CN104761929A - Modified nanometer SiO2 monomer used for polymer flooding - Google Patents

Modified nanometer SiO2 monomer used for polymer flooding Download PDF

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CN104761929A
CN104761929A CN201410751026.XA CN201410751026A CN104761929A CN 104761929 A CN104761929 A CN 104761929A CN 201410751026 A CN201410751026 A CN 201410751026A CN 104761929 A CN104761929 A CN 104761929A
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sio
nano
meter sio
monomer
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CN104761929B (en
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赖南君
张艳
叶仲斌
唐雷
郭欣
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Southwest Petroleum University
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Southwest Petroleum University
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Abstract

The invention relates to a modified nanometer SiO2 monomer used for polymer flooding. The monomer is prepared through the following steps: (1) reacting nanometer SiO2 with 3-aminopropyltriethoxysilane in an anhydrous toluene solution with a temperature of 80 to 100 DEG C for more than 12 h so as to obtain amino-modified nanometer SiO2, and controlling amino content on the surface of nanometer SiO2 by controlling the addition amount of 3-aminopropyltriethoxysilane; and (2) reacting excess maleic anhydride with amino-modified nanometer SiO2 so as to obtain modified nanometer SiO2 monomer with a reactive carbon-carbon double bond. The modified nanometer SiO2 monomer used for polymer flooding provided by the invention can quantitatively graft the carbon-carbon double bond with reaction activity on the surface of nanometer SiO2 as needed and can conveniently control the content of the grafted carbon-carbon double bond by controlling the content of a silane coupling agent containing amino.

Description

For the modified Nano SiO of the multipolymer displacement of reservoir oil 2monomer
Technical field
The present invention relates to Nano-meter SiO_2 2the technical field of surface modification, more particularly, the present invention relates to a kind of modified Nano SiO for the multipolymer displacement of reservoir oil 2monomer.
Background technology
Nano-meter SiO_2 2because specific surface energy is high, strong, the quantum size effect of surface adsorption ability and macro quanta tunnel effect, small-size effect, and the chemical property of high temperature resistant, acid and alkali-resistance and asepsis environment-protecting, be widely used as all conglomeraties such as support of the catalyst, macromolecular material.
As shown in Figure 1, Nano-meter SiO_2 2in tridimensional network, its surface is with the hydroxyl of a large amount of different states, thus Nano-meter SiO_2 2chemical mobility of the surface is higher, easy and properties-correcting agent generation chemical reaction, and utilizes this special property, the much properties-correcting agent with particular functional group can be connected to Nano-meter SiO_2 2surface, thus realize Nano-meter SiO_2 by surface chemical modification 2functionalization.
Silane coupling agent is Nano-meter SiO_2 2one the most frequently used in numerous properties-correcting agent.Although the kind of silane coupling agent is more, their structure basic simlarity.The general formula of silane coupling agent can be expressed as 3 (RO) SiR, and wherein RO is alkoxy grp, and R is other organo-functional groups.Silane coupling agent is to Nano-meter SiO_2 2surface modification can be divided into two steps: be first the alkoxyl group generation hydrolysis reaction on silane coupling agent, obtain silicone hydroxyl; Then be the silicone hydroxyl that obtains of hydrolysis reaction and Nano-meter SiO_2 2the silicone hydroxyl on surface is obtained by reacting silica singly-bound, and silane coupling agent is connected to Nano-meter SiO_2 2surface.The silane coupling agent with different organo-functional group can be selected as required, just organo-functional group can be connected to Nano-meter SiO_2 by surface modification 2surface.With polymkeric substance to Nano-meter SiO_2 2the method of carrying out surface modification mainly contains two kinds: graft on (Grafting from) method and be grafted to (Grafting onto) method.The method of grafting on is by properties-correcting agent and Nano-meter SiO_2 2the hydroxyl on surface reacts, and the group with reactive behavior is incorporated into Nano-meter SiO_2 2surface, then by itself and suitable monomer polymerization, reach Nano-meter SiO_2 2the object of surface chemical modification.The method of being grafted to refers to by the polymkeric substance that synthesizes in advance in the mode of covalent linkage directly and Nano-meter SiO_2 2combine, thus obtain by the Nano-meter SiO_2 of polymer modification 2matrix material.If polymkeric substance used is with groups such as alkoxysilane base or chlorosilyl groups, so they just can and Nano-meter SiO_2 2the hydroxyl on surface reacts, thus polymkeric substance is connected to Nano-meter SiO_2 2surface.Except silane coupling agent and polymkeric substance, Nano-meter SiO_2 2can also by other modifier modifications a lot.In order to play desirable modified effect, these properties-correcting agent need with carboxyl (-COOH) or isocyanate group (-NCO) etc. can with the functional group of hydroxyl reaction.At present, although both at home and abroad to Nano-meter SiO_2 2surface modification has carried out large quantifier elimination, but these researchs mainly concentrate on qualitative aspect, and what mainly pay close attention to is that different properties-correcting agent is to Nano-meter SiO_2 2and the impact of obtained composite property, and there is no bibliographical information to Nano-meter SiO_2 2the fixing quantity of surface modification degree.
Summary of the invention
In order to solve the above-mentioned technical problem existed in prior art, the object of the present invention is to provide a kind of modified Nano SiO for the multipolymer displacement of reservoir oil 2monomer.
To achieve these goals, present invention employs following technical scheme:
A kind of modified Nano SiO for the multipolymer displacement of reservoir oil 2monomer, is characterized in that being prepared by following methods: (1) utilizes Nano-meter SiO_2 2with 3-aminopropyl triethoxysilane in the anhydrous toluene solution of 80 ~ 100 DEG C, reaction more than 12h obtains amino modified Nano-meter SiO_2 2, and control Nano-meter SiO_2 by the addition of control 3-aminopropyl triethoxysilane 2the content of surface amino groups; (2) excessive MALEIC ANHYDRIDE and amino modified Nano-meter SiO_2 is utilized 2be obtained by reacting the carbon-carbon double bond modified Nano SiO with reactive behavior 2monomer.
Wherein, following operation is comprised in step (2): 1. in DMF solution, add MALEIC ANHYDRIDE, stirring and dissolving obtains mixing solutions completely; 2. at amino modified Nano-meter SiO_2 2in add DMF and stir and obtain dispersion liquid; 3. be then added in the mixing solutions that 1. operation obtain by operating the dispersant liquid drop that 2. obtains, then complete at 60 ~ 80 DEG C of stirring reactions, the reaction product obtained through washing, filter, can obtain after drying described in there is the carbon-carbon double bond modified Nano SiO of reactive behavior 2monomer.
Wherein, in step (2), hydrochloric acid-ethanol nonaqueous titrations is utilized to confirm amino modified Nano-meter SiO_2 2the amino on surface reacts completely.
Wherein, before the reaction of step (1), utilize Grignard reagent titration measuring Nano-meter SiO_2 2surface hydroxyl quantity, and utilize hydrochloric acid-ethanol nonaqueous titrations to measure Nano-meter SiO_2 after reacting 2the content of surface amino groups.
Wherein, in step (1), described 3-aminopropyl triethoxysilane and Nano-meter SiO_2 2mass ratio be 1: 5 ~ 20.
Wherein, in step (2), described MALEIC ANHYDRIDE and amino modified Nano-meter SiO_2 2mass ratio be 1: 1 ~ 4.
Compared with prior art, the modified Nano SiO for the multipolymer displacement of reservoir oil of the present invention 2monomer has following beneficial effect:
Modified Nano SiO for the multipolymer displacement of reservoir oil of the present invention 2monomer, not only can as required at Nano-meter SiO_2 2the grafting that surface can be quantitative has the carbon-carbon double bond of reactive behavior, and the content of the carbon-carbon double bond in grafting can be controlled conveniently by the amount controlled containing amino silane coupling agent.
Accompanying drawing explanation
Fig. 1 is Nano-meter SiO_2 2the structural representation of the chemical structure on surface.
Fig. 2 is Nano-meter SiO_2 2the determinator of surface hydroxyl quantity.
Fig. 3 is silane coupling agent KH540 addition and Nano-meter SiO_2 2the graph of a relation of surface modification degree.
Fig. 4 is MALEIC ANHYDRIDE and Nano-meter SiO_2 2the reaction schematic diagram of surface amino groups.
Fig. 5 is SiO 2-KH540 and SiO 2the thermogravimetric curve figure of-KH540-MA.
Fig. 6 is SiO 2-KH540 and SiO 2the infrared spectrum of-KH540-MA.
Fig. 7 is SiO 2the hydrogen spectrum of-KH540.
Fig. 8 is SiO 2the hydrogen spectrum of-KH540-MA.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is described in further detail.Should be appreciated that specific embodiment described herein only for setting forth technical scheme of the present invention, and be not used in the protection domain limiting invention.
1. measure Nano-meter SiO_2 2surface hydroxyl quantity
Adopt Grignard reagent titration measuring Nano-meter SiO_2 2the operation steps of surface hydroxyl quantity is as follows: 1. connect the titration apparatus shown in Fig. 1; 2. dry toluene is joined and Nano-meter SiO_2 is housed 2filter flask in, in order to dispersed sample; Phosphorus pentoxide desiccator is opened (eudiometer closedown), to the dry 10min of the pipeline of titration apparatus, then closes moisture eliminator, in filter flask, add the CH be stored in constant pressure funnel fast 3mgCl; 3. drainage eudiometer is adopted to collect the gas generated, until react completely; 4. blank assay: measure and do not add Nano-meter SiO_2 2the amount V of Shi Shengcheng gas k.Nano-meter SiO_2 is calculated by formula 1 2the quantity of surface silicon hydroxyl:
N = P × ( V - V K ) × N A R × T × S × m Formula 1
In formula: N-Nano-meter SiO_2 2the quantity of surface hydroxyl, individual/m 2; P-barometric point, Pa; V-generates the volume of gas, m 3; V k-blank assay generates the volume of gas, m 3; N a-Avogadro constant, individual/mol; R-gas law constant, (m 3pa)/(Kmol); T-experimental temperature, K; The specific surface area of S-sample, m 2/ g; The quality of m-sample, g.
According to above-mentioned determination of experimental method paper Nano-meter SiO_2 used 2the quantity of surface hydroxyl, Grignard reagent used is methylmagnesium-chloride (3mol/L, is stored in tetrahydrofuran (THF), Shanghai Jing Chun biochemical technology limited-liability company), and measurement result is as table 1.Get the mean value of 4 groups of parallel laboratory tests, obtain Nano-meter SiO_2 2the adsorbed hydroxyl content is 1.1223mmol/g.
Table 1 Nano-meter SiO_2 2the adsorbed hydroxyl content
2. Nano-meter SiO_2 2the mensuration of modified surface amino groups
At numerous Nano-meter SiO_2 2in properties-correcting agent, the application of silane coupling agent is more, and reaction conditions is comparatively ripe.If with the silane coupling agent with some specific groups, both can successfully with Nano-meter SiO_2 2reaction, can also calculate Nano-meter SiO_2 by the content measuring these special organo-functional groups 2the degree of surface modification.By large quantifier elimination, contriver finds that 3-TSL 8330 (KH540) is to Nano-meter SiO_2 2modifying surface, be because 3-TSL 8330 under certain condition can with Nano-meter SiO_2 2surface hydroxyl quantitative reaction, so just can calculate Nano-meter SiO_2 by measuring amino content 2the degree of surface modification.
Nano-meter SiO_2 is measured by hydrochloric acid-ethanol nonaqueous titrations 2surface institute connect amino content.Titration principle and the operation steps of the method are as follows: Nano-meter SiO_2 2modified through 3-TSL 8330, its surface with amine-based basic more weak, can not in water accurate titration amino content.Adopt thymol blue as indicator, under non-aqueous conditions, then can accurate titration amino content with the hydrochloric acid-ethanolic soln of known volumetric molar concentration.The chemical equation of drop reaction is as follows:
In 500mL dehydrated alcohol, add the concentrated hydrochloric acid that 10mL mass concentration is about 36%, be uniformly mixed.Accurately take 0.3g anhydrous sodium carbonate, be dissolved in 30mL deionized water, add tetrabromo-mcresolsulfonphthalein-methyl red mixture indicator solution that 5 mass concentrations are 1%, with the hydrochloric acid-ethanolic soln titration of preparation, color is garnet by green transition is titration end point, carries out blank test simultaneously.The volumetric molar concentration of hydrochloric acid-ethanolic soln is calculated by formula 2:
c = m 0.05299 × ( V - V 0 ) Formula 2
In formula: c-hydrochloric acid-ethanolic soln volumetric molar concentration, mol/L; M-anhydrous sodium carbonate quality, g; V-sample consumes the volume of hydrochloric acid-ethanolic soln, mL; V 0-blank sample consumes the volume of hydrochloric acid-ethanolic soln, mL.
Accurately take the Nano-meter SiO_2 that a certain amount of 3-TSL 8330 is modified 2sample, adds 20 ~ 30mL dehydrated alcohol, after sample dispersion is even, add the thymol blue solution that 5 mass concentrations are 1%, with the hydrochloric acid-ethanolic soln titration of known volumetric molar concentration, be titration end point when color from light yellow becomes pink, carry out blank assay simultaneously.Employing formula 3 calculates modified Nano SiO 2the content of surface amino groups.
C N = c × ( V - V 0 ) m × 100 Formula 3
In formula: C n-Nano-meter SiO_2 2surface amino groups content, mmol/g; M-Nano-meter SiO_2 2quality, g; The volumetric molar concentration of c-hydrochloric acid-ethanolic soln, mol/L; V-modified Nano SiO 2consume the volume of hydrochloric acid-ethanolic soln, mL; V 0-blank assay consumes the volume of hydrochloric acid-ethanolic soln, mL.
Solvent is on the impact of modification degree
Solvent has important impact to modified-reaction.First the solvent used is wanted to disperse reactant well, and the polarity of next solvent will be conducive to reaction and carry out.The experimental selection solvents of 5 kinds of reagent as modified-reaction, as follows according to the power sequence of polarity: water > methyl alcohol > ether > toluene > hexanaphthene.
(1) key instrument and medicine
Round-bottomed flask, serpentine condenser, stirrer, heat-collecting magnetic stirring device, water-bath, Rotary Evaporators, Erlenmeyer flask; Water is deionized water; A small amount of moisture that before methyl alcohol, ether, toluene, hexanaphthene (analytical pure, Chengdu Ke Long chemical reagent factory) use, first dry removing contains; 3-TSL 8330 (99%, Shanghai Jing Chun biochemical technology limited-liability company); Round-bottomed flask after cleaning and serpentine condenser vacuum-drying 24h at 110.0 DEG C.
(2) experimental procedure
Take 5g Nano-meter SiO_2 2(use before at 110.0 DEG C dry 8h), adds 1g 3-TSL 8330 and 80mL solvent, refluxes at 110.0 DEG C, stirring reaction 48h.After reaction terminates, decompression steams unreacted 3-TSL 8330 and solvent, and reaction product is vacuum-drying 24h at 110.0 DEG C.Hydrochloric acid-ethanol nonaqueous titrations is adopted to measure the amino content on modified product surface, then basis Nano-meter SiO_2 before modified 2the adsorbed hydroxyl content, can calculate Nano-meter SiO_2 2surface modification degree.
(3) experimental result and analysis
The modified product taking about 0.5g, in 100mL Erlenmeyer flask, adds 20mL dehydrated alcohol, then add 5 mass concentrations be 1% thymol blue solution make indicator, be 8.8236 × 10 by volumetric molar concentration -3hydrochloric acid-ethanolic soln titration modified Nano the SiO of mol/L 2the content of surface amino groups, measurement result is in table 2.Grignard reagent method records Nano-meter SiO_2 used 2the hydroxy radical content on surface is 1.1223mmol/g, and according to reaction principle, 1mol 3-TSL 8330 can be reacted with the silicone hydroxyl of 3mol.As shown in Table 2, toluene as during solvent closer to theoretical value 0.3741mmol/g.
Table 2 solvent is to Nano-meter SiO_2 2the impact of surface amino groups content
Temperature of reaction is on the impact of modification degree
Take 5g Nano-meter SiO_2 2(use before at 110.0 DEG C dry 8h), adds 1g 3-TSL 8330 and 80mL toluene, stirring reaction 48h at the temperature arranged.After reaction terminates, decompression steams unreacted 3-TSL 8330 and toluene, and reaction product is vacuum-drying 24h at the temperature of correspondence.Adopt hydrochloric acid-ethanol nonaqueous titrations to measure the amino content of its surface, calculate Nano-meter SiO_2 2surface modification degree, the results are shown in Table 3.As shown in Table 3, when temperature of reaction is lower, Nano-meter SiO_2 2surface amino groups content increases along with the rising of temperature; But when temperature of reaction is elevated to 80.0 DEG C, record modified Nano-meter SiO_2 2surface amino groups content is 0.3537mmol/g, continues to raise temperature of reaction, Nano-meter SiO_2 2the amino content on surface does not continue to increase, and 3-TSL 8330 and Nano-meter SiO_2 at 80.0 DEG C are described 2the reaction of surface hydroxyl is more complete.
Table 3 temperature of reaction is to Nano-meter SiO_2 2the impact of surface amino groups content
Reaction times is on the impact of modification degree
Take 5g Nano-meter SiO_2 2(Nano-meter SiO_2 2before using at 110.0 DEG C dry 8h), add 1g 3-TSL 8330 and 80mL toluene, at 80.0 DEG C, react different time.After reaction terminates, decompression steams unreacted 3-TSL 8330 and toluene, and reaction product is vacuum-drying 24h at 80.0 DEG C.Adopt hydrochloric acid-ethanol nonaqueous titrations to measure the amino content on modified product surface, and calculate Nano-meter SiO_2 2conducting modification of surface hydroxy group degree, measurement result is in table 4.As shown in Table 4, the reaction times has impact to a certain degree to modified-reaction.Make properties-correcting agent by 3-TSL 8330, when being 12h when reacted, record modified Nano-meter SiO_2 2surface amino groups content is 0.3535mmol/g, continues to extend the reaction times, Nano-meter SiO_2 2the amino content on surface does not obviously increase, and illustrates that the reaction times should control at about 12h.
Table 4 reaction times is to Nano-meter SiO_2 2the impact of surface amino groups content
Feed molar ratio is on the impact of modification degree
Found by above-mentioned experimental result, Nano-meter SiO_2 2compare thoroughly as solvent reaction with toluene at 80.0 DEG C with 3-TSL 8330, the reaction times can be controlled in about 12h.So control Nano-meter SiO_2 2surface modification degree, can realize by controlling feed molar ratio.Take 1g Nano-meter SiO_2 2(use before at 110.0 DEG C dry 8h), adds 3-TSL 8330 and the 16mL toluene of different amount, at 80.0 DEG C, reacts 12h.After reaction terminates, decompression steams unreacted 3-TSL 8330 and toluene, and reaction product is vacuum-drying 24h at 80.0 DEG C.Adopt hydrochloric acid-ethanol nonaqueous titrations to measure the amino content of its surface, calculate Nano-meter SiO_2 2conducting modification of surface hydroxy group degree, result as shown in Figure 3.As shown in Figure 3, modified Nano-meter SiO_2 can be controlled by the dosage of control 3-TSL 8330 2the content of surface amino groups.Along with the increase of 3-TSL 8330 dosage, amino content increases gradually, the corresponding increase of modification degree.When the dosage of 3-TSL 8330 is 0.1345g, modified Nano-meter SiO_2 2surface amino groups content 0.3586mmol/g, modification degree is 96%.These results suggest that the condition by controlling modified-reaction, can realize Nano-meter SiO_2 2surface hydroxyl controllable modified.
Nano-meter SiO_2 2the introducing of surface double-bond
Take the Nano-meter SiO_2 that 1g 3-TSL 8330 is modified 2, add 20mL DMF (DMF) and make solvent, dropped to by above-mentioned solution at 20.0 DEG C in the solution containing 0.4g MALEIC ANHYDRIDE and 20mL DMF, time for adding is 3h; At 70.0 DEG C, 12h is reacted, product deionized water wash, then vacuum-drying 24h at 70.0 DEG C after dripping.Adopt hydrochloric acid-ethanol nonaqueous titrations assaying reaction its surface there is no amino, illustrate that second step reaction is carried out completely.MALEIC ANHYDRIDE and Nano-meter SiO_2 2the reaction of surface amino groups as shown in Figure 4.
The sign of modified product
Thermogravimetric analysis
(1) key instrument
STA 449 F3 type simultaneous synthesis thermal analyzer, German Nai Chi company; The infrared tabletting machine of FW-5 type, Tianjin Bo Tianshengda development in science and technology company limited.
(2) laboratory sample
For the sample of thermogravimetric analysis by the product (SiO of the complete modification of 3-TSL 8330 2-KH540) and SiO 2product (the SiO of-KH540 and excessive MALEIC ANHYDRIDE complete reaction 2-KH540-MA).
(3) experimental technique
1. before thermogravimetric analysis, first balance is corrected; 2. by sample vacuum-drying 24h at 70.0 DEG C, infrared tabletting machine is used; 3. load the sample strip of compacting, require thin and even; 4. working sample weight loss at different temperatures.
(4) result and analysis
Simultaneous synthesis thermal analyzer is adopted to determine Nano-meter SiO_2 respectively 2through the product (SiO that silane coupling agent 3-TSL 8330 (KH540) is modified 2-KH540) and SiO 2reaction product (the SiO of-KH540 and MALEIC ANHYDRIDE 2-KH540-MA) thermogravimetric curve, as shown in Figure 5.From thermogravimetric curve, along with temperature raises, SiO 2-KH540 and SiO 2the weight loss of-KH540-MA increases gradually, and Nano-meter SiO_2 is described 2the organism on surface constantly decomposes along with temperature raises, and this can confirm at Nano-meter SiO_2 2surface has connected organism.When temperature is elevated to 150.0 DEG C from 40.0 DEG C, this one-phase is mainly the weightlessness of sample surfaces planar water, SiO 2the weight loss that-KH540 is corresponding is 0.2%, SiO 2the weight loss that-KH540-MA is corresponding is 0.8%, and both weight loss differences 0.6%, this is mainly because SiO 2-KH540 and SiO 2-KH540-MA surface properties is different, and surface adsorption water-content is different.Further raised temperature, SiO 2the weight loss of-KH540-MA increases gradually, and this is mainly because SiO 2-KH540-MA is SiO 2the product of-KH540 and MALEIC ANHYDRIDE, more organic components is contained on its surface, at the same temperature because organic decomposition makes mass loss degree larger.After temperature is elevated to 900.0 DEG C, SiO 2-KH540 and SiO 2the weight loss of-KH540-MA is respectively 9.8% and 6.2%, both weight losses difference 3.6%, after deducting the weight loss caused because of planar water, and SiO 2-KH540 and SiO 2the actual weight loss difference of-KH540-MA is about 3.0%.SiO 2-KH540 and SiO 2the theoretical value difference 3.2% of-KH540-MA surface organic matter content, known measured value differs less with theoretical value.Modified product SiO is confirmed by thermogravimetric analysis 2-KH540-MA and SiO 2-KH540 contains a certain amount of organism, can tentatively judge to obtain target modified product according to both Weight loss data.In order to characterize modified product SiO further 2-KH540 and SiO 2the structure of-KH540-MA, also needs in conjunction with characterizing methods such as first infrared spectra and nucleus magnetic resonance.
Infrared spectroscopy
(1) key instrument and reagent
WQF-520 type infrared spectrometer, Ruili, Beijing Analytical Instrument Co., Ltd; The infrared tabletting machine of FW-5 type, Tianjin Bo Tianshengda development in science and technology company limited; DZF-6500 type vacuum drying oven, Shanghai Qi Xin scientific instrument company limited; Potassium Bromide (KBr, spectroscopically pure), Chengdu Ke Long chemical reagent factory.
(2) experimental technique
By the modified product obtained vacuum-drying 48h at 70.0 DEG C; Take a morsel dried KBr, uses infrared tabletting machine; Infrared spectrum scanning is carried out, acquisition instrument background with WQF-520 type infrared spectrometer; Take a morsel dried sample, adds KBr and mix, and the mass ratio of KBr and sample is about 50: 1; The infrared tabletting machine of the KBr being added with sample; The sample strip WQF-520 type infrared spectrometer made is carried out Infrared spectrum scanning.
(3) results and analysis
Nano-meter SiO_2 2through the product (SiO that silane coupling agent 3-TSL 8330 (KH540) is modified obtained 2-KH540) and SiO 2reaction product (the SiO of-KH540 and MALEIC ANHYDRIDE 2-KH540-MA) infrared spectrum as shown in Figure 6.By Nano-meter SiO_2 2infrared spectrum known, at 3451.5cm -1and 1625.4cm -1neighbouring absorption peak is the absorption peak of water molecules; 1103.6cm -1neighbouring absorption peak is the asymmetric stretching vibration peak of Si-O-Si, 804.2cm -1neighbouring absorption peak is the symmetrical stretching vibration peak of Si-O-Si, and these absorption peaks are Nano-meter SiO_2 2characteristic peak.By SiO 2the infrared spectrum of-KH540 is known, at 3394.6cm -1neighbouring absorption peak is the stretching vibration peak of-NH, at 2924.7cm -1neighbouring absorption peak is-CH 2charateristic avsorption band, also obviously there is Nano-meter SiO_2 in infrared spectrum in addition 2characteristic peak.Above result shows, Nano-meter SiO_2 2reaction is there occurs, at Nano-meter SiO_2 with silane coupling agent KH540 2surface has connected amino.By SiO 2the infrared spectrum of-KH540-MA is known, at 2931.4cm -1neighbouring absorption peak is-CH 2charateristic avsorption band, infrared spectrum there is new absorption peak, at 1707.3cm -1neighbouring absorption peak is the charateristic avsorption band of carbonyl, at 1580.2cm -1neighbouring absorption peak is the charateristic avsorption band of carbon-carbon double bond.In addition, also obviously there is SiO in infrared spectrum 2characteristic peak.Above result shows, Nano-meter SiO_2 2hydroxyl and the KH540 on surface react, at Nano-meter SiO_2 2surperficial has connected amino; Nano-meter SiO_2 2the amino on surface reacts with MALEIC ANHYDRIDE, at Nano-meter SiO_2 again 2surface has connected the carbon-carbon double bond with reactive behavior.
Nuclear magnetic resonance spectroscopy
(1) instrument and reagent
Bruker AC-E 200 nuclear magnetic resonance spectrometer, Bruker Biospin company of Switzerland; Nuclear magnetic tube, WILMADLAB GLASS company of the U.S.; DZF-6500 type vacuum drying oven, Shanghai Qi Xin scientific instrument company limited; Deuterated acetone (Acetone), deuterated dimethyl sulfoxide (DMSO), in wide core (Beijing) Application of Nuclear Technology company limited.
(2) experimental technique
1. testing sample is placed in the vacuum drying oven inner drying 24h of 70.0 DEG C; 2. a certain amount of modified product obtained is joined in nuclear magnetic tube; 3. to adding SiO 2deuterated acetone is added, to adding SiO in the nuclear magnetic tube of-KH540 2deuterated dimethyl sulfoxide is added in the nuclear magnetic tube of-KH540-MA; 4. by the hydrogen spectrum of Bruker AC-E 200 nuclear magnetic resonance spectrometer scanning product, sweep rate is 200Hz.
(3) experimental result and analysis
SiO 2the hydrogen spectrum of-KH540 as shown in Figure 7.0.89ppm is-CH 2-CH 2-CH 2-NH 2the chemical shift of proton, 1.91ppm is-CH 2-CH 2-CH 2-NH 2the chemical shift of proton, 2.22ppm is-CH 2-CH 2-CH 2-NH 2the chemical shift of proton, 2.83ppm is-CH 2-CH 2-CH 2-NH 2the chemical shift of proton, by SiO 2the hydrogen spectrum of-KH540 is known, Nano-meter SiO_2 2by silane coupling agent KH540 success modification, thus at Nano-meter SiO_2 2surface introduces amino.SiO 2the hydrogen spectrum of-KH540-MA as shown in Figure 8.0.87ppm is-CH 2-CH 2-CH 2the chemical shift of-NH-proton, 1.99ppm is-CH 2-CH 2-CH 2the chemical shift of-NH-proton, 2.67ppm is-CH 2-CH 2-CH 2the chemical shift of-NH-proton, 6.68ppm is the chemical shift of-NH-C (O)-CH=CH-proton, and 7.22ppm is the chemical shift of-NH-C (O)-CH=CH-proton, by SiO 2the hydrogen spectrum of-KH540-MA is known, Nano-meter SiO_2 2modified by silane coupling agent KH540, Nano-meter SiO_2 2the amino that surface is introduced and MALEIC ANHYDRIDE react, thus at Nano-meter SiO_2 2surface introduces the carbon-carbon double bond that can participate in polyreaction.

Claims (6)

1. the modified Nano SiO for the multipolymer displacement of reservoir oil 2monomer, is characterized in that described monomer is prepared by following methods: (1) utilizes Nano-meter SiO_2 2with 3-aminopropyl triethoxysilane in the anhydrous toluene solution of 80 ~ 100 DEG C, reaction more than 12h obtains amino modified Nano-meter SiO_2 2, and control Nano-meter SiO_2 by the addition of control 3-aminopropyl triethoxysilane 2the content of surface amino groups; (2) excessive MALEIC ANHYDRIDE and amino modified Nano-meter SiO_2 is utilized 2be obtained by reacting the carbon-carbon double bond modified Nano SiO with reactive behavior 2monomer.
2. the modified Nano SiO for the multipolymer displacement of reservoir oil according to claim 1 2monomer, is characterized in that: comprise following operation in step (2): 1. in DMF solution, add MALEIC ANHYDRIDE, stirring and dissolving obtains mixing solutions completely; 2. at amino modified Nano-meter SiO_2 2in add DMF and stir and obtain dispersion liquid; 3. be then added in the mixing solutions that 1. operation obtain by operating the dispersant liquid drop that 2. obtains, then complete at 60 ~ 80 DEG C of stirring reactions, the reaction product obtained through washing, filter, can obtain after drying described in there is the carbon-carbon double bond modified Nano SiO of reactive behavior 2monomer.
3. the modified Nano SiO for the multipolymer displacement of reservoir oil according to claim 1 2monomer, is characterized in that: in step (2), utilize hydrochloric acid-ethanol nonaqueous titrations to confirm amino modified Nano-meter SiO_2 2the amino on surface reacts completely.
4. the modified Nano SiO for the multipolymer displacement of reservoir oil according to claim 1 2monomer, is characterized in that: before the reaction of step (1), utilize Grignard reagent titration measuring Nano-meter SiO_2 2surface hydroxyl quantity, and utilize hydrochloric acid-ethanol nonaqueous titrations to measure Nano-meter SiO_2 after reacting 2the content of surface amino groups.
5. the modified Nano SiO for the multipolymer displacement of reservoir oil according to claim 1 2monomer, is characterized in that: in step (1), described 3-aminopropyl triethoxysilane and Nano-meter SiO_2 2mass ratio be 1: 5 ~ 20.
6. the modified Nano SiO for the multipolymer displacement of reservoir oil according to claim 1 2monomer, is characterized in that: in step (2), described MALEIC ANHYDRIDE and amino modified Nano-meter SiO_2 2mass ratio be 1: 1 ~ 4.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104761930A (en) * 2015-01-15 2015-07-08 西南石油大学 Modified nanometer silica functional monomer for oil-displacement polymer
CN108410440A (en) * 2018-03-07 2018-08-17 中国石油大学(华东) A kind of surface modified nano silicon nano-fluid for improving recovery ratio

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101824238A (en) * 2009-12-09 2010-09-08 广州市创至峰塑料制品科技有限公司 Surface treatment method for powder composition of optical diffusion plastic
CN101914313A (en) * 2010-08-13 2010-12-15 南通纳威数码材料科技有限公司 Cation water-based nano silicon dioxide and preparation method and application thereof
CN103709342A (en) * 2013-12-23 2014-04-09 河北工业大学 Preparation method of magnetic cadmium ion surface imprinted polymer

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101824238A (en) * 2009-12-09 2010-09-08 广州市创至峰塑料制品科技有限公司 Surface treatment method for powder composition of optical diffusion plastic
CN101914313A (en) * 2010-08-13 2010-12-15 南通纳威数码材料科技有限公司 Cation water-based nano silicon dioxide and preparation method and application thereof
CN103709342A (en) * 2013-12-23 2014-04-09 河北工业大学 Preparation method of magnetic cadmium ion surface imprinted polymer

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ZHONGBIN YE,ET AL.: "Synthesis and Performance of an Acrylamide Copolymer Containing Nano-SiO2 as Enhanced Oil Recovery Chemical", 《JOURNAL OF CHEMISTRY》 *
张圣麟，等: "《化工分析技术》", 30 September 2008, 化学工业出版社•北京 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104761930A (en) * 2015-01-15 2015-07-08 西南石油大学 Modified nanometer silica functional monomer for oil-displacement polymer
CN108410440A (en) * 2018-03-07 2018-08-17 中国石油大学(华东) A kind of surface modified nano silicon nano-fluid for improving recovery ratio

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