CN113234185A - Method for preparing cyclic polymer by [3+2] cyclization reaction by using allyl monomer, polymer prepared by method and application of polymer - Google Patents
Method for preparing cyclic polymer by [3+2] cyclization reaction by using allyl monomer, polymer prepared by method and application of polymer Download PDFInfo
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- CN113234185A CN113234185A CN202110383670.6A CN202110383670A CN113234185A CN 113234185 A CN113234185 A CN 113234185A CN 202110383670 A CN202110383670 A CN 202110383670A CN 113234185 A CN113234185 A CN 113234185A
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- polymer
- photoinitiator
- reaction
- monomer
- allyl
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- 239000000178 monomer Substances 0.000 title claims abstract description 73
- 238000007363 ring formation reaction Methods 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 45
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 title claims abstract description 44
- 229920005565 cyclic polymer Polymers 0.000 title claims description 42
- 229920000642 polymer Polymers 0.000 title abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- 150000003254 radicals Chemical class 0.000 claims abstract description 43
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- 239000001257 hydrogen Substances 0.000 claims description 34
- 230000008569 process Effects 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- 238000000605 extraction Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- -1 benzoyl formic acid diethyl diester Chemical class 0.000 claims description 9
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical group C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 8
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 6
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- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 5
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- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 4
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 claims description 4
- 244000028419 Styrax benzoin Species 0.000 claims description 4
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
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- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 claims description 2
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 claims description 2
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- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 claims description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 claims description 2
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- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 claims description 2
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 2
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- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
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- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 claims description 2
- SPEXCGKGVJUPGG-UHFFFAOYSA-N phenyl-(2-sulfanylphenyl)methanone Chemical compound SC1=CC=CC=C1C(=O)C1=CC=CC=C1 SPEXCGKGVJUPGG-UHFFFAOYSA-N 0.000 claims description 2
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 claims description 2
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Classifications
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- 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
- C08F116/00—Homopolymers 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F116/12—Homopolymers 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F116/14—Monomers containing only one unsaturated aliphatic radical
- C08F116/16—Monomers containing no hetero atoms other than the ether oxygen
- C08F116/18—Acyclic compounds
- C08F116/20—Monomers containing three or more carbon atoms in the unsaturated aliphatic radical
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/001—Use of materials characterised by their function or physical properties
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
- A61L24/06—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- 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
Abstract
The invention discloses a method for preparing polymer by [3+2] cyclization reaction by allyl monomer and the polymer and application, the invention uses allyl monomer and photoinitiator, through [3+2] cyclization reaction, takes part in reaction by free radical or excited state, five-membered ring free radical product is formed by cyclization reaction, polymerization reaction is initiated to obtain polymer, reaction condition is mild at normal temperature, conversion rate of double bond is high, conversion rate of double bond of diallyl monomer can reach 45% or above at 500 seconds, polymer with high molecular weight of ten thousand can be obtained, and the obtained polymer is proved to be all five-membered ring containing carbon atom, the molecular chain of the polymer also contains ring structure, no heteroatom is contained in the ring, the prepared polymer has the characteristics of innocuity, easy obtaining and good biological property, can be applied to transcatheter arterial embolization.
Description
Technical Field
The invention relates to the technical field of photoinduced polymerization, in particular to a method for preparing a cyclic polymer by using an allyl monomer through a [3+2] cyclization reaction, a polymer prepared by the method and application of the polymer.
Background
Among cycloadditions, the synthesis of five-or six-membered ring compounds is the most common, of which the 1,3-dipolar cycloaddition proposed by Huisgen in 1960 is the [3+2] cycloaddition between a 1,3-dipolar body and an alkene, alkyne or corresponding derivative, or referred to as the Huisgen reaction, the product being a five-membered heterocyclic compound. Olefinic compounds are known as dipolar donors in reactions. The German chemist Rolf Huisgen first applied this type of reaction to prepare five-membered heterocyclic compounds, which is an important method for the synthesis of monocyclic and polycyclic compounds (Reisigo, Hans-Ulrich; Breugst, Martin. the Huisgen-reaction-Meiilenstein der 1,3-Dipolar Cycloaddition [ J ]. Angewandte Chemie,2020, 1-35.).
Allyl monomers are a class having H2C＝CH-CH2-important organic compounds of the structural characteristics X-R. Because the molecular structure of the compound has the characteristics of isomerization, unsaturated double bonds and the like, the compound is commonly used as a protective group in organic synthesis, a polymer raw material monomer or a cross-linking agent, and is applied to the fields of photocuring, thermocuring, air-drying coatings, flame-retardant resins and the like. Unlike vinyl monomers, the compounds have very low double bond conversion and only low molecular weight oligomers are formed. For example, chinese patent CN111072823A discloses a polymerized microsphere with a disaccharide based skeleton and a preparation method thereof, the polymerized microsphere with a disaccharide based skeleton prepared by using allyl disaccharide ether and a photoinitiator still cannot overcome the problem that the conversion rate of double bonds is low (not more than 30%) and only oligomers with a molecular weight of hundreds to thousands can be generated.
Disclosure of Invention
The invention aims to solve the technical problems that the conversion rate of double bonds of the existing polymer prepared by using allyl monomers is low, and only oligomers with low molecular weight can be generated, and provides a method for preparing a cyclic polymer by using the allyl monomers through [3+2] cyclization reaction, wherein the conversion rate of the double bonds is high, polymers with high molecular weight (the molecular weight can reach tens of thousands) can be generated, and the reaction can be carried out at normal temperature.
It is still another object of the present invention to provide a polymer prepared by the method of preparing a cyclic polymer through a [3+2] cyclization reaction using an allyl monomer.
Another object of the present invention is to provide the use of a polymer obtained by a process for preparing a cyclic polymer by a [3+2] cyclization reaction using an allyl monomer.
The above purpose of the invention is realized by the following technical scheme:
by passage of an allyl monomer through [3+2]]The method for preparing the cyclic polymer by the cyclization reaction utilizes a photoinitiator and an allyl monomer to carry out [3+2] by photoinitiating free radicals or triplet states under the radiation condition of ultraviolet light or visible light]Cyclizing to obtain a cyclic polymer; the molar ratio of functional groups of the photoinitiator to allyl monomers is 1: 1-4, the photoinitiator is a cracking type and/or hydrogen extraction type photoinitiator, and the allyl monomers are H2C＝CH-CH2-X-R0A monomer; wherein X is O, -NR, S, P, O-C ═ O, or CH2，R0Is H, alkyl-R, cycloalkyl, carbocyclic/heterocyclic aromatic hydrocarbons, -OR, nitro-NO2Dialkylamino group-NR1R2Halogen, alkene/alkyne, ester group/carboxyl COOR, quaternary ammonium salt NRR1R2R3 +Acid anhydride bond-CO-O-CO, carbonyl C ═ O, ether bond-O-, thioether bond-S, disulfide bond-S-S-, peroxy bond-O-O-, epoxy bond
Amide bond CO-NR1R2；R、R1、R2、R3Are independently selected from hydrogen or straight/branched alkanes of different lengths.
Photoinitiated free radical or triplet [3+2] of the invention]The cyclization reaction principle is as follows: the photoinitiator generates free radicals R/triplet state R under the illumination of ultraviolet light or visible light3Then extracting H2C＝CH-CH2C-H of hydrocarbon radicals next to the double bond of the-X-R monomer to form H2C ═ CH-X-R radical, which is in turn reacted with a second H2C＝CH-CH2the-X-R monomer forms a five-membered ring radical which undergoes intramolecular hydrogen transfer and then abstracts H2C＝CH-CH2Hydrogen of-X-R to form H2C-CH-X-R radical,and then with a third H2C＝CH-CH2The monomer-X-R forms a five-membered ring free radical, and the two processes of hydrogen extraction and cyclization are continuously carried out to finally obtain the polymer, wherein the mechanism is also called a free radical mediated cyclization reaction. The chemical formula of the five-membered ring free radical is shown as the following formula (Ia-ic) or formula (IIa-IIc):
preferably, the molar ratio of the photoinitiator to the functional groups of the allyl monomer is 1: 1-3.3.
Preferably, the allyl monomer is H2C＝CH-CH2-O-CH3。
Preferably, the photoinitiator is benzoin, benzoin dimethyl ether (commonly known as 651), benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-hydroxy-2-methyl-1-phenyl-1-propanone (commonly known as HMPP or 1173), alpha '-ethoxyacetophenone (commonly known as DEAP), 1-hydroxycyclohexyl phenyl ketone (commonly known as 184), 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone (commonly known as 2959), 1' - (methylenebis-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-propanone ] (commonly known as 127), methyl benzoylformate (commonly known as MBF), Diethylene glycol benzoylformate (commonly known as 754), tert-butyl peroxybenzoate, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide (commonly known as BAPO), 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide (commonly known as TPO), ethyl 2, 4, 6-trimethylbenzoylphenylphosphonate (commonly known as TPO-L), 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone (commonly known as 907), 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinylbenzyl-phenyl) butanone (commonly known as 369), methyl benzoylbenzoate, 1- [4- (4-phenylthio) -phenyl ] -octan-1, 2-dione-2-oxime-O-benzoate (commonly known as OXE-1), (1- [3'- (6' -O-toluoyl-N-ethylcarbazole) ] -1-ethanone oxime-O-acetate) (commonly known as OXE-2), coumarin, benzophenone, 4-phenylbenzophenone and thioxanthone (commonly known as TX), 2-isopropylthioxanthone (commonly known as ITX), 2-chlorothianthrone (commonly known as CTX), camphorquinone (commonly known as CQ); 4-p-toluene mercapto benzophenone (commonly known as a photoinitiator 4-BMS), benzoyl formic acid diethyl diester (commonly known as a photoinitiator 754), and bis 2, 6-difluoro-3-pyrrole phenyl cyclopentadienyl titanium (commonly known as a photoinitiator 784).
Preferably, the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-propanone (commonly known as HMPP or 1173) or 2-isopropylthioxanthone (commonly known as ITX). 1173 the photoinitiator is a typical commercial cleavage type photoinitiator, the ITX photoinitiator is a typical commercial hydrogen abstraction type photoinitiator, and the raw materials are readily available and inexpensive.
Preferably, the reaction is carried out in water or a non-aqueous system.
Preferably, the allyl monomer and the photoinitiator are dissolved in water, stirred, and irradiated by an ultraviolet lamp in the air at room temperature for [3+2] cyclization reaction for 15min to obtain the cyclic polymer.
More preferably, the allyl monomer and 1173 or ITX photoinitiator, are completely dissolved in distilled water, placed in a single-neck flask equipped with mechanical stirring, and reacted at room temperature with uv lamp irradiation in air for 15min to obtain the cyclic polymer.
Preferably, the irradiation conditions are medium pressure mercury lamps or LED lamps.
Preferably, the allyl monomer is monofunctional, difunctional or polyfunctional.
The invention also protects the cyclic polymer prepared by the method.
The invention also protects the application of the polymer in transcatheter arterial embolization.
Compared with the prior art, the invention has the beneficial effects that:
the invention uses photoinitiator to generate free radical or excited state under illumination, then forms five-membered ring free radical product through [3+2] cyclization reaction with allyl monomer, and initiates polymerization reaction continuously to obtain cyclic polymer, the reaction is at normal temperature, the reaction condition is mild, the double bond conversion rate is high, the double bond conversion rate of diallyl monomer can reach 45% or above in 500 seconds, and high molecular weight cyclic polymer reaching tens of thousands of molecular weight can be obtained, and the obtained cyclic polymer is proved to contain five-membered ring structure in the molecular chain of the polymer, all carbon atoms in the ring and no hetero atoms, the prepared cyclic polymer has the characteristics of no antigenicity, easy injection from catheter and no X-ray transmission, and can be applied to catheter arterial embolization.
Drawings
FIG. 1 is a graph showing the cleavage energy of allyl methyl ether in example 1.
FIG. 2 is a diagram of the mechanism of hydrogen abstraction between allyl methyl ether and 1173 photoinitiator in example 1.
FIG. 3 is a diagram showing the mechanism of the cyclization reaction of allyl methyl ether molecules with allyl radicals in example 1.
FIG. 4 is a diagram of the mechanism of hydrogen re-extraction of the allyl molecule by the free radical extraction of cyclopentane in example 1.
FIG. 5 is a scanning electron micrograph of polymerized microspheres prepared from the photoinitiator ITX and diallyl monomer of example 2.
FIG. 6 is a graph of the results of real-time infrared measurements of the diallyl monomers of example 2 with the photoinitiators ITX (panel a), DETX (panel b), BP (panel c) and CQ (panel d).
FIG. 7 is a diagram showing the mechanism of hydrogen abstraction between allyl methyl ether and the photoinitiator ITX in example 2.
FIG. 8 is a graph showing the results of optical microscopic examination of allyl methyl ether and a photoinitiator TPO in example 6.
FIG. 9 shows that the light-induced generation of free radicals or excited state mediated allyl monomers undergo a [3+2] cyclization reaction to form cyclic polymers.
FIG. 10 is a schematic molecular structure of a polymeric microsphere.
Fig. 11 is a DSA map of the left kidney of cyclic polymers (polymeric microspheres).
Figure 12 is a comparison of animal dissected kidneys 7 days after embolization of PVA and cyclic polymers (polymeric microspheres).
FIG. 13 is a graph comparing the testing of PVA and cyclic polymers (polymeric microspheres) for HUVEC cytotoxicity.
FIG. 14 is a COSY spectrum of a cyclization reaction of a diallyl monomer with a photoinitiator 1173.
Fig. 15 is a graph showing the results of real-time infrared detection of diallyl monomer and photoinitiator 1173.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
Example 1
By using allyl monomer through [3+2]]A process for preparing cyclic polymer by cyclization reaction features that 1mol of 1173 is used as photoinitiator and 3.3mol of H2C＝CH-CH2-O-CH3As monomer, 1g H was mixed with distilled water2C＝CH-CH2-O-CH30.1g of 1173 photoinitiator is completely dissolved in a single-mouth bottle with mechanical stirring, and the mixture is irradiated by an ultraviolet lamp in the air at normal temperature for reaction for 15min to prepare a cyclic polymer, wherein the name of the cyclic polymer is as follows: poly 1- (2- (allyloxy) ethoxy) -2- ((2- (allyloxy) ethoxy) methyl) cyclopentane or poly 1- (2- (allyloxy) ethoxy) -3- ((2- (allyloxy) ethoxy) methyl) cyclopentane.
The reaction process is as follows: 1173 the photoinitiator generates benzoyl radical under illumination, and the benzoyl radical extracts H2C＝CH-CH2-O-CH3C-H of hydrocarbon radicals next to double bonds, then H2C＝CH-CH·-O-CH3Free radicals, which are in turn reacted with H2C＝CH-CH2-O-CH3Forming five-membered ring free radical, which generates intramolecular hydrogen transfer to capture H2C＝CH-CH2-O-CH3Hydrogen of (2) to form H2C＝CH-CH·-O-CH3Free radicals, then with H2C＝CH-CH2-O-CH3Forming five-membered ring free radical, continuously carrying out hydrogen extraction-cyclization processes to continuously alternate, and finally obtaining the polymer.
All data of reaction path design are calculated by Gussian 16 based on DFT, coordinates of reactants and products are input into Gaussian, the reactants and the products in gas phase are optimized by using M06-2X functional and 6-311+ + G (d, p) base group to obtain the optimal conformation, the structure of the transition state of the reaction is guessed, and the coordinates of the transition state are input into Gaussian for optimization. And extracting the energy of each state of the optimized compound, and measuring each parameter of the transition state structure.
FIG. 1 shows the dissociation bond energy of allyl methyl ether at four hydrogen atoms in environment, and C-H of terminal carbon of allyl methyl ether is broken to generate CH ═ CH-CH2-O-CH3Has a bond energy of 109.97kcal/mol, and cleaves C-H of the second carbon atom of the carbon-carbon double bond of allyl methyl to form CH2＝C·CH2OCH3Has a bond energy of 107.78 kcal/mol, and the C-H bond energy of both environments is larger, which indicates that the hydrogen atom on the carbon-carbon double bond is not easy to leave. Cleavage of the C-H bond on the methyl group of allyl methyl ether to give CH2＝CH-CH2-OCH2The energy of this environment is 95.58 kcal/mol, and hydrogen atoms of this environment do not easily leave. Breaking the C-H bond on the methylene group connecting the allylic methyl ether to the carbon-carbon double bond to produce H2C＝CH-CH·-O-CH3Of the four environments of hydrogen atoms, the energy required to break the C-H bond is the smallest and the hydrogen atom leaves the easiest. Thus, the position of the hydrogen abstraction reaction of the active radical with allyl methyl ether is the hydrogen atom on the methylene group attached to the double bond. FIG. 2 is a hydrogen abstraction mechanism of allyl methyl ether and photoinitiator 1173 of example 1, Δ G is-12.22 kcal/mol, hydrogen atom transfer reaction (HAT) is a spontaneous reaction, the driving force of the reaction is greater, and the HAT reaction has greater reaction tendency and equilibrium constant. FIG. 3 is a reaction mechanism of cyclization of allyl methyl ether molecule with allyl radical, which is formed by terminal ═ CH in monomer2E of TS1 in which the carbon atom and-CH. near the radical form a first single bond, both Path 1 and Path 2aAnd intermediate Δ G, the second single bond being formed by ═ CH in the radical2E of two paths, Path 1 and Path 2, of TS2 formed by the upper carbon atom and one terminal ═ CH carbon atom in the monomeraAnd the product deltaG are close, so that ortho-or meta-compounds can be generated. The two paths of Path 3 and Path 4 are the reverse reactions of the two paths of Path 1 and Path 2, and TS1 and E of TS2 of Path 3 and Path 4aAnd Δ G and PatThe values of h 1 and Path 2 are matched, which shows that the invention proposes [3+2]]The cyclization reaction mechanism is feasible and rational. FIG. 4 is a re-hydrogen abstraction mechanism for the abstraction of an allyl molecule by a cyclopentane radical, E for the two cyclopentane radical hydrogen abstraction reactionaSimilar to the value of deltaG, the driving force is respectively-16.48 kcal/mol and-12.74 kcal/mol, the reaction driving force is larger, which indicates that four cyclopentane radicals have larger reaction tendency and equilibrium constant for hydrogen extraction reaction, and are all negative values, which indicates that HAT is spontaneous reaction.
FIG. 14 shows a COSY spectrum, wherein the chemical shift of the characteristic peak of the ring structure is about 1-2 ppm. The polymer was confirmed to have a cyclic structure.
Example 2
By using allyl monomer through [3+2]]Method for preparing cyclic polymers by cyclization reaction, using ITX as photoinitiator, H2C＝CH-CH2-O-CH3As monomer, distilled water was added with 3.3mol of H2C＝CH-CH2-O-CH31mol of ITX is completely dissolved in a single-mouth bottle with mechanical stirring, and the mixture is irradiated by an ultraviolet lamp in the air at normal temperature for reaction for 15min to prepare a cyclic polymer (PSAE polymeric microspheres), which is named as: poly 1- (2- (allyloxy) ethoxy) -2- ((2- (allyloxy) ethoxy) methyl) cyclopentane or poly 1- (2- (allyloxy) ethoxy) -3- ((2- (allyloxy) ethoxy) methyl) cyclopentane.
The process of the reaction is as follows: the photoinitiator ITX generates triplet species under irradiation with light, which extract H2C＝CH-CH2-O-CH3Hydrogen on methylene next to double bond, then H2C＝CH-CH·-O-CH3Allyl radical which is further reacted with H2C＝CH-CH2-O-CH3Forming five-membered ring free radical, which generates intramolecular hydrogen transfer and then captures a third H2C＝CH-CH2-O-CH3Hydrogen on the side methylene to form a second H2C＝CH-CH·-O-CH3And (3) continuously alternating the two processes of hydrogen extraction and cyclization by using the free radicals, and finally obtaining the polymer.
FIG. 5 is a field emission scanning electron microscope image of a cyclic polymer (polymeric microsphere) prepared from ITX and a diallyl monomer, and the prepared solid microsphere has a smooth surface and uniform dispersibility.
FIG. 6 is a graph of real-time infrared data showing that the conversion of diallyl monomer is approximated by the double bond conversion, the molar ratios of diallyl monomer (SAE) to ITX, DETX, BP, and CQ are 10: 1, 5: 1,3.3: 1,2.5: 1. it is found that when the ratio of the diallyl monomer (SAE) to ITX, DETX, BP and CQ is 3.3:1, the diallyl monomer shows higher conversion rate, the double bond conversion rate reaches more than 70% in 500 seconds, the double bond conversion rate is high, and the product has large molecular weight.
FIG. 7 shows the mechanism of hydrogen abstraction between allyl methyl ether and the photoinitiator ITX in example 2, Δ G is-24.27 kcal/mol, HAT is a spontaneous reaction, the driving force of the reaction is greater, and the HAT reaction has a greater tendency to react and equilibrium constant.
FIG. 9 shows the process of photo-induced generation of free radicals or excited states mediating the [3+2] cyclization reaction of allyl monomers and double bonds to form cyclized polymers.
Example 3
By using allyl monomer through [3+2]]Method for preparing cyclic polymer by cyclization reaction, using 1mol of BP as photoinitiator and 3.3mol of H2C＝CH-CH2-O-CH3As monomer, 1g H was mixed with distilled water2C＝CH-CH2-O-CH30.1g of BP, completely dissolved in a single-neck bottle with mechanical stirring, and irradiated by an ultraviolet lamp in the air at normal temperature for reaction for 15min to prepare a cyclic polymer, wherein the name is as follows: poly 1- (2- (allyloxy) ethoxy) -2- ((2- (allyloxy) ethoxy) methyl) cyclopentane or poly 1- (2- (allyloxy) ethoxy) -3- ((2- (allyloxy) ethoxy) methyl) cyclopentane.
The process of the reaction is as follows: the photoinitiator benzophenone generates triplet state substance under illumination, and the triplet state substance extracts H2C＝CH-CH2-O-CH3Hydrogen on methylene next to double bond, then H2C＝CH-CH·-O-CH3Allyl radical which is further reacted with H2C＝CH-CH2-O-CH3Forming five-membered ring free radical, which generates intramolecular hydrogen transfer and then captures a third H2C＝CH-CH2-O-CH3Hydrogen on the side methylene to form a second H2C＝CH-CH·-O-CH3A free radical. Thus, the two processes of hydrogen extraction and cyclization are continuously alternated, and finally the polymer is obtained.
Example 4
By using allyl monomer through [3+2]]Method for preparing polymer by cyclization reaction, 1mol of 184 is taken as photoinitiator, and 3.3mol of H2C＝CH-CH2-O-CH3As monomer, 1g H was mixed with distilled water2C＝CH-CH2-O-CH30.1g 184, dissolved completely in a single-neck flask equipped with mechanical stirring, and reacted under irradiation with an ultraviolet lamp in air at room temperature. The reaction lasts for 15min, and a cyclic polymer is prepared, and is named as: poly 1- (2- (allyloxy) ethoxy) -2- ((2- (allyloxy) ethoxy) methyl) cyclopentane or poly 1- (2- (allyloxy) ethoxy) -3- ((2- (allyloxy) ethoxy) methyl) cyclopentane.
The process of the reaction is as follows: the photoinitiator 184 generates benzoyl radicals under light irradiation, which extract H2C＝CH-CH2-O-CH3Hydrogen on methylene next to double bond, then H2C＝CH-CH·-O-CH3Allyl radical which is further reacted with H2C＝CH-CH2-O-CH3Forming five-membered ring free radical, which generates intramolecular hydrogen transfer and then captures a third H2C＝CH-CH2-O-CH3Hydrogen on the side methylene to form a second H2C＝CH-CH·-O-CH3A free radical. Thus, the two processes of hydrogen extraction and cyclization are continuously alternated, and finally the polymer is obtained.
Example 5
By using allyl monomer through [3+2]]Method for preparing cyclic polymer by cyclization reaction, using 1mol CQ as photoinitiator and 3.3mol H2C＝CH-CH2-O-CH3As monomer, 1g H was mixed with distilled water2C＝CH-CH2-O-CH30.1g CQ, completely dissolved in a single-neck flask equipped with mechanical stirring, was reacted in air under irradiation with an ultraviolet lamp at room temperature. The reaction lasts for 15min, and a cyclic polymer is prepared, and is named as: poly 1- (2- (allyloxy) ethoxy) -2- ((2- (allyloxy) ethoxy) methyl) cyclopentane or poly 1- (2- (allyloxy) ethoxy) -3- ((2- (allyloxy) ethoxy) methyl) cyclopentane.
The process of the reaction is as follows: the photoinitiator CQ generates triplet substances under illumination, which extract H2C＝CH-CH2-O-CH3Hydrogen on methylene next to double bond, then H2C＝CH-CH·-O-CH3Allyl radical which is further reacted with H2C＝CH-CH2-O-CH3Forming five-membered ring free radical, which generates intramolecular hydrogen transfer and then captures a third H2C＝CH-CH2-O-CH3Hydrogen on the side methylene to form a second H2C＝CH-CH·-O-CH3A free radical. Thus, the two processes of hydrogen extraction and cyclization are continuously alternated, and finally the cyclic polymer is obtained.
Example 6
By using allyl monomer through [3+2]]Method for preparing cyclic polymer by cyclization reaction, using 1mol TPO as photoinitiator, 3.3mol H2C＝CH-CH2-O-CH3As monomer, 1g H was mixed with distilled water2C＝CH-CH2-O-CH30.1g TPO, dissolved completely in a single-neck flask equipped with mechanical stirring, was reacted in air under irradiation with an ultraviolet lamp at room temperature. The reaction was continued for 15min to produce a cyclic polymer (polymeric microspheres) named: poly 1- (2- (allyloxy) ethoxy) -2- ((2- (allyloxy) ethoxy) methyl) cyclopentane or poly 1- (2- (allyloxy) ethoxy) -3- ((2- (allyloxy) ethoxy) methyl) cyclopentane.
The process of the reaction is as follows: the photoinitiator TPO generates a phosphorus-containing radical under irradiation with light, and the radical extracts H2C＝CH-CH2-O-CH3Hydrogen on methylene next to double bond, then H2C＝CH-CH·-O-CH3Allyl radical, the allyl radical being freeRadical re-and H2C＝CH-CH2-O-CH3Forming five-membered ring free radical, generating intramolecular hydrogen transfer, and capturing third H2C＝CH-CH2-O-CH3Hydrogen on the side methylene to form a second H2C＝CH-CH·-O-CH3And continuously alternating two processes of hydrogen extraction and cyclization by using the free radical to finally obtain the cyclic polymer. As can be seen from FIG. 8, the polymerized microspheres are spherical in shape, relatively smooth in surface, and good in particle dispersibility.
Comparative example 1
Preparation of commercial polyvinyl alcohol microspheres (PVA microspheres):
dissolving 0.16g of dispersant span-60 in 20mL of liquid paraffin under stirring to form a continuous phase (oil phase), and adding the continuous phase into a four-mouth bottle provided with a stirrer and a condenser tube; forming a dispersed phase aqueous phase by 8mL of 5% PVA solution and 1mL of 50% glutaraldehyde solution, and adding 1mol.L of 1mL of catalyst-1Adding hydrochloric acid to the aqueous phase; and adding the water phase into the oil phase, stirring to fully disperse the water phase, raising the temperature of the system to 65 ℃, carrying out polymerization, reacting for 6 hours, adding hot distilled water at the temperature of 65-70 ℃, and reacting for 1 hour to obtain the semitransparent crosslinking microspheres.
Comparative example 1 is a conventional polymer preparation method, in which polyvinyl alcohol (PVA) is subjected to an acetal exchange reaction in an acidic medium to prepare polyvinyl alcohol microspheres, which are commonly used in transcatheter arterial embolization.
As can be seen from the comparison of examples 1-6 with the method of preparing the polymer of comparative example 1, the method of the present invention has the following advantages: 1. high efficiency: comparative example 1 the reaction time was as long as 6 hours, [3+ 2%]The cyclization reaction can realize complete reaction within 15 minutes, the conversion rate of double bonds is high, the production efficiency is higher, the molecular weight of the product can reach tens of thousands, and the molecular weight is large; 2. energy conservation: comparative example 1 the reaction temperature was as high as 65 deg.C, and the reaction apparatus was required to be heated, [3+2]]The product of the cyclization reaction is a normal-temperature rapid reaction, a heating device is not needed, and the energy consumption is only 1/10-1/5 of thermal reaction generally; 3. and (3) environmental protection: [3+2]The material generated by the cyclization reaction contains no or only a small amount of organic solvent, and simultaneously [3+2]]Energy for cyclization reactionThe source is electric energy, and no fuel oil or gas or CO2Hydrochloric acid is used in the reaction process of the comparative example 1, so that the environment is polluted; 4. economy: [3+2]The device for cyclization reaction is compact and has high processing speed, thereby saving the field space, having high labor productivity and being beneficial to reducing the economic cost. Description of [3+2] above]The cyclization reaction is a new technology in green industry.
Comparative example 2
This comparative example utilizes the passage of an allyl monomer through [3+2]]The method for producing a cyclic polymer by cyclization was the same as in example 1 except that 1mol of 1173 was used as a photoinitiator and 0.5mol of H was used2C＝CH-CH2-O-CH3Is a monomer. The product obtained was a liquid, indicating that the product had a low molecular weight and could not form a solid.
Comparative example 3
This comparative example utilizes the passage of an allyl monomer through [3+2]]The method for producing a cyclic polymer by cyclization was the same as in example 1 except that 1mol of 1173 was used as a photoinitiator and 5mol of H was used2C＝CH-CH2-O-CH3Being a monomer, the resulting product was a liquid, indicating that the product was of low molecular weight and could not form a solid.
The conversion rate of the diallyl monomer is approximately simulated by the conversion rate of the double bonds, fig. 15 shows real-time infrared data of the diallyl monomer and the 1173 photoinitiator, and the molar ratio of the diallyl monomer to the 1173 photoinitiator is 10: 1,5: 1,3.3: 1,2.5: 1, wherein the double bond conversion rate of the diallyl monomer can reach about 45% in 500 seconds.
In addition, from the above results, it is understood that when the molar ratio of the photoinitiator to the allyl monomer functional group is not in the range of 1:1 to 4, the reaction product is an oligomer in a liquid state, and a scanning electron microscope cannot be detected in the liquid state, and when the molar ratio of the photoinitiator to the allyl monomer functional group is in the range of 1:1 to 4, a solid polymer with a large molecular weight is generated, which also indicates that the double bond conversion rate is high and the product has a large molecular weight.
Animal experiments
1. Water is forbidden for 12 hours before the experimental animals are subjected to catheter intravascular embolization, and 2% sodium pentobarbital (30mg/kg) is anesthetized by marginal intravenous injection (the rabbits are fixed on a fixer).
2. Fixing the anesthesia in supine position, shearing hairs and preparing skin on an experimental plate, and sterilizing by a conventional method.
3. The operation process comprises the following steps: laying a sterile surgical towel, cutting the skin, peeling fascia layer by layer, separating muscle fibers, exposing femoral artery, ligating free femoral artery with sterile surgical thread at the far end, lifting the near end with surgical silk thread, puncturing the front wall of the femoral artery by using a blood vessel puncture cannula, and pushing the puncture needle outer cannula into the femoral artery after success. And (3) loosening the proximal end of the femoral artery for lifting the surgical silk thread for hemostasis, sending in 0.035inch short exchange silk after blood spraying, withdrawing the puncture needle outer sleeve, placing a 5F vascular sheath along the exchange silk thread, and locally binding and fixing by tying the surgical silk thread. Injecting 5-10 ml of the mixture through a 5F super-smooth catheter. The iohexol contrast agent is used for abdominal cavity artery radiography and DSA film taking, the branch running of the renal artery is determined, a coaxial catheter technology is applied, a 1.2F micro-catheter is inserted into the renal artery, the tail end of the micro-catheter is positioned at the starting position of the left branch, a polymeric microsphere preparation prepared from ITX and diallyl monomers is suspended and shaken uniformly by a normal saline sterilization injection, and then the mixture is slowly injected into the renal artery branch through the catheter. Injecting iohexol for radiography 30min after embolization, and observing early embolization effect, and determining whether embolization agent is added according to degree of development. After the embolism is finished, the catheter, the microcatheter and the arterial sheath are removed, the proximal surgical thread of the femoral artery is ligated, the skin is sutured conventionally, the incision part is disinfected again, and 4 ten thousand units of penicillin is injected into the muscle to prevent infection. After the experiment is finished, the animals are returned to the animal room for 6 hours after being resuscitated at room temperature.
4. The body temperature of the rabbit after operation is cold, the rabbit keeps warm and waits for resuscitation, and antibiotics must be applied daily in the first three days.
FIG. 10 is a molecular structure diagram of a cyclic polymer having a structure consisting of n (n.gtoreq.1) five-membered rings, wherein R1Can be O, -NR, S, P, O-C ═ O or CH2，R2Is H, alkyl-R, cycloalkyl, carbocyclic/heterocyclic aromatic hydrocarbons, -OR, nitro-NO2Dialkylamino group-NR1R2Halogen, alkene/alkyne, ester group/carboxyl COOR, quaternary ammonium salt NRR1R2R3 +Acid anhydride bond-CO-O-CO, carbonyl C ═ O, ether bond-O-, thioether bond-S, disulfide bond-S-S-, peroxy bond-O-O-, epoxy bond
Amide bond CO-NR1R2。
The DSA image of rabbit left kidney of polymeric microspheres prepared from ITX and diallyl monomers can be seen from FIG. 11 that the polymer develops well and can successfully embolize renal arteries, indicating that the polymeric microspheres have no antigenicity, are easily injected through a catheter and do not transmit X-rays.
FIG. 12 is a diagram of animal anatomical kidney of rabbit after 7 days of embolization of left kidney by using polyvinyl alcohol microsphere of comparative example 1 and PSAE polymeric microsphere prepared in example 2, wherein the polymer is injected into renal artery to cause thrombosis, thus leading to renal artery occlusion and renal infarction, and the infarction area of kidney is larger than that of PVA after 7 days of psaE polymeric microsphere embolization, which shows that the embolization effect of PSAE polymeric microsphere is better than that of PVA microsphere.
FIG. 13 is a graph comparing the testing of PVA microspheres and PSAE polymeric microspheres for HUVEC cytotoxicity. As can be seen from fig. 13, the cytotoxicity of the PSAE polymeric microspheres was comparable to that of PVA in the first 48 hours, and the cell viability of the PSAE polymeric microspheres in 72 hours was still as high as 85%, indicating that the PSAE polymeric microspheres had lower cytotoxicity.
As can be seen from fig. 12 and 13, the PSAE polymeric microspheres of the present invention can be used as a novel embolization material in transcatheter arterial embolization instead of PVA microspheres.
The method for studying the mechanism of the free radical-mediated cyclization reaction in the above example comprises the following steps:
constructing an optimal organic small molecular compound calculation model, carrying out path design of possible reaction mechanisms, then carrying out reaction intermediate and transition state modeling, and optimizing reactants, intermediates, transition states and products on each reaction path by adopting a Density Functional Theory (DFT) method. The reaction mechanism is that chemical reaction parameters such as reaction energy barrier, energy, enthalpy change and the like of each step are obtained through TST theoretical research, and the process of the [3+2] cyclization reaction is explained from the perspective of transition state theory. The obtained chemical reaction parameters can analyze the microscopic mechanism and energy change of the reaction from the perspective of the potential energy surface and the aspect of the state-state layer on the relationship between the macroscopic reaction kinetics and the thermodynamics and the change of the macroscopic reaction kinetics. The energy changes are changes in activation energy, driving force, and enthalpy change.
The photo-initiation free radical/triplet [3+2] cyclization reaction provides possibility for theoretical cyclization, wherein ortho-position or meta-position compounds are easy to generate mainly through research under a water phase condition, and the hydrogen extraction reaction is deduced to be favorable for the whole reaction through further calculation of the hydrogen extraction reaction. The invention also uses transition state theory research to explain the process of the [3+2] cyclization reaction. To our knowledge, Diels-Alder proceeds via a synchronous coordination mechanism. However, the [3+2] cyclization reaction of the present invention is not completely analogous to the Diels-Alder reaction according to conformational analysis of the transition state, and the formation of the five-membered ring proceeds via an asynchronous or stepwise mechanism. The structure of the allyl monomer shows new polymerization characteristics in the polymerization process, lays a foundation for the cycloaddition mechanism of the allyl monomer, has a great application prospect when being used as a biological material, and creates a new world for fine medical treatment through deep research on the mechanism of the compound.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. By passage of an allyl monomer through [3+2]]A process for preparing cyclic polymers by cyclization reaction features that the photoinitiator and allyl monomer are used to photo-initiate free radical or triplet state under the radiation of ultraviolet light or visible light to generate [3+2]]Cyclizing to obtain a cyclic polymer; the photoinitiator is reacted with allyl monoThe molar ratio of functional groups of the photoinitiator is 1: 1-4, the photoinitiator is a cracking type photoinitiator and/or a hydrogen extraction type photoinitiator, and the allyl monomer is H2C＝CH-CH2-X-R0A monomer; wherein X is O, -NR, S, P, O-C ═ O, or CH2，R0Is H, alkyl-R, cycloalkyl, carbocyclic/heterocyclic aromatic hydrocarbons, -OR, nitro-NO2Dialkylamino group-NR1R2Halogen, alkene/alkyne, ester group/carboxyl COOR, quaternary ammonium salt NRR1R2R3 +Acid anhydride bond-CO-O-CO, carbonyl C ═ O, ether bond-O-, thioether bond-S, disulfide bond-S-S-, peroxy bond-O-O-, epoxy bond
Amide bond CO-NR1R2；R、R1、R2、R3Each independently selected from hydrogen or straight/branched alkanes.
2. The method of claim 1, wherein the molar ratio of the photoinitiator to the functional groups of the allyl monomer is 1:1 to 3.3.
3. The method of claim 1 or 2, wherein the allyl monomer is H2C＝CH-CH2-O-CH3。
4. The method of claim 1, wherein the photoinitiator is benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-hydroxy-2-methyl-1-phenyl-1-propanone, α '-ethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, 1' - (methylenebis-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-propanone ], methyl benzoylformate, diethylene glycol benzoylformate, tert-butyl peroxybenzoate, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2, 4, 6-trimethylbenzoylphenylphosphonate, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinobenzylphenyl) butanone, methyl O-benzoylbenzoate, 1- [4- (4-phenylthio) -phenyl ] -octa-1, 2-dione-2-oxime-O-benzoate, (1- [3'- (6' -O-toluoyl-N-ethylcarbazole) ] -1-ethanone oxime-O-acetate), Coumarin, benzophenone, 4-phenylbenzophenone and thioxanthone, 2-isopropylthioxanthone, 2-chlorothianthrone, camphorquinone; 4-p-toluene mercapto benzophenone, benzoyl formic acid diethyl diester, bis 2, 6-difluoro-3-pyrrole phenyl cyclopentadienyl titanium.
5. The method of claim 1 or 4, wherein the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-propanone or 2-isopropylthioxanthone.
6. The method of claim 1, wherein the reaction is carried out in water or a non-aqueous system.
7. The method according to claim 1, wherein the allyl monomer and the photoinitiator are dissolved in water, stirred, and subjected to the [3+2] cyclization reaction by irradiation with an ultraviolet lamp in air at room temperature for 15min to obtain the cyclic polymer.
8. The method according to claim 1, wherein the irradiation conditions are medium pressure mercury lamps or LED lamps.
9. A cyclic polymer obtainable by the process of any one of claims 1 to 8.
10. Use of the cyclic polymer of claim 9 in transcatheter arterial embolization.
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