Broad-spectrum absorption macromolecule ultraviolet absorber and preparation method thereof

Abstract

The invention discloses a broad-spectrum absorption macromolecular ultraviolet ray absorber preparation method, which comprises: carrying out a Diels-Alder reaction by using 3-(N,N,-2-maleimidoethyl propionate-amine methyl)-2,4-dihydroxybenzophenone and difurfuryl sebacate or difurfuryl adipate as raw material monomers to prepare the macromolecular ultraviolet ray absorber. The invention discloses the broad-spectrum absorption macromolecular ultraviolet ray absorber. According to the present invention, the prepared broad-spectrum absorption macromolecular ultraviolet ray absorber has excellent broad spectrum ultraviolet ray absorption function, contains long chain alkyl, heterocyclic ring and ester in the main chain, has good compatibility with polystyrene, ABS, polycarbonate, polyoxymethylene, polyurethane and other polymer materials prepared through the Diels-Alder click method, and is suitable for the light stabilization of the polymer materials.

Description

technical field

[0001] The invention belongs to the field of polymer additives, and relates to a broad-spectrum absorption macromolecular ultraviolet absorber and a preparation method thereof. Background technique

[0002] With the expansion of the ozone layer hole in the earth's atmosphere, the intensity of ultraviolet radiation on the ground is continuously increasing, which has extremely adverse effects on human beings and their living environment. Long-term exposure of polymer materials to ultraviolet radiation will accelerate aging and shorten the service life of materials. In order to reduce the aging phenomenon of polymer materials caused by this ultraviolet light, adding ultraviolet absorbers to polymer materials is an effective method.

[0003] Benzophenone UV absorbers have good UV absorption properties in the range of 200-400nm and are suitable for various light-colored products. They are an important class of UV absorbers and are widely used in plastics, coating...

Examples

preparation example Construction

[0028] The invention provides a kind of preparation method of the macromolecule ultraviolet absorber of broad-spectrum absorption, comprising: utilizing 3-(N, N-2-maleimido ethyl propionate-aminomethyl)-2,4 - A Diels-Alder reaction of dihydroxybenzophenone with difurfuryl sebacate or adipate as a raw material monomer.

[0029] The macromolecule ultraviolet absorber prepared in the broad-spectrum absorbing macromolecular ultraviolet absorber and the preparation method thereof of the present invention has excellent broad-spectrum ultraviolet absorbing function; The chain contains heterocycles and ester groups, and has good compatibility with most polymer materials such as polystyrene, ABS, polycarbonate, polyurethane, and Diels-Alder click polymers, and is suitable for this type of high polymer. Light stabilization of molecular materials; in addition, the reaction of the macromolecular ultraviolet absorber does not require a catalyst, and the reaction conditions are mild, which ...

Embodiment 1

[0041] (1) Synthesis of 3-(N, N-2-hydroxyethyl-aminomethyl)-2,4-dihydroxybenzophenone (HAHBP)

[0042] UV-0: diethanolamine=1: 1.3 (mol); UV-0: paraformaldehyde=1: 1.5 (mol),

[0043] Put 1.365g (0.013mol) of diethanolamine into a 150mL three-necked flask, and start adding 0.45g (0.015mol) of paraformaldehyde powder in batches when heating at 60°C, and put in 0.15g of paraformaldehyde every 15 minutes, and put in 3 batches After the addition, 60 ° C insulation reaction for 1.0 h, then 2.14 g (0.01 mol) of UV-0 dissolved in 8 mL of methanol, added to the above reaction solution, continued reaction at 60 ° C for 2.5 h. Then the product is washed with water to remove excess diethanolamine and paraformaldehyde, freeze-dried to obtain the product, and its synthetic route is:

[0044]

[0045] (2) Synthesis of 3-(N,N-2-maleimido ethyl propionate-aminomethyl)-2,4-dihydroxybenzophenone (EMIPAHBP)

[0046] MIPA:HAHBP=2:1 (mol), MIPA:DCC=1:1 (mol).

[0047] In a 150mL three-necked...

Embodiment 2

[0060] (1) Synthesis of 3-(N, N-2-hydroxyethyl-aminomethyl)-2,4-dihydroxybenzophenone (HAHBP)

[0061] UV-0: diethanolamine=1: 2 (mol): UV-0: paraformaldehyde=1: 1.5 (mol),

[0062] Put 2.23g (0.0212mol) of diethanolamine into a 150mL three-necked flask, and start adding paraformaldehyde powder in batches at 70°C, a total of 0.477g (0.0159), and put in 0.159g of paraformaldehyde every 15min, and put it in 3 batches. After the addition, the temperature was raised to 75°C for 2.5 hours, and then 2.27g (0.0106mol) of UV-0 was dissolved in 10mL of methanol, added to the above reaction solution, and the reaction was continued at 75°C for 5h. Then the product is washed with water to remove excess diethanolamine and paraformaldehyde, freeze-dried, and the synthetic route is:

[0063]

[0064] (2) Synthesis of 3-(N,N-2-maleimido ethyl propionate-aminomethyl)-2,4-dihydroxybenzophenone (EMIPAHBP)

[0065] MIPA:HAHBP=2.5:1, MIPA:DCC=1:1 (mol).

[0066] In a 150mL three-necked flask...

technical field

[0001] The invention belongs to the field of polymer additives, and relates to a broad-spectrum absorption macromolecular ultraviolet absorber and a preparation method thereof. Background technique

[0002] With the expansion of the ozone layer hole in the earth's atmosphere, the intensity of ultraviolet radiation on the ground is continuously increasing, which has extremely adverse effects on human beings and their living environment. Long-term exposure of polymer materials to ultraviolet radiation will accelerate aging and shorten the service life of materials. In order to reduce the aging phenomenon of polymer materials caused by this ultraviolet light, adding ultraviolet absorbers to polymer materials is an effective method.

[0003] Benzophenone UV absorbers have good UV absorption properties in the range of 200-400nm and are suitable for various light-colored products. They are an important class of UV absorbers and are widely used in plastics, coating...

Examples

preparation example Construction

[0028] The invention provides a kind of preparation method of the macromolecule ultraviolet absorber of broad-spectrum absorption, comprising: utilizing 3-(N, N-2-maleimido ethyl propionate-aminomethyl)-2,4 - A Diels-Alder reaction of dihydroxybenzophenone with difurfuryl sebacate or adipate as a raw material monomer.

[0029] The macromolecule ultraviolet absorber prepared in the broad-spectrum absorbing macromolecular ultraviolet absorber and the preparation method thereof of the present invention has excellent broad-spectrum ultraviolet absorbing function; The chain contains heterocycles and ester groups, and has good compatibility with most polymer materials such as polystyrene, ABS, polycarbonate, polyurethane, and Diels-Alder click polymers, and is suitable for this type of high polymer. Light stabilization of molecular materials; in addition, the reaction of the macromolecular ultraviolet absorber does not require a catalyst, and the reaction conditions are mild, which ...

Embodiment 1

[0041] (1) Synthesis of 3-(N, N-2-hydroxyethyl-aminomethyl)-2,4-dihydroxybenzophenone (HAHBP)

[0042] UV-0: diethanolamine=1: 1.3 (mol); UV-0: paraformaldehyde=1: 1.5 (mol),

[0043] Put 1.365g (0.013mol) of diethanolamine into a 150mL three-necked flask, and start adding 0.45g (0.015mol) of paraformaldehyde powder in batches when heating at 60°C, and put in 0.15g of paraformaldehyde every 15 minutes, and put in 3 batches After the addition, 60 ° C insulation reaction for 1.0 h, then 2.14 g (0.01 mol) of UV-0 dissolved in 8 mL of methanol, added to the above reaction solution, continued reaction at 60 ° C for 2.5 h. Then the product is washed with water to remove excess diethanolamine and paraformaldehyde, freeze-dried to obtain the product, and its synthetic route is:

[0044]

[0045] (2) Synthesis of 3-(N,N-2-maleimido ethyl propionate-aminomethyl)-2,4-dihydroxybenzophenone (EMIPAHBP)

[0046] MIPA:HAHBP=2:1 (mol), MIPA:DCC=1:1 (mol).

[0047] In a 150mL three-necked...

Embodiment 2

[0060] (1) Synthesis of 3-(N, N-2-hydroxyethyl-aminomethyl)-2,4-dihydroxybenzophenone (HAHBP)

[0061] UV-0: diethanolamine=1: 2 (mol): UV-0: paraformaldehyde=1: 1.5 (mol),

[0062] Put 2.23g (0.0212mol) of diethanolamine into a 150mL three-necked flask, and start adding paraformaldehyde powder in batches at 70°C, a total of 0.477g (0.0159), and put in 0.159g of paraformaldehyde every 15min, and put it in 3 batches. After the addition, the temperature was raised to 75°C for 2.5 hours, and then 2.27g (0.0106mol) of UV-0 was dissolved in 10mL of methanol, added to the above reaction solution, and the reaction was continued at 75°C for 5h. Then the product is washed with water to remove excess diethanolamine and paraformaldehyde, freeze-dried, and the synthetic route is:

[0063]

[0064] (2) Synthesis of 3-(N,N-2-maleimido ethyl propionate-aminomethyl)-2,4-dihydroxybenzophenone (EMIPAHBP)

[0065] MIPA:HAHBP=2.5:1, MIPA:DCC=1:1 (mol).

[0066] In a 150mL three-necked flask...

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