting of polyether polyols, polyether polyamines, and polyether glycidyl ethers.
  • the structural unit of the polyether is at least one of the following:
  • each x is independently an integer greater than or equal to 1.
  • the polyester is formed of at least one selected from the group consisting of polyester polyols, polyester polyamines, and polyester glycidyl ethers.
  • the structural unit of the polyester is at least one of the following:
  • each x is independently an integer greater than or equal to 1,
  • Each r is independently an integer from 0 to 18,
  • Each t is independently an integer of 2-12
  • R 1 is a hydrocarbon group or a hydrocarbyloxy group.
  • the topologies of the polyether and the polyester are each independently selected from at least one of a star shape and a multi-arm shape.
  • the topologies of the polyether and the polyester are each independently at least one of the following:
  • each of A 1 , A 2 , A 3 , ..., A n is independently a repeating unit of the polyether or the polyester,
  • R 2 is -H or -CH 2 -CH 3 ,
  • z is 0 or 2;
  • Each Y is independently a capping functional group, and the capping functional group is at least one of an acid anhydride, a carboxyl group, an amino group, a hydroxyl group, an epoxy group, and an isocyanate group;
  • Each x1, x2, x3, ..., xn represents the number of repeating units; each x1, x2, x3, ..., xn is independently an integer greater than or equal to 0, and satisfies x1 + x2 + x3 +, ..., + xn ⁇ 1.
  • a star topology, a polyether or polyester of a multi-arm topology may be formed by at least one of the following:
  • the shape of the nanoparticles is at least one selected from the group consisting of a sphere, a sheet, a rod, and a line.
  • the spherical nanoparticles, the rod-shaped nanoparticles, and the linear nanoparticles are at least one selected from the group consisting of metal oxide particles, metal sulfide particles, metal particles, metal particles indicating oxidation treatment, and surface-sulfur treated metal particles.
  • the metal oxide particles are selected from the group consisting of silica, alumina, zinc oxide, copper oxide, nickel oxide, cobalt oxide, iron oxide, magnesium oxide, titanium oxide, zirconium oxide, tungsten oxide, and oxidation. At least one of molybdenum.
  • the metal sulfide particles are at least one selected from the group consisting of zinc sulfide, cadmium sulfide, mercury sulfide, iron sulfide, cobalt sulfide, nickel sulfide, tungsten sulfide, and molybdenum sulfide.
  • the metal particles are at least one selected from the group consisting of cobalt, iron, magnesium, aluminum, titanium, zirconium, silver, gold, or alloys thereof.
  • the flaky nano-particles are selected from the group consisting of layered double hydroxides, clays, layered metal phosphates, layered metal tungstates, layered metal sulfides, graphite oxides, graphene oxides, At least one of its derivatives.
  • the invention provides a method of preparing a mixture comprising nanoparticles.
  • the method comprises mixing a block copolymer, a nanoparticle and a dispersion medium to obtain the nanoparticle-containing mixture.
  • the inventors have found that the nanoparticle-containing mixture having good dispersion stability can be prepared quickly and efficiently by the method of the present invention, and is simple in operation, convenient and quick, low in cost, and easy to realize mass production.
  • the invention provides a mixture comprising nanoparticles.
  • the nanoparticle-containing mixture is prepared by the method described above. The inventors have found that the present invention contains nanoparticles The mixture has good dispersion stability and can be stored for a long time without sedimentation.
  • FIG. 1 shows a schematic diagram of a mechanism for dispersing nanoparticles using a block copolymer according to an example of the present invention, the nanoparticles being represented by spherical particles, wherein:
  • FIG. 1(A) shows a schematic diagram of a mechanism for dispersing nanoparticles using a star or multi-arm block copolymer according to an example of the present invention
  • FIG. 1(B) shows an example of dispersing with a linear block copolymer according to an example of the present invention. Schematic diagram of the mechanism of nanoparticles
  • FIG. 2 is a schematic view showing the actual effect of dispersing ZrO 2 and TiO 2 using a three-arm block copolymer according to Example 5 of the present invention, wherein: “a1”, “a2”, “a3”, “a4", “a5"”a6” and “a7” represent a mixture of ZrO 2 nanoparticle mass fractions of 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4% and 1%, respectively; “b1”, “b2", “B3”,”b4",”b5",”b6", and “b7” represent the mass fractions of TiO 2 nanoparticles of 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, and 1%, respectively.
  • the mixture, the subgraphs in Figure 2 have the following meanings:
  • 2(A) is a view showing the effect of the nanoparticles immediately after being dispersed by ultrasound according to Example 5 of the present invention
  • 2(B) is a view showing the actual effect of the nanoparticles after being dispersed for one day according to Embodiment 5 of the present invention
  • 2(C) is a view showing the actual effect of the nanoparticles after being dispersed for four days according to Example 5 of the present invention
  • 2(D) is a view showing the actual effect of the nanoparticles after being dispersed for 12 days according to Example 5 of the present invention
  • 2(F) is a view showing the actual effect of the nanoparticles after being dispersed for fifty-five days according to Example 5 of the present invention
  • FIG 3 is a schematic view showing the actual effect of dispersing ZrO 2 and TiO 2 using a four-arm block copolymer according to Example 6 of the present invention, wherein: "a” represents ZrO 2 nanoparticles, and “b” represents TiO 2 nanoparticles;
  • Example 4 is a schematic view showing the actual effect of dispersing ZrO 2 and TiO 2 using a linear block copolymer according to Example 7 of the present invention, wherein: “a” represents ZrO 2 nanoparticles, and “b” represents TiO 2 nanoparticles;
  • Example 5 is a schematic view showing the actual effect of dispersing nano copper particles by using a three-arm block copolymer and a star block copolymer according to Example 8 of the present invention, wherein: “a” represents dispersing nano copper by using a three-arm block copolymer. Particles, “b” represents the dispersion of nano-copper particles using a star block copolymer;
  • Example 6 is a schematic view showing the actual effect of dispersing ZrO 2 and TiO 2 using oleic acid according to Example 9 of the present invention, wherein: “a” represents ZrO 2 nanoparticles, and “b” represents TiO 2 nanoparticles;
  • Figure 7 shows a synthetic route diagram of a block copolymer according to an embodiment of the present invention, wherein
  • Figure 7 (A) is a synthetic route diagram of a star or multi-arm block copolymer
  • Fig. 7(B) is a synthetic route diagram of the linear block copolymer.
  • the invention provides the use of a block copolymer in the preparation of a mixture comprising nanoparticles, the type of block copolymer comprising a star block copolymer, a multi-arm block copolymer and Linear block copolymer.
  • the inventors have found that the use of the block copolymer provided by the present invention can effectively disperse nanoparticles in an organic medium, and the resulting dispersion has high stability and can be stored for a long period of time without sedimentation.
  • the nanoparticle-containing mixture obtained by dispersion of the block copolymer is stable for at least two months at room temperature.
  • an ionic interaction force or a van der Waals force exists between a functional group on the surface of the nanoparticle and the block copolymer, whereby the block copolymer can be adsorbed on the surface of the nanoparticle, and after adsorbing the block copolymer, the nanoparticle They are mutually exclusive and thus can be stably dispersed in the dispersion medium.
  • the schematic diagram of the dispersion mechanism is shown in Fig. 1 (A) and Fig. 1 (B).
  • the nanoparticle-containing mixture is at least one selected from the group consisting of lubricating oils, greases, conductive pastes, inks, printing pastes, photoresists, coatings, coatings, and binders.
  • the block copolymer can be stably dispersed in the lubricating oil, the grease, the conductive paste, the ink, the printing paste, the photoresist, the coating, the coating and the binder to solve the nano material in the organic
  • the problem of poor dispersion and stability in the medium thereby effectively improving the tribological properties of the lubricating oil additive, the leveling property of the coating, and the conductivity of the conductive paste in the conductive device.
  • the mass fraction of the nanoparticles is 0.001% to 90% based on the total mass of the nanoparticle-containing mixture. Thereby, the dispersion and stability effects of the nanoparticles are better.
  • the mass ratio of the block copolymer to the nanoparticles is 0.0001 to 10.
  • the block copolymer shape comprises a star block copolymer, a multi-arm block copolymer and a linear block copolymer, preferably a star block copolymer or a multi-arm block copolymer.
  • the block copolymer chemical structure is composed of two types of segments: A segment and B segment, and the block copolymer can be prepared by the synthetic route shown in FIG. 7, wherein FIG. 7 (A) is a synthetic route diagram of a multi-arm or star block copolymer, and FIG. 7 (B) is a synthetic route diagram of a linear block copolymer.
  • the A segment of the block copolymer is formed from a polyolefin that is terminated on one side of the molecular chain backbone.
  • the single-side terminated polyolefin of the molecular chain skeleton is a raw material for forming the A segment, wherein the terminal functional group may be at least one of an acid anhydride, a carboxyl group, an amino group, a hydroxyl group, an epoxy group, and an isocyanate group.
  • the B segment of the block copolymer is formed of a polyether or a polyester, and the blocked functional group used for the B segment is at least one of an acid anhydride, a carboxyl group, an amino group, a hydroxyl group, an epoxy group, and an isocyanate group.
  • the blocked functional group used for the B segment is at least one of an acid anhydride, a carboxyl group, an amino group, a hydroxyl group, an epoxy group, and an isocyanate group.
  • the polyolefin which is mono-terminated at the molecular chain skeleton for forming the A segment is a polyisobutylene which is preferably unilaterally terminated from the molecular chain skeleton, a polybutene which is unilaterally terminated by a molecular chain skeleton, and a single side seal of a molecular chain skeleton. At least one of the polybutadienes at the ends.
  • the molecularly oriented single-side terminated polyisobutylene is at least one of the following:
  • n is independently an integer greater than or equal to 5.
  • the single-side terminated polybutene of the molecular chain skeleton is at least one of the following:
  • each of m1 and m2 is independently an integer greater than or equal to 0, and in each structural formula, m1+m2 is an integer greater than or equal to 5.
  • the molecular chain backbone unilaterally capped polybutadiene is at least one of the following:
  • n is independently an integer greater than or equal to 5.
  • the polyether used to form the B segment may be a polyether polyol, a polyether polyamine or a polyether glycidyl ether.
  • the diol, epoxy compound, siloxane or derivative thereof forms the basic structural unit of the polyether chemical structure, and preferably the repeating unit of the polyether chemical structure is flexible.
  • the glycol may be at least one selected from the group consisting of ethylene glycol, 1,2-propylene glycol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol; an epoxy compound It may be at least one selected from the group consisting of ethylene oxide, propylene oxide, 1,2-butylene oxide and tetrahydrofuran; the siloxane may be selected from dimethyl siloxane or diethyl siloxane. At least one of them. Thereby, the dispersion stability of the nanoparticles is good.
  • the repeating unit of the polyether When the number of carbon atoms of the repeating unit of the polyether is more than 2, the repeating unit is hydrophobic, and conversely it is hydrophilic.
  • the structural unit of the polyether is at least one of the following:
  • each x is independently an integer greater than or equal to 1.
  • another precursor forming the B segment consists of a polyester structure.
  • Polyester can be polyester Polyol, polyester polyamine, or polyester glycidyl ether.
  • the diol, siloxane or its derivative, alkyd/dicarboxylic acid/lactone or a derivative thereof form the basic structural unit of the polyester, and preferably the structural unit of the polyester is flexible.
  • the glycol may be at least one selected from the group consisting of ethylene glycol, 1,2-propylene glycol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol.
  • the siloxane may be at least one selected from the group consisting of dimethyl siloxane or diethyl siloxane; the alkyd/dicarboxylic acid/lactone or a derivative thereof may be an alkyl substituted ⁇ -butyl At least one of a lactone, an alkyl-substituted ⁇ -valerolactone, an alkyl-substituted ⁇ -caprolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, and a fatty acid. Thereby, the dispersion stability of the nanoparticles is good.
  • the repeating structural unit of the polyester does not contain a polyether structural unit, and the number of carbon atoms is more than 6, the repeating unit is hydrophobic, and conversely, it is hydrophilic.
  • the structural unit of the polyester is at least one of the following:
  • each x is independently an integer greater than or equal to 1
  • each r is independently an integer from 0 to 18, and each t is independently an integer from 2 to 12.
  • R 1 is a hydrocarbon group or a hydrocarbyloxy group, the hydrocarbon group is preferably an alkyl group of eight or less carbon atoms, and the alkoxy group is preferably an alkoxy group of eight or less carbon atoms.
  • the topologies of the polyethers or polyesters used to form the B segments are each independently selected from at least one of a star shape, a multi-arm shape and a linear shape, preferably a star shape or a multi-arm shape.
  • the topologies of the polyether and the polyester are each independently at least one of the following:
  • each of A 1 , A 2 , A 3 , ..., A n is independently a repeating unit of the polyether or the polyester, R 2 is -H or -CH 2 -CH 3 , and z is 0 or 2
  • Each Y is independently a capping functional group, and is at least one of an acid anhydride, a carboxyl group, an amino group, a hydroxyl group, an epoxy group, and an isocyanate group; each x1, x2, x3, ..., xn represents the number of repeating units; each x1, X2, x3, ..., xn are independently integers greater than or equal to 0, and satisfy x1 + x2 + x3 +, ..., + xn ⁇ 1.
  • a star topology a multi-arm topology
  • common raw materials for forming a star structure unit and a multi-arm structure unit are glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and three. Hydroxymethyl methylamine.
  • the raw material forming the star structure and the multi-arm structural unit is at least one of the following:
  • the macromolecular chemical reaction involved in the synthesis of the block copolymer may be one of these reactions: condensation of a carboxyl group with a hydroxyl group, condensation of a carboxyl group with an amino group, formation of an ester bond in an alcoholic hydroxyl environment, and an acid anhydride in an amino environment.
  • An amide bond is formed, an addition reaction of a hydroxyl group with an isocyanate, an addition reaction of an amino group with an isocyanate, an opening reaction of an epoxy group with an epoxy group, and a ring opening reaction of an epoxy group with an amino group.
  • block copolymer of the present invention can be synthesized by the macromolecular chemical reaction of one of the above.
  • the block copolymer was prepared by the general synthetic route shown in Figure 7.
  • a three-arm block copolymer can be prepared according to the synthetic route shown below:
  • a four-arm block copolymer can be prepared according to the synthetic route shown below:
  • star block copolymer can be prepared according to the synthetic route shown below:
  • a linear block copolymer can be prepared according to the synthetic route shown below:
  • a three-arm block copolymer can be prepared according to the synthetic route shown below:
  • a four-arm block copolymer can be prepared according to the synthetic route shown below:
  • star block copolymer can be prepared according to the synthetic route shown below:
  • the linear block copolymer can be prepared according to the synthetic route shown below:
  • the shape of the nanoparticles is at least one selected from the group consisting of a sphere, a sheet, a rod, and a line. Thereby, the dispersion effect and stability of the nanoparticles are good.
  • the spherical nanoparticles, the rod-shaped nanoparticles, and the linear nanoparticles are at least one selected from the group consisting of metal oxide particles, metal sulfide particles, metal particles, metal particles indicating oxidation treatment, and surface-sulfur treated metal particles.
  • the metal oxide particles are selected from the group consisting of silica, alumina, zinc oxide, copper oxide, nickel oxide, cobalt oxide, iron oxide, magnesium oxide, titanium oxide, zirconium oxide, tungsten oxide, and oxidation. At least one of molybdenum. Thereby, it is advantageous to improve the dispersion effect and stability of the nanoparticles.
  • the metal sulfide particles are at least one selected from the group consisting of zinc sulfide, cadmium sulfide, mercury sulfide, iron sulfide, cobalt sulfide, nickel sulfide, tungsten sulfide, and molybdenum sulfide.
  • the metal particles are at least one selected from the group consisting of cobalt, iron, magnesium, aluminum, titanium, zirconium, silver, gold, or alloys thereof. Thereby, it is advantageous to improve the dispersion effect and stability of the nanoparticles.
  • the flaky nano-particles are selected from the group consisting of layered double hydroxides, clays, layered metal phosphates, layered metal tungstates, layered metal sulfides, graphite oxides, graphene oxides, At least one of its derivatives.
  • the prepared block copolymer can stably disperse the nanoparticles in a suitable solvent regardless of whether the B segment formed by the polyether or the polyester is hydrophilic.
  • the B segment in the block copolymer is preferably hydrophobic; in order to better disperse the hydrophilic nanoparticles, it is preferred that the B segment is hydrophilic.
  • the invention provides a process for preparing a mixture comprising a block copolymer and a nanoparticle; the block copolymer types used include star block copolymers, multi-arm block copolymers and linear block copolymers.
  • the method comprises mixing a block copolymer, a nanoparticle and a dispersion medium to obtain the nanoparticle-containing mixture.
  • the inventors have found that the nanoparticle-containing mixture having good dispersion stability can be prepared quickly and efficiently by the method of the present invention, and is simple in operation, convenient and quick, low in cost, and easy to realize mass production.
  • block copolymers and nanoparticles described in the method of the present invention have all the features and advantages of the block copolymers and nanoparticles described above, and will not be further described herein.
  • the invention provides a mixture comprising a block copolymer and a nanoparticle, the type of block copolymer used comprising a star block copolymer, a multi-arm block copolymer and a linear block copolymer.
  • the nanoparticle-containing mixture is prepared by the method described above. The inventors have found that the nanoparticle-containing mixture of the present invention has a good dispersion stability and can be stored for a long period of time without being likely to cause sedimentation.
  • the block copolymers and nanoparticles have all of the features and advantages of the block copolymers and nanoparticles described above, and will not be further described herein.
  • PIBSA polyisobutylene succinic anhydride
  • 200 ml of n-hexane were dissolved in a 500 ml three-necked flask, and then the three-necked bottle was placed under a nitrogen atmosphere under continuous stirring.
  • PIBSA polyisobutylene succinic anhydride
  • polyetheramine T-403 molecular weight: 440 g/mol, three-armed polymer, one amino group at the end of the molecular chain of each arm
  • the polyetheramine T-403 solution is added dropwise to the three-necked bottle, and the resulting solution is stirred at 60 ° C for at least 8 hours until the solution turns yellow.
  • the white emulsion is evaporated in vacuo to remove the solvent to give the product as a viscous pale yellow liquid.
  • PIBSA polyisobutylene succinic anhydride
  • each molecular chain branch has a hydroxyl group at the end.
  • PIBSA polyisobutylene succinic anhydride
  • Example 5 Dispersion of ZrO 2 and TiO 2 using a three-arm block copolymer
  • the granules are mixed with liquid paraffin to prepare a mass fraction of isobutylene-glycerol-isobutylene three-arm block copolymer of 5%, and the mass fractions of ZrO 2 nanoparticles and TiO 2 nanoparticles are 0.01%, 0.05%, 0.1, respectively.
  • Mixture of %, 0.2%, 0.3%, 0.4% and 1% The dispersion effect is shown in Fig.
  • the prepared three-arm block copolymer has very good dispersion stability for different concentrations of nanoparticles.
  • the experimental results show that the dispersed nanoparticles can be stably left standing for at least two months.
  • the experimental results show that in the longer time scale range, the prepared three-arm block copolymer is used to disperse the nanoparticles. When the nanoparticles are settled to a small extent, the nanoparticles do not settle and the entire dispersion system reaches equilibrium.
  • Example 6 Dispersing ZrO 2 and TiO 2 using a four-arm block copolymer
  • the hydrophilic particles were mixed with liquid paraffin to prepare a mixture of an isobutylene-pentaerythritol propoxylate-isobutylene four-arm block copolymer having a mass fraction of 5% and a ZrO 2 nanoparticle and a TiO 2 nanoparticle of 1%.
  • the dispersion effect is shown in Fig. 3. As can be seen from Fig.
  • the prepared four-arm block copolymer has very good dispersion stability to the nanoparticles.
  • the experimental results show that the dispersed nanoparticles can be stably left standing for at least two months. Moreover, the experimental results show that the nanoparticles are dispersed by the prepared four-arm block copolymer in a longer time scale. After the nanoparticles are settled to a small extent, the nanoparticles do not settle and the entire dispersion reaches equilibrium.
  • Example 7 Dispersing ZrO 2 and TiO 2 using a linear block copolymer
  • the isobutylene-glycerol-isobutylene linear block copolymer prepared in Example 4 ZrO 2 nanoparticles (particle diameter 50 ⁇ 5 nm, high-temperature sintered particles), TiO 2 nanoparticles (particle diameter 25 ⁇ 5 nm, hydrophilicity)
  • the granules were mixed with liquid paraffin to prepare a mixture of an isobutylene-glycerol-isobutylene linear block copolymer having a mass fraction of 5% and a ZrO 2 nanoparticle and a TiO 2 nanoparticle of 1%.
  • the dispersion effect is shown in Fig. 4. As can be seen from Fig. 4, the prepared linear block copolymer has very good dispersion stability to the nanoparticles.
  • the experimental results show that the dispersed nanoparticles can be stably left standing for at least two months. Moreover, the experimental results show that in the longer time scale range, the prepared linear block copolymer disperses the nanoparticles, and after the nanoparticles are settled in a small amount, the nanoparticles do not settle and the entire dispersion system reaches equilibrium.
  • Example 8 Dispersing nano copper particles by using a three-arm block copolymer and a star block copolymer
  • the paraffin wax was mixed with a three-arm block copolymer and a star-block copolymer each having a mass fraction of 5% and a copper nanoparticle having a mass fraction of 1%.
  • the dispersion effect is shown in Fig. 5.
  • the prepared three-arm block copolymer and the star block copolymer have good dispersion stability to the nanoparticles.
  • the experimental results show that the dispersed nanoparticles can be stably left standing for at least two months. Moreover, the experimental results show that in the longer time scale range, the prepared three-arm block copolymer and the star block copolymer are used to disperse the nanoparticles, and after the nanoparticles are settled to a small part, the nanoparticles do not settle and the whole dispersion The system reached equilibrium.
  • Example 9 Dispersing ZrO 2 and TiO 2 with oleic acid
  • the mass fraction of oleic acid is 5%
  • the ZrO 2 nanoparticles and the TiO 2 nanoparticles have a mass fraction of 1%.
  • the dispersion effect is shown in Fig. 6.
  • the oleic acid small molecule surfactant has a poor dispersion effect on the nanoparticles, and the nanoparticles almost settled in about two days.

Abstract

Provided is a kind of mixture containing nano-particles, which is prepared by using a star-shaped block copolymer and a multi-arm block copolymer, and also provided are a method for preparing the mixture containing such block copolymers and nano-particles and a use thereof.

Description

星形/多臂嵌段共聚物在制备含有纳米粒子的混合物中的用途Use of star/multiarm block copolymers in the preparation of mixtures containing nanoparticles 技术领域Technical field
本发明涉及材料科学领域，具体的，涉及星形/多臂嵌段共聚物在制备含有纳米粒子的混合物中的用途。This invention relates to the field of materials science and, in particular, to the use of star/multiarm block copolymers in the preparation of mixtures containing nanoparticles.
背景技术Background technique
纳米材料在润滑油、润滑脂、导电浆料、油墨、打印胶、光刻胶、涂料、涂层和粘结剂等产品中有广泛应用。改善纳米材料在这些介质中的分散性，有望显著改善润滑油添加剂的摩擦学性能、涂料的流平性、导电浆料在导电装置中的导电性等。Nanomaterials are widely used in lubricants, greases, conductive pastes, inks, printing pastes, photoresists, coatings, coatings and adhesives. Improving the dispersibility of nanomaterials in these media is expected to significantly improve the tribological properties of the lubricant additive, the leveling of the coating, and the conductivity of the conductive paste in the conductive device.
纳米粒子粒度小，表面能高，粒子之间容易发生团聚，纳米材料在有机介质中的分散和稳定成为限制其广泛应用的主要技术问题之一。实际应用中常常用表面活性剂改善纳米颗粒的分散均匀性、稳定性。常用的低分子表面活性剂有长链烷基醇、长链烷基胺、长链烷基羧酸等。常用的聚合物表面活性剂有聚醚类表面活性剂、聚多糖类表面活性剂、梳状高分子表面活性剂等。Nanoparticles have small particle size, high surface energy, and easy agglomeration between particles. The dispersion and stabilization of nanomaterials in organic media has become one of the main technical problems that limit its wide application. In practical applications, surfactants are often used to improve the dispersion uniformity and stability of the nanoparticles. Commonly used low molecular surfactants are long chain alkyl alcohols, long chain alkyl amines, long chain alkyl carboxylic acids and the like. Commonly used polymer surfactants are polyether surfactants, polysaccharide surfactants, comb polymer surfactants, and the like.
现有的聚醚类表面活性剂包括烷基聚醚醇(Alkyl Polyether Alcohols)、烷基芳基聚醚醇(Alkylaryl Polyether Alcohols)和聚醚嵌段共聚物(Polyether Block Copolymers)。烷基聚醚醇中，用烷基链封端的乙氧基/丙氧基化物(Alkyl PEG/PPG Ethers)为该类代表。烷基芳基聚醚醇中，以辛基酚封端的乙氧基/丙氧基化物(Octylphenol PEG/PPG Ethers)为该类代表。聚醚嵌段共聚物中，以聚乙二醇、聚丙二醇为结构单元形成的嵌段共聚物为代表，包括Poloxamer、Hypermer、Zephrym线形聚醚嵌段共聚物、Tetronic支化水溶性聚醚嵌段共聚物。Existing polyether surfactants include Alkyl Polyether Alcohols, Alkylaryl Polyether Alcohols, and Polyether Block Copolymers. Among the alkyl polyether alcohols, an alkyl group-terminated ethoxy/propoxylate (Alkyl PEG/PPG Ethers) is representative of this class. Among the alkylaryl polyether alcohols, octylphenol-terminated ethoxy/propoxylate (Octylphenol PEG/PPG Ethers) is representative of this class. Among the polyether block copolymers, block copolymers formed by using polyethylene glycol and polypropylene glycol as structural units are representative, including Poloxamer, Hypermer, Zephrym linear polyether block copolymer, and Tetronic branched water-soluble polyether embedded. Segment copolymer.
已有的研究多用聚醚类表面活性剂在极性介质中分散纳米颗粒。然而，在这类应用中，现有的聚醚类表面活性剂只能在短时间内使低浓度的纳米颗粒体系保持分散均匀稳定。在时间延长(通常一周时间)或者高浓度纳米颗粒条件下，现有的聚醚类表面活性剂已经不能使纳米颗粒保持分散均匀稳定，这种不均匀、不稳定性在非极性介质中表现尤为明显。现有的聚醚类表面活性剂的这种使纳米颗粒不均匀、不稳定性质，限制了其应用范围，特别是限制了其在涂料技术和油墨技术中的应用。Previous studies have used polyether surfactants to disperse nanoparticles in polar media. However, in such applications, existing polyether surfactants can only maintain a uniform dispersion of low concentration nanoparticle systems in a short period of time. Under the condition of prolonged time (usually one week) or high concentration of nanoparticles, the existing polyether surfactants have been unable to keep the nanoparticles uniformly dispersed and stable. This unevenness and instability are manifested in non-polar media. Especially obvious. The non-uniform, unstable nature of the existing polyether surfactants limits the range of applications, and in particular limits their use in coating technology and ink technology.
因而，对纳米材料的分散技术仍有待改善。Therefore, the dispersion technology for nanomaterials still needs to be improved.
发明内容Summary of the invention
本发明旨在至少在一定程度上解决相关技术领域中的技术问题之一。为此，本发明的 一个目的在于提出星形嵌段共聚物、多臂嵌段共聚物在制备含有纳米粒子的混合物中的新用途。The present invention aims to solve at least one of the technical problems in the related art at least to some extent. To this end, the invention One purpose is to propose a new use of star block copolymers, multi-arm block copolymers in the preparation of mixtures containing nanoparticles.
本发明是基于发明人的以下发现而完成的：The present invention has been completed based on the following findings of the inventors:
纳米粒子表面通常带有羟基、羧基或其他极性官能团，由此，聚合物和纳米粒子之间存在离子相互作用力和范德华力。具体而言，离子键是阴离子和阳离子通过静电相互作用形成的化学键，离子键具有不饱和、无方向性的特征。当接触液体介质时，离子型分散剂通过对纳米粒子的吸附作用而覆盖在纳米粒子表面，从而使得纳米粒子表面带有电荷而彼此排斥。发明人发现，这种策略可以有效地用于分散表面带有羧基等离子官能团的纳米粒子。分散剂与纳米粒子表面上接枝基团中的未成键原子之间存在范德华力，低分子量分散剂和纳米粒子之间的范德华力作用甚微，但采用聚合物分散剂则效果完全不同。聚合物链中结构单元的数量非常庞大，而每一个结构单元均相当于一个小分子。范德华力没有指向性、且不会饱和，因此聚合物链和纳米粒子之间的范德华力足够大而使得聚合物能够包覆纳米粒子表面的至少一部分。发明人发现，这种策略可以用于分散表面带有非离子官能团的纳米粒子。The surface of the nanoparticles typically carries hydroxyl, carboxyl or other polar functional groups, whereby ionic interaction forces and van der Waals forces are present between the polymer and the nanoparticles. Specifically, the ionic bond is a chemical bond formed by an electrostatic interaction between an anion and a cation, and the ionic bond is characterized by being unsaturated and non-directional. When contacting the liquid medium, the ionic dispersant covers the surface of the nanoparticles by adsorbing the nanoparticles, so that the surfaces of the nanoparticles are charged with one another and repel each other. The inventors have found that this strategy can be effectively used to disperse nanoparticles having carboxyl-plasma functional groups on the surface. There is a van der Waals force between the dispersant and the unbonded atoms in the graft group on the surface of the nanoparticles. The van der Waals force between the low molecular weight dispersant and the nanoparticles has little effect, but the effect is completely different with the polymer dispersant. The number of structural units in a polymer chain is very large, and each structural unit is equivalent to a small molecule. Van der Waals forces are not directional and do not saturate, so the van der Waals forces between the polymer chains and the nanoparticles are large enough to allow the polymer to coat at least a portion of the surface of the nanoparticles. The inventors have found that this strategy can be used to disperse nanoparticles with nonionic functional groups on the surface.
因而，在本发明的第一方面，本发明提供了嵌段共聚物在制备含有纳米粒子的混合物中的用途，所述嵌段共聚物为选自星形嵌段共聚物和多臂嵌段共聚物中的至少一种。发明人发现，使用本发明提供的嵌段共聚物能够有效将纳米粒子分散于有机介质中，形成的分散体系稳定性高，能够长期储存而不发生沉降。Thus, in a first aspect of the invention, the invention provides the use of a block copolymer in the preparation of a mixture comprising nanoparticles selected from the group consisting of a star block copolymer and a multi-arm block copolymer At least one of the substances. The inventors have found that the use of the block copolymer provided by the present invention can effectively disperse nanoparticles in an organic medium, and the resulting dispersion has high stability and can be stored for a long period of time without sedimentation.
根据本发明的示例，所述含有纳米粒子的混合物为选自润滑油、润滑脂、导电浆料、油墨、打印胶、光刻胶、涂料、涂层和粘结剂中的至少一种。According to an example of the present invention, the nanoparticle-containing mixture is at least one selected from the group consisting of lubricating oils, greases, conductive pastes, inks, printing pastes, photoresists, coatings, coatings, and binders.
根据本发明的示例，基于所述含有纳米粒子的混合物的总质量，所述纳米粒子的质量分数为0.001％～90％。According to an example of the present invention, the mass fraction of the nanoparticles is 0.001% to 90% based on the total mass of the nanoparticle-containing mixture.
根据本发明的示例，所述嵌段共聚物和所述纳米粒子的质量比为(0.0001-10)：1。According to an example of the present invention, the mass ratio of the block copolymer to the nanoparticles is (0.0001-10):1.
根据本发明的示例，所述嵌段共聚物化学结构由A链段和B链段两类链段构成。According to an example of the present invention, the block copolymer chemical structure is composed of two types of segments, an A segment and a B segment.
根据本发明的示例，所述A链段由分子链骨架单侧封端的聚烯烃形成，所述A链段所用封端官能团为酸酐、羧基、氨基、羟基、环氧基和异氰酸酯基中的至少一种。According to an example of the present invention, the A segment is formed of a polyolefin terminated on one side by a molecular chain skeleton, and the blocked functional group used in the A segment is at least at least an acid anhydride, a carboxyl group, an amino group, a hydroxyl group, an epoxy group, and an isocyanate group. One.
根据本发明的示例，所述B链段由聚醚或聚酯形成，所述B链段所用封端官能团为酸酐、羧基、氨基、羟基、环氧基和异氰酸酯基中的至少一种。According to an example of the present invention, the B segment is formed of a polyether or a polyester, and the blocked functional group used for the B segment is at least one of an acid anhydride, a carboxyl group, an amino group, a hydroxyl group, an epoxy group, and an isocyanate group.
根据本发明的示例，所述分子链骨架单侧封端的聚烯烃为选自分子链骨架单侧封端的聚异丁烯、分子链骨架单侧封端的聚丁烯和分子链骨架单侧封端的聚丁二烯中的至少一种。According to an example of the present invention, the single-side terminated polyolefin of the molecular chain skeleton is a polyisobutylene which is one-side terminated from a molecular chain skeleton, a polybutene which is unilaterally terminated by a molecular chain skeleton, and a polybutene which is unilaterally terminated by a molecular chain skeleton. At least one of the dienes.
根据本发明的示例，所述分子链骨架单侧封端的聚异丁烯为下列至少之一： According to an example of the present invention, the molecularly oriented single-side terminated polyisobutylene is at least one of the following:
Figure PCTCN2015074326-appb-000001
Figure PCTCN2015074326-appb-000001
其中，各n独立地为大于等于5的整数。Wherein each n is independently an integer greater than or equal to 5.
根据本发明的示例，所述分子链骨架单侧封端的聚丁烯为下列至少之一：According to an example of the present invention, the single-side terminated polybutene of the molecular chain skeleton is at least one of the following:
Figure PCTCN2015074326-appb-000002
Figure PCTCN2015074326-appb-000002
其中，m1和m2各自独立地为大于等于0的整数，且m1+m2为大于等于5的整数。根据本发明的示例，所述分子链骨架单侧封端的聚丁二烯为下列至少之一：Wherein m1 and m2 are each independently an integer greater than or equal to 0, and m1+m2 is an integer greater than or equal to 5. According to an embodiment of the invention, the molecular chain backbone unilaterally capped polybutadiene is at least one of the following:
Figure PCTCN2015074326-appb-000003
Figure PCTCN2015074326-appb-000003
Figure PCTCN2015074326-appb-000004
Figure PCTCN2015074326-appb-000004
其中，i+j+k＝1，各n独立地为大于等于5的整数。Where i+j+k=1, each n is independently an integer greater than or equal to 5.
根据本发明的示例，所述聚醚由选自聚醚多元醇、聚醚多胺和聚醚缩水甘油醚中的至少一种形成。According to an example of the invention, the polyether is formed from at least one selected from the group consisting of polyether polyols, polyether polyamines, and polyether glycidyl ethers.
根据本发明的示例，所述聚醚的结构单元为下列至少之一：According to an example of the invention, the structural unit of the polyether is at least one of the following:
Figure PCTCN2015074326-appb-000005
Figure PCTCN2015074326-appb-000005
其中，各x独立地为大于等于1的整数。Wherein each x is independently an integer greater than or equal to 1.
根据本发明的示例，所述聚酯由选自聚酯多元醇、聚酯多胺和聚酯缩水甘油醚中的至少一种形成。According to an example of the present invention, the polyester is formed of at least one selected from the group consisting of polyester polyols, polyester polyamines, and polyester glycidyl ethers.
根据本发明的示例，所述聚酯的结构单元为下列至少之一：According to an example of the invention, the structural unit of the polyester is at least one of the following:
Figure PCTCN2015074326-appb-000006
Figure PCTCN2015074326-appb-000006
其中，各x独立地为大于等于1的整数，Wherein each x is independently an integer greater than or equal to 1,
各r独立地为0-18的整数， Each r is independently an integer from 0 to 18,
各t独立地为2-12的整数，Each t is independently an integer of 2-12,
R1为烃基或者烃氧基。R 1 is a hydrocarbon group or a hydrocarbyloxy group.
根据本发明的示例，所述聚醚与所述聚酯的拓扑结构各自独立的为选自星形、多臂形中的至少一种。According to an example of the present invention, the topologies of the polyether and the polyester are each independently selected from at least one of a star shape and a multi-arm shape.
根据本发明的示例，所述聚醚与所述聚酯的拓扑结构各自独立的为下列的至少之一：According to an example of the invention, the topologies of the polyether and the polyester are each independently at least one of the following:
Figure PCTCN2015074326-appb-000007
Figure PCTCN2015074326-appb-000007
其中，各A1,A2,A3,…,An独立地为所述聚醚或所述聚酯的重复单元，Wherein each of A 1 , A 2 , A 3 , ..., A n is independently a repeating unit of the polyether or the polyester,
R2为-H或-CH2-CH3， R 2 is -H or -CH 2 -CH 3 ,
z为0或2；z is 0 or 2;
各Y独立地为封端官能团，所述封端官能团为酸酐、羧基、氨基、羟基、环氧基和异氰酸酯基中的至少一种；Each Y is independently a capping functional group, and the capping functional group is at least one of an acid anhydride, a carboxyl group, an amino group, a hydroxyl group, an epoxy group, and an isocyanate group;
各x1,x2,x3,…,xn表示重复单元的数量；各x1,x2,x3,…,xn独立地为大于等于0的整数，且满足x1+x2+x3+,…,+xn≥1。Each x1, x2, x3, ..., xn represents the number of repeating units; each x1, x2, x3, ..., xn is independently an integer greater than or equal to 0, and satisfies x1 + x2 + x3 +, ..., + xn ≥ 1.
根据本发明的示例，星形拓扑结构、多臂形拓扑结构的聚醚或聚酯可以由下列至少之一形成：According to an example of the invention, a star topology, a polyether or polyester of a multi-arm topology may be formed by at least one of the following:
Figure PCTCN2015074326-appb-000008
Figure PCTCN2015074326-appb-000008
根据本发明的示例，所述纳米粒子的形状为选自球形、片状、棒状或线形中的至少一种。According to an example of the present invention, the shape of the nanoparticles is at least one selected from the group consisting of a sphere, a sheet, a rod, and a line.
根据本发明的示例，球形纳米粒子、棒状纳米粒子与线形纳米粒子为选自金属氧化物颗粒、金属硫化物颗粒、金属颗粒、表明氧化处理的金属颗粒和表面硫化处理的金属颗粒中的至少一种。According to an example of the present invention, the spherical nanoparticles, the rod-shaped nanoparticles, and the linear nanoparticles are at least one selected from the group consisting of metal oxide particles, metal sulfide particles, metal particles, metal particles indicating oxidation treatment, and surface-sulfur treated metal particles. Kind.
根据本发明的示例，所述金属氧化物颗粒为选自二氧化硅、氧化铝、氧化锌、氧化铜、氧化镍、氧化钴、氧化铁、氧化镁、氧化钛、氧化锆、氧化钨和氧化钼中的至少一种。According to an embodiment of the invention, the metal oxide particles are selected from the group consisting of silica, alumina, zinc oxide, copper oxide, nickel oxide, cobalt oxide, iron oxide, magnesium oxide, titanium oxide, zirconium oxide, tungsten oxide, and oxidation. At least one of molybdenum.
根据本发明的示例，金属硫化物颗粒为选自硫化锌，硫化镉，硫化汞，硫化铁，硫化钴，硫化镍，硫化钨和硫化钼中的至少一种。According to an example of the present invention, the metal sulfide particles are at least one selected from the group consisting of zinc sulfide, cadmium sulfide, mercury sulfide, iron sulfide, cobalt sulfide, nickel sulfide, tungsten sulfide, and molybdenum sulfide.
根据本发明的示例，所述金属颗粒为选自钴、铁、镁、铝、钛、锆、银、金或其合金中的至少一种。According to an example of the present invention, the metal particles are at least one selected from the group consisting of cobalt, iron, magnesium, aluminum, titanium, zirconium, silver, gold, or alloys thereof.
根据本发明的示例，片状纳米颗为选自层状双金属氢氧化物、粘土、层状金属磷酸盐，层状金属钨酸盐，层状金属硫化物、氧化石墨，石墨烯氧化物，及其衍生物中的至少一种。According to an example of the present invention, the flaky nano-particles are selected from the group consisting of layered double hydroxides, clays, layered metal phosphates, layered metal tungstates, layered metal sulfides, graphite oxides, graphene oxides, At least one of its derivatives.
在发明的第二方面，本发明提供制备含有纳米粒子混合物的方法。根据本发明的示例，该方法包括：将嵌段共聚物、纳米粒子和分散介质混合，以便获得所述含有纳米粒子的混合物。发明人发现，利用本发明的方法能够快速有效地制备获得分散稳定性良好的含有纳米粒子的混合物，且操作简单，方便快捷，成本低廉，易于实现大规模生产。In a second aspect of the invention, the invention provides a method of preparing a mixture comprising nanoparticles. According to an example of the invention, the method comprises mixing a block copolymer, a nanoparticle and a dispersion medium to obtain the nanoparticle-containing mixture. The inventors have found that the nanoparticle-containing mixture having good dispersion stability can be prepared quickly and efficiently by the method of the present invention, and is simple in operation, convenient and quick, low in cost, and easy to realize mass production.
在发明的第三方面，本发明提供了含有纳米粒子的混合物。根据本发明的示例，所述含有纳米粒子的混合物是利用前面所述的方法制备的。发明人发现，本发明的含有纳米粒 子的混合物分散稳定性较佳，能够较长时间储存而不发生沉降现象。In a third aspect of the invention, the invention provides a mixture comprising nanoparticles. According to an example of the invention, the nanoparticle-containing mixture is prepared by the method described above. The inventors have found that the present invention contains nanoparticles The mixture has good dispersion stability and can be stored for a long time without sedimentation.
附图说明DRAWINGS
图1显示了根据本发明的示例，利用嵌段共聚物分散纳米粒子的机理示意图，纳米粒子以球形颗粒为代表，其中：1 shows a schematic diagram of a mechanism for dispersing nanoparticles using a block copolymer according to an example of the present invention, the nanoparticles being represented by spherical particles, wherein:
图1(A)显示了根据本发明的示例，利用星形或者多臂嵌段共聚物分散纳米粒子的机理示意图；图1(B)显示了根据本发明的示例，利用线形嵌段共聚物分散纳米粒子的机理示意图；1(A) shows a schematic diagram of a mechanism for dispersing nanoparticles using a star or multi-arm block copolymer according to an example of the present invention; FIG. 1(B) shows an example of dispersing with a linear block copolymer according to an example of the present invention. Schematic diagram of the mechanism of nanoparticles;
图2显示根据本发明的实施例5，利用三臂嵌段共聚物分散ZrO2和TiO2的实际效果示意图，其中：“a1”、“a2”、“a3”、“a4”、“a5”、“a6”和“a7”分别代表ZrO2纳米粒子质量分数分别为0.01％、0.05％、0.1％、0.2％、0.3％、0.4％和1％的混合物；“b1”、“b2”、“b3”、“b4”、“b5”、“b6”和“b7”分别代表TiO2纳米粒子的质量分数分别为0.01％、0.05％、0.1％、0.2％、0.3％、0.4％和1％的混合物，图2各个子图含义如下： 2 is a schematic view showing the actual effect of dispersing ZrO 2 and TiO 2 using a three-arm block copolymer according to Example 5 of the present invention, wherein: "a1", "a2", "a3", "a4", "a5""a6" and "a7" represent a mixture of ZrO 2 nanoparticle mass fractions of 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4% and 1%, respectively; "b1", "b2", "B3","b4","b5","b6", and "b7" represent the mass fractions of TiO 2 nanoparticles of 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, and 1%, respectively. The mixture, the subgraphs in Figure 2 have the following meanings:
图2(A)显示根据本发明的实施例5，纳米粒子刚刚被超声分散后的效果图；2(A) is a view showing the effect of the nanoparticles immediately after being dispersed by ultrasound according to Example 5 of the present invention;
图2(B)显示根据本发明的实施例5，纳米粒子被分散一天后的实际效果图；2(B) is a view showing the actual effect of the nanoparticles after being dispersed for one day according to Embodiment 5 of the present invention;
图2(C)显示根据本发明的实施例5，纳米粒子被分散四天后的实际效果图；2(C) is a view showing the actual effect of the nanoparticles after being dispersed for four days according to Example 5 of the present invention;
图2(D)显示根据本发明的实施例5，纳米粒子被分散十二天后的实际效果图；2(D) is a view showing the actual effect of the nanoparticles after being dispersed for 12 days according to Example 5 of the present invention;
图2(E)显示根据本发明的实施例5，纳米粒子被分散二十五天后的实际效果图；2(E) shows a practical effect diagram of the nanoparticles after being dispersed for twenty-five days according to Example 5 of the present invention;
图2(F)显示根据本发明的实施例5，纳米粒子被分散五十五天后的实际效果图；2(F) is a view showing the actual effect of the nanoparticles after being dispersed for fifty-five days according to Example 5 of the present invention;
图2(G)显示根据本发明的实施例5，纳米粒子被分散六十五天后的实际效果图；2(G) shows a practical effect diagram of the nanoparticles after being dispersed for sixty-five days according to Example 5 of the present invention;
图3显示根据本发明的实施例6，利用四臂嵌段共聚物分散ZrO2和TiO2的实际效果示意图，其中：“a”代表ZrO2纳米粒子，“b”代表TiO2纳米粒子；3 is a schematic view showing the actual effect of dispersing ZrO 2 and TiO 2 using a four-arm block copolymer according to Example 6 of the present invention, wherein: "a" represents ZrO 2 nanoparticles, and "b" represents TiO 2 nanoparticles;
图4显示根据本发明的实施例7，利用线形嵌段共聚物分散ZrO2和TiO2的实际效果示意图，其中：“a”代表ZrO2纳米粒子，“b”代表TiO2纳米粒子；4 is a schematic view showing the actual effect of dispersing ZrO 2 and TiO 2 using a linear block copolymer according to Example 7 of the present invention, wherein: "a" represents ZrO 2 nanoparticles, and "b" represents TiO 2 nanoparticles;
图5显示根据本发明的实施例8，利用三臂嵌段共聚物、星形嵌段共聚物分散纳米铜颗粒的实际效果示意图，其中：“a”代表利用三臂嵌段共聚物分散纳米铜颗粒，“b”代表利用星形嵌段共聚物分散纳米铜颗粒；5 is a schematic view showing the actual effect of dispersing nano copper particles by using a three-arm block copolymer and a star block copolymer according to Example 8 of the present invention, wherein: "a" represents dispersing nano copper by using a three-arm block copolymer. Particles, "b" represents the dispersion of nano-copper particles using a star block copolymer;
图6显示根据本发明的实施例9，利用油酸分散ZrO2和TiO2的实际效果示意图，其中：“a”代表ZrO2纳米粒子，“b”代表TiO2纳米粒子；以及6 is a schematic view showing the actual effect of dispersing ZrO 2 and TiO 2 using oleic acid according to Example 9 of the present invention, wherein: "a" represents ZrO 2 nanoparticles, and "b" represents TiO 2 nanoparticles;
图7显示了根据本发明的实施例，嵌段共聚物的合成路线图，其中，Figure 7 shows a synthetic route diagram of a block copolymer according to an embodiment of the present invention, wherein
图7(A)为星形或多臂形嵌段共聚物的合成路线图，Figure 7 (A) is a synthetic route diagram of a star or multi-arm block copolymer,
图7(B)为线形嵌段共聚物的合成路线图。 Fig. 7(B) is a synthetic route diagram of the linear block copolymer.
具体实施方式detailed description
下面详细描述本发明的实施例。下面描述的实施例是示例性的，仅用于解释本发明，而不能理解为对本发明的限制。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。Embodiments of the present invention are described in detail below. The embodiments described below are illustrative only and are not to be construed as limiting the invention. Where specific techniques or conditions are not indicated in the examples, they are carried out according to the techniques or conditions described in the literature in the art or in accordance with the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are conventional products that can be obtained commercially.
在本发明的第一方面，本发明提供了一类嵌段共聚物在制备含有纳米粒子的混合物中的用途，所用嵌段共聚物类型包括星形嵌段共聚物、多臂嵌段共聚物和线形嵌段共聚物。发明人发现，使用本发明提供的嵌段共聚物能够有效将纳米粒子分散于有机介质中，形成的分散体系稳定性高，能够长期储存而不发生沉降。根据本发明的具体实施例，利用嵌段共聚物分散获得的含有纳米粒子的混合物在室温条件下至少可以稳定存在两个月。In a first aspect of the invention, the invention provides the use of a block copolymer in the preparation of a mixture comprising nanoparticles, the type of block copolymer comprising a star block copolymer, a multi-arm block copolymer and Linear block copolymer. The inventors have found that the use of the block copolymer provided by the present invention can effectively disperse nanoparticles in an organic medium, and the resulting dispersion has high stability and can be stored for a long period of time without sedimentation. According to a particular embodiment of the invention, the nanoparticle-containing mixture obtained by dispersion of the block copolymer is stable for at least two months at room temperature.
根据本发明的示例，纳米粒子表面的官能团与嵌段共聚物之间存在离子相互作用力或范德华力，由此，嵌段共聚物可以吸附于纳米粒子表面，吸附嵌段共聚物后，纳米粒子之间相互排斥，由此，可以稳定的分散于分散介质中，分散机理示意图见图1(A)和图1(B)。According to an example of the present invention, an ionic interaction force or a van der Waals force exists between a functional group on the surface of the nanoparticle and the block copolymer, whereby the block copolymer can be adsorbed on the surface of the nanoparticle, and after adsorbing the block copolymer, the nanoparticle They are mutually exclusive and thus can be stably dispersed in the dispersion medium. The schematic diagram of the dispersion mechanism is shown in Fig. 1 (A) and Fig. 1 (B).
根据本发明的示例，所述含有纳米粒子的混合物为选自润滑油、润滑脂、导电浆料、油墨、打印胶、光刻胶、涂料、涂层和粘结剂中的至少一种。由此，能够利用嵌段共聚物将纳米粒子稳定地分散于润滑油、润滑脂、导电浆料、油墨、打印胶、光刻胶、涂料、涂层和粘结剂中，解决纳米材料在有机介质中的分散和稳定性差的问题，进而有效提高润滑油添加剂的摩擦学性能、涂料的流平性、导电浆料在导电装置中的导电性等。According to an example of the present invention, the nanoparticle-containing mixture is at least one selected from the group consisting of lubricating oils, greases, conductive pastes, inks, printing pastes, photoresists, coatings, coatings, and binders. Thereby, the block copolymer can be stably dispersed in the lubricating oil, the grease, the conductive paste, the ink, the printing paste, the photoresist, the coating, the coating and the binder to solve the nano material in the organic The problem of poor dispersion and stability in the medium, thereby effectively improving the tribological properties of the lubricating oil additive, the leveling property of the coating, and the conductivity of the conductive paste in the conductive device.
根据本发明的示例，基于所述含有纳米粒子的混合物的总质量，所述纳米粒子的质量分数为0.001％～90％。由此，纳米粒子的分散和稳定性效果较佳。According to an example of the present invention, the mass fraction of the nanoparticles is 0.001% to 90% based on the total mass of the nanoparticle-containing mixture. Thereby, the dispersion and stability effects of the nanoparticles are better.
根据本发明的示例，所述嵌段共聚物和所述纳米粒子的质量比为0.0001-10。由此，有利于提高纳米粒子的分散和稳定性，且该比例具有显著优于其他比例的分散效果和稳定性。According to an example of the present invention, the mass ratio of the block copolymer to the nanoparticles is 0.0001 to 10. Thereby, it is advantageous to increase the dispersion and stability of the nanoparticles, and the ratio has a dispersion effect and stability which are remarkably superior to other ratios.
根据本发明的示例，所述嵌段共聚物形状包括星形嵌段共聚物、多臂嵌段共聚物和线形嵌段共聚物，优选星形嵌段共聚物或者多臂嵌段共聚物。由此，有利于提高纳米粒子的分散效果和稳定性。According to an example of the invention, the block copolymer shape comprises a star block copolymer, a multi-arm block copolymer and a linear block copolymer, preferably a star block copolymer or a multi-arm block copolymer. Thereby, it is advantageous to improve the dispersion effect and stability of the nanoparticles.
根据本发明的示例，所述嵌段共聚物化学结构由A链段和B链段两类链段构成，所述嵌段共聚物可以通过图7所示的合成路线进行制备，其中，图7(A)为多臂或星形嵌段共聚物的合成路线图，图7(B)为线形嵌段共聚物的合成路线图。According to an example of the present invention, the block copolymer chemical structure is composed of two types of segments: A segment and B segment, and the block copolymer can be prepared by the synthetic route shown in FIG. 7, wherein FIG. 7 (A) is a synthetic route diagram of a multi-arm or star block copolymer, and FIG. 7 (B) is a synthetic route diagram of a linear block copolymer.
根据本发明的示例，所述嵌段共聚物的A链段由分子链骨架单侧封端的聚烯烃形成。According to an example of the invention, the A segment of the block copolymer is formed from a polyolefin that is terminated on one side of the molecular chain backbone.
根据本发明的示例，分子链骨架单侧封端的聚烯烃是形成A链段的原料，其中，端基官能团可以为酸酐、羧基、氨基、羟基、环氧基和异氰酸酯基中的至少一种。 According to an example of the present invention, the single-side terminated polyolefin of the molecular chain skeleton is a raw material for forming the A segment, wherein the terminal functional group may be at least one of an acid anhydride, a carboxyl group, an amino group, a hydroxyl group, an epoxy group, and an isocyanate group.
根据本发明的示例，所述嵌段共聚物的B链段由聚醚或聚酯形成，B链段所用封端官能团为酸酐、羧基、氨基、羟基、环氧基和异氰酸酯基中的至少一种。According to an example of the present invention, the B segment of the block copolymer is formed of a polyether or a polyester, and the blocked functional group used for the B segment is at least one of an acid anhydride, a carboxyl group, an amino group, a hydroxyl group, an epoxy group, and an isocyanate group. Kind.
根据本发明的示例，形成A链段所用分子链骨架单侧封端的聚烯烃为优选自分子链骨架单侧封端的聚异丁烯、分子链骨架单侧封端的聚丁烯和分子链骨架单侧封端的聚丁二烯中的至少一种。According to an example of the present invention, the polyolefin which is mono-terminated at the molecular chain skeleton for forming the A segment is a polyisobutylene which is preferably unilaterally terminated from the molecular chain skeleton, a polybutene which is unilaterally terminated by a molecular chain skeleton, and a single side seal of a molecular chain skeleton. At least one of the polybutadienes at the ends.
根据本发明的示例，所述分子链骨架单侧封端的聚异丁烯为下列至少之一：According to an example of the present invention, the molecularly oriented single-side terminated polyisobutylene is at least one of the following:
Figure PCTCN2015074326-appb-000009
Figure PCTCN2015074326-appb-000009
其中，各n独立地为为大于等于5的整数。Wherein each n is independently an integer greater than or equal to 5.
需要说明的是，除非以其他方式明确指出，在本发明中所采用的描述方式“各…独立地为”与“…各自独立地为”和“…独立地为”可以互换，均应做广义理解，其既可以是指在不同化学结构中，相同符号之间所表达的具体选项之间互相不影响，也可以表示在相同的化学结构中，相同符号之间所表达的具体选项之间互相不影响。It should be noted that, unless otherwise explicitly stated, the descriptions used in the present invention, "each... independently" and "...each independently" and "...independently" are interchangeable and should be done. Broadly understood, it can mean that in different chemical structures, the specific options expressed between the same symbols do not affect each other, and can also be expressed in the same chemical structure, between the specific options expressed between the same symbols. Do not affect each other.
根据本发明的示例，所述分子链骨架单侧封端的聚丁烯为下列至少之一：According to an example of the present invention, the single-side terminated polybutene of the molecular chain skeleton is at least one of the following:
Figure PCTCN2015074326-appb-000010
Figure PCTCN2015074326-appb-000010
其中，各m1和m2各自独立地为大于等于0的整数，且在各个结构式中，m1+m2为大于等于5的整数。Wherein each of m1 and m2 is independently an integer greater than or equal to 0, and in each structural formula, m1+m2 is an integer greater than or equal to 5.
根据本发明的示例，所述分子链骨架单侧封端的聚丁二烯为下列至少之一：According to an embodiment of the invention, the molecular chain backbone unilaterally capped polybutadiene is at least one of the following:
Figure PCTCN2015074326-appb-000011
Figure PCTCN2015074326-appb-000011
其中，在各个结构式中，i+j+k＝1，各n独立地为大于等于5的整数。Here, in each structural formula, i+j+k=1, and each n is independently an integer greater than or equal to 5.
根据本发明的示例，形成B链段所用聚醚可以为聚醚多元醇、聚醚多胺或者聚醚缩水甘油醚。二元醇、环氧化合物、硅氧烷或其衍生物形成聚醚化学结构的基本结构单元，并且优选聚醚化学结构的重复单元是柔性的。其中，二元醇可以为选自乙二醇、1,2-丙二醇、1,2-丁二醇、1,3-丁二醇和1,4-丁二醇中的至少一种；环氧化合物可以为选自环氧乙烷、环氧丙烷、1,2-环氧丁烷和四氢呋喃中的至少一种；硅氧烷可以为选自二甲基硅氧烷或者二乙基硅氧烷中的至少一种。由此，纳米粒子的分散稳定性较好。According to an example of the invention, the polyether used to form the B segment may be a polyether polyol, a polyether polyamine or a polyether glycidyl ether. The diol, epoxy compound, siloxane or derivative thereof forms the basic structural unit of the polyether chemical structure, and preferably the repeating unit of the polyether chemical structure is flexible. Wherein the glycol may be at least one selected from the group consisting of ethylene glycol, 1,2-propylene glycol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol; an epoxy compound It may be at least one selected from the group consisting of ethylene oxide, propylene oxide, 1,2-butylene oxide and tetrahydrofuran; the siloxane may be selected from dimethyl siloxane or diethyl siloxane. At least one of them. Thereby, the dispersion stability of the nanoparticles is good.
当聚醚的重复单元的碳原子数大于2时，重复单元是疏水性的，反之则是亲水性的。When the number of carbon atoms of the repeating unit of the polyether is more than 2, the repeating unit is hydrophobic, and conversely it is hydrophilic.
根据本发明的示例，所述聚醚的结构单元为下列至少之一：According to an example of the invention, the structural unit of the polyether is at least one of the following:
Figure PCTCN2015074326-appb-000012
Figure PCTCN2015074326-appb-000012
其中，各x独立地为大于等于1的整数。由此，纳米粒子的分散稳定性较好。Wherein each x is independently an integer greater than or equal to 1. Thereby, the dispersion stability of the nanoparticles is good.
根据本发明的示例，另外一种形成B链段的前驱体由聚酯结构组成。聚酯可以为聚酯 多元醇、聚酯多胺、或聚酯缩水甘油醚。According to an example of the invention, another precursor forming the B segment consists of a polyester structure. Polyester can be polyester Polyol, polyester polyamine, or polyester glycidyl ether.
二元醇、硅氧烷或其衍生物、醇酸/二羧酸/内酯或其衍生物形成聚酯的基本结构单元，并且优选聚酯的结构单元为柔性的。根据本发明的一些示例，二元醇可以为选自乙二醇、1,2-丙二醇、1,2-丁二醇、1,3-丁二醇和1,4-丁二醇中的至少一种；硅氧烷可以为选自二甲基硅氧烷或者二乙基硅氧烷中的至少一种；醇酸/二羧酸/内酯或其衍生物可以为烷基取代的γ-丁内酯、烷基取代的δ-戊内酯、烷基取代的ε-己内酯、γ-丁内酯、δ-戊内酯、ε-己内酯和脂肪酸中的至少一种。由此，纳米粒子的分散稳定性较好。The diol, siloxane or its derivative, alkyd/dicarboxylic acid/lactone or a derivative thereof form the basic structural unit of the polyester, and preferably the structural unit of the polyester is flexible. According to some examples of the present invention, the glycol may be at least one selected from the group consisting of ethylene glycol, 1,2-propylene glycol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. The siloxane may be at least one selected from the group consisting of dimethyl siloxane or diethyl siloxane; the alkyd/dicarboxylic acid/lactone or a derivative thereof may be an alkyl substituted γ-butyl At least one of a lactone, an alkyl-substituted δ-valerolactone, an alkyl-substituted ε-caprolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, and a fatty acid. Thereby, the dispersion stability of the nanoparticles is good.
当聚酯的重复结构单元中不含聚醚结构单元时，并且碳原子数大于6时，则重复单元是疏水性的，反之则是亲水性的。When the repeating structural unit of the polyester does not contain a polyether structural unit, and the number of carbon atoms is more than 6, the repeating unit is hydrophobic, and conversely, it is hydrophilic.
根据本发明的示例，所述聚酯的结构单元为下列至少之一：According to an example of the invention, the structural unit of the polyester is at least one of the following:
Figure PCTCN2015074326-appb-000013
Figure PCTCN2015074326-appb-000013
其中，各x独立地为大于等于1的整数，各r独立地为0-18的整数，各t独立地为2-12的整数。R1为烃基或者烃氧基，烃基优选小于等于八个碳原子的烷基，烃氧基优选小于等于八个碳原子的烷氧基。由此，纳米粒子分散效果较好，稳定性较佳，能够长期保存而不发生沉降现象。Wherein each x is independently an integer greater than or equal to 1, each r is independently an integer from 0 to 18, and each t is independently an integer from 2 to 12. R 1 is a hydrocarbon group or a hydrocarbyloxy group, the hydrocarbon group is preferably an alkyl group of eight or less carbon atoms, and the alkoxy group is preferably an alkoxy group of eight or less carbon atoms. Thereby, the nanoparticle has a better dispersion effect, better stability, and can be stored for a long period of time without sedimentation.
根据本发明的示例，形成B链段所用聚醚或者聚酯的拓扑结构各自独立的为选自星形、多臂形和线形中的至少一种，优选星形或者多臂形。由此，有利于提高纳米粒子的分散效果和稳定性。According to an example of the invention, the topologies of the polyethers or polyesters used to form the B segments are each independently selected from at least one of a star shape, a multi-arm shape and a linear shape, preferably a star shape or a multi-arm shape. Thereby, it is advantageous to improve the dispersion effect and stability of the nanoparticles.
根据本发明的示例，所述聚醚和所述聚酯的拓扑结构各自独立的为下列的至少之一： According to an example of the invention, the topologies of the polyether and the polyester are each independently at least one of the following:
Figure PCTCN2015074326-appb-000014
Figure PCTCN2015074326-appb-000014
其中，各A1,A2,A3,…,An独立地为所述聚醚或所述聚酯的重复单元，R2为-H或-CH2-CH3，z为0或2；各Y独立地为封端官能团，为酸酐、羧基、氨基、羟基、环氧基和异氰酸酯基中的至少一种；各x1,x2,x3,…,xn表示重复单元的数量；各x1,x2,x3,…,xn独立地为大于等于0的整数，且满足x1+x2+x3+,…,+xn≥1。Wherein each of A 1 , A 2 , A 3 , ..., A n is independently a repeating unit of the polyether or the polyester, R 2 is -H or -CH 2 -CH 3 , and z is 0 or 2 Each Y is independently a capping functional group, and is at least one of an acid anhydride, a carboxyl group, an amino group, a hydroxyl group, an epoxy group, and an isocyanate group; each x1, x2, x3, ..., xn represents the number of repeating units; each x1, X2, x3, ..., xn are independently integers greater than or equal to 0, and satisfy x1 + x2 + x3 +, ..., + xn ≥ 1.
根据本发明的示例，在星形拓扑结构、多臂形拓扑结构中，常见的形成星形结构单元、多臂形结构单元的原料为甘油、三羟甲基丙烷、季戊四醇、二聚季戊四醇和三羟甲基甲胺。 优选地，形成星形结构、多臂形结构单元的原料为下列至少之一：According to an example of the present invention, in a star topology, a multi-arm topology, common raw materials for forming a star structure unit and a multi-arm structure unit are glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and three. Hydroxymethyl methylamine. Preferably, the raw material forming the star structure and the multi-arm structural unit is at least one of the following:
Figure PCTCN2015074326-appb-000015
Figure PCTCN2015074326-appb-000015
根据本发明的示例，合成嵌段共聚物所涉及的大分子化学反应可以为这些反应之一：羧基与羟基缩合、羧基与氨基缩合、酸酐在醇羟基环境中形成酯键、酸酐在氨基环境中形成酰胺键、羟基与异氰酸酯发生加成反应、氨基与异氰酸酯发生加成反应、醇羟基使环氧基团发生开环反应、氨基使环氧基团发生开环反应。According to an example of the present invention, the macromolecular chemical reaction involved in the synthesis of the block copolymer may be one of these reactions: condensation of a carboxyl group with a hydroxyl group, condensation of a carboxyl group with an amino group, formation of an ester bond in an alcoholic hydroxyl environment, and an acid anhydride in an amino environment. An amide bond is formed, an addition reaction of a hydroxyl group with an isocyanate, an addition reaction of an amino group with an isocyanate, an opening reaction of an epoxy group with an epoxy group, and a ring opening reaction of an epoxy group with an amino group.
简而言之，可以通过上述之一的大分子化学反应合成本发明示例的嵌段共聚物。所述嵌段共聚物通过图7所示的通用合成路线进行制备。In short, the block copolymer of the present invention can be synthesized by the macromolecular chemical reaction of one of the above. The block copolymer was prepared by the general synthetic route shown in Figure 7.
根据本发明的另一个具体示例，可以按照如下所示的合成路线制备三臂嵌段共聚物： According to another specific example of the present invention, a three-arm block copolymer can be prepared according to the synthetic route shown below:
Figure PCTCN2015074326-appb-000016
Figure PCTCN2015074326-appb-000016
根据本发明的另一个具体示例，可以按照如下所示的合成路线制备四臂嵌段共聚物：According to another specific example of the present invention, a four-arm block copolymer can be prepared according to the synthetic route shown below:
Figure PCTCN2015074326-appb-000017
Figure PCTCN2015074326-appb-000017
根据本发明的另一个具体示例，可以按照如下所示的合成路线制备星形嵌段共聚物：According to another specific example of the invention, the star block copolymer can be prepared according to the synthetic route shown below:
Figure PCTCN2015074326-appb-000018
Figure PCTCN2015074326-appb-000018
根据本发明的一个具体示例，可以按照如下所示的合成路线制备线形嵌段共聚物：According to a specific example of the present invention, a linear block copolymer can be prepared according to the synthetic route shown below:
Figure PCTCN2015074326-appb-000019
Figure PCTCN2015074326-appb-000019
根据本发明的另一个具体示例，可以按照如下所示的合成路线制备三臂嵌段共聚物：According to another specific example of the present invention, a three-arm block copolymer can be prepared according to the synthetic route shown below:
Figure PCTCN2015074326-appb-000020
Figure PCTCN2015074326-appb-000020
根据本发明的另一个具体示例，可以按照如下所示的合成路线制备四臂嵌段共聚物：According to another specific example of the present invention, a four-arm block copolymer can be prepared according to the synthetic route shown below:
Figure PCTCN2015074326-appb-000021
Figure PCTCN2015074326-appb-000021
根据本发明的另一个具体示例，可以按照如下所示的合成路线制备星形嵌段共聚物：According to another specific example of the invention, the star block copolymer can be prepared according to the synthetic route shown below:
Figure PCTCN2015074326-appb-000022
Figure PCTCN2015074326-appb-000022
根据本发明的另一个具体示例，可以按照如下所示的合成路线制备线形嵌段共聚物：According to another specific example of the present invention, the linear block copolymer can be prepared according to the synthetic route shown below:
Figure PCTCN2015074326-appb-000023
Figure PCTCN2015074326-appb-000023
根据本发明的示例，所述纳米粒子的形状为选自球形、片状、棒状或线形中的至少一种。由此，纳米粒子的分散效果和稳定性良好。According to an example of the present invention, the shape of the nanoparticles is at least one selected from the group consisting of a sphere, a sheet, a rod, and a line. Thereby, the dispersion effect and stability of the nanoparticles are good.
根据本发明的示例，球形纳米粒子、棒状纳米粒子与线形纳米粒子为选自金属氧化物颗粒、金属硫化物颗粒、金属颗粒、表明氧化处理的金属颗粒和表面硫化处理的金属颗粒中的至少一种。由此，有利于提高纳米粒子的分散效果和稳定性。According to an example of the present invention, the spherical nanoparticles, the rod-shaped nanoparticles, and the linear nanoparticles are at least one selected from the group consisting of metal oxide particles, metal sulfide particles, metal particles, metal particles indicating oxidation treatment, and surface-sulfur treated metal particles. Kind. Thereby, it is advantageous to improve the dispersion effect and stability of the nanoparticles.
根据本发明的示例，所述金属氧化物颗粒为选自二氧化硅、氧化铝、氧化锌、氧化铜、氧化镍、氧化钴、氧化铁、氧化镁、氧化钛、氧化锆、氧化钨和氧化钼中的至少一种。由此，有利于提高纳米粒子的分散效果和稳定性。According to an embodiment of the invention, the metal oxide particles are selected from the group consisting of silica, alumina, zinc oxide, copper oxide, nickel oxide, cobalt oxide, iron oxide, magnesium oxide, titanium oxide, zirconium oxide, tungsten oxide, and oxidation. At least one of molybdenum. Thereby, it is advantageous to improve the dispersion effect and stability of the nanoparticles.
根据本发明的示例，金属硫化物颗粒为选自硫化锌，硫化镉，硫化汞，硫化铁，硫化钴，硫化镍，硫化钨和硫化钼中的至少一种。由此，有利于提高纳米粒子的分散效果和稳定性。According to an example of the present invention, the metal sulfide particles are at least one selected from the group consisting of zinc sulfide, cadmium sulfide, mercury sulfide, iron sulfide, cobalt sulfide, nickel sulfide, tungsten sulfide, and molybdenum sulfide. Thereby, it is advantageous to improve the dispersion effect and stability of the nanoparticles.
根据本发明的示例，所述金属颗粒为选自钴、铁、镁、铝、钛、锆、银、金或其合金中的至少一种。由此，有利于提高纳米粒子的分散效果和稳定性。According to an example of the present invention, the metal particles are at least one selected from the group consisting of cobalt, iron, magnesium, aluminum, titanium, zirconium, silver, gold, or alloys thereof. Thereby, it is advantageous to improve the dispersion effect and stability of the nanoparticles.
根据本发明的示例，片状纳米颗为选自层状双金属氢氧化物、粘土、层状金属磷酸盐，层状金属钨酸盐，层状金属硫化物、氧化石墨，石墨烯氧化物，及其衍生物中的至少一种。 由此，有利于提高纳米粒子的分散效果和稳定性。According to an example of the present invention, the flaky nano-particles are selected from the group consisting of layered double hydroxides, clays, layered metal phosphates, layered metal tungstates, layered metal sulfides, graphite oxides, graphene oxides, At least one of its derivatives. Thereby, it is advantageous to improve the dispersion effect and stability of the nanoparticles.
根据本发明的示例，不论聚醚或聚酯形成的B链段是否亲水，制备得到的嵌段共聚物均能将纳米粒子稳定分散于适当的溶剂中。优选情况下，为了更好的分散疏水性纳米粒子，嵌段共聚物中的B链段优选为疏水性的；为了更好的分散亲水性纳米颗粒，优选B链段为亲水性的。由此，纳米粒子的分散效果和稳定性均较好，形成的含纳米粒子的混合物能够长期储存，不易发生沉降。According to an example of the present invention, the prepared block copolymer can stably disperse the nanoparticles in a suitable solvent regardless of whether the B segment formed by the polyether or the polyester is hydrophilic. Preferably, in order to better disperse the hydrophobic nanoparticles, the B segment in the block copolymer is preferably hydrophobic; in order to better disperse the hydrophilic nanoparticles, it is preferred that the B segment is hydrophilic. Thereby, the dispersion effect and stability of the nanoparticles are good, and the formed nanoparticle-containing mixture can be stored for a long period of time, and sedimentation is less likely to occur.
在发明的第二方面，本发明提供制备含有嵌段共聚物与纳米粒子混合物的方法；所用嵌段共聚物类型包括星形嵌段共聚物、多臂嵌段共聚物和线形嵌段共聚物。根据本发明的示例，该方法包括：将嵌段共聚物、纳米粒子和分散介质混合，以便获得所述含有纳米粒子的混合物。发明人发现，利用本发明的方法能够快速有效地制备获得分散稳定性良好的含有纳米粒子的混合物，且操作简单，方便快捷，成本低廉，易于实现大规模生产。In a second aspect of the invention, the invention provides a process for preparing a mixture comprising a block copolymer and a nanoparticle; the block copolymer types used include star block copolymers, multi-arm block copolymers and linear block copolymers. According to an example of the invention, the method comprises mixing a block copolymer, a nanoparticle and a dispersion medium to obtain the nanoparticle-containing mixture. The inventors have found that the nanoparticle-containing mixture having good dispersion stability can be prepared quickly and efficiently by the method of the present invention, and is simple in operation, convenient and quick, low in cost, and easy to realize mass production.
需要说明的是，在本发明的该方法中所描述的嵌段共聚物与纳米粒子具有前面所述的嵌段共聚物与纳米粒子的所有特征和优点，在此不再一一赘述。It should be noted that the block copolymers and nanoparticles described in the method of the present invention have all the features and advantages of the block copolymers and nanoparticles described above, and will not be further described herein.
在发明的第三方面，本发明提供了含有嵌段共聚物与纳米粒子的混合物，所用嵌段共聚物类型包括星形嵌段共聚物、多臂嵌段共聚物和线形嵌段共聚物。根据本发明的示例，所述含有纳米粒子的混合物是利用前面所述的方法制备的。发明人发现，本发明的含有纳米粒子的混合物分散稳定性较佳，能够较长时间储存而不易发生沉降现象。In a third aspect of the invention, the invention provides a mixture comprising a block copolymer and a nanoparticle, the type of block copolymer used comprising a star block copolymer, a multi-arm block copolymer and a linear block copolymer. According to an example of the invention, the nanoparticle-containing mixture is prepared by the method described above. The inventors have found that the nanoparticle-containing mixture of the present invention has a good dispersion stability and can be stored for a long period of time without being likely to cause sedimentation.
根据本发明的示例，所述嵌段共聚物和纳米粒子具有前面所描述的嵌段共聚物和纳米粒子的所有特征及优点，在此不再一一赘述。According to an example of the present invention, the block copolymers and nanoparticles have all of the features and advantages of the block copolymers and nanoparticles described above, and will not be further described herein.
实施例1：异丁烯-丙二醇-异丁烯三臂嵌段共聚物的合成Example 1: Synthesis of isobutylene-propylene glycol-isobutylene three-arm block copolymer
将173.25g(过量5％)聚异丁烯丁二酸酐(PIBSA)(分子量为1100g/mol)和200ml正己烷溶于500ml的三口瓶中，然后于氮气氛围、持续搅拌条件下，将三口瓶置于60℃油浴中，利用150ml的恒压滴液漏斗将22.0g聚醚胺T-403(分子量为440g/mol，三臂聚合物，每一个臂的分子链末端带一个氨基。)溶于100ml丙酮中，当三口瓶中的溶液的温度稳定在60℃时，将聚醚胺T-403溶液逐滴加入三口瓶中，所得到的溶液于60℃下搅拌至少8小时，至溶液变为黄白色乳液，真空旋转蒸发除去溶剂，得到粘性的淡黄色液体状产物，即为目标产物。173.25 g (5% excess) of polyisobutylene succinic anhydride (PIBSA) (molecular weight: 1100 g/mol) and 200 ml of n-hexane were dissolved in a 500 ml three-necked flask, and then the three-necked bottle was placed under a nitrogen atmosphere under continuous stirring. In a 60 ° C oil bath, 22.0 g of polyetheramine T-403 (molecular weight: 440 g/mol, three-armed polymer, one amino group at the end of the molecular chain of each arm) was dissolved in 100 ml using a 150 ml constant pressure dropping funnel. In acetone, when the temperature of the solution in the three-necked bottle is stabilized at 60 ° C, the polyetheramine T-403 solution is added dropwise to the three-necked bottle, and the resulting solution is stirred at 60 ° C for at least 8 hours until the solution turns yellow. The white emulsion is evaporated in vacuo to remove the solvent to give the product as a viscous pale yellow liquid.
实施例2：异丁烯-季戊四醇丙氧基化物-异丁烯四臂嵌段共聚物的合成Example 2: Synthesis of isobutylene-pentaerythritol propoxylate-isobutylene four-arm block copolymer
将115.5g(过量5％)聚异丁烯丁二酸酐(PIBSA)(分子量为1100g/mol)和200ml N，N-二甲基甲酰胺溶于500ml的三口瓶中，然后于氮气氛围、持续搅拌条件下，将三口瓶置于 100℃油浴中，利用150ml的恒压滴液漏斗将10.65g聚季戊四醇丙氧基化物(分子量426g/mol,CAS号：9051-49-4，四臂聚合物，每一个臂的分子链末端带一个羟基。)溶于80ml N，N-二甲基甲酰胺中，当三口瓶中的溶液的温度稳定在100℃时，将聚季戊四醇丙氧基化物溶液逐滴加入三口瓶中，所得到的溶液于100℃下搅拌至少24小时，至溶液变为黄白色乳液，真空旋转蒸发除去溶剂，得到粘性的淡黄色液体状产物，即为目标产物。115.5 g (5% excess) of polyisobutylene succinic anhydride (PIBSA) (molecular weight: 1100 g/mol) and 200 ml of N,N-dimethylformamide were dissolved in a 500 ml three-necked flask, followed by stirring under a nitrogen atmosphere. Next, put a three-neck bottle In a 100 ° C oil bath, 10.65 g of polypentaerythritol propoxylate (molecular weight 426 g / mol, CAS No.: 9054-49-4, four-arm polymer, molecular chain end of each arm) using a 150 ml constant pressure dropping funnel With a hydroxyl group.) Dissolved in 80ml of N,N-dimethylformamide. When the temperature of the solution in the three-necked bottle is stable at 100 °C, the polypentaerythritol propoxylate solution is added dropwise to the three-necked bottle. The solution was stirred at 100 ° C for at least 24 hours until the solution became a yellow-white emulsion. The solvent was evaporated in vacuo to give the product as a viscous pale yellow liquid.
实施例3：异丁烯-季戊四醇丙氧基化物-异丁烯星形嵌段共聚物的合成Example 3: Synthesis of isobutylene-pentaerythritol propoxylate-isobutylene star block copolymer
将115.5g(过量5％)聚异丁烯丁二酸酐(PIBSA)(分子量为1100g/mol)和200ml N，N-二甲基甲酰胺溶于500ml的三口瓶中，然后于氮气氛围、持续搅拌条件下，将三口瓶置于100℃油浴中，利用150ml的恒压滴液漏斗将7.86g聚季戊四醇丙氧基化物(分子量629g/mol,CAS号：9051-49-4，星形聚合物，含八个分子链分支，每一个分子链分支的末端带一个羟基。)溶于80ml N，N-二甲基甲酰胺中，当三口瓶中的溶液的温度稳定在100℃时，将聚季戊四醇丙氧基化物溶液逐滴加入三口瓶中，所得到的溶液于100℃下搅拌至少24小时，至溶液变为黄白色乳液，真空旋转蒸发除去溶剂，得到粘性的淡黄色液体状产物，即为目标产物。115.5 g (5% excess) of polyisobutylene succinic anhydride (PIBSA) (molecular weight: 1100 g/mol) and 200 ml of N,N-dimethylformamide were dissolved in a 500 ml three-necked flask, followed by stirring under a nitrogen atmosphere. Next, the three-necked flask was placed in a 100 ° C oil bath, and 7.86 g of polypentaerythritol propoxylate (molecular weight: 629 g/mol, CAS No.: 9041-49-4, star polymer, was used in a 150 ml constant pressure dropping funnel. Containing eight molecular chain branches, each molecular chain branch has a hydroxyl group at the end.) Dissolved in 80ml of N, N-dimethylformamide, when the temperature of the solution in the three-necked bottle is stable at 100 ° C, polypentaerythritol The propoxylate solution is added dropwise to the three-necked bottle, and the resulting solution is stirred at 100 ° C for at least 24 hours until the solution turns into a yellow-white emulsion, and the solvent is removed by evaporation in vacuo to give a viscous pale yellow liquid product. Target product.
实施例4：异丁烯-丙二醇-异丁烯线形嵌段共聚物的合成Example 4: Synthesis of isobutylene-propylene glycol-isobutylene linear block copolymer
将115.5g(过量5％)聚异丁烯丁二酸酐(PIBSA)(分子量为1100g/mol)和200ml正己烷溶于500ml的三口瓶中，然后于氮气氛围、持续搅拌条件下，将三口瓶置于60℃油浴中，利用150ml的恒压滴液漏斗将11.5g聚(乙二醇)二(2-氨基丙基醚)D230(分子量为230g/mol，线形聚合物，分子链的两个末端各带一个氨基。)溶于80ml丙酮中，当三口瓶中的溶液的温度稳定在60℃时，将聚(乙二醇)二(2-氨基丙基醚)D230溶液逐滴加入三口瓶中，所得到的溶液于60℃下搅拌至少8小时，至溶液变为黄白色乳液，真空旋转蒸发除去溶剂后，得到粘性的淡黄色液体状产物，即为目标产物。115.5 g (5% excess) of polyisobutylene succinic anhydride (PIBSA) (molecular weight 1100 g/mol) and 200 ml of n-hexane were dissolved in a 500 ml three-necked flask, and then the three-necked bottle was placed under a nitrogen atmosphere under continuous stirring. 11.5 g of poly(ethylene glycol) bis(2-aminopropyl ether) D230 (molecular weight 230 g/mol, linear polymer, both ends of the molecular chain) in a 60 ° C oil bath using a 150 ml constant pressure dropping funnel Each with an amino group.) Dissolved in 80ml of acetone, when the temperature of the solution in the three-necked bottle is stable at 60 ° C, the poly(ethylene glycol) bis(2-aminopropyl ether) D230 solution is added dropwise into the three-necked bottle. The resulting solution is stirred at 60 ° C for at least 8 hours until the solution becomes a yellow-white emulsion. After evaporation of the solvent in vacuo, a viscous pale yellow liquid product is obtained as the desired product.
实施例5：利用三臂嵌段共聚物分散ZrO2和TiO2 Example 5: Dispersion of ZrO 2 and TiO 2 using a three-arm block copolymer
将实施例1中制备的异丁烯-丙三醇-异丁烯三臂嵌段共聚物、ZrO2纳米粒子(粒径50±5nm,高温烧结颗粒)、TiO2纳米粒子(粒径25±5nm,亲水性颗粒)和液体石蜡混合，配制异丁烯-丙三醇-异丁烯三臂嵌段共聚物的质量分数为5％、ZrO2纳米粒子和TiO2纳米粒子的质量分数分别为0.01％,0.05％,0.1％,0.2％,0.3％,0.4％和1％的混合物。分散效果见图2(A)至图2(G)，由图可以看出，制备的三臂嵌段共聚物对不同浓度的纳米粒子均具有非常好的分散稳定性。实验结果显示，分散后的纳米粒子可以至少稳定地静置放置两个月。并且， 实验结果显示：在更长的时间尺度范围内，用制备的三臂嵌段共聚物分散纳米粒子，当纳米粒子沉降极少部分后，纳米粒子不再沉降，整个分散体系达到平衡。The isobutylene-glycerol-isobutylene tri-arm block copolymer prepared in Example 1, ZrO 2 nanoparticles (particle diameter 50±5 nm, high-temperature sintered particles), TiO 2 nanoparticles (particle diameter 25±5 nm, hydrophilic) The granules are mixed with liquid paraffin to prepare a mass fraction of isobutylene-glycerol-isobutylene three-arm block copolymer of 5%, and the mass fractions of ZrO 2 nanoparticles and TiO 2 nanoparticles are 0.01%, 0.05%, 0.1, respectively. Mixture of %, 0.2%, 0.3%, 0.4% and 1%. The dispersion effect is shown in Fig. 2(A) to Fig. 2(G). It can be seen from the figure that the prepared three-arm block copolymer has very good dispersion stability for different concentrations of nanoparticles. The experimental results show that the dispersed nanoparticles can be stably left standing for at least two months. Moreover, the experimental results show that in the longer time scale range, the prepared three-arm block copolymer is used to disperse the nanoparticles. When the nanoparticles are settled to a small extent, the nanoparticles do not settle and the entire dispersion system reaches equilibrium.
实施例6：利用四臂嵌段共聚物分散ZrO2和TiO2 Example 6: Dispersing ZrO 2 and TiO 2 using a four-arm block copolymer
将实施例2中制备的异丁烯-季戊四醇丙氧基化物-异丁烯四臂嵌段共聚物、ZrO2纳米粒子(粒径50±5nm,高温烧结颗粒)、TiO2纳米粒子(粒径25±5nm,亲水性颗粒)和液体石蜡混合，配制异丁烯-季戊四醇丙氧基化物-异丁烯四臂嵌段共聚物的质量分数为5％、ZrO2纳米粒子和TiO2纳米粒子均为1％的混合物。分散效果见图3，由图3可以看出，制备的四臂嵌段共聚物对纳米粒子具有非常好的分散稳定性。实验结果显示，分散后的纳米粒子可以至少稳定地静置放置两个月。并且，实验结果显示：在更长的时间尺度范围内，用制备的四臂嵌段共聚物分散纳米粒子，当纳米粒子沉降极少部分后，纳米粒子不再沉降，整个分散体系达到平衡。The isobutylene-pentaerythritol propoxylate-isobutylene four-arm block copolymer prepared in Example 2, ZrO 2 nanoparticles (particle diameter 50±5 nm, high-temperature sintered particles), and TiO 2 nanoparticles (particle diameter 25±5 nm, The hydrophilic particles were mixed with liquid paraffin to prepare a mixture of an isobutylene-pentaerythritol propoxylate-isobutylene four-arm block copolymer having a mass fraction of 5% and a ZrO 2 nanoparticle and a TiO 2 nanoparticle of 1%. The dispersion effect is shown in Fig. 3. As can be seen from Fig. 3, the prepared four-arm block copolymer has very good dispersion stability to the nanoparticles. The experimental results show that the dispersed nanoparticles can be stably left standing for at least two months. Moreover, the experimental results show that the nanoparticles are dispersed by the prepared four-arm block copolymer in a longer time scale. After the nanoparticles are settled to a small extent, the nanoparticles do not settle and the entire dispersion reaches equilibrium.
实施例7：利用线形嵌段共聚物分散ZrO2和TiO2 Example 7: Dispersing ZrO 2 and TiO 2 using a linear block copolymer
将实施例4中制备的异丁烯-丙三醇-异丁烯线形嵌段共聚物、ZrO2纳米粒子(粒径50±5nm,高温烧结颗粒)、TiO2纳米粒子(粒径25±5nm,亲水性颗粒)和液体石蜡混合，配制异丁烯-丙三醇-异丁烯线形嵌段共聚物的质量分数为5％、ZrO2纳米粒子和TiO2纳米粒子均为1％的混合物。分散效果见图4，由图4可以看出，制备的线形嵌段共聚物对纳米粒子具有非常好的分散稳定性。实验结果显示，分散后的纳米粒子可以至少稳定地静置放置两个月。并且，实验结果显示：在更长的时间尺度范围内，用制备的线形嵌段共聚物分散纳米粒子，纳米粒子沉降少量后，纳米粒子不再沉降，整个分散体系达到平衡。The isobutylene-glycerol-isobutylene linear block copolymer prepared in Example 4, ZrO 2 nanoparticles (particle diameter 50±5 nm, high-temperature sintered particles), TiO 2 nanoparticles (particle diameter 25±5 nm, hydrophilicity) The granules were mixed with liquid paraffin to prepare a mixture of an isobutylene-glycerol-isobutylene linear block copolymer having a mass fraction of 5% and a ZrO 2 nanoparticle and a TiO 2 nanoparticle of 1%. The dispersion effect is shown in Fig. 4. As can be seen from Fig. 4, the prepared linear block copolymer has very good dispersion stability to the nanoparticles. The experimental results show that the dispersed nanoparticles can be stably left standing for at least two months. Moreover, the experimental results show that in the longer time scale range, the prepared linear block copolymer disperses the nanoparticles, and after the nanoparticles are settled in a small amount, the nanoparticles do not settle and the entire dispersion system reaches equilibrium.
实施例8：利用三臂嵌段共聚物、星形嵌段共聚物分散纳米铜颗粒Example 8: Dispersing nano copper particles by using a three-arm block copolymer and a star block copolymer
将实施例1中制备的三臂嵌段共聚物、实施例3中制备的异丁烯-季戊四醇丙氧基化物-异丁烯星形嵌段共聚物，分别与铜纳米粒子(粒径80～100nm)和液体石蜡混合，配置三臂嵌段共聚物、星形嵌段共聚物的质量分数各为5％，铜纳米粒子的质量分数均为1％的混合物。分散效果见图5，由图5可以看出，制备的三臂嵌段共聚物、星形嵌段共聚物对纳米粒子具有较好的分散稳定性。实验结果显示，分散后的纳米粒子可以至少稳定地静置放置两个月。并且，实验结果显示：在更长的时间尺度范围内，用制备的三臂嵌段共聚物、星形嵌段共聚物分散纳米粒子，纳米粒子沉降少部分后，纳米粒子不再沉降，整个分散体系达到平衡。 The three-arm block copolymer prepared in Example 1, the isobutylene-pentaerythritol propoxylate-isobutylene star block copolymer prepared in Example 3, and copper nanoparticles (particle size 80 to 100 nm) and liquid, respectively The paraffin wax was mixed with a three-arm block copolymer and a star-block copolymer each having a mass fraction of 5% and a copper nanoparticle having a mass fraction of 1%. The dispersion effect is shown in Fig. 5. As can be seen from Fig. 5, the prepared three-arm block copolymer and the star block copolymer have good dispersion stability to the nanoparticles. The experimental results show that the dispersed nanoparticles can be stably left standing for at least two months. Moreover, the experimental results show that in the longer time scale range, the prepared three-arm block copolymer and the star block copolymer are used to disperse the nanoparticles, and after the nanoparticles are settled to a small part, the nanoparticles do not settle and the whole dispersion The system reached equilibrium.
实施例9利用油酸分散ZrO2和TiO2 Example 9 Dispersing ZrO 2 and TiO 2 with oleic acid
将油酸、ZrO2纳米粒子(粒径50±5nm,高温烧结颗粒)、TiO2纳米粒子(粒径25±5nm,亲水性颗粒)和液体石蜡混合，配置油酸的质量分数为5％、ZrO2纳米粒子和TiO2纳米粒子的质量分数均为1％的混合物。分散效果见图6，油酸小分子表面活性剂对纳米粒子的分散效果很差，大约两天时间，纳米粒子几乎全部沉降。Mixing oleic acid, ZrO 2 nanoparticles (particle size 50±5nm, high-temperature sintered particles), TiO 2 nanoparticles (particle size 25±5nm, hydrophilic particles) and liquid paraffin, the mass fraction of oleic acid is 5% The ZrO 2 nanoparticles and the TiO 2 nanoparticles have a mass fraction of 1%. The dispersion effect is shown in Fig. 6. The oleic acid small molecule surfactant has a poor dispersion effect on the nanoparticles, and the nanoparticles almost settled in about two days.
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。In the description of the present specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" and the like means a specific feature described in connection with the embodiment or example. A structure, material or feature is included in at least one embodiment or example of the invention. In the present specification, the schematic representation of the above terms is not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in a suitable manner in any one or more embodiments or examples. In addition, various embodiments or examples described in the specification, as well as features of various embodiments or examples, may be combined and combined.
尽管上面已经示出和描述了本发明的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本发明的限制，本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。 Although the embodiments of the present invention have been shown and described, it is understood that the above-described embodiments are illustrative and are not to be construed as limiting the scope of the invention. The embodiments are subject to variations, modifications, substitutions and variations.

Claims (28)

  1. 嵌段共聚物在制备含有纳米粒子的混合物中的用途，所述嵌段共聚物为选自星形嵌段共聚物和多臂嵌段共聚物中的至少一种。Use of a block copolymer in the preparation of a mixture comprising nanoparticles, the block copolymer being at least one selected from the group consisting of a star block copolymer and a multi-arm block copolymer.
  2. 根据权利要求1所述的用途，其特征在于，所述含有纳米粒子的混合物为选自润滑油、润滑脂、导电浆料、油墨、打印胶、光刻胶、涂料、涂层和粘结剂中的至少一种。The use according to claim 1, wherein the nanoparticle-containing mixture is selected from the group consisting of lubricating oils, greases, conductive pastes, inks, printing pastes, photoresists, coatings, coatings, and adhesives. At least one of them.
  3. 根据权利要求1所述的用途，其特征在于，基于所述含有纳米粒子的混合物的总质量，所述纳米粒子的质量分数为0.001％～90％。The use according to claim 1, characterized in that the mass fraction of the nanoparticles is from 0.001% to 90% based on the total mass of the mixture containing nanoparticles.
  4. 根据权利要求1所述的用途，其特征在于，在所述含有纳米粒子的混合物中，所述嵌段共聚物和所述纳米粒子的质量比为(0.0001-10)：1。The use according to claim 1, wherein in the mixture containing nanoparticles, the mass ratio of the block copolymer to the nanoparticles is (0.0001-10):1.
  5. 根据权利要求1所述的用途，其特征在于，所述嵌段共聚物化学结构由A链段和B链段两类链段构成。The use according to claim 1, wherein the block copolymer chemical structure is composed of two types of segments: A segment and B segment.
  6. 根据权利要求5所述的用途，其特征在于，所述A链段由分子链骨架单侧封端的聚烯烃形成，所述A链段所用封端官能团为酸酐、羧基、氨基、羟基、环氧基和异氰酸酯基中的至少一种。The use according to claim 5, wherein the A segment is formed of a polyolefin terminated on one side by a molecular chain skeleton, and the terminal functional groups used in the A segment are an acid anhydride, a carboxyl group, an amino group, a hydroxyl group, and an epoxy group. At least one of a group and an isocyanate group.
  7. 根据权利要求5所述的用途，其特征在于，所述B链段由聚醚或聚酯形成，所述B链段所用封端官能团为酸酐、羧基、氨基、羟基、环氧基和异氰酸酯基中的至少一种。The use according to claim 5, wherein the B segment is formed of a polyether or a polyester, and the blocked functional groups used in the B segment are an acid anhydride, a carboxyl group, an amino group, a hydroxyl group, an epoxy group and an isocyanate group. At least one of them.
  8. 根据权利要求6所述的用途，其特征在于，所述分子链骨架单侧封端的聚烯烃为选自分子链骨架单侧封端的聚异丁烯、分子链骨架单侧封端的聚丁烯和分子链骨架单侧封端的聚丁二烯中的至少一种。The use according to claim 6, wherein the single-side terminated polyolefin of the molecular chain skeleton is a polyisobutylene which is one-side terminated from a molecular chain skeleton, and a polybutene and a molecular chain which are unilaterally terminated by a molecular chain skeleton. At least one of the monobutadiene-terminated polybutadienes.
  9. 根据权利要求8所述的用途，其特征在于，所述分子链骨架单侧封端的聚异丁烯为下列至少之一：The use according to claim 8, wherein the molecularly oriented single-side terminated polyisobutylene is at least one of the following:
    Figure PCTCN2015074326-appb-100001
    Figure PCTCN2015074326-appb-100001
    其中，各n独立地为大于等于5的整数。Wherein each n is independently an integer greater than or equal to 5.
  10. 根据权利要求8所述的用途，其特征在于，所述分子链骨架单侧封端的聚丁烯为下列至少之一： The use according to claim 8, wherein the molecular chain skeleton unilaterally blocked polybutene is at least one of the following:
    Figure PCTCN2015074326-appb-100002
    Figure PCTCN2015074326-appb-100002
    其中，m1和m2各自独立地为大于等于0的整数，且m1+m2为大于等于5的整数。Wherein m1 and m2 are each independently an integer greater than or equal to 0, and m1+m2 is an integer greater than or equal to 5.
  11. 根据权利要求8所述的用途，其特征在于，所述分子链骨架单侧封端的聚丁二烯为下列至少之一：The use according to claim 8, wherein the molecularly oriented single-side terminated polybutadiene is at least one of the following:
    Figure PCTCN2015074326-appb-100003
    Figure PCTCN2015074326-appb-100003
    其中，i+j+k＝1，各n独立地为大于等于5的整数。Where i+j+k=1, each n is independently an integer greater than or equal to 5.
  12. 根据权利要求7所述的用途，其特征在于，所述聚醚由选自聚醚多元醇、聚醚多胺和聚醚缩水甘油醚中的至少一种形成。The use according to claim 7, wherein the polyether is formed of at least one selected from the group consisting of polyether polyols, polyether polyamines and polyether glycidyl ethers.
  13. 根据权利要求12所述的用途，其特征在于，所述聚醚的结构单元为下列至少之一： The use according to claim 12, characterized in that the structural unit of the polyether is at least one of the following:
    Figure PCTCN2015074326-appb-100004
    Figure PCTCN2015074326-appb-100004
    其中，各x独立地为大于等于1的整数。Wherein each x is independently an integer greater than or equal to 1.
  14. 根据权利要求7所述的用途，其特征在于，所述聚酯由选自聚酯多元醇、聚酯多胺和聚酯缩水甘油醚中的至少一种形成。The use according to claim 7, wherein the polyester is formed of at least one selected from the group consisting of polyester polyols, polyester polyamines, and polyester glycidyl ethers.
  15. 根据权利要求14所述的用途，其特征在于，所述聚酯的结构单元为下列至少之一：The use according to claim 14, wherein the structural unit of the polyester is at least one of the following:
    Figure PCTCN2015074326-appb-100005
    Figure PCTCN2015074326-appb-100005
    其中，各x独立地为大于等于1的整数，Wherein each x is independently an integer greater than or equal to 1,
    各r为独立地0-18的整数，Each r is an integer of 0-18 independently,
    各t为独立地2-12的整数，Each t is an integer of 2-12 independently,
    R1为烃基或者烃氧基。R 1 is a hydrocarbon group or a hydrocarbyloxy group.
  16. 根据权利要求7所述的用途，其特征在于，所述聚醚与所述聚酯的拓扑结构各自独立的为选自星形、多臂形中的至少一种。The use according to claim 7, characterized in that the topology of the polyether and the polyester are each independently selected from at least one of a star shape and a multi-arm shape.
  17. 根据权利要求16所述的用途，其特征在于，所述聚醚与所述聚酯的拓扑结构各自独立的为下列的至少之一： The use according to claim 16, characterized in that the topology of the polyether and the polyester are each independently at least one of the following:
    Figure PCTCN2015074326-appb-100006
    Figure PCTCN2015074326-appb-100006
    其中，各A1,A2,A3,…,An独立地为所述聚醚或所述聚酯的重复单元，Wherein each of A 1 , A 2 , A 3 , ..., A n is independently a repeating unit of the polyether or the polyester,
    R2为-H或-CH2-CH3，R 2 is -H or -CH 2 -CH 3 ,
    z为0或2；z is 0 or 2;
    各Y独立地为封端官能团，所述封端官能团为酸酐、羧基、氨基、羟基、环氧基和异氰酸酯基中的至少一种；Each Y is independently a capping functional group, and the capping functional group is at least one of an acid anhydride, a carboxyl group, an amino group, a hydroxyl group, an epoxy group, and an isocyanate group;
    各x1,x2,x3,…,xn表示重复单元的数量；各x1,x2,x3,…,xn独立地为大于等于0的整数，且满足x1+x2+x3+,…,+xn≥1。Each x1, x2, x3, ..., xn represents the number of repeating units; each x1, x2, x3, ..., xn is independently an integer greater than or equal to 0, and satisfies x1 + x2 + x3 +, ..., + xn ≥ 1.
  18. 根据权利要求16所述的用途，其特征在于，星形拓扑结构、多臂拓扑结构的聚醚 或聚酯由下列至少之一形成：The use according to claim 16, characterized in that the star topology, the polyether of the multi-arm topology Or polyester is formed by at least one of the following:
    Figure PCTCN2015074326-appb-100007
    Figure PCTCN2015074326-appb-100007
  19. 根据权利要求1所述的用途，其特征在于，所述纳米粒子的形状为选自球形、片状、棒状或线形中的至少一种。The use according to claim 1, wherein the shape of the nanoparticles is at least one selected from the group consisting of a sphere, a sheet, a rod, and a line.
  20. 根据权利要求19所述的用途，其特征在于，球形纳米粒子、棒状纳米粒子与线形纳米粒子为选自金属氧化物颗粒、金属硫化物颗粒、金属颗粒、表明氧化处理的金属颗粒和表面硫化处理的金属颗粒中的至少一种。The use according to claim 19, wherein the spherical nanoparticles, the rod-shaped nanoparticles and the linear nanoparticles are selected from the group consisting of metal oxide particles, metal sulfide particles, metal particles, metal particles indicating oxidation treatment, and surface vulcanization treatment. At least one of the metal particles.
  21. 根据权利要求20所述的用途，其特征在于，所述金属氧化物颗粒为选自二氧化硅、氧化铝、氧化锌、氧化铜、氧化镍、氧化钴、氧化铁、氧化镁、氧化钛、氧化锆、氧化钨和氧化钼中的至少一种。The use according to claim 20, wherein the metal oxide particles are selected from the group consisting of silica, alumina, zinc oxide, copper oxide, nickel oxide, cobalt oxide, iron oxide, magnesium oxide, titanium oxide, At least one of zirconia, tungsten oxide and molybdenum oxide.
  22. 根据权利要求20所述的用途，其特征在于，所述金属硫化物颗粒为选自硫化锌，硫化镉，硫化汞，硫化铁，硫化钴，硫化镍，硫化钨和硫化钼中的至少一种。The use according to claim 20, wherein the metal sulfide particles are at least one selected from the group consisting of zinc sulfide, cadmium sulfide, mercury sulfide, iron sulfide, cobalt sulfide, nickel sulfide, tungsten sulfide and molybdenum sulfide. .
  23. 根据权利要求20所述的用途，其特征在于，所述金属颗粒为选自钴、铁、镁、铝、钛、锆、银、金或其合金中的至少一种。The use according to claim 20, wherein the metal particles are at least one selected from the group consisting of cobalt, iron, magnesium, aluminum, titanium, zirconium, silver, gold or alloys thereof.
  24. 根据权利要求19所述的用途，其特征在于，片状纳米颗为选自层状双金属氢氧化物、粘土、层状金属磷酸盐，层状金属钨酸盐，层状金属硫化物、氧化石墨，石墨烯氧化物，及其衍生物中的至少一种。The use according to claim 19, wherein the flaky nano-particles are selected from the group consisting of layered double hydroxides, clays, layered metal phosphates, layered metal tungstates, layered metal sulfides, oxidation At least one of graphite, graphene oxide, and derivatives thereof.
  25. 一种制备含有纳米粒子的混合物的方法，其特征在于，包括：A method of preparing a mixture comprising nanoparticles, comprising:
    将嵌段共聚物、纳米粒子和分散介质混合，以便获得所述含有纳米粒子的混合物。The block copolymer, the nanoparticles, and the dispersion medium are mixed to obtain the mixture containing the nanoparticles.
  26. 根据权利要求25所述的方法，其特征在于，所述分散介质为非极性介质。The method of claim 25 wherein said dispersion medium is a non-polar medium.
  27. 根据权利要求26所述的方法，其特征在于，所述非极性介质为烃类介质。The method of claim 26 wherein said non-polar medium is a hydrocarbon medium.
  28. 一种含有纳米粒子的混合物，其特征在于，是利用权利要求25-27中任一项所述的方法制备的。 A mixture comprising nanoparticles prepared by the method of any one of claims 25-27.
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