WO2015163383A1 - Procédé de modification de surface, matériau à surface modifiée et liquide de polymérisation - Google Patents

Procédé de modification de surface, matériau à surface modifiée et liquide de polymérisation Download PDF

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WO2015163383A1
WO2015163383A1 PCT/JP2015/062305 JP2015062305W WO2015163383A1 WO 2015163383 A1 WO2015163383 A1 WO 2015163383A1 JP 2015062305 W JP2015062305 W JP 2015062305W WO 2015163383 A1 WO2015163383 A1 WO 2015163383A1
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meth
acrylamide
water
solid
acrylate
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PCT/JP2015/062305
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Japanese (ja)
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ギャリー ダンダーデール
篤 穂積
千尋 浦田
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国立研究開発法人産業技術総合研究所
ギャリー ダンダーデール
篤 穂積
千尋 浦田
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Priority to JP2016515191A priority Critical patent/JP6229989B2/ja
Publication of WO2015163383A1 publication Critical patent/WO2015163383A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials

Definitions

  • the present invention relates to a surface modification method, a surface modification material, and a polymerization liquid.
  • Polymer brushes are known as materials that can provide various excellent surface properties related to a wide range of industrial fields. Recently, application as a surface exhibiting oil repellency in water has also been proposed.
  • Non-Patent Document 1 discloses that polyhydroxy 2-hydroxyethyl methacrylate is prepared by using the ATRP method in an inert gas on gold having an 11- (2-bromoisobutyryloxy) undecylthio group introduced on the surface. A method of introducing a polymer brush is disclosed.
  • an ATRP method for generating an ATRP catalyst by reducing a metal salt for an ATRP catalyst using a reducing agent an AGEN (Activator Generated by Electron Transfer) ATRP method and an ARGET (Activator Regenerated by ElectroTrans) intelligent method are known. (For example, see Patent Documents 1 and 2).
  • One aspect of the present invention is a surface modification method in which a polymer brush excellent in oil repellency after being immersed in water having a predetermined pH can be easily introduced on a solid surface in view of the problems of the above-described conventional technology. And a polymerization solution can be provided.
  • an amino group or a hydroxyl group is introduced on the surface of a solid, and a solid having an amino group or a hydroxyl group introduced on the surface is reacted with a 2-bromo-2-methylpropionic acid derivative. Then, the step of introducing 2-bromoisobutyryl group on the surface of the solid and the solid having the 2-bromoisobutyryl group introduced on the surface are used in water for water-soluble monomer, water, ATRP catalyst.
  • a polymer brush is introduced on the surface of the solid by immersing in a polymerization solution containing a metal salt, a ligand for ATRP catalyst, and a reducing agent, and polymerizing the water-soluble monomer using the AGET ATRP method or the ARGET ATRP method.
  • the water-soluble monomer is (meth) acrylic acid, 2-dimethylaminoethyl (meth) acrylate, 2-diethylamino (meth) acrylate.
  • an amino group or a hydroxyl group is introduced on the surface of a solid, and a solid having an amino group or a hydroxyl group introduced on the surface is reacted with a 2-bromo-2-methylpropionic acid derivative.
  • a polymer solution containing a metal salt, an ATRP catalyst ligand, and a reducing agent is applied, and a polymer brush is introduced onto the solid surface by polymerizing the water-soluble monomer using the AGET ATRP method or the ARGET ATRP method.
  • the water-soluble monomer includes (meth) acrylic acid, 2-dimethylaminoethyl (meth) acrylate, 2-diethylamino (meth) acrylate Chill, 1,2-dihydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphorylcholine, [2- (meth) acryloyloxyethyl] dimethyl (3-sulfopropyl) ) Ammonium hydroxide, (meth) acrylamide, N-2-dimethylaminoethyl (meth) acrylamide, N-2-diethylaminoethyl (meth) acrylamide, N-1,2-dihydroxyethyl (meth) acrylamide or N-2- Hydroxyethyl (meth) acrylamide.
  • One embodiment of the present invention includes a polymerization solution containing a water-soluble monomer, water, a metal salt for ATRP catalyst, a ligand for ATRP catalyst, and a reducing agent, wherein the water-soluble monomer includes (meth) acrylic acid, (meth) 2-dimethylaminoethyl acrylate, 2-diethylaminoethyl (meth) acrylate, 1,2-dihydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphorylcholine, [2- (Meth) acryloyloxyethyl] dimethyl (3-sulfopropyl) ammonium hydroxide, (meth) acrylamide, N-2-dimethylaminoethyl (meth) acrylamide, N-2-diethylaminoethyl (meth) acrylamide, N -1,2-dihydroxyethy
  • a surface modification method and a polymerization solution capable of simply introducing a polymer brush having excellent oil repellency after being immersed in water having a predetermined pH on a solid surface. Can do.
  • Example 1-1 It is a figure which shows the relationship of the thickness of the polymer brush with respect to the polymerization time of Example 1-1.
  • 2 is a SEM photograph of a cross section of the polymer brush of Example 1-1. It is a figure which shows the relationship of the thickness of the polymer brush with respect to the polymerization time of Example 1-1, 1-2. 6 is a graph showing the relationship of the thickness of a polymer brush with respect to the polymerization time of Comparative Example 1.
  • FIG. The relationship of the thickness of the polymer brush to the concentration of ascorbic acid in the polymerization solutions of Examples 3-1 to 3-7 is shown.
  • the surface modification method comprises a step of introducing an amino group or a hydroxyl group on the surface of a solid, a reaction of a solid having an amino group or a hydroxyl group introduced on the surface with a 2-bromo-2-methylpropionic acid derivative, A step of introducing 2-bromoisobutyryl group on the surface of the solid, and a solid having the 2-bromoisobutyryl group introduced on the surface thereof, in the air, water-soluble monomer, water, metal salt for ATRP catalyst, ATRP It has the process of introduce
  • Water-soluble monomers include (meth) acrylic acid, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 1,2-dihydroxyethyl (meth) acrylate, (meth) acrylic acid 2 -Hydroxyethyl, 2- (meth) acryloyloxyethyl phosphorylcholine, [2- (meth) acryloyloxyethyl] dimethyl (3-sulfopropyl) ammonium hydroxide, (meth) acrylamide, N-2-dimethylaminoethyl (meth) Acrylamide, N-2-diethylaminoethyl (meth) acrylamide, N-1,2-dihydroxyethyl (meth) acrylamide or N-2-hydroxyethyl (meth) acrylamide.
  • the polymer brush excellent in oil repellency after being immersed in the water of predetermined
  • the concentration of the water-soluble monomer in the polymerization solution is preferably 1 to 50% by volume, and more preferably 5 to 45% by volume.
  • concentration of the water-soluble monomer in the polymerization solution is 1% by volume or more, the cost can be reduced, and when it is 50% by volume or less, the environmental load can be reduced.
  • the solid is not particularly limited, and examples thereof include metals, metal oxides, alloys, semiconductors, ceramics, and glass.
  • the shape of the solid surface is not particularly limited, and examples thereof include a flat surface, a curved surface, an uneven surface, and a porous surface.
  • the polymerization solution contains water
  • the water-soluble monomer can be polymerized in a short time at room temperature, and a thick polymer brush can be introduced on the solid surface.
  • the polymerization liquid may further contain an organic solvent that is miscible with water.
  • the organic solvent that can be mixed with water is not particularly limited, and examples thereof include ethanol.
  • the metal salt for ATRP catalyst is not particularly limited as long as it can be reduced by a reducing agent contained in the polymerization solution after being oxidized or not, but copper (I) chloride, copper (II) chloride , Copper (I) bromide, copper (II) bromide, titanium (II) chloride, titanium (III) chloride, titanium (IV) chloride, titanium (IV) bromide, iron (II) chloride, iron chloride (III) ), Iron (II) bromide, iron (III) bromide, cobalt (II) chloride, cobalt (II) bromide, nickel (II) chloride, nickel (II) bromide, molybdenum (III) chloride, molybdenum chloride (V), ruthenium (III) chloride, etc. are mentioned.
  • the molar ratio of the catalyst metal salt to the water-soluble monomer is preferably 0.004 to 0.03.
  • the ligand for ATRP catalyst is not particularly limited, but 2,2′-bipyridyl, 4,4′-dimethyl-2,2′-bipyridyl, 4,4′-di-t-butyl-2,2 ′ -Bipyridyl, 4,4'-dinonyl-2,2'-bipyridyl, N-butyl-2-pyridylmethanimine, N-octyl-2-pyridylmethanimine, N-dodecyl-N- (2-pyridylmethylene) amine N-octadecyl-N- (2-pyridylmethylene) amine, N, N, N ′, N ′′, N ′′ ′-pentamethyldiethylenetriamine, tris (2-pyridylmethyl) amine, 1,1,4, 7,10,10-hexamethyltriethylenetetramine, tris (2-dimethylaminoethyl
  • the molar ratio of the ATRP catalyst ligand to the ATRP catalyst metal salt is 0.50 to 1.5.
  • reducing agent examples include, but are not limited to, ascorbic acid, glucose, di-n-butyltin bis (2-ethylhexanoate) and the like.
  • ascorbic acid is preferable because it has a small environmental load and exhibits a strong reducing action.
  • the molar ratio of the reducing agent to the metal salt for ATRP catalyst is preferably 0.30 to 50, and more preferably 7 to 31.
  • the molar ratio of the reducing agent to the metal salt for ATRP catalyst is 0.30 or more, the decrease in the concentration of the metal salt for ATRP catalyst (for example, copper (I) chloride) as a reductant in the polymerization system is suppressed.
  • the polymerization termination reaction can be suppressed by being 50 or less.
  • the method for introducing an amino group or hydroxyl group onto the solid surface is not particularly limited, and examples thereof include a method for treating the solid surface with a silane coupling agent having an amino group or a hydroxyl group.
  • the silane coupling agent having an amino group is not particularly limited, and examples thereof include 3-aminopropyltriethoxysilane.
  • the 2-bromo-2-methylpropionic acid derivative is not particularly limited, but 2-bromoisobutyryl bromide, 2-bromoisobutyryl chloride, 2-bromoisobutyryl iodide, 2-bromo-2-methyl Examples include methyl propionate, ethyl 2-bromo-2-methylpropionate, and propyl 2-bromo-2-methylpropionate.
  • Other methods for introducing a 2-bromoisobutyryl group onto the surface of a solid include 3- (2-bromoisobutyrylamino) propyltrialkoxysilane or 3- (2-bromoisobutyryloxy) propyltrimethyl.
  • a method of chemical vapor deposition of an alkoxysilane on a solid surface comprising 3- (2-bromoisobutyrylamino) propyltrialkoxysilane or 3- (2-bromoisobutyryloxy) propyltrialkoxysilane, Accordingly, a method of applying a sol-gel solution further containing tetraalkoxysilane to a solid surface can be used.
  • the application method of the sol-gel solution is not particularly limited, and examples thereof include a spin coating method, a spray coating method, and a dip coating method.
  • the alkoxy group in the alkoxysilane is not particularly limited, and examples thereof include a methyl group, an ethyl group, and a propyl group.
  • the polymerization solution may be applied to the solid having 2-bromoisobutyryl group introduced on the surface.
  • the polymerization solution may further contain a thickener.
  • a thickener thereby, the repelling of a polymerization liquid can be prevented and a polymerization liquid can be uniformly apply
  • the thickener is not particularly limited, and examples thereof include polyvinyl alcohol.
  • the method for applying the polymerization solution is not particularly limited, and examples thereof include a method for applying the polymerization solution using a brush or a brush, and a method for dropping the polymerization solution using a dropper.
  • the coating material is not particularly limited, and examples thereof include filter paper and film.
  • the surface of the surface modifying material is modified by the surface modifying method described above.
  • the thickness of the polymer brush as the surface modifying material is preferably 4 to 700 nm.
  • the advancing contact angle ( ⁇ A ) and receding contact angle ( ⁇ R ) of n-hexadecane of the surface modifying material after being immersed in an acid aqueous solution having a pH of 2 is preferably 150 ° or more.
  • the contact angle hysteresis ⁇ A - ⁇ R with respect to n-hexadecane of the surface modifying material after being immersed in an acid aqueous solution having a pH of 2 is preferably 10 ° or less, and more preferably 5 ° or less. For this reason, oil droplets can be slid down at an inclination angle of 5 ° or less (referred to as sliding angle), and a surface modifying material having excellent oil repellency (droplet removal ability and antifouling property) can be obtained.
  • the surface modifying material When the surface modifying material is immersed in an acid aqueous solution or a base aqueous solution having different pHs, the advancing contact angle ( ⁇ A ), receding contact angle ( ⁇ R ), contact angle hysteresis ( ⁇ A ⁇ R ) and sliding angle with respect to the oil droplets are immersed. Changes. The pH responsiveness of this surface modifying material functions repeatedly.
  • the ratio of the contact angle hysteresis ⁇ A - ⁇ R to hexadecane is preferably 0.1 or less, and more preferably 0.05 or less. For this reason, the change in oil repellency due to the change in pH of the water to be immersed is large.
  • Surface modification material can be applied to lubrication treatment, antibacterial treatment, antifouling treatment, super water / oil repellent treatment, stimulus responsive surface, and the like.
  • Preparation of pretreatment substrate A 1 cm ⁇ 1 cm silicon substrate was ultrasonically cleaned in ethanol for 5 minutes and then dried in a nitrogen stream. Next, after ozone cleaning at 1 ⁇ 10 3 Pa for 30 minutes, together with about 100 ⁇ L of 3-aminopropyltriethoxysilane (APTES), it is put into a sealed Teflon (registered trademark) container and heated at 100 ° C. for 60 minutes. did. As a result, silanol groups present on the surface of the silicon substrate and the triethoxysilyl group of APTES were dehydrated and condensed to introduce amino groups on the surface of the silicon substrate.
  • APTES 3-aminopropyltriethoxysilane
  • APTES adsorbed on the silicon substrate was rinsed with toluene and then dried in a nitrogen stream.
  • the amino substrate-introduced silicon substrate was immersed overnight in a 0.1 M 1,4-dioxane solution of 2-bromoisobutyryl bromide (BIBB) as an ATRP initiator, and 2 -A bromoisobutyryl group was introduced to obtain a pretreated substrate.
  • BIBB 2-bromoisobutyryl bromide
  • Example 1-1 A polymer brush of poly (2- (dimethylamino) ethyl methacrylate) (PDMAEMA) was introduced onto the surface of the pretreated substrate using the AGET ATRP method. Specifically, 2-dimethylaminoethyl methacrylate (DMAEMA) 8 mL, water 7 mL, copper (II) chloride 16 mg and N, N, N ′, N ′′, N ′ ′′-pentamethyldiethylenetriamine 50 ⁇ L in 20 mL After putting in a glass bottle, 20 ⁇ L of a 1 mg / mL aqueous solution of ascorbic acid was added and stirred for about 2 minutes to obtain a polymerization solution.
  • DMAEMA 2-dimethylaminoethyl methacrylate
  • the glass bottle was sealed with a screw cap made of PTFE. At this time, since the polymerization solution was not degassed, the glass bottle contained about 4 mL of air. Further, after polymerization at room temperature (23 to 28 ° C.) without stirring, the glass substrate into which the polymer brush was introduced was taken out of the glass bottle and thoroughly rinsed with water to obtain a surface modified substrate.
  • FIG. 1 shows the relationship of the polymer brush thickness to the polymerization time.
  • FIG. 1 indicates that the thickness of the polymer brush increases linearly at about 2 nm / min after an incubation period of about 30 minutes and reaches 300 nm about 200 minutes after the start of polymerization.
  • the linear increase in the thickness of the polymer brush indicates that the polymerization is controlled at a high level and that bromo or chloro groups are retained at the ends of the growing polymer chain. After the thickness of the polymer brush reached 300 nm, the increase in the thickness of the polymer brush became gradual. This is considered to be because the number of growing polymer chains is decreased by decreasing the bromo group or chloro group at the terminal of the growing polymer chain. As a result, the thickness of the polymer brush reached 670 nm after 1380 minutes from the start of polymerization.
  • the thickness of the polymer brush was measured using an ellipsometer.
  • FIG. 2 shows an SEM photograph of the cross section of the polymer brush.
  • FIG. 2 shows that the polymer brush is smooth and homogeneous.
  • Example 1-2 Except for changing the addition amount of 1 mg / mL aqueous solution of copper (II) chloride, N, N, N ′, N ′′, N ′ ′′-pentamethyldiethylenetriamine and ascorbic acid to 8 mg, 25 ⁇ L and 10 ⁇ L, respectively.
  • a surface modified substrate was obtained in the same manner as in Example 1-1.
  • FIG. 3 shows the relationship between the polymer brush thickness and the polymerization time of Examples 1-1 and 1-2.
  • Example 1-2 From FIG. 3, it can be seen from Example 1-2 that the addition amounts of copper (II) chloride, pentamethyldiethylenetriamine and ascorbic acid are half the amount of Example 1-1, and the incubation period is from about 30 minutes to about 0.1 minutes in Example 1-1. It turns out that it increases in 80 minutes. This is considered to be because the rate at which oxygen that inhibits the polymerization reaction is removed from the polymerization system is slowed by the oxidation of Cu (I) to Cu (II).
  • Example 1-1 the polymer brush grew rapidly about 30 minutes after the start of polymerization, whereas in Example 1-2, the polymer brush was about 160 minutes after the start of polymerization. Grows rapidly.
  • the growth rate of the polymer brush is proportional to [Cu (I)] / [Cu (II)] in the polymerization system.
  • the growth of the polymer brush is slow because the amount of Cu (I) present in the polymerization system is small 80 minutes after the start of the polymerization.
  • 120 minutes after the start of the polymerization the amount of [Cu (I)] / [Cu (II)] in the polymerization system increases, so the growth of the polymer brush becomes faster and the polymerization starts.
  • About 160 minutes after the removal almost all oxygen is removed from the polymerization system, and [Cu (I)] / [Cu (II)] in the polymerization system becomes maximum and becomes constant.
  • Example 2 A polymer brush of poly (2- (diethylamino) ethyl methacrylate) (PDEAEMA) was introduced onto the surface of the pretreated substrate using the ARGET ATRP method. Specifically, 2-diethylaminoethyl methacrylate (DEAEMA) 8 mL, water 3 mL, ethanol 4 mL, copper (II) chloride 2.8 mg and N, N, N ′, N ′′, N ′ ′′-pentamethyldiethylenetriamine 5 ⁇ L was placed in a 20 mL glass bottle.
  • DEAEMA 2-diethylaminoethyl methacrylate
  • the glass bottle was sealed with a screw cap made of PTFE. At this time, since the polymerization solution was not degassed, the glass bottle contained about 4 mL of air. Furthermore, after polymerization for 24 hours at room temperature (23 to 28 ° C.) without stirring, the glass substrate with the polymer brush introduced was taken out of the glass bottle and thoroughly rinsed with water to obtain a surface modified substrate. .
  • the polymer brush introduced into the surface treatment substrate had a thickness of 70 nm.
  • a polymer brush of poly (sodium methacrylate) was introduced on the surface of the pretreatment substrate using the AGET ATRP method. Specifically, 3 g of sodium methacrylate, 4.6 mL of water, 8 mg of copper (II) chloride and 25 ⁇ L of N, N, N ′, N ′′, N ′ ′′-pentamethyldiethylenetriamine were placed in a 20 mL glass bottle. Then, 10 ⁇ L of a 1 mg / mL aqueous solution of ascorbic acid was added and stirred for about 2 minutes to obtain a polymerization solution.
  • the glass bottle was sealed with a screw cap made of PTFE. At this time, since the polymerization solution was not degassed, the glass bottle contained about 4 mL of air. Further, after polymerization at room temperature (23 to 28 ° C.) without stirring, the glass substrate into which the polymer brush was introduced was taken out of the glass bottle and thoroughly rinsed with water to obtain a surface modified substrate.
  • FIG. 4 shows the relationship of the polymer brush thickness to the polymerization time.
  • FIG. 4 shows that the thickness of the polymer brush increases without passing through the incubation period, but reaches 150 nm 1320 minutes after the start of polymerization.
  • Table 1 shows the evaluation results of the oil repellency after immersion in the acid aqueous solution having a pH of 2 or the base aqueous solution having a pH of 10 of the surface-modified substrates of Examples 1-1 and Comparative Example 1.
  • ⁇ pH means a change in ⁇ A and ⁇ R due to a change in pH.
  • the surface-modified substrates of Examples 1-1 and 2 were immersed in an aqueous acid solution having a pH of 2 with respect to the contact angle hysteresis ⁇ for n-hexadecane after being immersed in an aqueous base solution having a pH of 10. Since the ratio of the contact angle hysteresis ⁇ to n-hexadecane is 0.04 and 0.08, respectively, the change in oil repellency due to the change in pH of the immersion water is large.
  • the surface-modified substrate of Comparative Example 1 is n after being immersed in an acid aqueous solution having a pH of 2 with respect to the contact angle hysteresis ⁇ for n-hexadecane after being immersed in a basic aqueous solution having a pH of 10.
  • the ratio of the contact angle hysteresis ⁇ to hexadecane is 9, the change in oil repellency due to the change in the pH of the water to be immersed is small.
  • Example 3-1 A polymer brush of poly (2- (dimethylamino) ethyl methacrylate) (PDMAEMA) was introduced onto the surface of the pretreated substrate using the ARGET ATRP method. Specifically, 2-dimethylaminoethyl methacrylate (DMAEMA) 0.8 mL, water 15.2 mL, copper (II) chloride 2.8 mg and N, N, N ′, N ′′, N ′ ′′-penta After putting 5 ⁇ L of methyldiethylenetriamine in a 20 mL glass bottle, 1 mg of ascorbic acid was added and stirred for about 2 minutes to obtain a polymerization solution.
  • DMAEMA 2-dimethylaminoethyl methacrylate
  • the surface-modified substrate was immersed in water and then n-hexadecane was dropped onto the surface-modified substrate, the n-hexadecane droplet was able to move freely on the surface of the surface-modified substrate. From this, it was found that the surface-modified substrate was excellent in oil repellency after being immersed in water.
  • Examples 3-2 to 3-7 A surface-modified substrate was obtained in the same manner as in Example 3-1, except that the amount of ascorbic acid added was changed to 2 mg, 10 mg, 20 mg, 30 mg, 40 mg, and 80 mg.
  • the surface-modified substrate was immersed in water and then n-hexadecane was dropped onto the surface-modified substrate, the n-hexadecane droplet was able to move freely on the surface of the surface-modified substrate. From this, it was found that the surface-modified substrate was excellent in oil repellency after being immersed in water.
  • FIG. 5 shows the relationship between the thickness of the polymer brush and the concentration of ascorbic acid in the polymerization solution.
  • the thickness of the polymer brush was measured using an ellipsometer.
  • Example 4 DMAEMA 4.8 mL, water 7.0 mL, copper (II) chloride 8.0 mg, N, N, N ′, N ′′, N ′ ′′-pentamethyldiethylenetriamine 50 ⁇ L and polyvinyl alcohol 0.50 g are placed in a 20 mL glass bottle. Thereafter, 0.01 mg of ascorbic acid was added and stirred for about 2 minutes to obtain a polymerization solution.
  • a surface-modified substrate was obtained in the same manner as in Example 3-1, except that the surface of the pretreated substrate on which the polymerization solution was dropped was not coated with Whatman filter paper.
  • the polymer brush had a thickness of 4-6 nm.
  • the surface-modified substrate was immersed in water and then n-hexadecane was dropped onto the surface-modified substrate, the n-hexadecane droplet was able to move freely on the surface of the surface-modified substrate. From this, it was found that the surface-modified substrate was excellent in oil repellency after being immersed in water.
  • Example 5 DMAEMA 0.8 mL, water 15.2 mL, copper (II) chloride 2.8 mg and N, N, N ′, N ′′, N ′ ′′-pentamethyldiethylenetriamine 5 ⁇ L were placed in a 20 mL glass bottle, and then ascorbic acid 20 mg was added and stirred for about 2 minutes to obtain a polymerization solution.
  • a surface-modified substrate was obtained in the same manner as in Example 3-1, except that the obtained polymerization solution was used.
  • the polymer brush had a thickness of 10 nm.
  • the surface-modified substrate was immersed in water and then n-hexadecane was dropped onto the surface-modified substrate, the n-hexadecane droplet was able to move freely on the surface of the surface-modified substrate. From this, it was found that the surface-modified substrate was excellent in oil repellency after being immersed in water.

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Abstract

Un mode de réalisation de la présente invention comprend : une étape consistant à introduire un groupe amino ou un groupe hydroxyle à la surface d'un solide ; une étape consistant à faire réagir le solide, à la surface duquel a été introduit le groupe amino ou le groupe hydroxyle, avec un dérivé de l'acide 2-bromo-2-méthylpropionique, introduisant un groupe 2-bromoisobutyryle à la surface du solide ; et une étape consistant à, dans l'air, immerger le solide, à la surface duquel a été introduit un groupe 2-bromoisobutyryle, dans un liquide de polymérisation contenant un monomère hydrosoluble, de l'eau, un sel métallique de catalyseur d'ATRP, un ligand de catalyseur d'ATRP ainsi qu'un agent réducteur, et en faisant appel à un procédé d'ATRP à AGET ou à un procédé d'ATRP à ARGET, à introduire une brosse polymère à la surface du solide au moyen de la polymérisation du monomère hydrosoluble. Le monomère hydrosoluble est l'acide méthacrylique, le méthacrylate de 2-diméthylaminoéthyle, le méthacrylate de 2-diéthylaminoéthyle, le méthacrylate de 1,2-dihydroxyéthyle, le méthacrylate de 2-hydroxyéthyle, la 2-méthacryloyloxyéthylphosphorylcholine, l'hydroxyde de [2-méthacryloyloxyéthyl]diméthyl(3-sulfopropyl)ammonium, un méthacrylamide, un N-2-diméthylaminoéthylméthacrylamide, un N-2-diéthylaminoéthylméthacrylamide, un N-1,2-dihydroxyéthylméthacrylamide ou un N-2-hydroxyéthylméthacrylamide.
PCT/JP2015/062305 2014-04-25 2015-04-22 Procédé de modification de surface, matériau à surface modifiée et liquide de polymérisation WO2015163383A1 (fr)

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CN106334537A (zh) * 2016-09-18 2017-01-18 盐城工学院 磁性介孔二氧化硅表面印迹聚合物吸附材料及其制备方法
WO2018159836A1 (fr) * 2017-03-03 2018-09-07 独立行政法人国立高等専門学校機構 Composite et son procédé de production
US11274176B2 (en) 2017-03-03 2022-03-15 National Institute of Technology Composite and production method thereof
JP7046385B2 (ja) 2017-12-28 2022-04-04 国立研究開発法人産業技術総合研究所 ポリマーブラシ形成用基体及び該基体の製造方法並びに該方法に用いる前駆液
WO2019131872A1 (fr) 2017-12-28 2019-07-04 国立研究開発法人産業技術総合研究所 Substrat pour formation de brosse polymère, procédé de production de substrat pour formation de brosse polymère, et liquide précurseur destiné à être utilisé dans un procédé de production de substrat pour formation de brosse polymère
JPWO2019131872A1 (ja) * 2017-12-28 2021-03-11 国立研究開発法人産業技術総合研究所 ポリマーブラシ形成用基体及び該基体の製造方法並びに該方法に用いる前駆液
WO2019196999A1 (fr) * 2018-04-11 2019-10-17 Radisurf Aps Compositions pour former des brosses polymères
US11834541B2 (en) 2018-04-11 2023-12-05 Radisurf Aps Compositions for forming polymer brushes
CN111918892A (zh) * 2018-04-11 2020-11-10 拉迪瑟夫私人有限责任公司 形成聚合物刷的组合物
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JPWO2020045407A1 (ja) * 2018-08-28 2021-08-10 国立大学法人 奈良先端科学技術大学院大学 繊維用撥水撥油剤及び繊維製品
JP7058021B2 (ja) 2018-08-28 2022-04-21 国立大学法人 奈良先端科学技術大学院大学 繊維用撥水撥油剤及び繊維製品
KR102444556B1 (ko) 2018-08-28 2022-09-20 고쿠리츠다이가쿠호징 나라 센탄카가쿠기쥬츠 다이가쿠인 다이가쿠 섬유용 발수 발유제 및 섬유 제품
KR20210032448A (ko) * 2018-08-28 2021-03-24 고쿠리츠다이가쿠호징 나라 센탄카가쿠기쥬츠 다이가쿠인 다이가쿠 섬유용 발수 발유제 및 섬유 제품
WO2020045407A1 (fr) * 2018-08-28 2020-03-05 国立大学法人 奈良先端科学技術大学院大学 Agent hydrofuge oléofuge pour fibres et produit fibreux
CN114575153A (zh) * 2022-03-08 2022-06-03 南京工业大学 一种快速黏附细胞的智能纤维材料及其制备方法与应用
CN114575153B (zh) * 2022-03-08 2024-01-19 南京工业大学 一种快速黏附细胞的智能纤维材料及其制备方法与应用

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