CN112409628B - Super-wetting surface and preparation method and application thereof - Google Patents

Super-wetting surface and preparation method and application thereof Download PDF

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Publication number
CN112409628B
CN112409628B CN201910786287.8A CN201910786287A CN112409628B CN 112409628 B CN112409628 B CN 112409628B CN 201910786287 A CN201910786287 A CN 201910786287A CN 112409628 B CN112409628 B CN 112409628B
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gas
monomer
hydroxide
side group
polypropylene
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CN112409628A (en
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
张红彬
韩朋
姜超
郭照琰
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to BR112022002822A priority patent/BR112022002822A2/en
Priority to KR1020227009683A priority patent/KR20220044850A/en
Priority to EP20857732.0A priority patent/EP4019121A4/en
Priority to AU2020335669A priority patent/AU2020335669A1/en
Priority to PCT/CN2020/106910 priority patent/WO2021036716A1/en
Priority to US17/753,209 priority patent/US20220282054A1/en
Priority to JP2022512344A priority patent/JP2022545502A/en
Priority to TW109128107A priority patent/TWI789615B/en
Publication of CN112409628A publication Critical patent/CN112409628A/en
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    • 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
    • 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

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  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

The invention provides a super-wetting surface and a preparation method and application thereof. The super-wetting surface is a grafted polypropylene surface with a micro-nano structure, and hydrophilic side groups are grafted; or both lipophilic and hydrophilic side groups can be grafted. The super-wetting surface is obtained by carrying out grafting reaction on components including the monomer of the hydrophilic side group or the monomers including the monomer of the hydrophilic side group and the monomer of the lipophilic side group and the polypropylene surface by using microwave irradiation without adding a grafting initiator; the method also comprises a step of further reacting the surface of the obtained grafted polypropylene with hydroxide to salify. The polypropylene molecular weight of the super-wetting surface is not reduced, no monomer or initiator is left, the polypropylene super-wetting surface is colorless and tasteless, and the pure water flux and the oil flux are both improved. The preparation method and the equipment are simple, the cost is low, and the industrialization is easy to realize.

Description

Super-wetting surface and preparation method and application thereof
Technical Field
The invention relates to the field of high polymer materials, in particular to a super-wetting surface and a preparation method and application thereof.
Background
The wettability of the surface of a solid material is generally determined by the chemical nature and microstructure of the solid surface. The polymer surface with super-wetting property has important application in the aspects of liquid separation, self-cleaning, antifogging, liquid conveying, functional polymer film, printing, bonding and the like.
At present, numerous scholars have conducted intensive research on polymer surface modification, but most of the research on super-wetting materials is super-hydrophobic materials, reports on super-hydrophilic materials are few, and it is obvious that super-hydrophilic polymers are difficult to prepare. The polymer surface obtained by conventional grafting methods, such as ATRP, corona, plasma treatment, uv, etc., is only a hydrophilic surface but not a superhydrophilic surface.
Super-amphiphilic surfaces are more difficult to prepare than super-hydrophilic and super-oleophilic surfaces, which require both water and oil to wet the material surface in a very short time. In 1997, Wang first reported amphiphilic materials (Wang, R.; Hashimoto, K.; Fujishima, A.; Chikuni, M.; Kojima, E.; Kitamura, A.; Shimohigoshi, M.; Watanabe, T., Light-induced amphilicus surfac. Nature 1997 (388) (6641),431-432.) which were prepared by inducing titanium dioxide on a solid substrate using ultraviolet Light to produce an amphiphilic surface with antifouling capacity. Thereafter, a variety of super-wetting polymer surfaces were prepared using layer-by-layer assembly, electrospinning, etching, plasma treatment, dip coating, phase separation and templating methods. However, the super-wetting polymer surface prepared by the above method must be compounded with inorganic particles, and the brittleness of solid particles in flexible products limits the application of the material. Thus, to date, it has not been possible to prepare a super-amphiphilic polymer surface without using inorganic particles.
Disclosure of Invention
The super-wetting polypropylene surface provided by the invention has a good hydrophilic and lipophilic effect, is durable and stable, and the preparation method of the super-wetting polypropylene surface is simple and convenient and is easy to industrialize. The method is characterized in that a polypropylene surface with a micro-nano structure on the surface is subjected to grafting reaction with hydrophilic monomers such as organic acid, organic acid derivatives and vinyl silane under microwave irradiation, and an initiator and an auxiliary monomer are not added, so that a hydrophilic surface with a surface rich in the organic acid and the organic acid derivatives is obtained; it can also be reacted with a base afterwards, thus obtaining a more hydrophilic or even superhydrophilic surface rich in organic acid salts on the surface; and lipophilic monomers such as vinyl silicone oil, styrene and the like can be further grafted on the super-wetting surface of which the surface is rich in hydrophilic side groups, so that the lipophilicity of the hydrophilic surface can be further improved. The infiltration surface modified by the method has super-hydrophilic, super-oleophilic or super-amphiphilic infiltration properties.
It is an object of the present invention to provide a super-wetted surface.
The super-wetting surface is a polypropylene surface with a micro-nano structure, and hydrophilic side groups are grafted on the polypropylene surface; or grafting a lipophilic side group and a hydrophilic side group at the same time; the super-wetted surface is free of initiator residues.
The polypropylene surface with the micro-nano structure is characterized in that the micro-nano structure is a functional structure which has a characteristic dimension of micron or nanometer and is arranged according to a specific mode, and the functional structure comprises a porous structure or other structures; the size of the micro-nano structure is 1 nm-100 mu m.
The polypropylene surface with the micro-nano structure is from polypropylene with the micro-nano structure on various surfaces in the prior art.
The hydrophilic side group described above is preferably a monomer side group containing a heteroatom or a substituent thereof selected from oxygen, sulfur, nitrogen, silicon, and halogen, and a combination thereof, and containing a carbon-carbon double bond; the monomer of the hydrophilic side group is more preferably at least one of an organic acid, a derivative of an organic acid, and a vinylsilane.
The organic acid derivative includes at least one of an acid anhydride, an ester, and a salt of the organic acid. Such organic acids include, but are not limited to, carboxylic acids, sulfonic acids, sulfinic acids, thiocarboxylic acids, and the like.
The hydrophilic pendant monomers described above further preferably include maleic anhydride, maleic anhydride derivatives, (meth) acrylic acid derivatives (e.g., glycidyl methacrylate), vinyl acetate, alkenyl sulfonic acids and their derivatives (e.g., 2-acrylamido-2-methylpropane sulfonic acid, propene sulfonic acid, vinyl benzene sulfonic acid, vinyl sulfonic acid, and the like), p-styrenecarboxylic acid, p-styreneacetic acid, itaconic acid, oleic acid, arachidic acid, and combinations and salified forms thereof; and/or comprises a vinyl silane;
the vinyl silane is one or more of compounds shown in a formula (1):
CH2＝CH2(CH2)nSiX3formula (1)
Wherein N is 0-3, and X is at least one of chloro, methoxy, ethoxy and acetoxy;
the vinyl silane is more preferably at least one of vinyltrimethoxysilane and vinyltriethoxysilane.
The lipophilic side group is preferably vinyl silicone oil side group and styrene side group.
The vinyl silicone oil described above is preferably at least one of a terminal vinyl silicone oil and a high vinyl silicone oil, and more preferably at least one of a methyl vinyl silicone oil, a vinyl hydrogen silicone oil, and a divinyl silicone oil.
The water contact angle of the super-wetting surface is smaller than that of the polypropylene surface before the unmodified treatment. The water contact angle of the super-wetted surface is preferably less than 90 deg., most preferably 0 deg.. That is to say, after the polypropylene surface is grafted with hydrophilic groups, the super-wetting surface of the invention achieves the hydrophilic effect. Meanwhile, after the polypropylene surface is grafted with the vinyl silicone oil for oleophylic modification, the oleophylic property is further improved compared with that of the polypropylene surface which is not oleophylic modified and the polypropylene surface which is only hydrophilic modified.
The second objective of the present invention is to provide a method for preparing a super-wetting surface.
The preparation method of the super-wetting surface comprises the following steps:
carrying out grafting reaction on a component comprising the monomer of the hydrophilic side group or the components comprising the monomer of the hydrophilic side group and the monomer of the lipophilic side group and a polypropylene surface by using microwave irradiation under the condition of not adding a grafting initiator to obtain the super-wetting surface;
wherein when the component does not comprise a lipophilic pendant monomer, an inorganic microwave absorbing medium is optionally added; when the component comprises a monomer with lipophilic side group, adding an inorganic microwave absorbing medium;
or when the monomer of the hydrophilic side group in the above-mentioned method is at least one of an organic acid or an anhydride or an ester thereof, a step of reacting the product obtained after the grafting reaction with a base (so-called salting step) is included.
In the preparation method of the invention, the microwave irradiation grafting reaction only comprises the microwave irradiation grafting reaction of the oleophylic side group; or the microwave irradiation grafting reaction of the oleophylic side group and the microwave irradiation grafting reaction of the hydrophilic side group are included, the microwave irradiation grafting reactions of the two side groups can be simultaneously or sequentially carried out, and the sequence is not limited; the salting step is optional, and can be performed when the polypropylene surface is grafted with at least one pendant group of organic acid or anhydride or ester thereof, and is not limited to whether the pendant group is grafted before or after the microwave irradiation of the lipophilic pendant group, or the pendant group is grafted by the microwave irradiation of the lipophilic pendant group (i.e. the pendant group can be salted by adding base while the grafted polypropylene surface of which the monomer of the hydrophilic pendant group is at least one of organic acid or anhydride or ester thereof is grafted by the microwave irradiation of the lipophilic pendant group).
The preparation method of the invention can specifically comprise any one of the following schemes:
the first scheme comprises the steps of contacting and mixing the polypropylene surface with the hydrophilic side group monomer and/or a solution of the hydrophilic side group monomer dissolved in a solvent, wherein an inorganic microwave absorbing medium is optionally added; then the obtained mixture is grafted by microwave irradiation under the condition of not adding a grafting initiator; or a monomer further comprising a lipophilic side group and/or a solution thereof dissolved in a solvent in a mixture, and an inorganic microwave absorbing medium;
the second scheme comprises the steps of contacting and mixing the polypropylene surface with the hydrophilic side group monomer and/or a solution of the hydrophilic side group monomer dissolved in a solvent, wherein an inorganic microwave absorbing medium is optionally added; then the obtained mixture is grafted by microwave irradiation under the condition of not adding a grafting initiator; then mixing the obtained grafting product with the lipophilic side group monomer and/or the solution of the lipophilic side group monomer dissolved in the solvent and an inorganic microwave absorption medium, and grafting by microwave irradiation under the condition of not adding a grafting initiator;
contacting and mixing the polypropylene surface with the lipophilic side-group monomer and/or a solution of the lipophilic side-group monomer dissolved in a solvent and an inorganic microwave absorbing medium, and then grafting the obtained mixture by microwave irradiation without adding a grafting initiator; then mixing the obtained grafting product with the hydrophilic side group monomer and/or a solution of the hydrophilic side group monomer dissolved in a solvent, and grafting by microwave irradiation under the condition of not adding a grafting initiator;
and on the basis of any one of the three schemes, when the monomer of the hydrophilic side group is at least one of organic acid or anhydride or ester thereof, the method further comprises a step of contacting and mixing the polypropylene surface grafted with the side group of at least one of organic acid or anhydride or ester thereof with an aqueous solution of alkali and/or alkali (i.e. a so-called salting step).
According to the above preparation method, the super-wetting surface of the present invention does not contain initiator residues.
In the preparation method of the present invention, no grafting initiator is added, wherein the grafting initiator refers to a substance which is commonly used for initiating the polymerization reaction (including the grafting reaction) of the monomer in the prior art, such as a free radical type initiator, including a peroxide initiator, an azo initiator, a redox initiator and the like. Peroxide initiators can in turn be classified as organic peroxide initiators (e.g., dicumyl peroxide) and inorganic peroxide initiators. Especially refers to various initiators for polypropylene grafting functional monomers, such as dicumyl peroxide and the like. In the grafting method of the prior art, in order to graft the polypropylene with the monomer, the tertiary carbon of the polypropylene is dehydrogenated by the initiator, but the initiator can actually be dehydrogenated and also causes a great amount of beta chain scission reaction of the polypropylene, namely, the reaction is too violent and uncontrollable. Thereby affecting the mechanical properties of the grafted polypropylene. According to the preparation method, organic acid derivatives, vinyl silane, vinyl silicone oil, styrene and other side groups can be grafted on the surface of the polypropylene without adding an initiator. The super-wetting surface obtained by the invention does not contain initiator residues, and ensures that the mechanical property of the polypropylene surface is not influenced.
More specifically, the present invention is to provide a novel,
in the preparation method of the invention, the polypropylene surface can be the existing polypropylene surface with a micro-nano structure in the prior art. The size of the micro-nano structure on the polypropylene surface is 1 nm-100 mu m.
In the preparation method, the adopted polypropylene surface can be any polypropylene surface with a micro-nano structure, and the preparation method also adopts the existing preparation method in the prior art. The specific polypropylene surface with the micro-nano structure can be, for example, various existing polypropylene microporous surfaces in the prior art, and is preferably a polypropylene microporous plane prepared by a thermally induced phase separation process. The processing of the polypropylene surface micro-nano structure can also be realized by adopting the photoetching technology, the femtosecond laser processing technology, the plasma etching technology, the electrostatic spinning method, the nano imprinting, the nano casting technology, the ultra-precise micro milling technology and the like in the prior art, and specifically, for example, the micro-nano structure is extruded on the polypropylene surface by using a metal mold with the micro-nano structure on the surface. Or preparing a micro-nano structure and the like on the surface of the polypropylene by using an electric arc and other modes.
In the preparation method of the present invention, the hydrophilic side group monomer can adopt various hydrophilic monomers existing in the prior art, preferably a monomer containing a heteroatom or a substituent thereof selected from oxygen, sulfur, nitrogen, silicon and halogen and a combination thereof and containing a carbon-carbon double bond, and more preferably at least one of organic acid, a derivative of the organic acid and vinyl silane.
The organic acid derivative includes at least one of an acid anhydride, an ester, and a salt of the organic acid. Such organic acids include, but are not limited to, carboxylic acids, sulfonic acids, sulfinic acids, thiocarboxylic acids, and the like.
The organic acids and derivatives of the organic acids described above are preferably selected from the group consisting of maleic anhydride, maleic anhydride derivatives, (meth) acrylic acid derivatives (e.g., glycidyl methacrylate), vinyl acetate, alkenyl sulfonic acids and derivatives thereof (e.g., 2-acrylamido-2-methylpropane sulfonic acid, propene sulfonic acid, vinyl benzene sulfonic acid, vinyl sulfonic acid, and the like), p-styrenecarboxylic acid, p-styreneacetic acid, itaconic acid, oleic acid, arachidic acid, and combinations thereof, and salified forms thereof; most preferred are maleic anhydride, maleic anhydride derivatives, (meth) acrylic acid derivatives, and combinations thereof and their salified forms; most preferred are maleic anhydride and its salt forms.
The vinyl silane described above is preferably one or more of the compounds represented by formula (1):
CH2＝CH2(CH2)nSiX3formula (1)
Wherein N is 0-3, and X is at least one of chloro, methoxy, ethoxy and acetoxy; the vinyl silane is more preferably at least one of vinyltrimethoxysilane and vinyltriethoxysilane.
The monomer dosage of the hydrophilic side group is 0.1-10 wt% of the polypropylene surface dosage; preferably 1 to 8% wt.
The monomer of the hydrophilic side group can be directly contacted and mixed with the polypropylene surface or the polypropylene surface grafted with the lipophilic monomer, and can also be mixed by adopting a solution of the monomer of the hydrophilic side group for better mixing effect. The amount of the solvent is not limited as long as the monomer can be dissolved to form a solution, and the weight ratio of the monomer to the solvent in the hydrophilic side group monomer solution is preferably (0.1 to 100):100, preferably (0.5 to 50):100, and more preferably (1 to 30): 100. The monomer solution is preferably used in an amount to completely cover the polypropylene surface, more conveniently to allow intimate contact mixing of the two.
The solvent for dissolving the hydrophilic side group monomer is at least one of water and an organic solvent; preferably comprising at least one of an alcohol, a ketone, an ester, water, more preferably acetone or ethanol.
In the preparation method of the present invention, the lipophilic side group monomer can adopt various lipophilic monomers existing in the prior art, and preferably includes at least one of vinyl silicone oil and styrene. Wherein the vinyl silicone oil is preferably terminal vinyl silicone oil and high vinyl silicone oil, and more preferably at least one of methyl vinyl silicone oil, vinyl hydrogen silicone oil and divinyl silicone oil.
The dosage of the monomer of the lipophilic side group is 0.1-30 wt% of the dosage of the polypropylene surface; preferably 1 to 20% wt.
The monomer of the lipophilic side group can be directly contacted and mixed with the surface of polypropylene or the surface of the polypropylene grafted with the hydrophilic monomer, and can also be mixed by adopting the solution of the monomer of the lipophilic side group for better mixing effect. The amount of the solvent used is only required to be an amount capable of dissolving the monomer to form a solution, and the weight ratio of the lipophilic side group monomer to the solvent may be (0.1 to 100):100, preferably (0.5 to 50):100, and more preferably (1 to 30): 100. The monomer solution is preferably used in an amount to completely cover the polypropylene surface, more conveniently to allow intimate contact mixing of the two.
The solvent for dissolving the lipophilic side group monomer is at least one of water and an organic solvent; preferably comprising at least one of an alcohol, a ketone, an ester, water, more preferably acetone or ethanol.
In the preparation method of the invention, when only hydrophilic side groups are grafted on the polypropylene surface, the inorganic microwave absorbing medium can be not added into the mixture of the monomer and the polypropylene surface, and is preferably added to improve the grafting efficiency. When the surface of polypropylene needs to be grafted with a lipophilic side group, the monomer of the lipophilic side group generally raises the temperature under microwave not more than 200 ℃, and the grafting reaction cannot be well carried out. Therefore, an inorganic microwave absorbing medium must be added to promote the grafting reaction under microwave.
The inorganic microwave absorbing medium may be any inorganic substance capable of absorbing microwave, and preferably includes at least one of metal hydroxide, metal salt, metal oxide, graphite-based material, ferroelectric-based material, chalcopyrite, and electrolytic ore.
The metal hydroxide is at least one of potassium hydroxide, barium hydroxide, sodium hydroxide, lithium hydroxide, strontium hydroxide, calcium hydroxide, ferric hydroxide, ferrous hydroxide, zinc hydroxide, magnesium hydroxide, cobalt hydroxide, gold hydroxide, aluminum hydroxide, copper hydroxide, beryllium hydroxide and rare earth hydroxide; the metal salt is selected from at least one of 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, aluminum chloride, manganese chloride, zinc chloride, ferric chloride, ferrous chloride, copper chloride, ammonium sulfate, potassium sulfate, sodium sulfate, magnesium sulfate, aluminum sulfate, manganese sulfate, zinc sulfate, ferric sulfate, ferrous sulfate, copper sulfate, silver sulfate, ammonium carbonate, potassium carbonate, sodium carbonate, magnesium carbonate, calcium carbonate, barium carbonate, potassium dihydrogen phosphate, barium titanate, strontium titanate, and copper calcium titanate; the metal oxide is at least one selected from ferric oxide and ferroferric oxide; the graphite material is selected from at least one of carbon black, graphite powder, graphene, carbon nano tubes and activated carbon.
The single dosage of the inorganic microwave absorbing medium is 0.1-10 wt% of the surface dosage of the polypropylene; preferably 1 to 8% wt. The single dosage of the inorganic microwave absorbing medium refers to the dosage of the inorganic microwave absorbing medium in the single microwave irradiation if the inorganic microwave absorbing medium is added in the microwave irradiation for one time or several times in the preparation method of the invention.
The inorganic microwave absorbing medium can be directly added to contact and mix with the surface of polypropylene or the surface of grafted polypropylene, or the inorganic microwave absorbing medium solution or dispersion liquid obtained by dissolving or dispersing the inorganic microwave absorbing medium in a solvent is added to contact and mix in order to achieve better mixing effect. In order to achieve a better dispersive mixing of the inorganic microwave absorbing agent on the (grafted) polypropylene surface, it is preferred that the mixing of the inorganic microwave absorbing agent with the (grafted) polypropylene surface and with other components, such as monomers, is carried out stepwise, i.e. the (grafted) polypropylene surface may be dried separately from the monomer component, and the dried mixture is then mixed with at least one of the inorganic microwave absorbing agent or a solution or dispersion thereof.
The amount of the solvent for dissolving or dispersing the microwave absorbing medium may be sufficient to dissolve the inorganic microwave absorbing medium to form an inorganic microwave absorbing medium solution, or to disperse the inorganic microwave absorbing medium sufficiently and uniformly to form a dispersion. The weight ratio of the solvent to the inorganic microwave absorbing medium in the inorganic microwave absorbing medium solution or dispersion may be preferably (0.1-100): 100, more preferably (0.5-50): 100, and most preferably (1-30): 100.
The solution or dispersion of the inorganic microwave absorbing medium is preferably used in an amount to completely cover the mixture of the raw materials including the (grafted) polypropylene surface, more facilitating sufficient contact mixing and reaction of the raw materials.
The solvent in the inorganic microwave absorbing medium solution or dispersion is at least one selected from water and organic solvent; preferably comprises at least one of alcohol, ketone, ester and water, and more preferably alcohol and water.
In order to ensure that the inorganic microwave absorbing medium can form a dispersion liquid with sufficient dispersion stability with the solvent, a surfactant which is common in the prior art can be added into the inorganic microwave absorbing medium dispersion liquid. In general, a surfactant of polyoxyethylene type or polyol type is used in an amount of usually 0.1 to 100% by weight based on the inorganic microwave absorbing medium.
In the salinization step of the preparation method, the base is selected from any one of organic acid side groups, anhydride side groups and ester side groups which can graft on the surface of polypropylene in the prior art; preferably a hydroxide.
The above hydroxide is preferably at least one of a metal hydroxide and ammonia water; the metal hydroxide is preferably one or more of sodium hydroxide, potassium hydroxide, barium hydroxide, lithium hydroxide, strontium hydroxide, calcium hydroxide, ferric hydroxide, ferrous hydroxide, zinc hydroxide, magnesium hydroxide, cobalt hydroxide, gold hydroxide, aluminum hydroxide, copper hydroxide, beryllium hydroxide, ammonia water and rare earth hydroxide, and preferably one or more of sodium hydroxide, potassium hydroxide, barium hydroxide, lithium hydroxide, strontium hydroxide and calcium hydroxide.
The amount of the hydroxide is 0.1-10 wt% of the amount of the polypropylene surface; preferably 1 to 8% wt.
The above-mentioned alkali may be directly added to the surface of the grafted polypropylene for contact mixing, or for the sake of sufficient mixing, it is preferable to sufficiently mix the alkali in the form of an aqueous alkali solution. The amount of water in which the alkali is dissolved may be any amount as long as the alkali can be dissolved to form an aqueous solution. The weight ratio of water to alkali in the aqueous alkali solution may be preferably (0.1 to 100):100, more preferably (0.5 to 50):100, and most preferably (1 to 30): 100. The aqueous base solution is preferably in an amount to completely cover the surface of the grafted polypropylene, and to facilitate intimate contact mixing and reaction of the two.
The alkali and/or the alkali aqueous solution is fully mixed with the surface of the grafted polypropylene and reacts simultaneously, namely the common acid-base reaction, and the reaction time has no special requirement until the reaction is fully carried out. Generally, the reaction is carried out while further mixing the alkali and/or the aqueous solution after the addition of the alkali and/or the aqueous solution is completed, and the reaction time is within 30 minutes, for example, preferably within 5 to 10 minutes. The reaction temperature and pressure are not limited, and are generally normal temperature and normal pressure.
In the preparation method, the irradiation power of the microwave irradiation is 100 w-2000 w, preferably 500 w-1000 w, and more preferably 600 w-800 w; the radiation time is 1 s-120 min, preferably 1 min-30 min, and more preferably 3 min-10 min. The microwave irradiation is carried out in various microwave reactors in the prior art.
The microwave irradiation may be preferably performed under an inert atmosphere. The inert atmosphere can adopt inert gases in the prior art, preferably comprises one or more of nitrogen, helium and argon, and more preferably nitrogen.
In the preparation method of the present invention, the mixing is preferably performed under vacuum. The mixing comprises contact mixing of a monomer with a hydrophilic side group and/or a solution thereof with a (grafted) polypropylene surface, contact mixing of a monomer with a lipophilic side group and/or a solution thereof with a (grafted) polypropylene surface, contact mixing of a grafted polypropylene surface with an alkali and/or an aqueous alkali solution, and the like.
For the polypropylene surface with micro-nano structures such as micropores, the vacuum is beneficial to the contact and mixing of the grafted monomer and/or alkali and other components with the polypropylene surface, the grafted monomer and/or alkali and other components are promoted to enter the polypropylene surface, and the reaction is more favorably carried out.
The contact mixing in the preparation method can adopt various mixing methods and equipment in the prior art, the mixing conditions are common, and the materials can be fully and uniformly mixed; for example, raw materials including other components such as the monomer or a solution, dispersion or the like thereof may be coated, dropped, soaked, or coated on the polypropylene surface to achieve contact mixing.
In the preparation process according to the invention, the mixture of the monomers and the components comprising the (grafted) polypropylene surface is preferably dried before microwave irradiation.
In the preparation method of the present invention, the product after microwave irradiation grafting is preferably washed with a solvent to remove unreacted monomers or inorganic microwave absorbing medium not participating in reaction, and is preferably further dried after washing.
The cleaning of the product after microwave irradiation is not particularly limited, and the residual monomer or the microwave absorbing medium may be removed, and a general cleaning method may be employed. For example, soaking the polypropylene surface with a solvent with a volume exceeding that of the polypropylene surface for a certain time (for example, 5 to 15 minutes) immediately after the microwave, and then removing excessive water by using a filtering device; repeating soaking and filtering for multiple times (such as 2-6 times) to obtain cleaned super-wetted surface.
In the preparation method of the present invention, the product of the salination step (i.e., the product after the reaction of the grafting reaction product with the base) is preferably washed with a solvent to remove the base that has not reacted with the surface of the grafted polypropylene, and is preferably further dried after washing.
The cleaning of the salted product is not particularly limited, and any cleaning method can be used as long as the residual alkali can be removed. For example, soaking the grafted polypropylene in a solvent with a volume exceeding that of the surface of the grafted polypropylene for a certain time (for example, 5 to 15 minutes) immediately after the salination reaction, and then removing excessive water by using a filtering device; repeating soaking and filtering for multiple times (such as 2-6 times) to obtain the cleaned amphiphilic polypropylene surface.
In the preparation method, the cleaning solvent is at least one selected from water and organic solvents; preferably comprises at least one of alcohol, ketone, ester and water, and more preferably alcohol and water.
In the preparation method of the present invention, the drying treatment involved can adopt various conventional drying methods in the prior art, including but not limited to, for example, forced air drying, normal temperature drying, etc. The preferred drying temperature is one at which the polypropylene does not melt, for example, does not exceed 160 ℃.
It is a further object of the present invention to provide the use of the super-wetted surfaces of the present invention in the field of bonding (e.g., bonding of plastic articles, etc.), spraying (e.g., spraying of food bag overwrap, spraying of automobile bumpers, etc.), and the like.
The super-wetting surface of the invention can be hydrophilic and oleophilic at the same time, and even can reach super-amphiphilicity. The invention adopts the microwave irradiation to carry out grafting reaction between hydrophilic monomers such as organic acid, organic acid derivatives and the like and the surface of polypropylene without adding an initiator, even further salinization is included, and because the polypropylene is oleophilic, a hydrophilic and oleophilic surface is formed at the moment; or further carrying out grafting reaction with lipophilic monomers such as vinyl silicone oil by microwave irradiation without adding an initiator to prepare the amphiphilic super-wetting surface. Without being bound by any theory, it is believed that: polypropylene is microwave transparent in a microwave environment (little or no microwave absorption under microwave irradiation and therefore no heating under microwave irradiation). The organic acid and organic acid derivative and other monomers as grafting monomers can absorb microwave and raise the temperature to 200 ℃ or above under the condition of microwave and generate free radicals; meanwhile, the high temperature can also initiate nearby polypropylene molecular chains to generate free radicals, so that the free radicals can fully generate grafting reaction with the polypropylene, and the grafted polypropylene surface is obtained. Meanwhile, the microwave grafting reaction without adding the initiator can greatly avoid the beta chain scission reaction of the polypropylene when the initiator is added for grafting, and the molecular weight of the polypropylene is not reduced. Further, the polypropylene grafted with one side group of organic acid or anhydride or ester thereof is reacted with hydroxide to change the grafted polypropylene surface into organic acid salt grafted polypropylene surface, which further improves the hydrophilicity of the polypropylene. In order to further improve the lipophilicity of the polypropylene surface, lipophilic monomers such as vinyl silicone oil and the like are required to be grafted on the polypropylene, the polarity of the vinyl silicone oil and the like is low, the vinyl silicone oil and the like can not reach high temperature (the temperature in a microwave field is raised to be less than 200 ℃) after absorbing microwaves under microwave irradiation, and therefore nearby polypropylene molecular chains can not be effectively initiated to generate free radicals, and therefore an inorganic microwave absorbing medium is required to be added to help the polypropylene to generate the free radicals to further perform a grafting reaction with the vinyl silicone oil monomer. The inorganic microwave absorbing medium does not react with the surface of the polypropylene and the monomer, so that the inorganic microwave absorbing medium is only used as a heat source for grafting reaction and does not influence the surface performance of the polypropylene. The addition of the inorganic microwave absorbing medium can help the monomer which does not absorb microwaves to be grafted on the polypropylene; for monomers that themselves absorb microwaves, this can help to increase their grafting efficiency. The invention utilizes the selective heating of microwave to heat the inorganic microwave absorbing medium, the temperature which can be reached by heating the medium under the microwave is more than 200 ℃ and can reach the vicinity of the melting point of polypropylene, the polypropylene can not be chain-broken at the temperature, but the tertiary carbon of the polypropylene can be dehydrogenated, thereby the grafting reaction can be carried out but the chain-breaking reaction can not be caused. After the lipophilic monomers such as vinyl silicone oil and the like are grafted, the lipophilicity of the polypropylene surface is further improved, and the obtained polypropylene surface has amphiphilicity. Because the polypropylene surface has a micro-nano structure, the hydrophilic, oleophilic and amphiphilic surface can be changed into the effects of super-hydrophilic, super-oleophilic and super-amphiphilic by the capillary action.
The preparation process is simple and easy to operate. The amphiphilic modification method is suitable for the prepared polypropylene surface, and has the advantages of lasting and stable amphiphilic property, no residual grafting monomer, no residual alkali, no residual initiator and the like. Simple equipment, low cost and easy industrialization.
The grafted polypropylene on the super-wetting surface has the advantages of no reduction of the molecular weight, no residual monomer, no initiator residue, no color, no odor, greatly improved hydrophilicity and lipophilicity, durability and stability. The preparation process has the advantages of simple equipment, easy operation, low cost and easy industrialization, and is suitable for the existing polypropylene surface in the prior art.
Detailed Description
The present invention will be further described with reference to the following examples. The scope of the invention is not limited by these examples, but is set forth in the appended claims.
Contact angle test method:
adopting an EASY DROP contact angle tester of Germany KRUSS company, measuring the range of 1-180 degrees and the resolution of +/-0.1 degrees, adopting a dynamic contact angle measuring mode, dripping deionized water DROPs or white oil DROPs with the fixed volume of 2 mu L on the surface of polypropylene each time, taking the calculated initial contact angle as the contact angle measured value of the surface of the polypropylene, measuring the contact angle measured values in parallel for 6 times, and calculating the average value.
The method for measuring the grafting side group on the super-wetting polypropylene surface comprises the following steps: measuring the content of the main elements of the grafting components on the surface of the polypropylene by using an energy spectrum accessory of a scanning electron microscope of Hitachi, Japan; and the content of the graft on the polypropylene surface is reversely deduced by the molecular formula of the graft to be used as the surface grafting rate. (Note: higher than the monomer content in the starting material due to its surface content.)
Raw materials used in examples and comparative examples:
the preparation method of the polypropylene micro-nano surface comprises the following steps:
surface 1: the polypropylene flat membrane, Tianjin membrane Tianma engineering technology Limited (average pore diameter 0.8 μm, porosity 80%), is sealed and coated with epoxy resin glue on one side of the membrane, and the skin layer of the membrane is removed by a Leica CM3600 cryomicrotome in liquid nitrogen atmosphere to obtain the polypropylene micropore surface 1, wherein the average size of the micropores on the surface is 0.8 μm.
Surface 2: polypropylene resin (T30S Qilu petrochemical, MI ═ 3g/10min) is injected into a slice with the thickness of 5cm multiplied by 5cm and 1mm, a microminiature ultra-precision micro milling machine tool is used for preparing a surface with a micron structure, and specifically, the surface is milled respectively along the transverse direction and the longitudinal direction of the slice surface, so that a surface micro-nano structure with the average size of 0.5 mu m is obtained.
Surface 3: polypropylene resin (T30S Qilu petrochemical, MI ═ 3g/10min) was injected into a sheet of 5cm × 5cm thickness 1mm, and a nano-imprint machine was used to prepare a surface having a nano-structure, specifically, a surface micro-nano structure in which pits and projections having an average size of 80nm were imprinted.
Maleic anhydride (west Long science Co., Ltd.), acrylic acid (national medicine group chemical reagent Co., Ltd.), methacrylic acid (national medicine group chemical reagent Co., Ltd.), 2-acrylamide-2-methylpropanesulfonic acid (national medicine group chemical reagent Co., Ltd.), sodium hydroxide (west Long science Co., Ltd.), potassium hydroxide (west Long science Co., Ltd.), calcium hydroxide (west Long science Co., Ltd.), acetone (west Long science Co., Ltd.), sodium chloride (national medicine group chemical reagent Co., Ltd.), vinyl silicone oil (methyl vinyl silicone oil, Shandong big easy chemical industry Co., Ltd.), vinyl hydrogen silicone oil (Tokyo chemical industry Co., Ltd.), divinyl silicone oil (Shandong big easy chemical industry Co., Ltd.), sodium chloride (national medicine group chemical reagent Co., Ltd.), and sodium hydroxide (national medicine group chemical reagent Co., Ltd.) Graphene Oxide (GO) aqueous solution (tokyo giku nano technologies ltd), ascorbic acid (carbofuran), vinyltrimethoxysilane (tokyo chemical co., ltd), and styrene (national chemical group chemicals ltd).
Various other starting materials are commercially available.
Example 1:
dissolving maleic anhydride (5 parts by mass) in acetone (50 parts by mass) to obtain a maleic anhydride acetone solution, based on 100 parts by mass of the polypropylene surface (surface 1); dissolving sodium hydroxide (5 parts by mass) in deionized water (50 parts by mass) to obtain a sodium hydroxide aqueous solution; the maleic anhydride acetone solution is added to the polypropylene surface under vacuum condition for full contact mixing, and then the mixture is dried (80 ℃ forced air drying oven drying). Microwave (power 700W) the dried mixture of maleic anhydride and polypropylene surface for 5min in nitrogen atmosphere; soaking the microwave-finished product in deionized water for 10 minutes, replacing the deionized water, repeating for 3 times to ensure that maleic anhydride monomers which do not participate in the grafting reaction are removed, and then placing the product in a forced air drying oven at 80 ℃ for drying to obtain a dried maleic anhydride grafted polypropylene surface; and fully contacting and mixing the sodium hydroxide aqueous solution with the dried maleic anhydride grafted polypropylene surface under the vacuum condition, and mixing and reacting for 5 minutes after the sodium hydroxide aqueous solution is added. And after the reaction is finished, washing the reaction product by using deionized water according to the above washing step, and then placing the reaction product in an air-blast drying oven at 80 ℃ for drying to obtain the polypropylene surface grafted with the sodium maleate.
Dissolving vinyl silicone oil (5 parts by mass) in ethanol (50 parts by mass) to obtain a vinyl silicone oil ethanol solution, wherein the mass of the vinyl silicone oil ethanol solution is 100 parts by mass of the surface of the polypropylene; dissolving sodium chloride (5 parts by mass) in deionized water (50 parts by mass) to obtain a sodium chloride aqueous solution; adding vinyl silicone oil ethanol solution on the surface of the obtained grafted sodium maleate polypropylene under vacuum condition, fully contacting and mixing, and then drying the mixture (drying in a forced air drying oven at 80 ℃); fully contacting and mixing the dried mixture of the vinyl silicone oil and the surface of the grafted sodium maleate polypropylene with a sodium chloride aqueous solution, and then drying the mixture (drying in a forced air drying oven at 80 ℃); subjecting the dried mixture to microwave (power 700W) for 5min under nitrogen atmosphere; soaking the microwave-finished material in deionized water for 10 minutes, replacing the deionized water, repeating for 3 times to ensure that vinyl silicone oil monomers and sodium chloride which do not participate in the grafting reaction are removed, and then placing the obtained polypropylene surface in an air-blast drying oven at 80 ℃ for drying to obtain the polypropylene super-wetting surface grafted with sodium maleate and vinyl silicone oil side groups. The contact angles of water and oil on the super-wet surface and the surface grafting rate data are shown in Table 1.
Example 2:
maleic anhydride (5 parts by mass) was dissolved in acetone (50 parts by mass) to obtain a maleic anhydride acetone solution based on 100 parts by mass of the polypropylene surface (same as in example 1); dissolving sodium hydroxide (5 parts by mass) in deionized water (50 parts by mass) to obtain a sodium hydroxide aqueous solution; adding a maleic anhydride acetone solution onto the surface of the polypropylene under the condition of vacuum, fully contacting and mixing, and then drying the mixture (drying in a forced air drying oven at 80 ℃). Microwave (power 700W) the dried mixture of maleic anhydride and polypropylene surface for 5min in nitrogen atmosphere; soaking the microwave-finished product in deionized water for 10 minutes, replacing the deionized water, repeating for 3 times to ensure that maleic anhydride monomers which do not participate in the grafting reaction are removed, and then placing the product in a forced air drying oven at 80 ℃ for drying to obtain a dried maleic anhydride grafted polypropylene surface; and adding a sodium hydroxide aqueous solution to the surface of the dried maleic anhydride grafted polypropylene under a vacuum condition, fully contacting and mixing, and mixing and reacting for 5 minutes after the sodium hydroxide aqueous solution is added. After the reaction is finished, the reaction product is cleaned by deionized water according to the above cleaning steps and then is placed in an air-blast drying oven at the temperature of 80 ℃ for drying, and the polypropylene super-wetting surface grafted with the sodium maleate side group is obtained. The water and oil contact angles and surface grafting ratio data of the obtained super-wet surface are shown in table 1.
Example 3:
dissolving vinyl silicone oil (9 parts by mass) in ethanol (50 parts by mass) to obtain a vinyl silicone oil ethanol solution, based on 100 parts by mass of the polypropylene surface (same as in example 1); dissolving sodium chloride (4 parts by mass) in deionized water (50 parts by mass) to obtain a sodium chloride aqueous solution; adding a vinyl silicone oil ethanol solution onto the surface of the polypropylene under a vacuum condition, fully contacting and mixing, and then drying the mixture (drying in a forced air drying oven at 80 ℃); fully contacting and mixing the dried mixture of the vinyl silicone oil and the polypropylene surface with a sodium chloride aqueous solution, and then drying the mixture (drying in a forced air drying oven at 80 ℃); subjecting the dried mixture to microwave (power 1000W) for 3min under nitrogen atmosphere; soaking the microwave-finished material in deionized water for 10 minutes, replacing the deionized water, repeating for 3 times to ensure that vinyl silicone oil monomers and sodium chloride which do not participate in the grafting reaction are removed, and then placing the material in a forced air drying oven at 80 ℃ for drying; obtaining the polypropylene surface grafted with the vinyl silicone oil side group.
Dissolving acrylic acid (9 parts by mass) in acetone (50 parts by mass) to obtain an acrylic acid acetone solution, based on 100 parts by mass of the polypropylene surface; dissolving potassium hydroxide (6 parts by mass) in deionized water (50 parts by mass) to obtain a potassium hydroxide aqueous solution; the acrylic acid acetone solution is added on the surface of the grafted polypropylene under the vacuum condition to be fully contacted and mixed, and then the mixture is dried (the mixture is dried by a forced air drying oven at the temperature of 80 ℃). Microwave (power 1000W) the dried mixture of acrylic acid and the surface of the grafted polypropylene for 3min in the atmosphere of nitrogen; soaking the microwave-finished product in deionized water for 10 minutes, replacing the deionized water, repeating for 3 times to ensure that acrylic monomers which do not participate in the grafting reaction are removed, and then placing the product in a forced air drying oven at 80 ℃ for drying to obtain a dried grafted polypropylene surface grafted with acrylic acid and vinyl silicone oil; adding a potassium hydroxide aqueous solution to the dried polypropylene surface grafted with acrylic acid and vinyl silicone oil under a vacuum condition, fully contacting and mixing, and mixing and reacting for 5 minutes after the potassium hydroxide aqueous solution is added. And after the reaction is finished, washing the reaction product by using deionized water according to the above washing step, and then placing the reaction product in an air-blast drying oven at 80 ℃ for drying to obtain the polypropylene super-wetting surface grafted with the potassium acrylate and the vinyl silicone oil side group. The water and oil contact angles and surface grafting ratio data of the obtained super-wet surface are shown in table 1.
Example 4:
acrylic acid (9 parts by mass) was dissolved in acetone (50 parts by mass) to obtain an acrylic acid acetone solution, based on 100 parts by mass of the polypropylene surface (same as in example 1); dissolving potassium hydroxide (6 parts by mass) in deionized water (50 parts by mass) to obtain a potassium hydroxide aqueous solution; the acrylic acid acetone solution is added on the surface of the polypropylene under the vacuum condition to be fully contacted and mixed, and then the mixture is dried (dried by a forced air drying oven at 80 ℃). Microwave (power 1000W) the dried mixture of acrylic acid and polypropylene surface for 3min in nitrogen atmosphere; soaking the microwave-finished product in deionized water for 10 minutes, replacing the deionized water, repeating for 3 times to ensure that acrylic monomers which do not participate in the grafting reaction are removed, and then placing the product in a forced air drying oven at 80 ℃ for drying to obtain a dried acrylic grafted polypropylene surface; adding a potassium hydroxide aqueous solution to the surface of the dried acrylic acid grafted polypropylene under a vacuum condition, fully contacting and mixing, and mixing and reacting for 5 minutes after the potassium hydroxide aqueous solution is added. And after the reaction is finished, washing the reaction product by using deionized water according to the above washing step, and then placing the reaction product in an air-blast drying oven at 80 ℃ for drying to obtain the polypropylene super-wetting surface grafted with the potassium acrylate side group. The water and oil contact angles and surface grafting ratio data of the obtained super-wet surface are shown in table 1.
Comparative example 1:
the polypropylene surface (same as example 1) was directly tested, and the water and oil contact angle data of the polypropylene surface are shown in table 1.
Example 5:
dissolving 2-acrylamide-2-methylpropanesulfonic acid (10 parts by mass) in acetone (50 parts by mass) to obtain a 2-acrylamide-2-methylpropanesulfonic acid acetone solution, based on 100 parts by mass of the polypropylene surface (surface 2); dissolving potassium hydroxide (6 parts by mass) in deionized water (50 parts by mass) to obtain a potassium hydroxide aqueous solution; adding the 2-acrylamide-2-methylpropanesulfonic acid acetone solution onto the surface of the polypropylene under the vacuum condition, fully contacting and mixing, and then drying the mixture (drying in a forced air drying oven at 80 ℃). Microwave (power 1000W) the dried mixture of 2-acrylamide-2-methylpropanesulfonic acid and the polypropylene surface for 3min in the atmosphere of nitrogen; soaking the microwave-finished product in deionized water for 10 minutes, replacing the deionized water, repeating for 3 times to ensure that 2-acrylamide-2-methylpropanesulfonic acid monomers which do not participate in the grafting reaction are removed, and then placing the product in a forced air drying oven at 80 ℃ for drying to obtain a dried 2-acrylamide-2-methylpropanesulfonic acid grafted polypropylene surface; and (3) fully contacting and mixing a potassium hydroxide aqueous solution with the dried 2-acrylamide-2-methylpropanesulfonic acid grafted polypropylene surface under a vacuum condition, and mixing and reacting for 5 minutes after the potassium hydroxide aqueous solution is added. After the reaction is finished, the reaction product is washed by deionized water according to the above washing steps and then is placed in an air-blast drying oven at the temperature of 80 ℃ for drying, and the polypropylene surface grafted with the 2-acrylamide-2-methyl sodium propanesulfonate is obtained.
Dissolving 9 parts by mass of vinyl hydrogen-containing silicone oil in 50 parts by mass of ethanol to obtain an ethanol solution of the vinyl hydrogen-containing silicone oil, wherein the mass of the ethanol solution is 100 parts by mass of the surface of the polypropylene; dissolving sodium chloride (4 parts by mass) in deionized water (50 parts by mass) to obtain a sodium chloride aqueous solution; adding a vinyl hydrogen-containing silicone oil ethanol solution onto the surface of the polypropylene grafted with the 2-acrylamide-2-methylpropanesulfonic acid sodium salt under a vacuum condition, fully contacting and mixing, and then drying the mixture (drying in a forced air drying oven at 80 ℃); fully contacting and mixing the dried mixture of the vinyl hydrogen-containing silicone oil and the surface of the grafted polypropylene with a sodium chloride aqueous solution, and then drying the mixture (drying in a forced air drying oven at 80 ℃); subjecting the dried mixture to microwave (power 1000W) for 3min under nitrogen atmosphere; soaking the microwave-finished material in deionized water for 10 minutes, replacing the deionized water, repeating for 3 times to ensure that vinyl hydrogen-containing silicone oil monomers and sodium chloride which do not participate in the grafting reaction are removed, and then placing the material in a forced air drying oven at 80 ℃ for drying; to obtain the super-wetting surface grafted with the 2-acrylamide-2-methyl sodium propanesulfonate and the vinyl hydrogen-containing silicone oil side group. The water and oil contact angles and surface grafting ratio data of the obtained super-wet surface are shown in table 1.
Example 6:
2-acrylamido-2-methylpropanesulfonic acid (10 parts by mass) was dissolved in acetone (50 parts by mass) to obtain an acetone solution of 2-acrylamido-2-methylpropanesulfonic acid based on 100 parts by mass of the polypropylene surface (same as in example 5); dissolving potassium hydroxide (6 parts by mass) in deionized water (50 parts by mass) to obtain a potassium hydroxide aqueous solution; adding the 2-acrylamide-2-methylpropanesulfonic acid acetone solution onto the surface of polypropylene under vacuum condition, fully contacting and mixing, and then drying the mixture (drying in a forced air drying oven at 80 ℃). Microwave (power 1000W) the dried mixture of 2-acrylamide-2-methylpropanesulfonic acid and the polypropylene surface for 3min in the atmosphere of nitrogen; soaking the microwave-finished product in deionized water for 10 minutes, replacing the deionized water, repeating for 3 times to ensure that 2-acrylamide-2-methylpropanesulfonic acid monomers which do not participate in the grafting reaction are removed, and then placing the product in a forced air drying oven at 80 ℃ for drying to obtain a dried 2-acrylamide-2-methylpropanesulfonic acid grafted polypropylene surface; adding a potassium hydroxide aqueous solution to the surface of the dried 2-acrylamide-2-methylpropanesulfonic acid grafted polypropylene under a vacuum condition, fully contacting and mixing, and mixing and reacting for 5 minutes after the potassium hydroxide aqueous solution is added. After the reaction is finished, the reaction product is cleaned by deionized water according to the above cleaning steps and then is placed in an air-blast drying oven at the temperature of 80 ℃ for drying, and the super-wetting surface grafted with the 2-acrylamide-2-methylpropanesulfonic acid potassium lateral group is obtained. The water and oil contact angles and surface grafting ratio data of the obtained super-wet surface are shown in table 1.
Example 7:
methacrylic acid (10 parts by mass) was dissolved in acetone (50 parts by mass) to obtain an acetone-methacrylic acid solution per 100 parts by mass of the polypropylene surface (same as in example 5); dissolving calcium hydroxide (8 parts by mass) in deionized water (50 parts by mass) to obtain a calcium hydroxide aqueous solution; the acetone methacrylate solution was added to the polypropylene surface under vacuum conditions for thorough contact mixing, after which the mixture was dried (80 ℃ forced air drying oven drying). Microwave (power 2000W) the dried mixture of methacrylic acid and polypropylene surface for 1min in nitrogen atmosphere; soaking the microwave-finished product in deionized water for 10 minutes, replacing the deionized water, repeating for 3 times to ensure that methacrylic acid monomers which do not participate in the grafting reaction are removed, and then placing the product in a forced air drying oven at 80 ℃ for drying to obtain a dried methacrylic acid grafted polypropylene surface; and adding a calcium hydroxide aqueous solution to the surface of the dried methacrylic acid grafted polypropylene under a vacuum condition, fully contacting and mixing, and mixing and reacting for 5 minutes after the calcium hydroxide aqueous solution is added. And after the reaction is finished, washing the reaction product by using deionized water according to the above washing step, and then placing the reaction product in a forced air drying oven at 80 ℃ for drying to obtain the polypropylene surface grafted with the calcium methacrylate.
Dissolving divinyl silicone oil (8 parts by mass) in ethanol (50 parts by mass) to obtain a divinyl silicone oil ethanol solution based on 100 parts by mass of the polypropylene surface; dissolving sodium chloride (6 parts by mass) in deionized water (50 parts by mass) to obtain a sodium chloride aqueous solution; adding a divinyl silicone oil ethanol solution onto the surface of the polypropylene grafted with the potassium methacrylate under a vacuum condition, fully contacting and mixing, and then drying the mixture (drying in a forced air drying oven at 80 ℃); fully contacting and mixing the dried mixture of divinyl silicon oil and the surface of the grafted polypropylene with a sodium chloride aqueous solution, and then drying the mixture (drying in a forced air drying oven at the temperature of 80 ℃); subjecting the dried mixture to microwave (power 2000W) for 1min under nitrogen atmosphere; soaking the microwave-finished material in deionized water for 10 minutes, replacing the deionized water, repeating for 3 times to ensure that the divinyl silicon oil monomer and sodium chloride which do not participate in the grafting reaction are removed, and then placing the material in a forced air drying oven at 80 ℃ for drying; obtaining the polypropylene super-wetting surface grafted with the calcium methacrylate and the divinyl silicone oil side group. The water and oil contact angles and surface grafting ratio data of the obtained super-wet surface are shown in table 1.
Example 8:
methacrylic acid (10 parts by mass) was dissolved in acetone (50 parts by mass) to obtain an acetone-methacrylic acid solution per 100 parts by mass of the polypropylene surface (same as in example 5); dissolving calcium hydroxide (8 parts by mass) in deionized water (50 parts by mass) to obtain a calcium hydroxide aqueous solution; the acetone methacrylate solution was added to the polypropylene surface under vacuum conditions for thorough contact mixing, after which the mixture was dried (80 ℃ forced air drying oven drying). Microwave (power 2000W) the dried mixture of methacrylic acid and polypropylene surface for 1min in nitrogen atmosphere; soaking the microwave-finished product in deionized water for 10 minutes, replacing the deionized water, repeating for 3 times to ensure that methacrylic acid monomers which do not participate in the grafting reaction are removed, and then placing the product in a forced air drying oven at 80 ℃ for drying to obtain a dried methacrylic acid grafted polypropylene surface; and adding a calcium hydroxide aqueous solution to the surface of the dried methacrylic acid grafted polypropylene under a vacuum condition, fully contacting and mixing, adding the calcium hydroxide aqueous solution, mixing again and reacting for 5 minutes. And after the reaction is finished, washing the reaction product by using deionized water according to the above washing step, and then placing the reaction product in an air-blast drying oven at 80 ℃ for drying to obtain the polypropylene super-wetting surface grafted with the calcium methacrylate side group. The water and oil contact angles and surface grafting ratio data of the obtained super-wet surface are shown in table 1.
Comparative example 2:
the polypropylene surface (same as example 5) was directly tested, and the contact angles of water and oil on the polypropylene surface are shown in Table 1.
Example 9:
dissolving methacrylic acid (6 parts by mass) in acetone (50 parts by mass) to obtain an acetone-methacrylic acid solution per 100 parts by mass of the polypropylene surface (surface 3); the acetone methacrylate solution was added to the polypropylene surface under vacuum conditions for thorough contact mixing, after which the mixture was dried (80 ℃ forced air drying oven drying). Microwave (power 500W) the dried mixture of methacrylic acid and polypropylene surface for 30min in nitrogen atmosphere; and soaking the microwave-finished product in deionized water for 10 minutes, replacing the deionized water, repeating for 3 times to ensure that methacrylic acid monomers which do not participate in the grafting reaction are removed, and then placing the product in a forced air drying oven at 80 ℃ for drying to obtain a dried methacrylic acid grafted polypropylene surface.
Dissolving divinyl silicone oil (10 parts by mass) in ethanol (50 parts by mass) to obtain a divinyl silicone oil ethanol solution based on 100 parts by mass of the polypropylene surface; dissolving sodium chloride (6 parts by mass) in deionized water (50 parts by mass) to obtain a sodium chloride aqueous solution; adding a divinyl silicone oil ethanol solution onto the surface of the methacrylic acid grafted polypropylene under a vacuum condition, fully contacting and mixing, and then drying the mixture (drying in a forced air drying oven at 80 ℃); fully contacting and mixing the dried mixture of divinyl silicon oil and the grafted polypropylene surface with a sodium chloride aqueous solution, and then drying the mixture (drying by a forced air drying oven at the temperature of 80 ℃); subjecting the dried mixture to microwave (power 500W) for 30min under nitrogen atmosphere; soaking the microwave-finished material in deionized water for 10 minutes, replacing the deionized water, repeating for 3 times to ensure that the divinyl silicon oil monomer and sodium chloride which do not participate in the grafting reaction are removed, and then placing the material in a forced air drying oven at 80 ℃ for drying; obtaining the polypropylene super-wetting surface grafted with methacrylic acid and divinyl silicone oil. The water and oil contact angles and surface grafting ratio data of the obtained super-wet surface are shown in table 1.
Example 10:
methacrylic acid (1 part by mass) was dissolved in acetone (50 parts by mass) to obtain an acetone-methacrylic acid solution per 100 parts by mass of the polypropylene surface (same as in example 9); the acetone methacrylate solution was added to the polypropylene surface under vacuum conditions for thorough contact mixing, after which the mixture was dried (80 ℃ forced air drying oven drying). Microwave (power 500W) the dried mixture of methacrylic acid and polypropylene surface for 30min in nitrogen atmosphere; and soaking the microwave-finished product in deionized water for 10 minutes, replacing the deionized water, repeating for 3 times to ensure that methacrylic acid monomers which do not participate in the grafting reaction are removed, and then placing the product in a forced air drying oven at 80 ℃ for drying to obtain a dried methacrylic acid grafted polypropylene surface.
Dissolving 2 parts by mass of methyl vinyl silicone oil in 50 parts by mass of ethanol based on 100 parts by mass of the polypropylene surface to obtain a methyl vinyl silicone oil ethanol solution; dissolving Graphene Oxide (GO) aqueous solution (10 parts by mass) and ascorbic acid (1 part by mass) in deionized water (50 parts by mass) to obtain Graphene Oxide (GO) dispersion liquid; adding a methyl vinyl silicone oil ethanol solution onto the surface of the methacrylic acid grafted polypropylene under a vacuum condition, fully contacting and mixing, and then drying the mixture (drying in a forced air drying oven at 80 ℃); fully contacting and mixing dried powder of a mixture of methyl vinyl silicone oil and a grafted polypropylene surface with a Graphene Oxide (GO) dispersion liquid, and then drying the mixture (drying in an air-blast drying oven at 80 ℃), wherein graphene oxide, ascorbic acid and deionized water are mixed to form the graphene oxide dispersion liquid, the graphene oxide dispersion liquid is mixed with the mixture of the methyl vinyl silicone oil and the grafted polypropylene surface, and when drying and drying at 80 ℃, ascorbic acid is used as a reducing agent of the graphene oxide to reduce the graphene oxide into graphene, and the graphene is a microwave absorption medium for subsequent microwave irradiation grafting; subjecting the dried mixture to microwave (power 500W) for 30min under nitrogen atmosphere; soaking the microwave-finished material in deionized water for 10 minutes, replacing the deionized water, repeating for 3 times to ensure that methyl vinyl silicone oil monomers and graphene oxide which do not participate in the grafting reaction are removed, and then placing the material in an air-blast drying oven at 80 ℃ for drying; obtaining the polypropylene super-wetting surface grafted with methacrylic acid and methyl vinyl silicone oil side groups. The water and oil contact angles and surface grafting ratio data of the obtained super-wet surface are shown in table 1.
Example 11:
methacrylic acid (7 parts by mass) was dissolved in acetone (50 parts by mass) to obtain an acetone-methacrylic acid solution per 100 parts by mass of the polypropylene surface (same as in example 9); the acetone methacrylate solution was added to the polypropylene surface under vacuum conditions for thorough contact mixing, after which the mixture was dried (80 ℃ forced air drying oven drying). Microwave (power 500W) the dried mixture of methacrylic acid and polypropylene surface for 30min in nitrogen atmosphere; and soaking the microwave-finished product in deionized water for 10 minutes, replacing the deionized water, repeating for 3 times to ensure that methacrylic acid monomers which do not participate in the grafting reaction are removed, and then placing the product in a forced air drying oven at 80 ℃ for drying to obtain a dried methacrylic acid grafted polypropylene surface.
Dissolving methyl vinyl silicone oil (8 parts by mass) in ethanol (50 parts by mass) to obtain a methyl vinyl silicone oil ethanol solution, wherein the mass of the methyl vinyl silicone oil is 100 parts by mass of the surface of the polypropylene; dissolving Graphene Oxide (GO) aqueous solution (3 parts by mass) and ascorbic acid (0.3 part by mass) in deionized water (50 parts by mass) to obtain Graphene Oxide (GO) dispersion liquid; adding a methyl vinyl silicone oil ethanol solution onto the surface of the methacrylic acid grafted polypropylene under a vacuum condition, fully contacting and mixing, and then drying the mixture (drying in a forced air drying oven at 80 ℃); fully contacting and mixing a mixture of dried methyl vinyl silicone oil and the surface of grafted polypropylene with a Graphene Oxide (GO) dispersion liquid, and then drying the mixture (drying in an air-blast drying oven at 80 ℃), wherein graphene oxide, ascorbic acid and deionized water are mixed to form the graphene oxide dispersion liquid, the graphene oxide dispersion liquid is mixed with the mixture of the methyl vinyl silicone oil and the surface of the grafted polypropylene, and when drying and drying at 80 ℃, ascorbic acid is used as a reducing agent of the graphene oxide to reduce the graphene oxide into graphene, and the graphene is a microwave absorption medium grafted by subsequent microwave irradiation; subjecting the dried mixture to microwave (power 500W) for 30min under nitrogen atmosphere; soaking the microwave-finished material in deionized water for 10 minutes, replacing the deionized water, repeating for 3 times to ensure that methyl vinyl silicone oil monomers and graphene oxide which do not participate in the grafting reaction are removed, and then placing the material in an air-blast drying oven at 80 ℃ for drying; obtaining the polypropylene super-wetting surface grafted with methacrylic acid and methyl vinyl silicone oil. The water and oil contact angle data for the resulting super-wetted surfaces are shown in table 1.
Example 12:
vinyl trimethoxy silane (9 parts by mass) was dissolved in ethanol (50 parts by mass) to obtain a vinyl trimethoxy silane ethanol solution, based on 100 parts by mass of the polypropylene surface (same as in example 9); dissolving sodium chloride (3 parts by mass) in deionized water (50 parts by mass) to obtain a sodium chloride aqueous solution; adding vinyl trimethoxy silane ethanol solution on the surface of the polypropylene under vacuum condition, fully contacting and mixing, and then drying the mixture (drying in a forced air drying oven at 80 ℃). Fully contacting and mixing the dried mixture of the vinyltrimethoxysilane and the polypropylene surface with a sodium chloride aqueous solution, and then drying the mixture (drying in a forced air drying oven at 80 ℃); performing microwave (power 500W) on the dried mixture of the vinyltrimethoxysilane and the polypropylene surface for 30min in the atmosphere of nitrogen; and soaking the product subjected to microwave treatment in deionized water for 10 minutes, replacing the deionized water, repeating for 3 times to ensure that vinyl trimethoxy silane monomers and sodium chloride which do not participate in the grafting reaction are removed, and then placing the product in a blowing drying oven at the temperature of 80 ℃ for drying to obtain a dried vinyl trimethoxy silane grafted polypropylene surface.
Dissolving styrene (8 parts by mass) in ethanol (50 parts by mass) to obtain a styrene ethanol solution, based on 100 parts by mass of the surface of the polypropylene; dissolving Graphene Oxide (GO) aqueous solution (4 parts by mass) and ascorbic acid (0.4 part by mass) in deionized water (50 parts by mass) to obtain Graphene Oxide (GO) dispersion liquid; adding a styrene ethanol solution on the surface of the styrene grafted polypropylene under a vacuum condition, fully contacting and mixing, and then drying the mixture (drying in a forced air drying oven at 80 ℃); fully contacting and mixing dried powder of a mixture on the surfaces of styrene and grafted polypropylene with a Graphene Oxide (GO) dispersion liquid, and then drying the mixture (drying in a forced air drying oven at 80 ℃), wherein graphene oxide, ascorbic acid and deionized water are mixed to form the graphene oxide dispersion liquid, the graphene oxide dispersion liquid is mixed with the mixture on the surfaces of styrene and grafted polypropylene, and when the mixture is dried and dried at 80 ℃, the ascorbic acid is used as a reducing agent of the graphene oxide to reduce the graphene oxide into graphene, and the graphene is a microwave absorption medium for subsequent microwave irradiation grafting; subjecting the dried mixture to microwave (power 500W) for 30min under nitrogen atmosphere; soaking the microwave-finished material in deionized water for 10 minutes, replacing the deionized water, repeating for 3 times to ensure that styrene monomers and graphene oxide which do not participate in the grafting reaction are removed, and then placing the material in a forced air drying oven at 80 ℃ for drying; obtaining the amphiphilic polypropylene surface grafted with vinyl trimethoxy silane and styrene. The water and oil contact angles and surface grafting rate data of the obtained amphiphilic polypropylene surface are shown in the table 1.
Comparative example 3:
the polypropylene surface (same as example 9) was directly tested, and the contact angles of water and oil on the polypropylene surface are shown in Table 1.
TABLE 1
Figure BDA0002178111820000241
It can be seen from the examples in table 1 that, after the hydrophilic and oleophilic grafting modification is performed on the polypropylene surface by the invention, compared with the pure polypropylene surface, the water and oil fluxes are greatly improved, the modified polypropylene surface is both super-hydrophilic and oleophilic, and even the modified polypropylene surface reaches super-hydrophilic and super-oleophilic, which indicates that the amphiphilic modification of the polypropylene surface is very effective.

Claims (30)

1. A super-wetting surface is a polypropylene surface with a micro-nano structure, and a lipophilic side group and a hydrophilic side group are grafted on the polypropylene surface at the same time; the super-wetted surface is free of initiator residues;
the hydrophilic side group is a monomer side group containing heteroatoms selected from oxygen, sulfur, nitrogen, silicon, halogen or a combination thereof and containing a carbon-carbon double bond; the lipophilic side group is at least one of vinyl silicone oil side group and styrene side group.
2. A super-wettable surface according to claim 1, wherein:
the hydrophilic side group is a side group of at least one monomer of organic acid containing carbon-carbon double bonds, derivatives of organic acid containing carbon-carbon double bonds and vinyl silane; the organic acid derivative includes at least one of anhydride, ester and salt of organic acid.
3. The super-wetted surface of claim 1, wherein:
the monomer of the hydrophilic side group comprises at least one of maleic anhydride, maleic anhydride derivatives, (meth) acrylic acid derivatives, vinyl acetate, alkenyl sulfonic acid and derivatives thereof, p-styrene formic acid, p-styrene acetic acid, itaconic acid, oleic acid, arachidic acid and combinations thereof and salified forms thereof, and vinyl silane;
the vinyl silane is one or more of compounds shown in a formula (1):
CH2=CH2(CH2)nSiX3formula (1)
Wherein n = 0-3, and X is at least one of a chloro group, a methoxy group, an ethoxy group and an acetoxy group.
4. The super-wetted surface of claim 1, wherein:
the vinyl silicone oil is at least one of terminal vinyl silicone oil and high vinyl silicone oil.
5. The super-wetted surface of claim 4, wherein:
the vinyl silicone oil is at least one of methyl vinyl silicone oil, vinyl hydrogen-containing silicone oil and divinyl silicone oil.
6. A super-wettable surface according to any one of claims 1 to 5, wherein:
the super-wetting surface is obtained by carrying out grafting reaction on components including the monomer of the hydrophilic side group and the monomer of the lipophilic side group and the polypropylene surface by using microwave irradiation under the condition of not adding a grafting initiator; wherein inorganic microwave absorbing medium is also added;
or when the monomer of the hydrophilic side group in the method is at least one of organic acid or anhydride or ester thereof, the super-wetting surface is prepared by the method and comprises the step of reacting the product obtained after the grafting reaction with alkali.
7. The method of preparing a super-wetted surface as claimed in any one of claims 1 to 6, comprising:
carrying out grafting reaction on components including the monomer of the hydrophilic side group and the monomer of the lipophilic side group and the polypropylene surface by using microwave irradiation under the condition of not adding a grafting initiator to obtain the super-wetting surface; wherein inorganic microwave absorbing medium is also added;
or when the monomer of the hydrophilic side group in the above method is at least one of organic acid or anhydride or ester thereof, the method comprises the step of reacting the product obtained after the grafting reaction with a base.
8. The method of claim 7, characterized by comprising any one of the following schemes:
the first scheme comprises the steps of mixing the polypropylene surface with the hydrophilic side-group monomer and/or a solution of the hydrophilic side-group monomer dissolved in a solvent, a solution of the lipophilic side-group monomer dissolved in a solvent and an inorganic microwave absorbing medium in a contact manner; then the obtained mixture is grafted by microwave irradiation under the condition of not adding a grafting initiator;
the second scheme comprises the steps of contacting and mixing the polypropylene surface with the hydrophilic side group monomer and/or a solution of the hydrophilic side group monomer dissolved in a solvent, wherein an inorganic microwave absorbing medium is optionally added; then the obtained mixture is grafted by microwave irradiation under the condition of not adding a grafting initiator; then mixing the obtained grafting product with the lipophilic side group monomer and/or the solution of the lipophilic side group monomer dissolved in the solvent and an inorganic microwave absorption medium, and grafting by microwave irradiation under the condition of not adding a grafting initiator;
contacting and mixing the polypropylene surface with the lipophilic side-group monomer and/or a solution of the lipophilic side-group monomer dissolved in a solvent and an inorganic microwave absorbing medium, and then grafting the obtained mixture by microwave irradiation without adding a grafting initiator; then mixing the obtained grafting product with the hydrophilic side group monomer and/or a solution of the hydrophilic side group monomer dissolved in a solvent, and grafting by microwave irradiation under the condition of not adding a grafting initiator;
and fourthly, on the basis of any one of the three schemes, when the monomer of the hydrophilic side group is at least one of organic acid or anhydride or ester thereof, the method further comprises the step of contacting and mixing the polypropylene surface grafted with the at least one side group of the organic acid or anhydride or ester thereof with an aqueous solution of alkali and/or alkali.
9. The production method according to claim 7 or 8, characterized in that:
the hydrophilic side group monomer is a monomer containing heteroatoms selected from oxygen, sulfur, nitrogen, silicon, halogen or a combination thereof and containing a carbon-carbon double bond; and/or the presence of a gas in the gas,
the monomer dosage of the hydrophilic side group is 0.1-10 wt% of the polypropylene surface dosage; and/or the presence of a gas in the gas,
the weight ratio of the monomer to the solvent in the monomer solution of the hydrophilic side group is (0.1-100): 100; and/or the presence of a gas in the gas,
the solvent for dissolving the hydrophilic side group monomer is at least one of water and an organic solvent.
10. The method of claim 9, wherein:
the hydrophilic side group monomer is at least one of organic acid, organic acid derivative and vinyl silane; and/or the presence of a gas in the gas,
the monomer dosage of the hydrophilic side group is 1-8 wt% of the polypropylene surface dosage; and/or the presence of a gas in the gas,
the weight ratio of the monomer to the solvent in the monomer solution of the hydrophilic side group is (0.5-50): 100; and/or the presence of a gas in the gas,
the solvent for dissolving the hydrophilic side group monomer comprises at least one of alcohol, ketone, ester and water.
11. The method of manufacturing according to claim 10, wherein:
the organic acid or derivative of the organic acid is selected from the group consisting of maleic anhydride, maleic anhydride derivatives, (meth) acrylic acid derivatives, vinyl acetate, alkenyl sulfonic acids and derivatives thereof, p-styrene formic acid, p-styrene acetic acid, itaconic acid, oleic acid, arachidic acid, and combinations thereof, and salified forms thereof; and/or the presence of a gas in the gas,
the weight ratio of the monomer to the solvent in the monomer solution of the hydrophilic side group is (1-30): 100; and/or the presence of a gas in the gas,
the solvent for dissolving the hydrophilic side group monomer comprises acetone or ethanol.
12. The production method according to claim 7 or 8, characterized in that:
the monomer of the lipophilic side group comprises at least one of vinyl silicone oil and styrene; and/or the presence of a gas in the gas,
the dosage of the monomer of the lipophilic side group is 0.1-30 wt% of the dosage of the polypropylene surface; and/or the presence of a gas in the gas,
the weight ratio of the monomer to the solvent in the monomer solution of the lipophilic side group is (0.1-100): 100; and/or the presence of a gas in the gas,
the solvent for dissolving the lipophilic side group monomer is selected from at least one of organic solvents.
13. The method of manufacturing according to claim 12, wherein:
the vinyl silicone oil is at least one of terminal vinyl silicone oil and high vinyl silicone oil; and/or the presence of a gas in the gas,
the monomer dosage of the lipophilic side group is 1-20 wt% of the polypropylene surface dosage; and/or the presence of a gas in the gas,
the weight ratio of the monomer to the solvent in the monomer solution of the lipophilic side group is (0.5-50): 100; and/or the presence of a gas in the gas,
the solvent for dissolving the lipophilic side group monomer comprises at least one of alcohol, ketone and ester.
14. The method of manufacturing according to claim 12, wherein:
the vinyl silicone oil is at least one of methyl vinyl silicone oil, vinyl hydrogen-containing silicone oil and divinyl silicone oil; and/or the presence of a gas in the gas,
the weight ratio of the monomer to the solvent in the monomer solution of the lipophilic side group is (1-30): 100; and/or the presence of a gas in the gas,
the solvent for dissolving the lipophilic side group monomer is selected from acetone or ethanol.
15. The production method according to claim 7 or 8, characterized in that:
the base is a hydroxide; and/or the presence of a gas in the gas,
the weight ratio of the alkali to the water in the alkali water solution is (0.1-100): 100.
16. The method of claim 15, wherein:
the hydroxide is at least one of metal hydroxide and ammonia water; and/or the presence of a gas in the gas,
the amount of the hydroxide is 0.1-10 wt% of the amount of the polypropylene surface; and/or the presence of a gas in the gas,
the weight ratio of the alkali to the water in the alkali water solution is (0.5-50): 100.
17. The method of manufacturing according to claim 16, wherein:
the metal hydroxide is one or more of sodium hydroxide, potassium hydroxide, barium hydroxide, lithium hydroxide, strontium hydroxide, calcium hydroxide, ferric hydroxide, ferrous hydroxide, zinc hydroxide, magnesium hydroxide, cobalt hydroxide, gold hydroxide, aluminum hydroxide, copper hydroxide, beryllium hydroxide and rare earth hydroxide; and/or the presence of a gas in the gas,
the amount of the hydroxide is 1-8 wt% of the amount of the polypropylene surface; and/or the presence of a gas in the gas,
the weight ratio of the alkali to the water in the alkali water solution is (1-30): 100.
18. The production method according to claim 7 or 8, characterized in that:
the inorganic microwave absorbing medium comprises at least one of metal hydroxide, metal salt, metal oxide, graphite material, ferroelectric material, electrolytic stone and chalcopyrite; and/or the presence of a gas in the gas,
the single dosage of the inorganic microwave absorbing medium is 0.1-10 wt% of the surface dosage of the polypropylene; and/or the presence of a gas in the gas,
the inorganic microwave absorbing medium is added directly or dissolved or dispersed in a solvent to obtain an inorganic microwave absorbing medium solution or dispersion.
19. The method of claim 18, wherein:
the single dosage of the inorganic microwave absorbing medium is 1-8 wt% of the surface dosage of the polypropylene.
20. The method of claim 18, wherein:
the weight ratio of the solvent to the inorganic microwave absorbing medium in the inorganic microwave absorbing medium solution or dispersion liquid is (0.1-100): 100; and/or the presence of a gas in the gas,
the solvent in the inorganic microwave absorbing medium solution or dispersion is at least one selected from water and organic solvent; and/or the presence of a gas in the gas,
the inorganic microwave absorbing medium dispersion liquid contains a surfactant.
21. The method of claim 20, wherein:
the weight ratio of the solvent to the inorganic microwave absorbing medium in the inorganic microwave absorbing medium solution or dispersion liquid is (0.5-50): 100; and/or the presence of a gas in the gas,
the solvent in the inorganic microwave absorbing medium solution or dispersion comprises at least one of alcohol, ketone, ester and water.
22. The method of claim 20, wherein:
the weight ratio of the solvent to the inorganic microwave absorbing medium in the inorganic microwave absorbing medium solution or dispersion liquid is (1-30): 100; and/or the presence of a gas in the gas,
the solvent in the inorganic microwave absorbing medium solution or dispersion is selected from alcohol and water.
23. The method of claim 18, wherein:
the metal hydroxide is at least one of potassium hydroxide, barium hydroxide, sodium hydroxide, lithium hydroxide, strontium hydroxide, calcium hydroxide, ferric hydroxide, ferrous hydroxide, zinc hydroxide, magnesium hydroxide, cobalt hydroxide, gold hydroxide, aluminum hydroxide, copper hydroxide, beryllium hydroxide and rare earth hydroxide; the metal salt is selected from at least one of 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, aluminum chloride, manganese chloride, zinc chloride, ferric chloride, ferrous chloride, copper chloride, ammonium sulfate, potassium sulfate, sodium sulfate, magnesium sulfate, aluminum sulfate, manganese sulfate, zinc sulfate, ferric sulfate, ferrous sulfate, copper sulfate, silver sulfate, ammonium carbonate, potassium carbonate, sodium carbonate, magnesium carbonate, calcium carbonate, barium carbonate, potassium dihydrogen phosphate, barium titanate, strontium titanate, and copper calcium titanate; the metal oxide is at least one selected from ferric oxide and ferroferric oxide; the graphite material is selected from at least one of carbon black, graphite powder, graphene, carbon nano tubes and activated carbon.
24. The production method according to claim 7 or 8, characterized in that:
the microwave irradiation is carried out in an inert gas atmosphere; and/or the presence of a gas in the gas,
the irradiation power of the microwave irradiation is 100 w-2000 w; the radiation time is 1 s-120 min; and/or the presence of a gas in the gas,
and drying the mixture before microwave irradiation.
25. The method of claim 24, wherein:
the irradiation power of the microwave irradiation is 500 w-1000 w; and/or the radiation time is 1 min-30 min.
26. The production method according to claim 7 or 8, characterized in that:
at least one time of mixing the components is thorough mixing under vacuum conditions.
27. The production method according to claim 7 or 8, characterized in that:
washing the product after microwave irradiation grafting by using a solvent; and/or the presence of a gas in the gas,
washing a product obtained after the reaction of the grafting reaction product and alkali by using a solvent;
after the above-mentioned washing or also including drying;
the cleaning solvent is at least one selected from water and organic solvents.
28. The method of manufacturing according to claim 27, wherein:
the cleaning solvent is at least one selected from alcohol, ketone, ester and water.
29. A super-wetted surface prepared according to the method of any one of claims 7 to 28.
30. Use of a super-wettable surface according to any one of claims 1 to 7 or claim 29 in the field of bonding, spraying.
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