CN113072689B - Method for preparing degradable polymer based on light control of spiropyran and application - Google Patents
Method for preparing degradable polymer based on light control of spiropyran and application Download PDFInfo
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Abstract
The invention belongs to the technical field of polymer synthesis, and discloses a method for preparing a degradable polymer based on light control of spiropyran and application thereof. In the method, under inert atmosphere, spiropyran, micromolecular organic alcohol initiator, cyclic lactone, organic weak base hydrogen bond acceptor cocatalyst and solvent are mixed and react at room temperature; then using point light source ultraviolet light to irradiate reaction, then turning off the light source, carrying out reaction light-proof treatment, and then using point light source ultraviolet light to irradiate reaction; and repeating the operations for 1-3 times, controlling the transformation of the spiropyran-partial phthalocyanine by adjusting illumination to control ring-opening polymerization reaction, using glacial methanol as a precipitator after the reaction is finished, and performing suction filtration and vacuum drying to obtain the degradable polymer. According to the invention, the reversibility of open-loop and closed-loop of spiropyran under ultraviolet illumination condition is utilized, the open-loop partial phthalocyanine structure can be used as a hydrogen bond donor, and the polymerization reaction is controlled to be carried out and terminated under the coordination of a hydrogen bond acceptor, so that the degradable polymer is prepared by light control.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to a method for preparing a degradable polymer by light control based on spiropyran and application thereof.
Background
Aliphatic polyesters have excellent characteristics such as biocompatibility and biodegradability, and ring-opening polymerization (ROP) is the most commonly used method for synthesizing aliphatic polyesters, and the catalysts used in ring-opening polymerization are mainly metal-based catalysts. However, metal catalysts are unacceptable for specific applications, such as materials used in living organisms and microelectronic devices. Therefore, it is not necessary to develop new polymerization methods to solve these problems. Compared with metal-based catalysts, the non-metal catalyst has the characteristics of easy preparation, convenient storage and easy separation from a polymerization product, and is an ideal catalyst for preparing biodegradable polymers.
Spiropyrans are one of the most widely studied light-functional molecules at present, and can undergo a reversible transition between their closed-loop bulk Spiropyrans (SPs) and open-loop bulk phthalocyanines (MCs) under different external stimuli (such as light), thus exhibiting completely different physical and chemical properties. The photoinitiation or light-controlled polymerization reaction has been studied more, the controllable regulation of the ring-opening polymerization reaction under the action of the co-catalyst through the structural change of the light-controlled spiropyran has not been reported, and the method has important significance for the research of the ring-opening polymerization reaction, and especially for the preparation of biodegradable materials.
Disclosure of Invention
In order to solve the disadvantages and shortcomings of the prior art, the present invention provides a method for preparing a degradable polymer by light control based on spiropyran.
Another object of the present invention is to provide a degradable polymer prepared by the above method.
It is a further object of the present invention to provide the use of the above degradable polymers.
The purpose of the invention is realized by the following technical scheme:
a method for preparing a degradable polymer based on spiropyran by light control comprises the following specific steps:
s1, mixing spiropyran, a small molecular organic alcohol initiator, cyclic lactone, an organic weak base hydrogen bond acceptor cocatalyst and a solvent under an inert atmosphere to react at room temperature;
s2, using a point light source ultraviolet light to perform irradiation reaction, then closing a light source, performing reaction light-proof treatment, and then using the point light source ultraviolet light to perform irradiation reaction;
and S3, repeating the operation for 1-3 times, controlling the transformation of the spiropyran-phthalocyanine by adjusting illumination to control ring-opening polymerization reaction, using glacial methanol as a precipitator after the reaction is finished, and performing suction filtration and vacuum drying to obtain the degradable polymer.
Preferably, the small-molecule organic alcohol initiator in step S1 is one or more of benzyl alcohol, methanol, ethanol, n-butanol, n-hexanol, 1, 4-butanediol, glycerol, or propiolic alcohol.
Preferably, the cyclic lactone in step S1 is one or more of levolactide, caprolactone, valerolactone or trimethylene carbonate.
Preferably, the organic weak base hydrogen bond acceptor co-catalyst in step S1 is one or more of triethylamine, N-dimethylaminocyclohexane or pyridine.
Preferably, the solvent in step S1 is one or more of dichloromethane, chloroform, tetrahydrofuran, acetonitrile, dioxane or toluene.
Preferably, the spiropyran in step S1: small molecule organic alcohol initiator: organic weak base hydrogen bond acceptor co-catalyst: the molar ratio of the cyclic lactone is (0.1-0.5) to (30-100), and the volume ratio of the total mole of the spiropyran, the micromolecule organic alcohol initiator, the organic weak base hydrogen bond acceptor cocatalyst and the cyclic lactone to the solvent is (5-6) mmol and (1.5-2.5) mL.
Preferably, the inert atmosphere in step S1 is nitrogen or argon.
Preferably, the reaction time in the step S1 is 1-2 h, the ultraviolet irradiation reaction time in the step S2 is 1-4 h/time, and the light-shielding treatment time is 1-2 h; the time of the polymerization reaction in the step S3 is 9-50 h.
A degradable polymer is prepared by the method.
The degradable polymer is applied to the biomedical field.
The method comprises the steps of firstly preparing light-sensitive spiropyran, dropwise adding 1, 3-trimethyl-2-methylene indoline into ethanol solution containing salicylaldehyde, carrying out reflux reaction for 24 hours under inert atmosphere, and removing a reaction solvent to obtain a red viscous substance; dissolving the red sticky substance by using dichloromethane, washing the red sticky substance for 3 times by using deionized water, drying anhydrous magnesium chloride to obtain a dichloromethane solution for 2 hours, removing magnesium chloride hydrate, and removing the solvent to obtain pink solid Spiropyran (SP); the "reversible" transition of spiropyran-partial phthalocyanines, which can open ring-forming moieties under ultraviolet light (365nm, 50w), is shown in formula (1). Under the condition of keeping out of the sun, the ring can be closed to form SP, three methyl hydrogens carried by quaternary ammonium salt with positive charge in MC are equivalent to donors of hydrogen bonds, and the three methyl hydrogens and organic weak base hydrogen bond acceptor catalysts (triethylamine, pyridine and N, N-dimethylaminocyclohexane) can be used for co-catalyzing ring-opening polymerization of cyclic esters (including levo-Lactide (LA), caprolactone (CL), valerolactone (VL) and trimethylene carbonate (TMC)); the closed-loop SP can not provide a hydrogen bond donor, and the simple organic weak base is difficult to catalyze the ring-opening polymerization, so that the light response characteristic of the spiropyran can be utilized, the open-loop MC can provide the hydrogen bond donor, and the proceeding-terminating of the polymerization reaction is controlled, thereby realizing the light-operated preparation of the degradable polymer.
The invention converts spiropyran from closed ring body SP into open ring body MC through ultraviolet irradiation, the cation structure in the structure can be used as hydrogen bond donor, under the coordination of co-catalyst hydrogen bond acceptor, the ring-opening polymerization of cyclic monomer is realized, the open ring body MC and organic weak base hydrogen bond acceptor co-catalyst catalyze cyclic ester ring-opening polymerization as shown in formula (2):
compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the reversibility of open-loop and closed-loop of the spiropyran under the ultraviolet illumination condition is utilized, the open-loop part of the phthalocyanine structure can be used as a hydrogen bond donor, and the polymerization reaction can be regulated by light under the organic cooperation of a hydrogen bond acceptor. The method is a novel method for preparing the degradable polymer through nonmetal catalysis, particularly utilizes light to control whether polymerization reaction occurs or not, and has good reaction controllability.
2. The invention uses self-made spiropyran as photoresponse molecule, alcohol containing different functional groups as initiator, various cyclic lactones as monomer, and utilizes the 'reversible' opening and closing characteristic of spiropyran molecule under the action of cocatalyst. The start and the end of the polymerization process are controlled by using ultraviolet light, and degradable polymers with different molecular weights, terminal functional groups and various topological structures are obtained by adjusting the types and the proportions of monomers and initiators.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. The reagents, methods and apparatus employed in the present invention are conventional in the art, except as otherwise indicated.
Example 1
1.1, 3-trimethyl-2-methyleneindoline (1.836g, 10.59mmol) was added dropwise to an ethanol solution containing salicylaldehyde (1.239g, 10.14mmol), followed by refluxing under a high-purity nitrogen atmosphere for 24h. Vacuum evaporation is carried out to obtain pink crystals, the dichloromethane is washed for 3 times by deionized water after being dissolved, the dichloromethane after liquid separation is dried for 2 hours by anhydrous magnesium chloride, then filtration is carried out, the solvent is removed, and vacuum drying is carried out to obtain pink solid spiropyran;
2. under the protection of high-purity argon, 10mL of Schlenk is added with spiropyran (35.3 mg, 0.15mmol), initiator benzyl alcohol (10.8 mu L,0.1 mmol) and monomer in turnC3 lactide (ii) (LA) (720mg, 5mmol), dichloromethane (1.5 mL) as a solvent, and N, N-dimethylaminocyclohexane (32mg, 0.1mmol) as an organic weak base hydrogen bond acceptor. Reacting at room temperature for 1-2 h, irradiating with ultraviolet light (365nm, 50w) for reaction, sampling after the polymerization reaction is finished, and obtaining the LA monomer conversion rate of 22.4% by nuclear magnetic analysis. Precipitating the rest reaction mixture with excessive glacial methanol solution, filtering, and vacuum drying to obtain Polylactide (PLA)
1 H NMR(600MHz,CDCl 3 )：δ(ppm)1.48,(3H,-CH(CH 3 )OH),1.57,(3H,-CH 3 -),1.95(2H,ArCH 2 CH 2 -),2.66(2H,ArCH 2 -),4.14(2H,ArCH 2 CH 2 CH 2 -),4.34(1H,-CH(CH 3 )OH),5.20(-CH(CH 3 )O-)),7.29(5H,aromatic)。
Example 2
The difference from example 1 is that: the illumination time is 6h, and the sample is taken after the reaction is finishedThe conversion of LA monomer was calculated to be 51.8% by nuclear magnetism. The obtained polymerization product is polylactide
Example 3
The difference from example 1 is that: the illumination time is 12h, a sample is taken after the reaction is finished, and the conversion rate of the LA monomer is 81.8% through nuclear magnetism calculation. The obtained polymerization product is polylactide
Example 4
The difference from example 1 is that: the illumination time is 18h, after the reaction is finished, sampling is carried out, and the conversion rate of the LA monomer is 97.8% through nuclear magnetism calculation. The obtained polymerization product is polylactide
Example 5
The difference from the embodiment is that: the organic weak base hydrogen bond acceptor is triethylamine, and the final LA monomer conversion rate is 18.1%. Compared with triethylamine, the N, N-dimethylamino cyclohexane organic base hydrogen bond acceptor co-catalyst has higher activity.
Example 6
The difference from example 1 is that: the organic weak base hydrogen bond acceptor is pyridine, and the final LA monomer conversion rate is 17.1%. The N, N-dimethylaminocyclohexane organic base hydrogen bond acceptor co-catalyst is more active than pyridine, so we prefer N, N-dimethylaminocyclohexane as the co-catalyst in the examples that follow.
Examples 7 to 11
The difference from example 1 is that: the solvents are chloroform, tetrahydrofuran, acetonitrile, dioxane or toluene, and the obtained monomer conversion rates are 22.1%, 23.1%, 21.1%, 21.9% and 20.1%, respectively, so that the influence of the solvents on the polymerization reaction is not great, several solvents can be reaction solvents, and dichloromethane is adopted as the solvent in subsequent experiments from the viewpoint of easy post-treatment.
Examples 12 to 18
The difference from example 1 is that: the organic alcohol is methanol, ethanol, n-butanol, n-hexanol, 1, 4-butanediol, glycerol or propiolic alcohol respectively to obtain PLA products containing corresponding alcohol terminals, which shows that the open-loop body generated by ultraviolet irradiation and the open-loop polymerization substrate under the synergistic action of the cocatalyst have strong inclusion property to prepare various functionalized PLA.
Example 19
The differences from example 4 are: the molar ratio of the monomer LA to the initiator benzyl alcohol is 30:1, the monomer conversion was 97.1%. Number average relative molecular mass of PLA is M n ＝2600g/mol。
Example 20
The difference from example 4 is that: the molar ratio of the monomer LA to the initiator benzyl alcohol is 70:1, the amount of dichloromethane added was 2.0mL. The monomer conversion was 92.1%; number average relative molecular mass of PLA is M n ＝5800g/mol。
Example 21
The difference from example 4 is that: the molar ratio of the monomer LA to the initiator benzyl alcohol is 100:1, dichloromethane was added in an amount of 2.5mL. The monomer conversion was 85.5%. The number-average relative molecular mass of PLA is M n ＝8400g/mol。
From examples 19 to 21, it can be seen that the ring-opening polymerization reaction in which the ring-opening body is generated by the ultraviolet irradiation and the co-catalyst acts synergistically has a certain controllability, and polymers with different relative molecular weights can be prepared.
Example 22
History to 10mL under inert atmosphereA Lank bottle was charged with spiropyran (35.3mg, 0.15mmol), benzyl alcohol (10.8ul, 0.1mmol), LA (720mg, 5mmol), dichloromethane (1.5 mL) and N, N-dimethylaminocyclohexane (32mg, 0.1mmol) in this order. At room temperature, the reaction was carried out for 1 hour under ultraviolet illumination (365nm, 50w), the monomer conversion rate was 15.1% by sampling test nuclear magnetism, and then the reaction was carried out for 1 hour in the absence of light, the monomer conversion rate was 16.0% by sampling test nuclear magnetism, which indicates how much the monomer conversion rate did not increase in the 1 hour in the absence of light. After that, the above step was repeated 3 times, and the sample was taken for nuclear magnetic counting of the conversion. The monomer conversions were 22.6% at 3h, 23.3% at 4h, 36.4% at 5h, 6.8% at 6h, 45.3% at 7h and 45.9% at 8h, respectively, which indicates that no polymerization occurred during the light-shielding treatment. And then the reaction is carried out for 4 hours by ultraviolet irradiation, and the conversion rate of the monomer is tested to be 75.2% by sampling, thereby further confirming that the reaction can be promoted by the ultraviolet irradiation. Finally, excessive glacial methanol is used for precipitating the residual reaction mixture, and the solid product obtained after suction filtration and vacuum drying is polylactide
Example 23
The differences from example 22 are: n, N-dimethylaminocyclohexane (48.0 mg, 0.15mmol), the other reaction conditions were the same. The conversion rates of the obtained LA monomers are respectively 1h (illumination, 19.5%), 2h (protected from light, 19.9%), 3h (illumination, 30.5%), 4h (protected from light, 30.9%), 5h (illumination, 45.6%), 6h (protected from light, 46.0%), 7h (illumination, 60.1%), 8h (protected from light, 61.1%), and then 4h are continuously illuminated, the monomer conversion rate is finally 89.5%, and the obtained product
The above data show that the polymerization reaction can be controlled by controlling the ultraviolet irradiation time, and the reaction can be accelerated to some extent by increasing the content of the organic base.
Example 24
Example 24 differs from example 23 in that: the LA monomer is changed into CL monomer, and other conditions are consistent. The obtained CL monomer conversion rates were 1h (light, 12.5%), 2h (light-protected, 12.6%), 3h (light, 23.5%), 4h (light-protected, 23.9%), 5h (light, 31.6%), 6h (light-protected, 32.0%), 7h (light, 40.1%), 8h (light-protected, 41.1%), and thereafter 4h light, respectively, the final monomer conversion rate was 67.5%, and the obtained product was obtained
The experimental result shows that the ring-opening polymerization of the CL monomer can be effectively controlled to prepare Polycaprolactone (PCL) by the co-catalyst of the spiropyran and the N, N-dimethylamino-cyclohexane under the ultraviolet irradiation.
Example 25
The difference from example 23 is that: the monomer is a VL monomer. The VL monomer conversions obtained were 1h (light, 18.5%), 2h (dark, 19.6%), 3h (light, 28.5%), 4h (dark, 28.9%), 5h (light, 40.6%), 6h (dark, 41.0%), 7h (light, 56.1%), 8h (dark, 56.1%), and thereafter 4h light, respectively, with a final monomer conversion of 89.5%, and the product obtained
The experimental result shows that the ring-opening polymerization of the VL monomer can be effectively controlled to prepare the Polypentanone (PVL) by the co-catalyst of the spiropyran and the N, N-dimethylamino-cyclohexane under the ultraviolet irradiation.
Example 26
The differences from example 23 are: the monomer is TMC monomer. The obtained CL monomer conversion rates were 1h (light, 10.5%), 2h (light-protected, 10.6%), 3h (light, 18.5%), 4h (light-protected, 18.9%), 5h (light, 29.6%), 6h (light-protected, 30.0%), 7h (light, 40.1%), 8h (light-protected, 40.9%), and thereafter 4h light, respectively, the final monomer conversion rate was 57.5%, and the obtained product was
The experimental results show thatThe pyran and N, N-dimethylamino cyclohexane co-catalyst can effectively control the ring-opening polymerization of TMC monomer to prepare polytrimethylene carbonate (PTMC) by ultraviolet irradiation.
Comparative example 1
Under an inert atmosphere, 10mL of Schlenk was sequentially charged with spiropyran (35.3 mg, 0.15mmol), benzyl alcohol (10.8. Mu.L, 0.1 mmol), LA (720mg, 5mmol), dichloromethane (1.5 mL), N, N-dimethylaminocyclohexane (32mg, 0.1mmol). Reacting for 18 hours in a dark place at room temperature, sampling after the polymerization reaction is finished, obtaining the LA monomer conversion rate of only 5.4% by utilizing nuclear magnetic analysis, and further explaining that the spiropyran closed ring body and the N, N-dimethylamino cyclohexane are cooperatively catalyzed under the dark condition and do not effectively catalyze LA ring opening polymerization, and further explaining that the open ring body MC generated by ultraviolet illumination is the key for controlling the polymerization reaction. The remaining reaction mixture was precipitated with an excess of ice methanol solution, and no polymerization product was obtained.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.
Claims (4)
1. A method for preparing a degradable polymer based on light control of spiropyran is characterized by comprising the following specific steps:
s1, under an inert atmosphere, mixing spiropyran, a small molecular organic alcohol initiator, cyclic lactone, an organic weak base hydrogen bond acceptor cocatalyst and a solvent, and reacting at room temperature for 1 to 2 hours; the cyclic lactone is more than one of levo-lactide, caprolactone or valerolactone; the organic weak base hydrogen bond acceptor cocatalyst is more than one of triethylamine, N-dimethylamino cyclohexane or pyridine; the spiropyran: small molecule organic alcohol initiator: organic weak base hydrogen bond acceptor co-catalyst: the molar ratio of the cyclic lactone is (0.1 to 0.5): 0.1 to 0.5: 30 to 100, and the volume ratio of the total mole of the spiropyran, the small molecular organic alcohol initiator, the organic weak base hydrogen bond acceptor cocatalyst and the cyclic lactone to the solvent is (5 to 6) mmol, (1.5 to 2.5) mL;
s2, irradiating the mixture by using a point light source ultraviolet light for reaction for 1 to 4 hours/time, then closing the light source, performing the reaction for 1 to 2 hours in a dark place, and then irradiating the mixture by using the point light source ultraviolet light for reaction;
and S3, repeating the operation for 1-3 times, controlling the transformation of the spiropyran-phthalocyanine by adjusting illumination to control the ring-opening polymerization reaction for 9-50 h, using glacial methanol as a precipitator after the reaction is finished, and performing suction filtration and vacuum drying to obtain the degradable polymer.
2. The method for preparing a degradable polymer through spiropyran-based light control as claimed in claim 1, wherein said small molecule organic alcohol initiator in step S1 is one or more of benzyl alcohol, methanol, ethanol, n-butanol, n-hexanol, 1, 4-butanediol, glycerol or propiolic alcohol.
3. The method for preparing the degradable polymer through the spiropyran-based light control according to claim 1, wherein the solvent in step S1 is one or more of dichloromethane, trichloromethane, tetrahydrofuran, acetonitrile, dioxane or toluene.
4. The method for preparing degradable polymers based on spiropyran based on light control as claimed in claim 1, wherein said inert atmosphere in step S1 is nitrogen or argon.
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| CN108424482A (en) * | 2018-02-27 | 2018-08-21 | 同济大学 | A kind of dendritic of multiple response and preparation method thereof containing spiro-pyrans |
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| US4240447A (en) * | 1979-04-06 | 1980-12-23 | International Flavors & Fragrances Inc. | Use for preparing smoking tobacco compositions of spiropyran derivatives |
| US4927911A (en) * | 1989-02-22 | 1990-05-22 | General Electric Company | Preparation of linear polycarbonates from cyclic oligomer compositions using zwitterionic catalyst |
| JP2004292476A (en) * | 2003-03-25 | 2004-10-21 | Fuji Photo Film Co Ltd | Two-photon absorption polymerizable composition and method for polymerizing the same |
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