KR20020009107A - Polymeric Thin Film Having Multi-Functional Groups on Polymeric Supports and Method Thereof - Google Patents

Abstract

PURPOSE: Provided is a polymer membrane or film, having many reactive groups, produced by a plasma method or a UV irradiation method, which can be applied to a chemical sensor, a liquid- or gas-phase adsorption membrane, a separation membrane, or a lithography process. CONSTITUTION: The polymer membrane or film having many reactive groups is produced by covalent-bonding a dendritic polymer having many reactive groups to the polymer membrane or film by the plasma treatment in the presence of air or maleic anhydride or covalent-bonding a dendritic polymer not having reactive groups or a star-shaped polymer to the polymer membrane or film by the plasma treatment in the presence of the maleic anhydride, introducing an azide group, and then performing the UV irradiation. The terminal reactive group of the dendritic polymer is at least one selected from the group consisting of amine, carboxy, carboxylic ester, epoxy, isocyanate, hydroxy, and sulfhydryl.

Description

Polymer Thin Film Having Multi-Functional Groups on Polymeric Supports and Method Thereof}

The present invention relates to a polymer film or a polymer film having a nanometer-thick organic thin film, and more specifically, to a dendritic polymer or star-shaped polymer having a large number of terminal reactors on a polymer film or a polymer film through a simple plasma or UV irradiation method. The present invention relates to a polymer film or a polymer membrane in which polymers of various structures are covalently bonded, and a method of manufacturing the same.

Organic thin films have been studied for their extensive application to adhesion, corrosion protection, sensors, photoelectric devices and separators. Especially, dendritic polymers are nanometer-sized polymers, which have many reactors at their ends. Since the application range is wide, the research which makes organic thin film from such a dendritic polymer is also performed.

Generally, organic thin films using dendritic polymers have a self-assembled thin film method, a Langmuir-Blodgett method, an adsorptive binding method, or an electrostatic force method, or a surface on an inorganic surface such as metal or ceramic. It is prepared by fusing the stomach. For example, Tsukruk et al. Fabricated a multilayer dendrimer film by applying static electricity on a silicon wafer to adsorb dendrimers charged with opposite charges, and again applying electrostatic charges to adsorb dendrimers charged with opposite charges. [V. N. Bliznyuk, F. Rinderspacher, V. V. Tsukruk, Polymer, 39, 5249 (1998)]. In addition, Crooks et al prepared a self-assembled membrane with mercaptoundecanoic acid on the gold surface and then chemically reacted with a reactor on the dendrimer surface to produce a monolayer dendrimer film [M. Wells, R. M. Crook, J. Am. Chem. Sco. 118, 3988, 1996]. These are all methods of attaching a dendrimer to a metal or ceramic surface.

The manufacturing of organic thin film on the surface of the polymer film has advantages such as the applicability and simplicity of the process. However, researches for modifying the surface of the polymer film have been steadily progressed. The method used is a wet method.

This wet method uses a method of etching with acid or oxidizing the surface. In addition, it is prepared by coating on the surface of the swollen polymer or swelled in a solvent. However, the use of a solvent in these methods, for example, has a problem in that it is not economical because it is toxic or corrosive, and often has various processes such as washing or neutralization. In addition, polymers, unlike metals and ceramics, are dissolved or decomposed in various chemicals, resulting in damage to the polymer film. Therefore, there is a need for a new process for manufacturing an organic thin film on a polymer film.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polymer film or a polymer film in which an organic thin film is formed by using a dry method using plasma which solves the problems of the conventional wet process.

Another object of the present invention is that by attaching a dendritic polymer with a large number of end reactors to a polymer membrane or a film by covalent bonding, these reactors are subsequently substituted with other activators so that various applications such as chemical sensors, biocompatible materials, and separation membranes are possible. It is in one.

Still another object of the present invention is to provide a polymerization method filed by Kolluri et al. [U. S. Patent, 5,962,138; Unlike US Pat. No. 5,723,219, it is intended to increase the simplicity and practicality by attaching a dendrimer or a polymer prepared in a star-shaped or branched shape directly onto the surface of the polymer through a simple process.

1 is a diagram of a method for attaching a dendrimer on an polymeric support through air plasma treatment.

2 is a diagram of a method for attaching a dendrimer by plasma treatment in the presence of maleic anhydride on a polymer support.

3 is a diagram showing a method for attaching a reactor-free dendritic polymer or star-shaped polymer by plasma treatment in the presence of maleic anhydride on a polymer support and introducing an azide group.

4 is an IR spectrum of the surface of the polymer film or polymer film obtained in Example 1-3; a) Example 1, b) Example 2, c) Example 3.

5 is an IR spectrum of the surface of the polymer film or polymer film obtained in Example 7-9; a) Example 7, b) Example 8, c) Example 9.

6 is an IR spectrum of the surface of the polymer film or polymer film obtained in Example 13. FIG.

The present invention is a dendritic polymer having a multi-reactor using a simple plasma on the polymer film or film surface, that is, dendritic polymers, second-generation dendrimers, hyper-branched polymers, or dendritic polymers in which the active material is substituted at the terminal group Is to produce an organic thin film with many star-shaped polymer.

That is, plasma is used to activate the surface of the polymer film, and the activity generated on the surface of the polymer and the chemical bond with the outermost reactor of the dendritic polymer to form an organic thin film through the covalent bond on the dendritic polymer surface do.

In this case, the polymer film may be a dense film or an asymmetric film and the polymer film may be a polymer film such as polydimethylsilicone (PDMS), polysulfone, polyimide, polyethersulfone, cellulose, polypropylene, polyethylene, or the like. General purpose or specialty polymers.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

When manufacturing organic thin film with dendritic polymer with terminal reactor, it is prepared by plasma treatment in the presence of air plasma or maleic anhydride, and organic thin film with dendritic polymer or star polymer without terminal reactor It is prepared by introducing a compound having an azide (N ₃ ) group in the method of, and adding a UV irradiation process.

Each will be described in detail.

In the organic thin film manufacturing method using a dendrimer having an end reactor by air plasma treatment, the polymer film or film is placed in a plasma reactor and subjected to air plasma treatment as shown in FIG. 1. At this time, an oxidation reaction occurs on the surface to generate various kinds of reactors such as carboxyl group, hydroxyl group (hrdroxyl), ketone group, and peroxide group. When the polymer membrane or film treated in air is immersed in a solution containing dendritic polymer which is a terminal reactor capable of chemical bonding with the reactor formed on the surface, and reacted at 120 ° C, the terminal reactor and polymer membrane of the dendrimer are reacted. By chemically reacting with the surface reactors, a dendritic organic thin film is prepared on the polymer film surface. The reaction was confirmed through IR and detailed in the Examples.

The organic thin film manufacturing method of the dendritic polymer with a terminal reactor in the presence of maleic anhydride is a plasma treatment by placing a certain amount of maleic anhydride together with the polymer film or film in the plasma reactor as shown in FIG. As a gaseous monomer, a double bond is chemically reacted and adheres to the polymer membrane surface. Therefore, an anhydride or ring-opened reactor is introduced to produce a dendritic thin film on the surface of the polymer membrane through chemical reaction with a dendritic polymer having a terminally reactive group capable of chemically bonding thereto.

Terminal reactors usable here include amine, carboxy, carboxylic ester, epoxy, isocyanate, hydroxy, sulfhydryl and the like.

An organic thin film was prepared by using a dendrimer or a star-shaped polymer without a terminal reactor, as shown in FIG. 3, using UV irradiation.

When a certain amount of maleic anhydride is added to the plasma reactor together with a polymer film or film and subjected to plasma treatment, maleic anhydride becomes a gaseous monomer, and double bonds are chemically reacted, and anhydride groups adhere to the polymer film or film surface. The anhydride reacts with p-azidoaniline at pH 8.5 to form azide (N ₃ ) on the polymer membrane or film. When irreactive dendritic polymer or star-shaped polymer is placed on this, UV irradiation causes dendrimer or star polymer to adhere to polymer film or film surface through radicals generated by decomposition of azide. do.

The polymer film or the dendritic polymer on the film may be substituted with a material containing oxygen, nitrogen, sulfur, etc., depending on the application field.

The following examples are intended to illustrate the invention in more detail, but the invention is not limited thereto.

(Example 1)

Polydimethylsilicone (PDMS) membrane under the trade name SSPM100 from Specialty Silicone Product was used as the polymeric support. The PDMS scaffold, which was well washed with methanol several times, was placed in a plasma reactor and subjected to plasma treatment for 1 minute after vacuum. The plasma apparatus was treated with an autoelectric R-300A radio-frequency generator fixed at 50W at 13.56MHz. The reaction was completed by placing 3.1 × ^{10 −11} mol of a dendrimer per 1 cm ^{2 of the} treated PDMS support at 120 ° C. for 1 hour. After the reaction, the unreacted dendrimer was washed away, and the IR diagram of the PDMS surface to which the dendrimer was attached is shown by a of FIG. 4.

The characteristic peaks of the dendrimer, 1649 and 1551 cm ^-1, are shown.

(Example 2)

The PDMS membrane was treated in the same manner as in Example 1, and a 3.1x10 ^-10 mole dendrimer was placed per cm ^{2 of} the PDMS support, followed by 1 hour at 120 ° C to complete the reaction. After the reaction, the unreacted dendrimer was washed away, and the IR diagram of the PDMS surface to which the dendrimer was attached is shown in b of FIG. 4.

(Example 3)

The PDMS membrane was treated in the same manner as in Example 1, and a 3.1x10 ^-9 mole dendrimer was placed per cm ^{2 of} the PDMS support, and the reaction was completed at 120 ° C. for 1 hour. After the reaction, the unreacted dendrimer was washed away, and the IR diagram of the PDMS surface to which the dendrimer was attached is shown in FIG. 4C.

(Example 4-6)

The propane and propylene gas permeability of the polymer membranes with different dendrimers attached on the PDMS membranes prepared in Examples 1-3 were measured with a bubble flow meter. The results are shown in Table 1.

TABLE 1

Measuring film Propane Propylene Example 4 Example 1 8390 7770 Example 5 Example 2 6840 6820 Example 6 Example 3 7280 6270

(Unit = barrer)

(Example 7)

Into a plasma reactor, a PDMS scaffold washed well with methanol several times and Merck's maleic anhydride were added together with 30 mg of vacuum, followed by plasma treatment for 1 minute. The reaction was completed by placing 3.1 × ^{10 −11} mol of a dendrimer per 1 cm 2 of the treated PDMS support at 120 ° C. for 1 hour. After the reaction, the unreacted dendrimer was washed away, and the IR diagram of the PDMS surface to which the dendrimer was attached is shown in FIG. The characteristic peaks of maleic anhydride were 1858 and 1782 cm ^-1 , and the amide characteristic peaks of dendrimer 1640 and 1550 cm ^{-1 were shown} .

(Example 8)

In the same manner as in Example 7, the PDMS membrane was treated in the presence of maleic anhydride, and the reaction was completed by placing a 3.1x10 ^-10 mole dendrimer per 1 cm 2 of the treated PDMS support and placing it at 120 ° C for 1 hour. After the reaction, the unreacted dendrimer was washed away, and the IR diagram of the PDMS surface to which the dendrimer was attached is shown in FIG.

(Example 9)

In the same manner as in Example 7, the PDMS membrane was treated in the presence of maleic anhydride, and 3.1 × 10 ⁻⁹ mol of a dendrimer was placed per 1 cm 2 of the treated PDMS support, and the reaction was completed by placing at 120 ° C. for 1 hour. After the reaction, the unreacted dendrimer was washed away, and an IR diagram of the PDMS surface to which the dendrimer was attached is shown in FIG.

(Example 10-12)

A bubble flow meter was used to measure propane and propylene gas permeability of a polymer membrane having a dendrimer attached in different amounts on the PDMS membrane prepared in Example 7-9.

Was measured. The results are shown in Table 2.

TABLE 2

Measuring film Propane Propylene Example 10 Example 7 690 1710 Example 11 Example 8 - 1650 Example 12 Example 9 - 340

(Unit = barrer)

(Example 13)

In the same manner as in Example 7, the PDMS membrane was treated in the presence of maleic anhydride, and the treated PDMS support was reacted in a 5 mM aqueous solution of p-azidoaniline hydrochloride (p-azidoaniline hydrochloride) at pH 8.5 for 2 hours at 30 ° C. Let. After the reaction, wash the membrane well to remove any unreacted material.

After drying the membrane well, add 1 mL of 1 wt% star polyethylene oxide (PEO) dissolved in acetonitrile and irradiate UV in the dark for 20 minutes to complete the reaction. The thickness of the film obtained at this time is 400 kPa. The IR spectrum of the film surface obtained at this time is shown in FIG. a is a spectrum of the surface of the PDMS film, b is the surface of the film on which the maleic anhydride is attached to the PDMS film, c is the surface of the film on which the N ₃ is attached to the PDMS film, and d is the surface of the surface of the star PEO on the PDMS film.

(Example 14)

Gas permeability of the membrane prepared in Example 13 was measured. Propylene was 3770 barrer and propane was 3510 barrer.

(Example 15)

Polysulfone asymmetric membrane (Note, Saehan) was used as the polymer support. Polysulfone support and maleic anhydride were added together in a plasma reactor together with 30 mg of vacuum, followed by plasma treatment for 1 minute. The treated polysulfone support was reacted at 30 ° C. for 2 hours in a 5 mM aqueous solution of p-azidoaniline hydrochloride at pH 8.5. After the reaction, wash the membrane well to remove any unreacted material.

After drying the above membrane well, add 1 mL of 1% by weight star-shaped PEO dissolved in acetonitrile and irradiate UV in the dark for 20 minutes to complete the reaction.

(Example 16)

In the same manner as in Example 7, the PDMS membrane was treated in the presence of maleic anhydride, and the treated PDMS support was reacted in a 5 mM aqueous solution of p-azidoaniline hydrochloride (p-azidoaniline hydrochloride) at pH 8.5 for 2 hours at 30 ° C. Let. After the reaction, wash the membrane well to remove any unreacted material.

After drying the above membrane, 1 mL of PAMAM dendrimer substituted with 1% by weight of poly (2-ethyl-2-oxazoline) dissolved in acetonitrile was added. UV is irradiated for 20 minutes to complete the reaction.

(Example 17)

A terminal reactor reacts with carboxymethacrylate PEG (Shearwater, CM-PEG) to the membrane prepared in Example 9 to induce a chemical reaction with the terminal amine groups of the dendrimer attached to the surface of the PDMS surface to form a biocompatible material PEG. This substituted polymer membrane was prepared.

(Example 18)

Poly (2-ethyl-2-oxazoline) in which the terminal reactor was replaced with active ester in the membrane prepared in Example 9 (synthesis in lab; SCLee, Y Chang, J.-S. Yoon, C. Kim, IC Kwon, Y.-H. Kim, SY Jeong, Macromolecules, 1999, 32, 1847) to react the amine groups of the terminal amine groups of the dendrimer attached to the PDMS membrane surface. The reaction was induced to prepare a polymer membrane having olefin promoting transport activity.

According to the present invention, a dendritic polymer having a reactor at the end of a polymer film or a polymer film can be prepared in a thin film through a simple plasma treatment in the air or in the presence of maleic anhydride, and a dendritic polymer or a star without a reactor is formed. After a simple plasma treatment of the nanometer size of the polymer was introduced into the azide group was also produced a thin film on the polymer film or polymer film by UV irradiation. The present invention has the effect of coating a surface of a polymer film or a polymer film with a nanometer-sized thin film by using a simple plasma method, UV irradiation, etc., which is easy to process and has high applicability.

In the case of dendrimer thin films with many reactors on the surface, thin films simply made of biocompatible materials such as PEO can be used as biocompatible materials.If other materials are added or substituted depending on the application, chemical sensors, adsorbents, separators, etc. Suitable for use in a wide range of applications.

Claims (12)

A polymer film or film having a dendritic polymer substituted with a nanometer-thick dendritic polymer or an applicable material through plasma treatment. The polymer film or film according to claim 1, wherein a dendritic polymer having a terminal reactor is attached through plasma treatment in air or in the presence of maleic anhydride. The polymer film or film according to claim 1, wherein a dendritic polymer without a terminal reactor is covalently attached by introducing an azide group after plasma treatment in the presence of maleic anhydride and irradiating with UV. 3. The polymer of claim 1 or 2, wherein the terminal reactor of the dendritic polymer is one or more reactors selected from amine, carboxy, carboxylic ester, epoxy, isocyanate, hydroxy and sulfhydryl. Membrane or film. The polymer membrane or film of claim 1, wherein the dendritic polymer is a second generation or higher dendrimer, a hyperbranched polymer, or a branched star polymer. The method of claim 1, wherein the polymer film is in the group consisting of general-purpose or specialty polymers, which may be polymer films such as polydimethylsilicone (PDMS), polysulfone, polyimide, polyethersulfone, cellulose, polypropylene and polyethylene Wherein the polymer film is a dense film or an asymmetric film. The polymer membrane or film of claim 1, wherein the dendritic polymer is substituted with a compound having one or more elements selected from the group consisting of oxygen, nitrogen or sulfur in the chain. Plasma treatment on the polymer film or film to give activity to the polymer film or film surface; Dipping the treated polymer film or film in a dendritic polymer solution; Method for producing a polymer film or film with a dendritic polymer comprising a. 9. A method according to claim 8, wherein the plasma treatment is carried out in air or in the presence of maleic anhydride. [Claim 10] The method of claim 8, further comprising the step of introducing azide groups after plasma treatment in the presence of maleic anhydride and irradiating UV to attach dendritic polymers without terminal reactors by covalent bonds. Manufacturing method. The method of claim 8, wherein the dendritic polymer substituted with an applicable material is a polymer film or film production, characterized in that substituted with a compound having one or more elements selected from the group consisting of oxygen, nitrogen or sulfur in the chain Way. According to claim 1, wherein the compound having one or more elements selected from the group consisting of oxygen, nitrogen or sulfur in the chain using a terminal reactor of the dendritic polymer on the polymer film or polymer film to which the dendritic polymer is attached Polymer membrane or film, characterized in that substituted.