CN101235150A - Method and device for real time monitoring surface initiating polymeric membrane growth - Google Patents
Method and device for real time monitoring surface initiating polymeric membrane growth Download PDFInfo
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- CN101235150A CN101235150A CNA2007100631348A CN200710063134A CN101235150A CN 101235150 A CN101235150 A CN 101235150A CN A2007100631348 A CNA2007100631348 A CN A2007100631348A CN 200710063134 A CN200710063134 A CN 200710063134A CN 101235150 A CN101235150 A CN 101235150A
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Abstract
The invention relates to method for detecting the growth of macromolecule membrane induced at surface real-time and a relative equipment, which utilizes quartz crystal micro balance to detect the growth of macromolecule membrane induced at surface real-time in liquid condition. The method comprises arranging a QCM chip with inducer grown at surface into a QCM sensor chamber, feeding incomplete reaction solution to reach stable starting base line, feeding complete reaction solution and recording the frequency F detected by the QCM and the frequency change delta F of converted complete reaction solution, using ellipse polarizing equipment to measure and analyze the thickness of macromolecule membrane grown on the chip to make a curvature relative to the frequency change delta F-membrane thickness. The invention can accurately and simply control the macromolecule reaction induced at surface to control the thickness of surface modification membrane of 10<-10>m.
Description
Technical field
The invention belongs to surperficial Polymer Synthesizing and modify the field, specifically relate to a kind of method of polymeric membrane growth of real time monitoring surface initiation, and device.
Background technology
The high molecular weight reactive (Surface-Initiated Polymerization is hereinafter to be referred as SIP) that cause on the surface is a kind of novel finishing (" grafting from " promptly " grafts on ") method.Compare with traditional grafting method (" grafting to " promptly " is grafted to "), the less puzzlement that is subjected to the concentration gradient obstacle of SIP method, so can be used for preparing bigger density (0.6 chain/nanometer
2) and thicker film (greater than 100nm), thereby for density (＞0.06 chain/nm that is beyond one's reach with traditional grafting method
2) macromolecule layer and the surface character can further study and better utilised.For example, as controlled high molecular polymerization method, atom transition free radical polymerization reaction (the Surface InitiatedAtom Transfer Radical Polymerization that cause on the surface, hereinafter to be referred as SI-ATRP), cause on the surface, pointedly the high molecular thickness of controlled target, density, composition specific natures such as (as block polymers).At document 1:Zhao, B.; Brittain, W.J.Macromolecules 2000,33, disclose the segmented copolymer with the method preparation of sequence carbocationic polymerization and SI-ATRP among the 8813-8820, and it can form nano-pattern, and contact angle can respective change in immersing different solvents.The macromolecule layer that cause on the novel surface of this class not only has important scientific meaning, and brings very big promotion for the development of related science technical field.For example, can be used as the macromolecule modified means in surface and extensively apply to anti-etching, colloidal stability, biosensor, biomaterial and Nano/micron processing and other fields.
Because the restriction of existing analytical technology, few people pay close attention to the research of SI-ATRP from the kinetics angle.For solution polymerization, generally be to adopt in the polymeric process, to take a sample, utilize correlation means such as nucleus magnetic resonance to study the dynamic process of reaction then.The end that this method is not suitable for SIP is fixed on epontic polymer.
Or as document 2:Matyjaszewski, K.; Miller, P.J.; Shukla, N.; Immaraporn, B.; Gelman, A.; Luokala, B.B.; Siclovan, T.M.; Kickelbick, G.; Vallant, T.; Hoffmann, H.; Pakula, T.Macromolecules 1999,32, disclosed among the 8716-8724, in the SIP process, add free initiator, study the SIP process approx with the research solution polymerization process, but proved SIP because an end fixed growth arranged, it is also inequality with the dynamic process of solution polymerization.
In theory, also can adopt, take out the method for the chip that reacts with a collection of the same terms SIP one by one and carry out dynamics research, but in the actually operating,, can destroy the necessary oxygen free condition of system like this SI-ATRP reaction in different time points.And as document 3:Ma, H.; Hyun, J.; Stiller, P.; Chilkoti, A.Adv.Mater.2004,16, disclosed among the 338-341, this method adopts the off-line characterizing method, need do a series of experiment usually, and is very loaded down with trivial details.What is more important, owing to the inherent mechanism reason of SI-ATRP, the repeatability of reaction is very low.(monomer is the oligomeric ethylene glycol methacrylic ester for example to use QCM (Quartz Crystal Microbalance) (hereinafter to be referred as QCM) the monitoring SI-ATRP reaction under five identical conditions, initiator is as mercaptan ω-mercaptoundecyl bromoisobutyrate), carry out 30 minutes to 240 minutes reaction, 5 F-t curves that obtain, as scheme shown in the l, 5 curves do not have overlapping.This is because of the initiating stage at SIP, even under identical condition, the reaction of homogeneous does not still have very big difference, especially subtract the system of promoting agent for organic solvent and nothing, so use in this in stage and traditional to get the repeated very poor of empirical curve that a method obtains one by one, thereby influenced the practical application of this method.
Summary of the invention
The object of the present invention is to provide a kind of method and apparatus of polymeric membrane growth of real time monitoring surface initiation, this method is utilized the growth of the QCM (Quartz Crystal Microbalance) polymeric membrane that real time monitoring surface causes under liquid environment, can be accurately, the high molecular weight reactive that causes of control surface easily, thereby the thickness of the finishing film that control finally obtains is accurate to 10
-10Rice.
The objective of the invention is to realize by the following technical solutions:
The invention provides a kind of method of polymeric membrane growth of real time monitoring surface initiation, comprise following step:
1) according to ordinary method on the surface of QCM chip by the fixing initiator of covalent linkage, then this surface growth is had the QCM chip of initiator to put into the qcm sensor chamber, feed nitrogen protection 5-35 minute;
Described initiator is any initiator that can cause the growth polymeric membrane on the surface, as at document 4:Matyjaszewski, K.; Xia, J.H.Chem.Rev.2001,101, disclosed among the 2921-2990, comprise bromo acid-ω-sulfydryl undecyl ester ω-mercaptoundecyl bromoisobutyrate, 11-(2-bromine) propionyloxy undecyl trichlorosilane (11-(2-Bromo) propionyloxy) undecyltrichlorosilane, 11-(2-bromo-2-methyl) propionyloxy undecyl trichlorosilane (11-(2-Bromo-2-methyl) propionyloxy) undecyltrichlorosilane etc.
2) feed incomplete reaction liquid (incomplete reaction mixture is hereinafter to be referred as IRM) 0 to 10 minute, reach stable initial baseline;
Described incomplete reaction liquid only contains solution and monomer, does not contain catalyzer;
Described monomer comprises oligomeric ethylene glycol methacrylic ester (OEGMA), methyl methacrylate (MMA), Jia Jibingxisuanyizhi (EMA) etc.;
3) then with 50-90mL h
-1Speed feeds complete reaction liquid (complete reaction mixture is hereinafter to be referred as CRM), and pipeline after promptly CRM enters fully, drops to 1-10mL h with the CRM flow velocity by the colourless redness that becomes after 1-2 minute
-1, 25 ℃ of reactions, CRM is switched to the IRM termination reaction, and reaches stable termination baseline; Frequency change Δ F before and after frequency F that record QCM monitors in this process and CRM switch; Use the polymer thickness Thickness that generates on the chip of ellipsometer test Measurement and analysis reaction back simultaneously;
Described complete reaction liquid is in step 2) added catalyzer in the described incomplete reaction liquid;
4) repeating step 1)-step 3), the reaction times that CRM feeds in the step 3) was not waited from 10-1440 minute, after at least 4 times, according to the experimental value of resulting Δ F and Thickness, make the linear corresponding curve of frequency change (Δ F)-thickness (Thickness), and the k value in definite following formula;
5) when carrying out the polymeric membrane growth of real time monitoring surface initiation, repeating step 1)-3), obtain the k value of the curve of the linear correspondence of frequency change (Δ F)-thickness (Thickness) according to step 4), calculate the pairing frequency change Δ of the thickness of wishing to get F, during this Δ F of in the qcm sensor chamber, observing CRM is switched to IRM, termination reaction, the thickness that can obtain the finishing film 50nm with interior, be accurate to 10
-10The polymeric membrane that cause on the surface of rice.
The method of the polymeric membrane growth that real time monitoring surface provided by the invention causes also is included in before the step 1), further plates the coating of metal or inorganic materials on the QCM chip surface, preferred gold and silicon; And then according to ordinary method on the surface of this QCM chip by the fixing initiator of covalent linkage.
The method of the polymeric membrane growth that real time monitoring surface provided by the invention causes, also can be between the sensor cavities of QCM (Quartz Crystal Microbalance) and peristaltic pump polyphone one reaction chamber, and in reaction chamber, be placed with more than a slice, connected with sensor cavities in the QCM chip of same initiator, can pass through monitoring, realize the chip in the reaction chamber is monitored simultaneously the sensor cavities of QCM (Quartz Crystal Microbalance).
The invention provides a kind of device of polymeric membrane growth of real time monitoring surface initiation, as shown in Figure 2, comprise a liquid storage tank 1 that is communicated with successively by pipeline, sensor cavities 2, reaction chamber 3 and the peristaltic pump 4 of QCM (Quartz Crystal Microbalance), reaction solution flows in this pipeline, is placed with the chip 5 that has been connected same initiator in the sensor cavities of described QCM (Quartz Crystal Microbalance) and the reaction chamber.
Get a method one by one with the prior art employing and compare, the method for the polymeric membrane growth that the real time monitoring surface that the present invention utilizes QCM to provide causes has many good qualities.
1) can realize real-time monitoring.Because the sampling frequency of little balance has determined present method promptly can obtain a data point in per approximately half second, and traditional get the interval that a method needs 10min at least one by one;
2) tolerance range height.Because be proved to be, initiating stage at SIP, even under identical condition, the reaction of homogeneous does not still have very big difference, especially subtract the system of promoting agent for organic solvent and nothing, so use in this in stage and traditional to get the repeated very poor of empirical curve that a method obtains one by one, thereby influenced the practical application of this method.And method of the present invention has been avoided the uncertainty of high molecular weight reactive, utilized the simple linear relationship that exists between the frequency change of quartz crystal and the polymer thickness, and by the k value relevant with monomer, the thickness of controlling diaphragm accurately, its thickness can be as accurate as
(10
-10Rice) level, the time is accurate to second, provides a kind of new method thereby accurately control thickness for needs to the application of Nano grade, and very wide industrial application is arranged;
3) among the present invention the k value by comprising monomer structure, macromolecular structure, reaction soln and temperature etc. are in interior a plurality of combined factors decisions, in the scope of thickness less than 50nm, k is a fixed constant, and promptly frequency one thickness is linear change, is convenient to the process of monitoring reaction in real time.
Description of drawings
The monitoring curve that Fig. 1 obtains SI-ATRP repeatedly for QCM; Wherein, to represent the reaction times respectively be 30,120,60,80 and 240 minutes monitoring curve to curve 1,2,3,4 and 5;
Fig. 2 carries out the QCM device synoptic diagram of the polymeric membrane growth of real time monitoring surface initiation for the present invention; Wherein, 1 liquid storage tank, the sensor cavities of 2 QCM (Quartz Crystal Microbalance), 3 reaction chambers, 4 peristaltic pumps, 5 have connected the chip of initiator, 6 waste liquid pools;
Fig. 3 is frequency one time curve of the oligomeric ethylene glycol methacrylic ester film that cause on the surface among the embodiment 1;
Fig. 4 is the linear corresponding curve of frequency change (Δ the F)-thickness (Thickness) of the oligomeric ethylene glycol methacrylic ester film that cause on the surface among the embodiment 1;
Thickness-the time curve of Fig. 5 for obtaining after transforming by linear relationship shown in Figure 4 according to the frequency-time curve among Fig. 3 among the embodiment 1;
Fig. 6 is the linear corresponding curve of frequency change (Δ the F)-thickness (Thickness) of different monomers among the embodiment 2.
Embodiment
Initiator bromo acid-ω-sulfydryl undecyl ester ω-mercaptoundecylbromoisobutyrate that the present invention uses, 11-(2-bromine) propionyloxy undecyl trichlorosilane (11-(2-Bromo) propionyloxy) undecyltrichlorosilane, 11-(2-bromo-2-methyl) propionyloxy undecyl trichlorosilane (11-(2-Bromo-2-methyl) propionyloxy) undecyltrichlorosilane and QCM chip are all available from the big Bioisystech Co., Ltd in east, Hangzhou.
QCM chips all among the present invention clean with the UV/Ozone cleaning machine, and this UV/Ozone cleaning machine is BioForce Nanosciences, IA, USA.
QCM (Quartz Crystal Microbalance) is a Q-Sense E4 transmitter, Q-Sense, Gothenburg, Sweden.
Elliptical polarization: (J.A.Woollam Co. Inc) measures thickness, and taking measurement of an angle is 65 °, and 70 ° and 75 °, measuring wavelength is that 400nm is to 800nm by M-2000V type beam split ellipsometric measurement instrument.
The sensor cavities 2 and the peristaltic pump 4 of liquid storage tank 1, QCM (Quartz Crystal Microbalance) are used pipeline connection successively, install the device that is used for the polymeric membrane growth of real time monitoring surface initiation of the present invention.
According to document 5:Bain, C.D.; Evall, J.; Whitesides, G.M.J.Am.Chem.Soc.1989,111, reported method among the 7155-7164 is introduced the polymeric initiator that is used for the oligomeric ethylene glycol methacrylic ester at the QCM chip surface of buying.Concrete steps are: the gold-plated surface of QCM chip is carried out ozone ultraviolet ray cleaning with the UV/Ozone cleaning machine, remove surface impurity; Immerse immediately after the cleaning and contain in the ethanolic soln of initiator bromo acid-ω that concentration is 1 mmole-sulfydryl undecyl ester ω-mercaptoundecyl bromoisobutyrate; spend the night; can obtain having covered the QCM chip of fine and close initiator self-assembled monolayer; then this chip is inserted Q-Sense E4 transmitter, feed nitrogen protection 15 minutes.
Be ready to IRM and CRM simultaneously.IRM forms according to following proportional arrangement: the mixed solution of water and methyl alcohol (15mL, the volume ratio of water and methyl alcohol is 1: 2), and monomer-oligomeric ethylene glycol methacrylic ester (M
n=475, OEGMA475) (8mmol 0.42M), and is kept in the rare gas element; CRM is for adding catalyzer on the basis of IRM, CuBr (36mg, 0.25mmol) and dipyridyl (78mg 0.5mmol) disposes and forms, and is garnet liquid, is kept in the rare gas element.All earlier logical nitrogen deoxygenation was 15 minutes before IRM and CRM used.
After the reaction unit nitrogen protection 15 minutes, feed IRM, obtain stable initial baseline after 0 to 10 minute.70mL h then
-1Speed feeds CRM, and pipeline after promptly CRM enters fully, drops to lmL h with the CRM flow velocity by the colourless redness that becomes after 2 minutes
-1, 25 ℃ of reactions, CRM is switched to the IRM termination reaction, and reaches stable termination baseline.In this process the frequency F that monitors of record QCM over time, as shown in Figure 3.Located at 10 minutes, frequency (F) descends, and this mainly is because the instantaneous initiation of high molecular weight reactive.After reaction caused, the controlled high molecular weight reactive of atom transfer (ATRP mechanism) made that F continues to descend.After CRM switched to IRM, the very fast arrival stable state of F.The proof high molecular weight reactive stops fully and macromolecule layer does not have the desorption phenomenon.The difference that stops between baseline and the initial baseline is because high molecular weight reactive causes frequency change (Δ F).
Chip is taken out, use methyl alcohol, washed with de-ionized water dries up under nitrogen gas stream, uses ellipsometer test Measurement and analysis thickness (Thickness).
Use new chip, repeat above-mentioned IRM-CRM-IRM process, the reaction times that CRM feeds was not waited from 10-1440 minute, after at least 4 times, experimental value according to resulting Δ F and Thickness, just can obtain the linear corresponding curve of a frequency change (Δ F)-thickness (Thickness), as shown in Figure 4.Have simple linear relationship among the figure, available following equation is represented:
N is overtone number (Overtone number) in the formula, n=3, thickness obtains for the ellipsometer test data model fits, Poly (OEGMA) adopts the Cauchy model, (An Bn) is (1.46,0.01), the thickness of sample value is the average of three position measurements, and the report result is a mean+SD.
At last, as shown in Figure 4, k=0.0609.
When carrying out the polymerization of the surperficial oligomeric ethylene glycol methacrylic ester that causes of real-time chip monitoring, repeat above-mentioned IRM-CRM-IRM process, change the linear relationship of the curve of the linear correspondence of (Δ f)-thickness (Thickness) according to Fig. 4 medium frequency, with the thickness-time curve that obtains after the frequency among Fig. 3-time curve conversion as shown in Figure 5, like this, can calculate the pairing frequency change Δ of the thickness of wishing to get F, during this Δ F of in the qcm sensor chamber, observing CRM is switched to IRM, termination reaction, the thickness that can obtain the finishing film at 50nm with interior, be accurate to 10
-10The polymeric membrane that cause on the surface of rice.For example, need obtain 25nm oligomeric ethylene glycol methacrylic ester polymeric membrane, can when respective frequencies is 450Hz, CRM be switched to IRM, termination reaction according to Fig. 4.
When needs carry out the polymeric membrane growth of real time monitoring surface initiation to multi-plate chip simultaneously, as shown in Figure 2, polyphone one needs the reaction chamber 3 of monitoring between qcm sensor and peristaltic pump, with same growth the gold-plated chip 5 of initiator mercaptan place the sensor cavities and the reaction chamber of described QCM (Quartz Crystal Microbalance) respectively, the Δ F that observes in the qcm sensor chamber is in real time corresponding to the thickness of growing in the reaction chamber, the k value that obtains according to Fig. 4, to CRM be switched to IRM at the thickness place of wishing to get, termination reaction, the thickness that can finally obtain the finishing film at 50nm with interior, be accurate to 10
-10The polymeric membrane of the oligomeric ethylene glycol methacrylic ester of rice.
Method of the present invention is suitable for too to other monomers, is in the 50nm at thickness limit, and the experimental result that obtains is listed in table 1 as shown in Figure 6.
When the ellipsometer test data model fitted thickness, the QCM chip of initiator self-assembled monolayer adopted the Cauchy model, and (An Bn) is (1.45,0.01), the model that PMMA adopts manufacturers to provide for it.
Table 1, k value depend on monomer
Claims (7)
1. the method for the polymeric membrane growth that causes of a real time monitoring surface comprises following step:
1) fixes the initiator that can cause the growth polymeric membrane by covalent linkage on the surface of quartz crystal micro-balance chip on the surface, there is the quartz crystal micro-balance chip of initiator to put into the sensor cavities of QCM (Quartz Crystal Microbalance) this surface growth then, feeds nitrogen protection;
2) feed incomplete reaction liquid 0 to 10 minute, reach stable initial baseline;
Described incomplete reaction liquid only contains solution and monomer, does not contain catalyzer;
3) then with 50-90mL h
-1Speed feeds after complete reaction liquid enters fully to it, and the flow velocity of complete reaction liquid is dropped to 1-10mL h
-1, 25 ℃ of reactions, complete reaction liquid is switched to incomplete reaction liquid, termination reaction, and reach stable termination baseline; Frequency F that the record QCM (Quartz Crystal Microbalance) monitors in this process and the frequency change Δ F that switches front and back; Use the polymer thickness that generates on the chip of ellipsometer test Measurement and analysis reaction back simultaneously;
Described complete reaction liquid is in step 2) added catalyzer in the described incomplete reaction liquid;
4) repeating step 1)-step 3), the reaction times that complete reaction liquid feeds in the step 3) was not waited from 10-1440 minute, after at least 4 times, according to the experimental value of resulting Δ F and thickness, make the linear corresponding curve of frequency change Δ F-thickness, and the k value in definite following formula;
5) when carrying out the polymeric membrane growth of real time monitoring surface initiation, repeating step 1)-3), obtain the k value of the curve of the linear correspondence of frequency change Δ F-thickness according to step 4), calculate the pairing frequency change Δ of the thickness of wishing to get F, during this Δ F of in the quartz crystal microbalance sensor chamber, observing complete reaction liquid is switched to incomplete reaction liquid, termination reaction, the thickness that can obtain the finishing film 50nm with interior, be accurate to 10
-10The polymeric membrane that cause on the surface of rice.
2. the method for the polymeric membrane growth that real time monitoring surface as claimed in claim 1 causes, it is characterized in that: described initiator is bromo acid-ω-sulfydryl undecyl ester, 11-(2-bromine) propionyloxy undecyl trichlorosilane or 11-(2-bromo-2-methyl) propionyloxy undecyl trichlorosilane.
3. the method for the polymeric membrane growth that real time monitoring surface as claimed in claim 1 causes is characterized in that: the time that described step 1) feeds nitrogen protection is 5-35 minute.
4. the method for the polymeric membrane growth that real time monitoring surface as claimed in claim 1 causes, it is characterized in that: described monomer is oligomeric ethylene glycol methacrylic ester, methyl methacrylate or Jia Jibingxisuanyizhi.
5. the method for the polymeric membrane growth that real time monitoring surface as claimed in claim 1 causes is characterized in that: also be included in before the step 1), further plate the coating of metal or inorganic materials on the quartz crystal micro-balance chip surface.
6. the method for the polymeric membrane growth that real time monitoring surface as claimed in claim 5 causes, it is characterized in that: described coating is the coating of gold or silicon.
7. the device of the polymeric membrane growth that causes of a real time monitoring surface, comprise a liquid storage tank that is communicated with successively by pipeline, sensor cavities, reaction chamber and the peristaltic pump of QCM (Quartz Crystal Microbalance), reaction solution flows in this pipeline, is placed with the chip that has been connected same initiator in the sensor cavities of described QCM (Quartz Crystal Microbalance) and the reaction chamber.
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| JP2010057745A (en) * | 2008-09-04 | 2010-03-18 | Osaka Organic Chem Ind Ltd | Medical material |
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| CN108627380A (en) * | 2017-03-15 | 2018-10-09 | 中国人民解放军军事医学科学院毒物药物研究所 | The method for removing or reducing the method for noxious material and detecting noxious material |
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