KR102106060B1 - Method of hydrophilic surface modification for hydrophobic polylefin and use thereof - Google Patents

Abstract

The present invention comprises the steps of (a) preparing a polyolefin carrier by washing and drying it with an organic solvent, (b) applying an organic mixed solution to the polyolefin carrier prepared in step (a) and (c) step (b). After removing the organic mixed solution from the polyolefin carrier, it is immersed in an inorganic mixed solution to polymerize, and in the step (b), the organic mixed solution is prepared to include a urethane-based monomer and an acrylic monomer.
The hydrophilic polyolefin film produced by the polyolefin hydrophilization method as described above can be permanently reused.

Description

Hydrophobic polyolefin surface hydrophilic treatment method and use thereof {METHOD OF HYDROPHILIC SURFACE MODIFICATION FOR HYDROPHOBIC POLYLEFIN AND USE THEREOF}

The present invention relates to a method for treating hydrophilic surfaces of hydrophobic polyolefins and uses thereof.

Polyolefin refers to a polymer made by polymerizing a substance containing a double bond based on hydrocarbon. Polyolefins include polyethylene, polypropylene, polymethylpentene, polybutene, polyisobutylene, and ethylene propylene, which are widely used in various industries, from general household products to electronics, secondary batteries, medical, non-woven fabrics, and textiles. . According to Markets and Markets' 2016 report, polyolefins are projected to grow at an annual average rate of 7.82% by 2021, and the market is expected to increase to more than $ 2797 billion.

Since these polyolefins have hydrophobicity, they are widely used in places where physical chemical properties and deformation of the molding structure are not desired, such as separators of secondary batteries, delivery pipes, and various moldings.

However, since polyolefin is hydrophobic, it is difficult to impart functionality to the surface of a molded article. For example, since the electrolyte of a secondary battery is generally aqueous, in the case of a separator, it is necessary to develop a variety of hydrophilization technologies for this, since it is necessary to have hydrophilicity to increase the power generation capacity due to an increase in ion diffusion rate. As another example, polypropylene is often used as a packaging material because it has few harmful release substances in the food side, but it may be necessary to improve the adhesion by hydrophilizing the surface by all means because of its hydrophobic nature, adhesion is weak and sealing is impossible. Even for the same polyolefin, surface hydrophilization is also required to paint various surface colors. There are various product groups for the basic water safety of polyolefins, and these also require various surface hydrophilization techniques.

Typical surface treatment methods include corona discharge using high voltage, flame treatment, UV treatment, and plasma treatment methods. Depending on the purpose of the polyolefin, these technologies can be applied, but basically have the disadvantage that the price, maintenance, and 3D structure of the equipment are not completely processed by the shadow effect by the holder. In particular, these treatments seem to become hydrophilic at the moment of exposure to air due to the formation of radicals by high energy on the surface, but return to hydrophobicity over long periods of exposure. For permanent hydrophilization, plasma polymerization is a method of first inducing surface radical formation by plasma, and polymerization through a gaseous hydrophilic monomer. At this time, since the hydrophilic monomers that can be used are limited, this technology is also limited.

Direct chemical treatment will be able to induce various surface characterizations suited to the purpose by the variability of the selected chemical. However, most of the hydrophobic poly olefins have a stable chemical structure, so it is almost impossible to perform a chemical treatment method through a covalent bond having a very high chemical stability. Therefore, surface hydrophilization is proceeding through physical bonding, and the most representative material is a method using a surfactant. For example, US patent 4988449 is a hydrophilic composition used as an agent containing non-ionic surfactants, alkyl phosphates, quaternary ammonium salts and / or diethanol amides such as alkyl imidazolium salts and imparting fluid permeability to polyolefins. Is described. From US 5258129, a hydrophilic composition containing polyoxyalkylene-modified polydimethylsiloxane alone or in combination with a nonionic surfactant, alkyl phosphate, quaternary ammonium salt and / or alkyl imidazolium salt, EP 0 839 From 947 A2, a hydrophilic composition containing a nonionic surfactant in combination with a polyoxyalkylene-modified polydimethylsiloxane and / or quaternary ammonium compound, EP 1 600 532 B1 is an alkoxylated glycerol esterified with fatty acids and Hydrophilic compositions comprising fatty acids and esterified alkoxylated or alkoxylated and hydrogenated ricinoleins are described. However, the surfactants of the ionic / nonionic systems appear to be hydrophilic in the polyolefin surface in the dry form, but if the polyolefin is continuously impregnated in the water, it is all washed and desorbed. see.

As a permanent chemical hydrophilization method, there is a method of mixing melanic anhydride, benzoyl peroxide, and polyolefin in a high-temperature extruder and then mixing at about 180 degrees. This is the temperature-sensitive benzoyl peroxide (benzoyl peroxide) is formed at a high temperature lycal, the radical formed is decomposed polyolefin polymer chain to form a radical again. And, it induces a chemical bond with melanic anhydride. Although this method appears to be capable of stably hydrophilizing the surface, it cannot be said that the water contact angle was measured to have a total hydrophilicity of 70 degrees or more. In addition, since it is mixed in an extruder, melanic anhydride is also present in the inside of a molded product, which has a disadvantage of lowering the overall mechanical strength.

Recently, biomimetic chemicals have been introduced with hydrophilization technology through polydopamine. However, polydopamine has a disadvantage in that it is not suitable for coating low-cost polyolefins because of its very high price, and because it is surface hydrophilized by self-oxidation, it is impossible to reuse the solution once used. .

Therefore, as only the surface of the molded product becomes hydrophilic, research into a technology capable of permanently maintaining hydrophilicity is underway. This technology is expected to enable new product development by overcoming industrial limitations of polyolefins in the polymer market.

Republic of Korea Patent Publication No. 2015-0082329 U.S. Patent Publication No. 488449

 Primers for adhesive bonding to polyolefins, Volume 48, Issue 2, 1993, Pages 359-370  Chemical modification of polypropylene by maleic anhydride: melting grafting, characterization and mechanism; International journal of chemical engineering and application, vol 5, No 2. 2014

The present invention aims to provide a permanently reusable hydrophobic polyolefin surface hydrophilic treatment method and use thereof.

The object of the invention is not limited to the objects mentioned above. The object of the present invention will be more apparent from the following description, and will be realized by means described in the claims and combinations thereof.

The polyolefin hydrophilization method according to an embodiment of the present invention comprises: (a) preparing a polyolefin carrier by washing and drying it with an organic solvent, and (b) applying an organic mixed solution to the polyolefin carrier prepared in the step (a). And (c) removing the organic mixed solution from the polyolefin carrier of step (b), followed by immersing in an inorganic mixed solution to polymerize, and the organic mixed solution in step (b) includes a urethane-based monomer and an acrylic monomer. do.

In step (a), the polyolefin may be selected from the group consisting of homopolymers, copolymers of olefins such as ethylene, propylene, methylpentene, butene, isobutylene, ethylene propylene, and combinations thereof.

In step (b), the acrylic monomer may be included in an amount of 0.1 to 10% by weight based on the total weight of the organic mixed solution.

In step (b), the urethane-based monomer may be selected from the group consisting of aromatic isocyanate compounds, toluene diisocyanate compounds (TDI), aliphatic diisocyanates, triisocyanates, polyisocyanates, and combinations thereof.

In the step (b), the acrylic monomer may be selected from the group consisting of vinylbenzyl trimethylammonium, negatively charged monomer, alcohol group-containing monomer, and combinations thereof.

In the step (c), the inorganic mixed solution may include water, a radical initiator, and a catalyst.

The radical initiator may be selected from the group consisting of ammonium persulfate, potassium persulfate, benzoyl peroxide, and combinations thereof.

The catalyst is N, N, N, N-tetramethylethylenediamine (N, N, N, N-tetramethylethylenediamine), N'-benzyl-N, N-dimethylethylenediamine (N'-benzyl-N, N-dimethylethylenediamine ), N-benzylethylenediamine, N, N-diethyl-N'-phenylethylenediamine, N, N'-dibenzyl-N, N '-Dimethylethylenediamine (N, N'-dibenzyl-N, N'-dimethylethylenediamine), N, N'-dibenzylethylenediamine, N, N-diethyl-N', N '-Dimethylethylenediamine (N, N-diethyl-N', N'-dimethylethylenediamine), N, N, N ', N'-tetrakis (2-hydroxyethyl) ethylenediamine (N, N, N', N'-tetrakis (2-hydroxyethyl) ethylenediamine), N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine (N, N, N'N'-tetrakis (2-hydroxypropyl) ethylenediamine ), N, N, N ', N'-tetraallylethylenediamine (N, N, N', N'-tetraallylethylenediamine), N, N, N ', N'-tetraethylenediamine (N, N, N' , N'-tetraethylethylenediamine) and combinations thereof It can be selected from the group.

The composition for treating a polyolefin hydrophilic according to another embodiment of the present invention includes a urethane-based monomer and an acrylic monomer.

In the hydrophilic polyolefin film according to another embodiment of the present invention, the surface of the polyolefin is hydrophilized by a mixed solution containing a urethane-based monomer and an acrylic monomer.

The water contact angle of the polyolefin film may be 0 to 40 degrees.

The separator of the battery according to another embodiment of the present invention includes a polyolefin carrier on which the surface of the polyolefin is hydrophilized by an organic mixed solution containing a urethane-based monomer and an acrylic monomer.

According to an embodiment of the present invention, by using a urethane-based monomer and an acrylic monomer, it is possible to provide a hydrophobic polyolefin surface hydrophilic treatment method and its use, which can more easily hydrophilize the surface of the hydrophobic polyolefin.

1 is a process diagram for explaining a method for hydrophilizing the polyolefin of the present invention.
2 is an image showing a polymer network formed of a urethane-based monomer and an acrylic monomer on the polyolefin surface according to the present invention.
3 is a photograph showing the contact angle and impregnation ability of Example 1 and Comparative Example 1 according to the present invention.
4 is an image showing the contact angle and impregnation ability of Examples 1 to 3 and Comparative Examples 1 and 2;
5 is a graph showing the results of the hydrophilicity retention ability experiments of Examples 1 to 3 and Comparative Example 2 according to the present invention.
6A is a photograph showing the results of the microbial deposition ability experiment of Comparative Example 1, and FIG. 6B is a photograph showing the results of a microbial deposition ability experiment of Example 1.

The above objects, other objects, features and advantages of the present invention will be readily understood through the following preferred embodiments related to the accompanying drawings. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided to ensure that the disclosed contents are thorough and complete and that the spirit of the present invention is sufficiently conveyed to those skilled in the art.

Hereinafter, the method for hydrophilicizing the hydrophobic polyolefin surface of the present invention will be described in detail according to the drawings.

1 is a process diagram for explaining a method for hydrophilizing the polyolefin of the present invention.

Referring to Figure 1, first, the polyolefin carrier is prepared by washing and drying with an organic solvent (S10).

The polyolefin may be selected from the group consisting of homopolymers of olefins such as ethylene, propylene, methylpentene, butene, isobutylene, ethylenepropylene, copolymers, and mixtures thereof.

The organic solvent may be selected from the group consisting of isopropyl alcohol, acetone, dimethyl ketone, and combinations thereof, but is not limited thereto and is not particularly limited as long as it is a material capable of washing the polyolefin carrier.

Next, an organic mixed solution is applied to the polyolefin carrier (S20).

The pores of the polyolefin carrier prepared in step S10 can be sufficiently coated to impregnate the organic mixed solution. Here, the organic mixed solution may include an acrylic monomer and a urethane monomer, and may further include a crosslinking agent so that the acrylic monomer does not escape into the water.

The organic mixed solution may include 70 to 99% by weight of an organic solvent, 0.1 to 20% by weight of a urethane-based monomer, 0.1 to 10% by weight of an acrylic monomer, and 0.01 to 0.5% by weight of an initiator.

The organic solvent may be 70 to 99% by weight, preferably 75 to 85% by weight, more preferably 77 to 81% by weight.

The urethane-based monomer is a material for improving adhesion, and if it is less than 0.1% by weight, it is difficult to coat the entire surface of the hydrophobic urethane, and if it exceeds 20% by weight, the processing cost may be increased due to an amount more than necessary.

The acrylic monomer is a material that improves hydrophilicity. If it is less than 0.1% by weight, it is difficult to expect a degree of hydrophilicity due to a small content, and if it exceeds 10% by weight, the processing cost may be increased due to an amount more than necessary.

The organic solvent may be selected from the group consisting of dimethylformamide (DMF), dimethylsulfoxide (DMSO), dimethylacetamide (DMAc) N-methylpyrrolidone (NMP), chloroform and combinations thereof.

The acrylic monomers include vinylbenzyl trimethylammonium, a negatively charged monomer, a monomer having an alcohol group, and combinations thereof, preferably acrylic acid, vinylacylic monomer, vinylylacrylicmonomer, and methylene bis Acrylamide (metyulenebisacrylamide) and combinations thereof.

The urethane-based monomer is an aromatic isocyanate compound, preferably diphenylmethane diisocyanate compound (MDI): isomer thereof, carbodiimide modified MDI, diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,2 '-Diisocyanate, diphenyl-methane-2,4'-diisocyanate, and oligomer phenyl methylene isocyanate; Toluene diisocyanate compound (TDI): isomers thereof, tetramethylxylene diisocyanate (TMXDI), isomers of naphthylene diisocyanate, isomers of triphenylmethane triisocyanate; Aliphatic diisocyanates, preferably triisocyanates and polyisocyanates: isophorone diisocyanate, hydrogenated aromatic diisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate, and combinations thereof.

In the case of the hydrophobic polyolefin of the present invention, when the same material is basically applied, the physical adsorption capacity may be the best, for example, polypropylene is a copolymer having a polymer chain similar to polypropylene and an alcohol group in detail. When used, the ability to adhere to a hydrophilic material can be increased. In particular, in order for the permanent hydrophilic material to be continuously present on the surface, it is preferable to use a primer having a crosslink (network) structure rather than a linear polymer chain.

Finally, the polyolefin carrier is immersed in an inorganic mixed solution to polymerize (S30).

After removing the organic mixed solution from the polyolefin carrier in step S20, the polyolefin carrier can be polymerized by sufficiently immersing the polyolefin carrier in the inorganic mixed solution so that the urethane reaction can be induced by the inorganic mixed solution on the urethane monomer on the polyolefin carrier.

Specifically, urethane monomers are catalyzed by water, and radical initiators contained in water can polymerize hydrophilic monomers. Since these polymerizations go to different reaction mechanisms, they can form a network as they grow, and spontaneous hydrophilic monomers are applied in excess to the surface of the polyurethane because they are directed toward the water. In particular, the surface roughness of the foamed polyurethane Can be increased.

The inorganic mixed solution may include water, a radical initiator, and a catalyst, and preferably 90 to 99% by weight of water, 0.1 to 5% by weight of a radical initiator, and 0.1 to 5% by weight of a catalyst.

The radical initiator may be 0.1 to 5% by weight, preferably 0.5 to 3% by weight, and the catalyst may be 0.1 to 5% by weight, preferably 0.5 to 3% by weight.

Here, the radical initiator may be selected from the group consisting of ammonium persulfate, potassium persulfate, benzoyl peroxide and combinations thereof.

The catalyst is N, N, N, N-tetramethylethylenediamine (N, N, N, N-tetramethylethylenediamine), N'-benzyl-N, N-dimethylethylenediamine (N'-benzyl-N, N-dimethylethylenediamine ), N-benzylethylenediamine, N, N-diethyl-N'-phenylethylenediamine, N, N'-dibenzyl-N, N '-Dimethylethylenediamine (N, N'-dibenzyl-N, N'-dimethylethylenediamine), N, N'-dibenzylethylenediamine, N, N-diethyl-N', N '-Dimethylethylenediamine (N, N-diethyl-N', N'-dimethylethylenediamine), N, N, N ', N'-tetrakis (2-hydroxyethyl) ethylenediamine (N, N, N', N'-tetrakis (2-hydroxyethyl) ethylenediamine), N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine (N, N, N'N'-tetrakis (2-hydroxypropyl) ethylenediamine ), N, N, N ', N'-tetraallylethylenediamine (N, N, N', N'-tetraallylethylenediamine), N, N, N ', N'-tetraethylenediamine (N, N, N' , N'-tetraethylethylenediamine) and combinations thereof It can be selected from the group.

When the step of polymerizing by immersing the polyolefin carrier as described above in an inorganic mixed solution is completed, a hydrophilic polyolefin film (S40) having a stable structure in which two polymers are entangled to form a network is obtained.

2 is an image showing a polymer network formed of a urethane-based monomer and an acrylic monomer on the polyolefin surface according to the present invention.

Since the hydrophilic polyolefin film produced by the above-described manufacturing method has a structure in which the urethane-based and acrylic polymer chains are intertwined as shown in FIG. 2, a hydrophilic polymer material cannot be formed. In addition, at this time, the water contact angle of the hydrophilic polyolefin membrane may be 0 to 40 degrees, and may be used as a separator or water treatment membrane of the battery.

The separator or water treatment membrane of the battery is a hydrophilic surface of a polyolefin carrier by an organic mixed solution containing a urethane-based monomer and an acrylic monomer, and is permanently reusable.

The present invention can provide a composition for treating a polyolefin hydrophilicity comprising a urethane-based monomer and an acrylic monomer. Urethane-based monomers and acrylic-based monomers have already been described in detail above, and thus will be omitted.

Examples 1 to 3. Preparation of polyethylene film

After washing the polyethylene carrier with an organic solvent, it was sufficiently dried in a vacuum oven. Then, an organic mixed solution prepared by mixing each of the components and contents disclosed in Table 1 below was applied to the polyethylene carrier, and then the organic mixed solution was removed from the polyethylene carrier. And, by immersing in the inorganic mixture solution prepared by mixing each with the components and contents disclosed in Table 1 below to prepare a polyethylene film.

Table 1 is a table showing the respective components and contents (% by weight) of the organic mixed solution and the inorganic mixed solution.

division ingredient Example 1 Example 2 Example 3
Organic mixed solution Chloroform 79.6 79.6 79 Polyisocyanate prepolymer 0.2 0.2 0.4 Vinylbenzyltrimethylammonium chloride 0.1 - - Acrylic acid - 0.1 0.4 Methylene bisacrylamide 0.1 0.1 0.4 N-methylpyrrolidone 20 20 19.8
Inorganic mixed solution Ammonium persulfate One One One N, N, N, N-tetramethylethylenediamine One One One water 98 98 98

Comparative Example 1. Preparation of polyethylene film

A polyethylene carrier without hydrophilization treatment was used as it is.

Comparative Example 2. Preparation of polyethylene film

Polyethylene membranes were prepared in the same manner as in Example 1 to Example 3, except that an organic solvent and an urethane monomer were used as the organic mixed solution, and water was used as the inorganic mixed solution.

Experimental Example 1. Hydrophilization characteristics

In order to confirm the ability to maintain the hydrophilicity of the polyethylene film according to the present invention, an experiment was conducted as follows.

First, the polyethylene films obtained in Examples 1 to 3 and Comparative Examples 1 to 2 were respectively impregnated in distilled water, and then the contact angle was measured.

Thereafter, each polyethylene film was impregnated with distilled water at 40 ° C., and then ultrasonic cleaning was performed for 30 minutes using an ultrasonic cleaning method. Then, after washing and drying each polyethylene film with distilled water, the contact angle was measured. This process was repeated 6 times.

3 is a photograph showing the contact angle and impregnation ability of Example 1 and Comparative Example 1 according to the present invention, and FIG. 4 is a contact angle and impregnation of Examples 1 to 3 and Comparative Example 1 and Comparative Example 2 according to the present invention. Image showing the ability, Table 2 is a table showing the results of FIG.

As a result, referring to FIGS. 3, 4 and Table 2, it was confirmed that the contact angle of Example 1 was lower than that of Comparative Example 1. On the other hand, it was confirmed that the contact angles of Example 1 and Comparative Example 2 were not significantly different. Accordingly, it was found that the content of the urethane-based monomer does not significantly affect the change in the contact angle, but the content of the acrylic monomer affects the change in the contact angle.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Contact angle 40 35 0 93 degrees 45 degrees

5 is a graph showing the results of the hydrophilicity retention ability experiments of Examples 1 to 3 and Comparative Example 2 according to the present invention.

Referring to FIG. 5, in spite of repeated ultrasonic cleaning, Examples 1 to 3 were able to confirm that hydrophilization was relatively continuously maintained compared to Comparative Example 2.

Experimental Example 2. Microbial Deposition Characteristics

The experiment was conducted as follows to confirm the continuous microbial deposition ability of the polyethylene film according to the present invention.

After applying the polyethylene film obtained in Example 1 and Comparative Example 1 as a microbial treatment carrier in industrial wastewater, the degree of microbial deposition was measured for 3 months.

6A and 6B are photographs showing the results of microbial deposition ability experiments.

6A and 6B, it was confirmed that microorganisms were not deposited on the polyethylene film of Comparative Example 1, but microorganisms were impregnated on the polyethylene film of Example 1.

The invention made by the present inventors has been described in detail according to the above-described embodiments, but the present invention is not limited to the above-described embodiments and can be changed in various ways without departing from the gist thereof.

Claims (12)

(A) preparing a polyolefin carrier by washing and drying with an organic solvent;
(b) applying an organic mixed solution to the polyolefin carrier prepared in step (a); And
(c) after removing the organic mixed solution from the polyolefin carrier of step (b), immersing in an inorganic mixed solution to polymerize,
In the step (b), the organic mixed solution is at least one selected from the group consisting of vinylbenzyl trimethylammonium chloride, acrylic acid and methylene bisacrylamide, and a polyolefin hydrophilization method comprising a polyisocyanate prepolymer.
According to claim 1,
In step (a), the polyolefin is a polyolefin hydrophilization method selected from the group consisting of homopolymers, copolymers of olefins composed of ethylene, propylene, methylpentene, butene, isobutylene, and ethylene propylene, and combinations thereof.
According to claim 1,
In the step (b), one selected from the group consisting of vinylbenzyl trimethylammonium chloride, acrylic acid, and methylene bisacrylamide, based on the total weight of the organic mixed solution, contains 0.1 to 10% by weight of a polyolefin hydrophilization method.
delete delete According to claim 1,
In the step (c), the inorganic mixed solution comprises water, a radical initiator, and a catalyst.
The method of claim 6,
The radical initiator is a polyolefin hydrophilization method selected from the group consisting of ammonium persulfate (ammonium persulfate), potassium persulfate (potassium persulfate), benzoyl peroxide (benzoyl peroxide) and combinations thereof.
The method of claim 6,
The catalyst is N, N, N, N-tetramethylethylenediamine (N, N, N, N-tetramethylethylenediamine), N'-benzyl-N, N-dimethylethylenediamine (N'-benzyl-N, N-dimethylethylenediamine ), N-benzylethylenediamine, N, N-diethyl-N'-phenylethylenediamine, N, N'-dibenzyl-N, N '-Dimethylethylenediamine (N, N'-dibenzyl-N, N'-dimethylethylenediamine), N, N'-dibenzylethylenediamine, N, N-diethyl-N', N '-Dimethylethylenediamine (N, N-diethyl-N', N'-dimethylethylenediamine), N, N, N ', N'-tetrakis (2-hydroxyethyl) ethylenediamine (N, N, N', N'-tetrakis (2-hydroxyethyl) ethylenediamine), N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine (N, N, N'N'-tetrakis (2-hydroxypropyl) ethylenediamine ), N, N, N ', N'-tetraallylethylenediamine (N, N, N', N'-tetraallylethylenediamine), N, N, N ', N'-tetraethylenediamine (N, N, N' , N'-tetraethylethylenediamine) and combinations thereof Hydrophilic polyolefin method selected from the group.
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