CN102532768B - Method for preparing low-temperature soluble polymer thin film in neutral aqueous solution - Google Patents
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Abstract
The invention belongs to the technical field of nano polymer thin films, and relates to a method for preparing a low-temperature soluble polymer thin film in an aqueous solution based on a layer-by-layer assembly technique. Each deposition cycle comprises two steps of: (1) immersing a substrate containing amino, carboxyl or hydroxyl on the surface into a polymer A aqueous solution at selected temperature, and taking out after a certain time; and (2) immersing the substrate into a polymer B aqueous solution at the temperature identical to the temperature selected in the step (1), and taking out after a certain time; and a multilayer nano thin film is obtained by repeating the steps (1) and (2). As a polymer-polymer complex has temperature response property, when the thin film is immersed into purified water, the multilayer film is gradually dissolved along with the gradual decrease of the temperature, and the dissolving rate and surplus fraction of the water-soluble nano thin film are controllable. According to the invention, the method is simple for operation and wider in application range; and the thin film has great application value in the fields of biology, medicine, food, agriculture, chemical industry, intelligent sensor and the like.
Description
Technical field
The invention belongs to nano-high molecule thin film technique field, be specifically related to a kind of method that in the aqueous solution, prepares the soluble macromolecule membrane of low temperature based on the Layer by layer assembly technology.
Background technology
Nano thin-film refer to the film that consisted of at the crystal grain of nanometer scale by size or nanocrystal is scattered in the composite membrane that consists of in certain material or every layer thickness at the single or multiple lift film of nanometer scale.This class material has very special physical property and chemical property, thereby makes it have important using value in the fields such as national defence, electronics, chemical industry, metallurgy, aviation, light industry, medicine, nuclear technique.Wherein water miscible nano thin-film can load and discharge the sensor of Medicine small molecule and conduct intelligence, so it is significant to medicine and Artificial Intelligence Science development.
The preparation method of nano thin-film can be divided into physical method and chemical process two large classes by principle.The chemical process of preparation nano thin-film mainly comprises plasma chemical vapor deposition technique, sol-gel method, thermolysis chemical vapour deposition technique etc., and sputtering method and the low energy cluster beam sedimentation that occurs recently all belong to physical method.The major defect that aforesaid method prepares nano thin-film is high cost.Layer by layer assembly (layer-by-layer assembly) is as an important branch of supramolecule science, and the method for utilizing the Layer by layer assembly technology to prepare nano thin-film has been reported.At present, the method for preparing the water-soluble nano film based on the Layer by layer assembly technology has also obtained very large development.At first, because the Layer by layer assembly technology just simply is immersed in substrate in body and the receptor solution successively, so its preparation process is simple and film shape depends on the shape of substrate, so can prepare the film of different sizes, shape; Secondly, the motivating force that makes up the Layer by layer assembly multilayer film is selected to enrich, and can be that electrostatic force, hydrogen bond and charge transfer interact etc.; At last, be by different interaction preparations to being subjected between volume primitive because the Layer by layer assembly technology prepares film, need at least two kinds of heterogeneity materials, so be suitable for making composite membrane.The impellent great majority that prepare the water-soluble nano film based on the Layer by layer assembly technology depend on interaction of hydrogen bond, because it is subjected to external influence larger, for example pH and ionic strength can be destroyed interaction of hydrogen bond, and film is dissolved in water.The harshness that the destructible of film also means the film building condition with and the uncontrollability of dissolving, for example the multilayer film of polyacrylic acid and Polyvinylpyrolidone (PVP) need to be assembled under acidic conditions, and this film is when higher pH value dissolving, and dissolution rate can not be controlled again.These disadvantageous factors have seriously limited application conditions and the scope of film.
Heat-sensible high polymer (being also referred to as the temperature-responsive polymer) is a kind of intelligent material, heat-sensible high polymer solution has a Kraft point, if macromolecular solution only has a phase below a certain temperature, solution is separated when being higher than this temperature, such macromolecular solution system all has a lower critical solution temperature (lower critical solution temperature usually, LCST), i.e. the corresponding temperature of the lower-most point of macromolecular solution phase transition temperature-concentration curve.In contrast be high Kraft point.Phase transition temperature can obtain by the variation of measuring the scattered light intensity (or transmitance) of macromolecular solution in (or cooling) process that heats up, and perhaps detects the heat effect that changes mutually.
The patent of method for preparing the water-soluble nano film is less, simultaneously also because in the past when the water-soluble film for preparing based on the Layer by layer assembly technology, condition is relatively harsher, and the film dissolving is uncontrollable, so at this, we have proposed the soluble high molecular nanometer film process of preparation low temperature, this method implementation condition is simple, applied widely, and the dissolution rate of the nano thin-film of preparing has very high controllability.
Summary of the invention
The objective of the invention is to utilize the Layer by layer assembly technology, based on the temperature response character of the uniqueness of polymer-polymer composite, propose a kind of method that under neutrallty condition, prepares the water-soluble nano film, and the dissolving properties of this film can pass through temperature adjusting.
Because polymer-polymer composite has temperature-responsive, thereby can regulate and control the dissolution rate of two kinds of high molecular layered assembling films in water by temperature, we have just invented a kind of method for preparing water miscible nano thin-film like this.
A kind of method that in neutral aqueous solution, prepares the macromolecule membrane of dissolution in low temperature of the present invention, its step is as follows:
1. select different heat-sensible high polymer A and heat-sensible high polymer B as the assembling thing, the phase transition temperature of selected heat-sensible high polymer mixing solutions is lower than the phase transition temperature that mixes front any one heat-sensible high polymer solution;
2. 1. select a temperature to assemble between the phase transition temperature of the minimum value of the phase transition temperature of described two kinds of heat-sensible high polymer solution and mixing solutions in step, the substrate of surface with amino, carboxyl or hydroxyl is immersed in the aqueous solution of heat-sensible high polymer A, take out behind 1～30min, then be immersed in the pure water of same temperature 1～5 time, each 5S～20min, nitrogen dries up after each the taking-up; Outwell the water of using at every turn after embathing, change again clean water;
3. then above-mentioned substrate is immersed in temperature and step 2. in the aqueous solution of identical heat-sensible high polymer B, takes out behind 1～30min, then be immersed in the pure water of same temperature 1～5 time, each 10S～20min, nitrogen dries up after each the taking-up; Outwell the water of using at every turn after embathing, change again clean water; Thereby finish the preparation of a deposition cycle film in substrate;
4. repeating step 2.～3., thereby obtain the high molecular nanometer film of the water miscible dissolution in low temperature of multilayer in substrate.
The processing of substrate: described in technical background, the assembling of the multilayer film that this patent is related is not subjected to the impact of shape and the size of substrate, and the substrate of any shape all can be used for assembling.
Assembling preparation ultrathin membrane at first needs to assemble material and substrate has certain interaction, substrate surface is amino, the kinds of surface such as carboxyl and hydroxyl functional group all can be used for hydrogen bond assembling preparation multilayer film, present selectable substrate is a lot, comprises glass, quartzy, silicon single crystal, mica, evaporation has glass or the quartz of gold, the surface evaporation has glass and various plastics such as the terephthalic acid condensed ethandiol ester of indium tin oxide, poly-(4-methyl-1-pentene), polyethylene, voltalef, tetrafluoroethylene, metal, porous material is (such as molecular sieve, anodised aluminium) etc.Substrate can be plane, curved surface, bar-shaped, sphere or irregular surface.The method of introducing amino, carboxyl or hydroxy functional group at different substrate surfaces is different, in the existing introduction of Chinese patent " ZL200510016739.2, a kind of method for preparing film of inorganic phosphate in the aqueous solution ".
The selection of assembling material: the present invention utilizes the Layer by layer assembly technology, prepares the water-soluble nano film based on the temperature response function of heat-sensible high polymer uniqueness, so the selection of assembling material namely has uniqueness, ubiquity is arranged again.Heat-sensible high polymer has the developing history of decades, and kind is a lot.We find that part neutrality has the phase transition temperature of heat-sensible high polymer any one heat-sensible high polymer before mixed phase transition temperature is lower than mixing of lower critical solution temperature, find to have obvious interaction of hydrogen bond between the two by infrared spectra, two kinds of polymers of this explanation have formed polymer-polymer composite (polymer-polymer complex), and this polymer-polymer composite also has temperature-responsive.The polymer that can form polymer-polymer composite has one of following group usually: carbonyl, hydroxyl, phenolic group, ehter bond, amido, acid amides, nitrogen heterocyclic ring is (such as pyridyl, pyrryl, imidazolyl etc.), particularly, heat-sensible high polymer A and heat-sensible high polymer B are selected from PNIPAM, poly-isopropyl methyl acrylamide, poly-n-propyl acrylamide, poly-n-propyl Methacrylamide, Vinylcaprolactam homopolymer, poly-(3-ethyl-1-vinyl pyrrolidone), polyvinyl methyl ether, poly-(2-sec.-propyl-2-oxazoline), poly-(2-propyl group-2-oxazoline), poly-(2-sec.-propyl-2-oxazoline), the polyacrylic acid hydroxypropyl acrylate, poly-L-(methylol propyl group) Methacrylamide, poly-L-(methylol propyl group) acrylamide, methylcellulose gum, hydroxypropylcellulose, poly-N-(2-methylacryoyloxyethyl) pyrrolidone, poly-(N-(tetrahydrofuran (THF)-2-) methyl) acrylamide, poly-(N-(tetrahydrofuran (THF)-2-) methyl) Methacrylamide, the poly N-vinyl butyramide, the poly N-vinyl isobutyramide, the phase transition temperature reduction was the Main Basis that we screen the assembling material after two kinds of polymers mixed.
Determining of assembling temperature: we select a temperature to assemble at the phase transition temperature of single heat-sensible high polymer with after mixing between the phase transition temperature, make up the multi-layer nano film.Because assembling is that polymer is adsorbed onto from solution on the substrate, the assembling temperature is lower than every kind of high molecular phase transition temperature and can ensures high molecular dissolving; It is stable existence (namely not dissolved) in order to promote high molecular absorption and multilayer film that the assembling temperature is higher than mixed phase transition temperature.
Step 2., 3. in the assembling temperature can select as required, can the control group loading amount by temperature, temperature is higher, every tunic is thicker; Immersing the substrate of assembling unitary film in the pure water is to want the flush away substrate surface to adsorb to get unstable material, embathes to be conducive to construct more solid nano thin-film.
Step 2., 3. in, constant if the time of immersing macromolecular solution, prolongs immersion time adsorptive capacity greater than corresponding high molecular saturated adsorption time, but sometimes be conducive to high molecular rearrangement; If immerse the time of macromolecular solution less than corresponding high molecular saturated adsorption time, shorten so immersion time adsorptive capacity and reduce, also affect the homogeneity of film and the repeatability of film preparation simultaneously.
The saturated adsorption time of heat-sensible high polymer A and two kinds of materials of heat-sensible high polymer B depends on the character of material itself, the saturated adsorption time of different substances may be different, testing method is as follows: substrate is immersed in a certain heat-sensible high polymer solution, high molecular adsorptive capacity in the equal time section monitoring substrate, can detect the variation of absorbancy or detect the variation of vibrational frequency with QCM (Quartz Crystal Microbalance) (QCM) by ultraviolet-visible spectrophotometer, when absorbancy no longer changes or vibrational frequency corresponding time when no longer changing, be the saturated adsorption time of this material just.
Method of the present invention has realized the water-soluble nano thin film technology, has well improved in the past water-soluble nano thin film technology drawback, makes the gentleer and environmental protection of assembling condition; Every layer of package thickness can be controlled by changing the assembling temperature; We have adopted the Layer by layer assembly technology, thereby can be at the substrate preparation water-soluble nano film of different shape; The dissolution rate of this type of water-soluble film can be controlled by temperature simultaneously, and controllability is very high; This film is a kind of of great value intelligent material, and this low-temperature water-soluble thin film technology method has wide practical use in fields such as biology, medicine, food, agricultural, chemical industry, intelligence sensors.
Description of drawings
The change curve of phase transition temperature after Fig. 1: PVCL mixes with the PHPA different ratios; (phase transition temperature is to obtain by the variation of measuring the transmitance of visible light (500nm) in the temperature-rise period)
Fig. 2: under 29 ℃ of temperature, at the uv-visible absorption spectra (illustration is the relation of 203nm place absorbancy and deposition cycle) of quartz plate assembling multilayer PVCL and PHPA film;
Fig. 3: pure PVCL, pure PHPA, PVCL and PHPA (mol ratio 1: 1) mixing solutions film and PVCL and PHPA at Fourier's infrared spectra of the multilayer film of 29 ℃ of assemblings;
Fig. 4: during the differing temps assembling, the multilayer film of PVCL and PHPA is in the relation of 203nm place absorbancy and temperature;
Fig. 5: when progressively reducing temperature, the relation of PVCL and PHPA multilayer film Residual fraction and temperature;
Fig. 6: the kinetics of in differing temps water, dissolving at PVCL and the PHPA multilayer film of 29 ℃ of assemblings;
Fig. 7: at 33 ℃ of uv-visible absorption spectras (illustration is the relation of 198nm place absorbancy and deposition cycle) at quartz plate assembling multilayer PVCL and P (L-HMPMAm) film;
Fig. 8: during the differing temps assembling, PVCL and P (L-HMPMAm) multilayer film is in the absorbancy at 198nm place and the relation of temperature;
Fig. 9: reduce gradually temperature, in the PVCL of 33 ℃ of assemblings and the relation of P (L-HMPMAm) multilayer film Residual fraction and temperature.
Embodiment
Embodiment 1: preparation and the water-soluble property research of Vinylcaprolactam homopolymer (PVCL) and polyacrylic acid hydroxypropyl acrylate (PHPA) multilayer film
We study phase transition temperature and the mixed phase transition temperature of different ratios of heat-sensible high polymer (PVCL and the PHPA) solution of two kinds of neutrality.The total concn of solution is 2.87mmol/L, the phase transition temperature of pure PVCL is 35.6 ℃, the phase transition temperature of pure PHPA solution is 37.2 ℃, phase transition temperature had obvious reduction (Fig. 1) after two kinds of macromolecular solutions mixed, and when the molar fraction of PVCL was 0.17, mixed phase transition temperature was 20.3 ℃, it is the lower-most point of phasor, therefore we carry out Layer by layer assembly with these two kinds of polymers, the preparation nano thin-film, and the assembling temperature is 29 ℃.Because polymer-polymer composite has temperature-responsive, thereby can regulate and control the dissolution rate of two kinds of high molecular layered assembling films in water by temperature.
Vinylcaprolactam homopolymer (PVCL) polyacrylic acid hydroxypropyl acrylate (PHPA)
Viscosity-average molecular weight: 3.8 * 10
4Weight-average molecular weight: 6.5 * 10
3
The mixing solutions (H of 98% mass concentration of quartz plate at little sulfuric acid that boils and hydrogen peroxide
2SO
4, the H of 30% mass concentration
2O
2, volume ratio V
1: V
2=70: process 30), make its surface hydroxylation, then substrate is immersed in the xylene solution of (3-aminopropyl) dimethyl methyl TMOS 12 hours, use successively afterwards dimethylbenzene, tetrahydrofuran (THF) and washed with de-ionized water clean.Substrate has amino after treatment on the surface, can be used for Layer by layer assembly.
Under 29 ℃, proceed as follows with the substrate of modified: 1. be immersed in the aqueous solution of 2.87mmol/L PVCL 10 minutes, clean 3 times (each 1 minute) of pure water washing dries up with nitrogen; 2. be immersed in the aqueous solution of 2.87mmol/L PHPA 10 minutes, clean 3 times (each 1 minute) of pure water washing dries up with nitrogen.
More than be a deposition cycle of film, repeat the nano thin-film that this process can prepare a plurality of cycles.How many cycles the film that this example obtains is
We characterize the multilayer film of preparation with the following method:
When assembling temperature during at 29 ℃, we have detected the deposition process of PVCL and PHPA multilayer film on quartz substrate with uv-visible absorption spectra, draw the deposition of PVCL and PHPA multilayer film and number of deposition cycles near linear relationship.Because absorbancy is directly proportional with the deposition of PVCL and PHPA multilayer film, so show that at the linear growth of 203nm place absorbance each double-deck deposition is constant (Fig. 2 illustration).We have also followed the tracks of the assembling process of multilayer film with QCM (Quartz Crystal Microbalance), calculating average each double-deck surface deposition density is 5.2 μ g/cm
2
By Fourier's infrared spectra, we have studied the interaction between PVCL and the PHPA, and then infer the formation reason of polymer-polymer composite.Such as Fig. 3, in the PVCL infrared spectrum, at 1636cm
-1The absorption peak at place is the stretching vibration absorption peak of free carbonyl; In the PHPA infrared spectra, 1730cm
-1The broad peak at place belongs to the carbonylic stretching vibration of two kinds of forms, 1730cm
-1The absorption peak at place is the stretching vibration absorption peak of free carbonyl, 1710cm
-1The absorption peak at place is the stretching vibration absorption peak of the carbonyl of formation hydrogen bond; In the infrared spectra of the PVCL that mixes and PHPA film, at 1615cm
-1A new absorption peak has appearred in the place, and it is because PVCL part carbonyl has formed hydrogen bond that this peak occurs, simultaneously at 1710cm
-1The absorption peak at place weakens, and illustrates that the hydrogen bond action of PHPA self weakens, and between the change indication PVCL of these spectrum and the PHPA interaction of hydrogen bond is arranged.Compare with pure PHPA, the hydroxyl absorption peak of PVCL and PHPA hybrid films is from 3420cm
-1Red shift is to 3350cm
-1, illustrate that the part of hydroxyl of PHPA and the carbonyl of PVCL have formed hydrogen bond.
In order to prove that this type of film assembling amount can regulate and control, we have done Layer by layer assembly in differing temps, such as Fig. 4.Absorbancy by the 203nm place changes, we find that temperature is higher, the assembling amount is larger, when temperature is lower than 21 ℃, the assembling amount is substantially constant, in a word, assembling amount and the temperature of PVCL and PHPA multilayer film have close relationship, we just can select suitable assembling temperature according to the requirement of every layer thickness like this, make up nano thin-film.
In order to study the dissolving properties of this type of film, we immerse 1min with PVCL and the PHPA multilayer film of 29 ℃ of assemblings in the water of gradually cooling, study the dissolution rate of film.By Fig. 5, can find out the reduction along with temperature, film dissolves gradually, when to 17 ℃, 90% film dissolving has been arranged.We have further studied the controllability of PVCL and the dissolving of PHPA nano thin-film, soak in the water of multilayer film in steady temperature that we will assemble in the time of 29 ℃, and the result who obtains at last is when differing temps, the meltage of film different (Fig. 6).In the time of 29 ℃, film does not dissolve substantially; In the time of 23 ℃, the Residual fraction of telolemma is 40%; In the time of 17 ℃, film in 1min, basic dissolve complete.These experimental results show that the dissolution rate of this type of water-soluble nano film and Residual fraction are controlled.Film 29 ℃ of preparations is insoluble in 32 ℃ water.
Embodiment 2: preparation and the water-soluble property research of Vinylcaprolactam homopolymer (PVCL) and poly-L-(methylol propyl group) Methacrylamide (P (L-HMPMAm)) multilayer film
We study phase transition temperature and the mixed phase transition temperature of different ratios of heat-sensible high polymer (PVCL and P (the L-HMPMAm)) solution of two kinds of neutrality.The total concn of solution is 2.87mmol/L, the phase transition temperature of pure PVCL and P (L-HMPMAm) solution is respectively 34.3 ℃ and 39.3 ℃, phase transition temperature also had obvious reduction after PVCL mixed with P (L-HMPMAm), when the molar fraction of P (L-HMPMAm) is 0.16, phase transition temperature is 28.4 ℃, is the phasor lower-most point.We prepare the soluble PVCL of low temperature and P (L-HMPMAm) nano thin-film by this kind method, the assembling temperature fixes on 33 ℃, assembling concentration is 2.87mmol/L, the built-up time of PVCL is 10 minutes, the built-up time of P (L-HMPMAm) is 40 minutes, identical in working method and the example 1.
Vinylcaprolactam homopolymer (PVCL) gathers L-(methylol propyl group) Methacrylamide (P (L-HMPMAm))
Viscosity-average molecular weight: 3.8 * 10
4Weight-average molecular weight: 2.5 * 10
5
Characterize by the preparation process of uv-visible absorption spectra to PVCL and P (L-HMPMAm) multilayer film, draw the absorbancy of PVCL and P (L-HMPMAm) multilayer film and deposition cycle near linear relationship (Fig. 7), and the assembling amount of PVCL and P (L-HMPMAm) multilayer film of finding reduces (Fig. 8) along with the reduction of assembling temperature.When PVCL and P (L-HMPMAm) multilayer film are immersed in the pure water, along with the progressively reduction of temperature, multilayer film is dissolved (Fig. 9) gradually.This examples prove can adopt different polymers to obtain the film of low-temperature water-soluble by this kind method.
Claims (3)
1. the method for macromolecule membrane of a preparation dissolution in low temperature in neutral aqueous solution, its step is as follows:
1. select different heat-sensible high polymer A and heat-sensible high polymer B as the assembling thing, the phase transition temperature of selected heat-sensible high polymer mixing solutions is lower than the phase transition temperature that mixes front any one heat-sensible high polymer solution;
2. 1. select a temperature to assemble between the phase transition temperature of the minimum value of the phase transition temperature of described two kinds of heat-sensible high polymer solution and mixing solutions in step, the substrate of surface with amino, carboxyl or hydroxyl is immersed in the aqueous solution of heat-sensible high polymer A, take out behind 1～30min, then be immersed in the pure water of same temperature 1～5 time, each 5s～20min, nitrogen dries up after each the taking-up; Outwell the water of using at every turn after embathing, change again clean water;
3. then above-mentioned substrate is immersed in temperature and step 2. in the aqueous solution of identical heat-sensible high polymer B, takes out behind 1～30min, then be immersed in the pure water of same temperature 1～5 time, each 10s～20min, nitrogen dries up after each the taking-up; Outwell the water of using at every turn after embathing, change again clean water; Thereby finish the preparation of a deposition cycle film in substrate;
4. repeating step 2.～3., thereby obtain the high molecular nanometer film of the water miscible dissolution in low temperature of multilayer in substrate;
Heat-sensible high polymer A and heat-sensible high polymer B are selected from PNIPAM, poly-isopropyl methyl acrylamide, poly-n-propyl acrylamide, poly-n-propyl Methacrylamide, Vinylcaprolactam homopolymer, poly-(3-ethyl-1-vinyl pyrrolidone), polyvinyl methyl ether, poly-(2-propyl group-2-oxazoline), poly-(2-sec.-propyl-2-oxazoline), the polyacrylic acid hydroxypropyl acrylate, poly-L-(methylol propyl group) Methacrylamide, poly-L-(methylol propyl group) acrylamide, methylcellulose gum, hydroxypropylcellulose, poly-N-(2-methylacryoyloxyethyl) pyrrolidone, poly-(N-(tetrahydrofuran (THF)-2-) methyl) acrylamide, poly-(N-(tetrahydrofuran (THF)-2-) methyl) Methacrylamide, poly N-vinyl butyramide or poly N-vinyl isobutyramide.
As claimed in claim 1 a kind of in neutral aqueous solution the method for macromolecule membrane of preparation dissolution in low temperature, it is characterized in that: substrate is that glass, quartz, silicon single crystal, mica, evaporation have the glass of gold or quartz, surperficial evaporation that glass, terephthalic acid condensed ethandiol ester, poly-(4-methyl-1-pentene), polyethylene, voltalef, tetrafluoroethylene, metal, molecular sieve or the anodised aluminium of indium tin oxide are arranged.
As claimed in claim 1 a kind of in neutral aqueous solution the method for macromolecule membrane of preparation dissolution in low temperature, it is characterized in that: substrate is plane, curved surface, bar-shaped, sphere or irregular surface.
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