CN112225881B - Ultraviolet absorbent, preparation method and composition thereof - Google Patents
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3328—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms alkyne-based
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- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Abstract
The invention discloses an ultraviolet absorbent, a preparation method and a composition thereof, belonging to the field of ultraviolet absorption. The preparation method comprises the following steps: the 1, 4-dilithio diacetylene solution reacts with aromatic ether to obtain the diacetylene polyaromatic hydrocarbon alkyl. The butadiynyl polyaromatic hydrocarbon alkyl compound of the invention takes conjugated polyyne molecules as a main chain, and the conjugated polyyne structure has a one-dimensional carbon chain structure formed by alternating single bonds and triple bonds, thereby forming cylindrical electron delocalization, having excellent intramolecular electron and charge transmission properties, enabling the ultraviolet absorption wavelength of the compound to generate red shift, introducing oxygen atoms rich in electrons at the ortho position of a benzene ring, stabilizing by using alkyl or alkylene or aromatic hydrocarbon, exploring optimal reaction conditions and obtaining the ultraviolet absorbent with stable effect.
Description
Technical Field
The invention belongs to the field of ultraviolet absorption, and particularly relates to an ultraviolet absorbent, a preparation method and a composition thereof.
Background
The demand for products related to ultraviolet absorbers is becoming higher and higher. Sustainability, low cost, environmental friendliness, safety, health, etc. are issues that need to be addressed.
The ultraviolet absorbent in the prior art comprises an inorganic ultraviolet absorbent and an organic ultraviolet absorbent, wherein the organic ultraviolet absorbent mainly comprises a pi-conjugated system in molecules, absorbs ultraviolet rays by utilizing a specific structure of the ultraviolet absorbent to change the ultraviolet absorbent into an excited state, releases the absorbed energy in the form of heat energy or harmless low-energy radiation, or generates intramolecular tautomerism, consumes a part of energy, returns to a ground state, and absorbs the ultraviolet rays repeatedly, thereby playing a role in protecting substances. However, these uv absorbers are hydrogen rich bonds and rely on intramolecular proton transfer to convert uv light into heat release or harmless low energy radiation, which limits their application to heat sensitive substrates.
Disclosure of Invention
The invention aims to: an ultraviolet absorber, a method for preparing the same, and a composition are provided to solve the problems involved in the background art.
The technical scheme is as follows: an ultraviolet absorber, method of making and composition comprising:
the structural formula of the compound is shown as follows,
wherein, R group is C1～6 alkyl or alkenyl or aromatic hydrocarbon, and n is an integer of 100 to 300.
In further embodiments, the R group is a methyl, phenyl, or toluene group.
In a further embodiment, the relative molecular mass of the UV absorber is 50000-150000 g/mol.
The invention also provides a preparation method of the ultraviolet absorbent, which is characterized by comprising the following steps:
step 1 preparation of aromatic ethers
Under the protection of inert gas, mixing 2, 5-dichlorophenol and halogenated hydrocarbon according to a volume ratio of 1: (1-3), reacting under the action of a catalyst, and then carrying out fractional distillation to obtain aromatic ether;
step 2, preparing 1, 4-dilithio diacetylene
Under the protection of inert gas, mixing n-butyllithium and an organic solvent according to a volume ratio of l (1-5), dropwise adding the mixed solution into a solution of the organic solvent and hexachlorobutadiene according to a volume ratio of (8-12) to 1, and stirring for reaction to obtain a 1, 4-dilithio diacetylene solution;
step 3, preparing butynyl polyaromatic hydrocarbon alkyl
Slowly dropwise adding the obtained 1, 4-dilithio diacetylene solution into aromatic ether under stirring, continuously reacting, evaporating the solvent, and purifying a crude product through a silica gel column to obtain the butadiynyl polyaromatic alkyl compound.
In further embodiments, the halogenated hydrocarbon is monochlorobutane, chlorobenzene or p-chlorotoluene.
In a further embodiment, the organic solvent is tetrahydrofuran. The separation difficulty of the butyl dialkynyl aromatic hydrocarbon alkyl compound in the later period can be reduced.
In a further embodiment, the reaction conditions in step 3 are: adding 1, 4-dilithio diacetylene solution at the rate of 1-3%/min of the total mass at the temperature of 0-25 ℃; and then stirring and reacting for 10-16 hours at 45-60 ℃.
The present invention also provides a composition of an ultraviolet absorber, characterized in that the composition comprises: the ultraviolet absorber, the acrylic ester polymer and the volatile organic solvent are characterized in that the mass of the ultraviolet absorber is 5-20% of that of the acrylic ester polymer.
In further embodiments, the volatile organic solvent is an alcohol or an ether.
In a further embodiment, the acrylate polymer has a relative molecular mass of 2000-4000 g/mol.
Has the advantages that: the invention relates to an ultraviolet absorbent, a preparation method and a composition thereof, wherein a conjugated polyacetylene molecule is taken as a main chain, the conjugated polyacetylene structure has a one-dimensional carbon chain structure formed by alternating single bonds and triple bonds to form a cylindrical electron delocalization, the ultraviolet absorbent has excellent intramolecular electron and charge transmission properties, can enable the ultraviolet absorption wavelength of a compound to generate red shift, introduces oxygen atoms rich in electrons at the ortho position of a benzene ring, is stabilized by alkyl or alkenyl or aromatic hydrocarbon, explores the optimal reaction condition and can obtain the ultraviolet absorbent with stable effect.
Drawings
FIG. 1 is a graph showing ultraviolet absorption spectra of Synthesis examples 1 to 3 of the present invention.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present invention. It will be apparent, however, to one skilled in the art, that the present invention may be practiced without one or more of these specific details. In other instances, well-known features have not been described in order to avoid obscuring the invention.
At present, the ultraviolet absorbent mainly consists of a pi-conjugated system in a molecule, absorbs ultraviolet rays by utilizing a specific structure of the ultraviolet absorbent to change the ultraviolet absorbent into an excited state, releases absorbed energy in the form of heat or light, or generates intramolecular tautomerism, consumes a part of energy, returns to a ground state, and absorbs the ultraviolet rays repeatedly, thereby playing a role in protecting substances. However, these compounds are rich in hydrogen bonds, and rely on intramolecular proton transfer to convert ultraviolet light into heat for release, which limits the application to heat-sensitive substrates.
Based on the technical problems, the ultraviolet absorbent provided by the application takes a conjugated polyacetylene molecule as a main chain, and the conjugated polyacetylene structure has a one-dimensional carbon chain structure formed by alternating single bonds and triple bonds, so that cylindrical electron delocalization is formed, the ultraviolet absorbent has excellent intramolecular electron and charge transmission properties, the ultraviolet absorption wavelength of the compound can be subjected to red shift, an oxygen atom rich in electrons is introduced to the ortho-position of a benzene ring, and the ultraviolet absorbent is stabilized by alkyl or alkylene or aromatic hydrocarbon, so that the ultraviolet absorbent with stable effect can be obtained.
However, the ultraviolet absorbent is uniformly mixed with the monomer, the resin and the auxiliary agent, and a film coating experiment is carried out, so that the ultraviolet absorbent does not initiate the resin to form a film through crosslinking, and the ultraviolet absorbent is added into the cured coating, but the film hardness and the adhesive force are improved. Applicants therefore mix the uv absorber with paint to form a composition, specifically, the composition comprises: the ultraviolet light absorbing agent comprises an ultraviolet light absorbing agent, an acrylic ester polymer and a volatile organic solvent, wherein the mass of the ultraviolet light absorbing agent is 5-20% of that of the acrylic ester polymer. In the using process, the ultraviolet absorbent and the acrylic polymer form an inert system, so that the ultraviolet absorbent does not participate in the reaction, the fluidity is maintained, the solvent is volatilized, the acrylic polymer and the ultraviolet absorbent migrate outwards, and the ultraviolet absorbent is relatively large in molecular mass and slow in migration rate, so that when the acrylic polymer is cured to form a solid state, the ultraviolet absorbent is also fixed between the acrylic polymer and a matrix, and the film hardness and the adhesion strength are relatively strong.
Therefore, in the process of preparing the ultraviolet absorbent, the reaction conditions of the 1, 4-dilithiylbutylkyne solution and the aromatic ether are further optimized, and specifically: adding 1, 4-dilithio diacetylene solution at the rate of 1-3%/min of the total mass at the temperature of 0-25 ℃; and then stirring and reacting for 10-16 hours at 45-60 ℃. The ultraviolet absorber thus obtained has a relative molecular mass of 50000 to 150000 g/mol. The curing process is realized by matching with an acrylic ester polymer with the relative molecular mass of 2000-4000 g/mol.
The invention will now be further described with reference to the following examples, which are intended to be illustrative of the invention and are not to be construed as limiting the invention.
Synthesis example 1
Step 1 preparation of aromatic ethers
Mixing 50ml of 2, 5-dichlorophenol and 100ml of n-butyl chloride in a three-neck flask, keeping the temperature at low temperature under the action of ferric trichloride serving as a catalyst, stirring for reacting for 2 hours, and then obtaining colorless and transparent aromatic ether by fractional distillation;
step 2, preparing 1, 4-dilithio diacetylene
In a three-neck flask, mixing 50ml of n-butyllithium and 80ml of tetrahydrofuran, dropwise adding the mixture into a mixed solution of 80ml of tetrahydrofuran and 8ml of tetrahydrofuran hexachlorobutadiene under the protection of nitrogen, stirring and reacting the mixture in the three-neck flask, gradually raising the temperature to 5 ℃ after the dropwise addition is finished, and continuously stirring and reacting for 8 hours to obtain an off-white turbid 1, 4-dilithio diacetylene solution;
step 3, preparing the diacetylene polyaromatic hydrocarbon alkyl
Slowly dripping the obtained 1, 4-dilithio diacetylene solution into aromatic ether in a three-neck flask at the speed of 1.5% per min of the total mass under the protection of nitrogen and at the temperature of 0-25 ℃ while stirring, then stirring and reacting for 12 hours at the temperature of 45-60 ℃, standing and layering, wherein the upper layer is a brownish red clear liquid, the lower layer is a light yellow precipitate, and purifying a crude product through a silica gel column to obtain a yellow solid butadiynyl polyaromatic alkyl compound. The structural formula is as follows:
wherein n is an integer of 100 to 300.
Spectrogram analysis of the alkyl substance containing the diacetylene polyaromatic hydrocarbon comprises the following steps: 1 H NMR(600MHz, CDCl 3 ): δ 2.18 (s, 3H, CH3), 6.68 – 7.03 (m, 6H，CH2), 7.08 (t, J=7.4 Hz, 1H, ArH), 7.16 (t, J=7.6 Hz, 1H, ArH), 7.21-7.36 (m, 3H, ArH), 7.48 (d, J=7.6 Hz, 2H, ArH), 7.57 (d, J=7.6 Hz, 1H, Ar H). 13 C NMR(150MHz, CDCl3): δ136.7, 135.1, 133.1, 130.1, 129.4, 128.6, 127.9, 124.5, 88.9, 87.8。
synthesis example 2
Step 1 preparation of aromatic ethers
Mixing 50ml of 2, 5-dichlorophenol and 120ml of chlorobenzene chloride in a three-neck flask, keeping the temperature at low temperature under the action of Lewis acid as a catalyst, stirring for reacting for 2 hours, and then obtaining colorless and transparent aromatic ether by fractional distillation;
step 2, preparing 1, 4-dilithio diacetylene
In a three-neck flask, mixing 50ml of n-butyllithium and 80ml of tetrahydrofuran, dropwise adding the mixture into a mixed solution of 80ml of tetrahydrofuran and 8ml of tetrahydrofuran hexachlorobutadiene under the protection of nitrogen, stirring and reacting the mixture in the three-neck flask, gradually raising the temperature to 5 ℃ after the dropwise addition is finished, and continuously stirring and reacting for 8 hours to obtain an off-white turbid 1, 4-dilithio diacetylene solution;
step 3, preparing the diacetylene polyaromatic hydrocarbon alkyl
Slowly dripping the obtained 1, 4-dilithio diacetylene solution into aromatic ether under stirring in a three-neck flask at the speed of 1.5% per min of the total mass under the condition of nitrogen protection and at the temperature of 0-25 ℃, then stirring and reacting for 12 hours at the temperature of 45-60 ℃, standing and layering, wherein the upper layer is a brownish red clear liquid, the lower layer is a light yellow precipitate, and purifying a crude product through a silica gel column to obtain a yellow solid butadiynyl polyaromatic alkyl compound. The structural formula is as follows:
wherein n is an integer of 100 to 300.
The spectrogram analysis comprises the following steps: 1 H NMR(600MHz, CDCl 3 ): δ 7.03 (d, J=7.9 Hz, 1H, ArH), 7.18 (t, J=7.5 Hz, 1H, ArH), 7.23 (t, J=7.7 Hz, 1H, ArH), 7.35-7.41 (m, 3H, ArH), 7.51 (d, J=7.6 Hz, 2H, ArH), 7.54 (d, J=7.6 Hz, 1H, Ar H). 13 C NMR(150MHz, CDCl3): δ 142.2, 133.9, 133.6, 133.4, 129.8, 129.5, 128.4, 128.6, 125.9, 121.4, 80.9, 79.8。
synthesis example 3
Step 1 preparation of aromatic ethers
Mixing 50ml of 2, 5-dichlorophenol and 125ml of chlorotoluene in a three-neck flask, keeping the temperature at low temperature under the action of Lewis acid as a catalyst, stirring for reacting for 2 hours, and then obtaining colorless and transparent aromatic ether by fractional distillation;
step 2, preparing 1, 4-dilithio diacetylene
In a three-neck flask, mixing 50ml of n-butyllithium and 80ml of tetrahydrofuran, dropwise adding the mixture into a mixed solution of 80ml of tetrahydrofuran and 8ml of tetrahydrofuran hexachlorobutadiene under the protection of nitrogen, stirring and reacting the mixture in the three-neck flask, gradually raising the temperature to 5 ℃ after the dropwise addition is finished, and continuously stirring and reacting for 8 hours to obtain an off-white turbid 1, 4-dilithio diacetylene solution;
step 3, preparing the diacetylene polyaromatic hydrocarbon alkyl
Slowly dripping the obtained 1, 4-dilithio diacetylene solution into aromatic ether in a three-neck flask at the speed of 1.5% per min of the total mass under the protection of nitrogen and at the temperature of 0-25 ℃ while stirring, then stirring and reacting for 12 hours at the temperature of 45-60 ℃, standing and layering, wherein the upper layer is a brownish red clear liquid, the lower layer is a light yellow precipitate, and purifying a crude product through a silica gel column to obtain a yellow solid butadiynyl polyaromatic alkyl compound. The structural formula is as follows:
wherein n is an integer of 100 to 300.
And (3) spectrogram analysis: 1 H NMR (600MHz, CDCl3): δ 2.40 (s, 3H, CH3), 6.89 (d, J=7.8 Hz, 1H, ArH), 7.10 (t, J=7.3 Hz, 1H, ArH), 7.17 (t, J=7.4 Hz, 1H, ArH), 7.23 (d, J=7.3 Hz, 2H, ArH), 7.43-7.45 (m, 2H, ArH), 7.53 (d, J=7.4 Hz, 1H, ArH). 13C NMR(150MHz, CDCl3): δ 143.3, 138.9, 134.5, 133.7, 130.4, 129.5, 128.7, 127.4, 125.2, 120.4, 80.7, 79.8, 21.3.
example 1
The composition comprises the following components in percentage by mass: 45% of polyurethane acrylic resin, 40% of hexanediol diacrylate, 10% of butynyl polyaromatic alkyl in synthetic example 1, 2% of triethanolamine and 3% of initiator.
Example 2
The composition comprises the following components in percentage by mass: 45% of polyurethane acrylic resin, 40% of hexanediol diacrylate, 10% of butynyl polyaromatic alkyl in synthetic example 2, 2% of triethanolamine and 3% of initiator.
Example 3
The composition comprises the following components in percentage by mass: 45% of polyurethane acrylic resin, 40% of hexanediol diacrylate, 10% of butynyl polyaromatic alkyl in synthetic example 3, 2% of triethanolamine and 3% of initiator.
Example 4
The composition comprises the following components in percentage by mass: 80% of an acrylate polymer, 10% of a butynylpolyaromatic alkyl compound in synthetic example 1, and 10% of isopropanol. Wherein the relative molecular mass of the acrylate polymer is 2000-4000 g/mol.
Example 5
The composition comprises the following components in percentage by mass: 80% of an acrylate polymer, 10% of a butynylpolyaromatic alkyl compound in synthetic example 2, and 10% of isopropanol. Wherein the relative molecular mass of the acrylate polymer is 2000-4000 g/mol.
Example 6
The composition comprises the following components in percentage by mass: 80% of an acrylate polymer, 10% of a butynylpolyaromatic alkyl compound in synthetic example 3, and 10% of isopropanol. Wherein the relative molecular mass of the acrylate polymer is 2000-4000 g/mol.
Example 7
The composition comprises the following components in percentage by mass: synthesis example 3 contained 80% of butynylpolyaromatic alkyl compound and 20% of isopropyl alcohol.
Detection example 1
The products of Synthesis examples 1 to 3 were each prepared as a solution of 0.1mmol/L concentration, placed in a transparent container, exposed to a 1KW ultraviolet lamp for 24 hours, and then tested for ultraviolet absorption spectrum. The UV absorption spectrum is shown in figure 1 (comparative example is a commercially available UV absorber UV-0).
Detection example 2
The coating experiments of examples 1 to 7 were carried out, and the results are shown in Table 1.
Table 1:
it is understood from the examination of example 1 that the diacetylene-based polyaromatic hydrocarbon alkyl compounds obtained in synthesis examples 1 to 3 have a higher absorption capacity than the existing commercially available ultraviolet absorption peak. Has stronger ultraviolet absorption peak in the wide range of 260-375nm, in particular between 260-300 nm. Through the experimental data of comparative example 2, the diacetylene-based polyaromatic alkyl compound obtained in synthesis examples 1 to 3 was mixed with an acrylic polymer paint having a relative molecular mass of 2000 to 4000g/mol to form a composition, which was capable of forming a smooth transparent film having high film hardness and adhesion.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
Claims (6)
1. A preparation method of an ultraviolet absorbent is characterized by comprising the following steps:
step 1 preparation of aromatic ethers
Under the protection of inert gas, 2, 5-dichlorophenol and halogenated hydrocarbon are mixed according to the volume ratio of 1: (1-3), reacting under the action of a catalyst, and then carrying out fractional distillation to obtain aromatic ether;
step 2, preparing 1, 4-dilithio diacetylene
Under the protection of inert gas, mixing n-butyllithium and an organic solvent according to a volume ratio of l (1-5), then dropwise adding the mixture into a solution in which the organic solvent and hexachlorobutadiene are mixed according to a volume ratio of (8-12) to 1, and stirring for reaction to obtain a 1, 4-dilithio diacetylene solution;
step 3, preparing the ultraviolet absorbent
Slowly dripping the obtained 1, 4-dilithio diacetylene solution into aromatic ether under stirring, continuously reacting, evaporating the solvent, and purifying a crude product through a silica gel column to obtain an ultraviolet absorbent; the structural formula of the ultraviolet absorbent is as follows,
wherein, R group is C1～6 alkyl or alkenyl or aromatic hydrocarbon, and n is an integer of 100 to 300.
2. The method for producing an ultraviolet absorber according to claim 1, wherein the R group is a methyl group, a phenyl group, or a toluene group.
3. The method for producing an ultraviolet absorber according to claim 1, wherein the ultraviolet absorber has a relative molecular mass of 50000 to 150000 g/mol.
4. The method for preparing an ultraviolet absorber according to claim 1, wherein the halogenated hydrocarbon is monochlorobutane, chlorobenzene or p-chlorotoluene.
5. The method for producing an ultraviolet absorber according to claim 1, wherein the organic solvent is tetrahydrofuran.
6. The method for preparing an ultraviolet absorber according to claim 1, wherein the reaction conditions in step 3 are: adding 1, 4-dilithio diacetylene solution at the rate of 1-3%/min of the total mass at the temperature of 0-25 ℃; and then stirring and reacting for 10-16 hours at 45-60 ℃.
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| CN112225881A (en) | 2021-01-15 |
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