KR100644879B1 - Methods increase the polarity of EPDM by Halogenation - Google Patents

Abstract

The present invention relates to a method for improving the polarity of ethylene propylene diene terpolymer (EPDM) using a halogenation reaction, and more specifically, to a polar monomer by grafting a halogenated compound to a diene of EPIDM having weak adhesive and adhesive properties. It relates to a method for improving the polarity of EPDM can be improved.

In the polarity enhancement method of EPDM of the present invention, the polarity enhancement method of the conventional EPDM,

(1) reacting an initiator with EPDM to generate free radicals in diene of EPDM;

(2) a step of substituting a halogen compound with diene of IPMD where free radicals are produced.

Meanwhile, in the above-mentioned steps (1) and (2), a halogen compound is substituted with a halogen compound in diene of IPMD where free radicals are generated as step (2) as step (3), and then an ammonium catalyst is present. Further comprising the step of reacting with a metal compound under which bromine can further enhance the polarity of EPIDM.

Description

Method for increasing polarity of EPDM using halogenation reaction {Methods increase the polarity of EPDM by Halogenation}             

1 is a graph confirming the reaction after the bromination reaction of IPD.

2 is a graph confirming the reaction after the bromination reaction of IPD.

3 is a graph confirming the reaction after the bromination reaction of IPD.

Figure 4 is a graph confirming this after the substitution reaction with sodium compound after bromination reaction of IPD.

The present invention relates to a method for improving the polarity of ethylene propylene diene terpolymer (EPDM) using a halogenation reaction, and more specifically, to a polar monomer by grafting a halogenated compound to a diene of EPIDM having weak adhesive and adhesive properties. It relates to a method for improving the polarity of EPDM can be improved.

The present invention is intended to improve the polarity of EPDM by grafting polar monomers to diene of nonpolar EPDM, which is very weak in adhesion and adhesiveness due to the properties of polyolefins.

Conventional ethylene, propylene, diene elastomers (EPDM) have a lower specific gravity than other synthetic rubbers, and can be filled with fillers, oils, etc. and have excellent physical properties such as ozone resistance, weather resistance, heat resistance, and solvent resistance. As a material, it is preferable for various uses, but since it is non-polar, compatibility with polar substrates such as nylon, polyester, aluminum, iron, paper, wood, and the like is poor, and its use range has been limited.

In order to solve this problem, a so-called primer method for chemically etching a non-polar polyolefin resin to impart a polar group, or pretreatment of a surface using a strong solvent such as toluene has been devised. In addition, a method of grafting a polar group on a polyolefin backbone to improve adhesion and adhesion has also been sought.

Meanwhile, as related arts related to the present invention, U.S. Patent No. 4,957,968 and Japanese Patent Application Laid-open No. Hei 1-259049 use grafting agents or modifiers such as maleic anhydride and poly (1,2-vinylbutadiene) and organosilanes. Disclosed is a method and composition of a thermoplastic elastomer with increased adhesion.

Korean Patent Publication No. 1990-16344 discloses a thermoplastic elastomer having excellent elongation and adhesion by reacting a crosslinkable olefin copolymer with an olefin monomer containing an amino group, an unsaturated carboxylic acid and a derivative thereof in the presence of an organic peroxide. It discloses how to.

However, the method for preparing a thermoplastic elastomer resin having excellent adhesive properties of US Pat. No. 4,957,968 and Japanese Patent Application Laid-Open No. Hei 1-259049 and Korean Patent Application Laid-Open No. 1990-16344 may include a grafting agent and an initiator in the process of preparing the thermoplastic elastomer. Due to the simultaneous addition of crosslinking and grafting reactions, the grafting efficiency is lowered, and thus the adhesion performance is limited, and the decomposition reaction of the polyolefin main chain is caused by the grafting initiator, resulting in deterioration of mechanical properties such as impact properties. There is a problem.

The present invention has been made to improve the above-mentioned problems, the present invention is to generate a radical by using a reaction initiator in the diene of IPD diem and to improve the polarity of IMP DM by the substitution reaction of the halogen compound and At the same time, it is an object of the present invention to provide a method for improving the polarity of EPDM that can inhibit the crosslinking reaction and the decomposition reaction of the main chain of other chains.

In addition, the present invention is to generate a radical in the aryl diene of the IMPDIM and then to carry out the halogenation reaction by substituting the halogen compound to the aryl of the diene and then further reacted with the salt compound to further improve the polarity. It is possible to provide a method for improving the polarity of EPDM.

Since the EPDM used in the present invention can improve the polarity by immediately processing the produced in liquid form, the step of purifying and solidifying EPDM for the storage and transport of EPDM before the bromination reaction of EPDM is unnecessary. It is possible to improve the overall manufacturing processability of EPDM with improved polarity.

In order to achieve the above-mentioned object, the polarity improvement method of EPDM of the present invention in the conventional polarity enhancement method of EPDM,

(1) reacting an initiator with EPDM to generate free radicals in diene of EPDM;

(2) a step of substituting a halogen compound with diene of IPMD where free radicals are produced.

The present invention provides a diene containing an aryl group to chemically bromination the diene of EPDM to improve the polarity of EPDM and to prevent crosslinking due to decomposition of the polyolefin main chain and reaction of propylene in the carbon chain. It is good to have.

As an example of diene containing such an aryl group, 5-ethylidene-2-norbornene (ENB), 1,4-cycloheptadiene, 1,5-cyclooctadiene, 4,7, 8,9-tetrahydroindene, bicyclo [3,2,0] 2,6-heptadiene, 1,2-divinylcyclobutane, 1,2,4-trivinylcyclohexane, dicyclopentadiene, Any one selected from methylidene norbornene, ethylidene norbornene and 1,6-hexadiene can be used.

In the present invention, IMPDM made of various contents is applied to each component constituting EPDM, the diene is 5 to 13wt%, the ethylene content is 40 to 70wt%, the propylene content is 25 to 60wt% It was found that it is appropriate to improve the polarity of EPDM using DM. Therefore, in the present invention, EPDM is preferably used in the diene 5 to 13wt%, ethylene content 40 to 70wt%, propylene content 25 to 60wt%.

In the present invention, radical polymerization is carried out using an initiator to generate free radicals in dienes of EPDM, prior to being halogenated at the aryl sites of dienes of EPDM.

In the present invention, the initiator is 1 to 10% by weight of the organic peroxide selected from acyl peroxide, dialkyl peroxide, arylalkyl peroxide, peroxyester, hydroperoxide, ketone peroxide, azo compound May react with EPDM to generate free radicals in the diene of EPDM.

In the present invention, when the organic peroxide, which is an initiator, is used in an amount of less than 1% by weight of EPDM, free radical generation is insufficient, and when it is more than 10%, excess free radical is generated, which is not suitable for a subsequent bromination reaction. Therefore, the initiator used for generating free radicals of EPDM in the present invention is preferably used 1 to 10% by weight of EPDM.

As an example of the acyl peroxide in the initiator, any one selected from benzoyl peroxide and lauroyl peroxide may be used.

In the initiator, any one selected from di-t-butyl peroxide, cumyl butyl peroxide, acetyl peroxide and dicumyl peroxide may be used as an example of dialkyl peroxide or aralkyl peroxide.

As one example of the peroxyester in the initiator, any one selected from t-butyl perbenzoate, t-butyl peroxy pivalate, t-butyl peroxy acetate, and cumyl peroxy neodecanoate can be used.

As one example of the hydroperoxide in the initiator, any one selected from t-butyl hydroperoxide cumene hydro peroxide and ethyl hydroperoxide may be used.

Among the initiators, any one selected from methyl ethyl ketone peroxide and carbamide peroxide may be used as an example of the ketone peroxide.

Azobis isobutyronitrile, azodimethylvareronitrile, azobismethylbutylonitrile, azobiscyanobaric acid, azobisamidinopropane, azobisdimethylene isobutyl amidine as an example of an azo compound in the said initiator , Azobiscyclohexenecarbonitrile can be used.

The polarity of the EPDM may be improved by generating a radical in the diene of EPDM with the initiator and then halogenating the halogen compound with EPDM to displace the halogen compound with EPDM.

In this case, as the halogen compound that can be used in the bromination reaction, any halogen compound selected from fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and asstatin (At) or a compound containing a halogen element may be used. Can be.

N-halosuccinimide can be used as an example of the halogen compound containing a halogen element in the above, N-bromosuccinimide (NBS), N-chlorosuccinimide as an example of such N-halosuccinimide (NCS), N-fluorosuccinimide (NFS), or N-iodosuccinimide (NIS) can be used.

In the present invention, a compound consisting of a halogen element or a compound containing such a halogen element may be reacted with 0.5 equivalents to 5 equivalents relative to the diene equivalent of EPDM.

In the present invention, it is preferable for the purpose of the present invention to use bromine or a bromine compound in the halogenation reaction to which the above-mentioned halogen compound is applied.

When bromine or bromine compound is used less than 0.5 equivalents of diene equivalents of EPDIDM in the substitution reaction by reacting bromine or bromine compound with EPDM diene, the bromine or bromine compound is less than diene equivalents of EPDM. If used in excess of the equivalent, there is a problem of being oxidized due to the remaining halogen compounds. Therefore, in the present invention, during the halogenation reaction of EPDM, it is preferable to react the halogen compound with 0.5 equivalents to 5 equivalents with respect to the diene equivalent of EPDM.

Meanwhile, in the above-mentioned steps (1) and (2), a halogen compound is substituted with a halogen compound in diene of IPMD where free radicals are generated as step (2) as step (3), and then an ammonium catalyst is present. Further comprising the step of reacting with a metal compound under which bromine can further enhance the polarity of EPIDM.

That is, the polarity of EPDM may be improved by controlling the polarity of EPDM by secondary reaction of the bromine-substituted EPDM.

The metal compound may be used as long as it can secondaryly react with bromine-substituted EPDM to control the polarity of EPDM and consequently improve the polarity of EPDM.

As an example of such a metal compound in the present invention, a metal compound containing a Group 1A metal or a Group 2A metal of the periodic table of elements can be used.

In the present invention, as an example of the metal compound, any one metal compound selected from sodium compounds, potassium compounds, lithium compounds, and magnesium compounds may be used.

Sodium acetate, sodium acrylate, sodium amide, sodium benzoate, sodium tetrabutoxide, sodium chlorate, sodium chloroacetate, sodium cyanate, sodium cyanide, sodium cyclohexane butyrate, sodium dichloro Acetate, sodium ethoxide, sodium ethane acrylate, sodium formate, sodium hydrochloride, sodium methacrylate, sodium octanoate, sodium periodate, sodium propionate sodium iodate, sodium iodoacetate, sodium 3- Any one selected from chlorodifluoroacetate can be used.

 Examples of the above potassium compounds include potassium acetate, potassium acrylate, potassium amide, potassium benzoate, potassium tetrabutoxide, potassium chlorate, potassium chloroacetate, potassium cyanate, potassium cyanide, potassium cyclohexanebutyrate, potassium dichloro Acetate, Potassium Ethoxide, Potassium Ethane Ethyl Oate, Potassium Formate, Potassium Hydrochloride, Potassium Metaacrylate, Potassium Octanoate, Potassium Periodate, Potassium Propionate, Potassium Iodide, Potassium Iodoacetate, Potassium Any one selected from 3-chlorodifluoroacetate can be used.

Lithium acetate, lithium acrylate, lithium amide, lithium benzoate, lithium tetrabutoxide, lithium chlorate, lithium chloroacetate, lithium cyanate, lithium cyanide, lithium cyclohexanebutylate, lithium dichloro Acetate, Lithium Ethoxide, Lithium Ethyl Olate, Lithium Formate, Lithium Hydrochloride, Lithium Methacrylate, Lithium Octanoate, Lithium Periodate, Lithium Propionate, Lithium Iodate, Lithium Iodoacetate, Lithium 3 Any one selected from -chlorodifluoroacetate can be used.

Magnesium acetate, magnesium acrylate, magnesium amide, magnesium benzoate, magnesium tetrabutoxide, magnesium chlorate, magnesium chloroacetate, magnesium cyanate, magnesium cyanide, magnesium cyclohexanebutylate, magnesium dichloro Acetate, Magnesium Ethoxide, Magnesium Ethane Ethylate, Magnesium Formate, Magnesium Hydrochloride, Magnesium Methacrylate, Magnesium Octanoate, Magnesium Periodate, Magnesium Propionate, Magnesium Iodate, Magnesium Iodoacetate, Magnesium 3 Any one selected from -chlorodifluoroacetate can be used.

In the present invention, the metal compound may be reacted with 0.5 equivalents to 5 equivalents relative to the diene equivalent of EPDM.

If the metal compound is less than 0.5 equivalent to the diene equivalent of EPDM, the reactivity is low, and if the metal compound is used more than 5 equivalents to the diene equivalent of EPDM, there is a problem of being oxidized due to the remaining metal compound. Therefore, in the present invention, the metal compound is preferably reacted with 0.5 equivalents to 5 equivalents relative to the diene equivalent of EPDM.

In the above, the metal compound is preferably reacted in the presence of an ammonium catalyst in order to improve reactivity.

Tetrabutylammonium chloride (TBAC), tetrahexyl ammonium chloride (THAC), tetraoctyl ammonium chloride (TOAC), tetrabutylammonium bromide (TBAB), tetrabutylammonium iodide (TBAI) as an example of such an ammonium catalyst in the present invention Any quaternary ammonium catalyst selected from among can be used.

In the present invention, the ammonium catalyst may improve the secondary reaction rate of the sodium compound by using 1/200 equivalents to 1/50 equivalents relative to the diene equivalent of EPDM.

If the ammonium catalyst is used less than 1/200 equivalents of the diene equivalent of EPDM, there is a problem that the reactivity is low, and if the sodium compound is used in excess of 1/50 equivalents of the diene equivalent of EPDM, the manufacturing cost increases. Therefore, in the present invention, the ammonium catalyst is preferably used in an amount of 1/200 equivalent to 1/50 equivalent relative to the diene equivalent of EPDM.

Hereinafter, the present invention will be described by the following examples and comparative examples. However, these are only examples of the present invention, which illustrate the present invention in more detail, and the scope of the present invention is not limited thereto.

<Example 1>

The solvent and the sample used what was stored under nitrogen atmosphere after purification.

80% of the volume inside the 200 ml flask was replaced with nitrogen. Into the flask, 5 g of EPDM (ethylene content: 59 wt%, 5-ethylidene-2-norbornene (ENB): 8.7 wt%) and 100 cc of toluene were added to dissolve IPMD and the temperature was decreased. It was kept at 90 ° C.

After completely dissolving EPDM in toluene, 0.2 g of benzoyl peroxide (BPO), a reaction initiator, was added to the flask and stirred at 350 rpm for 10 minutes, and 0.5 equivalent (0.6 g) of N-bromosuccinimide (NBS) was added to the ENB equivalent. The bromination reaction was carried out at 350 rpm for 6 hours.

After the bromination was completed, the precipitate was precipitated with methanol to replace NBS with ENB of diene of IPD. The modified EPDM was dried for 12 hours at 50 ° C., 30 in. Hg vacuum. The dried EPDM again undergoes a 24 hour soxhlet extraction under acetone. Again, wet EPDM was dried for 12 hours at room temperature, 30 in. Hg vacuum.

The EPDM thus produced was stored in a desiccator, and the structure of the grafted EPDM-g-Br was confirmed by infrared spectroscopy, and is shown in FIG. 1. Figure C-Br peak of the aryl bromide as in 1 is the new absorption were observed in a range from 1075cm ^-1 and 1030cm ^-1, the bending absorption appeared in the range of from 1250cm ^-1 to 1190cm ^-1.

Then, the fully dried EPDM (EPDM-g-Br 1) was compressed for 20 minutes at 250 kg _f / cm ² with a heating press (160 ° C at the top and 160 ° C at the bottom), and then removed from the heating press and cooled at room temperature for 2 minutes. After that, the contact angle and the adhesive force were measured three times, respectively, and the results are shown in Table 1 below.

The contact angle in the above using the method of ASTM C 813-90, the adhesion (Work of Adhesion) is Jounal of Applied Polymer Science, Vol. 61, 501-506, (1996). At this time, the adhesive force was calculated by the formula W _A = l _i (1 + cos q) < l _i = 72.8 mJ / cm ² (in water), q = degree>.

<Examples 2-5>

NBS was subjected to the bromination reaction in the same manner as in Example 1, except that 1 equivalent (1.2 g), 1.5 equivalents (1.8 g), 2 equivalents (2.4 g), and 5 equivalents (3 g) of NBS were used. Modified EPDM was prepared.

One equivalent of NBS was used EPDM-g-Br 2 (Example 2), one equivalent of NBS was used EPDM-g-Br 3 (Example 2), and two equivalents of NBS were used EPDM-g-Br 4 (Example Example 3) The thing using 5 equivalents of NBS was called EPDM-g-Br 5 (Example 4).

The structures of the grafted EPDM-g-Br of each of EPDM-g-Br 2 to EPDM-g-Br 4 prepared above were confirmed by infrared spectroscopy and are shown in FIG. 1.

The method of measuring the contact angle and adhesion of each modified EPDM was measured by the method mentioned in Example 1, and the results are shown in Table 1 below.

Comparative Example 1

The contact angle and adhesion of EPDM (ethylene content: 59 wt%, ENB: 8.7 wt%) used in Example 1 were measured three times by the method mentioned in Example 1 and the results are shown in Table 1 below.

<Table 1> Contact angle (Θ) and cohesion (W _A ) of EPDM with aryl bromination

Θ ₁ Θ ₂ Θ ₃ Θ _T Θ _A W _A Comparative Example 1 (EPDM 1) 83 83 83 249 83 81.67 Example 1 (EPDM-g-Br 6) 70 71 72 213 71 96.5 Example 2 (EPDM-g-Br 6) 70 72 70 212 70.7 98.86 Example 3 (EPDM-g-Br 6) 74 73 75 222 74 92.87 Example 4 (EPDM-g-Br 6) 73 73.05 74 220.5 73.5 93.48 Example 5 (EPDM-g-Br 6) 73 74 72 219 73 94.08

* Θ _T is the total of the contact angles Θ ₁ to Θ ₃ .

** Θ _A is the average value (Average) of the contact angles Θ ₁ to Θ ₃ .

<Example 6>

The solvent and the sample were stored under nitrogen atmosphere after purification.

80% of the volume inside the 500 ml flask was replaced with nitrogen. 200 cc of EPDM stock solution (containing water) in which 6 wt% of EPDM (ethylene content: 59 wt%, ENB: 8.9 wt%) was dissolved in a hexane solution was added to the flask, and the temperature was maintained at 70 ° C.

0.2 g of benzoyl peroxide (BPO), a reaction initiator, was placed in a flask containing EPDM and stirred at 600 rpm for 15 minutes. Slowly dropwise into Dropwise for 30 minutes and bromination reaction for 1 hour and 30 minutes at 600rpm.

After the bromination was completed, the precipitate was precipitated with methanol to replace NBS with ENB of diene of IPD. The modified EPDM was dried for 12 hours at 50 ° C., 30 in. Hg vacuum. The dried EPDM was again subjected to 24 hours soxhlet extraction under acetone. The wet EPDM was again dried for 12 hours at room temperature, 30 in. Hg vacuum.

The EPDM thus produced was stored in a desiccator, and the structure of the grafted EPDM-g-Br was confirmed by infrared spectroscopy, and the results are shown in FIG. 2. Figure C-Br peak of aryl bromide 2, as is shown bending absorption in the range of from the stretching absorption appeared in the range of 1075cm ^-1 and 1030cm ^-1, 1250cm ^-1 to 1190cm ^-1.

After fully drying EPDM (EPDM-g-Br 6) was compressed for 20 minutes at 250 kg _f / cm ² with a heating press (upper 160 ° C, lower 160 ° C), taken out of the heating press and cooled at room temperature for 2 minutes. The contact angle and adhesive force were measured three times by the contact angle and adhesive force measurement method mentioned in Table 1, and the results are shown in Table 2 below.

<Examples 7-9>

Except for using NBS, 1 equivalent (1.07 g), 1.5 equivalents (1.6 g), and 2 equivalents (2.14 g) of ENB equivalents, the bromination reaction was carried out in the same manner as in Example 6 to prepare each modified EPDM. It was.

EPDM-g-Br 7 (Example 7) using 1 equivalent of NBS, EPDM-g-Br 8 (Example 8) using 1.5 equivalents of NBS, EPDM-g-Br 9 (using 2 equivalents) of NBS Example 9).

The structures of the grafted EPDM-g-Br of each of EPDM-g-Br 7, EPDM-g-Br 8 and EPDM-g-Br 9 prepared above were confirmed by infrared spectroscopy and shown in FIG. 2.

The method of measuring the contact angle and adhesion of each modified EPDM was measured three times by the method mentioned in Example 1, and the results are shown in Table 2 below.

Comparative Example 2

After precipitating EPDM (ethylene content: 59 wt%, ENB: 8.9 wt%) dissolved in 6% by weight of hexane solution with methanol, the wet EPDM was dried at 50 ° C. under 30 in. Hg vacuum for 12 hours.

The dried EPDM was again subjected to soxhlet extraction for 24 hours under acetone. Again, wet EPDM was dried for 12 hours at room temperature, 30 in. Hg vacuum, it was called EPDM 2. The contact angle and adhesion of EPDM 2 were measured three times by the method mentioned in Example 1 and the results are shown in Table 2 below.

<Table 2> Contact Angle (Θ) and Adhesion (W _A ) of EPDM with Aryl Bromination

Θ ₁ Θ ₂ Θ ₃ Θ _T Θ _A W _A Comparative Example 2 (EPDM 2) 87 87 87 261 87 76.6 Example 6 (EPDM-g-Br 6) 79 78 79 236 78.7 87 Example 7 (EPDM-g-Br 7) 75 77 78 230 76.7 90 Example 8 (EPDM-g-Br 8) 76 77 78 231 77 89 Example 9 (EPDM-g-Br 9) 78 79 77 234 78 88

* Θ _T is the total of the contact angles Θ ₁ to Θ ₃ .

** Θ _A is the average value (Average) of the contact angles Θ ₁ to Θ ₃ .

<Example 10>

The solvent and the sample were stored under nitrogen atmosphere after purification.

First, 80% of the volume inside the 500 ml flask was sufficiently substituted with nitrogen. Here, 200 cc of EPDM stock solution (not containing water) in which 6 wt% of EPDM (ethylene content: 59 wt%, ENB: 8.9 wt%) was dissolved in a hexane solution was added to the flask, and the temperature was maintained at 70 ° C.

Next, 0.2 g of benzoyl peroxide (BPO), a reaction initiator, was added to the flask and stirred at 600 rpm for 10 minutes. Then, NBS was dropped in acetone (1 g / 100 g of solvent at 25 ° C.) to 1 equivalent (1.07 g). Slowly 30 minutes into the wise and bromination reaction was carried out for 1 hour at 600rpm.

After the reaction was completed, precipitated with methanol to replace NBS with ENB of the diene of IPDM to obtain a modified EPDM. The modified wet EPDM was dried at 50 ° C., 30 in. Hg vacuum for 12 hours. The dried EPDM was again subjected to soxhlet extraction for 24 hours under acetone. The wet EPDM was dried for 12 hours at room temperature and 30in.Hg vacuum.

The EPDM thus produced was stored in a desiccator, and the structure of the grafted EPDM-g-Br was confirmed by infrared spectroscopy, and the results are shown in FIG. 3. Figure C-Br peak of the aryl bromide as in 3, the new absorption were observed in a range from 1075cm ^-1 and 1030cm ^-1, the bending absorption appeared in the range of from 1250cm ^-1 to 1190cm ^-1.

After fully drying EPDM (EPDM-g-Br 10) was compressed for 20 minutes at 250 kg _f / cm ² with a heating press (160 ° C top plate, 160 ° C bottom plate) and then removed from the heating press and cooled at room temperature for 2 minutes. The contact angle and adhesive force were measured three times by measuring the contact angle and the adhesive force mentioned above, and the results are shown in Table 3 below.

<Examples 11-14>

The same method as in Example 10 except that the content ratio of NBS and ENB was fixed to 1 equivalent (1.07 g) in Example 10, the NBS solution was slowly added to Dropwise for 30 minutes, and the reaction was terminated by time. The reaction proceeded.

EPDM-g-Br 11 (Example 11) which added 15 minutes of NBS and reacted for 15 minutes compared with Example 10, and EPDM-g-Br 12 which reacted for 30 minutes compared to Example 10 after adding NBS. (Example 12) The reaction was performed for 45 minutes compared to Example 10 after adding NBS, called EPDM-g-Br 13 (Example 13), and reacting for 60 minutes compared to Example 10 after adding NBS. One was called EPDM-g-Br 14 (Example 14).

The structure confirmation method of each modified EPDM was also confirmed by infrared spectroscopy and the results are shown in FIG. 3. In addition, the contact angle and adhesive force were measured three times each by the method mentioned in Example 1 and the results are shown in Table 3 below.

<Table 3> Contact Angle (Θ) and Adhesion (W _A ) of EPDM with Aryl Bromination

Θ ₁ Θ ₂ Θ ₃ Θ _T * Θ _A ** W _A Comparative Example 2 (EPDM 2) 87 87 87 261 87 76.6 Example 10 (EPDM-g-Br 10) 79 80 78 237 79 87 Example 11 (EPDM-g-Br 11) 76 76 77 229 75.3 91 Example 12 (EPDM-g-Br 12) 73 75 75 223 74.3 92 Example 13 (EPDM-g-Br 13) 73 74 74 221 73.7 88 Example 14 (EPDM-g-Br 14) 75 77 78 230 76.7 90

* Θ _T is the total of the contact angles Θ ₁ to Θ ₃ .

** Θ _A is the average value (Average) of the contact angles Θ ₁ to Θ ₃ .

<Example 15>

The solvent and the sample were stored under nitrogen atmosphere after purification.

First, 80% of the 500 ml internal volume was replaced with nitrogen. The flask was charged with 200 cc of EPDM stock solution (containing water) in which 6 wt% EPDM (ethylene content: 59 wt%, ENB: 8.9 wt%) was dissolved in a hexane solution, and the temperature was maintained at 70 ° C.

Next, 0.2 g of benzoyl peroxide (BPO), a reaction initiator, was added to the flask, and stirred at 600 rpm for 10 minutes, and NBS was dropped into acetone (1 g / 100 g of solvent at 25 ° C.) for 1 equivalent (1.07 g) to ENB equivalent. The mixture was slowly added for 30 minutes and brominated at 600 rpm for 30 minutes.

After the bromination was completed, 0.057 g of tetra-octyl ammonium bromide (TOAC) (TOAC 0.005 mol / salt 0.2 mol), a quaternary ammonium salt catalyst, was added to the flask and completely dissolved. The reaction was carried out at 600 rpm for 5 hours.

After completion of the bromination and sodium acetate reaction, precipitated with methanol to replace NBS with ENB of diene of IPD, and sodium acetate reacted to obtain modified EPDM.

The separated wet EPDM was dried at 50 ° C. under 30 in. Hg vacuum for 12 hours. The dried EPDM was again subjected to soxhlet extraction for 24 hours under acetone. The wet EPDM was dried for 12 hours at room temperature and 30in.Hg vacuum.

The EPDM thus produced was stored in a desiccator, and the structure of the grafted EPDM-g-Acetate was confirmed by infrared spectroscopy, and the results are shown in FIG. 4. 4, as in C = O peak in the aryl group is a new absorption appeared in the vicinity of 1760cm ^-1, we were confirmed what appeared weak bands in the range of from 1300cm ^-1 to 1000cm ^-1.

After fully drying EPDM (EPDM-g-Acetate 1) was compressed for 20 minutes at 250 kg _f / cm ² with a heating press (160 ° C top plate, 160 ° C bottom plate) and then removed from the heating press and cooled at room temperature for 2 minutes. The contact angle and adhesive force were measured three times by measuring the contact angle and the adhesive force mentioned above, and the results are shown in Table 4 below.

<Examples 16-20>

The reaction proceeds with 2 equivalents of sodium chlorodifluoro acetate (1.8 g) as a sodium compound. ) 0.15g, tetrabutylammonium bromide (TBAB0) .083g, 0.1g of tetrabutylammonium iodide (TBAI) was added in the same manner as in Example 15 except that the reaction of diene die NBS was substituted for ENB and sodium chlorodifluoro acetate was reacted to obtain a modified EPDM.

Use of sodium chlorodifluoro acetate as the sodium compound and TBAC as the catalyst to obtain modified IPDM was used in EPDM-g-Acetate 2 (Example 16), sodium chlorodifluoro acetate as the sodium compound and catalyzed. EPDM-g-Acetate 3 (Example 17), using sodium chlorodifluoro acetate as the sodium compound and TOAC as catalyst, to obtain modified IPDM using EPAC. -g-Acetate 4 (Example 18), EPDM-g-Acetate 5 (Example 19), sodium compound, using sodium chlorodifluoro acetate as sodium compound and TBAB as catalyst It was called EPDM-g-Acetate 6 (Example 20) to obtain a modified IPDM using rhodium chlorodifluoro acetate and TBAI as catalyst.

The structure of each modified EPDM, the contact angle and the adhesive force of EPDM were measured in the same manner as in Example 14. The confirmation of the structure of EPDM is shown in FIG. 4, and the contact angles and the adhesion results of EPDM are shown in Table 4 below.

<Table 4> Contact angle (Θ) and cohesion (W _A ) of EPDM reacted with sodium compound after bromination

Θ ₁ Θ ₂ Θ ₃ Θ _T Θ _A W _A Comparative Example 2 (EPDM 2) 87 87 87 261 87 76.6 Example 15 (EPDM-g-Acetate 1) 80 81 79 240 80 86 Example 16 (EPDM-g-Acetate 2) 75 74 72 221 73.7 93 Example 17 (EPDM-g-Acetate 3) 77 76 74 227 75.7 91 Example 18 (EPDM-g-Acetate 4) 73 75 73 221 73.7 93 Example 19 (EPDM-g-Acetate 5) 75 78 77 230 76.7 90 Example 20 (EPDM-g-Acetate 6) 79 78 77 234 78 88

* Θ _T is the total of the contact angles Θ ₁ to Θ ₃ .

** Θ _A is the average value (Average) of the contact angles Θ ₁ to Θ ₃ .

As shown in the results of the present embodiment it can be seen that the EPDM improved polarity by the present invention is superior to the conventional EPDM.                     

As described above, although described with reference to a preferred embodiment of the present invention, those skilled in the art will be variously modified and modified within the scope of the present invention without departing from the spirit and scope of the present invention described in the claims below. It will be appreciated that it can be changed.

Claims (9)

In the method of improving the polarity of EPDM (1) reacting an initiator with EPDM to generate free radicals in diene of EPDM; (2) a method for improving the polarity of EPDM, comprising the step of substituting a halogen compound with diene of EPDM which has free radicals. The method of claim 1, wherein the initiator is 1-10% by weight of any one selected from acyl peroxide, dialkyl peroxide, arylalkyl poroxide, peroxyester, hydroperoxide, ketone peroxide, azo compound Method for improving the polarity of EPDM, characterized in that the reaction with EPDM. The halogen compound of claim 1, wherein the halogen compound is fluorine, chlorine, bromine, iodine, asstatin, N-bromosuccinimide (NBS), N-chlorosuccinimide (NCS), N-fluorosuccinimide (NFS). , N-iodo succinimide (NIS) 0.5 to 5 equivalents of any one selected from the diene and the equivalent ratio of IPD diem, the method of improving polarity of EPDM. The method of claim 1, further comprising the step of reacting the bromine compound in the diene of the Ipidem produced free radicals with a metal compound in the presence of an ammonium catalyst after the substitution reaction. The method of claim 4, wherein the ammonium catalyst is tetrabutylammonium chloride (TBAC), tetrahexyl ammonium chloride (THAC), tetraoctyl ammonium chloride (TOAC), tetrabutylammonium bromide (TBAB), tetrabutylammonium iodide (TBAI) Method for improving the polarity of EPDM, characterized in that any one of the quaternary ammonium catalyst selected from. The method of claim 4 wherein the metal compound is sodium acetate, sodium acrylate, sodium amide, sodium benzoate, sodium tetrabutoxide, sodium chlorate, sodium chloroacetate, sodium cyanate, sodium cyanide, sodium cyclohexane butyrate, Sodium Dichloroacetate, Sodium Ethoxide, Sodium Ethaneyl Olate, Sodium Formate, Sodium Hydrochloride, Sodium Methacrylate, Sodium Octanoate, Sodium Periodate, Sodium Propionate Sodium Iodate, Sodium Iodoacetate, Sodium Method for improving the polarity of EPDM, characterized in that any one selected from 3-chlorodifluoroacetate. The metal compound of claim 4, wherein the metal compound comprises potassium acetate, potassium acrylate, potassium amide, potassium benzoate, potassium tetrabutoxide, potassium chlorate, potassium chloroacetate, potassium cyanate, potassium cyanide, potassium cyclohexanebutylate, Potassium dichloroacetate, potassium ethoxide, potassium ethoxylate, potassium formate, potassium hydrochloride, potassium methacrylate, potassium octanoate, potassium periodate, potassium propionate, potassium iodate, potassium iodoacetate , Potassium 3-chlorodifluoroacetate any one selected from the polarity improvement method. The metal compound of claim 4, wherein the metal compound is lithium acetate, lithium acrylate, lithium amide, lithium benzoate, lithium tetrabutoxide, lithium chlorate, lithium chloroacetate, lithium cyanate, lithium cyanide, lithium cyclohexanebutylate, Lithium dichloroacetate, lithium ethoxide, lithium ethane acrylate, lithium formate, lithium hydrochloride, lithium methacrylate, lithium octanoate, lithium periodate, lithium propionate, lithium iodate, lithium iodoacetate, Method for improving the polarity of EPDM, characterized in that any one selected from lithium 3-chlorodifluoroacetate. The metal compound of claim 4, wherein the metal compound is magnesium acetate, magnesium acrylate, magnesium amide, magnesium benzoate, magnesium tetrabutoxide, magnesium chlorate, magnesium chloroacetate, magnesium cyanate, magnesium cyanide, magnesium cyclohexanebutylate, Magnesium Dichloroacetate, Magnesium Ethoxide, Magnesium Ethane Acrylate, Magnesium Formate, Magnesium Hydrochloride, Magnesium Methacrylate, Magnesium Octanoate, Magnesium Periodate, Magnesium Propionate, Magnesium Iodate, Magnesium Iodoacetate , Magnesium 3-chlorodifluoroacetate any one selected from the polarity improvement method.

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