CN111925462B - Application of water-soluble pillar (calixarene) as photoinitiator - Google Patents
Application of water-soluble pillar (calixarene) as photoinitiator Download PDFInfo
- Publication number
- CN111925462B CN111925462B CN202010916467.6A CN202010916467A CN111925462B CN 111925462 B CN111925462 B CN 111925462B CN 202010916467 A CN202010916467 A CN 202010916467A CN 111925462 B CN111925462 B CN 111925462B
- Authority
- CN
- China
- Prior art keywords
- water
- soluble
- photoinitiator
- calixarene
- column
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical compound COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 title abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 231100000252 nontoxic Toxicity 0.000 claims abstract description 3
- 230000003000 nontoxic effect Effects 0.000 claims abstract description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 150000002016 disaccharides Chemical group 0.000 claims description 2
- -1 heterocyclic aryl Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 2
- 150000002772 monosaccharides Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 230000009965 odorless effect Effects 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000003999 initiator Substances 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
Abstract
The invention relates to the technical field of photoinitiators, and provides application of water-soluble column (calixarene) as a photopolymerization initiator. The water-soluble column (calixarene) has a macrocyclic structure shown in the following figure 1 and is a novel water-soluble photoinitiator. Under the condition of light irradiation, the column (calixarene) cyclic molecules are broken to form the diradical linear oligomer, and the photopolymerization reaction of the monomer can be efficiently initiated. Compared with the traditional commercial photoinitiator, the photoinitiator provided by the invention has good water solubility, is safe and nontoxic, does not need any other auxiliary agent, forms linear chain oligomer after being subjected to light irradiation and fracture, can initiate monomer photopolymerization in a water system, and has low mobility and no odor.
Description
The technical field is as follows:
the invention belongs to the field of photopolymerization and photocuring, and particularly relates to application of water-soluble column (calixarene) as a photoinitiator.
Background art:
photopolymerization has played an important role in the fields of printing inks, coatings, dental treatment, photolithography, laser imaging, and the like, and has received increasing attention. The development and application of the water-soluble photoinitiator have great advantages in the aspects of environmental protection and safety. Water-soluble groups are introduced into the I-type cracking and II-type hydrogen-abstraction radical photoinitiators through chemical modification, and the method is a main means and idea for developing the water-soluble photoinitiators at present. However, the problems of insufficient water solubility, influence of the introduced water-soluble group on the initiation efficiency, poor storage stability of the system and the like still exist. In addition, the inherent toxicity, strong odor, leaching of harmful substances after photolysis and the like of the type I and type II initiators also limit further application thereof.
In response to these problems, the present invention proposes the use of water-soluble pillar (calixarenes) as photoinitiators. The water-soluble column (cup) arene photoinitiator is soluble in water or can be dispersed in a water-soluble monomer, and under the irradiation of light, the column (cup) arene cyclic molecules are broken to form a diradical linear oligomer, so that the photopolymerization reaction of the monomer can be efficiently initiated. Compared with the traditional commercial photoinitiator, the photoinitiator provided by the invention has good solubility in water, is safe and nontoxic, does not need any other auxiliary agent, forms linear oligomer after being subjected to light irradiation fracture, and can initiate monomer photopolymerization in a water system. In addition, the photoinitiation performance of the water-soluble column (calixarene) depends on the magnitude of ring tension, and the modification of water-soluble groups at two ends of the photoinitiation performance does not influence the initiation efficiency of the column (calixarene).
Disclosure of Invention
The invention aims to provide a novel water-soluble column (cup) aromatic photoinitiator, which has water solubility and low mobility so as to meet the increasing requirements of safety, non-toxicity and environmental protection of the photoinitiator.
A water-soluble column (calix) arene photoinitiator is characterized by having a macrocyclic structure formed by methylene bridging benzene units, and modifying water-soluble groups at two ends to make the photoinitiator water-soluble. Has a structure shown in a general formula I:
in formula I: r1, R2 and R3 can be hydrogen, polyethylene glycol with different degrees of polymerization, polyvinyl alcohol or alkyl, aryl, heterocyclic aryl, alkenyl, alkoxy and alkynyl substituted by soluble groups including but not limited to hydroxyl, carboxyl, amino, quaternary ammonium, sulfonic acid group, monosaccharide, disaccharide and the like. Wherein n = 2-10. And the bond points with the aromatic ring.
Under the condition of light irradiation, the cyclic molecules of the water-soluble column (calixarene) are broken to form the diradical linear oligomer, and the photopolymerization reaction of the monomer can be efficiently initiated.
The water-soluble column (calixarenes) to which the present invention relates are synthesized according to published literature: guocan Yu, Min Xue, Zibin Zhang, Jinying Li, Chengyou Han, and Feihe Huang, A Water-Soluble pilar [6]]arene: Synthesis, Host−Guest Chemistry, and Its Application in Dispersion of Multiwalled Carbon Nanotubes in Water. J. Am. Chem. Soc. 2012, 134, 13248−13251
Yingjie Ma, Jie Yang, Jinying Li, Xiaodong Chi and Min Xue, A cationic water-soluble pillar[6]arene: synthesis, host–guest properties, and self-assembly with amphiphilic guests in water. RSC Adv., 2013, 3, 23953-23956.
The following examples are provided to illustrate the embodiments of the present invention in detail. They are not to be construed as limiting the scope of the invention.
Description of the drawings:
FIG. 1 shows the general chemical structure of water-soluble pillar (calixarene).
FIG. 2 is a schematic diagram of column [6] arene (P6COONa) with carboxyl groups at two ends as a photoinitiator and chemical structural formulas of different monomers.
Example 1
Preferably, as shown in FIG. 2, we select a column [6] with carboxyl groups at both ends]Aromatic hydrocarbon (P6COONa) is used as a water-soluble column aromatic hydrocarbon initiator, HEA with one double bond and PEGDA with two double bonds are selected as polymerization monomers. Weighing 10 mg of P6COONa, respectively dissolving in 1 g of HEA and PEGDA monomers, and preparing an initiator-monomer mixed system with the mass fraction of 1%. Then at 20 mW/cm 2 The photopolymerization kinetic curve is measured by real-time infrared under the irradiation of mercury lamp.
The experimental result shows that the double bonds of the two monomers of HEA and PEGDA are rapidly converted under the irradiation of light by P6OC2H5, and the final conversion rate reaches more than 90%. The P6COONa is used as a water-soluble photoinitiator and can efficiently initiate the photopolymerization of two monomers, namely HEA and PEGDA.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (2)
1. The application of the water-soluble column aromatic hydrocarbon photoinitiator in the field of photopolymerization is characterized in that the water-soluble column aromatic hydrocarbon has a macrocyclic structure formed by methylene bridging benzene units, is water-soluble and has a structure shown in a general formula I:
general formula I
In formula I: r 1 ，R 2 ，R 3 The aromatic ring is hydrogen, polyethylene glycol with different polymer degrees, polyvinyl alcohol or alkyl, aryl, heterocyclic aryl, alkenyl, alkoxy and alkynyl substituted by hydroxyl, carboxyl, amino, quaternary ammonium, sulfonic acid group, monosaccharide and disaccharide soluble group, wherein n =2-10, and is a bonding point with an aromatic ring.
2. The use of claim 1, wherein the water-soluble aromatic photoinitiator is soluble in water or is dispersible in a water-soluble monomer, initiates photopolymerization of the monomer upon irradiation with light, and is safe, non-toxic, low in mobility and odorless.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010916467.6A CN111925462B (en) | 2020-09-03 | 2020-09-03 | Application of water-soluble pillar (calixarene) as photoinitiator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010916467.6A CN111925462B (en) | 2020-09-03 | 2020-09-03 | Application of water-soluble pillar (calixarene) as photoinitiator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111925462A CN111925462A (en) | 2020-11-13 |
| CN111925462B true CN111925462B (en) | 2022-09-20 |
Family
ID=73309153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010916467.6A Active CN111925462B (en) | 2020-09-03 | 2020-09-03 | Application of water-soluble pillar (calixarene) as photoinitiator |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111925462B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112457174B (en) * | 2020-11-24 | 2023-11-14 | 北京化工大学常州先进材料研究院 | Prismatic aromatic hydrocarbon initiator and preparation method thereof |
| CN112409510A (en) * | 2020-11-24 | 2021-02-26 | 北京化工大学常州先进材料研究院 | Anthracene nucleus column aromatic hydrocarbon initiator and preparation method thereof |
| CN113004170B (en) * | 2021-03-05 | 2023-06-02 | 天津孚信阳光科技有限公司 | Covalent macrocyclic polymer based on column [5] arene and preparation and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337865A (en) * | 2008-08-11 | 2009-01-07 | 同济大学 | Method for preparing hydroxyl-containing calix[4]arene derivates |
| CN103435603A (en) * | 2013-08-22 | 2013-12-11 | 贵州大学 | Coumarin-oxacalix[3]arene fluorescent reagents as well as preparation method and application thereof |
| CN104447363A (en) * | 2014-11-11 | 2015-03-25 | 西北师范大学 | Cationic water-soluble column [5] aromatic hydrocarbon and preparation thereof and application of cationic water-soluble column [5] aromatic hydrocarbon in silver ion detection serving as acceptor |
-
2020
- 2020-09-03 CN CN202010916467.6A patent/CN111925462B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337865A (en) * | 2008-08-11 | 2009-01-07 | 同济大学 | Method for preparing hydroxyl-containing calix[4]arene derivates |
| CN103435603A (en) * | 2013-08-22 | 2013-12-11 | 贵州大学 | Coumarin-oxacalix[3]arene fluorescent reagents as well as preparation method and application thereof |
| CN104447363A (en) * | 2014-11-11 | 2015-03-25 | 西北师范大学 | Cationic water-soluble column [5] aromatic hydrocarbon and preparation thereof and application of cationic water-soluble column [5] aromatic hydrocarbon in silver ion detection serving as acceptor |
Non-Patent Citations (1)
| Title |
|---|
| A Water-Soluble Pillar[6] arene:Synthesis ,Host-Guest Chemistry ,and Its Application in Dispersion of Multiwalled Carbon Nanotubes in Water;Guocan Yu et al.,;《 Journal of the American Chemical Society》;20120815;第134 卷(第32期);第13248-13251页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111925462A (en) | 2020-11-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111925462B (en) | Application of water-soluble pillar (calixarene) as photoinitiator | |
| Wu et al. | Thioxanthone based one-component polymerizable visible light photoinitiator for free radical polymerization | |
| Yaǧci et al. | Mechanistic and kinetic studies on the photoinitiated polymerization of tetrahydrofuran | |
| He et al. | Ketone‐Functionalized Polymer Nano‐Objects Prepared via Photoinitiated Polymerization‐Induced Self‐Assembly (Photo‐PISA) Using a Poly (diacetone acrylamide)‐Based Macro‐RAFT Agent | |
| Temel et al. | Polymeric side chain thioxanthone photoinitiator for free radical polymerization | |
| Shi et al. | Amphiphilic heteroarm star polymer synthesized by RAFT dispersion polymerization in water/ethanol solution | |
| Jiang et al. | A novel amphipathic polymeric thioxanthone photoinitiator | |
| WO2008016956A3 (en) | Methods for manufacturing ary-aryl coupled polymers | |
| Denizligil et al. | Photosensitized cationic polymerization using allyl sulfonium salt | |
| Zhao et al. | Copolymers featuring pentafluorophenyl ester and photolabile amine units: synthesis and application as reactive photopatterns | |
| Gencoglu et al. | A Water Soluble, Low Migration, and Visible Light Photoinitiator by Thioxanthone‐Functionalization of Poly (ethylene glycol)‐Containing Poly (β‐amino ester) | |
| Xin et al. | NIR-sensitized cationic frontal polymerization of vinyl ether and epoxy monomers | |
| Yang et al. | Visible macrophotoinitiators with Si-H: High efficient anti-oxygen inhibition and modified cured polymer materials | |
| Chen et al. | Photoreactivity study of photoinitiated free radical polymerization using Type II photoinitiator containing thioxanthone initiator as a hydrogen acceptor and various amine-type co-initiators as hydrogen donors | |
| Huo et al. | Preparation and photochemical properties of PEG based alpha-hydroxyalkylphenone photoinitiator | |
| Lai et al. | N-Aryl glycines as versatile initiators for various polymerizations | |
| CN112029016B (en) | Application of liposoluble column (calixarene) as photoinitiator | |
| CN111448280A (en) | Photosensitizer and active energy ray-curable composition | |
| Zhou et al. | Synthesis and characterization of organozirconiums with type-II photoinitiator ligands as multifunctional photoinitiators for free radical photopolymerization | |
| Wu et al. | Synthesis and characterization of a novel kind of water-soluble macromolecular photoinitiators and their application for the preparation of water-soluble branched polymers | |
| Sato et al. | Photocuring of Radically Polymerizable Hyperbranched Polymers Having Degradable Linkages | |
| Kayaman et al. | Photosensitized free radical polymerization using pyridinium salts | |
| Lu et al. | Application of new photolabile protecting groups as photocleavable joints of block copolymers | |
| Yusubov et al. | HYPERVALENT IODINE COMPOUNDS AS POLYMERIZATION INITIATORS | |
| Avci et al. | Monomeric and polymeric Photoinitiators |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |