KR20150097180A - ultraviolet absorber comprising benzophenone compound with maleimide group, preparation methode thereof, polymer compound grafted ultraviolet absorber onto and preparation methode thereof - Google Patents

Abstract

The present invention relates to a benzophenone-based ultraviolet absorber comprising a novel maleimide group, a preparation method thereof, a polymer compound grafted with the benzophenone-based ultraviolet absorber comprising the maleimide group, and a preparation method thereof. The preparation method of the polymer compound grafted with the benzophenone-based ultraviolet absorber comprising the maleimide group has an effect of grafting the ultraviolet absorber easily onto a polymer with highly reactive properties of the maleimide group and a polymer comprising radicals, after introducing the radical to the polymer simply by the melting without a radical initiator. In addition, the polymer compound grafted with the benzophenone-based ultraviolet absorber comprising the maleimide group shows an effect of continuously preventing photo-oxidation since the ultraviolet absorber is not separated from the polymer even in long-term use.

Description

TECHNICAL FIELD [0001] The present invention relates to a benzophenone-based ultraviolet absorber, a maleimide group-containing ultraviolet absorber, a preparation method thereof, a benzophenone-based ultraviolet absorber-grafted high molecular compound, onto and preparation methode thereof}

The present invention relates to a benzophenone-based ultraviolet absorber comprising a maleimide group, a process for producing the same, a macromolecule compound obtained by grafting a benzophenone ultraviolet absorber, and a process for producing the same.

Ultraviolet rays are sunlight rays having a wavelength range of 200 to 400 nm. When ultraviolet rays reach the earth surface, they cause spots, freckles, cause skin irritation, and cause sunburn. Polymers such as plastics and rubbers cause discoloration, Cracks, deterioration of mechanical properties, and the like.

Most polymer compounds have unsaturated carbon-carbon, carbon-oxygen bonds or tertiary carbon which are easily decomposable in the molecular structure, and when they are exposed to ultraviolet rays, they are easily decomposed to generate free radicals, Through the chain reaction of free radicals, the polymer inherent properties are significantly weakened.

In order to solve such problems, attempts have been made to improve the physical properties of polymers by adding an ultraviolet absorber to polymer compounds, and dihydrocyclic benzophenone (DHBP) is known as a typical ultraviolet absorber (Minagawa M. New developments in polymer stabilization. Polym Deg Stab 1989; 25: 121-41). However, such low-molecular substances are easily separated from the polymer by migration, extraction, and evaporation, resulting in a serious degradation of the polymer performance. Therefore, research and development Chemistry polymer additives such as ultraviolet absorbers, or to permanently bond to the polymer a has been in progress (Munteanu D, Csunderlik C Polyethylene- bound antioxidants Polym Deg Stab 1991; 34 (1-3):... 295-307 ).

Sharma et al. Have melt-grafted benzophenone acrylate compounds as low-molecular substances as ultraviolet absorbers into polypropylene, low-density polyethylene, and polystyrene, but have problems such as addition reaction such as copolymerization reaction. (Sharma YN, Naqvi MK, Gawande PS, Bhardwaj IS.Structurally bound stabilizers: Melt grafting of UV stabilizers onto polypropylene, polyethylene, and polystyrene.J Appl Polym Sci 1982; 27 (7): 2605-13).

Minagawa M., Polym Deg Stab 1989; 25: 121-41 Munteanu D, Csunderlik C, Polym Deg Stab 1991; 34 (1-3): 295-307 Sharma YN, Naqvi MK, Gawande PS, Bhardwaj IS., J Appl Polym Sci 1982; 27 (7): 2605-13

The present invention aims to provide a benzophenone-based ultraviolet absorber containing a novel maleimide group and a process for producing the same.

The present invention also aims to provide a polymer compound in which a benzophenone-based ultraviolet absorber containing a maleimide group is grafted, and a process for producing the same.

The present invention provides a benzophenone-based ultraviolet absorber comprising a maleimide group represented by the following Chemical Formula 1 to solve the above problems.

[Chemical Formula 1]

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are each independently selected from the group consisting of hydrogen, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, a phenyl group, Phenyl group)

In the benzophenone ultraviolet absorber comprising a maleimide group according to the present invention, the above-mentioned formula (1) is characterized by the following formula (2).

(2)

The present invention also relates to

Dissolving a compound represented by the formula (3) in an organic solvent;

(3)

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently selected from the group consisting of hydrogen, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, a phenyl group and an alkoxyphenyl group having 1 to 10 carbon atoms Group)

Mixing the solution with an organic base to prepare a first solution;

Dissolving a compound represented by the following formula (4) in an organic solvent to prepare a second solution;

[Chemical Formula 4]

(Wherein R ₇ is independently selected from the group consisting of hydrogen, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, a phenyl group, and an alkoxyphenyl group having 1 to 10 carbon atoms,

X is Cl or Br)

Dropping the second solution into the first solution to prepare a mixed solution; And

And reacting the mixed solution at room temperature for 20 minutes to 1 hour. The present invention also provides a method for producing a benzophenone-based ultraviolet absorbent comprising the maleimide group of the present invention.

In the method for producing a benzophenone-based ultraviolet absorber comprising a maleimide group of the present invention, the formula (3) is represented by the following formula (5).

[Chemical Formula 5]

In the method for producing a benzophenone-based ultraviolet absorber comprising a maleimide group of the present invention, the formula (4) is characterized by the following formula (6).

[Chemical Formula 6]

In the process for producing a benzophenone-based ultraviolet absorber comprising maleimide group of the present invention, the organic base may be selected from the group consisting of trimethylamine, triethylamine, diisopropylethylamine, tri-n-propylamine, tributylamine, And the like.

The present invention also provides a macromolecular compound in which the benzophenone-based ultraviolet absorber of the present invention is grafted.

In the polymer compound of the present invention wherein the benzophenone-based ultraviolet absorber is grafted, the polymer is characterized by being polyethylene or polypropylene.

The present invention also relates to

Preparing a benzophenone-based ultraviolet absorbent comprising the maleimide group of the present invention;

Mixing the ultraviolet absorber with a polymer; And

And reacting the mixture with stirring at 150 to 300 ° C for 5 minutes to 1 hour. The present invention also provides a method for producing a high molecular compound having a benzophenone-based ultraviolet absorber.

In the present invention, radicals are easily introduced into a polymer by melting as shown in the following reaction formula 1, and ultraviolet absorbers containing a maleimide group are easily grafted onto a polymer by utilizing the high reactivity of a maleimide group with a polymer containing the radical. .

[Reaction Scheme 1]

In the method for producing a polymer compound in which the benzophenone-based ultraviolet absorber of the present invention is grafted, 0.1 to 10 parts by weight of an ultraviolet absorber is mixed per 100 parts by weight of the polymer.

The present invention can easily introduce a radical into a polymer by melting and then graft the ultraviolet absorber containing a maleimide group onto the polymer more easily by utilizing the high reactivity of the polymer containing the radical and the maleimide group, The polymer compound obtained by grafting a benzophenone-based ultraviolet absorber containing the maleimide group thus produced has a long-term use, and the ultraviolet absorber does not escape from the polymer.

Figure 1 shows the IR spectra of the compounds prepared in one example and comparative example of the present invention.
Figure 2 shows UV spectral results of the compounds prepared in one example and comparative example of the present invention.
Figure 3 shows the grafting yield results of the compounds prepared in one embodiment of the present invention.
Figure 4 shows the IR spectra of the compounds prepared in one example and comparative example of the present invention.
Figure 5 shows the UV spectral results of the compounds prepared in one example and comparative example of the present invention.
Figure 6 shows the grafting yield results of the compounds prepared in one embodiment of the present invention.
7 shows the results of measurement of the carbonyl indices of the compounds prepared in the examples and comparative examples of the present invention.

Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited by the following examples.

< Example  1> N -(4- Benzoyl -3- Hydraciphenoxycarbonylphenyl ) Maleimide  Preparation of ultraviolet absorber

N - (4-benzoyl-3-hydra-phenoxycarbonylphenyl) maleimide (PCPM) was prepared using the following reaction scheme.

First, 2,4-dihydroxybenzophenone (1.82 g, 8 mmol) was dissolved in anhydrous dichloromethane, stirred at room temperature, and triethylamine (1.3 g, 12 mmol) was added thereto and then dissolved in CH ₂ Cl ₂ N -4-chlorocarbonylphenylmaleimide (2.0 g, 8.5 mmol) was added dropwise at room temperature and reacted for 30 minutes. After completion of the reaction, the product was extracted with dichloromethane, washed with distilled water three times, dried, and recrystallized from a mixed solution of dichloromethane and n-hexane in a ratio of 9: 1 by volume to obtain N - (4-benzoyl- Hydraciphenoxycarbonylphenyl) maleimide (PCPM) was obtained.

The above-mentioned N - (4-benzoyl-3-hydra-phenoxycarbonylphenyl) maleimide (PCPM) was obtained in a yield of 60%, and its structure was confirmed by IR-spectrum, ¹ H-NMR and elemental analysis .

R _f = 0.3 (dichloromethane)

m.p. 189-191 DEG C

_{^{1 H NMR (CDCl 3) d}} 12.31 (1H, s, OH), 8.30 (2H, d, COCHCHCO), 7.72-6.76 (12H, m, phenyl)

^{_{IR (CDCl 3, cm -1)}} 3465 (OH), 1741 (C = O), 1723 (C = O)

Anal. Calcd for C ₂₅ H ₁₅ NO ₆ : C 69.73, H 3.66, N 3.39; found C 70.03, H 3.71, N 3.41.

< Example  2-1> Polypropylene Grafted  Preparation of ultraviolet absorber

The N - (4-benzoyl-3-hydra-phenoxycarbonylphenyl) maleimide (PCPM) ultraviolet absorber synthesized in Example 1 was pulverized in a mortar and mixed with 4 g of PCPM in 100 g of polypropylene mini-max-molder CS 183MM-065 (custom scientific instruments) reaction vessel. The number of revolutions of the reactor was fixed at 100 rpm, and the reaction was carried out at 210 캜 for 10 minutes at atmospheric pressure. The product obtained in the above reaction was completely dissolved by adding xylene and heating at 150 DEG C for 2 hours, followed by washing with distilled tetrahydrofuran. The above washing was repeated three times and then filtered to obtain polypropylene grafted with N - (4-benzoyl-3-hydraxyphenoxycarbonylphenyl) maleimide (PCPM) ultraviolet absorber and polypropylene grafted This was separated to prepare an ultraviolet absorbent grafted to polypropylene.

< Experimental Example > IR  And UV  Spectrum Measurement

The IR and UV spectra were measured to determine whether the ultraviolet absorber comprising the maleimide group was grafted on the polypropylene and is shown in Figures 1 and 2.

As shown in FIG. 1, the carbonyl peak was observed at 1710 cm ^-1 in the case of the compound prepared in Example 2-1, and the n → π ^* and π → π transition of the carbonyl band Applicable UV absorption was observed at 345 nm and 270 nm. It can be seen from this that the ultraviolet absorber containing the maleimide group was grafted to the polypropylene by heat.

< Experimental Example > Grafting  Yield measurement

The ultraviolet absorber grafted to polypropylene was prepared by varying the amount of the ultraviolet absorber added, and the yield of the grafting was measured by IR analysis.

As shown in FIG. 3, when 4 g of ultraviolet absorber was added to 100 g of polypropylene, the grafting yield was the highest.

< Example  2-2> Polyethylene Grafted  Preparation of ultraviolet absorber

The N - (4-benzoyl-3-hydra-phenoxycarbonylphenyl) maleimide (PCPM) ultraviolet absorber synthesized in Example 1 was made into a fine powder state in a mortar, and 2 g of PCPM was mixed with 100 g of high density polyethylene And packed in a mini-max-molder CS 183MM-065 (custom scientific instruments) reaction vessel. The number of revolutions of the reactor was fixed at 100 rpm, and the reaction was carried out at 190 ° C for 10 minutes under atmospheric pressure. The product obtained in the above reaction was completely dissolved by adding xylene and heating at 150 DEG C for 2 hours, followed by washing with distilled tetrahydrofuran. The above washing is repeated three times and then filtered to obtain polyethylene and non-grafted polyethylene grafted with N - (4-benzoyl-3-hydraxyphenoxycarbonylphenyl) maleimide (PCPM) To prepare a polyethylene-grafted ultraviolet absorber .

< Experimental Example > IR  And UV  Spectrum Measurement

The IR and UV spectra were measured to determine whether an ultraviolet absorber comprising a maleimide group in polyethylene was grafted and is shown in Figures 4 and 5.

As shown in FIG. 4, the carbonyl peak was observed at 1710 cm ^-1 in the case of the compound prepared in Example 2-2, and the n → π ^* and π → π transition of the carbonyl band Applicable UV absorption was observed at 345 nm and 270 nm. From this, it can be seen that the ultraviolet absorbent containing the maleimide group was grafted to polyethylene by heat.

< Experimental Example > Grafting  Yield measurement

An ultraviolet absorber grafted to polyethylene was prepared by varying the amount of ultraviolet absorber added, and the yield of grafting was measured by IR analysis. The result is shown in FIG.

As shown in FIG. 6, when 4 g of ultraviolet absorber was added to 100 g of polyethylene, the grafting yield was the highest.

< Comparative Example  1>

< Comparative Example  1-1>

The polymer made of only polypropylene was designated as Comparative Example 1-1.

< Comparative Example  1-2>

The polymer made of only polyethylene was designated as Comparative Example 1-2.

< Comparative Example  2>

< Comparative Example  2-1>

A mixture of polypropylene and low molecular dihydroxybenzophenone (DHBP) was used as Comparative Example 2-1.

< Comparative Example  2-2>

A mixture of polypropylene and N - (4-benzoyl-3-hydra-phenoxycarbonylphenyl) maleimide was used as Comparative Example 2-2.

< Experimental Example > Mineralization  Effect measurement

In order to confirm the photo-oxidizing effect of the ultraviolet absorbent bound to the polyolefin, the polymers of Examples 2-1 and 2-2 and Comparative Examples 1 and 2 were formed into a film having a thickness of 50 μm using a weatherometer (xenon lamp 7500 W) , And the degree of photo-oxidation according to the change of the time was measured by IR spectroscopy. The results are shown in FIG. The carbonyl index (A ₁₇₁₅ ) of the carbonyl peak of 1715 cm ^-1 formed by oxidation of polyolefin and the intrinsic peak of polypropylene of 2725 cm ^-1 and high-density polyethylene of 2025 cm ^-1 is defined as the carbonyl index And the degree of oxidation was compared and analyzed. That is, as the index value is increased, photo-oxidation of the polymer is progressed.

As shown in FIG. 7, it can be seen that the carbonyl index of the films made of the polymers of Examples 2-1 and 2-2 is gradually increased. As a result, it can be seen that, in the case of the present invention, the ultraviolet absorber binds to the polymer skeleton and is continuously extracted without being extracted

On the other hand, in the case of the film made of the polymer of Comparative Example 1, the carbonyl index is rapidly increased. After 30 minutes, the film is decomposed and the physical IR measurement becomes impossible. In the case of the film made of the polymer of Comparative Example 2, it can be seen that the carbonyl index increases sharply with time, because the low molecular ultraviolet absorber is extracted by water.

Claims (10)

A benzophenone-based ultraviolet absorber comprising a maleimide group represented by the following formula (1).
[Chemical Formula 1]

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ Are each independently selected from the group consisting of hydrogen, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, a phenyl group, and an alkoxyphenyl group having 1 to 10 carbon atoms)
The method according to claim 1,
The benzophenone-based ultraviolet absorber comprising a maleimide group, wherein the formula (1) is represented by the following formula (2).
(2)

Dissolving a compound represented by the formula (3) in an organic solvent;
(3)

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ Are each independently selected from the group consisting of hydrogen, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, a phenyl group, and an alkoxyphenyl group having 1 to 10 carbon atoms)
Mixing the solution with an organic base to prepare a first solution;
Dissolving a compound represented by the following formula (4) in an organic solvent to prepare a second solution;
[Chemical Formula 4]

(In the formula 4, R &lt; ₇ &gt; Are each independently selected from the group consisting of hydrogen, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, a phenyl group, and an alkoxyphenyl group having 1 to 10 carbon atoms,
X is Cl or Br)
Dropping the second solution into the first solution to prepare a mixed solution; And
And reacting the mixed solution at room temperature for 20 minutes to 1 hour. The method for producing a benzophenone-based ultraviolet absorbent according to claim 1,
The method of claim 3,
Wherein the benzophenone-based ultraviolet absorbent comprises a maleimide group.
[Chemical Formula 5]

The method of claim 3,
Wherein the benzophenone-based ultraviolet absorbent comprises a maleimide group.
[Chemical Formula 6]

The method of claim 3,
Wherein the organic base is selected from the group consisting of trimethylamine, triethylamine, diisopropylethylamine, tri-n-propylamine, tributylamine, pyridine, and combinations thereof. .
Wherein the benzophenone-based ultraviolet absorber comprising the maleimide group of claim 1 is grafted.
8. The method of claim 7,
Wherein the polymer is polyethylene or polypropylene. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt;
Preparing a benzophenone-based ultraviolet absorbent comprising the maleimide group of claim 1;
Mixing the ultraviolet absorber with a polymer; And
And reacting the mixture with stirring at 150 to 300 ° C for 5 minutes to 1 hour. The method for producing a polymer compound according to claim 1, wherein the benzophenone-based ultraviolet absorber is grafted.
10. The method of claim 9,
Wherein the benzophenone-based ultraviolet absorber is grafted by mixing 0.1 to 10 parts by weight of an ultraviolet absorber per 100 parts by weight of the polymer.

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