CN103755939A - Hydroxyl-terminated hyperbranched polyurethane-ester polymer as well as modified micro-fluidic chip and application thereof - Google Patents
Hydroxyl-terminated hyperbranched polyurethane-ester polymer as well as modified micro-fluidic chip and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of pesticide residue detection, and in particular relates to a hydroxyl-terminated hyperbranched polyurethane-ester polymer. The hydroxyl-terminated hyperbranched polyurethane-ester polymer is prepared by the following steps: implementing reaction between diisopropanol amine and methyl acrylate which are equal in molar mass to obtain an AB2 monomer; and carrying out reaction among AB2 monomer, p-toluenesulfonic acid and triethanolamine to obtain the hydroxyl-terminated hyperbranched polyurethane-ester polymer. The invention further relates to a hyperbranched polymer modified polydimethyl siloxane (PDMS) micro-fluidic chip and application of the hyperbranched polymer in the technical field of pesticide residue detection. The prepared PDMS micro-fluidic chip disclosed by the invention has permanent hydrophilcity, and is capable of effectively improving stability of a polymer coating, free from use of expensive instrument and reasonable in price; and the coated capillary has the characteristics of small size, simple operation, low sample dosage, high separation efficiency and high analysis speed, and is capable of separating and detecting organic pesticide residue very well.
Description
Technical field
The present invention relates to the Detection Technologies of Pesticide Residues field, particularly a kind of superbrnaching end-hydroxy polyamine-ester polymer, also relates to described hyperbranched polymer modification PDMS(polydimethylsiloxane) application of micro-fluidic chip in the Detection Technologies of Pesticide Residues field.
Background technology
At present, China has become second largest agricultural chemicals in the world and has used state, and particularly concerning vegetative period short vegetables, melon and fruit based food, because insect pest is many, excess dispenser, causes the pesticide residue phenomenon that exceeds standard day by day to increase the weight of.Organic pesticide life-time service it is easily adsorbed in the soil organism, and can absorb and enter food chain by plant, be there is to potential threat in ecotope and HUMAN HEALTH, therefore in food, Organic pesticide residues problem receives people's concern always, and it is one of key link of controlling vegetable soil Pesticide Residues that the residual quantity of vegetable soil Pesticides is carried out analyzing in time and accurately, detecting.
Micro-fluidic chip claims again chip lab, to adopt Micrometer-Nanometer Processing Technology, on the chip of more than square centimeters, produce microchannel network structure and other functional units, and the elementary operations such as sample introduction, pre-treatment, biology and chemical reaction, separation and detection are integrated in to a new technology of carrying out on chip.This technology has that volume is little, simple to operate, separation efficiency is high, amount of samples is few, analysis speed is fast, operate the features such as easy automatization, has been acknowledged as one of of paramount importance cutting edge technology of 21 century.The concern that micro-fluidic chip take polydimethylsiloxane as representative has low price, is easy to processing, stable chemical performance and the excellent properties such as good light transmission and dielectricity are more and more subject to people.
But, dimethyl silicone polymer micro flow control chip itself also exists some defects, as the hydrophobicity of surface elevation, make the sample molecules such as organic pesticide because the reason strong adsorption such as hydrophobic interaction are in its microchannel surface, cause the repeatability of detached peaks hangover broadening, separation efficiency and transition time to decline, adsorb when serious and can cause separating unsuccessfully, even form irreversible adsorption and make to separate and cannot carry out; And, the surperficial heterogeneity of PDMS micro-fluidic chip microchannel, electroosmotic flow is unstable, easily with the variation of ambient conditions, changes the separating effect of impact to organic pesticide.Therefore, be necessary the modifying surface of PDMS micro-fluidic chip to suppress the absorption to organic pesticide sample, improve its separation performance.
China Patent No. is that the patent of CN201010534403 discloses a kind of superbrnaching end-hydroxy polyamine-ester polymer, micro-fluidic chip after this polymer modification, for the DeGrain of while separation detection Multiple Pesticides, the invention provides one and through Michael addition, prepares AB with methyl acrylate and diisopropanolamine (DIPA)
2monomer, the novel hyperbranched polyamine-ester making through transesterification reaction take trolamine as core molecule, the globosity inside of this space multistory hyperbranched polymer a large amount of methyl that distributed, make the inner reticulated structure of spheroid spatially more fine and close, the inner group of this hyperbranched polymer direction of extension spatially influences each other, form a finer and close ball shape structure, take trolamine as core molecule with TriMethylolPropane(TMP) compared with core molecule, make spatially even calibration of three branches of hyperbranched polymer, make this polymkeric substance closer to Spatial Sphere body structure, cavity is larger.A large amount of end active groups is contained again in hyperbranched polyamine-ester outside, when organic pesticide small molecules passes through internal cavities, hyperbranched polyamine-ester realizes good separation to the attached asynchronism(-nization) of grabbing of different pesticide molecules, and it is clear that detected peaks separates, and peak type is sharp-pointed without hangover.
Hyperbranched polymer has highly branched, three-dimensional netted three-dimensional arrangement feature, with conventional linear polymer phase ratio, the features such as it has low viscosity, high resolution, be difficult for crystallization, intermolecular difficult winding, a large amount of functional end-group and strong chemical reactivity, being widely used aspect surface modification, paint field, pharmaceutical carrier etc., so also need it to carry out darker, farther research.
Summary of the invention
In order to solve the more existing defects of dimethyl silicone polymer micro flow control chip, the invention provides the superbrnaching end-hydroxy polyamine-ester polymer that a kind of end that is different from structure in patent CN201010534403 contains a large amount of terminal hydroxy group.
The present invention also provides the dimethyl silicone polymer micro flow control chip of above-mentioned superbrnaching end-hydroxy polyamine-ester polymer modification, suppresses the absorption to analyte, improves separating effect.
Another object of the present invention has been to provide the application of the above-mentioned dimethyl silicone polymer micro flow control chip through the modification of superbrnaching end-hydroxy polyamine-ester polymer in Detecting Pesticide.
The present invention is achieved by the following measures:
A kind of superbrnaching end-hydroxy polyamine-ester polymer, obtains by following steps:
(1) get equimolar diisopropanolamine (DIPA) and methyl acrylate, reaction obtains AB
2monomer;
(2) by AB
2monomer, tosic acid and trolamine reaction, obtain superbrnaching end-hydroxy polyamine-ester polymer.
Described superbrnaching end-hydroxy polyamine-ester polymer, at 35 ℃ of reaction 4h, reacts 24h at 85 ℃ in step (2) in step (1).
Described superbrnaching end-hydroxy polyamine-ester polymer,
As trolamine and AB
2when the mol ratio of monomer is 1:9, obtain s-generation superbrnaching end-hydroxy polyamine-ester polymer;
As trolamine and AB
2when the mol ratio of monomer is 1:21, obtain third generation superbrnaching end-hydroxy polyamine-ester polymer;
As trolamine and AB
2when the mol ratio of monomer is 1:45, obtain the 4th generation superbrnaching end-hydroxy polyamine-ester polymer.
Described superbrnaching end-hydroxy polyamine-ester polymer,
S-generation superbrnaching end-hydroxy polyamine-ester polymer molecular structural formula is as follows:
Third generation superbrnaching end-hydroxy polyamine-ester polymer molecular structural formula is as follows:
The 4th generation superbrnaching end-hydroxy polyamine-ester polymer molecular structural formula as follows:
, on the internal surface of the microchannel of dimethyl silicone polymer micro flow control chip, there is silane coupling agent and superbrnaching end-hydroxy polyamine-ester polymer in the dimethyl silicone polymer micro flow control chip of described superbrnaching end-hydroxy polyamine-ester polymer modification.
Described dimethyl silicone polymer micro flow control chip, obtains by following steps:
Silane coupling agent is pressed in dimethyl silicone polymer micro flow control chip microchannel with nitrogen, put into the baking oven reaction 40min of 105 ℃-115 ℃, then the methanol solution that contains superbrnaching end-hydroxy polyamine-ester and catalyzer is pressed in microchannel, at 55 ℃-65 ℃, react 4h, repeatedly rinse microchannel with distilled water, with nitrogen, dry up again, obtain the dimethyl silicone polymer micro flow control chip of superbrnaching end-hydroxy polyamine-ester modification.
Described dimethyl silicone polymer micro flow control chip, passing into before silane coupling agent, carries out pre-treatment to dimethyl silicone polymer micro flow control chip: with NaOH and H
2o
2mixed aqueous solution is oxidized dimethyl silicone polymer micro flow control chip substrate, keeps in Dark Place and takes out and another polydimethylsiloxane cover plate sealing-in afterwards for three days, obtains the dimethyl silicone polymer micro flow control chip of modification.In step (b), the concentration of NaOH solution is 1mol/L, H
2o
2the massfraction of solution is 30%, V(NaOH): V(H
2o
2)=1:4
Described dimethyl silicone polymer micro flow control chip, described silane coupling agent is γ-glycidoxypropyltrime,hoxysilane, with the s-generation, the third generation, the 4th generation superbrnaching end-hydroxy polyamine-ester mol ratio be respectively 4:1,8:1,16:1, described catalyzer is boron trifluoride ethyl ether, is the 0.1-0.5% of superbrnaching end-hydroxy polyamine-ester polymer quality.
The application of described dimethyl silicone polymer micro flow control chip in Detecting Pesticide.
Described agricultural chemicals is SD-1750, Malathion, Volaton, triazophos or Chlorpyrifos 94.
γ-glycidoxypropyltrime,hoxysilane of using in the present invention is a kind of silicoorganic compound with special construction.Si-OCH is contained in one end of its molecule
3can react with the Si-OH on the PDMS surface of processing through oxygen atmosphere, the other end of its molecule contain epoxy group(ing) can with the hydroxyl reaction of hyperbranched polyamine-ester end, thereby grafted by super branched polymer, to PDMS micro-fluidic chip surface, is arrived to the object of surface modification.Hyperbranched polyamine-ester have low viscosity high-dissolvability can overcome simple linear polymer in modification, have high viscosity stop up problem, simultaneously hyperbranched polyamine-ester end contain a large amount of terminal hydroxy group and stereoscopic three-dimensional reticulated structure can be well and PDMS micro-fluidic chip bonding, improve surface hydrophilicity and effectively suppress the absorption to organic pesticide molecule, improve separating effect.
Beneficial effect of the present invention: the present invention has synthesized a kind of novel hyperbranched polyamine-ester polymkeric substance, its molecular end contains a large amount of terminal hydroxy group has effectively improved the wetting ability of PDMS, be made into a kind of PDMS micro-fluidic chip, for the separation detection of organic pesticide, it is little that this device has volume, simple to operate, amount of samples is few, analysis speed is fast, operate easy automatization, cost is low, the features such as many residual detections simultaneously, the method can vigorously promote the use, can save the spending of country for Detecting Pesticide, improved the sensitivity detecting, for human consumer's health provides guarantee.
Accompanying drawing explanation
Fig. 1 second, third, the 4th generation superbrnaching end-hydroxy polyamine-ester molecule infrared spectrogram;
Fig. 2 PDMS micro-fluidic chip pre-treatment schematic diagram;
The unmodified PDMS micro-fluidic chip of Fig. 3 and through the electroosmotic flow of the PDMS micro-fluidic chip of the s-generation, the third generation, the superbrnaching end-hydroxy polyamine-ester modification of the 4th generation;
The contact angle of the unmodified micro-fluidic chip of Fig. 4;
Fig. 5 is through the contact angle of the micro-fluidic coated chip of s-generation hyperbranched polyamine-ester modification;
Fig. 6 is through the contact angle of the micro-fluidic coated chip of third generation hyperbranched polyamine-ester modification;
Fig. 7 is through the contact angle of the micro-fluidic coated chip of the 4th generation hyperbranched polyamine-ester modification;
The fluorescence photo of the PDMS micro-fluidic chip of the 4th generation hyperbranched polyamine-ester modification that Fig. 8 end contains fluorophor;
Fig. 9 separates SD-1750, Malathion, Volaton, triazophos, Chlorpyrifos 94 separation graph through the PDMS micro-fluidic chip of s-generation hyperbranched polyamine-ester modification;
Figure 10 separates SD-1750, Malathion, Volaton, triazophos, Chlorpyrifos 94 separation graph through the PDMS micro-fluidic chip of third generation hyperbranched polyamine-ester modification;
Figure 11 separates SD-1750, Malathion, Volaton, triazophos, Chlorpyrifos 94 separation graph through the PDMS micro-fluidic chip of the 4th generation hyperbranched polyamine-ester modification;
Figure 12 separates SD-1750, Malathion, Volaton, triazophos, Chlorpyrifos 94 separation graph through the PDMS of S4 modification micro-fluidic chip.
Embodiment
By specific embodiment, the present invention is further set forth below, should indicate, following explanation is only in order to explain the present invention, its content is not limited.
embodiment 1preparation s-generation superbrnaching end-hydroxy polyamine-ester polymer
In 250 mL there-necked flasks, lead to nitrogen 10 min, get 26.638g diisopropanolamine (DIPA), 17.218g methyl acrylate and 10 ml methyl alcohol, after mixing in small beaker, add in there-necked flask, mixture is logical nitrogen 10 min at room temperature, stir 30 min and be warming up to 40 ℃ of reaction 4 h, methyl alcohol is removed in underpressure distillation, obtains water white transparency oily AB
2monomer, reaction formula is as follows.
In 250 mL four-hole bottles, lead to nitrogen 10 min, add the synthetic AB of 9.8676g
2monomer, 0.0493 g tosic acid and 0.74595g trolamine, be warming up to 85 ℃, continue logical nitrogen, stirring reaction 24 h, underpressure distillation, except methyl alcohol and unreacted micromolecular compound in dereaction, obtains s-generation superbrnaching end-hydroxy polyamine amine-ester polymkeric substance again.Wherein, trolamine and AB
2the mol ratio of monomer is 1:9.As indicated earlier, reaction formula is as follows for the structural formula of s-generation superbrnaching end-hydroxy polyamine-ester polymer.
embodiment 2prepare third generation superbrnaching end-hydroxy polyamine-ester polymer
In 250 mL four-hole bottles, lead to nitrogen 10 min, add the AB of 21.928g embodiment 1 synthesized
2monomer, 0.1096g tosic acid and 0.74595g trolamine, be warming up to 85 ℃, continue logical nitrogen, stirring reaction 24 h, underpressure distillation, except methyl alcohol and unreacted micromolecular compound in dereaction, obtains third generation superbrnaching end-hydroxy polyamine-ester polymer again.Wherein, trolamine and AB
2the mol ratio of monomer is 1:21, and the structural formula of third generation superbrnaching end-hydroxy polyamine-ester polymer as indicated earlier.
embodiment 3prepare the 4th generation superbrnaching end-hydroxy polyamine-ester polymer
In 250 mL four-hole bottles, lead to nitrogen 10 min, add the AB of 43.856g embodiment 1 synthesized
2monomer, 0.2193g tosic acid and 0.74595g trolamine, be warming up to 85 ℃, continue logical nitrogen, stirring reaction 24 h, underpressure distillation is except methyl alcohol and unreacted micromolecular compound in dereaction again, obtain the 4th generation superbrnaching end-hydroxy polyamine-ester polymer.Wherein, trolamine and AB
2the mol ratio of monomer is 1:45, the 4th generation superbrnaching end-hydroxy polyamine-ester polymer structural formula as indicated earlier.
embodiment 4prepare end contain fluorophor the 4th generation hyperbranched polyamine-ester
To add in 250 mL four-hole bottles 10g embodiment 3 synthesizeds the 4th generation superbrnaching end-hydroxy polyamine-ester polymer, 0.05g tosic acid and 7.9303g methyl p-hydroxybenzoate, be warming up to 80 ℃, stirring reaction 24 h, underpressure distillation is except methyl alcohol and unreacted micromolecular compound in dereaction again, obtain end contain fluorophor the 4th generation hyperbranched polyamine-ester polymkeric substance, because phenyl ring has larger sterically hindered, not every hyperbranched terminal hydroxy group all can grafting on fluorophor, but hyperbranched polymer end can be connected to part fluorophor, end contain fluorophor the 4th generation superbrnaching end-hydroxy polyamine-ester polymer structural formula as follows.
embodiment 5the making of PDMS micro-fluidic chip
(1) prepare PDMS micro-fluidic chip substrate:
With two T-shape micro-fluidic chips microchannel of CAD software design, split tunnel width design is 50 μ m, length 4 cm; Sample intake passage width design is 50 μ m; Terminal part connecting passage width design is 200 μ m, length 1 cm.According to the design of CAD drawing, using even glue chromium plate sheet glass as substrate, make passage by lithography, in glass erosion liquid, erode away passage, remove photoresist material and chromium layer, obtain the substrate with microchannel, by uv-exposure, make SU-8 adhesive curing, on silicon chip, prepare formpiston.Micro-fluidic chip prepolymer and the initiator in mass ratio ratio of 10:1 mix, and vacuum outgas, casts in mixture on mould, and 75 ℃ of curing 2h peel off mould and obtain PDMS micro-fluidic chip substrate.
The pre-treatment of PDMS micro-fluidic chip:
PDMS micro-fluidic chip substrate is oxidized in oxygen atmosphere, in 250 mL reagent bottles, adds the NaOH aqueous solution of 10 mL 1 mol/L and the H that 40mL massfraction is 30%
2o
2the aqueous solution, mixes, and adds a cover and establishes a single-way gas-discharge valve covering, and the oxygen that reaction is produced is full of bottle.The PDMS micro-fluidic chip substrate of clean dried is inserted in bottle and more than being fixed on liquid level, keep in Dark Place, after 3d, take out and another dry clean smooth PDMS cover plate sealing-in the PDMS micro-fluidic chip having obtained.
embodiment 6the wetting ability PDMS micro-fluidic chip of preparation s-generation hyperbranched polyamine-ester modification
Getting γ-glycidoxypropyltrime,hoxysilane, to be made into massfraction be that 10% methanol solution nitrogen is pressed in PDMS micro-fluidic chip microchannel, the flow velocity of controlling nitrogen reacts 40min at 110 ℃, obtain the PDMS micro-fluidic chip of silane coupling agent graft modification, then 9.17175g s-generation hyperbranched polyamine-ester is made into massfraction and is 10% methanol solution, the mixing solutions nitrogen that wherein contains 2.5% the boron trifluoride ethyl ether catalyzer that accounts for hyperbranched polymer quality is pressed in microchannel, the mol ratio of γ-glycidoxypropyltrime,hoxysilane and s-generation hyperbranched polyamine-ester polymkeric substance is 4:1, control 60 ℃ of reaction 4h of nitrogen flow rate, repeatedly rinse microchannel with intermediate water, with nitrogen, dry up again, obtain the wetting ability PDMS micro-fluidic chip of s-generation hyperbranched polyamine-ester modification, modifying process principle as shown in Figure 2.
embodiment 7prepare the wetting ability PDMS micro-fluidic chip of third generation hyperbranched polyamine-ester modification
Modifying process is as embodiment 5, s-generation hyperbranched polyamine-ester in embodiment 5 is changed to s-generation hyperbranched polyamine-ester, the mol ratio of γ-glycidoxypropyltrime,hoxysilane and third generation hyperbranched polyamine-ester polymkeric substance is 8:1, can obtain the wetting ability PDMS micro-fluidic chip of third generation hyperbranched polyamine-ester modification.
embodiment 8prepare the wetting ability PDMS micro-fluidic chip of the 4th generation hyperbranched polyamine-ester modification
Modifying process is as embodiment 5, by the s-generation hyperbranched polyamine-ester in embodiment 5 be changed to the 4th generation hyperbranched polyamine-ester, γ-glycidoxypropyltrime,hoxysilane and the 4th generation hyperbranched polyamine-ester polymkeric substance mol ratio be 16:1, can obtain the wetting ability PDMS micro-fluidic chip of the 4th generation hyperbranched polyamine-ester modification.
embodiment 9prepare the wetting ability PDMS micro-fluidic chip of the 4th generation hyperbranched polyamine-ester modification that end contains fluorophor
Modifying process is as embodiment 6, by the s-generation hyperbranched polyamine-ester in embodiment 6 be changed to end contain fluorophor the 4th generation hyperbranched polyamine-ester, although the molecular end of that fluorophor has active group in grafting, do not affect the making of the wetting ability PDMS micro-fluidic chip of the 4th generation hyperbranched polyamine-ester modification that contains fluorophor, by embodiment six, can obtain the wetting ability PDMS micro-fluidic chip of the 4th generation hyperbranched polyamine-ester modification.
The s-generation that above-described embodiment 1,2,3 is obtained, the third generation, the 4th generation superbrnaching end-hydroxy polyamine-ester carry out Infrared Characterization, as shown in Figure 1, three generations's hyperbranched polyamine-ester is at 3400cm for its absorption peak
-1there is obvious absorption peak left and right, and this hyperbranched polyamine-ester end that shows synthesized contains a large amount of hydroxyl activity groups, can improve well the hydrophobicity on PDMS micro-fluidic chip surface.
Unmodified PDMS micro-fluidic chip and embodiment 5 that above-described embodiment 5 is obtained, 6, 7 s-generations that obtain, the third generation, in the wetting ability PDMS micro-fluidic chip of the 4th generation superbrnaching end-hydroxy polyamine-ester modification, being full of pH is 8.2, concentration is boric acid-borax buffer solution of 40mmol/L, wash away continuously 8h every day, wash away continuously 20 days, measure the electroosmotic flow of coated chip, as shown in Figure 3, discovery is along with the increase of number of days, electroosmotic flow intensity of variation is very little, illustrate that the hyperbranched polyamine-ester coating being coated in PDMS micro-fluidic chip microchannel surface has satisfactory stability, it can also be seen that compared with unmodified PDMS micro-fluidic chip simultaneously, chip electroosmotic flow after modification significantly reduces, this explanation coating has played the effect that suppresses the ionization of silicon methyl, thereby effectively reduce electroosmotic flow.
The wetting ability PDMS micro-fluidic chip of the s-generation that the unmodified PDMS micro-fluidic chip that above-described embodiment 5 is obtained and embodiment 6,7,8 obtain, the third generation, the superbrnaching end-hydroxy polyamine-ester modification of the 4th generation carries out the mensuration of surface contact angle, at room temperature by two, drip and drop on chip surface, the contact angle of measuring chip surface water after 30s, result shows: the chip surface contact angle of uncoated modification is 105 ° (Fig. 4); The contact angle of the micro-fluidic chip applying through s-generation hyperbranched polyamine-ester is 58.9 ° (Fig. 5); 36.1 ° of the contact angles (Fig. 6) of the micro-fluidic chip applying through third generation hyperbranched polyamine-ester; Through the 4th generation the contact angle of micro-fluidic coated chip that applies of hyperbranched polyamine-ester be 32.3 ° (Fig. 7), this illustrates that the contact angle on the PDMS micro-fluidic chip surface after modification has had significantly reduction, make chip surface change wetting ability into, made up the deficiency of PDMS micro-fluidic chip surface hydrophobicity.
The wetting ability PDMS micro-fluidic chip of the 4th generation hyperbranched polyamine-ester modification that the end that above-described embodiment 9 is obtained contains fluorophor, under excitation wavelength 450-480nm, adopt fluorescent microscope to take fluorescence photo (Fig. 8), by the provable hyperbranched polyamine-ester of figure, really can be grafted to micro-fluidic chip surface, and form from the teeth outwards the coating of one deck densification.The feasibility of utilizing hyperbranched polyamine-ester modification PDMS micro-fluidic chip to be used for preparing micro-fluidic chip coating column is described.
test case 5
With PH=8.2, boric acid-borax buffer solution of 40mmol/L is runtime buffer solution, separation voltage is 18KV, detection wavelength is 220nm, unmodified PDMS micro-fluidic chip and embodiment 6 that above-described embodiment 5 is obtained, 7, 8 s-generations that obtain, the third generation, the wetting ability PDMS micro-fluidic chip of the 4th generation superbrnaching end-hydroxy polyamine-ester modification is respectively to SD-1750, triazophos, Chlorpyrifos 94, Malathion, five kinds of agricultural chemicals of Volaton carry out separation detection, unmodified micro-fluidic chip can not be realized effective separation to five kinds of agricultural chemicals, this is mainly because microflow controlled chip internal-surface is to due to the absorption of organic pesticide molecule, through the s-generation, the third generation, the separation spectrogram of the wetting ability PDMS micro-fluidic chip of the 4th generation superbrnaching end-hydroxy polyamine-ester modification is respectively Fig. 9, Figure 10, shown in Figure 11.
From the electrophoretic image separating, can find out, through the chip applying, five kinds of agricultural chemicals have been realized to good separation, especially the detached peaks obtaining through the third generation, the chip of the 4th generation coating modification is clear, peak type is sharp-pointed, illustrate that coated chip has effectively suppressed the absorption to organic pesticide, has improved separation performance.
In the wetting ability PDMS micro-fluidic chip of the s-generation that above-described embodiment 6,7,8 is obtained, the third generation, the superbrnaching end-hydroxy polyamine-ester modification of the 4th generation and the patent that the patent No. is CN201010534403, the micro-fluidic chip of the s-generation, the third generation, the superbrnaching end-hydroxy polyamine-ester modification of the 4th generation is (with S2, S3, S4 representative) under identical testing conditions, respectively SD-1750, triazophos, Chlorpyrifos 94, Malathion, five kinds of agricultural chemicals of Volaton are carried out to separation detection, its separation performance is compared.S2, the chip of S3 fails to detect completely the detached peaks of five kinds of organic pesticide, unrealized effective separation, S4 to the separation spectrogram of five kinds of organophosphorus pesticides as shown in figure 12, by spectrogram, can find out that S4 can detect five kinds of detached peakses, but can not realize completely, separate, through G2, G3, G4 generation hyperbranched coated chip with the transition time of S4 coated chip, post imitate and resolution as shown in table 1, table 2.
Table 1 hyperbranched polyamine-ester separator column effect contrast table
Table 2 hyperbranched polyurethane resolution contrast table
From table 1, table 2, can find out, through G2, G3, G4 for the theoretical plate number of the PDMS micro-fluidic chip of hyperbranched polyamine-ester modification the chip far above S4 modification, the resolution in G2, G3, G4 generation is also high than the resolution of S4 modification chip, the hyperbranched polyamine-ester that it can be said that bright novel texture can better separate organic pesticide molecule, realize fast and effectively the baseline separation of five kinds of agricultural chemicals, improve separation efficiency.This separation performance that further illustrates the PDMS micro-fluidic chip after the modification of novel texture hyperbranched polymer is significantly improved.
The present invention is not limited only to the above five kinds of agricultural chemicals of separation detection, and the organic pesticide such as organophosphorus, organochlorine, carbamate, pyrethroid all can use this micro-fluidic chip coating column to carry out separation detection.
3 superbrnaching end-hydroxy polyamine-ester polymers that molecular structure is more regular in above-described embodiment, have just been enumerated, trolamine and AB
2the mol ratio of monomer is the polymkeric substance that other ratios obtain, and also can realize above-mentioned functions, just considers as space is limited, cannot more enumerate.
Above embodiment is the detailed description that the present invention is carried out; its object is to illustrate design of the present invention and feature; can not limit the scope of the invention with this, all equivalences that spirit is done according to the present invention change or modify, within all should being encompassed in protection scope of the present invention.
Claims (10)
1. a superbrnaching end-hydroxy polyamine-ester polymer, is characterized in that obtaining by following steps:
(1) get equimolar diisopropanolamine (DIPA) and methyl acrylate, reaction obtains AB
2monomer;
(2) by AB
2monomer, tosic acid and trolamine reaction, obtain superbrnaching end-hydroxy polyamine-ester polymer.
2. superbrnaching end-hydroxy polyamine-ester polymer according to claim 1, is characterized in that at 35 ℃, reacting 4h in step (1), in step (2), at 85 ℃, reacts 24h.
3. superbrnaching end-hydroxy polyamine-ester polymer according to claim 1, is characterized in that
As trolamine and AB
2when the mol ratio of monomer is 1:9, obtain s-generation superbrnaching end-hydroxy polyamine-ester polymer;
As trolamine and AB
2when the mol ratio of monomer is 1:21, obtain third generation superbrnaching end-hydroxy polyamine-ester polymer;
As trolamine and AB
2when the mol ratio of monomer is 1:45, obtain the 4th generation superbrnaching end-hydroxy polyamine-ester polymer.
4. superbrnaching end-hydroxy polyamine-ester polymer according to claim 3, is characterized in that
S-generation superbrnaching end-hydroxy polyamine-ester polymer molecular structural formula is as follows:
Third generation superbrnaching end-hydroxy polyamine-ester polymer molecular structural formula is as follows:
The 4th generation superbrnaching end-hydroxy polyamine-ester polymer molecular structural formula as follows:
5. a dimethyl silicone polymer micro flow control chip for the superbrnaching end-hydroxy polyamine-ester polymer modification described in any one in claim 1-4, is characterized in that existing silane coupling agent and superbrnaching end-hydroxy polyamine-ester polymer on the internal surface of the microchannel of dimethyl silicone polymer micro flow control chip.
6. dimethyl silicone polymer micro flow control chip according to claim 5, is characterized in that obtaining by following steps:
Silane coupling agent is pressed in dimethyl silicone polymer micro flow control chip microchannel with nitrogen, at 105 ℃-115 ℃, react 40min, then the methanol solution that contains superbrnaching end-hydroxy polyamine-ester and catalyzer is pressed in microchannel, at 55 ℃-65 ℃, react 4h, repeatedly rinse microchannel with distilled water, with nitrogen, dry up again, obtain the dimethyl silicone polymer micro flow control chip of superbrnaching end-hydroxy polyamine-ester modification.
7. dimethyl silicone polymer micro flow control chip according to claim 6, is characterized in that, passing into before silane coupling agent, dimethyl silicone polymer micro flow control chip being carried out to pre-treatment: with NaOH and H
2o
2mixed aqueous solution is oxidized dimethyl silicone polymer micro flow control chip substrate, keeps in Dark Place and takes out and another polydimethylsiloxane cover plate sealing-in afterwards for three days, obtains the dimethyl silicone polymer micro flow control chip of modification.
8. according to the dimethyl silicone polymer micro flow control chip described in claim 6 or 7, it is characterized in that described silane coupling agent is γ-glycidoxypropyltrime,hoxysilane, with the mol ratio of superbrnaching end-hydroxy polyamine-ester polymer be 4-16:1, described catalyzer is boron trifluoride ethyl ether, is the 0.1-0.5% of superbrnaching end-hydroxy polyamine-ester polymer quality.
9. the application of the dimethyl silicone polymer micro flow control chip described in any one in Organic pesticide residues detects in a claim 5-8.
10. application according to claim 9, is characterized in that described agricultural chemicals is SD-1750, Malathion, Volaton, triazophos or Chlorpyrifos 94.
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| CN107561169A (en) * | 2016-07-01 | 2018-01-09 | 彤程化学（中国）有限公司 | The resolution and quantitative analysis method of p-methyl benzenesulfonic acid triethanolamine salt in phenolic resin |
| CN112574428A (en) * | 2020-12-16 | 2021-03-30 | 济南大学 | Hyperbranched fluorine-containing silicon high-temperature-resistant release agent and application thereof |
| CN114890694A (en) * | 2022-04-13 | 2022-08-12 | 安徽永茂泰环保科技有限公司 | Cement material based on aluminum ash recycling and preparation method thereof |
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| CN112574428A (en) * | 2020-12-16 | 2021-03-30 | 济南大学 | Hyperbranched fluorine-containing silicon high-temperature-resistant release agent and application thereof |
| CN112574428B (en) * | 2020-12-16 | 2022-04-12 | 济南大学 | Hyperbranched fluorine-containing silicon high-temperature-resistant release agent and application thereof |
| CN114890694A (en) * | 2022-04-13 | 2022-08-12 | 安徽永茂泰环保科技有限公司 | Cement material based on aluminum ash recycling and preparation method thereof |
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| CN103755939B (en) | 2016-04-06 |
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