KR101970698B1 - A high molecule copolymer with a excellent water-resisting, chemical-resisting, and weather-resisting property, and it's fabrication method. - Google Patents
A high molecule copolymer with a excellent water-resisting, chemical-resisting, and weather-resisting property, and it's fabrication method. Download PDFInfo
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- KR101970698B1 KR101970698B1 KR1020120086173A KR20120086173A KR101970698B1 KR 101970698 B1 KR101970698 B1 KR 101970698B1 KR 1020120086173 A KR1020120086173 A KR 1020120086173A KR 20120086173 A KR20120086173 A KR 20120086173A KR 101970698 B1 KR101970698 B1 KR 101970698B1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
- C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
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- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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Abstract
The present invention has been made in order to remove a hydrophilic group of a conductive emulsifier having a hydrophilic group, and to form a hydrophobic group through reaction with another alcoholic polymer. In addition, by inducing a chemical bond by copolymerization without physical bonding by a non-conductive binder, it has excellent water resistance and maintains the intrinsic electrical properties of the conductive emulsifier or conductive material. Therefore, a dehydration condensation reaction between the conductive emulsifier and the alcoholic polymer is produced to produce a graft copolymer having an electrical conductivity that can be applied as a conductive material, and the film is impregnated with a polar solvent or left in the air for a long time. The present invention also provides a graft copolymer between a conductive emulsifier and an alcoholic polymer having a property of intrinsic physical properties such as electrical conductivity and a manufacturing method thereof.
Description
The present invention relates to a conductor having water resistance, chemical resistance, and weather resistance to moisture or the surrounding environment, wherein an alcoholic polymer is added to a conductive emulsifier and mixed therewith, followed by heat treatment to induce a dehydration condensation reaction. And it relates to a technique capable of producing a graft copolymer (graft copolymer) having weather resistance.
Conductive emulsifiers have unique properties that allow electricity to pass through the inherent properties of the emulsifier, which dissolves or disperses components that are insoluble in solvents, and can maintain conductivity while dispersing conductive polymers or nanowires. It has been active.
Particularly in the fields of electricity and electronics, it is applied to electrolytic capacitors, electric double layer capacitors, switching elements, nonlinear elements, field effect transistors, optical recording materials, display elements, and anisotropic conductor sensors, and continues to be applied to new fields. Research is ongoing.
However, despite the advantages of the conductive emulsifiers, most of the conductive polymers or nanowires to which the conductive emulsifiers are to be dispersed are sensitive to moisture or polar solvents in the air, and most conductive emulsifiers also contain hydrophilic groups. When exposed to the atmosphere, the original intrinsic properties are lost, and the reliability as a unit functional film of an electric component or an integrated circuit is very weak. As such, the conductive emulsifier is vulnerable to moisture and polar solvents, and thus, it is difficult to safely maintain the target material to be dispersed in the air, and thus is limited to applications such as electric and electronic components requiring long-term reliability.
In order to solve this problem, there is a method of adding an additive such as an additional binder or an adhesive to the conductive emulsifier, but it can be protected from moisture by generating a physical bond between the conductive materials, but most of the additive such as a binder is a nonconductor. When used, there is a problem of inhibiting the inherent electrical properties of the inherently conductive emulsifier or dispersed conductive material. Therefore, the development of a conductive emulsifier to maintain the intrinsic electrical properties while having water resistance or chemical resistance is practical. It is required.
The present invention has been made in order to remove a hydrophilic group of a conductive emulsifier having a hydrophilic group, and to form a hydrophobic group through reaction with another alcoholic polymer. In addition, by inducing chemical bonding by copolymerization without physical bonding by a non-conductive binder, it is possible to maintain the inherent electrical properties of the conductive emulsifier or conductive material while having excellent water resistance. Accordingly, the present invention causes a dehydration and condensation reaction between a conductive emulsifier and an alcoholic polymer to produce a graft copolymer having an electrical conductivity that can be applied as a conductive material, which is impregnated in a polar solvent or in the air. It is an object of the present invention to provide a graft copolymer between a conductive emulsifier and an alcoholic polymer having a characteristic of intrinsic physical properties such as electrical conductivity even after being left for a long time, and a method of manufacturing the same.
In order to solve the above problems, the present invention is to first convert the hydrophilic group of the conductive emulsifier to a hydrophobic group in order to prevent the reaction of the conductive emulsifier with water and the polar solvent. In more detail, the conductive emulsifier and the alcoholic polymer were mixed and heat-treated at a range of temperatures to induce a graft copolymerization in which the hydrophilic group of the conductive emulsifier and the hydrophilic group of the alcoholic polymer were removed through a dehydration condensation reaction. . The graft copolymer between the conductive emulsifier and the alcoholic polymer produced by the copolymerization reaction does not have a hydrophilic group and does not react with water or a polar solvent, thereby having excellent water resistance and chemical resistance, and thus, may be left in the air. Even when the physical properties do not change shows excellent weather resistance.
Secondly, in particular, by not using a binder added for the physical bonding between the conductive emulsifier and the material to be dispersed, it is possible to prevent the decrease in the electrical conductivity due to the use of the binder as a nonconductor. Therefore, the present invention can be applied as an emulsifier having water resistance, chemical resistance, and weather resistance while maintaining the electrical properties of the conductive material. In addition, by maintaining such a relatively high electrical conductivity, it has an antistatic property, and application as an antistatic functional film is also possible. The graft copolymer between the conductive emulsifier and the alcoholic polymer according to the present invention dehydrates an alcoholic polymer having a conductive emulsifier having a hydrophilic group and two end groups, a first end group having a hydrophilic group, and a second end group having a hydrophobic group. Characterized in that it is formed by the condensation reaction, the conductive emulsifier 4-toluenesulfonic acid (p-Toluenesulfonic acid), 1-naphthalene sulfonic acid (1-Naphthalenesulfonic acid), dodecyl benezene sulfonic acid, poly Poly (acrylic acid) and polymethacrylic acid [poly (acrylic acid)] and polymethacrylic acid [poly (acrylic acid)] poly (methacrylic acid)] any one or a combination of two or more selected from among the alcoholic polymer is polyethylene glycol methyl ether [Poly (ethylene glycol) methyl ether], polypropylene glycol acrylate [Poly (propylene glycol) acrylate], polypropylene glycol methacrylate [Poly (propylene) methacrylate], polypropylene glycol monobutyl ether [Poly (propylene glycol) monobutyl ether], a polypropylene glycol monooctyl ether [Poly (propylene glycol) monooctyl ether] is characterized in that the material consisting of any one or a combination of two or more.
First, the conductive emulsifier and the alcoholic polymer are mixed and heat-treated to remove the hydrophilic group of the conductive emulsifier and the hydrophilic group of the alcoholic polymer through a dehydration condensation reaction. By preventing the reaction and the like can have excellent water resistance.
Second, the graft copolymer between the conductive emulsifier and the alcoholic polymer has only a hydrophobic group, and thus has strong chemical resistance to polar solvents such as methanol and ethanol.
Third, the graft copolymer between the conductive emulsifier and the alcoholic polymer does not react with moisture in the air, and when used in the air, the graft copolymer has weather resistance without change in physical properties over time.
Fourth, physical bonding is generally used to remove the binder used to improve weather resistance, and instead, a small amount of alcoholic polymer is added to induce chemical bonding by copolymerization, thereby reducing the electrical conductivity caused by the non-conductive binder. You can stop it. That is, the intrinsic electrical properties of the conductive material can be maintained.
1 relates to a method for preparing a graft copolymer consisting of a conductive emulsifier and an alcoholic polymer.
Figure 2 relates to a method for producing a film comprising a graft copolymer (graft copolymer) consisting of a conductive emulsifier and an alcoholic polymer.
1 shows a method for preparing a graft copolymer composed of a conductive emulsifier and an alcoholic polymer. First, a conductive emulsifier solution including a conductive emulsifier having a hydrophilic group is prepared, and on the other hand, it has two end groups. The first terminal group is a hydrophilic group, and the second terminal group prepares an alcoholic polymer which is a hydrophobic group. Thereafter, the alcoholic polymer is mixed with the conductive emulsifier solution to prepare a mixed solution. Finally, the mixed solution is heat-treated to dehydrate-condense the hydrophilic group of the conductive emulsifier and the hydrophilic group of the alcoholic polymer to form a graft copolymer having only hydrophobic groups.
The conductive emulsifier solution of the manufacturing method may be prepared by mixing the deionized water and the conductive emulsifier, the solid content is preferably 5 to 20% by weight. In addition, the mixing process of the conductive emulsifier solution and the alcoholic polymer is made to dissolve by stirring, it is preferable to dissolve by stirring for a time of 5 minutes or more and 120 minutes or less at a temperature of 10 ℃ or more and 150 ℃ or less. In particular, the heat treatment process for the dehydration condensation reaction is preferably carried out for a time of more than 5 minutes and less than 60 minutes at a temperature of 50 ° C or more and 300 ° C or less.
The conductive emulsifier has any one of sulfonic acid, paratoluenesulfonic acid, and carboxylic acid as a functional group as an organic acid, and may be selected and used as one of Formulas 1 and 2 below.
Formula (1) is a polymer having a molecular weight of 100 to 1000,000, 4-toluene sulfonic acid (p-Toluenesulfonic acid), 1-naphthalene sulfonic acid (1-Naphthalenesulfonic acid), dodecyl benzene sulfonic acid (Dodecyl benezene sulfonic acid), polyvinyl sulfonic acid [poly (vinyl sulfonic acid)], and polystyrene sulfonic acid [poly (4-styrene sulfonic acid).
In addition, the formula (2) is a polymer having a molecular weight of 100 to 1000,000 consisting of any one or a combination of two or more selected from poly (acrylic acid) and polymethacrylic acid (poly (methacrylic acid)) It is a substance.
The alcoholic polymer has the following formula (3).
R 3 of Formula 3 includes an ether, Formula 3 is a polymer material having a molecular weight of 100 or more and 1,000,000 or less, R 4 has a carbon number of 1 or more and 100 or less, and formula (3) is a polyethylene glycol methyl ether. Propylene glycol acrylate [Poly (propylene glycol) acrylate], polypropylene glycol methacrylate [Poly (propylene) methacrylate], polypropylene glycol monobutyl ether [Poly (propylene glycol) monobutyl ether], polypropylene glycol monooctyl A substance consisting of any one or a combination of two or more of poly (propylene glycol) monooctyl ether].
The alcoholic polymer is used to convert the hydrophilic group of the conductive polymer emulsifier into a hydrophobic group by chemically bonding the hydrophilic group of the polymer emulsifier by a dehydration condensation polymerization reaction. The short term should be an alcoholic polymer composed of hydrophobic groups.
When the content of the alcoholic polymer is less than 20% by weight, the conversion to dehydration condensation polymerization is low, and the reaction product has an excessive amount of hydrophilic groups that are not converted to hydrophobic groups, thereby lowering the water resistance. Although the conversion to the reaction is high, it is not preferable because the intrinsic properties of the conductive emulsifier can be changed by the influence of the remaining alcoholic polymer. In addition, considering the mass production, there is a disadvantage that is not economical due to the increase in material costs. Therefore, the amount of alcoholic polymer is preferably used in 20 to 50% by weight relative to the weight of the conductive emulsifier.
Specifically describing the copolymerization reaction by the heat treatment, the dehydration condensation reaction between the hydrophilic group of the conductive emulsifier and the hydrophilic group of the alcoholic polymer during the heat treatment process may be described by the formulas (4) and (5) below. However, this is only a representative example for explaining the present invention, and it is clear that both of the conductive emulsifier and the alcoholic polymer having a hydrophilic group are capable of such a dehydration condensation reaction.
Formula (4) is a case where the conductive emulsifier is a polymer containing sulfonic acid, which has a hydrophilic -OH group, and the alcoholic polymer has a hydrophilic group only at one end. When the mixture is mixed and heat-treated, when the hydrophilic group of the conductive emulsifier reacts with the hydrophilic group of the alcoholic polymer, a graft copolymer having only H20 molecules and hydrophobic groups is formed through a dehydration condensation reaction.
Formula (5) is a case where the conductive emulsifier is a polymer containing carboxylic acid, has a hydrophilic -OH group, and the alcoholic polymer has a hydrophilic group only at one end. When the mixture is mixed and heat treated, as in the formula (4), when the hydrophilic group of the conductive emulsifier and the hydrophilic group of the alcoholic polymer react, a graft copolymer having only H 2 0 molecules and a hydrophobic group is formed through a dehydration condensation reaction.
R1, R2, R3, and R4 are of course the same kind of polymer as described for the conductive emulsifier and the alcoholic polymer.
In addition, the copolymer finally obtained by the manufacturing process as described above has only a hydrophobic group at the terminal, the remaining graft copolymer (graft copolymer) excluding water in the reaction products of formulas (4) and (5) do. It is also evident that, depending on the choice of conductive emulsifier, various graft copolymers can be obtained as a result.
Such a graft copolymer (graft copolymer) can also be prepared in the form of a film. As shown in FIG. 2, a conductive emulsifier solution including a conductive emulsifier having a substrate and a hydrophilic group is prepared, and together with two end groups, a first terminal group is a hydrophilic group and a second terminal group is a hydrophobic group. Choose to prepare. The alcoholic polymer is added to the conductive emulsifier solution, dissolved, to prepare a mixed solution, the mixed solution is coated on the substrate, coated, and heat treated to thereby form the hydrophilic group of the conductive emulsifier and the first word of the alcoholic polymer. The short-term dehydration condensation reaction can form a film made of a graft copolymer having only a hydrophobic group.
The coating of the mixed solution is wet coating including at least one of spin coating, spray coating, roll to roll, or bar coating. The conductive emulsifier may be represented in the same manner as in Chemical Formulas (1) and (2), and the alcoholic polymer may also be represented in Chemical Formula (3).
Copolymerization Reaction on Film When the hydrophilic group of the conductive emulsifier and the hydrophilic group of the alcoholic polymer react with each other, a dehydration condensation reaction forms a graft copolymer having only H 2 0 molecules and a hydrophobic group. It may be represented by the formula (4), (5) the same as when not.
Table 1 shows the experimental results showing the change of the sheet resistance according to the immersion time of the film prepared only with the conductive emulsifier, Table 2 summarizes the results of the water resistance test for the graft copolymer between the conductive emulsifier and the alcoholic polymer to be. In particular, in order to view only the conductive properties of the conductive emulsifier, the substrate was selected as a glass substrate. When the conductive emulsifier was composed only, the initial sheet resistance was 10 6 Ω / □, but the sheet resistance value increased greatly during the first 6 hours of immersion, which means that after a certain time, the conductive emulsifier was dissolved and the characteristics of the conductive emulsifier could not be measured. it means. Therefore, it has insulation characteristics exceeding 10 13 Ω / □ which is the sheet resistance measurement limit of the 4-point probe.
Water temperature (℃)
Immersion time
0
6
12
24
48
10
10 6 Ω / □
> 10 13 Ω / □
> 10 13 Ω / □
> 10 13 Ω / □
> 10 13 Ω / □
30
10 6 Ω / □
> 10 13 Ω / □
> 10 13 Ω / □
> 10 13 Ω / □
> 10 13 Ω / □
50
10 6 Ω / □
> 10 13 Ω / □
> 10 13 Ω / □
> 10 13 Ω / □
> 10 13 Ω / □
Water temperature (℃)
Immersion time
0
6
12
24
48
10
10 6 Ω / □
10 6 Ω / □
10 6 Ω / □
10 6 Ω / □
10 6.1 Ω / □
30
10 6 Ω / □
10 6 Ω / □
10 6 Ω / □
10 6 Ω / □
10 6.1 Ω / □
50
10 6 Ω / □
10 6 Ω / □
10 6 Ω / □
10 6 Ω / □
10 6.1 Ω / □
As shown in Table 2, the change of the sheet resistance according to the immersion time of the graft copolymer between the conductive emulsifier and the alcoholic polymer is kept constant at 10 6 Ω / □ up to 24 hours regardless of the water temperature, and 48 hours It was found to change slightly to 10 6.1 Ω / □. The results show that the graft copolymer formed by the dehydration condensation reaction by adding alcoholic polymer to the conductive emulsifier is very stable to moisture, compared to the film composed only of the conductive emulsifier which is very vulnerable to moisture.
Table 3 is a result of the chemical resistance test of the film prepared only with the conductive emulsifier, acetone (Methanol), methanol (Dimethylformamide), THF (Tetrahydrofuran) was selected for the chemical resistance test, It is the data which measured the change of sheet resistance with time by precipitation in a solvent. As with the water resistance test results, the initial sheet resistance was 10 6 Ω / □, but the sheet resistance value increased greatly during the first 6 hours of settling time, exceeding 10 13 Ω / □, the sheet resistance measurement limit of the 4-point probe, By exhibiting the properties, it can be seen that the chemical resistance is very weak.
menstruum
Settling time (hour)
0
6
12
24
48
Acetone
10 6 Ω / □
> 10 13 Ω / □
> 10 13 Ω / □
> 10 13 Ω / □
> 10 13 Ω / □
Methanol
10 6 Ω / □
> 10 13 Ω / □
> 10 13 Ω / □
> 10 13 Ω / □
> 10 13 Ω / □
DMF
10 6 Ω / □
> 10 13 Ω / □
> 10 13 Ω / □
> 10 13 Ω / □
> 10 13 Ω / □
THF
10 6 Ω / □
> 10 13 Ω / □
> 10 13 Ω / □
> 10 13 Ω / □
> 10 13 Ω / □
Table 4 shows the change of the sheet resistance according to the immersion time of the graft copolymer (graft copolymer) between the conductive emulsifier and the alcoholic polymer. Irrespective of the type of solvent, it was kept constant at 10 6 Ω / □ up to 24 hours, and did not change significantly to a value of 10 6 to 10 6.2 Ω / □ even after 48 hours. The results show that the graft copolymer formed by the dehydration condensation reaction by adding alcoholic polymer to the conductive emulsifier is very stable in the polar solvent, compared to the film composed only of the conductive emulsifier, which is vulnerable to the polar solvent.
menstruum
Settling time (hour)
0
6
12
24
48
Acetone
10 6 Ω / □
10 6 Ω / □
10 6 Ω / □
10 6.1 Ω / □
10 6.1 Ω / □
Methanol
10 6 Ω / □
10 6 Ω / □
10 6 Ω / □
10 6 Ω / □
10 6 Ω / □
DMF
10 6 Ω / □
10 6 Ω / □
10 6 Ω / □
10 6 Ω / □
10 6.1 Ω / □
THF
10 6 Ω / □
10 6 Ω / □
10 6 Ω / □
10 6.1 Ω / □
10 6.2 Ω / □
Table 5 shows the results of the weather resistance test of the film prepared only with the conductive emulsifier, and the conditions for the weather resistance test were selected from the following conditions. The change of sheet resistance with time was measured in the state left to stand. The first sheet resistance of 10 6 Ω / □ but, after 48 hours is in the condition of the sheet resistance value at room temperature was increased to 10 7.4 Ω / □, in the high temperature and humidity conditions of 10 4-point sheet resistance measurement limit of the probe Beginning 96 hours 13 Ω In excess of / □, the characteristics of the insulator are exhibited, indicating that the weather resistance is weak overall.
Temperature (℃)
Neglect time
0
12
24
48
96
168
Room temperature
10 6 Ω / □
10 6.5 Ω / □
10 6.9 Ω / □
10 7.4 Ω / □
10 7.8 Ω / □
10 8.9 Ω / □
High temperature (80 ℃)
10 6 Ω / □
10 6.9 Ω / □
10 7.2 Ω / □
10 7.6 Ω / □
10 8.1 Ω / □
10 9.2 Ω / □
High temperature and high humidity
(80 ℃,
Relative Humidity 85%)
10 6 Ω / □
10 8.0 Ω / □
10 9.0 Ω / □
10 11 Ω / □
> 10 13 Ω / □
> 10 13 Ω / □
Table 6 shows the results of the weather resistance test of the film made of the copolymer of the conductive emulsifier and the alcoholic polymer. ) Was measured and the change of sheet resistance with time was left to stand in each condition. The initial sheet resistance was 10 6 Ω / □, but after 48 hours, the sheet resistance was maintained in the range of 10 6.1 to 10 6.2 Ω / □ under all conditions, and even after high temperature and humidity conditions, the sheet resistance value was 10 6.3 Ω / □ even after 168 hours. However, the increase was not large, and it can be seen that weather resistance was greatly increased under all conditions.
Temperature (℃)
Neglect time
0
12
24
48
96
168
Room temperature
10 6 Ω / □
10 6 Ω / □
10 6 Ω / □
10 6.1 Ω / □
10 6.1 Ω / □
10 6.1 Ω / □
High temperature (80 ℃)
10 6 Ω / □
10 6 Ω / □
10 6 Ω / □
10 6.2 Ω / □
10 6.3 Ω / □
10 6.3 Ω / □
High temperature and high humidity
(80 ℃,
Relative Humidity 85%)
10 6 Ω / □
10 6.1 Ω / □
10 6.1 Ω / □
10 6.2 Ω / □
10 6.3 Ω / □
10 6.3 Ω / □
A conductive emulsifier solution having a solid content of 8 wt% was prepared by mixing 12.5 g of deionized water at 25 ° C. and 10 g of an aqueous 18 wt% polystyrene sulfonic acid solution, which was prepared by sequentially passing distilled water through a cation and an anion exchange resin. It was.
0.73 g of an alcoholic polymer having a molecular weight of 2000 as an additive to the conductive emulsifier solution was added to the solution, followed by stirring at a temperature of 50 ° C. for about 30 minutes. Dissolved. In order to shorten the heat treatment time of the solution after 30 minutes of stirring, 22.5 g of isopropyl alcohol (Isopropryl alcohol) was added to the solution, followed by further stirring at a temperature of 25 ° C. for about 10 minutes to prepare a mixed solution.
The mixed solution was prepared using a 14s bar on a PC (Polycarbonate) film of 10 x 30 cm, a film was prepared by a bar coating method, and then heat-treated in a drying oven at 150 ° C. for 15 minutes, to obtain polystyrene sulfonic acid and poly (ethylene glycol) methyl. A graft copolymer was prepared by dehydrating poly (ethylene glycol) methyl ether.
The graft copolymer films of the conductive emulsifiers and alcoholic polymers prepared were measured with a 4-point probe, and exhibited sheet resistance values of 10 1.0 to 10 13.0 Ω / □ depending on the thickness and process variables.
For comparative measurement of the copolymer films, a specimen having a sheet resistance of 10 6 Ω / □ was selected and impregnated in a bath containing water at a temperature of 25 ° C., followed by taking out different immersion time, and then dried it naturally. As a result of remeasurement of the sheet resistance after the standard water resistance test, it was confirmed that the sheet resistance was maintained at 10 6.0 Ω / □. This showed that the sheet resistance value increased within 5% in any film having a sheet resistance value between 10 1.0 and 10 13.0 Ω / □.
Acetone, THF (Tetrahydrofuran), DMF (Dimethylformamide), DMSO (Dimethyl sulfoxide), Methanol (Methanol) for graft copolymer films of the conductive emulsifier and alcoholic polymer prepared by the above method for chemical resistance test After impregnation with polar solvents, such as ethanol (Ethanol), the precipitation time was taken out and dried by varying the precipitation time, as a result of measuring the sheet resistance value, it was confirmed that the increase rate is maintained within 5% of the initial sheet resistance value.
In addition, the graft copolymer films of the conductive emulsifier and alcoholic polymer prepared by the above method were left to stand for 500 hours in a space having a relative humidity of 85% at room temperature and high temperature for weather resistance test, and then the sheet resistance value was measured again. As a result, it was confirmed that the sheet resistance value was increased within 5% of the initial sheet resistance value at 10 1.0 to 10 13.0 ohm / sq.
Although the present invention has been described with reference to the accompanying drawings, it is merely one example of various embodiments including the gist of the present invention, which can be easily implemented by those skilled in the art. It is clear that the present invention is not limited to the above-described embodiment only. Therefore, the protection scope of the present invention should be interpreted by the following claims, and all technical ideas within the scope equivalent to the change, substitution, substitution, etc. within the scope not departing from the gist of the present invention shall be the right of the present invention. It will be included in the scope. In addition, some of the components of the drawings are intended to more clearly describe the configuration, and it is clear that the exaggerated or reduced size is provided.
Claims (17)
The conductive emulsifier is 4-toluenesulfonic acid (p-Toluenesulfonic acid), 1-naphthalenesulfonic acid (1-Naphthalenesulfonic acid), dodecyl benezene sulfonic acid (dodecyl benezene sulfonic acid), polyvinyl sulfonic acid (poly (vinyl sulfonic acid) )] And poly (4-styrene sulfonic acid), any one or a combination of two or more selected from poly (acrylic acid) and polymethacrylic acid (poly (methacrylic acid)] One or a combination of two or more,
The alcoholic polymer is polyethylene glycol methyl ether [Poly (ethylene glycol) methyl ether], polypropylene propylene glycol acrylate [Poly (propylene glycol) acrylate], polypropylene glycol methacrylate [Poly (propylene) methacrylate], polypropylene glycol Graphene between the conductive emulsifier and the alcoholic polymer, characterized in that the material consisting of any one or a combination of two or more of poly (propylene glycol) monobutyl ether], polypropylene glycol monooctyl ether (poly (propylene glycol) monooctyl ether) Graft copolymer.
(i) preparing a conductive emulsifier solution comprising a conductive emulsifier having a hydrophilic group,
(ii) preparing an alcoholic polymer having two end groups, wherein the first end group is a hydrophilic group and the second end group is a hydrophobic group,
(iii) adding the alcoholic polymer to the conductive emulsifier solution and dissolving it to prepare a mixed solution,
(iv) heat treating the mixed solution to dehydrocondensate the hydrophilic group of the conductive emulsifier and the first terminal group of the alcoholic polymer to form a graft copolymer having only a hydrophobic group;
Method for producing a graft copolymer (graft copolymer) consisting of a conductive emulsifier and an alcoholic polymer comprising a.
The conductive emulsifier solution of step (i) is a mixture of deionized water and a conductive emulsifier to prepare a graft copolymer consisting of a conductive emulsifier and an alcoholic polymer, characterized in that the solid content of 5 to 20% by weight Way.
Step (iii) is a graft copolymer made of a conductive emulsifier and an alcoholic polymer, characterized in that the solution is dissolved by stirring at a temperature of 10 ° C or more and 150 ° C or less for 5 minutes or more and 120 minutes or less. Way.
The heat treatment of step (iv) is a method of producing a graft copolymer (graft copolymer) consisting of a conductive emulsifier and an alcoholic polymer, characterized in that for 5 minutes to 60 minutes or less at a temperature of 50 ℃ to 300 ℃ or less .
The conductive emulsifier is 4-toluenesulfonic acid (p-Toluenesulfonic acid), 1-naphthalenesulfonic acid (1-Naphthalenesulfonic acid), dodecyl benezene sulfonic acid (dodecyl benezene sulfonic acid), polyvinyl sulfonic acid (poly (vinyl sulfonic acid) )] And poly (4-styrene sulfonic acid), any one or a combination of two or more selected from poly (acrylic acid) and polymethacrylic acid (poly (methacrylic acid)] Method for producing a graft copolymer (graft copolymer) consisting of a conductive emulsifier and an alcoholic polymer, characterized in that the material consisting of one or two or more combinations.
The alcoholic polymer is a method of producing a graft copolymer (graft copolymer) consisting of a conductive emulsifier and an alcoholic polymer, characterized in that the first terminal is a hydroxyl group, the second terminal is a polyethylene-based reactant is an alkyl group.
The alcoholic polymer is polyethylene glycol methyl ether [Poly (ethylene glycol) methyl ether], polypropylene propylene glycol acrylate [Poly (propylene glycol) acrylate], polypropylene glycol methacrylate [Poly (propylene) methacrylate], polypropylene glycol Conductive emulsifier and alcoholic polymer, characterized in that the material consisting of any one or a combination of two or more of poly (propylene glycol) monobutyl ether, poly (propylene glycol) monoooctyl ether] Method for preparing a graft copolymer.
(i) preparing the substrate
(ii) preparing a conductive emulsifier solution comprising a conductive emulsifier having a hydrophilic group,
(iii) preparing an alcoholic polymer having two end groups, wherein the first end group is a hydrophilic group and the second end group is a hydrophobic group,
(iv) adding the alcoholic polymer to the conductive emulsifier solution and dissolving it to prepare a mixed solution,
(v) coating the mixed solution on the substrate and coating the same;
(vi) heat-treating the coated mixed solution to dehydrocondensate the hydrophilic group of the conductive emulsifier and the first terminal group of the alcoholic polymer to form a film made of a graft copolymer having only a hydrophobic group;
Method of producing a film comprising a graft copolymer (graft copolymer) between the conductive emulsifier and the alcoholic polymer comprising a.
The conductive emulsifier is 4-toluenesulfonic acid (p-Toluenesulfonic acid), 1-naphthalenesulfonic acid (1-Naphthalenesulfonic acid), dodecyl benezene sulfonic acid (dodecyl benezene sulfonic acid), polyvinyl sulfonic acid (poly (vinyl sulfonic acid) )] And poly (4-styrene sulfonic acid), any one or a combination of two or more selected from poly (acrylic acid) and polymethacrylic acid (poly (methacrylic acid)] Method for producing a film comprising a graft copolymer (graft copolymer) consisting of a conductive emulsifier and an alcoholic polymer, characterized in that the material consisting of one or two or more combinations.
The alcoholic polymer is polyethylene glycol methyl ether [Poly (ethylene glycol) methyl ether], polypropylene propylene glycol acrylate [Poly (propylene glycol) acrylate], polypropylene glycol methacrylate [Poly (propylene) methacrylate], polypropylene glycol Conductive emulsifier and alcoholic polymer, characterized in that the material consisting of any one or a combination of two or more of poly (propylene glycol) monobutyl ether, poly (propylene glycol) monoooctyl ether] Method for producing a film comprising a graft copolymer (graft copolymer).
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| KR1020120086173A KR101970698B1 (en) | 2012-08-07 | 2012-08-07 | A high molecule copolymer with a excellent water-resisting, chemical-resisting, and weather-resisting property, and it's fabrication method. |
| PCT/KR2013/007113 WO2014025200A1 (en) | 2012-08-07 | 2013-08-07 | Composite including high molecular weight copolymer having good water resistance, chemical resistance, and weather resistance, and method for preparing same |
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| KR1020120086173A KR101970698B1 (en) | 2012-08-07 | 2012-08-07 | A high molecule copolymer with a excellent water-resisting, chemical-resisting, and weather-resisting property, and it's fabrication method. |
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| WO2010080230A1 (en) | 2008-12-19 | 2010-07-15 | Sabic Innovative Plastics Ip B.V. | Moisture resistant polyimide compositions |
| KR101143304B1 (en) | 2010-01-06 | 2012-05-08 | 전자부품연구원 | Substrate improved adhesion stability of carbon nanotube conductive film and manufacturing method thereof |
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| JPH10330650A (en) | 1996-09-06 | 1998-12-15 | Dainippon Printing Co Ltd | Antistatic coating material and destaticization using the same |
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| WO2010080230A1 (en) | 2008-12-19 | 2010-07-15 | Sabic Innovative Plastics Ip B.V. | Moisture resistant polyimide compositions |
| KR101143304B1 (en) | 2010-01-06 | 2012-05-08 | 전자부품연구원 | Substrate improved adhesion stability of carbon nanotube conductive film and manufacturing method thereof |
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| Chien-Shun Wu et al. Journal of Power Sources. 2006, 160, 1204-1210 |
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