WO2021036716A1 - 超浸润表面及其制备方法和应用 - Google Patents

超浸润表面及其制备方法和应用 Download PDF

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Publication number
WO2021036716A1
WO2021036716A1 PCT/CN2020/106910 CN2020106910W WO2021036716A1 WO 2021036716 A1 WO2021036716 A1 WO 2021036716A1 CN 2020106910 W CN2020106910 W CN 2020106910W WO 2021036716 A1 WO2021036716 A1 WO 2021036716A1
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Prior art keywords
polypropylene
hydroxide
super
grafted
mass
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PCT/CN2020/106910
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English (en)
French (fr)
Inventor
乔金樑
王崧合
张晓红
戚桂村
宋志海
蔡传伦
王湘
赖金梅
李秉海
蒋海斌
茹越
张江茹
高建明
张红彬
韩朋
姜超
郭照琰
Original Assignee
中国石油化工股份有限公司
中国石油化工股份有限公司北京化工研究院
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Priority claimed from CN201910786287.8A external-priority patent/CN112409628B/zh
Priority claimed from CN201910786213.4A external-priority patent/CN112403282B/zh
Application filed by 中国石油化工股份有限公司, 中国石油化工股份有限公司北京化工研究院 filed Critical 中国石油化工股份有限公司
Priority to AU2020335669A priority Critical patent/AU2020335669A1/en
Priority to KR1020227009683A priority patent/KR20220044850A/ko
Priority to BR112022002822A priority patent/BR112022002822A2/pt
Priority to JP2022512344A priority patent/JP7602533B2/ja
Priority to EP20857732.0A priority patent/EP4019121A4/en
Priority to US17/753,209 priority patent/US20220282054A1/en
Publication of WO2021036716A1 publication Critical patent/WO2021036716A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0093—Chemical modification
    • B01D67/00931—Chemical modification by introduction of specific groups after membrane formation, e.g. by grafting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/06—Flat membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
    • B01D71/262—Polypropylene
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/02—Hydrophilization
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/38—Graft polymerization
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/38—Graft polymerization
    • B01D2323/385—Graft polymerization involving radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B01D2325/0283—Pore size
    • B01D2325/02833—Pore size more than 10 and up to 100 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/32—Hydrocarbons, e.g. oil
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene

Definitions

  • the present invention relates to the field of polymer materials, in particular to the field of polymer membrane materials, in particular to a super-wetting surface and a preparation method and application thereof.
  • the wettability of the surface of a solid material is usually determined by the chemical properties and microstructure of the solid surface. Polymer surfaces with super-wetting properties have important applications in liquid separation, self-cleaning, anti-fogging, liquid transport, functional polymer films, printing and bonding.
  • Membrane technology as an emerging high-efficiency separation technology, is an industrialized high-efficiency and energy-saving separation method, which has developed rapidly in recent years.
  • membrane materials are the foundation and core of the development and application of membrane technology.
  • the performance of the membrane material directly affects the separation performance of the membrane, so its preparation process has always been a hot spot for scholars.
  • macromolecules and inorganic materials are two types of membrane materials widely used: macromolecules and inorganic materials.
  • the preparation methods of polymer microporous membranes mainly include phase inversion method, stretching method, dissolution method, sintering method and nuclear track method.
  • TIPS thermally-induced phase separation
  • the polymer and diluent that can only be miscible at higher temperatures are first heated to melt, and then the solution is cast or extruded into a film and then cooled. When the temperature of the solution drops below a certain temperature, the polymer chains in the solution interact to form a gel structure, and finally pores are formed due to phase separation.
  • the separated gel is immersed in the extract to remove the diluent to form a porous membrane.
  • Polypropylene has the characteristics of high melting point, low density, high strength, etc., and has excellent corrosion resistance, chemical stability, heat resistance, etc., and has great advantages as a raw material for preparing membrane materials. Since the surface of polypropylene does not contain polar groups, its surface energy is very small, and its critical surface tension is only 31-34 ⁇ 10 -5 N/cm, so it is lipophilic. When polypropylene is prepared into a microporous membrane, it will exhibit stronger lipophilicity, which requires higher pressure for water permeation, high power consumption, and low membrane flux.
  • silicone oil still needs to be added to increase its lipophilicity; lipophilic separation membranes also have application prospects in gas separation and other fields.
  • polypropylene porous membranes with amphiphilic functions are rarely reported.
  • the modification methods of membrane materials are mainly divided into physical methods and chemical methods.
  • the physical methods include surfactant modification, surface coating modification, and blending modification of membrane materials.
  • Chemical methods include plasma modification, ultraviolet radiation grafting, high-energy radiation grafting, or introducing polar groups through other chemical reactions.
  • Chinese Patent Application Publication CN105195031A discloses a method for hydrophilic modification of separation membranes, mixing hydrophilic prepolymers and initiators with membrane-forming polymers, and then crosslinking by ultraviolet radiation;
  • Chinese patent CN1299810C (published as CN1539550A The hydrophilic modification method of) is to pre-coat the monomer on the surface of the polypropylene separation membrane and use plasma irradiation to graft.
  • the above methods are complicated in equipment, and it is difficult to achieve uniform effects for the treatment of porous membranes, which is not conducive to industrial applications.
  • blending modification is the more commonly used method.
  • the blending modification method is simple, easy to control, can retain the respective characteristics of multiple polymers at the same time, and the modification effect is obvious.
  • water-soluble polymers and nanomaterials are two commonly used additives.
  • Water-soluble polymers such as polyvinylpyrrolidone and polyethylene glycol can significantly increase the membrane flux, but the membrane has poor pressure resistance.
  • Chinese Patent Application Publication CN103768958A provides a method for blending a hydrophilic polymer with a polyolefin molecular membrane.
  • the polyolefin is melt blended with a compatibilizer and a hydrophilic polymer and then thermally induced phase separation is used to prepare a hydrophilic porous membrane.
  • the membrane prepared by nano-materials has high flux and good pressure resistance, but it is difficult for the nanoparticles to be uniformly distributed in the membrane-forming liquid, which leads to the cumbersome membrane-making process and is not suitable for industrial production.
  • Chinese Patent Application Publication CN104548950A adds inorganic nanoparticles treated with a coupling agent and a diluent to polypropylene resin for melt blending, and uses a thermally induced phase separation method to prepare an inorganic nanoparticle-enhanced polypropylene hollow fiber separation membrane.
  • Plasma modification, UV radiation grafting and other modification methods have serious degradation of hydrophilicity with the increase of running time; or require more complicated chemical reactions, which makes it difficult to scale up industrially.
  • the purpose of the present invention is to provide a new type of super-wetting surface, which is at least super-hydrophilic, the super-wetting properties of the surface is durable and stable and the super-wetting surface does not have the hydrophilic properties of the prior art. And/or the shortcomings of lipophilic surfaces.
  • Another object of the present invention is to provide a method for preparing such a super-wetting surface, by which the super-wetting surface can be easily prepared, and the method can be easily industrialized.
  • the object is achieved by the super-wetting polypropylene surface and the preparation method thereof according to the present invention.
  • the surface of polypropylene with micro-nano structure and hydrophilic monomers such as organic acids and organic acid derivatives, vinyl silanes, etc.
  • hydrophilic monomers such as organic acids and organic acid derivatives, vinyl silanes, etc.
  • grafting reaction optionally further salinization, a super-hydrophilic surface can be obtained; it can also be further grafted with lipophilic monomers such as vinyl silicone oil and styrene, thereby further improving the super-hydrophilic surface Lipophilic, even super-parent surface can be achieved.
  • the present invention provides a super-wetting surface, which is a polypropylene surface with a micro-nano structure grafted with hydrophilic side groups, wherein the super-wetting surface is at least super-hydrophilic And the super-wet surface does not contain initiator residues.
  • surface refers to the interface between a solid and air.
  • the surface according to the invention is a super wet surface.
  • super-wetting refers to super-hydrophilic, super-lipophilic, or super-amphiphilic (super-hydrophilic and super-lipophilic) properties.
  • super-hydrophilic means that the water contact angle of the surface is less than or equal to 10°, preferably less than or equal to 5°, more preferably less than or equal to 1°, most preferably up to about 0°, especially about 0.5 The above angle is reached within s.
  • the term "super lipophilic” as used herein means that the oil contact angle of the surface is less than or equal to 10°, preferably less than or equal to 5°, more preferably less than or equal to 1°, most preferably up to about 0°, especially about 0.5
  • the above angle is reached within s.
  • the contact angle is measured with a contact angle tester in a dynamic contact angle measurement mode using water droplets or oil droplets (for example, white oil or peanut oil droplets).
  • the water contact angle of the super-wetting surface according to the present invention can reach 10° or less, preferably 8° or less, more preferably 5° or less, even more preferably 1° or less, most preferably about 0°, especially The above angle is reached in about 0.5s.
  • the super-wetting surface of the present invention can be attached to the substrate, or it can be a self-supporting, independent product.
  • the super-wetting surface of the present invention is prepared by grafting reaction under microwave irradiation without adding an initiator, the super-wetting surface of the present invention does not contain initiator residues.
  • initiator refers to a substance commonly used in the art to initiate polymerization reactions (including grafting reactions) of monomers, such as free radical initiators, including peroxide initiators, such as organic peroxide initiators. Agents (such as dicumyl peroxide) and inorganic peroxide initiators; and azo initiators and redox initiators, etc.; and photoinitiators (or photosensitizers), such as benzophenone.
  • the super-wetting surface according to the present invention is a polypropylene surface with a micro-nano structure grafted with hydrophilic side groups.
  • micro-nano structure refers to a functional structure with micron or nano-scale feature sizes and arranged in a specific manner.
  • the functional structure includes pore-like structures or structures with other shapes; usually the characteristics of this micro-nano structure
  • the size is in the range of 1nm-100 ⁇ m.
  • the feature size refers to the average size of the feature structure of the micro-nano structure.
  • the polypropylene surface with micro-nano structure used as the grafting base can be various polypropylene surfaces with micro-nano structure, and can be prepared by using existing preparation methods in the prior art.
  • the characteristic size of the micro-nano structure on the surface of the polypropylene is 1 nm-100 ⁇ m.
  • various polypropylene microporous surfaces can be used, preferably polypropylene microporous planes prepared by a thermally induced phase separation process.
  • the existing technology of photolithography, femtosecond laser processing technology, plasma etching technology, electrostatic spinning method, nano-imprinting, nano-casting and ultra-precision micro-milling technology can also be used to realize the processing of the surface micro-nano structure of polypropylene.
  • a metal mold with a micro-nano structure on the surface is used to extrude the micro-nano structure on the surface of the polypropylene.
  • the surface of the polypropylene with micro-nano structure as the grafting base can be an independent article or exist on the substrate.
  • the substrate may be composed mainly of polypropylene.
  • the substrate is, for example, a film, sheet, sheet, or molded article.
  • the polypropylene surface with a micro-nano structure as a graft base may be a polypropylene porous membrane, a polypropylene flat membrane or a polypropylene hollow fiber microporous membrane.
  • the polypropylene porous membrane may have an average pore diameter of less than 100 ⁇ m, preferably 10 nm-80 ⁇ m, and the porosity of the polypropylene porous membrane may be 50-90%, preferably 60-80%.
  • the average pore size is determined by observing the surface of the micropores using a scanning electron microscope, statistical pore size data, and making a pore size distribution diagram. The porosity is measured using the mercury intrusion method (MIP).
  • polypropylene as used herein includes homopolymers and copolymers of propylene and mixtures thereof.
  • the hydrophilic side groups grafted according to the present invention may include units formed from hydrophilic monomers, for example, including one or more heteroatoms or heteroatoms selected from oxygen, sulfur, nitrogen, silicon, and halogen, and combinations thereof. It is a unit formed by a monomer containing a carbon-carbon double bond and its substituents.
  • the hydrophilic side group is preferably a monomer side group containing a heteroatom selected from oxygen, sulfur, nitrogen, silicon, and halogen, and a combination thereof or a substituent thereof, and containing a carbon-carbon double bond.
  • the monomer of the hydrophilic side group is preferably at least one of an organic acid, a derivative of an organic acid, and a vinyl silane.
  • the derivative of the organic acid may include at least one of anhydride, ester, and salt of an organic acid.
  • the organic acid includes, but is not limited to, carboxylic acid, sulfonic acid, sulfinic acid, thiocarboxylic acid (RCOSH) and the like.
  • the monomers of the hydrophilic side groups further preferably include organic acids and derivatives of organic acids selected from the group consisting of maleic anhydride, maleic anhydride derivatives, (meth)acrylic acid, and (meth)acrylic acid derivatives.
  • organic acids and derivatives of organic acids selected from the group consisting of maleic anhydride, maleic anhydride derivatives, (meth)acrylic acid, and (meth)acrylic acid derivatives.
  • organic acids and derivatives of organic acids selected from the group consisting of maleic anhydride, maleic anhydride derivatives, (meth)acrylic acid, and (meth)acrylic acid derivatives.
  • glycidyl methacrylate vinyl acetate
  • alkenyl sulfonic acid and its derivatives e.g.
  • the vinyl silane may be one or more of the compounds represented by formula (1):
  • each X is the same or different independently represents a chloro group, a methoxy group, an ethoxy group, an acetoxy group.
  • the vinyl silane is preferably at least one of vinyl trimethoxy silane and vinyl triethoxy silane.
  • the hydrophilic side group contains or consists of a unit formed of a salt of an organic acid.
  • the surface of the polypropylene may be grafted with lipophilic side groups at the same time to further improve the lipophilicity of the surface.
  • the oil contact angle of the super-wetting surface can reach less than 90°, preferably less than or equal to 10°, more preferably less than or equal to 5°, still more preferably less than or equal to 1°, and most preferably up to about 0° , It is preferable to reach the above-mentioned angle within about 0.5s.
  • the lipophilic side group may include a unit formed from a lipophilic monomer.
  • the lipophilic monomer preferably includes at least one of vinyl silicone oil and styrene.
  • the lipophilic side groups are preferably selected from vinyl silicone oil side groups, styrene side groups and combinations thereof.
  • the vinyl silicone oil generally refers to a polysiloxane with a vinyl group and is liquid at room temperature, and mainly refers to a linear polydimethylsiloxane with vinyl groups in the middle segment or at both ends.
  • the vinyl silicone oil can be used as a macromonomer.
  • the vinyl silicone oil can be selected from vinyl-terminated silicone oils, high-vinyl silicone oils, and combinations thereof, and preferably can be at least one of methyl vinyl silicone oil, vinyl hydrogen-containing silicone oil, and divinyl silicone oil.
  • the water contact angle of the super-wetting surface according to the present invention is significantly smaller than the water contact angle of the polypropylene surface before the unmodified treatment.
  • the resulting super-wetting surface can achieve super-hydrophilic effect.
  • the polypropylene surface can be further grafted with lipophilic monomers for lipophilic modification, further improving the lipophilicity of the superhydrophilic surface, which is compared with unmodified polypropylene surfaces and only hydrophilic modified poly The acrylic surface has been improved.
  • the membrane after grafting hydrophilic side groups according to the present invention, the membrane can achieve super-hydrophilic effect, and water The throughput is also greatly improved.
  • the hydrophilically modified membrane can be further grafted with lipophilic monomers such as vinyl silicone oil, so that the lipophilicity of the membrane is further improved, and its oil flux is compared with unmodified membranes and only hydrophilic modified membranes. The membrane has been improved.
  • the present invention provides a method for preparing a super-wetting surface according to the present invention, which comprises adding a monomer for forming a pendant group in the absence of an initiator, optionally after adding an inorganic microwave
  • the grafting reaction is carried out by microwave irradiation with the surface of polypropylene with micro-nano structure as the grafting base.
  • auxiliary grafting monomers may not be used.
  • microwave refers to electromagnetic waves with a frequency of 300MHz-300GHz.
  • the components including the monomers of the hydrophilic side groups, or the monomers including the hydrophilic side groups and the monomers of the lipophilic side groups may be combined
  • the internal components are grafted with the polypropylene surface using microwave irradiation without adding a grafting initiator to obtain the super-wetting surface.
  • an inorganic microwave absorbing medium is optionally and preferably added; when the component includes a lipophilic side group monomer, an inorganic microwave absorbing medium is added.
  • the method may further include a step of reacting the product obtained after the grafting reaction with a base (i.e., a so-called salt Step).
  • the microwave irradiation grafting reaction may include only the microwave irradiation grafting reaction of hydrophilic side groups; or the microwave irradiation grafting reaction including both lipophilic side groups and hydrophilic side groups
  • the microwave irradiation grafting reaction of two kinds of side groups can occur simultaneously or successively, and the order is not limited.
  • the salting step is an optional step.
  • a salting step can be carried out, but it is not limited to whether it is in the microwave irradiation grafting reaction of the lipophilic pendant group.
  • microwave irradiation grafting of lipophilic side groups is carried out before and after or during the process, it is possible to carry out microwave irradiation grafting of lipophilic side groups on the surface of grafted polypropylene when the monomer of hydrophilic side groups is organic acid or at least one of its anhydrides or esters. Alkali is added at the same time as the branch to salify the above-mentioned hydrophilic side groups.
  • the preparation method of the present invention may specifically include any one of the following schemes:
  • the monomer of the hydrophilic side group when it is at least one of an organic acid or its anhydride or its ester, it also includes grafting an organic A step of contacting and mixing the polypropylene surface of at least one pendant group of the acid or its anhydride or its ester with a base and/or an aqueous solution of the base (a so-called salinization step).
  • the super-wetting surface of the present invention obtained by the preparation method does not contain initiator residues.
  • the initiator refers to a substance used in the art to initiate the polymerization reaction (including grafting reaction) of monomers, such as free radical initiators, including peroxide initiators, azo initiators, redox initiators, etc. , There are also photoinitiators (or photosensitizers), such as benzophenone. Peroxide initiators can be divided into organic peroxide initiators (such as dicumyl peroxide) and inorganic peroxide initiators.
  • the initiator especially refers to various initiators used for polypropylene grafting functional monomers, such as dicumyl peroxide and the like.
  • the tertiary carbon of polypropylene is dehydrogenated by an initiator, but the initiator can actually not only dehydrogenate, but also cause a large amount of ⁇ chain scission reaction in polypropylene. , That is, the reaction is too violent and uncontrollable, which affects the mechanical properties of grafted polypropylene.
  • the preparation method of the present invention can graft organic acid, organic acid derivative, vinyl silane, vinyl silicone oil, styrene and other side groups on the surface of polypropylene without adding an initiator. Therefore, the super-wetting surface obtained by the present invention does not contain initiator residues, which ensures that the mechanical properties of the polypropylene surface are not adversely affected.
  • the monomers of the hydrophilic side groups used in the preparation method of the present invention may be various hydrophilic monomers, as specifically described above.
  • the monomer dosage of the hydrophilic side groups may be 0.1-10% by weight based on the surface dosage of the polypropylene; preferably 1-8% by weight.
  • the amount of the polypropylene surface as the graft base is calculated according to the total weight of the product; if the thickness of the product is greater than 1mm, the amount of the polypropylene surface is calculated according to the weight of the product with a thickness of 1mm.
  • the amount of the polypropylene surface is in the direction from the polypropylene surface to the inside of the substrate according to the entire substrate including the polypropylene surface.
  • the monomers of the hydrophilic side groups can be directly contacted and mixed with the polypropylene surface or the polypropylene surface grafted with lipophilic monomers, or the monomers of the hydrophilic side groups can be mixed in one type for better mixing effect. Or mixed solutions in multiple solvents.
  • the amount of the solvent only needs to be able to dissolve the monomer to form a solution.
  • the weight ratio of the monomer to the solvent in the monomer solution of the hydrophilic side group is (0.1-100): 100, preferably (0.5- 50):100, more preferably (1-30):100.
  • the amount of the monomer solution preferably can completely cover the surface of the polypropylene, which is more convenient for the full contact and mixing of the two.
  • the solvent used to dissolve the hydrophilic side group monomer can be selected from at least one of water and organic solvents; preferably, it includes at least one of alcohol, ketone, ester, and water, and more preferably acetone or ethanol.
  • the lipophilic side group monomer used in the preparation method of the present invention may be various lipophilic monomers, and the details are as described above.
  • the monomer dosage of the lipophilic side group may be 0.1-30% by weight based on the surface dosage of the polypropylene; preferably 1-20% by weight.
  • the monomers of the lipophilic side groups can be directly contacted and mixed with the polypropylene surface or the polypropylene surface grafted with hydrophilic monomers, or the monomers of the lipophilic side groups can be mixed in one or more for better mixing effect.
  • the solutions in the two solvents are mixed.
  • the amount of solvent used only needs to be able to dissolve the monomer to form a solution.
  • the weight ratio of the lipophilic pendant monomer to the solvent can be (0.1-100): 100, preferably (0.5-50): 100, more preferably (1-30):100.
  • the amount of the monomer solution can completely cover the surface of the polypropylene, which is more convenient for the full contact and mixing of the two.
  • the solvent used to dissolve the lipophilic pendant monomer can be selected from at least one of water and organic solvents; preferably, it includes at least one of alcohol, ketone, ester, and water, more preferably acetone or ethanol.
  • the mixture of monomer and polypropylene surface may not be added with inorganic microwave absorbing medium, but it is preferable to add inorganic microwave absorbing medium to improve the grafting. effectiveness.
  • the temperature of the monomers of the lipophilic side groups generally does not exceed 200° C. under microwave, and the grafting reaction cannot be performed well. Therefore, it is necessary to add an inorganic microwave absorbing medium to promote the grafting reaction under microwave.
  • the inorganic microwave absorbing medium can use various inorganic substances that can absorb microwaves, preferably including at least one of metal hydroxides, metal salts, metal oxides, graphite materials, ferroelectric materials, chalcopyrite, and electrolytic stone. kind.
  • the metal hydroxide can be potassium hydroxide, barium hydroxide, sodium hydroxide, lithium hydroxide, strontium hydroxide, calcium hydroxide, iron hydroxide, ferrous hydroxide, zinc hydroxide, magnesium hydroxide, hydrogen At least one of cobalt oxide, gold hydroxide, aluminum hydroxide, copper hydroxide, beryllium hydroxide, and rare earth hydroxide;
  • the metal salt can be selected from ammonium nitrate, potassium nitrate, sodium nitrate, barium nitrate, calcium nitrate , Magnesium nitrate, aluminum nitrate, manganese nitrate, zinc nitrate, ferric nitrate, ferrous nitrate, copper nitrate, silver nitrate, ammonium chloride, potassium chloride, sodium chloride, barium chloride, calcium chloride, magnesium chloride, chloride Aluminum, manganese chloride, zinc chloride, ferric chloride, ferrous chloride, copper chloride,
  • the single dosage of the inorganic microwave absorbing medium can be 0.1-10% by weight of the surface dosage of polypropylene; preferably 1-8% by weight.
  • the single dosage of the inorganic microwave absorbing medium means that the preparation method of the present invention may include one or several times of microwave irradiation. If the inorganic microwave absorbing medium is added to it, the dosage is for a single microwave irradiation. The amount added.
  • the inorganic microwave absorbing medium can be directly added to the surface of polypropylene or grafted polypropylene to contact and mix, or for better mixing effect, an inorganic microwave absorbing medium that is dissolved or dispersed in one or more solvents can be used.
  • the solution or dispersion undergoes contact mixing.
  • the mixing of the inorganic microwave absorbing medium and the (grafted) polypropylene surface and the mixing with other components such as monomers are carried out step by step. That is, the (grafted) polypropylene surface can be separately mixed with monomer components and dried, and then the dried mixture is mixed with at least one of the inorganic microwave absorbing medium or its solution or dispersion.
  • the amount of solvent used to dissolve or disperse the microwave absorbing medium only needs to be able to dissolve the inorganic microwave absorbing medium to form an inorganic microwave absorbing medium solution, or to enable the inorganic microwave absorbing medium to be sufficiently uniformly dispersed to form a dispersion.
  • the weight ratio of the inorganic microwave absorbing medium to the solvent in the inorganic microwave absorbing medium solution or dispersion may preferably be (0.1-100): 100, more preferably (0.5-50): 100, most preferably (1-30): 100 Within range.
  • the amount of the inorganic microwave absorbing medium solution or dispersion is preferably such that it can completely cover the raw material mixture including the (grafted) polypropylene surface, thereby facilitating sufficient contact mixing and reaction of the raw materials.
  • the solvent in the inorganic microwave absorbing medium solution or dispersion is selected from at least one of water and organic solvents; preferably, it includes at least one of alcohol, ketone, ester, and water, and more preferably alcohol and water.
  • a surfactant commonly used in the prior art can be added to the inorganic microwave absorbing medium dispersion.
  • surfactants such as polyoxyethylene type and polyol type can be used, and the amount is usually 0.1-100% by weight of the inorganic microwave absorbing medium.
  • the base used in the salinization step can be selected from any one of the organic acid side groups, the acid anhydride side groups, and the ester side groups that can be grafted onto the surface of the polypropylene; preferably, it is a hydroxide.
  • the hydroxide is preferably at least one of metal hydroxide and ammonia; wherein the metal hydroxide is preferably sodium hydroxide, potassium hydroxide, barium hydroxide, lithium hydroxide, strontium hydroxide, calcium hydroxide, One or more of iron hydroxide, ferrous hydroxide, zinc hydroxide, magnesium hydroxide, cobalt hydroxide, gold hydroxide, aluminum hydroxide, copper hydroxide, beryllium hydroxide, and rare earth hydroxide, preferably One or more of sodium hydroxide, potassium hydroxide, barium hydroxide, lithium hydroxide, strontium hydroxide, and calcium hydroxide.
  • the metal hydroxide is preferably sodium hydroxide, potassium hydroxide, barium hydroxide, lithium hydroxide, strontium hydroxide, and calcium hydroxide.
  • the amount of the alkali (for example, hydroxide) can be 0.1-10% by weight based on the surface amount of the polypropylene; preferably 1-8% by weight.
  • the alkali can be directly added for contact mixing, or in order to facilitate sufficient mixing, it is preferable to perform sufficient mixing in the form of an aqueous alkali solution.
  • the amount of water used to dissolve the alkali is sufficient as long as it can dissolve the alkali to form an aqueous solution.
  • the weight ratio of alkali to water in the aqueous alkali solution may preferably be (0.1-100):100, more preferably (0.5-50):100, and most preferably (1-30):100.
  • the amount of the aqueous alkali solution can completely cover the surface of the grafted polypropylene, so that the two can be fully contacted, mixed and reacted.
  • the alkali and/or the aqueous solution of alkali can be fully mixed with the surface of the grafted polypropylene and react at the same time, which is a common acid-base reaction, and the reaction time has no special requirements until it is fully reacted.
  • the reaction time has no special requirements until it is fully reacted.
  • further contact mixing and simultaneous reaction for a period of time are sufficient, for example, it can be within 30 minutes, preferably 5-10 minutes.
  • the reaction temperature and pressure there are no restrictions on the reaction temperature and pressure, and it can generally be normal temperature and pressure.
  • the microwave irradiation process in the preparation method of the present invention can be carried out in various microwave reactors.
  • the microwave irradiation process can be carried out with any suitable irradiation power and lasted for any suitable time, as long as a suitable graft modification effect can be achieved on the polypropylene surface and thus the super-wetting property according to the present invention can be achieved.
  • the irradiation power may be 100w-2000w, preferably 500-1000w, more preferably 600w-800w;
  • the irradiation time may be 1s-120min, preferably 1min-30min, more preferably 3min-10min.
  • the microwave irradiation can preferably be carried out under an inert atmosphere.
  • the inert atmosphere can be an inert gas, preferably including one or more of nitrogen, helium, and argon, and more preferably nitrogen.
  • the above-mentioned mixing is preferably carried out under vacuum conditions.
  • the mixing includes contact mixing of hydrophilic side group monomers and/or its solution with the surface of (grafted) polypropylene, and contact mixing of lipophilic side group monomers and/or its solution with the surface of (grafted) polypropylene Mixing, contact mixing of grafted polypropylene surface with alkali and/or alkali aqueous solution, etc.
  • vacuum is conducive to the contact and mixing of grafted monomers and/or alkalis and other components more fully, and promotes the grafting of monomers and/or alkalis.
  • Other components enter the micro-nano structure of the polypropylene surface, which is more conducive to the reaction.
  • the contact mixing can be carried out by various mixing methods and equipment, and the mixing conditions are also commonly used conditions, as long as the materials can be fully and uniformly mixed;
  • the raw materials of other components including the monomers or their solutions, dispersions, etc. are coated, dripped, infiltrated, and covered on the surface of the polypropylene to achieve contact mixing.
  • the mixture of the components including the monomer and the (grafted) polypropylene surface is dried before the microwave irradiation.
  • the product after the microwave irradiation grafting can be washed with a solvent to remove unreacted monomers or inorganic microwave absorbing media that do not participate in the reaction, and is preferably further dried after washing.
  • the cleaning of the product after microwave irradiation there is no special restriction on the cleaning of the product after microwave irradiation, as long as the residual monomer or inorganic microwave absorbing medium can be removed.
  • the usual cleaning methods can be used. For example, after microwave, at high temperature, immediately use a solvent whose volume exceeds the surface of polypropylene to soak for a certain period of time (for example, 5-15 minutes), and then use a filter device to remove excess water; repeat the soaking and filtering many times (for example, 2-6 times) A clean super-wet surface is obtained.
  • the product of the salinization step (that is, the product after the reaction of the graft reaction product and the alkali) can preferably be washed with a solvent to remove the alkali that has not reacted with the surface of the grafted polypropylene, and is preferably further dried after washing.
  • the cleaning solvent can be selected from at least one of water and organic solvents; preferably includes at least one of alcohols, ketones, esters, and water, and more preferably alcohols and water.
  • the preferred drying temperature is preferably a temperature that does not melt polypropylene, for example, not more than 160°C.
  • the present invention provides an article consisting of or comprising a super-wetting surface according to the present invention.
  • the product can be a film, sheet, plate or molded product, such as polypropylene porous film, polypropylene flat film or polypropylene hollow fiber microporous film, plastic products to be bonded, outer packaging of food bags to be sprayed, and Sprayed car bumpers, etc.
  • the article may be composed mainly of polypropylene.
  • the present invention provides the super-wetting surface according to the present invention or the products containing the super-wetting surface in bonding (such as plastic product bonding, etc.), spraying (such as spraying of food bag outer packaging, automobile insurance Spraying of bars, etc.), or applications in the fields of oil-water separation, water treatment, biology, medicine, and energy.
  • the present invention also provides bonding, spraying, oil-water separation or water treatment methods using the super-wetting surface or products according to the present invention, such as for preparing bonded plastic products, spraying food bag outer packaging, spraying automobile bumpers.
  • amphiphilic polypropylene porous membrane obtained according to the present invention can be particularly used in oil-water separation, water treatment, biology, medicine, energy and other fields.
  • the super-wetting surface of the present invention can achieve super-hydrophilicity, and can even be super-parent.
  • the hydrophilic monomers such as organic acids and organic acid derivatives are irradiated with the surface of polypropylene by microwave irradiation without the addition of initiators to carry out the grafting reaction and even further salinization to obtain super-hydrophilic
  • a lipophilic and superhydrophilic surface has been formed at this time; optionally, it can be further irradiated with lipophilic monomers such as vinyl silicone oil without adding initiators.
  • the lipophilicity of the super-wetting surface is further improved, and the super-wetting surface of the super amphiphile can even be obtained.
  • Polypropylene is microwave transparent in a microwave environment (little or no microwave absorption under microwave irradiation, so it does not generate heat under microwave irradiation).
  • the organic acids and organic acid derivatives as grafting monomers will absorb microwaves under microwave conditions and increase the temperature to 200°C and above, and generate free radicals; at the same time, high temperature will also cause the production of nearby polypropylene molecular chains. Free radicals, therefore, will fully undergo grafting reaction with polypropylene to obtain the surface of grafted polypropylene.
  • such a microwave grafting reaction without the addition of an initiator can greatly avoid the ⁇ chain scission reaction of polypropylene during grafting with the addition of an initiator, thereby not reducing the molecular weight of the polypropylene.
  • the surface of the grafted polypropylene becomes the surface of the organic acid salt grafted polypropylene, which further improves Improve the hydrophilicity of the polypropylene surface.
  • alkali such as hydroxide
  • inorganic microwave absorbing medium can help monomers that do not absorb microwaves to be grafted onto polypropylene; for monomers that absorb microwaves, they can help improve the grafting efficiency.
  • the invention uses microwave selective heating to heat the inorganic microwave absorbing medium.
  • the temperature that can be raised under microwave is above 200 DEG C, and can reach near the melting point of polypropylene. At this temperature, polypropylene will not break the chain, but polypropylene tertiary carbon It can be dehydrogenated, so the grafting reaction will occur but will not cause the chain scission reaction.
  • lipophilic monomers such as vinyl silicone oil, the lipophilicity of the superhydrophilic polypropylene surface is further improved.
  • the capillary action existing in the structure further improves the hydrophilic and lipophilic effects of the surface.
  • the preparation method of the invention has simple process and easy operation. Such a modification method is suitable for various polypropylene surfaces; the equipment is simple, the cost is low, and it is easy to industrialize.
  • the super-wetting properties of the obtained super-wetting surface are durable and stable, and there is no residual grafting monomer, no residual alkali, no residual initiator, etc.
  • the molecular weight of the grafted polypropylene does not decrease during the preparation process.
  • the water flux or both water flux and oil flux of the graft-modified membrane are greatly improved.
  • the measuring range is 1-180°, the resolution is ⁇ 0.1°, and the dynamic contact angle measurement mode is adopted.
  • a fixed volume of 2 ⁇ L deionized water droplets or oil droplets (white oil droplets or oil droplets) Peanut oil droplets) drop on the surface to be tested, take the calculated initial contact angle (within 0.5s) as the measured value of the contact angle of the surface, measure 6 times in parallel, and calculate the average value.
  • the measured value is lower than the lower measurement limit (1°) of the instrument, the data is recorded as 0.
  • the white oil was purchased from Tianma (Karamay) Petroleum Company; the peanut oil was purchased from Shandong Luhua Group Co., Ltd.
  • the method for measuring the content of grafted side groups on the surface use the energy spectrum accessory of Hitachi S4800 scanning electron microscope to measure the content of the main elements of the grafted components on the surface to be tested;
  • the surface content is taken as the surface grafting rate. Since the content is the surface content (usually refers to the content in the thickness of 1-2 mm from the surface of the object), the content is higher than the content of the monomer in the raw material.
  • Water and oil flux test method Take 5 pieces of surface to be tested, such as polypropylene porous membrane, and use a cryostat to remove the skin layer to make a membrane module. Filtered with deionized water, chloroform and peanut oil for 30 minutes under normal pressure, and the obtained value is the water and oil flux of the surface or membrane.
  • the method for measuring the average pore size and the average size of the micropores use a scanning electron microscope (Japan Hitachi S-4800 field emission scanning electron microscope, magnification: 5000) to observe the surface of the pore or micropore, count the pore size data, and make the pore size
  • the distribution map determines the average pore size and the average size of the micropores.
  • the porosity was measured using the mercury intrusion method (MIP), in which a mercury porosimeter (Poremaster-33, Quantachrome, USA) was used.
  • MIP mercury intrusion method
  • Surface sample 1 Polypropylene flat membrane, Tianjin Motianme Engineering Technology Co., Ltd. (average pore size 0.8 ⁇ m, porosity 80%), use epoxy resin glue (DP100NS from 3M Company) on one side of the membrane to seal, and the other side is in liquid In a nitrogen atmosphere, a Leica CM3600 cryomicrotome was used to remove the skin layer of the membrane to obtain a polypropylene microporous surface sample 1, with an average size of micropores on the surface of 0.8 ⁇ m.
  • epoxy resin glue DP100NS from 3M Company
  • Microwave equipment SINEO (new instrument) multifunctional microwave synthesis extraction instrument, model: UWave-2000.
  • the mixture of dried maleic anhydride and polypropylene surface sample was irradiated with microwave (power 700W) for 5 minutes under a nitrogen atmosphere; the product after microwave irradiation was immersed in deionized water for 10 minutes and replaced with deionized water.
  • Repeat 3 To ensure the removal of the maleic anhydride monomer that did not participate in the grafting reaction, and then place it in a blast drying oven at 80°C to obtain a dry maleic anhydride grafted polypropylene surface sample; put the sodium hydroxide aqueous solution in a vacuum condition Then, fully contact and mix with the dried maleic anhydride grafted polypropylene surface sample, and mix and react for 5 minutes after the sodium hydroxide aqueous solution is added. After the reaction is completed, the reaction product is cleaned with deionized water according to the same cleaning procedure as above, and then placed in a blast drying oven at 80° C. to dry, to obtain a polypropylene surface sample grafted with sodium maleate.
  • maleic anhydride (5 parts by mass) was dissolved in acetone (50 parts by mass) to obtain a maleic anhydride acetone solution; sodium hydroxide (5 parts by mass) Dissolve in deionized water (50 parts by mass) to obtain an aqueous sodium hydroxide solution; add the maleic anhydride and acetone solution to the polypropylene surface sample under vacuum conditions to fully contact and mix, and then dry the mixture (80°C drum Air drying oven drying).
  • the mixture of dried maleic anhydride and polypropylene surface sample was irradiated with microwave (power 700W) for 5 minutes under a nitrogen atmosphere; the product after microwave irradiation was immersed in deionized water for 10 minutes and replaced with deionized water.
  • Repeat 3 To ensure the removal of the maleic anhydride monomer that did not participate in the grafting reaction, and then place it in a blast drying oven at 80°C to obtain a dry maleic anhydride grafted polypropylene surface sample; put the sodium hydroxide aqueous solution under vacuum
  • the maleic anhydride grafted polypropylene surface sample added to the drying is fully contacted and mixed, and the sodium hydroxide aqueous solution is added and then mixed and reacted for 5 minutes.
  • the reaction product is cleaned with deionized water according to the same cleaning procedure as above, and then placed in a blast drying oven at 80° C. to dry, to obtain a polypropylene super-soaked surface sample grafted with sodium maleate side groups. See Table 1 for the water and oil contact angles and surface grafting rate data of the obtained super-wet surface.
  • the polypropylene surface sample dissolve vinyl silicone oil (9 parts by mass) in ethanol (50 parts by mass) to obtain a vinyl silicone oil ethanol solution; add sodium chloride (4 parts by mass) Parts) was dissolved in deionized water (50 parts by mass) to obtain an aqueous sodium chloride solution; the vinyl silicone oil ethanol solution was added to the polypropylene surface sample under vacuum to fully contact and mix, and then the mixture was dried (80°C) Drying in a blast drying oven); fully contact and mix the dried mixture of vinyl silicone oil and polypropylene surface sample with sodium chloride aqueous solution, and then dry the mixture (dry in a blast drying oven at 80°C); The dried mixture was irradiated with microwave under nitrogen atmosphere (power 1000W) for 3min; the material after microwave irradiation was soaked in deionized water for 10 minutes and replaced with deionized water.
  • power 1000W microwave under nitrogen atmosphere
  • the polypropylene surface sample (same as Example 1) was directly tested, and the water and oil contact angle data of the polypropylene surface are shown in Table 1.
  • 2-acrylamide-2-methylpropanesulfonic acid 10 parts by mass was dissolved in acetone (50 parts by mass) to obtain 2-acrylamide-2- Methyl propane sulfonate acetone solution; potassium hydroxide (6 parts by mass) was dissolved in deionized water (50 parts by mass) to obtain a potassium hydroxide aqueous solution; the 2-acrylamide-2-methyl propane sulfonate solution in acetone Under vacuum conditions, it is added to the polypropylene surface sample to fully contact and mix, and then the mixture is dried (drying in a blast drying oven at 80°C).
  • the dried mixture of 2-acrylamide-2-methylpropanesulfonic acid and polypropylene surface sample was microwave-irradiated (power 1000W) for 3min in a nitrogen atmosphere; the product after microwave irradiation was immersed in deionized water Replace the deionized water for 10 minutes and repeat 3 times to ensure the removal of the 2-acrylamide-2-methylpropanesulfonic acid monomer that is not involved in the grafting reaction, and then place it in a blast drying oven at 80°C to dry it.
  • 2-acrylamide-2-methylpropanesulfonic acid 10 parts by mass was dissolved in acetone (50 parts by mass) to obtain 2-acrylamide-2 -Methyl propane sulfonate acetone solution; potassium hydroxide (6 parts by mass) was dissolved in deionized water (50 parts by mass) to obtain a potassium hydroxide aqueous solution; 2-acrylamide-2-methyl propane sulfonate in acetone solution Under vacuum conditions, it was added to the polypropylene surface sample to fully contact and mix, and then the mixture was dried (drying in a blast drying oven at 80°C).
  • the dried mixture of 2-acrylamide-2-methylpropanesulfonic acid and polypropylene surface sample was microwave-irradiated (power 1000W) for 3min in a nitrogen atmosphere; the product after microwave irradiation was immersed in deionized water Replace the deionized water for 10 minutes and repeat 3 times to ensure the removal of the 2-acrylamide-2-methylpropanesulfonic acid monomer that has not participated in the grafting reaction, and then place it in a blast drying oven at 80°C to obtain a dry 2 -Acrylamide-2-methylpropanesulfonic acid grafted polypropylene surface sample; potassium hydroxide aqueous solution was added to the dried 2-acrylamide-2-methylpropanesulfonic acid grafted polypropylene surface under vacuum conditions The sample is fully contacted and mixed, and the potassium hydroxide aqueous solution is added and then mixed and reacted for 5 minutes.
  • the mixture of dried methacrylic acid and polypropylene surface sample was irradiated with microwave (power 2000W) for 1 min under a nitrogen atmosphere; the product after microwave irradiation was immersed in deionized water for 10 minutes and replaced with deionized water.
  • Repeat 3 To ensure the removal of methacrylic acid monomers that did not participate in the grafting reaction, and then place them in a blast drying oven at 80°C to obtain a dry methacrylic acid grafted polypropylene surface sample; put the calcium hydroxide aqueous solution in a vacuum condition
  • reaction product is cleaned with deionized water according to the same cleaning procedure as above, and then placed in a blast drying oven at 80° C. to dry, to obtain a surface sample of polypropylene grafted with calcium methacrylate.
  • the mixture of dried methacrylic acid and polypropylene surface sample was irradiated with microwave (power 2000W) for 1 min under a nitrogen atmosphere; the product after microwave irradiation was immersed in deionized water for 10 minutes and replaced with deionized water.
  • Repeat 3 To ensure the removal of methacrylic acid monomers that did not participate in the grafting reaction, and then place them in a blast drying oven at 80°C to obtain a dry methacrylic acid grafted polypropylene surface sample; put the calcium hydroxide aqueous solution in a vacuum condition
  • the reaction product is cleaned with deionized water according to the same cleaning procedure as above, and then placed in a blast drying oven at 80° C. to dry, to obtain a polypropylene super-wetting surface sample grafted with calcium methacrylate side groups. See Table 1 for the water and oil contact angles and surface grafting rate data of the obtained super-wet surface.
  • the polypropylene surface sample (same as Example 5) was directly tested, and the water and oil contact angle data of the polypropylene surface are shown in Table 1.
  • the polypropylene surface sample dissolve methyl vinyl silicone oil (2 parts by mass) in ethanol (50 parts by mass) to obtain a methyl vinyl silicone oil ethanol solution; the graphene oxide (GO) aqueous solution ( 10 parts by mass), ascorbic acid (1 part by mass) were dissolved in deionized water (50 parts by mass) to obtain a graphene oxide (GO) dispersion; the methyl vinyl silicone oil ethanol solution was added to the above methacrylic acid under vacuum conditions
  • the grafted polypropylene surface sample is fully contacted and mixed, and then the mixture is dried (drying in a blast drying oven at 80°C); the dried methyl vinyl silicone oil and the powder of the grafted polypropylene surface sample mixture are dried with The graphene oxide (GO) dispersion is fully contacted and mixed, and then the mixture is dried (dry in a blast drying oven at 80°C), where the graphene oxide, ascorbic acid and deionized water are mixed to form a graphene oxide dis
  • Graphene is the follow-up microwave Irradiate the grafted microwave absorbing medium; microwave the dried mixture under nitrogen atmosphere (power 500W) for 30min; soak the microwave-irradiated material in deionized water for 10 minutes and replace the deionized water and repeat 3 times to ensure Remove the methyl vinyl silicone oil monomer and graphene oxide that did not participate in the grafting reaction, and then place them in a blast drying oven at 80°C for drying; obtain polypropylene grafted with methacrylic acid and methyl vinyl silicone oil side groups Super wet surface sample. See Table 1 for the water and oil contact angles and surface grafting rate data of the obtained super-wet surface.
  • the dried vinyltrimethoxysilane and polypropylene surface sample mixture was fully contacted and mixed with sodium chloride aqueous solution after drying, and then the mixture was dried (drying in a blast drying oven at 80°C); the dried ethylene was dried.
  • the mixture of trimethoxysilane and polypropylene surface sample was microwave irradiated (power 500W) for 30min under a nitrogen atmosphere; the product after microwave irradiation was immersed in deionized water for 10 minutes and replaced with deionized water.
  • the graphene oxide dispersion is mixed with styrene and grafted polypropylene on the surface of the sample. After the mixture is mixed and dried at 80°C, ascorbic acid is used as a reducing agent for graphene oxide to reduce graphene oxide to graphene.
  • Graphene is the microwave absorbing medium for subsequent microwave irradiation grafting; the dried mixture is exposed to nitrogen. Microwave irradiation (power 500W) in the atmosphere for 30 minutes; the microwave-irradiated material is soaked in deionized water for 10 minutes and replaced with deionized water and repeated 3 times to ensure that the styrene monomer and graphene oxide that are not involved in the grafting reaction are removed.
  • the polypropylene surface sample (same as Example 9) was directly tested, and the water and oil contact angle data of the polypropylene surface are shown in Table 1.
  • the super-wetting surface obtained after hydrophilic graft modification or further lipophilic graft modification on the surface of polypropylene according to the present invention is compared with the surface of unmodified polypropylene.
  • the hydrophilic and lipophilic properties are greatly improved.
  • the super-wet surface can reach super-hydrophilic, lipophilic, and even super-hydrophilic and super-lipophilic (super amphiphilic) in some cases, which shows that it has achieved very effective treatment of polypropylene. Amphiphilic modification of the surface.
  • maleic anhydride 5 parts by mass is dissolved in acetone (50 parts by mass) to obtain maleic anhydride Acetone solution; sodium hydroxide (5 parts by mass) was dissolved in deionized water (50 parts by mass) to obtain an aqueous sodium hydroxide solution; the maleic anhydride acetone solution was added to the polypropylene porous under vacuum accompanied by mechanical stirring The film is fully mixed, and then the mixture is dried (drying in a blast drying oven at 80°C).
  • the dried mixture of maleic anhydride and polypropylene porous membrane was irradiated with microwave (power 700W) for 5 minutes under a nitrogen atmosphere; the product after microwave irradiation was immersed in deionized water for 10 minutes and replaced with deionized water.
  • maleic anhydride 5 parts by mass was dissolved in acetone (50 parts by mass) to obtain a maleic anhydride acetone solution; sodium hydroxide (5 parts by mass) Dissolve in deionized water (50 parts by mass) to obtain an aqueous sodium hydroxide solution; add the maleic anhydride and acetone solution to the polypropylene porous membrane under vacuum with mechanical stirring and mix thoroughly, and then dry the mixture (80 °C blast drying oven drying).
  • the dried mixture of maleic anhydride and polypropylene porous membrane was irradiated with microwave (power 700W) for 5 minutes under a nitrogen atmosphere; the product after microwave irradiation was immersed in deionized water for 10 minutes and replaced with deionized water.
  • amphiphilic polypropylene porous membrane grafted with sodium maleate side groups The water and oil contact angles, water and oil fluxes, and surface grafting rate data of the obtained amphiphilic polypropylene porous membrane are shown in Table 2.
  • vinyl silicone oil (10 parts by mass) was dissolved in ethanol (50 parts by mass) to obtain a vinyl silicone oil ethanol solution; sodium chloride (5 parts by mass) Parts) was dissolved in deionized water (50 parts by mass) to obtain an aqueous sodium chloride solution; the vinyl silicone oil ethanol solution was added to the polypropylene porous membrane under vacuum with mechanical stirring and mixed thoroughly, and then the mixture was dried (80°C blast drying oven drying); the dried vinyl silicone oil and polypropylene porous film mixture powder is thoroughly mixed with sodium chloride aqueous solution, and then the mixture is dried (80°C blast drying oven drying Dry); microwave the dried mixture under a nitrogen atmosphere (power 1000W) for 3min; soak the microwave-irradiated material in deionized water for 10 minutes and replace the deionized water to repeat 3 times to ensure that the grafting reaction is removed Vinyl silicone oil monomer and sodium chloride, and then put the membrane in 80 °
  • Acrylic acid acetone solution is added to the above grafted vinyl silicone oil side-group polypropylene porous film under vacuum with mechanical stirring, and then the mixture is dried (80°C blast drying oven drying).
  • the mixture of dried acrylic acid and grafted polypropylene porous membrane was irradiated with microwave (power 1000W) for 3min under nitrogen atmosphere; the product after microwave irradiation was immersed in deionized water for 10 minutes and replaced with deionized water.
  • amphiphilic polypropylene porous membrane grafted with potassium acrylate and vinyl silicone oil side groups.
  • the water and oil contact angles, water and oil fluxes, and surface grafting rate data of the obtained amphiphilic polypropylene porous membrane are shown in Table 2.
  • the mixture of dried acrylic and polypropylene porous film was irradiated with microwave (power 1000W) for 3min under a nitrogen atmosphere; the product after microwave irradiation was immersed in deionized water for 10 minutes and replaced with deionized water and repeated 3 times.
  • microwave power 1000W
  • the product after microwave irradiation was immersed in deionized water for 10 minutes and replaced with deionized water and repeated 3 times.
  • make sure to remove the acrylic monomers that are not involved in the grafting reaction and then place the membrane in a blast drying oven at 80°C to dry to obtain a dry acrylic grafted polypropylene porous membrane; add the potassium hydroxide aqueous solution to the drying under vacuum stirring conditions
  • the acrylic acid grafted polypropylene porous membrane is fully mixed, and the potassium hydroxide aqueous solution is added and then stirred and mixed and reacted for 5 minutes.
  • the reaction product is cleaned with deionized water according to the same cleaning procedure as above, and then placed in a blast drying oven at 80° C. to dry, to obtain an amphiphilic polypropylene porous membrane grafted with potassium acrylate side groups.
  • the water and oil contact angles, water and oil fluxes, and surface grafting rate data of the obtained amphiphilic polypropylene porous membrane are shown in Table 2.
  • the polypropylene porous membrane (same as Example 13) was directly tested, and the water and oil contact angles and water and oil flux data of the polypropylene porous membrane are shown in Table 2.
  • the dried mixture of 2-acrylamide-2-methylpropanesulfonic acid and polypropylene porous membrane was microwave-irradiated (power 1000W) for 3min under a nitrogen atmosphere; the product after microwave irradiation was immersed in deionized water Replace the deionized water for 10 minutes and repeat 3 times to ensure the removal of the 2-acrylamide-2-methylpropanesulfonic acid monomer that is not involved in the grafting reaction, and then place the membrane in a blast drying oven at 80°C to obtain a dry 2 -Acrylamide-2-methylpropanesulfonic acid grafted polypropylene porous membrane; the potassium hydroxide aqueous solution was grafted with dried 2-acrylamide-2-methylpropanesulfonic acid under vacuum stirring conditions The porous membrane is fully mixed, and after the potassium hydroxide aqueous solution is added, the mixture is stirred and mixed and reacted for 5 minutes.
  • reaction product is cleaned with deionized water according to the same cleaning procedure as above, and then placed in a blast drying oven at 80° C. to dry, to obtain a polypropylene porous membrane grafted with potassium 2-acrylamide-2-methylpropanesulfonate.
  • Potassium polypropylene porous membrane is fully mixed, and then the mixture is dried (80°C air-dried drying oven); the dried vinyl hydrogen-containing silicone oil polypropylene porous membrane mixture powder and sodium chloride aqueous solution are dried after drying Mix thoroughly, then dry the mixture (dry in a blast drying oven at 80°C); microwave the dried mixture under a nitrogen atmosphere (power 1000W) for 3 minutes; soak the microwave-irradiated material in deionized water for 10 minutes Replace the deionized water and repeat 3 times to ensure that the vinyl hydrogen-containing silicone oil monomer and sodium chloride that are not involved in the grafting reaction are removed, and then the membrane is dried in a blast drying oven at 80°C; the grafted 2-acrylamide is obtained.
  • amphiphilic polypropylene porous membrane with pendant 2-methyl propane sulfonate and vinyl hydrogen-containing silicone oil The water and oil contact angles, water and oil fluxes, and surface grafting rate data of the obtained amphiphilic polypropylene porous membrane are shown in Table 2.
  • the dried mixture of 2-acrylamide-2-methylpropanesulfonic acid and polypropylene porous membrane was microwave-irradiated (power 1000W) for 3min under a nitrogen atmosphere; the product after microwave irradiation was immersed in deionized water Replace the deionized water for 10 minutes and repeat 3 times to ensure the removal of the 2-acrylamide-2-methylpropanesulfonic acid monomer that is not involved in the grafting reaction, and then place the membrane in a blast drying oven at 80°C to obtain a dry 2 -Acrylamide-2-methylpropanesulfonic acid grafted polypropylene porous membrane; the potassium hydroxide aqueous solution was added to the dried 2-acrylamide-2-methylpropanesulfonic acid grafted poly The propylene porous membrane is fully mixed, and after the potassium hydroxide aqueous solution is added, the mixture is stirred and mixed and reacted for 5 minutes.
  • the dried mixture of methacrylic acid and polypropylene porous membrane was irradiated with microwave (power 2000W) for 1 min under a nitrogen atmosphere; the product after microwave irradiation was immersed in deionized water for 10 minutes and replaced with deionized water.
  • the film was placed in a blast drying oven at 80°C to obtain a dry methacrylic acid grafted polypropylene porous film; the calcium hydroxide aqueous solution was stirred in a vacuum Under the conditions, the dried methacrylic acid grafted polypropylene porous membrane is fully mixed, and the calcium hydroxide aqueous solution is added and then stirred and mixed and reacted for 5 minutes.
  • the reaction product is cleaned with deionized water according to the same cleaning procedure as above, and then placed in a blast drying oven at 80° C. to dry, to obtain a polypropylene porous membrane grafted with calcium methacrylate.
  • divinyl silicone oil (10 parts by mass) in ethanol (50 parts by mass) to obtain a divinyl silicone oil ethanol solution; dissolve sodium chloride (5 parts by mass) in Sodium chloride aqueous solution was obtained in deionized water (50 parts by mass); the divinyl silicone oil ethanol solution was added to the above-mentioned polypropylene porous membrane grafted with calcium methacrylate under vacuum with mechanical stirring, and then mixed thoroughly.
  • the dried mixture of methacrylic acid and polypropylene porous membrane was irradiated with microwave (power 2000W) for 1 min under a nitrogen atmosphere; the product after microwave irradiation was immersed in deionized water for 10 minutes and replaced with deionized water.
  • the film was placed in a blast drying oven at 80°C to obtain a dry methacrylic acid grafted polypropylene porous film; the calcium hydroxide aqueous solution was stirred in a vacuum Under the conditions, the dried methacrylic acid grafted polypropylene porous film is fully mixed, and the calcium hydroxide aqueous solution is added and then stirred and mixed and reacted for 5 minutes. After the reaction is completed, the reaction product is cleaned with deionized water according to the same cleaning procedure as above, and then placed in a blast drying oven at 80° C.
  • amphiphilic polypropylene porous membrane grafted with calcium methacrylate side groups The water and oil contact angles, water and oil fluxes, and surface grafting rate data of the obtained amphiphilic polypropylene porous membrane are shown in Table 2.
  • the dried mixture of methacrylic acid and polypropylene porous membrane was irradiated with microwave (power 500W) for 30min under a nitrogen atmosphere; the product after microwave irradiation was immersed in deionized water for 10 minutes and replaced with deionized water.
  • microwave power 500W
  • the film is placed in a blast drying oven at 80°C for drying to obtain a dry methacrylic acid grafted polypropylene porous film.
  • the calcium hydroxide aqueous solution is added to the dried methacrylic acid grafted polypropylene porous membrane under vacuum stirring conditions and mixed thoroughly, and the calcium hydroxide aqueous solution is added and then stirred and mixed and reacted for 5 minutes after the addition of the calcium hydroxide aqueous solution.
  • the reaction product is cleaned with deionized water according to the same cleaning procedure as above, and then placed in a blast drying oven at 80° C. to dry, to obtain a polypropylene porous membrane grafted with calcium methacrylate.
  • Graphene is a subsequent microwave Irradiate the grafted microwave absorbing medium; microwave the above-mentioned dry mixture under a nitrogen atmosphere (power 500W) for 30 minutes; soak the microwave-irradiated materials in deionized water for 10 minutes and replace the deionized water and repeat 3 times to Make sure to remove the methyl vinyl silicone oil monomer and graphene oxide that have not participated in the grafting reaction, and then place the film in a 80 °C blast drying oven to dry; obtain the amphiphilic polymerization of grafted calcium methacrylate and methyl vinyl silicone oil Propylene porous membrane.
  • the water and oil contact angles, water and oil fluxes, and surface grafting rate data of the obtained amphiphilic polypropylene porous membrane are shown in Table 2.
  • vinyl trimethoxysilane (10 parts by mass) was dissolved in ethanol (50 parts by mass) to obtain an ethanol solution of vinyl trimethoxysilane;
  • the ethanol solution of vinyltrimethoxysilane was added to the polypropylene porous membrane under vacuum with mechanical stirring. After mixing, the mixture is dried (drying in a blast drying oven at 80°C).
  • trimethoxysilane and polypropylene porous membrane mixture were mixed with the sodium chloride aqueous solution thoroughly, and then dry the mixture (dry in a blast drying oven at 80°C); dry the dried vinyl
  • the mixture of trimethoxysilane and polypropylene porous membrane was microwave irradiated (power 500W) for 30min under a nitrogen atmosphere; the product after microwave irradiation was soaked in deionized water for 10 minutes and replaced with deionized water and repeated 3 times to ensure the removal of impurities Participate in the grafting reaction of vinyltrimethoxysilane monomer and sodium chloride, and then the film is placed in a blast drying oven at 80°C for drying to obtain a dry vinyltrimethoxysilane grafted polypropylene porous film.
  • the mixture is thoroughly mixed, and then the mixture is dried (80°C blast drying oven drying); the dried powder of the dried styrene and grafted polypropylene porous membrane mixture is thoroughly mixed with the graphene oxide (GO) dispersion , Then the mixture is dried (80°C blast drying oven drying), where graphene oxide, ascorbic acid and deionized water are mixed to form a graphene oxide dispersion.
  • the graphene oxide dispersion is porous with styrene and grafted polypropylene.
  • ascorbic acid is used as a reducing agent for graphene oxide to reduce graphene oxide to graphene.
  • Graphene is the microwave absorbing medium for subsequent microwave irradiation grafting; Microwave irradiation (power 500W) under a nitrogen atmosphere for 30 minutes; the microwave-irradiated material is soaked in deionized water for 10 minutes and replaced with deionized water. Repeat 3 times to ensure that the styrene monomer and graphite oxide that are not involved in the grafting reaction are removed Then, the film is placed in a blast drying oven at 80°C for drying; an amphiphilic polypropylene porous film grafted with vinyltrimethoxysilane and styrene is obtained.
  • Table 2 The water and oil contact angles, water and oil fluxes, and surface grafting rate data of the obtained amphiphilic polypropylene porous membrane are shown in Table 2.
  • the polypropylene porous membrane (same as Example 17) was directly tested, and the water and oil contact angles and water and oil flux data of the polypropylene porous membrane are shown in Table 2.

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Abstract

本发明提供了一种超浸润表面及其制备方法和应用。所述超浸润表面为接枝有亲水性侧基的具有微纳结构的聚丙烯表面，其中所述超浸润表面是至少超亲水的并且不含有引发剂残留物。所述超浸润表面通过将用于形成侧基的单体在不存在引发剂的情况下，通过微波辐照与作为接枝基础物的具有微纳结构的聚丙烯表面进行接枝反应而制备。本发明的制备方法简单、易操作、设备简单、成本低、易于工业化。超浸润表面的制备中接枝后聚丙烯分子量不下降、无残留单体、无引发剂残留，且所得表面的超浸润效果持久稳定。该超浸润表面可用于粘接、喷涂、油水分离、水处理、生物、医药和能源领域。

Description

超浸润表面及其制备方法和应用 技术领域
本发明涉及高分子材料领域，尤其涉及高分子膜材料领域，具体涉及一种超浸润表面及其制备方法和应用。
背景技术
固体材料表面的润湿性通常是由固体表面的化学性质和微观结构决定的。具有超润湿性能的聚合物表面在液体分离、自清洁、防雾、液体输送、功能性聚合物薄膜、印刷和粘接等方面有重要用途。
目前，已有众多学者对聚合物表面改性进行了深入研究，但超浸润材料方面的研究得到的大部分是超疏水材料，超亲水材料的报道十分少，显然超亲水聚合物较难制备。通过传统的接枝方法，例如ATRP、电晕法、等离子体处理、紫外光等方法得到的聚合物表面只能是亲水表面却不是超亲水表面。
超双亲表面比超亲水和超亲油表面更难制备，该表面要求水和油均能浸润材料表面。1997年，Wang首次报道了双亲材料(Wang,R.；Hashimoto,K.；Fujishima,A.；Chikuni,M.；Kojima,E.；Kitamura,A.；Shimohigoshi,M.；Watanabe,T.,Light-induced amphiphilic surfaces，Nature 1997,388(6641),431-432)，它是通过将二氧化钛使用紫外光诱导在固体基材上制备出双亲表面，该表面具有防污能力。在此之后，人们利用逐层组装、静电纺丝、蚀刻、等离子体处理、浸涂、相分离和模板方法制备出多种超浸润聚合物表面。然而，通过上述方法制备的超浸润聚合物表面必须复合无机颗粒，在柔性制品中固体颗粒的脆性限制了材料的应用。因此，到目前为止，现有方法仍然不可能在不使用无机颗粒的情况下制备超双亲聚合物表面。
膜技术作为一种新兴的高效分离技术，是一种已经产业化的高效节能的分离方法，近年来得到迅速发展。在膜技术的应用中，膜材料则是膜技术发展和应用的基础和核心。膜材料的性能直接影响到膜的分离性能，因此其制备工艺一直是学者研究的热点。目前，广泛应用的膜材料有高分子和无机材料两类。其中，聚合物微孔膜的制备方法主要有相转化法、拉伸法、溶出法、烧结法和核径迹法等。20世纪80年代初，Castro提交了一件专利申请，其中提出了热致相分离(thermally-induced phase separation，简称TIPS)法，该 法属于温差凝胶相转换制膜法。将只能在温度较高时才能互溶的聚合物和稀释剂，先加热使之熔融，然后将溶液流延或挤压成薄膜后冷却。当溶液温度下降到某一温度以下时，溶液中聚合物链相互作用形成凝胶结构，最后因相分离而形成细孔，将分离后的凝胶浸入萃取液中除去稀释剂可形成多孔膜。
聚丙烯具有高熔点、低密度、高强度等特点，并且具有优良的耐腐蚀性、化学稳定性、耐热性等优点，作为制备膜材料的原材料具有很大优势。由于聚丙烯表面不含极性基团，其表面能很小，临界表面张力只有31-34×10 -5N/cm，因此表现为亲油性。聚丙烯制备成微孔膜后会表现更强的亲油性，使得水透过需要较高的压力，动力能耗高，膜通量也低。在使用过程中，由于膜的疏水性容易引起有机物和胶体在膜表面和膜孔内吸附，如蛋白质吸附，造成膜污染。为了使膜分离过程正常进行，需要提高压力或进行频繁清洗，使得操作能耗和清洗费用提高，限制了聚丙烯微孔膜的进一步广泛应用。这样的膜的亲水化改性是提高膜水通量和耐污染性能的重要方法，因此这也成为当今膜研究的热点之一。另外，聚丙烯虽然是亲油的，但其亲油性仍然不足，例如聚丙烯注射器中，仍然需要添加硅油增加其亲油性；亲油分离膜在气体分离等领域也有应用前景。但具有双亲功能的聚丙烯多孔膜罕有报道。
目前膜材料的改性方法主要分为物理方法和化学方法，物理方法包括表面活性剂改性、表面涂覆改性以及膜材料的共混改性等。化学方法包括等离子改性、紫外辐照接枝、高能辐射接枝或者通过其他化学反应引入极性基团等。例如中国专利申请公开CN105195031A公开了一种分离膜亲水改性方法，将亲水性预聚体及引发剂与制膜聚合物混合，再利用紫外光辐射交联；中国专利CN1299810C(公布为CN1539550A)的亲水改性方法是将单体预涂覆在聚丙烯分离膜表面，使用等离子体辐照接枝。以上方法设备复杂，对于多孔膜的处理难以达到均匀的效果，不利于工业应用。
这些聚丙烯膜改性方法中共混改性是较为常用的方法。共混改性方法简单、易于控制，能同时保留多种聚合物的各自特点，改性效果明显。在共混改性中，水溶性聚合物和纳米材料是两种常用的添加剂。水溶性聚合物如聚乙烯吡咯烷酮、聚乙二醇可以明显提高膜通量，但膜耐压性能差。中国专利申请公开CN103768958A提供了一种亲水聚合物与聚烯烃分子膜共混的方法，将聚烯烃与相容剂以及亲水聚合物熔融共混再采用热致相分离制备亲水多孔膜。纳米材料制备的膜通量高，耐压性好，但是纳米粒子很难均匀分布在成膜液中， 这导致制膜过程繁琐，不适合工业生产。中国专利申请公开CN104548950A在聚丙烯树脂中加入偶联剂处理的无机纳米粒子、稀释剂进行熔融共混，采用热致相分离法制备无机纳米粒子增强型聚丙烯中空纤维分离膜。等离子改性、紫外辐照接枝等其他改性方法，随着运行时间的增加亲水性衰减严重；或是需要较为复杂的化学反应，工业化放大困难。
发明内容
鉴于现有技术，本发明的目的是提供一种新型的超浸润表面，其是至少超亲水的，所述表面的超浸润性质持久稳定并且所述超浸润表面不具有现有技术中亲水和/或亲油表面的缺点。
本发明的另一个目的是提供这种超浸润表面的制备方法，通过该方法可以简便地制备超浸润表面，并且所述方法可容易工业化。
通过根据本发明的超浸润聚丙烯表面及其制备方法实现了所述目的。
根据本发明，预料不到地发现，将具有微纳结构的聚丙烯表面与例如有机酸及有机酸衍生物、乙烯基硅烷等的亲水性单体在微波辐照下，在不添加引发剂的情况下进行接枝反应，任选地进一步盐化，可以得到超亲水的表面；还可以进一步接枝例如乙烯基硅油、苯乙烯等亲油性单体，由此进一步提高超亲水表面的亲油性，甚至可以实现超双亲表面。
因此，根据本发明的第一方面，本发明提供一种超浸润表面，其为接枝有亲水性侧基的具有微纳结构的聚丙烯表面，其中所述超浸润表面是至少超亲水的并且所述超浸润表面不含有引发剂残留物。
本文中使用的术语“表面”是指固体与空气的界面。
根据本发明的表面是超浸润表面。本文中使用的术语“超浸润”是指超亲水、超亲油或者超双亲(超亲水并且超亲油)的性质。本文中使用的术语“超亲水”是指表面的水接触角小于或等于10°，优选小于或等于5°，更优选小于或等于1°，最优选达到约0°，尤其是在约0.5s内达到上述角度。本文中使用的术语“超亲油”是指表面的油接触角小于或等于10°，优选小于或等于5°，更优选小于或等于1°，最优选达到约0°，尤其是在约0.5s内达到上述角度。所述接触角采用接触角测试仪，以动态接触角测量模式，使用水滴或者油滴(例如白油或花生油油滴)测定。
根据本发明的超浸润表面的水接触角可达到小于或等于10°，优选小于或等于8°，更优选小于或等于5°，再更优选小于或等于1°，最优选约0°，尤其是在约0.5s内达到上述 角度。
本发明的超浸润表面可以依附于基底上，也可以是自支撑型、独立的产品。
由于本发明的超浸润表面通过在微波辐照下，在不添加引发剂的情况下进行接枝反应而制备，因此本发明的超浸润表面不含有引发剂残留物。本文中使用的术语“引发剂”是指本领域常用于引发单体的聚合反应(包括接枝反应)的物质，例如自由基型引发剂，包括过氧化物引发剂，如有机过氧化物引发剂(例如过氧化二异丙苯)和无机过氧化物引发剂；和偶氮引发剂及氧化还原引发剂等；还有光敏引发剂(或光敏剂)，例如二苯甲酮。
根据本发明的超浸润表面为接枝有亲水性侧基的具有微纳结构的聚丙烯表面。本文中使用的术语“微纳结构”为具有微米或纳米尺度的特征尺寸、按照特定方式排布的功能结构，所述的功能结构包括孔状结构或其他形状结构；通常这个微纳结构的特征尺寸在1nm-100μm范围内。所述特征尺寸是指微纳结构的特征结构的平均尺寸。
作为接枝基础物的具有微纳结构的聚丙烯表面可以是各种带有微纳结构的聚丙烯表面，并且可采用现有技术中已有的制备方法制备。所述聚丙烯表面的微纳结构的特征尺寸为1nm-100μm。例如可采用各种聚丙烯微孔表面，优选采用热致相分离工艺制备的聚丙烯微孔平面。还可以采用现有技术的光刻技术、飞秒激光加工技术、等离子刻蚀技术、静电纺丝法、纳米压印、纳米铸造和超精密微铣技术等实现聚丙烯表面微纳结构的加工。具体地，例如使用表面具有微纳结构的金属模具，在聚丙烯表面压出微纳结构。或者，使用电弧等方式在聚丙烯表面制备出微纳结构等。
作为接枝基础物的具有微纳结构的聚丙烯表面可以是独立的制品或存在于基底上。所述基底可以主要由聚丙烯构成。所述基底例如为膜、薄片、板材或模塑制品。
在一种实施方案中，作为接枝基础物的具有微纳结构的聚丙烯表面可以是聚丙烯多孔膜、聚丙烯平板膜或者聚丙烯中空纤维微孔膜。
所述聚丙烯多孔膜可以具有小于100μm，优选为10nm-80μm的平均孔径，并且所述聚丙烯多孔膜的孔隙率可以为50-90％，优选为60-80％。所述平均孔径通过使用扫描电镜对微孔表面进行观测，统计孔径数据，并做孔径分布图来测定。所述孔隙率使用压汞法(MIP)测定。
本文中所用的术语“聚丙烯”包括丙烯的均聚物和共聚物及其混合物。
根据本发明接枝的亲水性侧基可包含由亲水性单体形成的单元，例如包含由一种或多种含有选自氧、硫、氮、硅和卤素及其组合的杂原子或其取代基并且含有碳碳双键的单体形成的单元。
所述亲水性侧基优选为含有选自氧、硫、氮、硅和卤素及其组合的杂原子或其取代基并且含有碳碳双键的单体侧基。所述亲水性侧基的单体优选为有机酸、有机酸的衍生物、乙烯基硅烷中的至少一种。所述有机酸的衍生物可包括有机酸的酸酐、酯、盐中的至少一种。所述的有机酸包括但不限于羧酸、磺酸、亚磺酸、硫羧酸(RCOSH)等。
所述的亲水性侧基的单体进一步优选包括选自以下的有机酸和有机酸的衍生物：马来酸酐、马来酸酐衍生物、(甲基)丙烯酸、(甲基)丙烯酸衍生物(例如甲基丙烯酸缩水甘油酯)、乙酸乙烯酯、烯基磺酸及其衍生物(例如2-丙烯酰胺-2-甲基丙磺酸、丙烯磺酸、乙烯基苯磺酸、乙烯基磺酸等)、乙烯基苯甲酸、衣康酸、油酸、花生烯酸及其组合以及它们的成盐形式；最优选马来酸酐、马来酸酐衍生物、(甲基)丙烯酸、(甲基)丙烯酸衍生物及其组合以及它们的成盐形式；最最优选马来酸酐及其成盐形式。
所述乙烯基硅烷可以为式(1)所示的化合物中的一种或多种：
CH 2＝CH-(CH 2) nSiX 3                 式(1)
其中n＝0至3，每个X相同或不同地独立地表示氯基、甲氧基、乙氧基、乙酰氧基。
所述乙烯基硅烷优选为乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷中的至少一种。
优选地，所述亲水性侧基包含由有机酸的盐形成的单元或由这样的单元组成。
在一种优选的实施方案中，所述聚丙烯表面可同时接枝有亲油性侧基来进一步改进所述表面的亲油性。优选地，改性后，超浸润表面的油接触角可达到小于90°，优选小于或等于10°，更优选小于或等于5°，再更优选小于或等于1°，最优选达到约0°，优选在约0.5s内达到上述角度。
所述亲油性侧基可包含由亲油性单体形成的单元。所述亲油性单体优选包括乙烯基硅油、苯乙烯中的至少一种。所述亲油性侧基优选选自乙烯基硅油侧基和苯乙烯侧基及其组合。
所述乙烯基硅油通常是指带有乙烯基基团并且在室温下为液体的聚硅氧烷，主要是指中间链段或者两端带有乙烯基的线形聚二甲基硅氧烷。所述乙烯基硅油可作为大分子单体使用。
所述乙烯基硅油可选自端乙烯基硅油和高乙烯基硅油及其组合，优选可为甲基乙烯基硅油、乙烯基含氢硅油、二乙烯基硅油中的至少一种。
根据本发明的超浸润表面的水接触角比未改性处理前的聚丙烯表面的水接触角明显更小。根据本发明在将具有微纳结构的聚丙烯表面接枝亲水性侧基后，所得的超浸润表面可达到超亲水的效果。同时，该聚丙烯表面可以进一步接枝亲油性单体进行亲油改性， 进一步提高超亲水表面的亲油性，该亲油性相比未改性的聚丙烯表面以及仅亲水改性的聚丙烯表面都有所提高。
在所述聚丙烯多孔膜、聚丙烯平板膜或者聚丙烯中空纤维微孔膜的情况下，在根据本发明接枝亲水性侧基后，所述膜可达到超亲水的效果，同时水通量也大幅提高。经亲水改性的膜可进一步接枝乙烯基硅油等亲油性单体，由此所述膜的亲油性也进一步提高，其油通量相比未改性的膜以及仅亲水改性的膜都有所提高。
在根据本发明的第二方面中，本发明提供根据本发明的超浸润表面的制备方法，包括将用于形成侧基的单体在不存在引发剂的情况下，任选地在加入无机微波吸收介质的情况下，通过微波辐照与作为接枝基础物的具有微纳结构的聚丙烯表面进行接枝反应。在该接枝反应过程中可以不使用辅助接枝单体。
本文中使用的术语“微波”是指频率为300MHz-300GHz的电磁波。
在根据本发明的方法中，可将包括所述亲水性侧基的单体在内的组分、或者将包括所述亲水性侧基的单体和所述亲油性侧基的单体在内的组分，与聚丙烯表面在不加接枝引发剂的情况下使用微波辐照进行接枝反应而得到所述超浸润表面。
当组分不包括亲油性侧基的单体时，任选并且优选加入无机微波吸收介质；当组分包括亲油性侧基的单体时，加入无机微波吸收介质。
当所述亲水性侧基的单体为有机酸或其酸酐或其酯中的至少一种时，所述方法可进一步包括将接枝反应后所得产物与碱反应的步骤(即所谓的盐化步骤)。
本发明的制备方法中，微波辐照接枝反应可以只包括亲水性侧基的微波辐照接枝反应；或者既包括亲油性侧基的微波辐照接枝反应又包括亲水性侧基的微波辐照接枝反应，两种侧基的微波辐照接枝反应可以同时发生，也可先后发生，顺序不限。
所述的盐化步骤为任选的步骤。当在聚丙烯表面接枝上有机酸或其酸酐或其酯中的至少一种侧基时，可进行这样的盐化步骤，但是不限于其是否在亲油性侧基的微波辐照接枝反应的前后或其过程中进行，即可以在对亲水性侧基的单体为有机酸或其酸酐或其酯中的至少一种时的接枝聚丙烯表面进行亲油性侧基微波辐照接枝的同时加入碱对上述亲水性侧基进行盐化。
本发明的制备方法具体可包括以下方案中的任一种：
1)包括将所述聚丙烯表面与所述亲水性侧基单体和/或其溶解在溶剂中的溶液接触混合，其中任选加入无机微波吸收介质；之后将所得的混合物在不加接枝引发剂的情况下微波辐照接枝；其中所述混合物任选地还包含亲油性侧基的单体和/或其溶解在溶剂中的溶 液，以及无机微波吸收介质；
2)包括将所述聚丙烯表面与所述亲水性侧基单体和/或其溶解在溶剂中的溶液接触混合，其中任选加入无机微波吸收介质；之后将所得的混合物在不加接枝引发剂的情况下微波辐照接枝；然后将所得接枝产物与所述亲油性侧基单体和/或其溶解在溶剂中的溶液以及无机微波吸收介质混合，在不加接枝引发剂的情况下微波辐照接枝；
3)包括将所述聚丙烯表面与所述亲油性侧基单体和/或其溶解在溶剂中的溶液以及无机微波吸收介质接触混合，之后将所得的混合物在不加接枝引发剂的情况下微波辐照接枝；然后将所得接枝产物与所述亲水性侧基单体和/或其溶解在溶剂中的溶液在任选加入无机微波吸收介质的情况下混合，在不加接枝引发剂的情况下微波辐照接枝；
4)在以上所述三种方案的任一种基础上，当所述亲水性侧基的单体为有机酸或其酸酐或其酯中的至少一种时，还包括将接枝了有机酸或其酸酐或其酯中的至少一种侧基的聚丙烯表面与碱和/或碱的水溶液接触混合的步骤(即所谓的盐化步骤)。
由于在本发明的制备方法中不添加引发剂或接枝引发剂，因此通过该制备方法获得的本发明的超浸润表面中不含有引发剂残留物。所述引发剂是指本领域中用于引发单体的聚合反应(包括接枝反应)的物质，例如自由基型引发剂，包括过氧化物引发剂和偶氮引发剂及氧化还原引发剂等，还有光敏引发剂(或光敏剂)，例如二苯甲酮。过氧化物引发剂又可分为有机过氧化物引发剂(例如过氧化二异丙苯)和无机过氧化物引发剂。所述引发剂尤其是指各种用于聚丙烯接枝功能单体的引发剂，例如过氧化二异丙苯等。现有技术的接枝方法中为了聚丙烯能与单体接枝，通过引发剂使聚丙烯的叔碳脱氢，但引发剂实际上不仅可以脱氢，还造成聚丙烯大量的β断链反应，也就是反应太剧烈，不可控，从而影响接枝聚丙烯的力学性能。本发明的制备方法无需添加引发剂即可在聚丙烯表面上接枝有机酸、有机酸衍生物、乙烯基硅烷、乙烯基硅油、苯乙烯等侧基。因此，本发明所得到的超浸润表面不含引发剂残留物，保证了聚丙烯表面的力学性能不受不利影响。
本发明的制备方法中使用的所述亲水性侧基的单体可以是各种亲水性单体，具体如上文所述。所述亲水性侧基的单体用量可以为基于所述聚丙烯表面用量计的0.1-10重量％；优选为1-8重量％。
本文中，当作为接枝基础物的所述聚丙烯表面是独立的制品时，如果制品的厚度小于或等于1mm，则所述聚丙烯表面的用量按照制品的总重量计算；如果制品的厚度大于1mm，则所述聚丙烯表面的用量按照1mm厚度的制品的重量计算。当作为接枝基础物的所述聚丙烯表面存在于基底上时，所述聚丙烯表面的用量按照包含所述聚丙烯表面在内的 基底整体沿着从所述聚丙烯表面向基底内部的方向，从接触空气的表面到厚度1mm处的重量计算；如果包含所述聚丙烯表面在内的基底整体厚度小于或等于1mm，则按照包含所述聚丙烯表面在内的基底整体的总重量计算。
所述亲水性侧基的单体既可以与聚丙烯表面或接枝亲油单体的聚丙烯表面直接接触混合，也可以为了混合效果更好采用亲水性侧基的单体在一种或多种溶剂中的溶液进行混合。所述溶剂的用量只要能够溶解所述单体形成溶液即可，优选亲水性侧基的单体溶液中所述单体与其溶剂的重量比为(0.1-100):100，优选(0.5-50):100，更优选(1-30):100。所述单体溶液的用量优选可以完全覆盖聚丙烯表面，更便于两者的充分接触混合。
用于溶解亲水性侧基单体的溶剂可选自水、有机溶剂中的至少一种；优选包括醇、酮、酯、水中至少一种，更优选丙酮或乙醇。
本发明的制备方法中使用的所述亲油性侧基的单体可以是各种亲油性单体，具体如上文所述。所述亲油性侧基的单体用量可以为基于所述聚丙烯表面用量计的0.1-30重量％；优选为1-20重量％。
所述亲油性侧基的单体既可以与聚丙烯表面或接枝亲水单体的聚丙烯表面直接接触混合，也可以为了混合效果更好采用亲油性侧基的单体在一种或多种溶剂中的溶液进行混合。溶剂的用量只要能够溶解所述单体形成溶液即可，优选所述亲油性侧基单体与溶剂的重量比可以在(0.1-100):100，优选(0.5-50):100，更优选(1-30):100。所述单体溶液的用量优选可以完全覆盖所述聚丙烯表面，更便于两者的充分接触混合。
用于溶解亲油性侧基单体的溶剂可选自水、有机溶剂中的至少一种；优选包括醇、酮、酯、水中至少一种，更优选丙酮或乙醇。
本发明的制备方法中，当聚丙烯表面只接枝亲水性侧基时，其单体与聚丙烯表面的混合物中可以不加入无机微波吸收介质，但是优选加入无机微波吸收介质以提高接枝效率。当聚丙烯表面需要接枝亲油性侧基时，由于所述亲油性侧基的单体普遍在微波下升温不超过200℃，不能很好地进行接枝反应。因此需要加入无机微波吸收介质以促进微波下的接枝反应。
所述无机微波吸收介质可采用各种可以吸收微波的无机物，优选包括金属氢氧化物、金属盐、金属氧化物、石墨类材料、铁电类材料、黄铜矿、电解石中的至少一种。
所述金属氢氧化物可以为氢氧化钾、氢氧化钡、氢氧化钠、氢氧化锂、氢氧化锶、氢氧化钙、氢氧化铁、氢氧化亚铁、氢氧化锌、氢氧化镁、氢氧化钴、氢氧化金、氢氧化铝、氢氧化铜、氢氧化铍、稀土氢氧化物中的至少一种；所述金属盐可选自硝酸铵、 硝酸钾、硝酸钠、硝酸钡、硝酸钙、硝酸镁、硝酸铝、硝酸锰、硝酸锌、硝酸铁、硝酸亚铁、硝酸铜、硝酸银、氯化铵、氯化钾、氯化钠、氯化钡、氯化钙、氯化镁、氯化铝、氯化锰、氯化锌、氯化铁、氯化亚铁、氯化铜、硫酸铵、硫酸钾、硫酸钠、硫酸钙、硫酸镁、硫酸铝、硫酸锰、硫酸锌、硫酸铁、硫酸亚铁、硫酸铜、硫酸银、碳酸铵、碳酸钾、碳酸钠、碳酸镁、碳酸钙、碳酸钡、磷酸二氢钾、钛酸钡、钛酸锶、钛酸铜钙中的至少一种；所述金属氧化物可选自三氧化二铁、四氧化三铁中的至少一种；所述石墨类材料可选自炭黑、石墨粉、石墨烯、氧化石墨烯的还原产物(还原剂例如为抗坏血酸)、碳纳米管、活性炭中的至少一种。
所述无机微波吸收介质的单次用量可以为聚丙烯表面用量的0.1-10重量％；优选为1-8重量％。所述无机微波吸收介质的单次用量是指，本发明的制备方法中可包括一次或若干次微波辐照，如果其中加入无机微波吸收介质，则所述用量是在单次微波辐照时的加入量。
所述无机微波吸收介质既可以直接加入与聚丙烯表面或接枝聚丙烯表面接触混合，也可以为了混合效果更好，采用加入溶解或分散于一种或多种溶剂中得到的无机微波吸收介质溶液或分散体进行接触混合。为了使得无机微波吸收介质更好地分散混合在(接枝)聚丙烯表面上，优选无机微波吸收介质与(接枝)聚丙烯表面的混合和与其他组分比如单体的混合分步进行，即(接枝)聚丙烯表面可以单独与单体组分混合、烘干，然后烘干后的混合物再与无机微波吸收介质或其溶液或其分散体中至少之一混合。
所述溶解或分散微波吸收介质的溶剂用量只要能够溶解无机微波吸收介质形成无机微波吸收介质溶液、或是能够使得无机微波吸收介质充分均匀分散形成分散体即可。所述无机微波吸收介质溶液或分散体中无机微波吸收介质与溶剂的重量比优选可以在(0.1-100):100，更优选(0.5-50):100，最优选(1-30):100范围内。
所述无机微波吸收介质溶液或分散体的用量优选使得可以完全覆盖包括(接枝)聚丙烯表面在内的原料混合物，从而便于原料的充分接触混合和反应。
所述无机微波吸收介质溶液或分散体中的溶剂选自水、有机溶剂中的至少一种；优选包括醇、酮、酯、水中至少一种，更优选醇、水。
为了保障无机微波吸收介质能够与溶剂形成充分分散稳定的分散体，可以在所述无机微波吸收介质分散体中加入现有技术中常用的表面活性剂。一般可以选用聚氧乙烯型、多元醇型等表面活性剂，用量通常可以为无机微波吸收介质的0.1-100重量％。
所述盐化步骤中使用的碱可选自可以使得聚丙烯表面接枝的有机酸侧基、其酸酐侧 基、其酯侧基的任一种盐化的碱；优选为氢氧化物。
所述氢氧化物优选为金属氢氧化物和氨水中的至少一种；其中金属氢氧化物优选为氢氧化钠、氢氧化钾、氢氧化钡、氢氧化锂、氢氧化锶、氢氧化钙、氢氧化铁、氢氧化亚铁、氢氧化锌、氢氧化镁、氢氧化钴、氢氧化金、氢氧化铝、氢氧化铜、氢氧化铍、稀土氢氧化物中的一种或几种，优选氢氧化钠、氢氧化钾、氢氧化钡、氢氧化锂、氢氧化锶、氢氧化钙中的一种或几种。
所述碱(例如氢氧化物)的用量可以为基于所述聚丙烯表面用量计的0.1-10重量％；优选为1-8重量％。
为了使所述的碱与接枝聚丙烯表面接触混合，可以选择直接加入碱进行接触混合，也可以为了便于混合充分，优选以碱的水溶液形式进行充分混合。用于溶解碱的水的用量也是只要能够溶解碱形成水溶液的即可。碱的水溶液中碱与水的重量比可以优选在(0.1-100):100，更优选(0.5-50):100，最优选(1-30):100。所述碱的水溶液的量优选可以完全覆盖接枝聚丙烯表面，以便于两者的充分接触混合和反应。
可将所述碱和/或碱的水溶液与接枝聚丙烯表面充分混合并同时反应，其为通常的酸碱反应，其反应时间无特殊要求，直至充分反应即可。一般是在碱和/或水溶液添加完毕后进一步接触混合并同时反应一段时间即可，比如可以在30分钟以内，优选5-10分钟。对反应温度及压力都无限制，一般可为常温常压。
本发明的制备方法中的微波辐照过程可在各种微波反应器中进行。可以采用任何合适的辐照功率进行所述微波辐照过程，并持续任何合适的时间，只要可在聚丙烯表面上实现合适的接枝改性效果并由此实现根据本发明的超浸润性质。例如，辐照功率可以为100w-2000w，优选为500-1000w，更优选600w-800w；辐射时间可以为1s-120min，优选1min-30min，再优选3min-10min。
所述的微波辐照可优选在惰性气氛下进行。所述惰性气氛可以采用惰性的气体，优选包括氮气、氦气、氩气中的一种或几种，更优选氮气。
本发明制备方法中，上文所述的混合优选在真空条件下进行。所述混合包括亲水性侧基的单体和/或其溶液与(接枝)聚丙烯表面的接触混合、亲油性侧基单体和/或其溶液与(接枝)聚丙烯表面的接触混合、接枝聚丙烯表面与碱和/或碱水溶液的接触混合等。
对于本身带有微孔等微纳结构的聚丙烯表面来说，真空有利于接枝的单体和/或碱等其他组分与其接触混合的更充分，促进接枝单体和/或碱等其他组分进入到聚丙烯表面的微纳结构中，更有利于反应进行。
本发明制备方法中，所述的接触混合可采用各种混合方法和设备进行，混合条件也为常用条件，只要能够实现各物料充分均匀混合即可；比如可以将包含除了聚丙烯表面以外的包括所述单体在内的其他组分的原料或其溶液、分散体等涂覆、滴加、浸润、覆盖在所述聚丙烯表面实现接触混合。
优选地，将包括所述单体与(接枝)聚丙烯表面在内的组分的混合物在微波辐照前进行干燥处理。
优选地，所述微波辐照接枝后的产物可使用溶剂清洗，以去除未反应的单体或者以及不参加反应的无机微波吸收介质，并优选在清洗后进一步干燥处理。
所述的对微波辐照后的产物的清洗没有特殊限制，只要能够将残余的单体或者无机微波吸收介质去除即可。可采用通常的清洗方法。比如在微波后在高温的情况下立即使用体积超过聚丙烯表面的溶剂浸泡一定时间(比如5-15分钟)，然后使用过滤装置去除多余水分；重复多次(比如2-6次)浸泡、过滤即得到清洗干净的超浸润表面。
所述盐化步骤的产物(即接枝反应产物与碱反应后的产物)优选可使用溶剂清洗，以去除未与接枝聚丙烯表面反应的碱，并优选在清洗后进一步干燥处理。
所述对盐化后产物的清洗没有特殊限制，只要能够将残余的碱去除即可，可采用通常的清洗方法。比如在盐化反应后立即使用体积超过接枝聚丙烯表面的溶剂浸泡一定时间(比如5-15分钟)，然后使用过滤装置去除多余水分；重复多次(比如2-6次)浸泡、过滤即得到清洗干净的双亲性聚丙烯表面。
所述的清洗用溶剂可选自水、有机溶剂中的至少一种；优选包括醇、酮、酯、水中至少一种，更优选醇、水。
所涉及的干燥处理可采用各种常规干燥方法，包括但不限于如鼓风干燥、常温干燥等。优选的干燥温度以不使聚丙烯发生熔融的温度为宜，例如不超过160℃。
在本发明的第三方面，本发明提供一种制品，其由根据本发明的超浸润表面构成，或者包含根据本发明的超浸润表面。所述制品可以是膜、薄片、板材或者模塑制品，例如聚丙烯多孔膜、聚丙烯平板膜或聚丙烯中空纤维微孔膜，待粘接的塑料制品、待喷涂的食品袋外包装、待喷涂的汽车保险杠等。所述制品可以主要由聚丙烯构成。
在本发明的第四方面，本发明提供根据本发明的超浸润表面或包含该超浸润表面的制品在粘接(例如塑料制品粘接等)、喷涂(例如食品袋外包装的喷涂、汽车保险杠的喷涂等)领域，或油水分离、水处理、生物、医药、能源领域中的应用。相应地，本发明也提供应用根据本发明的超浸润表面或制品的粘接、喷涂、油水分离或水处理方法，例如用于 制备粘接塑料制品、喷涂食品袋外包装、喷涂汽车保险杠。
例如，根据本发明获得的双亲聚丙烯多孔膜尤其可用于油水分离、水处理，生物、医药、能源等领域。
本发明的超浸润表面能达到超亲水，甚至可以达到超双亲。本发明采用将有机酸及有机酸衍生物等亲水性的单体与聚丙烯表面使用微波辐照在不添加引发剂的情况下进行接枝反应甚至包括进一步的盐化获得了超亲水的聚丙烯表面，又因聚丙烯本身亲油，所以此时已形成了亲油并且超亲水的表面；任选地再进一步与乙烯基硅油等亲油性单体使用微波辐照在不添加引发剂的情况下进行接枝反应，进一步提高了超浸润表面的亲油性，甚至可获得超双亲的超浸润表面。聚丙烯在微波环境下是微波透明的(微波辐照下很少或者不吸收微波，因此在微波辐照下不发热)。所述作为接枝单体的有机酸及有机酸衍生物等单体在微波的条件下会吸收微波而升温达200℃及以上，并产生自由基；同时高温也会引发附近聚丙烯分子链产生自由基，因此会与聚丙烯充分发生接枝反应，进而获得接枝聚丙烯表面。而同时这样的不添加引发剂的微波接枝反应可以大幅避免添加引发剂接枝时的聚丙烯的β断链反应，从而不降低聚丙烯的分子量。
当将接枝有有机酸或其酸酐或其酯之一侧基的聚丙烯再与氢氧化物等的碱反应时，接枝聚丙烯表面变成有机酸盐接枝聚丙烯表面，这进一步提高了聚丙烯表面的亲水性。对于聚丙烯多孔膜、聚丙烯平板膜、聚丙烯中空纤维微孔膜等，这还大幅提高了水通量。
在对超亲水聚丙烯表面进一步亲油改性的情况下，由于乙烯基硅油等亲油性单体极性较低，其在微波辐照下吸收微波升温不能够达到很高温度(微波场中的温度升高至小于200℃)，从而不能有效地引发附近聚丙烯分子链产生自由基，因此需要添加无机微波吸收介质来帮助聚丙烯产生自由基进而与乙烯基硅油单体发生接枝反应。无机微波吸收介质不与聚丙烯表面及单体反应，因此仅作为接枝反应热源，不影响聚丙烯表面性能。无机微波吸收介质的添加，对于不吸收微波的单体，可以帮助其接枝在聚丙烯上；对于本身吸收微波的单体，可以帮助提高其接枝效率。本发明利用微波的选择性加热，加热无机微波吸收介质，其微波下升温可达到的温度在200℃以上，可达到聚丙烯熔点附近，这个温度下聚丙烯不至于断链，但是聚丙烯叔碳可以脱氢，因此会发生接枝反应但不会造成断链反应。接枝乙烯基硅油等亲油性单体后，超亲水聚丙烯表面的亲油性进一步提高。
同时，由于本发明中使用的聚丙烯表面具有微纳结构，该结构中存在的毛细作用进一步提高了表面的亲水和亲油的效果。
本发明的制备方法工艺简单，易操作。这样的改性方法适用于各种聚丙烯表面；设备简单，成本低，易于工业化。所得超浸润表面的超浸润性质持久稳定，且无残留接枝单体、无残留碱、无引发剂残留等。制备过程中接枝后的聚丙烯分子量不下降。对于聚丙烯多孔膜、聚丙烯平板膜、聚丙烯中空纤维微孔膜等，接枝改性后的膜的水通量或水通量和油通量两者都大幅提高。
具体实施方式
下面结合实施例，进一步举例说明本发明。但是，本发明的范围不受这些实施例的限制，而是本发明的范围在所附的权利要求书中提出。
1.测量方法
1)接触角测试方法：
采用德国KRUSS公司EASY DROP接触角测试仪，测量范围1-180°，分辨率±0.1°，采用动态接触角测量模式，每次固定体积为2μL的去离子水滴或者油滴(白油油滴或花生油油滴)，滴于待测表面上，取计算的初始(在0.5s内)接触角为该表面的接触角测量值，平行测量6次，计算平均值。当测量值低于仪器的测量下限(1°)时，数据记录为0。
所述白油购自天马(克拉玛依)石油公司；所述花生油购自山东鲁花集团有限公司。
2)表面的接枝侧基含量测定方法：使用日本日立公司S4800扫描电镜的能谱配件对待测表面的接枝成分主要元素的含量进行测量；并通过接枝物分子式反推接枝物在该表面的含量作为表面接枝率。由于该含量是表面含量(通常是指从物体表面起1-2mm的厚度中的含量)，故该含量比单体在原料中的含量偏高。
3)水、油通量测试方法：取5片待测表面，例如聚丙烯多孔膜，使用冷冻切片刀去除皮层，制作成膜组件。在常压下采用去离子水、三氯甲烷及花生油过滤30min，得到的值为所述表面或膜的水、油通量。
4)平均孔径和微孔平均尺寸的测定方法：使用扫描电镜(日本Hitachi S-4800型场发射扫描电子显微镜，放大倍率：5000)对孔或微孔表面进行观测，统计孔径数据，并做孔径分布图确定平均孔径和微孔平均尺寸。
孔隙率使用压汞法(MIP)测定，其中使用压汞仪(Poremaster-33，Quantachrome，美国)。
2.实施例及对比例中所用原料和设备
1)具有微纳结构的聚丙烯表面样品
表面样品1：聚丙烯平板膜，天津膜天膜工程技术有限公司(平均孔径0.8μm，孔隙率80％)，在膜的一面使用环氧树脂胶水(3M公司DP100NS)封涂，另一面在液氮氛围中，使用Leica CM3600冷冻切片机去除膜的皮层即得到聚丙烯微孔表面样品1，其表面的微孔平均尺寸为0.8μm。
表面样品2：使用聚丙烯树脂(T30S齐鲁石化，MI＝3g/10min)注射出5cm×5cm厚度1mm的薄片，使用微小型超精密微细铣削机床，制备出具有微米结构的表面，具体为沿薄片表面横向纵向分别铣削，得到平均上表面尺寸为0.5μm的表面微纳结构。
表面样品3：使用聚丙烯树脂(T30S齐鲁石化，MI＝3g/10min)注射出5cm×5cm厚度1mm的薄片，使用纳米压印机，制备出具有纳米结构的表面，具体为压印出平均尺寸为80nm小坑及凸起的表面微纳结构。
表面样品4：聚丙烯多孔膜(天津膜天膜工程技术有限公司，规格1：平均孔径0.8μm，孔隙率80％)。
表面样品5：聚丙烯多孔膜(天津膜天膜工程技术有限公司，规格2：平均孔径0.22μm，孔隙率45％)。
2)马来酸酐(西陇科学股份有限公司)，丙烯酸(国药集团化学试剂有限公司)、甲基丙烯酸(国药集团化学试剂有限公司)、2-丙烯酰胺-2-甲基丙磺酸(国药集团化学试剂有限公司)、氢氧化钠(西陇科学股份有限公司)、氢氧化钾(西陇科学股份有限公司)、氢氧化钙(西陇科学股份有限公司)、丙酮(西陇科学股份有限公司)、氯化钠(国药集团化学试剂有限公司)、乙烯基硅油(甲基乙烯基硅油，山东大易化工有限公司，牌号：DY-V401，直链型，分子式：(CH 2＝CH)Si(CH 3) 2O[(CH 3) 2SiO] n(CH 3) 2Si(CH＝CH 2))、乙烯基含氢硅油(山东大易化工有限公司，牌号：DY-H202，分子式：(CH 3) 3SiO[(CH 3)(H)SiO] nSi(CH 3) 3)、二乙烯基硅油(山东大易化工有限公司，牌号：DY-V421，直链型，分子式：(CH 2＝CH)(CH 3) 2SiO[(CH 3) 2SiO] m[(CH 2＝CH)(CH 3)SiO] nSi(CH 3) 2(CH 2＝CH))、氯化钠(国药集团化学试剂有限公司)、氧化石墨烯(GO)水溶液(南京吉仓纳米科技有限公司，浓度为1wt％)、抗坏血酸(百灵威公司)、乙烯基三甲氧基硅烷(东京化成工业株式会社)、苯乙烯(国药集团化学试剂有限公司)。
其他各种原料来自市售。
3)微波设备：SINEO(新仪)多功能微波合成萃取仪，型号：UWave-2000。
实施例1
按聚丙烯表面样品(表面样品1)100质量份计，将马来酸酐(5质量份)溶解在丙酮(50质量份)中得到马来酸酐丙酮溶液；将氢氧化钠(5质量份)溶解在去离子水(50质量份)中得到氢氧化钠水溶液；将马来酸酐丙酮溶液在真空条件下加入到所述聚丙烯表面样品上充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)。将烘干后干燥的马来酸酐与聚丙烯表面样品的混合物在氮气的氛围下微波辐照(功率700W)5min；微波辐照完毕的产物在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的马来酸酐单体，然后将其置于80℃鼓风干燥箱烘干得到干燥的马来酸酐接枝聚丙烯表面样品；将氢氧化钠水溶液在真空条件下与烘干的马来酸酐接枝聚丙烯表面样品充分接触混合，氢氧化钠水溶液加入完后再混合并反应5分钟。反应完毕后使用去离子水按同上清洗步骤清洗反应产物然后将其置于80℃鼓风干燥箱烘干，得到接枝马来酸钠的聚丙烯表面样品。
按所述聚丙烯表面样品100质量份计，将乙烯基硅油(5质量份)溶解在乙醇(50质量份)中得到乙烯基硅油乙醇溶液；将氯化钠(5质量份)溶解在去离子水(50质量份)中得到氯化钠水溶液；将乙烯基硅油乙醇溶液在真空条件下加入到上述所得的接枝马来酸钠聚丙烯表面样品上充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将烘干后干燥的乙烯基硅油和接枝马来酸钠聚丙烯表面样品的混合物与氯化钠水溶液充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将干燥的混合物在氮气的氛围下微波辐照(功率700W)5min；微波辐照完毕的物料在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的乙烯基硅油单体以及氯化钠，然后将所得聚丙烯表面样品置于80℃鼓风干燥箱烘干，得到接枝马来酸钠和乙烯基硅油侧基的聚丙烯超浸润表面样品。所得超浸润表面的水、油接触角、表面接枝率数据见表1。
实施例2
按聚丙烯表面样品(同实施例1)100质量份计，将马来酸酐(5质量份)溶解在丙酮(50质量份)中得到马来酸酐丙酮溶液；将氢氧化钠(5质量份)溶解在去离子水(50质量份)中得到氢氧化钠水溶液；将马来酸酐丙酮溶液在真空的条件下加入到所述聚丙烯表面样品上充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)。将烘干后干燥的马来酸酐与聚丙烯表面样品的混合物在氮气的氛围下微波辐照(功率700W)5min； 微波辐照完毕的产物在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的马来酸酐单体，然后其置于80℃鼓风干燥箱烘干得到干燥的马来酸酐接枝聚丙烯表面样品；将氢氧化钠水溶液在真空条件下加入至烘干的马来酸酐接枝聚丙烯表面样品充分接触混合，氢氧化钠水溶液加入完后再混合并反应5分钟。反应完毕后使用去离子水按同上清洗步骤清洗反应产物然后将其置于80℃鼓风干燥箱烘干，得到接枝马来酸钠侧基的聚丙烯超浸润表面样品。所得超浸润表面的水、油接触角、表面接枝率数据见表1。
实施例3
按所述聚丙烯表面样品(同实施例1)100质量份计，将乙烯基硅油(9质量份)溶解在乙醇(50质量份)中得到乙烯基硅油乙醇溶液；将氯化钠(4质量份)溶解在去离子水(50质量份)中得到氯化钠水溶液；将乙烯基硅油乙醇溶液在真空条件下加入到所述聚丙烯表面样品上充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将烘干后干燥的乙烯基硅油与聚丙烯表面样品的混合物与氯化钠水溶液充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将干燥的混合物在氮气的氛围下微波辐照(功率1000W)3min；微波辐照完毕的物料在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的乙烯基硅油单体以及氯化钠，然后将其置于80℃鼓风干燥箱烘干；得到接枝乙烯基硅油侧基的聚丙烯表面样品。
按所述聚丙烯表面样品100质量份计，将丙烯酸(9质量份)溶解在丙酮(50质量份)中得到丙烯酸丙酮溶液；将氢氧化钾(6质量份)溶解在去离子水(50质量份)中得到氢氧化钾水溶液；将丙烯酸丙酮溶液在真空条件下加入到接枝聚丙烯表面样品上充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)。将烘干后干燥的丙烯酸与接枝聚丙烯表面样品的混合物在氮气的氛围下微波辐照(功率1000W)3min；微波辐照完毕的产物在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的丙烯酸单体，然后将其置于80℃鼓风干燥箱烘干得到干燥的接枝有丙烯酸和乙烯基硅油接枝聚丙烯表面样品；将氢氧化钾水溶液在真空条件下加入至烘干的接枝有丙烯酸和乙烯基硅油的聚丙烯表面样品充分接触混合，氢氧化钾水溶液加入完后再混合并反应5分钟。反应完毕后使用去离子水按同上清洗步骤清洗反应产物然后将其置于80℃鼓风干燥箱烘干，得到接枝有丙烯酸钾和乙烯基硅油侧基的聚丙烯超浸润表面样品。所得超浸润表面的水、油接触角、表面接枝率数据见表1。
实施例4
按聚丙烯表面样品(同实施例1)100质量份计，将丙烯酸(9质量份)溶解在丙酮 (50质量份)中得到丙烯酸丙酮溶液；将氢氧化钾(6质量份)溶解在去离子水(50质量份)中得到氢氧化钾水溶液；将丙烯酸丙酮溶液在真空条件下加入到所述聚丙烯表面样品上充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)。将烘干后干燥的丙烯酸与聚丙烯表面样品的混合物在氮气的氛围下微波辐照(功率1000W)3min；微波辐照完毕的产物在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的丙烯酸单体，然后将其置于80℃鼓风干燥箱烘干得到干燥的丙烯酸接枝聚丙烯表面样品；将氢氧化钾水溶液在真空条件下加入至烘干的丙烯酸接枝的聚丙烯表面样品充分接触混合，氢氧化钾水溶液加入完后再混合并反应5分钟。反应完毕后使用去离子水按同上清洗步骤清洗反应产物然后将其置于80℃鼓风干燥箱烘干，得到接枝丙烯酸钾侧基的聚丙烯超浸润表面样品。所得超浸润表面的水、油接触角、表面接枝率数据见表1。
对比例1
将聚丙烯表面样品(同实施例1)直接进行测试，聚丙烯表面的水、油接触角数据见表1。
实施例5
按聚丙烯表面样品(表面样品2)100质量份计，将2-丙烯酰胺-2-甲基丙磺酸(10质量份)溶解在丙酮(50质量份)中得到2-丙烯酰胺-2-甲基丙磺酸丙酮溶液；将氢氧化钾(6质量份)溶解在去离子水(50质量份)中得到氢氧化钾水溶液；将2-丙烯酰胺-2-甲基丙磺酸丙酮溶液在真空条件下加入到所述聚丙烯表面样品上充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)。将烘干后干燥的2-丙烯酰胺-2-甲基丙磺酸与聚丙烯表面样品的混合物在氮气的氛围下微波辐照(功率1000W)3min；微波辐照完毕的产物在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的2-丙烯酰胺-2-甲基丙磺酸单体，然后将其置于80℃鼓风干燥箱烘干得到干燥的2-丙烯酰胺-2-甲基丙磺酸接枝聚丙烯表面样品；将氢氧化钾水溶液在真空条件下与烘干的2-丙烯酰胺-2-甲基丙磺酸接枝的聚丙烯表面样品充分接触混合，氢氧化钾水溶液加入完后再混合并反应5分钟。反应完毕后使用去离子水按同上清洗步骤清洗反应产物然后将其置于80℃鼓风干燥箱烘干，得到接枝有2-丙烯酰胺-2-甲基丙磺酸钾的聚丙烯表面样品。
按所述聚丙烯表面样品100质量份计，将乙烯基含氢硅油(9质量份)溶解在乙醇(50质量份)中得到乙烯基含氢硅油乙醇溶液；将氯化钠(4质量份)溶解在去离子水(50质量份)中得到氯化钠水溶液；将乙烯基含氢硅油乙醇溶液在真空条件下加入到上述接枝2-丙烯酰胺-2-甲基丙磺酸钾的聚丙烯表面样品上充分接触混合，之后将混合物烘干(80℃ 鼓风干燥烘箱烘干)；将烘干后干燥的乙烯基含氢硅油与接枝聚丙烯表面样品的混合物与氯化钠水溶液充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将干燥的混合物在氮气的氛围下微波辐照(功率1000W)3min；微波辐照完毕的物料在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的乙烯基含氢硅油单体以及氯化钠，然后将其置于80℃鼓风干燥箱烘干；得到接枝有2-丙烯酰胺-2-甲基丙磺酸钾和乙烯基含氢硅油侧基的超浸润表面样品。所得超浸润表面的水、油接触角、表面接枝率数据见表1。
实施例6
按聚丙烯表面样品(同实施例5)100质量份计，将2-丙烯酰胺-2-甲基丙磺酸(10质量份)溶解在丙酮(50质量份)中得到2-丙烯酰胺-2-甲基丙磺酸丙酮溶液；将氢氧化钾(6质量份)溶解在去离子水(50质量份)中得到氢氧化钾水溶液；将2-丙烯酰胺-2-甲基丙磺酸丙酮溶液在真空条件下加入到聚丙烯表面样品上充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)。将烘干后干燥的2-丙烯酰胺-2-甲基丙磺酸与聚丙烯表面样品的混合物在氮气的氛围下微波辐照(功率1000W)3min；微波辐照完毕的产物在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的2-丙烯酰胺-2-甲基丙磺酸单体，然后其置于80℃鼓风干燥箱烘干得到干燥的2-丙烯酰胺-2-甲基丙磺酸接枝聚丙烯表面样品；将氢氧化钾水溶液在真空条件下加入至烘干的2-丙烯酰胺-2-甲基丙磺酸接枝的聚丙烯表面样品充分接触混合，氢氧化钾水溶液加入完后再混合并反应5分钟。反应完毕后使用去离子水按同上清洗步骤清洗反应产物然后将其置于80℃鼓风干燥箱烘干，得到接枝有2-丙烯酰胺-2-甲基丙磺酸钾侧基的超浸润表面样品。所得超浸润表面的水、油接触角、表面接枝率数据见表1。
实施例7
按聚丙烯表面样品(同实施例5)100质量份计，将甲基丙烯酸(10质量份)溶解在丙酮(50质量份)中得到甲基丙烯酸丙酮溶液；将氢氧化钙(8质量份)溶解在去离子水(50质量份)中得到氢氧化钙水溶液；将甲基丙烯酸丙酮溶液在真空条件下加入到所述聚丙烯表面样品上充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)。将烘干后干燥的甲基丙烯酸与聚丙烯表面样品的混合物在氮气的氛围下微波辐照(功率2000W)1min；微波辐照完毕的产物在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的甲基丙烯酸单体，然后将其置于80℃鼓风干燥箱烘干得到干燥的甲基丙烯酸接枝聚丙烯表面样品；将氢氧化钙水溶液在真空条件下加入至烘干的甲 基丙烯酸接枝的聚丙烯表面样品充分接触混合，氢氧化钙水溶液加入完后再混合并反应5分钟。反应完毕后使用去离子水按同上清洗步骤清洗反应产物然后将其置于80℃鼓风干燥箱烘干，得到接枝甲基丙烯酸钙的聚丙烯表面样品。
按所述聚丙烯表面样品100质量份计，将二乙烯基硅油(8质量份)溶解在乙醇(50质量份)中得到二乙烯基硅油乙醇溶液；将氯化钠(6质量份)溶解在去离子水(50质量份)中得到氯化钠水溶液；将二乙烯基硅油乙醇溶液在真空条件下加入到上述接枝甲基丙烯酸钾的聚丙烯表面样品上充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将烘干后干燥的二乙烯基硅油与接枝聚丙烯表面样品的混合物与氯化钠水溶液充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将干燥的混合物在氮气的氛围下微波辐照(功率2000W)1min；微波辐照完毕的物料在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的二乙烯基硅油单体以及氯化钠，然后将其置于80℃鼓风干燥箱烘干；得到接枝甲基丙烯酸钙和二乙烯基硅油侧基的聚丙烯超浸润表面样品。所得超浸润表面的水、油接触角、表面接枝率数据见表1。
实施例8
按聚丙烯表面样品(同实施例5)100质量份计，将甲基丙烯酸(10质量份)溶解在丙酮(50质量份)中得到甲基丙烯酸丙酮溶液；将氢氧化钙(8质量份)溶解在去离子水(50质量份)中得到氢氧化钙水溶液；将甲基丙烯酸丙酮溶液在真空条件下加入到所述聚丙烯表面样品上充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)。将烘干后干燥的甲基丙烯酸与聚丙烯表面样品的混合物在氮气的氛围下微波辐照(功率2000W)1min；微波辐照完毕的产物在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的甲基丙烯酸单体，然后将其置于80℃鼓风干燥箱烘干得到干燥的甲基丙烯酸接枝聚丙烯表面样品；将氢氧化钙水溶液在真空条件下加入至烘干的甲基丙烯酸接枝的聚丙烯表面样品充分接触混合，氢氧化钙水溶液加入后再混合并反应5分钟。反应完毕后使用去离子水按同上清洗步骤清洗反应产物然后将其置于80℃鼓风干燥箱烘干，得到接枝甲基丙烯酸钙侧基的聚丙烯超浸润表面样品。所得超浸润表面的水、油接触角、表面接枝率数据见表1。
对比例2
将聚丙烯表面样品(同实施例5)直接进行测试，聚丙烯表面的水、油接触角数据见表1。
实施例9
按聚丙烯表面样品(表面样品3)100质量份计，将甲基丙烯酸(6质量份)溶解在丙酮(50质量份)中得到甲基丙烯酸丙酮溶液；将甲基丙烯酸丙酮溶液在真空条件下加入到所述聚丙烯表面样品上充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)。将烘干后干燥的甲基丙烯酸与聚丙烯表面样品的混合物在氮气的氛围下微波辐照(功率500W)30min；微波辐照完毕的产物在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的甲基丙烯酸单体，然后将其置于80℃鼓风干燥箱烘干得到干燥的甲基丙烯酸接枝聚丙烯表面样品。
按所述聚丙烯表面样品100质量份计，将二乙烯基硅油(10质量份)溶解在乙醇(50质量份)中得到二乙烯基硅油乙醇溶液；将氯化钠(6质量份)溶解在去离子水(50质量份)中得到氯化钠水溶液；将二乙烯基硅油乙醇溶液在真空条件下加入到上述甲基丙烯酸接枝的聚丙烯表面样品上充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将烘干后干燥的二乙烯基硅油和接枝聚丙烯表面样品的混合物与氯化钠水溶液充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将干燥的混合物在氮气的氛围下微波辐照(功率500W)30min；微波辐照完毕的物料在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的二乙烯基硅油单体以及氯化钠，然后将其置于80℃鼓风干燥箱烘干；得到接枝甲基丙烯酸和二乙烯基硅油的聚丙烯超浸润表面样品。所得超浸润表面的水、油接触角、表面接枝率数据见表1。
实施例10
按聚丙烯表面样品(同实施例9)100质量份计，将甲基丙烯酸(1质量份)溶解在丙酮(50质量份)中得到甲基丙烯酸丙酮溶液；将甲基丙烯酸丙酮溶液在真空条件下加入到所述聚丙烯表面样品上充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)。将烘干后干燥的甲基丙烯酸与聚丙烯表面样品的混合物在氮气的氛围下微波辐照(功率500W)30min；微波辐照完毕的产物在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的甲基丙烯酸单体，然后将其置于80℃鼓风干燥箱烘干得到干燥的甲基丙烯酸接枝聚丙烯表面样品。
按所述聚丙烯表面样品100质量份计，将甲基乙烯基硅油(2质量份)溶解在乙醇(50质量份)中得到甲基乙烯基硅油乙醇溶液；将氧化石墨烯(GO)水溶液(10质量份)、抗坏血酸(1质量份)溶解在去离子水(50质量份)中得到氧化石墨烯(GO)分散体；将甲基乙烯基硅油乙醇溶液在真空条件下加入到上述甲基丙烯酸接枝聚丙烯表面样品上充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将烘干后干燥的甲基乙烯 基硅油和接枝聚丙烯表面样品混合物的粉料与氧化石墨烯(GO)分散体充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)，其中氧化石墨烯、抗坏血酸与去离子水混合形成氧化石墨烯分散体，氧化石墨烯分散体在与甲基乙烯基硅油和接枝聚丙烯表面样品的混合物混合后，在80℃烘干干燥时，抗坏血酸作为氧化石墨烯的还原剂将氧化石墨烯还原成石墨烯，石墨烯是后续微波辐照接枝的微波吸收介质；将干燥的混合物在氮气的氛围下微波辐照(功率500W)30min；微波辐照完毕的物料在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的甲基乙烯基硅油单体以及氧化石墨烯，然后将其置于80℃鼓风干燥箱烘干；得到接枝甲基丙烯酸和甲基乙烯基硅油侧基的聚丙烯超浸润表面样品。所得超浸润表面的水、油接触角、表面接枝率数据见表1。
实施例11
按聚丙烯表面样品(同实施例9)100质量份计，将甲基丙烯酸(7质量份)溶解在丙酮(50质量份)中得到甲基丙烯酸丙酮溶液；将甲基丙烯酸丙酮溶液在真空条件下加入到所述聚丙烯表面样品上充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)。将烘干后干燥的甲基丙烯酸与聚丙烯表面样品的混合物在氮气的氛围下微波辐照(功率500W)30min；微波辐照完毕的产物在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的甲基丙烯酸单体，然后将其置于80℃鼓风干燥箱烘干得到干燥的甲基丙烯酸接枝聚丙烯表面样品。
按所述聚丙烯表面样品100质量份计，将甲基乙烯基硅油(8质量份)溶解在乙醇(50质量份)中得到甲基乙烯基硅油乙醇溶液；将氧化石墨烯(GO)水溶液(3质量份)、抗坏血酸(0.3质量份)溶解在去离子水(50质量份)中得到氧化石墨烯(GO)分散体；将甲基乙烯基硅油乙醇溶液在真空条件下加入到上述甲基丙烯酸接枝聚丙烯表面样品上充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将烘干后干燥的甲基乙烯基硅油和接枝聚丙烯表面样品的混合物与氧化石墨烯(GO)分散体充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)，其中氧化石墨烯、抗坏血酸与去离子水混合形成氧化石墨烯分散体，氧化石墨烯分散体在与甲基乙烯基硅油和接枝聚丙烯表面样品的混合物混合后，在80℃烘干干燥时，抗坏血酸作为氧化石墨烯的还原剂将氧化石墨烯还原成石墨烯，石墨烯是后续微波辐照接枝的微波吸收介质；将干燥的混合物在氮气的氛围下微波辐照(功率500W)30min；微波辐照完毕的物料在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的甲基乙烯基硅油单体以及氧化石墨烯，然后将其置于80℃鼓风干燥箱烘干；得到接枝甲基丙烯酸和甲基乙烯基硅油的聚丙烯超浸润表面样 品。所得超浸润表面的水、油接触角数据见表1。
实施例12
按聚丙烯表面样品(同实施例9)100质量份计，将乙烯基三甲氧基硅烷(9质量份)溶解在乙醇(50质量份)中得到乙烯基三甲氧基硅烷乙醇溶液；将氯化钠(3质量份)溶解在去离子水(50质量份)中得到氯化钠水溶液；将乙烯基三甲氧基硅烷乙醇溶液在真空条件下加入到所述聚丙烯表面样品上充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)。将烘干后干燥的乙烯基三甲氧基硅烷和聚丙烯表面样品混合物与氯化钠水溶液充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将烘干后干燥的乙烯基三甲氧基硅烷与聚丙烯表面样品的混合物在氮气的氛围下微波辐照(功率500W)30min；微波辐照完毕的产物在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的乙烯基三甲氧基硅烷单体和氯化钠，然后将其置于80℃鼓风干燥箱烘干得到干燥的乙烯基三甲氧基硅烷接枝聚丙烯表面样品。
按所述聚丙烯表面样品100质量份计，将苯乙烯(8质量份)溶解在乙醇(50质量份)中得到苯乙烯乙醇溶液；将氧化石墨烯(GO)水溶液(4质量份)、抗坏血酸(0.4质量份)溶解在去离子水(50质量份)中得到氧化石墨烯(GO)分散体；将苯乙烯乙醇溶液在真空条件下加入到上述苯乙烯接枝聚丙烯表面样品上充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将烘干后干燥的苯乙烯和接枝聚丙烯表面样品混合物的粉料与氧化石墨烯(GO)分散体充分接触混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)，其中氧化石墨烯、抗坏血酸与去离子水混合形成氧化石墨烯分散体，氧化石墨烯分散体在与苯乙烯和接枝聚丙烯表面样品的混合物混合后，在80℃烘干干燥时，抗坏血酸作为氧化石墨烯的还原剂将氧化石墨烯还原成石墨烯，石墨烯是后续微波辐照接枝的微波吸收介质；将干燥的混合物在氮气的氛围下微波辐照(功率500W)30min；微波辐照完毕的物料在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的苯乙烯单体以及氧化石墨烯，然后将其置于80℃鼓风干燥箱烘干；得到接枝乙烯基三甲氧基硅烷和苯乙烯的双亲聚丙烯表面样品。所得双亲聚丙烯表面的水、油接触角、表面接枝率数据见表1。
对比例3
将聚丙烯表面样品(同实施例9)直接进行测试，聚丙烯表面的水、油接触角数据见表1。
表1
Figure PCTCN2020106910-appb-000001
从表1中可以看出，根据本发明对聚丙烯表面进行亲水接枝改性或进一步亲油接枝改性后得到的超浸润表面，相比于未改性的聚丙烯表面，实现了亲水、亲油性均大幅度改进，所述超浸润表面达到超亲水、亲油，甚至有些情况下达到超亲水和超亲油(超双亲)，这说明实现了非常有效的对聚丙烯表面的双亲改性。
实施例13
按聚丙烯多孔膜(规格1：平均孔径0.8μm，孔隙率80％；表面样品4)100质量份计，将马来酸酐(5质量份)溶解在丙酮(50质量份)中得到马来酸酐丙酮溶液；将氢氧化钠(5质量份)溶解在去离子水(50质量份)中得到氢氧化钠水溶液；将马来酸酐丙 酮溶液在真空伴随机械搅拌的条件下加入到所述聚丙烯多孔膜中充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)。将烘干后干燥的马来酸酐与聚丙烯多孔膜的混合物在氮气的氛围下微波辐照(功率700W)5min；微波辐照完毕的产物在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的马来酸酐单体，然后将膜置于80℃鼓风干燥箱烘干得到干燥的马来酸酐接枝聚丙烯多孔膜；将氢氧化钠水溶液在真空搅拌的条件下与烘干的马来酸酐接枝聚丙烯多孔膜充分混合，氢氧化钠水溶液加入完后再搅拌混合并反应5分钟。反应完毕后使用去离子水按同上清洗步骤清洗反应产物然后将其置于80℃鼓风干燥箱烘干，得到接枝马来酸钠的聚丙烯多孔膜。
按所述聚丙烯多孔膜100质量份计，将乙烯基硅油(5质量份)溶解在乙醇(50质量份)中得到乙烯基硅油乙醇溶液；将氯化钠(5质量份)溶解在去离子水(50质量份)中得到氯化钠水溶液；将乙烯基硅油乙醇溶液在真空伴随机械搅拌的条件下加入到上述所得的接枝马来酸钠聚丙烯多孔膜中充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将烘干后干燥的乙烯基硅油和接枝马来酸钠聚丙烯多孔膜混合物的粉料与氯化钠水溶液充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将干燥的混合物在氮气的氛围下微波辐照(功率700W)5min；微波辐照完毕的物料在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的乙烯基硅油单体以及氯化钠，然后将所得聚丙烯多孔膜置于80℃鼓风干燥箱烘干，得到接枝马来酸钠和乙烯基硅油侧基的双亲聚丙烯多孔膜。所得双亲聚丙烯多孔膜的水、油接触角，水、油通量，表面接枝率数据见表2。
实施例14
按聚丙烯多孔膜(同实施例13)100质量份计，将马来酸酐(5质量份)溶解在丙酮(50质量份)中得到马来酸酐丙酮溶液；将氢氧化钠(5质量份)溶解在去离子水(50质量份)中得到氢氧化钠水溶液；将马来酸酐丙酮溶液在真空伴随机械搅拌的条件下加入到所述聚丙烯多孔膜中充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)。将烘干后干燥的马来酸酐与聚丙烯多孔膜的混合物在氮气的氛围下微波辐照(功率700W)5min；微波辐照完毕的产物在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的马来酸酐单体，然后膜置于80℃鼓风干燥箱烘干得到干燥的马来酸 酐接枝聚丙烯多孔膜；将氢氧化钠水溶液在真空搅拌的条件下加入至烘干的马来酸酐接枝聚丙烯多孔膜充分混合，氢氧化钠水溶液加入完后再搅拌混合并反应5分钟。反应完毕后使用去离子水按同上清洗步骤清洗反应产物然后将其置于80℃鼓风干燥箱烘干，得到接枝马来酸钠侧基的双亲聚丙烯多孔膜。所得双亲聚丙烯多孔膜的水、油接触角，水、油通量，表面接枝率数据见表2。
实施例15
按所述聚丙烯多孔膜(同实施例13)100质量份计，将乙烯基硅油(10质量份)溶解在乙醇(50质量份)中得到乙烯基硅油乙醇溶液；将氯化钠(5质量份)溶解在去离子水(50质量份)中得到氯化钠水溶液；将乙烯基硅油乙醇溶液在真空伴随机械搅拌的条件下加入到所述聚丙烯多孔膜中充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将烘干后干燥的乙烯基硅油与聚丙烯多孔膜混合物的粉料与氯化钠水溶液充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将干燥的混合物在氮气的氛围下微波辐照(功率1000W)3min；微波辐照完毕的物料在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的乙烯基硅油单体以及氯化钠，然后将膜置于80℃鼓风干燥箱烘干；得到接枝有乙烯基硅油侧基的双亲聚丙烯多孔膜；
按聚丙烯多孔膜100质量份计，将丙烯酸(10质量份)溶解在丙酮(50质量份)中得到丙烯酸丙酮溶液；将氢氧化钾(8质量份)溶解在去离子水(50质量份)中得到氢氧化钾水溶液；将丙烯酸丙酮溶液在真空伴随机械搅拌的条件下加入到上述接枝乙烯基硅油侧基聚丙烯多孔膜的中充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)。将烘干后干燥的丙烯酸与接枝聚丙烯多孔膜的混合物在氮气的氛围下微波辐照(功率1000W)3min；微波辐照完毕的产物在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的丙烯酸单体，然后将膜置于80℃鼓风干燥箱烘干得到干燥的丙烯酸和乙烯基硅油接枝聚丙烯多孔膜；将氢氧化钾水溶液在真空搅拌的条件下加入至烘干的丙烯酸和乙烯基硅油接枝的聚丙烯多孔膜充分混合，氢氧化钾水溶液加入完后再搅拌混合并反应5分钟。反应完毕后使用去离子水按同上清洗步骤清洗反应产物然后将其置于80℃鼓风干燥箱烘干，得到接枝有丙烯酸钾和乙烯基硅油侧基的双亲聚丙烯多孔膜。所得双亲聚丙烯多孔膜的水、油接触角，水、油通量，表面接枝率数据见表2。
实施例16
按聚丙烯多孔膜(同实施例13)100质量份计，将丙烯酸(10质量份)溶解在丙酮(50质量份)中得到丙烯酸丙酮溶液；将氢氧化钾(8质量份)溶解在去离子水(50质量份)中得到氢氧化钾水溶液；将丙烯酸丙酮溶液在真空伴随机械搅拌的条件下加入到所述聚丙烯多孔膜中充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)。将烘干后干燥的丙烯酸与聚丙烯多孔膜的混合物在氮气的氛围下微波辐照(功率1000W)3min；微波辐照完毕的产物在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的丙烯酸单体，然后膜置于80℃鼓风干燥箱烘干得到干燥的丙烯酸接枝聚丙烯多孔膜；将氢氧化钾水溶液在真空搅拌的条件下加入至烘干的丙烯酸接枝的聚丙烯多孔膜充分混合，氢氧化钾水溶液加入完后再搅拌混合并反应5分钟。反应完毕后使用去离子水按同上清洗步骤清洗反应产物然后将其置于80℃鼓风干燥箱烘干，得到接枝丙烯酸钾侧基的双亲聚丙烯多孔膜。所得双亲聚丙烯多孔膜的水、油接触角，水、油通量，表面接枝率数据见表2。
对比例4
将聚丙烯多孔膜(同实施例13)直接进行测试，聚丙烯多孔膜的水、油接触角，水、油通量数据见表2。
实施例17
按聚丙烯多孔膜(规格2：平均孔径0.65μm，孔隙率70％；表面样品5)100质量份计，将2-丙烯酰胺-2-甲基丙磺酸(10质量份)溶解在丙酮(50质量份)中得到2-丙烯酰胺-2-甲基丙磺酸丙酮溶液；将氢氧化钾(8质量份)溶解在去离子水(50质量份)中得到氢氧化钾水溶液；将2-丙烯酰胺-2-甲基丙磺酸丙酮溶液在真空伴随机械搅拌的条件下加入到所述聚丙烯多孔膜中充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)。将烘干后干燥的2-丙烯酰胺-2-甲基丙磺酸与聚丙烯多孔膜的混合物在氮气的氛围下微波辐照(功率1000W)3min；微波辐照完毕的产物在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的2-丙烯酰胺-2-甲基丙磺酸单体，然后膜置于80℃鼓风干燥箱烘干得到干燥的2-丙烯酰胺-2-甲基丙磺酸接枝聚丙烯多孔膜；将氢氧化钾水溶液在真空搅拌的条件下与烘干的2-丙烯酰胺-2-甲基丙磺酸接枝的聚丙烯多孔膜充分混合， 氢氧化钾水溶液加入完后再搅拌混合并反应5分钟。反应完毕后使用去离子水按同上清洗步骤清洗反应产物然后将其置于80℃鼓风干燥箱烘干，得到接枝2-丙烯酰胺-2-甲基丙磺酸钾的聚丙烯多孔膜。
按所述聚丙烯多孔膜100质量份计，将乙烯基含氢硅油(10质量份)溶解在乙醇(50质量份)中得到乙烯基含氢硅油乙醇溶液；将氯化钠(5质量份)溶解在去离子水(50质量份)中得到氯化钠水溶液；将乙烯基含氢硅油乙醇溶液在真空伴随机械搅拌的条件下加入到上述接枝2-丙烯酰胺-2-甲基丙磺酸钾的聚丙烯多孔膜中充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将烘干后干燥的乙烯基含氢硅油聚丙烯多孔膜混合物的粉料与氯化钠水溶液充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将干燥的混合物在氮气的氛围下微波辐照(功率1000W)3min；微波辐照完毕的物料在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的乙烯基含氢硅油单体以及氯化钠，然后将膜置于80℃鼓风干燥箱烘干；得到接枝2-丙烯酰胺-2-甲基丙磺酸钠和乙烯基含氢硅油侧基的双亲聚丙烯多孔膜。所得双亲聚丙烯多孔膜的水、油接触角，水、油通量，表面接枝率数据见表2。
实施例18
按聚丙烯多孔膜(同实施例17)100质量份计，将2-丙烯酰胺-2-甲基丙磺酸(10质量份)溶解在丙酮(50质量份)中得到2-丙烯酰胺-2-甲基丙磺酸丙酮溶液；将氢氧化钾(8质量份)溶解在去离子水(50质量份)中得到氢氧化钾水溶液；将2-丙烯酰胺-2-甲基丙磺酸丙酮溶液在真空伴随机械搅拌的条件下加入到聚丙烯多孔膜中充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)。将烘干后干燥的2-丙烯酰胺-2-甲基丙磺酸与聚丙烯多孔膜的混合物在氮气的氛围下微波辐照(功率1000W)3min；微波辐照完毕的产物在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的2-丙烯酰胺-2-甲基丙磺酸单体，然后膜置于80℃鼓风干燥箱烘干得到干燥的2-丙烯酰胺-2-甲基丙磺酸接枝聚丙烯多孔膜；将氢氧化钾水溶液在真空搅拌的条件下加入至烘干的2-丙烯酰胺-2-甲基丙磺酸接枝的聚丙烯多孔膜充分混合，氢氧化钾水溶液加入完后再搅拌混合并反应5分钟。反应完毕后使用去离子水按同上清洗步骤清洗反应产物然后将其置于80℃鼓风干燥箱烘干，得到接枝2-丙烯酰胺-2-甲基丙磺酸钾侧基的双亲聚丙烯多孔膜。所得双亲 聚丙烯多孔膜的水、油接触角，水、油通量，表面接枝率数据见表2。
实施例19
按聚丙烯多孔膜(同实施例17)100质量份计，将甲基丙烯酸(8质量份)溶解在丙酮(50质量份)中得到甲基丙烯酸丙酮溶液；将氢氧化钙(6质量份)溶解在去离子水(50质量份)中得到氢氧化钙水溶液；将甲基丙烯酸丙酮溶液在真空伴随机械搅拌的条件下加入到所述聚丙烯多孔膜中充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)。将烘干后干燥的甲基丙烯酸与聚丙烯多孔膜的混合物在氮气的氛围下微波辐照(功率2000W)1min；微波辐照完毕的产物在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的甲基丙烯酸单体，然后膜置于80℃鼓风干燥箱烘干得到干燥的甲基丙烯酸接枝聚丙烯多孔膜；将氢氧化钙水溶液在真空搅拌的条件下加入至烘干的甲基丙烯酸接枝的聚丙烯多孔膜充分混合，氢氧化钙水溶液加入完后再搅拌混合并反应5分钟。反应完毕后使用去离子水按同上清洗步骤清洗反应产物然后将其置于80℃鼓风干燥箱烘干，得到接枝甲基丙烯酸钙的聚丙烯多孔膜。
按所述聚丙烯多孔膜100质量份计，将二乙烯基硅油(10质量份)溶解在乙醇(50质量份)中得到二乙烯基硅油乙醇溶液；将氯化钠(5质量份)溶解在去离子水(50质量份)中得到氯化钠水溶液；将二乙烯基硅油乙醇溶液在真空伴随机械搅拌的条件下加入到上述接枝甲基丙烯酸钙的聚丙烯多孔膜中充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将烘干后干燥的二乙烯基硅油与接枝聚丙烯多孔膜混合物与氯化钠水溶液充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将干燥的混合物在氮气的氛围下微波辐照(功率2000W)1min；微波辐照完毕的物料在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的二乙烯基硅油单体以及氯化钠，然后将膜置于80℃鼓风干燥箱烘干；得到接枝甲基丙烯酸钙和二乙烯基硅油侧基的双亲聚丙烯多孔膜。所得双亲聚丙烯多孔膜的水、油接触角，水、油通量，表面接枝率数据见表2。
实施例20
按聚丙烯多孔膜(同实施例17)100质量份计，将甲基丙烯酸(8质量份)溶解在丙酮(50质量份)中得到甲基丙烯酸丙酮溶液；将氢氧化钙(6质量份)溶解在去离子水(50质量份)中得到氢氧化钙水溶液；将甲基丙烯酸丙酮溶液在真空伴随机械搅拌的条件 下加入到所述聚丙烯多孔膜中充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)。将烘干后干燥的甲基丙烯酸与聚丙烯多孔膜的混合物在氮气的氛围下微波辐照(功率2000W)1min；微波辐照完毕的产物在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的甲基丙烯酸单体，然后膜置于80℃鼓风干燥箱烘干得到干燥的甲基丙烯酸接枝聚丙烯多孔膜；将氢氧化钙水溶液在真空搅拌的条件下加入至烘干的甲基丙烯酸接枝的聚丙烯多孔膜充分混合，氢氧化钙水溶液加入后再搅拌混合并反应5分钟。反应完毕后使用去离子水按同上清洗步骤清洗反应产物然后将其置于80℃鼓风干燥箱烘干，得到接枝甲基丙烯酸钙侧基的双亲聚丙烯多孔膜。所得双亲聚丙烯多孔膜的水、油接触角，水、油通量，表面接枝率数据见表2。
实施例21
按聚丙烯多孔膜(同实施例17)100质量份计，将甲基丙烯酸(8质量份)溶解在丙酮(50质量份)中得到甲基丙烯酸丙酮溶液；将甲基丙烯酸丙酮溶液在真空伴随机械搅拌的条件下加入到所述聚丙烯多孔膜中充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)。将烘干后干燥的甲基丙烯酸与聚丙烯多孔膜的混合物在氮气的氛围下微波辐照(功率500W)30min；微波辐照完毕的产物在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的甲基丙烯酸单体，然后膜置于80℃鼓风干燥箱烘干得到干燥的甲基丙烯酸接枝聚丙烯多孔膜。
按所述聚丙烯多孔膜100质量份计，将二乙烯基硅油(10质量份)溶解在乙醇(50质量份)中得到二乙烯基硅油乙醇溶液；将氯化钠(5质量份)溶解在去离子水(50质量份)中得到氯化钠水溶液；将二乙烯基硅油乙醇溶液在真空伴随机械搅拌的条件下加入到上述甲基丙烯酸接枝的聚丙烯多孔膜中充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将烘干后干燥的二乙烯基硅油和接枝聚丙烯多孔膜混合物与氯化钠水溶液充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将干燥的混合物在氮气的氛围下微波辐照(功率500W)30min；微波辐照完毕的物料在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的二乙烯基硅油单体以及氯化钠，然后将膜置于80℃鼓风干燥箱烘干；得到接枝甲基丙烯酸和二乙烯基硅油的双亲聚丙烯多孔膜。所得双亲聚丙烯多孔膜的水、油接触角，水、油通量，表面接枝率数据见表2。
实施例22
按聚丙烯多孔膜(同实施例17)100质量份计，将甲基丙烯酸(8质量份)溶解在丙酮(50质量份)中得到甲基丙烯酸丙酮溶液；将氢氧化钙(5质量份)溶解在去离子水(50质量份)中得到氢氧化钙水溶液；将甲基丙烯酸丙酮溶液在真空伴随机械搅拌的条件下加入到所述聚丙烯多孔膜中充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)。将烘干后干燥的甲基丙烯酸与聚丙烯多孔膜的混合物在氮气的氛围下微波辐照(功率500W)30min；微波辐照完毕的产物在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的甲基丙烯酸单体，然后膜置于80℃鼓风干燥箱烘干得到干燥的甲基丙烯酸接枝聚丙烯多孔膜。将氢氧化钙水溶液在真空搅拌的条件下加入至烘干的甲基丙烯酸接枝的聚丙烯多孔膜充分混合，氢氧化钙水溶液加入完后再搅拌混合并反应5分钟。反应完毕后使用去离子水按同上清洗步骤清洗反应产物然后将其置于80℃鼓风干燥箱烘干，得到接枝甲基丙烯酸钙的聚丙烯多孔膜。
按所述聚丙烯多孔膜100质量份计，将甲基乙烯基硅油(10质量份)溶解在乙醇(50质量份)中得到甲基乙烯基硅油乙醇溶液；将氧化石墨烯(GO)水溶液(5质量份)、抗坏血酸(0.5质量份)溶解在去离子水(50质量份)中得到氧化石墨烯(GO)分散体；将甲基乙烯基硅油乙醇溶液在真空伴随机械搅拌的条件下加入到上述甲基丙烯酸钙接枝聚丙烯多孔膜中充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将烘干后干燥的甲基乙烯基硅油和接枝聚丙烯多孔膜混合物与氧化石墨烯(GO)分散体充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)，其中氧化石墨烯、抗坏血酸与去离子水混合形成氧化石墨烯分散体，氧化石墨烯分散体在与甲基乙烯基硅油和接枝聚丙烯多孔膜的混合物混合后，在80℃烘干干燥时，抗坏血酸作为氧化石墨烯的还原剂将氧化石墨烯还原成石墨烯，石墨烯是后续微波辐照接枝的微波吸收介质；将上述干燥的混合物在氮气的氛围下微波辐照(功率500W)30min；微波辐照完毕的物料在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的甲基乙烯基硅油单体以及氧化石墨烯，然后将膜置于80℃鼓风干燥箱烘干；得到接枝甲基丙烯酸钙和甲基乙烯基硅油的双亲聚丙烯多孔膜。所得双亲聚丙烯多孔膜的水、油接触角，水、油通量，表面接枝率数据见表2。
实施例23
按聚丙烯多孔膜(同实施例17)100质量份计，将乙烯基三甲氧基硅烷(10质量份)溶解在乙醇(50质量份)中得到乙烯基三甲氧基硅烷乙醇溶液；将氯化钠(5质量份)溶解在去离子水(50质量份)中得到氯化钠水溶液；将乙烯基三甲氧基硅烷乙醇溶液在真空伴随机械搅拌的条件下加入到所述聚丙烯多孔膜中充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)。将烘干后干燥的乙烯基三甲氧基硅烷和聚丙烯多孔膜混合物与氯化钠水溶液充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将烘干后干燥的乙烯基三甲氧基硅烷与聚丙烯多孔膜的混合物在氮气的氛围下微波辐照(功率500W)30min；微波辐照完毕的产物在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的乙烯基三甲氧基硅烷单体和氯化钠，然后膜置于80℃鼓风干燥箱烘干得到干燥的乙烯基三甲氧基硅烷接枝聚丙烯多孔膜。
按所述聚丙烯多孔膜100质量份计，将苯乙烯(10质量份)溶解在乙醇(50质量份)中得到苯乙烯乙醇溶液；将氧化石墨烯(GO)水溶液(5质量份)、抗坏血酸(0.5质量份)溶解在去离子水(50质量份)中得到氧化石墨烯(GO)分散体；将苯乙烯乙醇溶液在真空伴随机械搅拌的条件下加入到上述苯乙烯接枝聚丙烯多孔膜中充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将烘干后干燥的苯乙烯和接枝聚丙烯多孔膜混合物的粉料与氧化石墨烯(GO)分散体充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)，其中氧化石墨烯、抗坏血酸与去离子水混合形成氧化石墨烯分散体，氧化石墨烯分散体在与苯乙烯和接枝聚丙烯多孔膜的混合物混合后，在80℃烘干干燥时，抗坏血酸作为氧化石墨烯的还原剂将氧化石墨烯还原成石墨烯，石墨烯是后续微波辐照接枝的微波吸收介质；将干燥的混合物在氮气的氛围下微波辐照(功率500W)30min；微波辐照完毕的物料在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的苯乙烯单体以及氧化石墨烯，然后将膜置于80℃鼓风干燥箱烘干；得到接枝乙烯基三甲氧基硅烷和苯乙烯的双亲聚丙烯多孔膜。所得双亲聚丙烯多孔膜的水、油接触角，水、油通量，表面接枝率数据见表2。
对比例5
将聚丙烯多孔膜(同实施例17)直接进行测试，聚丙烯多孔膜的水、油接触角，水、油通量数据见表2。
表2
Figure PCTCN2020106910-appb-000002
从表2中可以看出，根据本发明对聚丙烯多孔膜进行亲水接枝改性或进一步亲油接枝改性后获得的超浸润表面，相比于未改性的聚丙烯多孔膜，实现了水、油通量均大幅度提升，改性后的聚丙烯多孔膜达到超亲水、亲油，甚至有些情况下达到超亲水并且超亲油，这说明实现了非常有效的对聚丙烯多孔膜的双亲改性。

Claims (16)

  1. 一种超浸润表面，其为接枝有亲水性侧基的具有微纳结构的聚丙烯表面，其中所述超浸润表面是至少超亲水的并且不含有引发剂残留物。
  2. 根据权利要求1所述的超浸润表面，其特征在于，所述超浸润表面的水接触角小于或等于10°，优选小于或等于8°，更优选小于或等于5°，再更优选小于或等于1°，最优选约0°。
  3. 根据权利要求1或2所述的超浸润表面，其特征在于，作为接枝基础物的聚丙烯表面具有的微纳结构的特征尺寸为1nm-100μm；优选地，所述微纳结构是采用热致相分离工艺、光刻技术、飞秒激光加工技术、等离子刻蚀技术、静电纺丝法、纳米压印、纳米铸造、超精密微铣技术或使用电弧在聚丙烯表面上产生的结构。
  4. 根据权利要求3所述的超浸润表面，其特征在于，作为接枝基础物的聚丙烯表面是聚丙烯多孔膜、聚丙烯平板膜或聚丙烯中空纤维微孔膜；其中所述聚丙烯多孔膜优选具有小于100μm，优选为10nm-80μm的平均孔径；优选具有50-90％，更优选为60-80％的孔隙率。
  5. 根据权利要求1-4中任一项所述的超浸润表面，其特征在于，所述亲水性侧基包含由一种或多种含有选自氧、硫、氮、硅和卤素及其组合的杂原子或其取代基并且含有碳碳双键的单体形成的单元；优选地，所述单体选自有机酸及其衍生物(例如酸酐、酯、盐)和乙烯基硅烷中的至少一种；其中所述有机酸及其衍生物优选选自马来酸酐及其衍生物、(甲基)丙烯酸及其衍生物(例如甲基丙烯酸缩水甘油酯)、乙酸乙烯酯、烯基磺酸及其衍生物、乙烯基苯甲酸及其衍生物、衣康酸及其衍生物、油酸及其衍生物、花生烯酸及其衍生物(尤其是它们的成盐形式)及其组合；其中所述乙烯基硅烷优选为式(1)所示的化合物中的一种或多种：
    CH 2＝CH-(CH 2) nSiX 3  式(1)
    其中n＝0至3，每个X相同或不同地独立地表示氯基、甲氧基、乙氧基或乙酰氧基；
    更优选地，所述亲水性侧基包含由有机酸的盐形成的单元或由有机酸的盐形成的单元 组成。
  6. 根据权利要求1-5中任一项所述的超浸润表面，其特征在于，所述聚丙烯表面另外接枝有亲油性侧基；所述亲油性侧基优选选自乙烯基硅油侧基和苯乙烯侧基及其组合；所述乙烯基硅油优选选自端乙烯基硅油和高乙烯基硅油及其组合，更优选选自甲基乙烯基硅油、乙烯基含氢硅油、二乙烯基硅油及其组合；优选地，超浸润表面的油接触角小于90°，优选小于或等于10°，更优选小于或等于5°，再更优选小于或等于1°，最优选为约0°。
  7. 根据权利要求1-6中任一项所述的超浸润表面，其特征在于，所述超浸润表面通过如下方法制备：将用于形成所述侧基的单体，在不存在引发剂的情况下，任选地在加入无机微波吸收介质的情况下，通过微波辐照与作为接枝基础物的具有微纳结构的聚丙烯表面进行接枝反应；优选地，当所述单体包括用于形成亲油性侧基的单体时，加入无机微波吸收介质；优选地，当所述单体选自有机酸或其酸酐或其酯及其组合时，所述方法进一步包括将接枝反应后所得产物与碱反应的步骤。
  8. 制备根据权利要求1-6中任一项所述的超浸润表面的方法，包括：
    将用于形成侧基的单体，在不存在引发剂的情况下，通过微波辐照与作为接枝基础物的具有微纳结构的聚丙烯表面进行接枝反应。
  9. 根据权利要求8所述的方法，其特征在于所述方法包括以下方案1)-4)中的任一种：
    1)将聚丙烯表面与用于形成亲水性侧基的单体接触混合，其中任选加入无机微波吸收介质；之后将所得的混合物在不加引发剂的情况下微波辐照接枝；其中所述混合物任选地还包含亲油性侧基的单体以及无机微波吸收介质；
    2)将聚丙烯表面与用于形成亲水性侧基单体接触混合，其中任选加入无机微波吸收介质；之后将所得的混合物在不加引发剂的情况下微波辐照接枝；然后将所得接枝产物与用于形成亲油性侧基的单体以及无机微波吸收介质混合，在不加引发剂的情况下微波辐照接枝；
    3)将聚丙烯表面与用于形成亲油性侧基的单体以及无机微波吸收介质接触混合，之后将所得的混合物在不加引发剂的情况下微波辐照接枝；然后将所得接枝产物与用于形成 亲水性侧基的单体在任选加入无机微波吸收介质的情况下混合，在不加引发剂的情况下微波辐照接枝；
    4)在以上1)-3)的任一种中，当用于形成亲水性侧基的单体为有机酸或其酸酐或其酯中的至少一种时，还包括将接枝了有机酸或其酸酐或其酯中的至少一种侧基的聚丙烯表面与碱接触混合的步骤；优选地，所述碱为一种或多种氢氧化物，所述氢氧化物优选选自金属氢氧化物和氨水；其中金属氢氧化物优选选自氢氧化钠、氢氧化钾、氢氧化钡、氢氧化锂、氢氧化锶、氢氧化钙、氢氧化铁、氢氧化亚铁、氢氧化锌、氢氧化镁、氢氧化钴、氢氧化金、氢氧化铝、氢氧化铜、氢氧化铍、稀土氢氧化物及其组合，优选选自氢氧化钠、氢氧化钾、氢氧化钡、氢氧化锂、氢氧化锶、氢氧化钙及其组合；优选地，所述碱用量为基于所述聚丙烯表面用量计的0.1-10重量％；优选为1-8重量％；优选地，所述碱以水溶液形式使用；
    优选地，至少一个上述的混合过程在真空条件下进行。
  10. 根据权利要求9的方法，其特征在于用于形成亲水性侧基的单体用量为基于所述聚丙烯表面用量计的0.1-10重量％；优选为1-8重量％；所述用于形成亲水性侧基的单体可以溶解在一种或多种溶剂中的溶液的形式使用；优选地，所述溶剂选自醇、酮、酯、水及其组合。
  11. 根据权利要求9或10的方法，其特征在于用于形成亲油性侧基的单体用量为基于所述聚丙烯表面用量计的0.1-30重量％；优选为1-20重量％；所述用于形成亲油性侧基的单体可以溶解在一种或多种溶剂中的溶液的形式使用；优选地，所述溶剂选自醇、酮、酯、水及其组合。
  12. 根据权利要求8-11中任一项的方法，其特征在于加入无机微波吸收介质；优选地，所述无机微波吸收介质选自金属氢氧化物、金属盐、金属氧化物、石墨类材料、铁电类材料、电解石、黄铜矿及其组合；优选地，所述金属氢氧化物选自氢氧化钾、氢氧化钡、氢氧化钠、氢氧化锂、氢氧化锶、氢氧化钙、氢氧化铁、氢氧化亚铁、氢氧化锌、氢氧化镁、氢氧化钴、氢氧化金、氢氧化铝、氢氧化铜、氢氧化铍、稀土氢氧化物及其组合；所述金属盐选自硝酸铵、硝酸钾、硝酸钠、硝酸钡、硝酸钙、硝酸镁、硝酸铝、硝酸锰、硝酸锌、硝酸铁、硝酸亚铁、硝酸铜、硝酸银、氯化铵、氯化钾、氯化钠、氯化钡、氯化钙、氯化 镁、氯化铝、氯化锰、氯化锌、氯化铁、氯化亚铁、氯化铜、硫酸铵、硫酸钾、硫酸钠、硫酸钙、硫酸镁、硫酸铝、硫酸锰、硫酸锌、硫酸铁、硫酸亚铁、硫酸铜、硫酸银、碳酸铵、碳酸钾、碳酸钠、碳酸镁、碳酸钙、碳酸钡、磷酸二氢钾、钛酸钡、钛酸锶、钛酸铜钙及其组合；所述金属氧化物选自三氧化二铁、四氧化三铁及其组合；所述石墨类材料优选选自炭黑、石墨粉、石墨烯、氧化石墨烯的还原产物(还原剂例如为抗坏血酸)、碳纳米管、活性炭及其组合；优选地，所述无机微波吸收介质的单次用量为基于聚丙烯表面用量的0.1-10重量％；优选为1-8重量％；优选地，所述无机微波吸收介质直接加入，或者是以溶解或分散于一种或多种溶剂中的溶液或分散体形式加入；优选地，所述一种或多种溶剂选自醇、酮、酯、水及其组合；优选地，所述分散体中含有表面活性剂。
  13. 通过根据权利要求8-12中任一项所述的方法制备的超浸润表面。
  14. 一种制品，其由根据权利要求1-7中任一项或根据权利要求13的超浸润表面构成，或者包含根据权利要求1-7中任一项或根据权利要求13的超浸润表面；所述制品优选是膜、薄片、板材或者模塑制品。
  15. 根据权利要求1-7中任一项或权利要求13所述的超浸润表面或根据权利要求14所述的制品用于粘接(例如粘接塑料制品)、喷涂(例如喷涂食品袋外包装、喷涂汽车保险杠)、油水分离、水处理、生物、医药或能源领域的用途。
  16. 粘接、喷涂、油水分离或水处理方法，其中应用根据权利要求1-7中任一项或权利要求13所述的超浸润表面或根据权利要求14所述的制品。
PCT/CN2020/106910 2019-08-23 2020-08-04 超浸润表面及其制备方法和应用 WO2021036716A1 (zh)

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BR112022002822A BR112022002822A2 (pt) 2019-08-23 2020-08-04 Superfície super-umectante, método para preparar a superfície super-umectante, artigo, uso da superfície super-umectante e método de colagem, pulverização, separação óleo-água ou tratamento de água
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