CN103058902B - Photoactive reversible addition-breakage chain transfer reagent and preparation and application thereof - Google Patents
Photoactive reversible addition-breakage chain transfer reagent and preparation and application thereof Download PDFInfo
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- CN103058902B CN103058902B CN201210561401.5A CN201210561401A CN103058902B CN 103058902 B CN103058902 B CN 103058902B CN 201210561401 A CN201210561401 A CN 201210561401A CN 103058902 B CN103058902 B CN 103058902B
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Abstract
The invention discloses a photoactive reversible addition-breakage chain transfer reagent with photo-initiation activity and preparation method and application of the reagent. Halomethylbenzophenone is synthesized by alpha halogenation between raw material including methylbenzophenone and a halogenated reagent, and then reacts with carbon disulfide to obtain the reversible addition-breakage chain transfer reagent with photo-initiating activity. The invention further discloses application of the reagent to preparation of a self-repairable polymer, and a cross-linked polymer of a trithiocarbonate structure can be prepared and has wide application prospects as a new polymer capable of self-repairing repeatedly.
Description
technical field
The present invention relates to chemical field, especially a kind of reversible addition-fracture chain with light-initiated activity shift (RAFT) reagent synthetic and preparation can self-healing polymers.
background technology
Prepare that molecular size range is controlled, the polymer of narrow molecular weight distribution, there is important using value.Realizing one of method of above-mentioned controllable polymerization is activity/controllable free-radical polymerisation (L/CRP), and this method has the plurality of advantages such as suitable monomers is wide, reaction conditions is easy to realize, can carry out in the different systems such as water.(Ouchi,?M;?Terashima,?T;?Sawamoto,?M.?
Acc.?Chem.?Res . 2008,?
41,?1120-1132.)。
Since the reversible addition-fracture of discovered in recent years chain shifts (RAFT) active free radical polymerization, this method has obtained extensive and deep research.The outstanding advantages of RAFT active free radical polymerization shows as: 1) suitable monomers kind is very wide, comprises (methyl) acrylicacidandesters class, vinyl acetate class, Styrene and its derivatives class monomer etc.; 2) made molecular weight distribution is narrow; 3) without metal catalyst and more expensive part; 4) made polymer ends can be carried out the conversion of multiple functional group; 5) can prepare multipolymer (as block, random, grafting, alternately, gradient, star, comb shape, hyperbranched, crosslinked, water solubility copolymer etc.) and the homopolymer (as distant pawl, novel terminally functionalized polymers etc.) of multiple topological structure; 6) can in different systems such as water base grade, carry out (M. Semsarilar and S. Perrier.
nature Chem.,
2010, 2,811-820.).
Macromolecular material in use can produce tiny crack, and this small damage is difficult to detect by macroscopical means, the therefore self-repair function of mimic biology tissue, and the development of carrying out self-repair material has important using value.Self-repair material is realized self-repair function and is mainly contained four kinds of methods: (1), thermal compression welding technology; (2), reversible high cross-linked polymer; (3), liquid core fibre technology; (4), microcapsulary.The selfreparing that utilizes reversible high cross-linked polymer to carry out material is a kind of new technology growing up in recent years, have simple to operate, can repeatedly repeat the advantages such as reparation (Gui Taijiang, Liu Xiyan.
modern coatings and application,
2007, 10 (12), 29-31.).
The luminous energy that photochemical reaction utilization is clean, has green, efficient advantage.Wherein, utilize UV-light to carry out solidifying of material, have advantages of that traditional curing technologies such as inertialess solvent evaporates, set time are short, low-temperature curable are incomparable.Photocuring technology be widely used in many fields such as coating, ink, tackiness agent, printing board material, electronic industry, microfabrication and rapid shaping (Wu Shikang. high-molecular optical chemistry introduction-basis and apply [M]. Science Press: October in 2003 the 1st edition .).
Summary of the invention
The object of this invention is to provide a kind of reversible addition-fracture chain with light-initiated activity shift (RAFT) reagent synthetic and preparation can self-repairing cross-linked polymer.
In order to utilize the polymkeric substance that RAFT reagent preparation can selfreparing, the invention provides a kind of structural formula (
i) compound
Wherein, the substituting group of benzophenone at ortho position, a position or contraposition.
The present invention provide simultaneously a kind of structural formula (
i) the preparation method of compound, described method steps is as follows:
By structural formula (
iI)
Wherein methyl at ortho position, a position, contraposition, carry out the halogenating reaction on methyl, obtain structural formula (
iII) compound
Wherein X represents chlorine or bromine.The halide reagent of described halogenating reaction be chlorine, bromine,
n-neoprene imide (NCS),
n-bromo-succinimide (NBS) or Hydrogen bromide.The solvent of described halogenating reaction is selected from methylene dichloride, tetrahydrofuran (THF), 1,4-dioxane, acetone, ethyl acetate, butylacetate, methylene bromide, methenyl bromide, carbon tetrabromide, chloroform, tetracol phenixin, 1,2-ethylene dichloride, 1，1，1-trichloroethane, acetonitrile, dimethyl sulfoxide (DMSO),
n,None or more in-dimethyl formamide.Should illustrate, these solvents just play the effect of dissolving or disperseing reactant and product, select different solvents, and reaction be there is no to obvious impact.The temperature of reaction of described halogenating reaction is from 0
oc, to the reflux temperature of solvent, is preferably 25
oc to the reflux temperature of solvent, considers from the angle of speed of response and conserve energy, most preferably is 25
oc.
By structural formula (
iII) compound under alkaline condition, react with dithiocarbonic anhydride, obtain structural formula (
i) compound.The alkali that reacts used is sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, cesium carbonate, pyridine, triethylamine or diisopropyl ethyl amine.Reaction solvent for use be tetrahydrofuran (THF), acetone, acetonitrile,
n,None or more in-dimethyl formamide, dimethyl sulfoxide (DMSO), ethyl acetate.Temperature of reaction is-30
oc is to the reflux temperature of solvent, considers preferably 25 from the angle of speed of response and conserve energy
oc.
The present invention also provide structural formula (
i) compound simultaneously as light trigger and the application of RAFT chain transfer agents in prepared by self-healing polymers.In the preparation of described self-healing polymers, first utilize common radical polymerization or active free radical polymerization, prepare structural formula (
iV) simple linear polymer, wherein R
1represent hydrogen or methyl, R
3represent hydrogen or methyl, R
2represent carboxylicesters, phenyl; R
4represent C
2-C
10alkyl, cycloalkyl, hydroxyalkyl; A=0-1, b=0-1, c=0-1, d=0-1, m=0-200, n=0-200, and b and d can not be that zero, m and n can not be zero simultaneously simultaneously.The initiator of described common radical polymerization is one or more in Sodium Persulfate, Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate; Described common Raolical polymerizable is for carrying out mass polymerization, solution polymerization, letex polymerization.Described active free radical polymerization is active free radical polymerization (ITP), the single electron transfer active free radical polymerization (SET-LRP) that atom transfer radical polymerization (AGET ATRP), reversible addition-fracture chain of atom transfer radical polymerization (ATRP), reverse atom transfer radical polymerization (RATRP), transfer transport generation spike shifts (RAFT) polymerization, nitroxyl free radical living polymerization (NMP), iodine initiation; Described active free radical polymerization is for carrying out mass polymerization, solution polymerization, letex polymerization; The solvent of described active free radical polymerization or medium be tetrahydrofuran (THF), benzene, toluene, acetonitrile, methyl-phenoxide, dimethyl sulfoxide (DMSO),
n,N-dimethyl formamide, water.
Common radical polymerization of the present invention or active free radical polymerization prepare structural formula (
iV) simple linear polymer time, monomer used must have beyond vinylformic acid binary or polyol ester or methacrylic acid binary or polyol ester, other monomer is selected from acrylicacidandesters, methacrylic acid and ester thereof, styrenic, vinyl acetate, and wherein acrylate is C
1-C
18straight chain, side chain or cycloalkyl alcohol ester, or C
1-C
6binary or polyol ester; Methacrylic ester is C
1-C
18straight chain, side chain or cycloalkyl alcohol ester, or C
1-C
6binary or polyol ester.It should be pointed out that above-mentioned vinyl monomer, principle, can carry out RAFT active free radical polymerization, select different monomers, only the performance of speed of response, resin is exerted an influence, polyreaction itself be there is no to impact.
The preparation of self-healing polymers of the present invention be by compound (I) and compound (IV) under UV-irradiation, there is light-initiated Raolical polymerizable, obtain the cross-linked polymer of structure formula V.In polymkeric substance (V), contain trithiocarbonic acid ester group, under illumination, reversible chain transfer reaction can occur, thereby there is self-repair function repeatedly.Compound (I) is (2-200) with the mol ratio of compound (IV): (1-100), be preferably (1-100): (1-10).When compound (I) and compound (IV) proportioning, solvent for use is selected from tetrahydrofuran (THF), 1,4-dioxane, acetone, ethyl acetate, butylacetate, methylene dichloride, chloroform, tetracol phenixin, 1,2-ethylene dichloride, 1,1,1-trichloroethane, benzene,toluene,xylene, acetonitrile, methyl-phenoxide, dimethyl sulfoxide (DMSO),
n,N-dimethyl formamide and mixed solvent thereof.
Reversible addition-fracture chain of light-initiated activity that what the present invention was designed have shifts (RAFT) reagent (I), light harvesting initiator and reversible addition-fracture chain shift (RAFT) reagent in one, can be under illumination and the polymkeric substance generation free radical reaction that contains hydroxyl, obtain having the cross-linked polymer of trithiocarbonic acid ester structure, this polymkeric substance is being subject to after small damage, can under illumination, carry out selfreparing.The cross-linked polymer of prepared by the present invention have trithiocarbonic acid ester structure, as the polymkeric substance of the novel repeatedly selfreparing of a class, is with a wide range of applications.
embodiment
Further set forth the present invention below in conjunction with embodiment.Should be appreciated that, these embodiment only, for the present invention is described, limit the scope of the invention and be not used in.The experimental technique of the unreceipted actual conditions of the following example, conventionally according to normal condition, or the condition that provides or advise according to manufacturer.Unless otherwise indicated, the same meaning that all specialties used herein and scientific terminology and those skilled in the art are familiar.In addition any method similar or impartial to present method and material all can be used in the inventive method.
the preparation of embodiment 1 4-(brooethyl) benzophenone (IIIa)
With 4-methyldiphenyl ketone,
n-bromo-succinimide is that raw material is prepared target compound.
Take 4-methyldiphenyl ketone (1.96 g, 10 mmol),
n-bromo-succinimide (3.56 g, 20 mmol), Diisopropyl azodicarboxylate (0.14 g, 1 mmol) are also dissolved in methylene dichloride (30 mL).Reaction solution stirs after 15 h under reflux temperature, cooling.Boil off after most of solvent, crude product is crossed silicagel column purifying (eluent: petrol ether/ethyl acetate=10/1, v/v) and is obtained white crystal (1.68 g, 62%).
M.p.?109-110?
oC;
1H-NMR?(CDCl
3,?
δ?ppm):?7.80-7.77?(m,?4H),?7.60-7.58?(m,?1H?),?7.51-7.47?(?m,?4H?),?4.53?(?s,?2H?);
13C?NMR?(CDCl
3,?
δ?ppm):?196.0,?142.1,?137.5,?137.4,?132.6,?130.6,?130.0,?129.0,?128.4,?32.3.
the preparation of embodiment 2 4-(brooethyl) benzophenone (IIIa)
Prepare target compound taking 4-methyldiphenyl ketone, Hydrogen bromide, hydrogen peroxide as raw material.
In reaction flask, add 1 of 4-methyldiphenyl ketone 1.96 g (10 mmol), 2-ethylene dichloride (30mL) solution, 40% HBr 1. 60 mL (11mmol), are warming up to backflow under stirring, drip 30% H
2o
22.04 mL (20 mmol), drip and finish, incandescent light (100 W) illumination reaction system, reaction 20 h.Reaction solution is carried out to separatory, and organic phase washes twice by saturated sodium sulfite, then washes with water three times, and the water after merging extracts once with 1,2-ethylene dichloride; Merge organic phase, dry with Calcium Chloride Powder Anhydrous, distillation is except desolventizing, and ethyl acetate/acetone for resistates (1/1) recrystallization obtains faint yellow needle-like crystal 2.42 g, productive rate 88%.
Characterization of The Products data are identical with embodiment 1.
the preparation of embodiment 3 4-(brooethyl) benzophenone (IIIa)
Prepare target compound taking 4-methyldiphenyl ketone, Hydrogen bromide, urea peroxide as raw material.
In reaction flask, add methylene dichloride (30 mL) solution of 4-methyldiphenyl ketone 1.25 g (6.4 mmol) and urea peroxide 1.2 g (12.8 mmol), under room temperature condition, stir, with 100 W incandescent light irradiations, drip 48% Hydrogen bromide 1.4 mL (6.9 mmol) (approximately 20 min), react after 40 min, distillation is except desolventizing, in resistates, add water, then be extracted with ethyl acetate, organic layer is washed after three times with saturated sodium sulfite solution, wash with water respectively once again, saturated common salt is washed once, anhydrous sodium sulfate drying, after last solvent evaporated, obtain crude product.Ethyl acetate/acetone for crude product (1/1) recrystallization obtains product IIIa (1.60 g, 91%).
Characterization of The Products data are identical with embodiment 1.
the preparation of embodiment 4 trithiocarbonic acids two (4-Benzoylbenzene first) ester (Ia)
Under argon shield, in reaction flask, add successively 15 mL acetonitriles, 8 mL dithiocarbonic anhydride, aqueous sodium hydroxide solution (10 g sodium hydroxide are dissolved in 15 mL water), 0.16 g Tetrabutyl amonium bromide, then stirring at normal temperature 30 min.Add again 4-(brooethyl) benzophenone (IIIa) (0.50 g, 1.8 mmol), system heating reflux reaction 10 h.After cooling, in system, add 50 mL water, separatory, water extracted with diethyl ether 3 times, merge organic phase, saturated common salt washing 3 times for organic phase, anhydrous sodium sulfate drying, filters and removes after desolventizing, obtains crude product, finally purify and obtain oily product (0.38 g, 81%) with silicagel column.
1H-NMR?(CDCl
3,?
δ?ppm):?7.79-7.75?(m,?8?H),?7.60-7.57?(m,?2H),?7.50-7.45?(m,?8?H),?4.70?(s,?4H);
13C?NMR?(CDCl
3,?
δ?ppm):?221.5,?196.2,?142.1,?140.0,?137.4,?132.6,?130.5,?130.0,?129.2,?128.4,?41.0.
the preparation of embodiment 5 Hydroxyethyl acrylates and methyl methacrylate random copolymers (IVa)
Adopt atom transfer radical polymerization (AGET ATRP) legal system of transfer transport generation spike standby.
Take Hydroxyethyl acrylate (2.98 g, 25.8 mmol) and methyl methacrylate (7.88 g, 77.3 mmol), then mix with the aqueous sodium hydroxide solution of 20 mL 5%, stir after 30 min, separatory, organic phase anhydrous sodium sulfate drying, for subsequent use after filtering.
Under argon shield; the monomer Hydroxyethyl acrylate of above-mentioned processing and methyl methacrylate are added in reaction flask; then add successively cupric bromide (0.1 g), 2; 2 '-dipyridyl (0.2 g), 2-isobutyl ethyl bromide (1 g, 5 mmol), toluene (5 mL), (0.34 g) for xitix.Add after material, temperature of reaction is adjusted to 75
oc, continues to stir 3 h.Reaction solution is cooling, add ethanol to precipitate, to pour out after clear liquid, solids is placed in vacuum drying oven (temperature 50
oc) dry 2 h in, 5.67 g that weigh to obtain, transformation efficiency 52.2%.
embodiment 6 can self-healing polymers (Va) preparation
(1.0 g) (1.0 g), is jointly dissolved in 20 mL acetone with trithiocarbonic acid two (4-Benzoylbenzene first) ester (Ia) to take random copolymers (IVa).Solution is layered on slide glass or polyfluortetraethylene plate uniformly, after equal solvent volatilization, above-mentioned plank is irradiated under ultraviolet lamp, ultraviolet wavelength is 365 nm.Irradiate after 10 min, become solid-state film, being can self-healing polymers (Va).
embodiment 7 can self-healing polymers (Va) Performance Detection
Prepared by embodiment 6 can proceed uviolizing by self-healing polymers (Va), carries out Performance Detection according to irradiation time difference.
With pencil method measure changes in hardness be: irradiate 10 min, hardness is B; Irradiate 20 min, hardness is 3H; Irradiate 30 min, hardness is 3H; Irradiate 40 min, hardness is 4H; Irradiate 50 min, hardness is 4H.
The detection of self-healing properties: prepare at embodiment 6 can self-healing polymers (Va) film on, mark the cut of approximately 30 microns of width with blade, then be the uviolizing of 365 nm with wavelength, observations is as follows: irradiate 5 min, do not change; Irradiate 10 min, cut shoals; Irradiate 30 min, cut disappears substantially.
Prepared by embodiment 6 can do powdered and pile up by self-healing polymers (Va), is then the uviolizing of 365 nm with wavelength, and observations is: irradiating 5 min, is still Powdered; Irradiate 10 min, powder becomes blocks of solid.
Claims (3)
1. the compound of a structural formula (I)
The substituting group of benzophenone simultaneously at ortho position, a position or contraposition.
2. a preparation method for structural formula claimed in claim 1 (I) compound, described method comprises the steps:
(1) by structural formula be
, wherein methyl at ortho position, the methyldiphenyl ketone of a position or contraposition, carry out the halogenating reaction on methyl with halide reagent, obtain the compound of structural formula (III):
wherein X represents chlorine or bromine;
(2) compound of the structural formula (III) step (1) being obtained reacts with dithiocarbonic anhydride under alkaline condition, obtains the compound of structural formula (I).
3. preparation method according to claim 2, is characterized in that: step (1) react halide reagent used be chlorine, bromine,
n-neoprene imide, N-bromo-succinimide or Hydrogen bromide, solvent is methylene dichloride, tetrahydrofuran (THF), 1,4-dioxane, acetone, ethyl acetate, butylacetate, methylene bromide, methenyl bromide, carbon tetrabromide, chloroform, tetracol phenixin, 1,2-ethylene dichloride, 1,1,1-trichloroethane, acetonitrile, dimethyl sulfoxide (DMSO),
n,None or more in-dimethyl formamide; Step (2) is described reacts with dithiocarbonic anhydride under alkaline condition, alkali used is sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, cesium carbonate, pyridine, triethylamine, diisopropyl ethyl amine, reaction solvent for use is tetrahydrofuran (THF), acetone, acetonitrile, N, one or more in dinethylformamide, dimethyl sulfoxide (DMSO), ethyl acetate, temperature of reaction is-30
oc is to the reflux temperature of solvent.
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| CN103450372B (en) * | 2013-07-17 | 2015-07-01 | 苏州大学 | Synthesis of chain transfer agent with thermal initiation function |
| CN104262217B (en) * | 2014-09-25 | 2016-04-06 | 陕西师范大学 | Trithiocarbonic acid-two (PFBBR) ester and its preparation method and application |
| CN105131154A (en) * | 2015-10-19 | 2015-12-09 | 湖南理工学院 | Atom transfer radical polymerization polymer-preparing method adopting plant ingredients as photoinitiator |
| CN105294524B (en) * | 2015-11-11 | 2017-10-20 | 陕西师范大学 | Carbodithioic acid PFBBR ester and its preparation method and application |
| CN109219644B (en) * | 2016-06-07 | 2022-01-11 | 爱克发有限公司 | Photoinitiator and curable composition |
| CN106491243B (en) * | 2016-10-20 | 2019-04-23 | 深圳大学 | Artificial cornea optical centre portion and preparation method thereof, artificial cornea |
| CN108866667A (en) * | 2018-07-31 | 2018-11-23 | 晋江瑞碧科技有限公司 | The preparation method and its usage of CdS-PAN/CNT hybridization compounding nanofiber |
| CN114249852B (en) * | 2022-01-10 | 2023-04-14 | 中山大学 | Method for preparing monodisperse photoactive polymer microspheres |
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