CN109679129B - Method for modifying surface of polyolefin material - Google Patents
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J7/12—Chemical modification
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C08J7/16—Chemical modification with polymerisable compounds
- C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
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- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
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- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
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- 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
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- 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
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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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
- 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
Abstract
The invention relates to a method for modifying the surface of a polyolefin material, which comprises the following steps: (a) carrying out surface chlorination reaction on the polyolefin material in a chlorine-containing solution to obtain a chlorinated polyolefin material; (b) and immersing the chlorinated polyolefin material into a grafting reaction solution, and carrying out photocatalysis-atom transfer radical reaction under the action of light irradiation. The surface modification of the polyolefin material can be realized by carrying out surface chlorination reaction and photocatalysis-atom transfer radical reaction, the surface of the polyolefin material is not deeply damaged, the reaction temperature can be reduced to room temperature, and the grafting time is greatly shortened; and the polyolefin material surface functionalization treatment is uniform, and corresponding functional groups can be obtained on the surface of the polyolefin material according to requirements.
Description
Technical Field
The invention belongs to the field of material surface modification, relates to a method for modifying the surface of a polyolefin material, and particularly relates to a surface treatment method of polyethylene, polypropylene and a copolymer thereof based on a photocatalysis-ATPR grafting technology.
Background
Polyethylene, polypropylene and copolymers thereof are important general-purpose thermoplastics and are widely used for their good mechanical properties, processability, corrosion resistance, electrical insulation and the like. The thermoplastic polyolefin material can be conveniently formed by adopting the processes of extrusion, blow molding, injection molding, tape casting, stretching and the like to prepare various product forms such as molding materials, pipes, films, fibers, porous separation films and the like. Because the polyolefin consists of inert methylene and methyl and has certain crystallinity, the surface of the polyolefin is lack of active groups and has low surface energy, so that the surface of the polyolefin has poor wettability and adhesiveness, and the application of the polyolefin material in the fields of water environment, surface coating, surface adhesion, composite materials and the like is limited, therefore, the chemical grafting modification of the surface of the polyolefin material has important significance and wide application prospect.
The existing surface modification method mainly comprises chemical oxidation, plasma treatment, corona discharge treatment, surface grafting treatment and the like. Although the method of chemical oxidation, plasma treatment, corona discharge treatment and the like can effectively introduce micromolecular polar groups on the surface of the polyolefin material, the polar groups are unstable, the modified surface performance has timeliness, and the surface polarity is easy to lose under the action of air oxidation or thermal motion of molecular chains. The surface grafting method can introduce polar polymer with high molecular weight on the surface of polyolefin material, and the modified surface has good durability, but the traditional polyolefin surface grafting method has the defects of low grafting efficiency, high reaction temperature, long reaction time and the like, so that the application of the method is limited, ZL201610587498.5 provides a method for modifying ultra-high polyethylene fibers by using an ARTP technology, but the method has high polymerization temperature, volatile solvent, long grafting time and no continuous production and use, so that the development of an ARTP surface modification technology which not only can carry out normal-temperature polymerization, but also can shorten the grafting time is required.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for modifying the surface of a polyolefin material based on a photocatalysis-ATPR grafting technology.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for modifying the surface of a polyolefin material, comprising the steps of:
(a) carrying out surface chlorination reaction on the polyolefin material in a chlorine-containing solution to obtain a chlorinated polyolefin material;
(b) and immersing the chlorinated polyolefin material into a grafting reaction solution, and carrying out photocatalysis-atom transfer radical reaction under the action of light irradiation.
Optimally, in the step (a), the chlorine-containing solution comprises the following components in parts by weight:
90-95 parts of deionized water;
5-10 parts of sodium hypochlorite;
0.5-1 part of sodium bicarbonate.
Further, in the step (a), the surface chlorination reaction conditions are as follows: the temperature of the chlorine-containing solution is 30-40 ℃ and the UV light irradiates for 5-20 min.
Further, in the step (a), the surface chlorination degree of the chlorinated polyolefin material is 30-50%.
Optimally, in the step (b), the grafting reaction solution comprises the following components in parts by weight:
100 parts of a grafting monomer, wherein the grafting monomer is a propylene derivative monomer or/and a styrene derivative monomer;
0.1-0.2 part of a reducing agent, wherein the reducing agent is organic amine;
0.001-0.003 part of photocatalyst, wherein the photocatalyst is a transition metal complex.
Further, in the step (b), the light irradiation is performed under the conditions of: 400-500 nm monochromatic light or waveband light source, radiation intensity of 0.3-0.7W/m2And reacting for 2-10 min at normal temperature.
Further, the grafting monomer is a mixture of one or more selected from hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) acrylic acid, glycidyl (meth) acrylate, acrylamide, p-carboxystyrene and p-hydroxystyrene.
Further, the reducing agent is a mixture consisting of one or more selected from tri-n-propylamine, triethylamine, triethanolamine, pentamethyldiethyltriamine, diethylacetamide and diethylenetriamine.
Further, the photocatalyst is a complex formed by transition metal ruthenium, iridium or/and osmium and one or more of ligand bipyridine, bipyridyl, dinitrile pyridine, bipyridine, trimethylpyridine, terpyridyl and dinitrile pyridine.
Preferably, in the step (b), the photocatalytic-atom transfer radical reaction is further followed by cleaning and drying.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: according to the method for modifying the surface of the polyolefin material, the surface of the polyolefin material can be modified by carrying out surface chlorination reaction and photocatalysis-atom transfer radical reaction, the surface of the polyolefin material is not deeply damaged, the reaction temperature can be reduced to room temperature, and the grafting time is greatly shortened; and the polyolefin material surface functionalization treatment is uniform, and corresponding functional groups can be obtained on the surface of the polyolefin material according to requirements.
Drawings
FIG. 1 is a schematic diagram of the photocatalytic-atom transfer radical reaction of the present invention.
Detailed Description
The method for modifying the surface of the polyolefin material comprises the following steps: (a) carrying out surface chlorination reaction on the polyolefin material in a chlorine-containing solution to obtain a chlorinated polyolefin material; (b) and immersing the chlorinated polyolefin material into a grafting reaction solution, and carrying out photocatalysis-atom transfer radical reaction under the action of light irradiation. The surface modification of the polyolefin material can be realized by carrying out surface chlorination reaction and photocatalysis-atom transfer radical reaction, the surface of the polyolefin material is not deeply damaged, the reaction temperature can be reduced to room temperature, and the grafting time is greatly shortened; the polyolefin material surface functionalization treatment is uniform, and corresponding functions can be obtained on the polyolefin material surface according to requirementsAn energy group. Atom Transfer Radical Polymerization (ATRP) is divided into three stages, initiation, propagation and termination. And (3) an initiation stage: transition metal ion Ru of initiator R-Cl in low valence stateIICatalytic elimination of halogen Cl by/L (ligand) into radical R.IIthe/L will be oxidized to high valence RuIIIAnd L. After the monomer M is added, the free radical R-C reacts with the monomer to form a free radical R-M, which can continue to react with the monomer to form a long-chain free radical R-MnCompletion of propagation and also formation of inactive dormant species R-M by abstraction of a halogen atomnX to terminate the reaction. Because the concentration of active free radicals is controlled by the low-valence transition metal catalyst, the concentration of R & lt- & gt is controlled in a lower range, and the reaction speed of the graft polymerization is greatly reduced although the termination of the coupling of the free radicals is prevented. In the present invention, the principle of the above-mentioned photocatalytic-ATRP grafting reaction is shown in FIG. 1: ru by metal-ligand charge transfer effect under excitation of lightIIthe/L (ligand) is excited to (Ru)II/L)*Simultaneous surface chlorinated polyethylene PE-Cl oxidation (Ru)II/L)*Formation of PE chain radicals R.and Cl-Corresponding to (Ru)II/L)*To a higher valence state RuIIIAnd L. After addition of the monomer M, the PE chain radical R is subjected to an ATPR grafting reaction with the monomer.
In step (a), the chlorine-containing solution preferably comprises the following components in parts by weight: 90-95 parts of deionized water, 5-10 parts of sodium hypochlorite and 0.5-1 part of sodium bicarbonate. Specifically, the conditions of the surface chlorination reaction are as follows: the temperature of the chlorine-containing solution is 30-40 ℃ and the chlorinated polyolefin material is irradiated by UV light for 5-20 min, so that the surface chlorination degree of the chlorinated polyolefin material is 30-50%. And the polyolefin material is conventional polyethylene, polypropylene, polyethylene-propylene copolymer and the like.
In the step (b), the grafting reaction solution comprises the following components in parts by weight: 100 parts of a grafting monomer, wherein the grafting monomer is a propylene derivative monomer or/and a styrene derivative monomer; 0.1-0.2 part of a reducing agent, wherein the reducing agent is organic amine; 0.001-0.003 part of photocatalyst, wherein the photocatalyst is a transition metal complex, and the content of the grafting reaction solution in the photocatalyst is very lowThe catalyst has a catalytic effect. Specifically, the conditions of the light irradiation are: 400-500 nm monochromatic light or waveband light source, radiation intensity of 0.3-0.7W/m2And reacting at normal temperature for 2-10 min (at the moment, the surface tension can reach 35-40 mN/m), and the reaction condition is simple and convenient for industrial production. The grafting monomer is one or more selected from hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, meth) acrylic acid, glycidyl (meth) acrylate, acrylamide, p-carboxystyrene and p-hydroxystyrene. The reducing agent is a mixture consisting of one or more of triethylamine, triethanolamine, pentamethyldiethyltriamine, diethylacetamide and diethylenetriamine. The photocatalyst is a complex formed by transition metal ruthenium, iridium or/and osmium and one or more of ligand bipyridine, bipyridine methyl, bipyridine carboxyl, bipyridine nitrile group, bipyridine triple, bipyridine trimethyl, terpyridine carboxyl pyridine and terpyridyl group; when the grafting monomer is hydroxypropyl methacrylate, the reducing agent is pentamethyl diethyl triamine and the photocatalyst is RuIIWhen the/dicarboxy pyridine complex is used, the polyolefin material surface modification has the advantages of high reaction speed, high grafting efficiency and high surface tension improvement, and the effect is best.
The invention is further described below with reference to the illustrated embodiments.
Example 1
This example provides a method for modifying the surface of polyolefin material, which comprises the following steps:
(a) immersing a commercially available polyethylene sheet into a sodium hypochlorite aqueous solution with the mass content of 10%, adding a small amount of sodium bicarbonate (0.5-1% of the mass content of the solution) to adjust the pH value of the aqueous solution to be 5.5-6, and performing UV illumination for 20min (the UV wavelength is 280-400 nm) at the temperature of 30-40 ℃ to perform chlorination treatment to obtain a chlorinated polyolefin material (the surface chlorination degree of the chlorinated polyolefin material is 30-50%);
(b) soaking a chlorinated polyolefin material (namely a polyethylene sheet with a chlorinated surface) in a grafting reaction solution to carry out photocatalysis-ATPR (atom transfer radical polymerization), wherein the grafting reaction solution contains: 100 parts of methyl propylHydroxyethyl enoate, 0.2 part of pentamethyldiethyltriamine and 0.002 part of ruthenium bipyridine complex, wherein the grafting reaction temperature is 30 ℃, and the grafting reaction is performed by irradiating an LED lamp with the wavelength of 410 nm: radiation intensity 0.6W/m2And (3) carrying out irradiation reaction for 5min, washing the polyethylene material subjected to the grafting reaction by deionized water, and drying by hot air at 80 ℃ to obtain a polyethylene sheet with hydroxyl on the surface, wherein the surface tension of the polyethylene sheet is improved to 40 +/-2 mN/m from about 31 mN/m.
Example 2
This example provides a method for modifying the surface of polyolefin material, which comprises the following steps:
(a) immersing a commercially available polypropylene biaxially-oriented film into a 5% sodium hypochlorite aqueous solution, adding a small amount of sodium bicarbonate (0.5-1% of the mass content of the solution) to adjust the pH value of the aqueous solution to 5.5-6, and performing UV (same as in example 1) illumination for 10min at 30-40 ℃ to perform chlorination treatment to obtain a chlorinated polyolefin material (the surface chlorination degree of the chlorinated polyolefin material is 30-50%);
(b) the chlorinated polyolefin material (namely the polypropylene biaxial stretching film with the chlorinated surface) is dipped in a grafting reaction solution for photocatalysis-ATPR grafting polymerization, and the grafting reaction water solution contains: 100 parts of hydroxyethyl methacrylate, 0.1 part of pentamethyldiethyltriamine and 0.001 part of ruthenium dicarboxylpyridine complex, wherein the grafting reaction temperature is 30 ℃, and a xenon lamp is adopted for irradiation: radiation intensity 0.5W/m2@340nm, irradiating for 3min, washing the polypropylene material after the grafting reaction by deionized water, and drying by hot air at 80 ℃ to obtain the polypropylene film with hydroxyl on the surface, wherein the surface tension of the polypropylene is improved from about 29mN/m to 42 +/-2 mN/m.
Example 3
This example provides a method for modifying the surface of polyolefin material, which comprises the following steps:
(a) immersing a commercially available polyethylene-propylene copolymer film into a sodium hypochlorite aqueous solution with the concentration of 8%, adding a small amount of sodium bicarbonate (0.5-1% of the mass content of the solution) to adjust the pH value of the aqueous solution to 5.5-6, and carrying out UV (same as that in example 1) illumination for 15min at the temperature of 30-40 ℃ to carry out chlorination treatment to obtain a chlorinated polyolefin material (the surface chlorination degree of the chlorinated polyolefin material is 30-50%);
(b) the chlorinated polyolefin material (namely the polyethylene-propylene copolymer film with chlorinated surface) is dipped in a grafting reaction solution for photocatalysis-ATPR grafting polymerization, and the grafting reaction aqueous solution contains: 100 parts of acrylamide, 0.2 part of triethanolamine and 0.0015 part of bitridyl pyridine iridium complex, wherein the grafting reaction temperature is room temperature, and a xenon lamp is adopted for irradiation: radiation intensity 0.5W/m2@340nm, irradiating for 3min, washing the polyethylene-propylene copolymer film after the grafting reaction by deionized water, and drying by hot air at 80 ℃ to obtain the polypropylene material with amino on the surface, wherein the surface tension of the polyethylene-propylene is improved to 40 +/-2 mN/m from about 30 mN/m.
Example 4
This example provides a method for modifying the surface of polyolefin material, which comprises the following steps:
(a) soaking a commercial ultrahigh molecular weight polyethylene fiber into a 5% sodium hypochlorite aqueous solution, adding a small amount of sodium bicarbonate (0.5-1% of the mass content of the solution) to adjust the pH value of the aqueous solution to 5.5-6, and performing UV (same as in example 1) illumination for 10min at 30-40 ℃ to perform chlorination treatment to obtain a chlorinated polyolefin material (the surface chlorination degree of the chlorinated polyolefin material is 30-50%);
(b) the chlorinated polyolefin material (i.e. high molecular weight polyethylene fiber with chlorinated surface) is dipped in a grafting reaction solution to carry out photocatalysis-ATPR grafting polymerization, and the grafting reaction aqueous solution contains: 100 parts of glycidyl methacrylate, 0.2 part of diethylenetriamine and 0.0015 part of ruthenium bis (carboxypyridine) complex, wherein the grafting reaction temperature is room temperature, and the grafting reaction is carried out by adopting a 410nm LED for irradiation: radiation intensity 0.5W/m2And irradiating for 3min, washing the ultra-high molecular weight polyethylene fiber subjected to the grafting reaction by deionized water, and drying by hot air at 55 ℃ to obtain the ultra-high molecular weight polyethylene fiber with ester groups on the surface, wherein the surface tension of the ultra-high molecular weight polyethylene fiber reaches 38 +/-3 mN/m.
Example 5
This example provides a method for modifying the surface of polyolefin material, which comprises the following steps:
(a) immersing a commercially available polyethylene microporous membrane into a 5% sodium hypochlorite aqueous solution, adding a small amount of sodium bicarbonate (0.5-1% of the mass content of the solution) to adjust the pH value of the aqueous solution to 5.5-6, and performing UV (same as in example 1) illumination for 10min at 30-40 ℃ to perform chlorination treatment to obtain a chlorinated polyolefin material (the surface chlorination degree of the chlorinated polyolefin material is 30-50%);
(b) the chlorinated polyolefin material (namely the polyethylene microporous membrane with the chlorinated surface) is soaked in a grafting reaction solution for photocatalysis-ATPR grafting polymerization, and the grafting reaction aqueous solution contains: 100 parts of hydroxyethyl methacrylate, 0.15 part of diethyl acetamide and 0.002 part of bis (methylpyridine) osmium complex, wherein the grafting reaction temperature is room temperature, and the grafting reaction is carried out by adopting an LED with the wavelength of 450 nm: radiation intensity 0.4W/m2Carrying out irradiation reaction for 10min, washing the polyethylene microporous membrane subjected to the grafting reaction by deionized water, and drying by hot air at 80 ℃ to obtain the polyethylene microporous membrane with hydroxyl on the surface; the pressure on both sides of the membrane is 0.2atm, the water flux before modification is 0, and the water flux after modification is 30 kg/h.m2The hydrophilic effect is obvious.
Comparative example 1
This example provides a comparative method for treating the surface of a polyolefin material, comprising the steps of:
(a) immersing a commercially available polyethylene sheet into a sodium hypochlorite aqueous solution with the mass content of 10%, adding a small amount of sodium bicarbonate (0.5-1% of the mass content of the solution) to adjust the pH value of the aqueous solution to be 5.5-6, and performing UV illumination for 20min (the UV wavelength is 280-400 nm) at the temperature of 30-40 ℃ to perform chlorination treatment to obtain a chlorinated polyolefin material (the surface chlorination degree of the chlorinated polyolefin material is 30-50%);
(b) soaking a chlorinated polyolefin material (namely a polyethylene sheet with the chlorinated surface) in 100 parts of hydroxyethyl methacrylate (without adding pentamethyldiethylenetriamine and parts of ruthenium bipyridyl complex), and irradiating at 30 ℃ (solvent temperature) by using a 410nm LED lamp: radiation intensity 0.6W/m2Irradiating for 5min, washing polyethylene material with deionized water, and drying with 80 deg.C hot air to obtain polyethylene material with surface tension of 31mN/mAnd (4) surface modification.
Comparative example 2
The present embodiment provides a method for modifying the surface of the existing conventional polyolefin material, which specifically adopts the steps in the chinese patent with application number 201610587498.5, and some conditions are as follows: and (3) carrying out grafting reaction at the temperature of 40-60 ℃, wherein the dipping time is 10-60 min, and the oxidation-reduction catalyst is 0.5-1 part.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (8)
1. A method for modifying the surface of a polyolefin material, characterized in that it comprises the following steps:
(a) carrying out surface chlorination reaction on the polyolefin material in a chlorine-containing solution to obtain a chlorinated polyolefin material; the chlorine-containing solution comprises the following components in parts by weight: 90-95 parts of deionized water, 5-10 parts of sodium hypochlorite and 0.5-1 part of sodium bicarbonate;
(b) immersing the chlorinated polyolefin material into a grafting reaction solution, and carrying out photocatalysis-atom transfer free radical reaction under the action of light irradiation; the grafting reaction solution comprises the following components in parts by weight: 100 parts of a grafting monomer, wherein the grafting monomer is a propylene derivative monomer or/and a styrene derivative monomer; 0.1-0.2 part of a reducing agent, wherein the reducing agent is organic amine; 0.001-0.003 part of photocatalyst, wherein the photocatalyst is a transition metal complex.
2. The method for surface modification of polyolefin material according to claim 1, wherein in step (a), the surface chlorination reaction conditions are as follows: the temperature of the chlorine-containing solution is 30-40 ℃ and the UV light irradiates for 5-20 min.
3. The method for modifying the surface of the polyolefin material according to claim 2, wherein in the step (a), the surface chlorination degree of the chlorinated polyolefin material is 30-50%.
4. The method for modifying the surface of a polyolefin material according to claim 1, wherein in step (b), the conditions of said light irradiation are: 400-500 nm monochromatic light or waveband light source, radiation intensity of 0.3-0.7W/m2And reacting for 2-10 min at normal temperature.
5. The method for surface modification of polyolefin material according to claim 1, characterized in that: the grafting monomer is a mixture consisting of one or more of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) acrylic acid, glycidyl (meth) acrylate, acrylamide, p-carboxystyrene and p-hydroxystyrene.
6. The method for surface modification of polyolefin material according to claim 1, characterized in that: the reducing agent is a mixture consisting of one or more of tri-n-propylamine, triethylamine, triethanolamine, pentamethyldiethyltriamine, diethylacetamide and diethylenetriamine.
7. The method for surface modification of polyolefin material according to claim 1, characterized in that: the photocatalyst is a complex formed by transition metal ruthenium, iridium or/and osmium and one or more of ligand bipyridine, bipyridine methyl, bipyridyl dicarboxyl, dinitrile pyridine, terpyridine trimethyl pyridine, terpolypyridine and dinitrile pyridine.
8. The method for surface modification of polyolefin material according to claim 1, characterized in that: in the step (b), after the photocatalysis-atom transfer free radical reaction, cleaning and drying are carried out.
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