CN106543428B - Aggretion type ultra-violet absorber of the side group containing UV-0 and preparation method thereof - Google Patents
Aggretion type ultra-violet absorber of the side group containing UV-0 and preparation method thereof Download PDFInfo
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- 239000006097 ultraviolet radiation absorber Substances 0.000 title claims abstract description 37
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 10
- 125000004386 diacrylate group Chemical group 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 10
- 238000012650 click reaction Methods 0.000 claims abstract description 4
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 15
- 229920002866 paraformaldehyde Polymers 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 13
- 239000012965 benzophenone Substances 0.000 claims description 13
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 13
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical class OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- DEQUKPCANKRTPZ-UHFFFAOYSA-N (2,3-dihydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1O DEQUKPCANKRTPZ-UHFFFAOYSA-N 0.000 claims 3
- 229940043237 diethanolamine Drugs 0.000 claims 2
- CWXZAJNUTOBAOI-UHFFFAOYSA-N 1-(2,3-dimethoxyphenyl)-2-hydroxy-2-phenylethanone Chemical compound COC1=CC=CC(C(=O)C(O)C=2C=CC=CC=2)=C1OC CWXZAJNUTOBAOI-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 239000002861 polymer material Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 8
- 125000003396 thiol group Chemical group [H]S* 0.000 abstract description 3
- 239000006096 absorbing agent Substances 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 4
- SCCCIUGOOQLDGW-UHFFFAOYSA-N 1,1-dicyclohexylurea Chemical compound C1CCCCC1N(C(=O)N)C1CCCCC1 SCCCIUGOOQLDGW-UHFFFAOYSA-N 0.000 description 3
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical group CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 3
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 229960002130 benzoin Drugs 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- -1 coatings Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
- C08G65/3344—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur
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Abstract
本发明公开了一种含UV‑0侧基的聚合型紫外线吸收剂的制备方法，包括：利用3‑(N,N,‑2‑巯基丙酸乙酯‑胺甲基)‑2,4‑二羟基二苯甲酮与聚乙二醇二丙烯酸酯作为原料单体发生巯基‑烯点击反应，然后加入光敏剂，其中，光敏剂的加入量为原料单体总重的0.5‑1.5％，3‑(N,N,‑2‑马来酰亚胺基丙酸乙酯‑胺甲基)‑2,4‑二羟基二苯甲酮与聚乙二醇二丙烯酸酯的摩尔比为1:1。本发明公开了一种含UV‑0侧基的聚合型紫外线吸收剂。本发明所制备得到的聚合型紫外线吸收剂分子链中含有可反应的双键与巯基，可以作为可反应型紫外线吸收剂应用到高分子材料中；另外分子链中引入了亲水基团，进一步扩大了应用范围。
The invention discloses a preparation method of a polymeric ultraviolet absorber containing UV-0 side groups, comprising: using 3-(N,N,-2-ethylmercaptopropionate-aminomethyl)-2,4- Dihydroxybenzophenone and polyethylene glycol diacrylate undergo a mercapto-ene click reaction as a raw material monomer, and then add a photosensitizer, wherein the amount of the photosensitizer is 0.5-1.5% of the total weight of the raw material monomer, 3 ‑(N,N,‑2‑Ethyl maleimidopropionate‑aminomethyl)‑2,4‑dihydroxybenzophenone to polyethylene glycol diacrylate in a molar ratio of 1:1 . The invention discloses a polymeric ultraviolet absorber containing UV-0 side groups. The molecular chain of the polymerized ultraviolet absorber prepared by the present invention contains a reactive double bond and a mercapto group, which can be applied to a polymer material as a reactive ultraviolet absorber; in addition, a hydrophilic group is introduced in the molecular chain, further The scope of application has been expanded.
Description
技术领域technical field
本发明属于高分子助剂类领域，涉及一种含UV-0侧基的聚合型紫外线吸收剂及其制备方法。The invention belongs to the field of polymer additives, and relates to a polymeric ultraviolet absorber containing UV-0 side groups and a preparation method thereof.
背景技术Background technique
随着地球大气中臭氧层空洞化的扩大，使地面紫外线辐射强度不断增大，对人类及其生存环境造成极为不利的影响。高分子材料长期受到紫外光的辐射会发生变色、变脆、性能劣化等加速老化现象，从而使材料失去使用性能。在高分子材料中添加紫外线吸收剂可以明显改善材料的过快老化，从而延长材料的使用寿命。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. Polymer materials exposed to ultraviolet radiation for a long time will undergo accelerated aging phenomena such as discoloration, brittleness, and performance degradation, which will cause the material to lose its usability. Adding ultraviolet absorbers to polymer materials can significantly improve the rapid aging of materials, thereby prolonging the service life of materials.
二苯甲酮类紫外线吸收剂因在200～400nm范围内有较好的紫外光吸收性能，适用于各种浅色制品，被广泛应用于塑料、涂料、黏合剂、橡胶等高分子材料用于防御紫外光老化。但低分子光紫外线吸收剂在高分子材料中应用存在因热分解温度低在加工过程中分解损失以及易于迁移造成喷霜等不足，随着加工方法的不断更新，在加工及应用中存在的不足凸显出来，大分子及高分子紫外线吸收剂研究成为当前的一种发展趋势。Benzophenone UV absorbers have good UV absorption properties in the range of 200-400nm, and are suitable for various light-colored products. They are widely used in polymer materials such as plastics, coatings, adhesives, and rubber. Defense against UV aging. However, the application of low-molecular-weight UV absorbers in polymer materials has deficiencies such as low thermal decomposition temperature, decomposition loss during processing, and easy migration, resulting in blooming. With the continuous updating of processing methods, there are deficiencies in processing and application. Highlighted, macromolecule and macromolecule UV absorber research has become a current development trend.
发明内容Contents of the invention
针对上述技术问题，本发明设计开发了一种含UV-0侧基的聚合型紫外线吸收剂的制备方法。Aiming at the above-mentioned technical problems, the present invention designs and develops a preparation method of a polymeric ultraviolet absorber containing UV-0 side groups.
本发明设计开发了一种含UV-0侧基的聚合型紫外线吸收剂。本发明制备得到的聚合型紫外线吸收剂的分子链中含有可反应的双键与巯基，可以作为可反应型聚合型紫外线吸收剂应该到高分子材料中，另外分子链中同时含有亲水链段与亲油链段，可以应用到两亲性高分子材料、以及乳胶涂料等大部分高分子材料中，进一步扩大了该紫外线吸收剂的应用范围。The present invention designs and develops a polymeric ultraviolet absorber containing UV-0 side groups. The molecular chain of the polymeric ultraviolet absorber prepared by the present invention contains reactive double bonds and mercapto groups, which can be used as a reactive polymeric ultraviolet absorber and should be added to polymer materials. In addition, the molecular chain also contains hydrophilic segments With the lipophilic segment, it can be applied to most polymer materials such as amphiphilic polymer materials and latex coatings, which further expands the application range of the ultraviolet absorber.
本发明提供的技术方案为：The technical scheme provided by the invention is:
一种含UV-0侧基的聚合型紫外线吸收剂的制备方法，包括：A preparation method of a polymeric ultraviolet absorber containing UV-0 side groups, comprising:
利用3-(N,N,-2-巯基丙酸乙酯-胺甲基)-2,4-二羟基二苯甲酮与聚乙二醇二丙烯酸酯作为原料单体发生巯基-烯点击反应，然后加入光敏剂，用365nm紫外光照射反应4-24h，制备得到聚合型紫外线吸收剂，其中，光敏剂的加入量为原料单体总重的0.5-1.5％，3-(N,N,-2-马来酰亚胺基丙酸乙酯-胺甲基)-2,4-二羟基二苯甲酮与聚乙二醇二丙烯酸酯的摩尔比为1∶1。Mercapto-ene click reaction using 3-(N,N,-2-mercaptopropionate-aminomethyl)-2,4-dihydroxybenzophenone and polyethylene glycol diacrylate as raw material monomers , then add a photosensitizer, and react with 365nm ultraviolet light for 4-24h to prepare a polymeric ultraviolet absorber, wherein the photosensitizer is added in an amount of 0.5-1.5% of the total weight of the raw material monomers, 3-(N,N, - The molar ratio of ethyl 2-maleimidopropionate-aminomethyl)-2,4-dihydroxybenzophenone to polyethylene glycol diacrylate is 1:1.
优选的是，所述的含UV-0侧基的聚合型紫外线吸收剂的制备方法中，3-(N,N,-2-巯基丙酸乙酯-胺甲基)-2,4-二羟基二苯甲酮的合成路线包括：Preferably, in the preparation method of the polymeric ultraviolet absorber containing UV-O side groups, 3-(N,N,-2-mercaptopropionic acid ethyl ester-aminomethyl)-2,4-di The synthetic routes of hydroxybenzophenones include:
取3-巯基丙酸、2,4-二羟基-3-(N,N-二乙醇基甲氨基)二苯甲酮溶解于丙酮中，加入DCC室温搅拌24-48h，其中，3-巯基丙酸与2,4-二羟基-3-(N，N-二乙醇基甲氨基)二苯甲酮的摩尔比为2∶1，3-巯基丙酸和DCC的摩尔比为1∶1。Dissolve 3-mercaptopropionic acid and 2,4-dihydroxy-3-(N,N-diethanolylmethylamino)benzophenone in acetone, add DCC and stir at room temperature for 24-48h, wherein, 3-mercaptopropane The molar ratio of acid to 2,4-dihydroxy-3-(N,N-diethanolylmethylamino)benzophenone is 2:1, and the molar ratio of 3-mercaptopropionic acid to DCC is 1:1.
优选的是，所述的含UV-0侧基的聚合型紫外线吸收剂的制备方法中，3-(N,N,-2-羟乙基-胺甲基)-2,4-二羟基二苯甲酮的合成路线包括：Preferably, in the preparation method of the polymeric ultraviolet absorber containing UV-O side groups, 3-(N,N,-2-hydroxyethyl-aminomethyl)-2,4-dihydroxydi The synthetic route of benzophenone includes:
将二乙醇胺加热50-70℃时开始分批次投入多聚甲醛，每15min投入多聚甲醛，分2-6批次投入，加料结束，升温至60-80℃反应1.0-2.5h，然后将UV-0溶于有机溶剂，加入到上述反应液中，于60-80℃继续反应2.5-5h；其中，UV-0与二乙醇胺的摩尔比为1∶1.0-2.0；UV-0与多聚甲醛的摩尔比为1∶1-1.5。When the diethanolamine is heated to 50-70°C, start to add paraformaldehyde in batches, add paraformaldehyde every 15 minutes, and put in 2-6 batches. UV-0 is dissolved in an organic solvent, added to the above reaction solution, and the reaction is continued at 60-80°C for 2.5-5h; wherein, the molar ratio of UV-0 to diethanolamine is 1:1.0-2.0; UV-0 and polymer The molar ratio of formaldehyde is 1:1-1.5.
优选的是，所述的含UV-0侧基的聚合型紫外线吸收剂的制备方法中，所述光敏剂为2-羟基-2-甲基苯丙酮或安息香二甲醚。Preferably, in the preparation method of the polymeric ultraviolet absorber containing UV-0 side groups, the photosensitizer is 2-hydroxy-2-methylpropiophenone or benzoin dimethyl ether.
一种含UV-0侧基的聚合型紫外线吸收剂，其结构式为：A polymeric ultraviolet absorber containing UV-0 side groups, its structural formula is:
n取自然数，m为20-45之间的自然数。n is a natural number, and m is a natural number between 20-45.
本发明所述的含UV-0侧基的聚合型紫外线吸收剂及其制备方法所制备得到的聚合型紫外线吸收剂分子链中含有可反应的双键与巯基，可以作为可反应型聚合型紫外线吸收剂应该到高分子材料中；另外分子链中同时含有亲水链段与亲油链段，可以应用到两亲性高分子材料、以及乳胶涂料等大部分高分子材料中，进一步扩大了该紫外线吸收剂的应用范围。The polymeric ultraviolet absorber containing UV-0 side groups and the preparation method thereof according to the present invention contain reactive double bonds and mercapto groups in the molecular chain of the polymeric ultraviolet absorber, which can be used as a reactive polymeric ultraviolet absorber. Absorbents should be included in polymer materials; in addition, the molecular chain contains both hydrophilic segments and lipophilic segments, which can be applied to most polymer materials such as amphiphilic polymer materials and latex coatings, further expanding the Applications of UV absorbers.
附图说明Description of drawings
图1为实施例1所得聚合型紫外线吸收剂P1的红外谱图。Fig. 1 is the infrared spectrogram of the polymerized ultraviolet absorber P 1 obtained in Example 1.
图2为实施例1所得聚合型紫外线吸收剂P1的紫外吸收谱图。Fig. 2 is the ultraviolet absorption spectrogram of polymeric ultraviolet absorber P 1 obtained in embodiment 1.
具体实施方式Detailed ways
下面结合附图对本发明做进一步的详细说明，以令本领域技术人员参照说明书文字能够据以实施。The present invention will be further described in detail below in conjunction with the accompanying drawings, so that those skilled in the art can implement it with reference to the description.
本发明提供了一种含UV-0侧基的聚合型紫外线吸收剂的制备方法，包括：利用3-(N,N,-2-巯基丙酸乙酯-胺甲基)-2,4-二羟基二苯甲酮与聚乙二醇二丙烯酸酯作为原料单体发生巯基-烯点击反应，然后加入光敏剂，用365nm紫外光照射反应4-24h，制备得到聚合型紫外线吸收剂，其中，光敏剂的加入量为原料单体总重的0.5-1.5％，3-(N,N,-2-马来酰亚胺基丙酸乙酯-胺甲基)-2,4-二羟基二苯甲酮与聚乙二醇二丙烯酸酯的摩尔比为1∶1。The invention provides a preparation method of a polymeric ultraviolet absorber containing UV-O side groups, comprising: using 3-(N,N,-2-mercaptopropionic acid ethyl ester-aminomethyl)-2,4- Dihydroxybenzophenone and polyethylene glycol diacrylate as raw material monomers undergo a mercapto-ene click reaction, then add a photosensitizer, and react with 365nm ultraviolet light for 4-24h to prepare a polymeric ultraviolet absorber, wherein, The amount of photosensitizer added is 0.5-1.5% of the total weight of raw material monomers, 3-(N,N,-2-maleimido ethyl propionate-aminomethyl)-2,4-dihydroxydi The molar ratio of benzophenone to polyethylene glycol diacrylate is 1:1.
优选的是，所述的含UV-0侧基的聚合型紫外线吸收剂的制备方法中，3-(N,N,-2-巯基丙酸乙酯-胺甲基)-2,4-二羟基二苯甲酮的合成路线包括：Preferably, in the preparation method of the polymeric ultraviolet absorber containing UV-O side groups, 3-(N,N,-2-mercaptopropionic acid ethyl ester-aminomethyl)-2,4-di The synthetic routes of hydroxybenzophenones include:
取3-巯基丙酸、2,4-二羟基-3-(N,N-二乙醇基甲氨基)二苯甲酮溶解于丙酮中，加入DCC室温搅拌24-48h，其中，3-巯基丙酸与2,4-二羟基-3-(N,N-二乙醇基甲氨基)二苯甲酮的摩尔比为2∶1，3-巯基丙酸和DCC的摩尔比为1∶1。Dissolve 3-mercaptopropionic acid and 2,4-dihydroxy-3-(N,N-diethanolylmethylamino)benzophenone in acetone, add DCC and stir at room temperature for 24-48h, wherein, 3-mercaptopropane The molar ratio of acid to 2,4-dihydroxy-3-(N,N-diethanolylmethylamino)benzophenone is 2:1, and the molar ratio of 3-mercaptopropionic acid to DCC is 1:1.
优选的是，所述的含UV-0侧基的聚合型紫外线吸收剂的制备方法中，3-(N,N,-2-羟乙基-胺甲基)-2,4-二羟基二苯甲酮的合成路线包括：Preferably, in the preparation method of the polymeric ultraviolet absorber containing UV-O side groups, 3-(N,N,-2-hydroxyethyl-aminomethyl)-2,4-dihydroxydi The synthetic route of benzophenone includes:
将二乙醇胺加热50-70℃时开始分批次投入多聚甲醛，每15min投入多聚甲醛，分2-6批次投入，加料结束，升温至60-80℃反应1.0-2.5h，然后将UV-0溶于有机溶剂，加入到上述反应液中，于60-80℃继续反应2.5-5h；其中，UV-0与二乙醇胺的摩尔比为1∶1.0-2.0；UV-0与多聚甲醛的摩尔比为1∶1-1.5。When the diethanolamine is heated to 50-70°C, start to add paraformaldehyde in batches, add paraformaldehyde every 15 minutes, and put in 2-6 batches. UV-0 is dissolved in an organic solvent, added to the above reaction solution, and the reaction is continued at 60-80°C for 2.5-5h; wherein, the molar ratio of UV-0 to diethanolamine is 1:1.0-2.0; UV-0 and polymer The molar ratio of formaldehyde is 1:1-1.5.
优选的是，所述的含UV-0侧基的聚合型紫外线吸收剂的制备方法中，所述光敏剂为2-羟基-2-甲基苯丙酮或安息香二甲醚。Preferably, in the preparation method of the polymeric ultraviolet absorber containing UV-0 side groups, the photosensitizer is 2-hydroxy-2-methylpropiophenone or benzoin dimethyl ether.
本发明提供了一种含UV-0侧基的聚合型紫外线吸收剂，其结构式为：The invention provides a polymeric ultraviolet absorber containing UV-0 side groups, the structural formula of which is:
n取自然数，m为20-45之间的自然数。n is a natural number, and m is a natural number between 20-45.
实施例1Example 1
(1)3-(N,N,-2-羟乙基-胺甲基)-2,4-二羟基二苯甲酮(HAHBP)的合成(1) Synthesis of 3-(N,N,-2-hydroxyethyl-aminomethyl)-2,4-dihydroxybenzophenone (HAHBP)
UV-0与二乙醇胺的摩尔比为1∶1(mol)；UV-0与多聚甲醛的摩尔比为1∶1(mol)。将2.23g(0.0212mol)二乙醇胺投入150mL的三口烧瓶(二乙醇胺可以过量加入，以促使反应充分进行)，加热50℃时开始分批次投入多聚甲醛粉末，每15min投入0.165g多聚甲醛，分4批次投入，加料结束，升温至60℃保温1.0h，然后将4.54g(0.0212mol)UV-0溶于8mL甲醇，加入到上述反应液中，于60℃保温2.5h。然后将产物用水洗除去过量的二乙醇胺和多聚甲醛，冷冻干燥(真空干燥)，合成路线为：The molar ratio of UV-0 to diethanolamine is 1:1 (mol); the molar ratio of UV-0 to paraformaldehyde is 1:1 (mol). Put 2.23g (0.0212mol) of diethanolamine into a 150mL three-necked flask (diethanolamine can be added in excess to promote the reaction to proceed fully), and when heated to 50°C, start to put in paraformaldehyde powder in batches, and put in 0.165g of paraformaldehyde every 15 minutes , put in 4 batches, after the addition, the temperature was raised to 60°C for 1.0h, and then 4.54g (0.0212mol) of UV-0 was dissolved in 8mL of methanol, added to the above reaction solution, and kept at 60°C for 2.5h. Then the product is washed with water to remove excess diethanolamine and paraformaldehyde, freeze-dried (vacuum-dried), and the synthetic route is:
(2)3-(N,N,-2-巯基丙酸乙酯-胺甲基)-2,4-二羟基二苯甲酮(EMPAHBP)的合成(2) Synthesis of 3-(N,N,-2-mercaptopropionate-aminomethyl)-2,4-dihydroxybenzophenone (EMPAHBP)
在150mL三口瓶中，加入3-巯基丙酸1.25g(0.0118mol)，1.655g 2,4-二羟基-3-(N，N-二乙醇基甲氨基)二苯甲酮(0.005mol)溶解于30mL的丙酮中，加入2.43g DCC(0.0118mol)室温搅拌48h后，过滤除去生成的N，N-二环己基脲(DCU)得到滤液，水浴微热除去丙酮，倒入冰水洗涤3次，冷冻干燥，得到橙黄色晶体。合成路线为：In a 150mL three-neck flask, add 1.25g (0.0118mol) of 3-mercaptopropionic acid and 1.655g of 2,4-dihydroxy-3-(N,N-diethanolylmethylamino)benzophenone (0.005mol) to dissolve In 30 mL of acetone, add 2.43 g of DCC (0.0118 mol) and stir at room temperature for 48 hours, then filter to remove the generated N,N-dicyclohexyl urea (DCU) to obtain the filtrate, remove the acetone by slightly heating in a water bath, pour into ice water and wash 3 times , freeze-dried to obtain orange-yellow crystals. The synthetic route is:
(3)聚合型紫外线吸收剂P1的合成(3) Synthesis of polymeric UV absorber P 1
取0.5g(0.001mol)EMPAHBP，1.0g(0.001mol)聚乙二醇二丙烯酸酯(1000g/mol)，加入到有10ml二氯甲烷溶液的单口瓶中，加入光敏剂2-羟基-2-甲基苯丙酮，为原料单体重量的0.5％，在暗室中用365nm紫外光照射反应24h，去除溶剂，真空干燥，得聚合型紫外线吸收剂PI。合成路线为：Take 0.5g (0.001mol) of EMPAHBP, 1.0g (0.001mol) of polyethylene glycol diacrylate (1000g/mol), add it to a single-necked bottle with 10ml of dichloromethane solution, add photosensitizer 2-hydroxyl-2- Methylpropiophenone is 0.5% of the weight of the raw material monomers, irradiated with 365nm ultraviolet light for 24 hours in a dark room, removed the solvent, and dried in vacuum to obtain the polymeric ultraviolet absorber P I . The synthetic route is:
n取自然数。m为20-45之间的自然数。n is a natural number. m is a natural number between 20-45.
图1给出了该实施例1所制备聚合型紫外线吸收剂P1的红外谱图。Fig. 1 shows the infrared spectrogram of the polymeric ultraviolet absorber P 1 prepared in Example 1.
图2给出了该实施例1所制备聚合型紫外线吸收剂P1的紫外吸收谱图。Figure 2 shows the UV absorption spectrum of the polymeric UV absorber P1 prepared in Example 1.
实施例2Example 2
(1)3-(N,N,-2-羟乙基-胺甲基)-2,4-二羟基二苯甲酮(HAHBP)的合成(1) Synthesis of 3-(N,N,-2-hydroxyethyl-aminomethyl)-2,4-dihydroxybenzophenone (HAHBP)
UV-0∶二乙醇胺＝1∶2.0(mol)：UV-0∶多聚甲醛＝1∶1.5(mol)，UV-0: diethanolamine=1: 2.0 (mol): UV-0: paraformaldehyde=1: 1.5 (mol),
将2.23g(0.0212mol)二乙醇胺投入150mL的三口烧瓶，加热70℃时开始分批次投入多聚甲醛粉末，每15min投入0.2475g多聚甲醛，分4批次投入，加料结束，升温至80℃保温2.5h，然后将2.27g(0.0106mol)UV-0溶于15mL甲醇，加入到上述反应液中，于80℃保温5h。然后将产物用水洗除去过量的二乙醇胺和多聚甲醛，冷冻干燥(真空干燥)。合成路线为：Put 2.23g (0.0212mol) of diethanolamine into a 150mL three-necked flask, and start adding paraformaldehyde powder in batches when heating at 70°C, add 0.2475g of paraformaldehyde every 15min, and put it in 4 batches. Insulate at ℃ for 2.5h, then dissolve 2.27g (0.0106mol) of UV-0 in 15mL of methanol, add to the above reaction solution, and incubate at 80°C for 5h. The product was then washed with water to remove excess diethanolamine and paraformaldehyde, and freeze-dried (vacuum-dried). The synthetic route is:
(2)3-(N,N,-2-巯基丙酸乙酯-胺甲基)-2,4-二羟基二苯甲酮(EMPAHBP)的合成(2) Synthesis of 3-(N,N,-2-mercaptopropionate-aminomethyl)-2,4-dihydroxybenzophenone (EMPAHBP)
在150mL三口瓶中，加入3-巯基丙酸1.25g(0.0118mol，106g/mol)，1.655g 2,4-二羟基-3-(N,N-二乙醇基甲氨基)二苯甲酮(0.005mol，331g/mol)溶解于30mL的丙酮中，加入2.43gDCC(0.0118mol)室温搅拌24h后，过滤除去生成的N，N-二环己基脲(DCU)得到滤液，蒸馏除去丙酮，倒入冰水洗涤3次，冷冻干燥，得到橙黄色晶体。合成路线为：In a 150mL three-necked flask, add 1.25g of 3-mercaptopropionic acid (0.0118mol, 106g/mol), 1.655g of 2,4-dihydroxy-3-(N,N-diethanolylmethylamino)benzophenone ( 0.005mol, 331g/mol) was dissolved in 30mL of acetone, after adding 2.43gDCC (0.0118mol) and stirring at room temperature for 24h, the resulting N,N-dicyclohexylurea (DCU) was removed by filtration to obtain the filtrate, the acetone was removed by distillation, poured into Washed 3 times with ice water and freeze-dried to obtain orange-yellow crystals. The synthetic route is:
(3)聚合型紫外线吸收剂PII的合成(3) Synthesis of polymeric UV absorber P II
取0.5g(0.001mol)EMPAHBP，1.0g(0.001mol)聚乙二醇二丙烯酸酯(1000g/mol)，加入到有10ml二氯甲烷溶液的单口瓶中，加入光敏剂安息香二甲醚，加入量为原料单体重的1.5％，在暗室中用365nm紫外光照射反应4h，去除溶剂，真空干燥，得聚合型紫外线吸收剂PII。合成路线为：Take 0.5g (0.001mol) EMPAHBP, 1.0g (0.001mol) polyethylene glycol diacrylate (1000g/mol), join in the one-necked bottle that has 10ml dichloromethane solution, add photosensitizer benzoin dimethyl ether, add The amount is 1.5% of the weight of the raw material monomers, irradiated with 365nm ultraviolet light for 4 hours in a dark room, removed the solvent, and dried in vacuum to obtain the polymeric ultraviolet absorber P II . The synthetic route is:
n为自然数。m为20-45之间的自然数。n is a natural number. m is a natural number between 20-45.
尽管本发明的实施方案已公开如上，但其并不仅仅限于说明书和实施方式中所列运用，它完全可以被适用于各种适合本发明的领域，对于熟悉本领域的人员而言，可容易地实现另外的修改，因此在不背离权利要求及等同范围所限定的一般概念下，本发明并不限于特定的细节和这里示出与描述的图例。Although the embodiment of the present invention has been disclosed as above, it is not limited to the use listed in the specification and implementation, it can be applied to various fields suitable for the present invention, and it can be easily understood by those skilled in the art Therefore, the invention is not limited to the specific details and examples shown and described herein without departing from the general concept defined by the claims and their equivalents.
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