CN114609102B - Method for in-situ monitoring polymer film forming process by using fluorescent probe - Google Patents
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Abstract
The invention relates to the field of high polymer materials, in particular to a novel method for detecting a polymer film forming process by using an aggregation-induced emission fluorescent probe. The invention provides a method for in-situ monitoring a polymer film forming process by using a fluorescent probe, which comprises the following steps: 1) Uniformly blending the polymer solution and the aggregation-induced emission substance to obtain a polymer/aggregation-induced emission substance mixed solution; 2) And (3) monitoring the uniform mixed solution obtained in the step 1) in real time by adopting a laser confocal microscope, so as to realize in-situ monitoring of the polymer film forming process. The invention improves a novel method for detecting the polymer film forming process by using an aggregation-induced emission fluorescent probe, takes an aggregation-induced emission substance such as TTVP or TVP as a fluorescent probe, prepares a uniformly dispersed mixed solution with the polymer, and sensitively, conveniently and intuitively monitors the polymer film forming process by using a laser-induced fluorescence technology.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a novel method for detecting a polymer film forming process by using an aggregation-induced emission fluorescent probe.
Background
Polyvinyl alcohol (PVA) is a biodegradable and biocompatible environment-friendly polymer with good physical properties, and can be widely applied to the fields of fiber, textile, adhesive, cosmetic industry, medicine, biomedical materials and the like. Since PVA has good film forming properties, it can also be applied in the fields of packaging materials, composite films, polarizing films, etc., and the process of forming PVA film from solution is very critical.
In the process of drying a hydrolyzed polyvinyl alcohol film, as exemplified by polyvinyl alcohol, the surface concentration of the solution increases due to evaporation of water, so that a glass transition temperature (Tg) of the polyvinyl alcohol increases, a vitrified layer, namely a 'skin layer', is formed at an air-sample interface, and due to the characteristic of a semi-crystalline polymer, the formation of the skin layer causes the evaporation of a surface solvent to be different from other parts of the sample, and the evaporation speed of the solvent is higher, thereby forming the difference between the skin layer and the core layer.
The formation and evolution of the exhibiting skin-core heterogeneity has been a challenge due to the continued lack of effective detection means. Sushata et al have observed the evaporation process of polyvinyl alcohol films in situ using low field nuclear magnetism and analyzed the molecular mobility by analyzing the behavior of nuclear magnetic resonance relaxation times. The nuclear magnetic resonance result shows that two processes appear in the dynamic heterogeneity presented in the film forming process, and the film shrinkage rate in the first stage is obviously reduced; after the film concentration reaches a critical value, the film formation process enters a second stage. This may be due to the fact that when the solution concentration is raised to a certain value, no free water is present in the system, the mobility of the water changes, while the polymer still maintains a higher mobility. The difference of the two mechanisms is influenced by the surface cortex structure in the polyvinyl alcohol evaporation process, namely the non-uniformity of the polymer in the thickness direction in the film forming process is influenced by the evaporation dynamics of solvent water molecules in a solution system. However, problems related to the formation mechanism of the critical concentration, influencing factors and the like remain to be discussed.
The fluorescence biological imaging technology has the advantages of quick response, excellent time resolution and sensitivity, in-situ detection, simple operation and good reproducibility, and becomes a powerful non-invasive analysis tool, so that a new thought is provided for the evolution of a detection structure on the premise of not damaging a film forming process.
Disclosure of Invention
In order to reveal the structural change in the heterogeneous film forming process of the polymer, the invention improves a new method for detecting the film forming process of the polymer by using an aggregation-induced emission fluorescent probe, wherein aggregation-induced emission substances such as TTVP or TVP are used as fluorescent probes, and the aggregation-induced emission substances and the polymer are prepared into uniformly dispersed mixed solution, so that the film forming process of the polymer is sensitively, conveniently and intuitively monitored by a laser-induced fluorescence (LIF) technology.
The technical scheme of the invention is as follows:
the first technical problem to be solved by the present invention is to provide a method for in-situ monitoring of polymer film forming process by using fluorescent probe, the method comprises the following steps:
1) Uniformly blending the polymer solution and the aggregation-induced emission substance to obtain a polymer/aggregation-induced emission substance mixed solution;
2) And (3) monitoring the uniform mixed solution obtained in the step 1) in real time by adopting a laser confocal microscope, so as to realize in-situ monitoring of the polymer film forming process.
Further, in step 1), the aggregation-inducing emission substance is: 5- (4-vinyl- (diphenylamino) phenyl) thiophene-2- (4-methyl-1- (3- (trimethylammonium) propyl) pyridine-1-ammonium bromide) (TTVP), 4-vinyl- (diphenylamino) phenyl-4-methyl-1- (3- (trimethylammonium) propyl) pyridine-1-ammonium bromide (TVP).
Further, in step 1), the 5- (4-vinyl- (diphenylamino) phenyl) thiophene-2- (4-methyl-1- (3- (trimethylammonium) propyl) pyridine-1-ammonium bromide) (TTVP) was synthesized by the following method: firstly, carrying out Suzuki Miyaura coupling reaction on 4-bromo-N, N-diphenyl aniline and (5-formylthiophene-2-yl) boric acid to generate 5- (4- (diphenylamino) phenyl) thiophene-2-carbofuran; then carrying out condensation reaction with 4-methyl-1- (3-trimethylaminopropyl) pyridine-1-ammonium bromide pyridinium to obtain TTVP.
Further, in step 1), the polymer solution is an aqueous polyvinyl alcohol solution or a polystyrene benzene solution; in the present invention, the aggregation-inducing emission material is selected so as to be soluble in the solvent of the polymer solution.
Further, in step 1), the amounts of the aggregation-inducing emission substance and the polymer are as follows: 5 to 30 parts of polymer and 0.1 to 0.4 part of aggregation-induced emission substance.
Further, in the step 1), the mass fraction of the polymer solution is 10wt% -20 wt%; i.e., the mass ratio of polymer to polymer solution; if the concentration is too high, the viscosity of the solution is easy to be increased, and a homogeneous mixed solution which is uniformly mixed is not easy to be obtained.
Preferably, the polymer solution is a water solution of polyethanol, and the aggregation-inducing emission material is 5- (4-vinyl- (diphenylamino) phenyl) thiophene-2- (4-methyl-1- (3- (trimethylammonium) propyl) pyridine-1-ammonium bromide).
Further, when the polymer solution is an aqueous polyvinyl alcohol solution and the aggregation-induced emission material is 5- (4-vinyl- (diphenylamino) phenyl) thiophene-2- (4-methyl-1- (3- (trimethylammonium) propyl) pyridine-1-ammonium bromide) (TTVP), the polymer/aggregation-induced emission material mixture is prepared by: firstly, adding 40-100 g of water into 6-15 g of polymer powder, heating to 95-120 ℃ and stirring and mixing for 2-4 h to obtain a polymer solution; and adding 2.5-10 mu mol of aggregation-induced emission substance into the polymer solution, and defoaming and centrifuging for 10-15 min to obtain uniform polymer/aggregation-induced emission substance mixed solution.
Further, the polymerization degree of the polyvinyl alcohol is 1500 to 3000.
In the preparation method of the mixed solution, the defoaming centrifugal rate is 4000-5000 r/min.
Further, the method of the step 2) is as follows: pouring the uniform polymer/aggregation-induced emission substance mixed solution obtained in the step 1) into a mold frame, and monitoring the change of film thickness and fluorescence intensity along with time in the polymer film forming process in real time by using a laser confocal microscope, and simultaneously measuring the solution quality of the polymer in the monitoring process to detect the actual concentration change condition until the moisture volatilizes to cause the surface curling wrinkling to stop monitoring.
In step 2), the environment temperature of the whole real-time monitoring process is 15-25 ℃, and the humidity condition is 40-60% RH.
The invention has the beneficial effects that:
according to the method, the aggregation-induced emission substance TTVP is taken as a fluorescent probe, the polymer polyvinyl alcohol is taken as an example, a laser confocal microscope is used for monitoring the change of the film thickness and fluorescence intensity along with time in the film forming process of the polyvinyl alcohol, and an analytical balance is used for measuring the mass of the solution of the polyvinyl alcohol at the same time to detect the actual concentration change.
Description of the drawings:
FIG. 1 shows that the variation in MFI of fluorescence intensity of a polyvinyl alcohol solution in the thickness direction was detected for a 50 mm. Times.50 mm. Times.1 mm mold frame (a) and a 50 mm. Times.50 mm. Times.2 mm mold frame (b) in example 1 at different times; indicating that the film formation process accelerates as the thickness of the mold frame decreases.
FIG. 2 is a graph showing the real-time solution quality (FIG. a), solution concentration (FIG. b), solution thickness (FIG. c) and density changes (FIG. d) of PVA solutions during film formation using 50 mm. Times.50 mm. Times.1 mm and 50 mm. Times.50 mm. Times.2 mm mold frames in example 1, as a function of the experimental time for the film formation process; as can be seen from fig. 2, the solution skin layer diffuses faster and forms a homogeneous morphology more easily with a decrease in the thickness of the mold frame due to the change in the solution properties.
FIG. 3 is a graph showing the results of processing the data of FIGS. 1 and 2 when the 50 mm.times.50 mm.times.1 mm and 50 mm.times.50 mm.times.2 mm mold frames of example 1 were formed, namely, the results of the change in the ratio of the slope of the fluorescence intensity MFI of PVA solution to the thickness with the concentration (FIG. 3 a) and the results of the change in the skin/core layer thickness with the concentration (FIG. 3 b); further disclosed are variations in skin-core structure as the film formation process proceeds.
FIGS. 4a and 4b are scanning electron microscope pictures of cross sections of the polyvinyl alcohol film of example 1 at different magnifications; the gradual diffusion of the skin layer during film formation is intuitively revealed.
Detailed Description
The invention adopts the method that the aggregation-induced emission substance TTVP is uniformly dispersed in the polyvinyl alcohol aqueous solution to prepare a homogeneous mixed solution, and the near infrared fluorescent substance TTVP molecules with aggregation-induced emission characteristics (AIE) have the characteristics of dissolving in a solvent and not emitting light, but showing strong fluorescence in an aggregation state; so that the fluorescence intensity of TTVP increases with the increase of the concentration of the polyvinyl alcohol solution and the limitation of molecular chain movement; indirectly revealing the structural evolution of the polymer polyvinyl alcohol in the film forming process by using the fluorescence imaging of TTVP; provides a new method for monitoring polymer film formation.
The invention uses laser confocal and laser induced fluorescence technique to track the gradient change of the polymer structure in situ in the process of solvent volatilization film forming. The method creatively applies aggregation-induced emission substances in film forming detection, takes a film forming process of polyvinyl alcohol as an example, reveals feasibility of sensitively and efficiently detecting gradient change of a polymer structure in the film forming process, and utilizes a laser confocal microscope to visually visualize the process.
The following describes the invention in further detail with reference to examples, which are not intended to limit the invention thereto.
Example 1
The method for observing the polymer film forming process in situ by using the fluorescent probe takes the polyvinyl alcohol film forming process as an example, and comprises the following implementation steps:
1) 10.59g of polyvinyl alcohol powder with the polymerization degree of 1700 is mixed with 60g of water, added into a three-neck flask, heated to 115 ℃ and dissolved, stirred and mixed for 3 hours to obtain a polyvinyl alcohol solution; according to the invention, if no special description exists, the alcoholysis degree of the polyvinyl alcohol powder raw materials with different polymerization degrees is 99%;
2) Adding 7.5 mu mol of TTVP into the polyvinyl alcohol solution, mixing for 5min by using a deaeration machine at the rotating speed of 2000r/min, and centrifuging for 10min by using a centrifuge at the centrifuging speed of 5000r/min to obtain a uniform mixed solution of polyvinyl alcohol and TTVP;
3) Pouring the uniformly mixed polyvinyl alcohol-TTVP blend solution into two different mold frames, wherein one mold frame is 50mm multiplied by 1mm, the other mold frame is 50mm multiplied by 2mm, and after the mold is reversed, scraping by a scraper to fill the whole mold with the solution, so that the surface of the solution is smooth and even;
4) Setting germany Carl Zeiss LSCM800 confocal laser microscope with five-fold objective hd=0.13, observation range 256×256 μm 2 The scanning mode is to scan a series of two-dimensional X-Y images along the Z-axis direction, and the coarse focusing spiral and the fine focusing spiral are adjusted in the BF modeJiao Luoxuan until a clear surface of the polyvinyl alcohol solution is observed;
5) The method comprises the steps of monitoring the changes of film thickness and fluorescence intensity along with time in the film forming process of the polyvinyl alcohol in real time by using a laser confocal microscope, measuring the mass of the polyvinyl alcohol solution at the same time by using an analytical balance to detect the actual concentration change, and monitoring after 300-480min of observation until the surface curling wrinkling caused by water volatilization.
The environment temperature of the whole real-time detection process is 25 ℃, and the humidity condition is 50% RH; the scanning mode is to scan a series of two-dimensional X-Y images along the Z-axis direction; the scanning speed of the laser confocal microscope is 1fps, the vertical step length is 20 mu m, and the excitation wavelength selection interval is 600-800 nm. In the embodiment of the invention, the model of a laser confocal microscope used for detecting the film thickness and the fluorescence intensity in real time in the film forming process is LSCM800 (the outline and the structure of the equipment are shown in figure 1) of Carl Zeiss company of Germany.
In the process of monitoring the polyethylene film formation, a laser confocal microscope applies a laser-induced fluorescence technology to measure the real-time fluorescence intensity, and the excitation wavelength is selected to be 600-800 nm. In the film forming process, when the cross section of the confocal laser microscope along the Z-axis direction (namely the thickness direction of the PVA solution) and the like is scanned from the surface to the bottom surface, the TTVP is red and shows weak signals under laser irradiation, and the thickness range of the polyvinyl alcohol film can be judged through the existence of fluorescent signals; the real-time thickness of the PVA film can thus be determined by the distance between the upper and lower planes where the fluorescent signal completely disappears in the image. The real-time fluorescence intensity of the PVA film in the film forming process is obtained by averaging the average fluorescence intensity of five areas in each two-dimensional image. As the moisture of the polyvinyl alcohol solution volatilizes and the concentration rises, the movement of polyvinyl alcohol molecular chains is limited, TTVP molecules aggregate to emit fluorescence, and the fluorescence intensity also increases along with the increase of the concentration; the change of fluorescence intensity is used for indicating the difference of solution concentration in different thickness directions of the polyvinyl alcohol film, and the change of PVA structure is tracked by a Laser Induced Fluorescence (LIF) technology, so that the change of structure is indicated.
In addition, analytical balance is used for the mass of solution in the film forming processThe amount was weighed, and since the volatile matter was distilled water alone, the polymer and the aggregation-inducing emission substance TTVP were retained, and thus the real-time concentration (C t )：
M is in 0 、C 0 、m t The initial mass, the initial concentration and the real-time mass at time t of the solution are respectively.
The linear relation between the luminescence intensity (I) of the aggregation-induced emission substance TTVP in the solution and the TTVP is scanned by utilizing laser confocal scanning, as shown in the formula 2:
wherein A is collection optical efficiency, I i For local incident laser intensity, epsilon is the absorption efficiency of the fluorescent dye,photoluminescence quantum efficiency of the fluorescent dye; then the concentration of the fluorescent dye is measured in real time and calculated from formula (3):
wherein C is 0 For the initial concentration of fluorescent dye, I 0 And I t The initial fluorescence intensity and the emission intensity at time t, respectively.
FIG. 1 shows that the variation in MFI of fluorescence intensity of a polyvinyl alcohol solution in the thickness direction was detected for a 50 mm. Times.50 mm. Times.1 mm mold frame (a) and a 50 mm. Times.50 mm. Times.2 mm mold frame (b) in example 1 at different times; as shown in fig. 1, the MFI does not change much with thickness at the initial stage of drying the PVA solution; after a period of drying, evaporation of the water leads to an increased concentration change, so that the MFI increases drastically. Furthermore, in the later drying step, two slopes of the MFI versus thickness curve occur; the MFI value near the upper surface has smaller variation with thickness, and the MFI value far away from the surface has larger variation, and the range of the skin layer and the core layer in the polyvinyl alcohol film forming process is distinguished according to the gradient variation of the MFI and the thickness, so that the gradient variation of the structure in the polyvinyl alcohol film forming process is explained. The turning point at which the MFI increases sharply with the thickness slope is defined as the transition point between the skin layer and the core layer of the polyvinyl alcohol film, the skin layer near the upper surface and the core layer near the lower surface. The evaporation of the polyvinyl alcohol solution can be divided into three phases as indicated by the slope change of MFI versus thickness: in the first stage, the MFI slope does not change much over time, and then exhibits a significant rise, and in the third stage, the MFI curve slope again returns to gentle.
FIG. 2 is a graph showing the real-time solution quality (FIG. a), solution concentration (FIG. b), solution thickness (FIG. c) and density changes (FIG. d) of PVA solutions during film formation using 50 mm. Times.50 mm. Times.1 mm and 50 mm. Times.50 mm. Times.2 mm mold frames in example 1, as a function of the experimental time for the film formation process; as can be seen from fig. 2, as the film thickness of the solution decreases, the real-time concentration and density of the solution increases sharply, and the MFI of the real-time fluorescence intensity in the thickness direction can reflect the trend of the structural change of the PVA solution during the drying process, according to the positive correlation between the fluorescence intensity and the polymer concentration.
FIG. 3 is a graph showing the results of processing the data of FIGS. 1 and 2 when the 50 mm.times.50 mm.times.1 mm and 50 mm.times.50 mm.times.2 mm mold frames of example 1 were formed, namely, the results of the change in the ratio of the slope of the fluorescence intensity MFI of PVA solution to the thickness with the concentration (FIG. 3 a) and the results of the change in the skin/core layer thickness with the concentration (FIG. 3 b); further, the change of the skin-core structure along with the film forming process is revealed, and as the thickness of the film increases, the difference of the real-time fluorescence intensity of the skin layer and the core layer becomes smaller, and as the film forming time increases, the skin layer gradually expands, the core layer contracts, and finally the whole film is composed of the skin layer.
FIGS. 4a and 4b are scanning electron microscope pictures of cross sections of the polyvinyl alcohol film of example 1 at different magnifications; the gradual diffusion of the skin layer during film formation is intuitively revealed.
The foregoing description of the preferred embodiments of the present disclosure is not intended to limit the disclosure, but rather to cover all modifications, equivalents, improvements and alternatives falling within the spirit and principles of the disclosure.
Claims (8)
1. A method for in-situ monitoring of a polymer film formation process using a fluorescent probe, the monitoring method comprising the steps of:
1) Uniformly blending the polymer solution and the aggregation-induced emission substance to obtain a polymer/aggregation-induced emission substance mixed solution; wherein the polymer solution is a polyvinyl alcohol aqueous solution, and the aggregation-induced emission substance is 5- (4-vinyl- (diphenylamino) phenyl) thiophene-2- (4-methyl-1- (3- (trimethylammonium) propyl) pyridine-1-ammonium bromide);
2) And (3) adopting a laser confocal microscope to monitor the uniform mixed solution obtained in the step 1) in real time, so as to realize in-situ monitoring of the polymer film forming process: pouring the uniform polymer/aggregation-induced emission substance mixed solution obtained in the step 1) into a mold frame, and monitoring the change of film thickness and fluorescence intensity along with time in the polymer film forming process in real time by using a laser confocal microscope, and simultaneously measuring the solution quality of the polymer in the monitoring process to detect the actual concentration change condition until the moisture volatilizes to cause the surface curling wrinkling to stop monitoring.
2. The method for in situ monitoring of polymer film formation process using fluorescent probes according to claim 1, wherein in step 1), the 5- (4-vinyl- (diphenylamino) phenyl) thiophene-2- (4-methyl-1- (3- (trimethylammonium) propyl) pyridine-1-ammonium bromide) is synthesized by the following method: firstly, carrying out Suzuki Miyaura coupling reaction on 4-bromo-N, N-diphenyl aniline and (5-formylthiophene-2-yl) boric acid to generate 5- (4- (diphenylamino) phenyl) thiophene-2-carbofuran; then the product is obtained by condensation reaction with 4-methyl-1- (3-trimethylaminopropyl) pyridine-1-ammonium bromide pyridine salt.
3. The method for in situ monitoring of polymer film formation using fluorescent probes according to claim 1, wherein in step 1), the amounts of aggregation-induced emission material and polymer used are: 5 to 30 parts of polymer and 0.1 to 0.4 part of aggregation-induced emission substance.
4. The method for in situ monitoring of polymer film formation process using fluorescent probe according to claim 1, wherein in step 1), the mass fraction of the polymer solution is 10wt% to 20wt%.
5. The method for in situ monitoring of a polymer film forming process using a fluorescent probe as claimed in claim 1,
the preparation method of the polymer/aggregation-induced emission substance mixed solution comprises the following steps: firstly, adding 40-100 g of water into 6-15 g of polymer powder, heating to 95-120 ℃ and stirring and mixing for 2-4 h to obtain a polymer solution; and adding 2.5-10 mu mol of aggregation-induced emission substance into the polymer solution, and defoaming and centrifuging for 10-15 min to obtain uniform polymer/aggregation-induced emission substance mixed solution.
6. The method for in situ monitoring of a polymer film forming process using a fluorescent probe as claimed in claim 5, wherein the polymerization degree of the polyvinyl alcohol is 1500-3000.
7. The method for in-situ monitoring of a polymer film formation process using a fluorescent probe as claimed in claim 5, wherein the defoamation centrifugation rate is 4000-5000 r/min.
8. The method for in-situ monitoring of a polymer film forming process by using a fluorescent probe according to claim 1, wherein in the step 2), the environmental temperature of the whole real-time monitoring process is 15-25 ℃ and the humidity condition is 40% -60%.
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