KR102518739B1 - Process for preparing cyclodextrin maleic anhydride graft polyolefin in situ - Google Patents

Abstract

The present invention relates to a method for preparing cyclodextrin maleic anhydride graft polyolefin in situ. More specifically, it relates to a manufacturing method in which a polyolefin-based resin, maleic anhydride and cyclodextrin are introduced into the same reaction system to carry out a graft reaction.

Description

Method for preparing cyclodextrin maleic anhydride graft polyolefin in situ {Process for preparing cyclodextrin maleic anhydride graft polyolefin in situ}

The present invention relates to a method for preparing cyclodextrin maleic anhydride graft polyolefin in situ. More specifically, it relates to a manufacturing method in which a polyolefin-based resin, maleic anhydride and cyclodextrin are introduced into the same reaction system to carry out a graft reaction.

Cyclodextrin is a cylindrical compound obtained by cyclizing 6 to 12 glucose residues obtained by liquefying starch with CGTase. Cyclodextrin is a compound in which 6, 7, and 8 α-D-glucopyranose units are linked 1 → 4, respectively, into α-cyclodextrin (α-CD) and β-cyclodextrin (β-cyclodextrin). CD), and γ-cyclodextrin (γ-CD).

The size of the empty space inside the cyclodextrin is 0.57 nm for α-CD, 0.78 nm for β-CD, and 0.95 nm for γ-CD. It can be applied to various fields because it can form an inclusion complex through host-guest interaction.

There is an attempt to impart a deodorizing function to fibers or packaging materials using cyclodextrin.

Korean Patent Registration No. 10-1120203 (2012.02.17) discloses a thermoplastic polymer composition comprising a mixture of a polyolefin resin and a chemically grafted polyolefin resin, wherein the chemically grafted polyolefin resin includes a polymethylene skeleton , the polymethylene backbone includes a cyclodextrin compound and the cyclodextrin compound is bonded to the polymethylene backbone; The thermoplastic polymer composition is disclosed in which the cyclodextrin compound is characterized in that there is no compound in the central cavity of the cyclodextrin ring.

The patent was prepared by chemically grafting cyclodextrin onto a polyolefin polymer having a functional group, and the graft reaction injects polyolefin having a functional group into the first barrel section of the mixer, and injects dried cyclodextrin into the second additional injection part to carry out the grafting reaction. However, in the case of the above patent, the entire process for producing a polyolefin having a functional group is required. In addition, in the case of a polyolefin having a functional group attached thereto, reaction efficiency may decrease due to modification of the functional group. There is a problem that the reaction efficiency is not high due to the steric hindrance effect that inhibits the access of cyclodextrins due to the presence of modified functional groups. Therefore, in order to solve these problems, a method for minimizing functional group modification and overcoming the steric hindrance effect, and a method for preparing a graft polymer having maleic anhydride graft efficiency and high substitution degree of cyclodextrin through a simplified process A study on the manufacturing method was needed.

Republic of Korea Patent Registration No. 10-1120203 (2012.02.17)

One problem of the present invention to solve the above conventional problems is to perform a graft reaction by introducing polyolefin-based resin, maleic anhydride and cyclodextrin into the same reaction system, thereby simplifying the manufacturing process and easily adjusting the content of cyclodextrin In addition, it is intended to provide a method for preparing cyclodextrin maleic anhydride grafted polyolefin having high maleic anhydride graft efficiency and cyclodextrin substitution degree, and excellent durability and deodorization.

Another object of the present invention is to provide a method for preparing cyclodextrin maleic anhydride grafted polyolefin having excellent deodorization even after washing with water.

In addition, it is intended to provide a method for preparing cyclodextrin maleic anhydride grafted polyolefin having high maleic anhydride graft efficiency and high substitution degree of cyclodextrin.

In addition, it is intended to provide a method for producing cyclodextrin maleic anhydride graft polyolefin, which can be produced continuously by continuously introducing raw materials as well as a batch method, thereby improving productivity.

In addition, it is intended to provide optimal conditions for increasing the graft rate while reducing yellowing by suppressing deterioration.

The inventors of the present invention found that the reaction can be performed in the same reaction system and that this can be achieved under specific reaction conditions as a result of research to derive optimal conditions for maleic anhydride and cyclodextrin to bind well to polyolefin-based resins. Thus, the present invention was completed.

Specifically, one aspect of the present invention

a) introducing a polyolefin-based resin, maleic anhydride, cyclodextrin, and a peroxide catalyst into the in situ reaction system of a mixer; and

b) performing a grafting reaction at a temperature of 100 to 300 °C for 1 to 60 minutes;

In one aspect of the present invention, in step b), the reaction may be performed at 10 to 100 rpm.

In one aspect of the present invention, after step b), c) preparing a molded article using the obtained graft polymer; may further include.

Specifically, the molded body may be, for example, a film, fiber, container, and the like, but is not limited thereto.

In one aspect of the present invention, in step a), the polyolefin-based resin, maleic anhydride, cyclodextrin, and peroxide catalyst may be simultaneously introduced into the same reaction system.

In one aspect of the present invention, in step a), maleic anhydride and cyclodextrin may be first introduced, and then the polyolefin-based resin and the peroxide catalyst may be introduced.

In one aspect of the present invention, the mixer may be a rotary mixer.

In one aspect of the present invention, the manufacturing method may be a continuous process in which steps a) and b) are continuously performed.

In one aspect of the present invention, in step a), 2 to 15 parts by weight of maleic anhydride and 2 to 10 parts by weight of cyclodextrin are used with respect to 100 parts by weight of polyolefin-based resin, and based on 100 parts by weight of maleic anhydride , 10 to 100 parts by weight of the peroxide catalyst may be used.

In one aspect of the present invention, the step b) may include a step of removing unreacted materials using a solvent after performing the graft reaction.

In one aspect of the present invention, in step b), the reaction is carried out in a temperature range of 150 to 200 ° C., the first temperature (T1), the second temperature (T2) and the third temperature (T3), and carried out sequentially , T2 > T1 ≥ T3 may be performed under temperature conditions.

In one aspect of the present invention, the reaction time t1 at the first temperature (T1), the reaction time t2 at the second temperature (T2), and the reaction time t3 at the third temperature (T3) are t2 < t1 ≤ t3 may be satisfactory.

In one aspect of the present invention, the cyclodextrin maleic anhydride-grafted polyolefin may have a deodorization change rate of 50% or less according to Formula 1 below.

[Equation 1]

(W2 - W1)/W1 × 100 ≤ 50%

In Equation 1, after leaving the cyclodextrin maleic anhydride-grafted polyolefin film in a sealed Erlenmeyer flask, ammonia water was dropped to form an ammonia atmosphere, and the concentration of ammonia gas was measured through a gas detector and a gas detector tube, The W2 is the concentration when using the film before washing with water, and W1 is the concentration when using the film after washing with water and 5 days.)

In one aspect of the present invention, the cyclodextrin maleic anhydride grafted polyolefin may have C=O and C-O-C peaks observed both before and after washing with water upon FT-IR analysis.

In one aspect of the present invention, the cyclodextrin maleic anhydride graft polyolefin may have a graft ratio of 0.5 to 2%.

The method for producing a modified graft polymer according to one aspect of the present invention is simple, easy to control the process, easy to control the content of cyclodextrin, and can produce a modified graft polymer having excellent durability and deodorization. .

Specifically, since it is prepared by simultaneous introduction into the same reaction system, the manufacturing process can be simplified compared to the conventional manufacturing process, and the reaction time can be shortened, so productivity can be further improved.

In addition, the modified graft polymer prepared by the manufacturing method of the modified graft polymer according to one aspect of the present invention has excellent deodorization even after washing with water, can impart semi-permanent deodorization, and can be used as a material for functional clothing, packaging material, and storage container. There is an effect that can expand the applicability of various plastic industries such as

1 is a result of FT-IR analysis of the graft polymer before washing with water.
2 is a result of FT-IR analysis of the graft polymer after washing with water.
Figure 3 is a photograph evaluating the yellowing of the polymer according to Example 3.
Figure 4 is a photograph evaluating the yellowing of the polymer according to Example 9.

Hereinafter, the present invention will be described in more detail through specific examples or examples including the accompanying drawings. However, the following specific examples or examples are only one reference for explaining the present invention in detail, but the present invention is not limited thereto, and may be implemented in various forms.

Also, unless defined otherwise, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms used in the description in the present invention are merely to effectively describe specific embodiments and are not intended to limit the present invention.

Also, the singular forms used in the specification and appended claims may be intended to include the plural forms as well, unless the context dictates otherwise.

In addition, when a certain component is said to "include", this means that it may further include other components without excluding other components unless otherwise stated.

Hereinafter, each configuration of the present invention will be described in more detail.

In one aspect of the present invention, the polyolefin-based resin is not limited as long as it is a commonly used resin, and specifically, for example, it may be a homopolymer such as polyethylene or polypropylene or a copolymer thereof. More preferably, it may be a polypropylene homopolymer.

In one aspect of the present invention, the maleic anhydride may be used in an amount of 2 to 15 parts by weight, more preferably 2 to 5 parts by weight, based on 100 parts by weight of the polyolefin-based resin. By using it within the above range, the graft rate due to co-injection with cyclodextrin can be further improved, and it is more preferable to provide a polymer with less yellowing. The graft rate means the graft rate of maleic anhydride. More specifically, it is possible to provide a polymer having a graft rate of 0.5 to 5%, more specifically 0.2 to 2% in the above content range.

In one aspect of the present invention, the cyclodextrin is any one or a mixture of two or more selected from α-cyclodextrin (α-CD), β-cyclodextrin (β-CD), γ-cyclodextrin (γ-CD), etc. it could be More specifically, β-cyclodextrin may be used as the cyclodextrin, and by using the cyclodextrin, the degree of substitution may be further increased during the graft reaction with maleic anhydride and polyolefin-based resin.

The cyclodextrin may be used in an amount of 2 to 10 parts by weight, more preferably 5 to 8 parts by weight, based on 100 parts by weight of the polyolefin resin. By using in the above range, the graft rate according to the simultaneous introduction of maleic anhydride can be further improved.

The peroxide catalyst is used to carry out a graft reaction of maleic anhydride and cyclodextrin on a polyolefin resin, specifically, for example, diisobutyl peroxide, t-amylperoxyneodicarbonate ( t-amylperoxydicarbonate), di(4-t-butylcyclohexyl)peroxydicarbonate (di(4-tert-butylcyclohexyl)peroxydicarbonate), diethylhexylperoxydicarbonate, dibutylperoxydicarboxynite ( dibutyl peroxydicarbonate), diisopropyl peroxydicarbonate, dicetyl peroxydicarbonate, dimyristyl peroxydicarbonate, tert-butyl peroxypivalate, Dilauroyl peroxide, didecanoyl peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane (2,5-dimethyl-2,5 -di(2-ethylhexanoylperoxy)hexane), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate), t-amylfer Oxy-2-ethylhexanoate (tert-amylperoxy-2-ethylhexanoate), dibenzoyl peroxide, t-butylperoxy-2-ethylhexanoate (tert-butylperoxy-2-ethylhexanoate), t -Butylperoxyethyl acetate (tert-butylperoxy ethyl acetate), t-butylperoxyisobutyrate (tert-butylperoxy isobutylate) and 1,4-di (t-butylperoxycarbo) cyclohexane (1,4-di ( tert-butylperoxy carbo)cyclohexane) and the like, or a mixture of two or more selected from the group consisting of Even better, by using di (4-t-butylcyclohexyl) peroxydicarbonate, the graft rate is high, and the graft is maintained even after washing with water, so the deodorant change is small, so the deodorant change rate is reduced. Low graft polymers can be provided.

The content of the peroxide catalyst may be 10 to 100 parts by weight, more preferably 25 to 75 parts by weight, based on 100 parts by weight of the maleic anhydride.

Next, the manufacturing method will be described in detail.

First, in step a) of the present invention, unlike the prior art in which the maleic anhydride-grafted polyolefin resin is first melted and cyclodextrin is added thereto, the polyolefin-based resin, maleic anhydride, cyclodextrin, and peroxide catalyst are mixed in a mixer. This is the step of injecting into the in situ reaction system.

In this case, each raw material may be quantitatively introduced into the same reaction system using a quantitative injector, or the polyolefin resin, maleic anhydride, cyclodextrin, and peroxide catalyst may be mixed in advance in a quantitative amount and then introduced at once. By such simultaneous introduction, continuous production is possible, and the content of cyclodextrin can be easily controlled. In addition, it is possible to provide a graft polymer having a higher deodorization rate and a higher deodorization retention rate, that is, less change in deodorization property even after washing with water and 5 days, compared to reacting by introducing cyclodextrin into polyolefin grafted with maleic anhydride. there is.

Alternatively, maleic anhydride and cyclodextrin may be first introduced and melt-mixed, and then polyolefin-based resin and peroxide catalyst may be introduced.

In one aspect of the present invention, step b) is a step of performing a graft reaction at a temperature of 100 to 300 ° C. for 1 to 60 minutes. More preferably, it may be performed at 150 to 200 ° C. for 5 minutes to 30 minutes. Graft reaction may be more well achieved in the above range. At this time, although not limited to, stirring may be performed at 10 to 100 rpm. A mixer for the reaction may be a rotary mixer. The rotary mixer refers to a mixer equipped with a screw or the like for mixing melts, and may be a closed rotary mixer.

More preferably, the reaction in step b) is carried out in a temperature range of 150 to 200 ° C, but is performed sequentially at a first temperature (T1), a second temperature (T2) and a third temperature (T3), T2 > T1 It may be performed under a temperature condition that satisfies ≥ T3. Specifically, for example, after reacting in a temperature range of 150 to 160 ° C (first temperature), reacting by raising the temperature to a temperature range of 160 to 200 ° C (second temperature), and reacting again in a temperature range of 150 to 160 ° C (third temperature) By reacting by lowering the furnace temperature, deterioration can be prevented to provide a polymer with less yellowing, and a polymer with a further increased graft rate can be provided.

In addition, the reaction time t1 at the first temperature T1, the reaction time t2 at the second temperature T2, and the reaction time t3 at the third temperature T3 may satisfy t2 < t1 ≤ t3. . More specifically, for example, after reacting for 3 to 20 minutes in a temperature range of 150 to 160 ° C (first temperature), raising the temperature to a temperature range of 160 to 200 ° C (second temperature), reacting for 1 to 10 minutes, and then reacting for 1 to 10 minutes, and By lowering the temperature to 160 ℃ temperature range (third temperature) and reacting for 3 to 20 minutes, deterioration may be prevented and the graft rate may be further increased.

In addition, in one embodiment, in step a), maleic anhydride and cyclodextrin are first introduced, and then, when polyolefin-based resin and peroxide catalyst are introduced, maleic anhydride and cyclodextrin are added, and then the temperature range is 150 to 160 ° C. After reacting at (first temperature) for 3 to 20 minutes, then polypropylene and peroxide catalyst are added, and the temperature is raised to 160 to 200 ℃ temperature range (second temperature) to react for 1 to 10 minutes, and then to 150 to 160 ℃ temperature range It may be to react for 3 to 20 minutes by lowering the temperature to (third temperature).

In one aspect of the present invention, it may be a continuous process in which steps a) and b) are continuously performed. That is, the graft polymer may be continuously produced by continuously introducing raw materials and carrying out the grafting reaction instead of batchwise reaction.

In one aspect of the present invention, the step b) may include a step of removing unreacted materials using a solvent after performing the graft reaction. The unreacted material may be unreacted maleic anhydride and cyclodextrin.

When the unreacted material is removed, the reactant may be completely dissolved using xylene, and then re-precipitated in acetone to obtain a graft polymer from which the unreacted material is removed. More specifically, for example, after adding a reactant to xylene, dissolving it by stirring at 130 to 170 ° C. for 10 minutes to 2 hours, and reprecipitating it again in acetone to obtain a graft polymer from which unreacted materials are removed it could be

In one aspect of the present invention, the cyclodextrin maleic anhydride grafted polyolefin prepared by the above production method may have a deodorization change rate of 50% or less according to Formula 1 below. More preferably, it may be 10 to 40%. That is, in the case of grafting cyclodextrin to a polyolefin resin grafted with maleic anhydride as in the conventional method, the deodorant change rate was 50% or more, more specifically 60% or more, and it was confirmed that the deodorization property was greatly reduced. It was confirmed that the cyclodextrin maleic anhydride grafted polyolefin prepared by the manufacturing method according to the above method, that is, prepared by simultaneous introduction, showed little change in deodorizing property even after washing with water, and it was also confirmed that durability according to washing with water was excellent.

[Equation 1]

(W2 - W1)/W1 × 100 ≤ 50%

In Equation 1, after leaving the cyclodextrin maleic anhydride-grafted polyolefin film in a sealed Erlenmeyer flask, ammonia water was dropped to form an ammonia atmosphere, and the concentration of ammonia gas was measured through a gas detector and a gas detector tube, The W2 is the concentration when using the film before washing with water, and W1 is the concentration when using the film after washing with water and 5 days.)

In one aspect of the present invention, upon FT-IR analysis of the cyclodextrin maleic anhydride-grafted polyolefin, C=O peaks were observed both before and after washing with water, confirming that maleic anhydride and cyclodextrin were grafted thereto. there is.

In one aspect of the present invention, the cyclodextrin maleic anhydride grafted polyolefin may have a graft ratio of 0.5 to 5%, more specifically, 0.9 to 2%, to provide a polymer with low yellowing within the above range. can

The present invention will be described in more detail based on the following Examples and Comparative Examples. However, the following Examples and Comparative Examples are only one example for explaining the present invention in more detail, and the present invention is not limited by the following Examples and Comparative Examples.

Physical properties were measured as follows.

1. Deodorization function

The deodorization function was evaluated by the 'gas detection tube method'.

The prepared film is divided into before and after washing with water (5 days) and left in a sealed Erlenmeyer flask, and then ammonia water is added dropwise to form an ammonia atmosphere. In addition, deodorization is evaluated by measuring the concentration (PPM) of the gas detection tube through the gas detector and the gas detection tube.

The test conditions are as follows.

1) Sample amount: 10cm x 10cm (1.6g)

2) Test gas: Ammonia (NH ₃ )

3) Concentration of injected test gas: 500μg/mL

4) Container volume: 1000mL

5) Test environment: temperature 20℃, humidity 65%

6) Deodorization (%) = [(Blank gas concentration - Sample gas concentration) / Blank gas concentration] x 100

2. FT-IR analysis

After the prepared graft polymer is powdered using a ball mill device, about 0.1 g is taken and analyzed at room temperature using a spectrophotometer (FT-IR: Thermo Scientific, Nicolet 380).

O: C = O (Carbonyl group) peak by maleic anhydride can be observed at around 1800 cm ^-1 .

△: A COC (Ethers group) peak by cyclodextrin can be observed in the vicinity of 1000 cm ⁻¹ to 1100 cm ⁻¹ .

X: C=O (Carbonyl group) peak and C-O-C (Ethers group) peak are not observed

3. Graft rate (%)

Put 1g of sample in a 250ml Erlenmeyer flask, add 50ml of xylene, put it in a constant temperature oil bath, and close the reflux tube. Connect cooling water to the reflux pipe, and heat the oil bath to about 150℃ to reflux until the sample is completely dissolved. Raise the Erlenmeyer flask equipped with the reflux tube to a higher level out of the oil bath and cool it to 100°C. The dissolved solution is poured into a 500 ml Erlenmeyer flask containing 100 ml acetone to precipitate. After precipitation, the solution is poured into a vacuum suction filter, and the solution of the precipitate is suction filtered as cleanly as possible. Then, the sample is moved to a glass container and put in an oven at 80° C. to vacuum dry for about 2 hours. The sample is removed and weighed exactly 0.5 g of the dried sample on an analytical balance, designated as M, and placed in a 250 ml Erlenmeyer flask. Then, add 100ml of xylene, attach a reflux tube, put it in an oil bath, and heat it at 150℃ for 30 minutes to reflux. After waiting for the sample to be completely dissolved, raise the Erlenmeyer flask with the reflux tube to the top so that it is out of the oil bath, cool for 10 minutes, and then add 10ml of 0.5N KOH-Ethanol solution accurately collected with a pipette. Then, put the flask in an oil bath and heat it at 130 ° C for 10 minutes, then take the Erlenmeyer flask out of the oil bath, observe whether there is no reflux liquid in the reflux tube, and remove the reflux tube. Add 3 drops of phenolphthalein indicator, titrate with a 0.5N mixed solution of acetic acid and xylene to the end point, measure the change, and call it M1.

For the polypropylene without maleic anhydride and β-cyclodextrin, the change in titration was measured in the same manner as above, and was defined as M0.

Titration value of graft polymer M1 = Titration amount of mixed solution of Acetic acid and Xylene

Titration value of polypropylene M0 = Titration amount of mixed solution of acetic acid and xylene

MS = M1-M0

Graft rate = MS÷M×4.9 (GMA/100 g-g-MA)

In the above formula, M is the weight of the graft polymer, GMA is the graft rate, and 100g-g-MA means the amount of graft in 100g.

[Example 1]

Based on 100 parts by weight of polypropylene, 5 parts by weight of maleic anhydride, β- 5 parts by weight of cyclodextrin and 50 parts by weight of peroxide catalyst (Di(tert-butylperoxyisopropyl)benzene) based on 100 parts by weight of maleic anhydride were simultaneously added, and mixed in a rotary mixer at 170 ° C. at 50 rpm for 10 minutes to obtain a graft polymer. was manufactured.

Thereafter, the prepared graft polymer was added to xylene, stirred at 170° C. for 1 hour to completely dissolve, then re-precipitated in acetone to remove unreacted materials, and dried at 150° C. for 2 hours.

As a result of measuring the graft rate of the dried graft polymer, it was 1.47%.

3 g of the obtained graft polymer was taken and pressed through a film press at 170° C. for 60 seconds to prepare a film having an average thickness of 350 μm.

The deodorization of the prepared film was evaluated and shown in Table 1 below.

In addition, the results of FT-IR analysis of the prepared graft polymers are shown in FIGS. 1 and 2 and Table 2 below.

[Example 2]

Maleic anhydride and β-cyclodextrin were first put into the hopper of the same rotary mixer as in Example 1, and mixed at 50 rpm for 10 minutes at 150 ° C. Then, polypropylene and a peroxide catalyst were added and mixed at 170 ° C. for 10 minutes at 50 ° C. Mixed at rpm. The content of each component was used the same as in Example 1.

A film was prepared in the same manner as in Example 1 using the graft polymer thus prepared, and deodorization was evaluated and shown in Table 1 below.

[Comparative Example 1]

Based on 100 parts by weight of commercially available maleic anhydride graft polypropylene (Woosung Chemical Co., Ltd., NB1620), 5 parts by weight of β-cyclodextrin was put into a rotary mixer and mixed at 170 ° C. for 10 minutes at 50 rpm to obtain a graft polymer. manufactured.

A film was prepared using the obtained graft polymer in the same manner as in Example 1 through a film press.

The deodorization of the prepared film was evaluated and shown in Table 1 below.

In addition, the results of FT-IR analysis of the prepared graft polymers are shown in FIGS. 1 and 2 and Table 2 below.

[Comparative Example 2]

Based on 100 parts by weight of polypropylene, 5 parts by weight of β-cyclodextrin was added to a rotary mixer and mixed at 170° C. for 10 minutes at 50 rpm to prepare a polymer composition.

A film was prepared using the obtained polymer composition through a film press in the same manner as in Example 1.

The deodorization of the prepared film was evaluated and shown in Table 1 below.

In addition, the results of FT-IR analysis of the prepared graft polymers are shown in FIGS. 1 and 2 and Table 2 below.

Sample classification Before washing (ppm) After washing (ppm) Deodorant change rate (%) Example 1 50 70 40 Example 2 50 80 60 Comparative Example 1 50 85 70 Comparative Example 2 50 90 80

In Table 1, the lower the gas concentration (ppm), the better the deodorizing performance. As shown in Table 1, Examples 1 and 2 of the present invention confirmed that the change in deodorization was small even after washing with water.

Existence/nonexistence classification Example 1 Comparative Example 1 Comparative Example 2 centuries ago after several years centuries ago after several years centuries ago after several years C=O O O O O X X C-O-C O O O △ O X

As shown in Table 2, in Example 1, C=O and C-O-C were confirmed both before and after washing with water. Accordingly, it can be confirmed that the durability is excellent compared to Comparative Examples 1 and 2 even after washing with water.

1 is a result of FT-IR analysis before washing with water, and FIG. 2 is a result of FT-IR analysis after washing with water. As confirmed in the graph, it can be confirmed that Example 1 has excellent durability compared to Comparative Examples 1 and 2 even after washing with water.

[Example 3]

In Example 1, as shown in Table 3 below, the content of maleic anhydride and the content of peroxide catalyst (Di(tert-butylperoxyisopropyl)benzene) were changed, and the reaction temperature and time were changed as follows. In Table 3 below, the content of maleic anhydride is based on 100 parts by weight of polypropylene, and the content of the peroxide catalyst is based on 100 parts by weight of maleic anhydride.

Polypropylene, maleic anhydride, β-cyclodextrin and a peroxide catalyst (Di( The graft polymer was manufactured.

Thereafter, the prepared graft polymer was added to xylene, stirred at 170° C. for 1 hour to completely dissolve, then re-precipitated in acetone to remove unreacted materials, and dried at 150° C. for 2 hours.

The graft rate of the prepared graft polymer was measured and shown in Table 3 below, and as shown in FIG. 3, it was confirmed that yellowing did not occur.

[Examples 4 to 17]

As shown in Table 3 below, the content of maleic anhydride and the content of the peroxide catalyst (Di(tert-butylperoxyisopropyl)benzene) were changed, and the reaction was carried out at the same reaction temperature and time as in Example 3.

The graft rate of the prepared graft polymer was measured and shown in Table 3, and yellowing was evaluated and shown in Table 3 below.

[Example 18]

The same content of maleic anhydride and peroxide catalyst as in Example 3 was used, but the reaction temperature and time were reacted at 210 ° C. for 15 minutes and reacted at 170 ° C. for 10 minutes to prepare a graft polymer.

The graft rate of the prepared graft polymer was measured and shown in Table 3, and yellowing was evaluated and shown in Table 3 below. As shown in Table 3, when reacting for a long time in a state where the initial reaction temperature was set high, it was confirmed that yellowing occurred and the graft rate was reduced.

Maleic anhydride content (parts by weight) Peroxide catalyst content (parts by weight) Graft rate (%) Whether or not yellowing occurs Example 3 2.5 25 0.98 No yellowing (see Figure 3) Example 4 2.5 50 0.49 no yellowing Example 5 2.5 75 0.98 no yellowing Example 6 5 25 1.47 no yellowing Example 7 5 50 1.47 no yellowing Example 8 5 75 1.47 no yellowing Example 9 7.5 25 1.47 Occurrence of yellowing (see Fig. 4) Example 10 7.5 50 1.96 yellowing occurs Example 11 7.5 75 1.96 yellowing occurs Example 12 10 25 2.94 yellowing occurs Example 13 10 50 3.92 yellowing occurs Example 14 10 75 3.43 yellowing occurs Example 15 15 25 4.41 yellowing occurs Example 16 15 50 4.41 yellowing occurs Example 17 15 75 3.92 yellowing occurs Example 18 2.5 25 0.90 yellowing occurs

In Table 3, the graft rate was measured as shown in Table 4 below.

M(g) Mo(ml) M ₁ (ml) Graft rate (%) Example 3 0.5 8 8.10 0.98 Example 4 0.5 8 8.05 0.49 Example 5 0.5 8 8.10 0.98 Example 6 0.5 8 8.15 1.47 Example 7 0.5 8 8.15 1.47 Example 8 0.5 8 8.15 1.47 Example 9 0.5 8 8.15 1.47 Example 10 0.5 8 8.20 1.96 Example 11 0.5 8 8.20 1.96 Example 12 0.5 8 8.30 2.94 Example 13 0.5 8 8.40 3.92 Example 14 0.5 8 8.35 3.43 Example 15 0.5 8 8.45 4.41 Example 16 0.5 8 8.45 4.41 Example 17 0.5 8 8.40 3.92

As described above, the present invention has been described by specific details and limited embodiments and drawings, but this is only provided to help a more general understanding of the present invention, the present invention is not limited to the above embodiments, and the present invention Those skilled in the art can make various modifications and variations from these descriptions.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and it will be said that not only the claims to be described later, but also all modifications equivalent or equivalent to these claims belong to the scope of the present invention. .

Claims (14)

a) introducing a polyolefin-based resin, maleic anhydride, cyclodextrin, and a peroxide catalyst into the in situ reaction system of a mixer; and
b) performing a grafting reaction at a temperature of 100 to 300 ° C for 1 to 60 minutes;
including,
In step a), 2 to 5 parts by weight of maleic anhydride and 2 to 10 parts by weight of cyclodextrin are used based on 100 parts by weight of polyolefin resin,
A method for producing a cyclodextrin maleic anhydride graft polyolefin, wherein 10 to 100 parts by weight of the peroxide catalyst is used based on 100 parts by weight of the maleic anhydride. According to claim 1,
In step b), the reaction is performed at 10 to 100 rpm. According to claim 1,
A method for producing a cyclodextrin maleic anhydride graft polyolefin, further comprising c) preparing a molded article using the obtained graft polymer after step b). According to claim 1,
In step a), the polyolefin-based resin, maleic anhydride, cyclodextrin and peroxide catalyst are simultaneously introduced into the same reaction system. According to claim 1,
In step a), maleic anhydride and cyclodextrin are first introduced, and then a polyolefin-based resin and a peroxide catalyst are introduced. According to claim 1,
The mixer is a method for producing a cyclodextrin maleic anhydride graft polyolefin, wherein the mixer is a rotary mixer. According to claim 1,
The method for producing cyclodextrin maleic anhydride graft polyolefin, wherein the production method is a continuous process in which steps a) and b) are continuously performed. delete According to claim 1,
In the step b), after performing the graft reaction, the method for producing a cyclodextrin maleic anhydride grafted polyolefin comprising the step of removing unreacted materials using a solvent. According to claim 1,
In step b), the reaction is carried out in a temperature range of 150 to 200 ° C,
Cyclodextrin maleic anhydride graft polyolefin, which is sequentially performed at the first temperature (T1), the second temperature (T2), and the third temperature (T3), and is performed under temperature conditions satisfying T2> T1≥ T3 manufacturing method. According to claim 10,
Cyclodextrin male, wherein the reaction time t1 at the first temperature (T1), the reaction time t2 at the second temperature (T2), and the reaction time t3 at the third temperature (T3) satisfy t2 < t1 ≤ t3 Method for producing acid anhydride graft polyolefin. According to any one selected from claims 1 to 7 and 9 to 11,
The method for producing cyclodextrin maleic anhydride graft polyolefin, wherein the cyclodextrin maleic anhydride graft polyolefin has a deodorant change rate of 50% or less according to the following formula 1.
[Equation 1]
(W2 - W1)/W1 × 100 ≤ 50%
In Equation 1, after leaving the cyclodextrin maleic anhydride-grafted polyolefin film in a sealed Erlenmeyer flask, ammonia water was dropped to form an ammonia atmosphere, and the concentration of ammonia gas was measured through a gas detector and a gas detector tube, The W2 is the concentration when using the film before washing with water, and W1 is the concentration when using the film after washing with water and 5 days.) According to any one selected from claims 1 to 7 and 9 to 11,
In the FT-IR analysis of the cyclodextrin maleic anhydride graft polyolefin, C=O and COC peaks are observed both before and after washing with water. According to any one selected from claims 1 to 7 and 9 to 11,
The method for producing cyclodextrin maleic anhydride graft polyolefin, wherein the cyclodextrin maleic anhydride graft polyolefin has a graft ratio of 0.5 to 2%.

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