CN104761929B - Modified nanometer SiO2 monomer used for polymer flooding - Google Patents
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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
Technical field
The present invention relates to Nano-meter SiO_22The modified technical field in surface, it is more particularly related to a kind of for altogether
The modified Nano SiO of the polymers displacement of reservoir oil2Monomer.
Background technology
Nano-meter SiO_22Because specific surface energy is high, surface adsorption ability is strong, quantum size effect and macro quanta tunnel effect,
Small-size effect, and the chemical characteristic of high temperature resistant, acid and alkali-resistance and asepsis environment-protecting, are widely used as catalyst carrier, high score
All conglomeraties such as sub- material.
As shown in figure 1, Nano-meter SiO_22In tridimensional network, hydroxyl of its surface with a large amount of different conditions, thus receive
Rice SiO2Chemical mobility of the surface is higher, chemical reaction easily occurs with modifying agent, and utilizes this special nature, will can be permitted
Many modifying agent with particular functional group are connected to Nano-meter SiO_22Surface, so as to realize Nano-meter SiO_2 by surface chemical modification2Work(
Energyization.
Silane coupler is Nano-meter SiO_22The most frequently used one kind in numerous modifying agent.Although the species of silane coupler compared with
It is many, but their structure basic simlarity.The formula of silane coupler is represented by 3 (RO) SiR, and wherein RO is alkoxy grp, R
For other organo-functional groups.Silane coupler is to Nano-meter SiO_22Surface modified can be divided into two steps：It is silane coupler first
On alkoxyl occur hydrolysis, obtain silicone hydroxyl；Followed by the silicone hydroxyl that obtains of hydrolysis and Nano-meter SiO_22Surface
Silicone hydroxyl reaction obtains silica singly-bound, and silane coupler is connected to Nano-meter SiO_22Surface.Can be selected with not as needed
With the silane coupler of organo-functional group, just organo-functional group can be connected to Nano-meter SiO_2 by surface is modified2Surface.With
Polymer is to Nano-meter SiO_22Carrying out the modified method in surface mainly has two kinds：Graft on (Grafting from) method and be grafted to
(Grafting onto) method.The method of grafting on is by modifying agent and Nano-meter SiO_22The hydroxyl on surface reacts, will be with reaction
The group of activity is incorporated into Nano-meter SiO_22Surface, then which is polymerized with suitable monomer, reach Nano-meter SiO_22Surface chemical modification
Purpose.The method of being grafted to refer to will in advance synthesis polymer in the way of covalent bond directly and Nano-meter SiO_22Combine, so as to
To by the Nano-meter SiO_2 of polymer modification2Composite.If polymer used carries alkoxysilane base or chlorosilyl group etc.
Group, then they just can and Nano-meter SiO_22The hydroxyl on surface reacts, so as to polymer is connected to Nano-meter SiO_22Table
Face.Except silane coupler and polymerization beyond the region of objective existence, Nano-meter SiO_22Can also be by a lot of other modifier modifications.Preferably change to play
Property effect, these modifying agent need can be with the sense of hydroxyl reaction with carboxyl (- COOH) or NCO (- NCO) etc.
Group.At present, although both at home and abroad to Nano-meter SiO_22Surface is modified to have carried out substantial amounts of research, but these researchs are focused primarily upon to be determined
In terms of property, different modifying agent are concern is primarily with to Nano-meter SiO_22And the impact of obtained composite property, without text
Report is offered to Nano-meter SiO_22The quantitative control of surface modification degree.
The content of the invention
In order to solve above-mentioned technical problem present in prior art, it is an object of the invention to provide a kind of be used for copolymerization
The modified Nano SiO of the thing displacement of reservoir oil2Monomer.
To achieve these goals, present invention employs technical scheme below：
A kind of modified Nano SiO for the copolymer displacement of reservoir oil2Monomer, it is characterised in that prepared by following methods：(1)
Using Nano-meter SiO_22With 3- aminopropyl triethoxysilanes in 80～100 DEG C of anhydrous toluene solution, 12h is derived above for reaction
Amino modified Nano-meter SiO_22, and by controlling the addition of 3- aminopropyl triethoxysilanes controlling Nano-meter SiO_22Surface ammonia
The content of base；(2) using excessive maleic anhydride and amino modified Nano-meter SiO_22Reaction is obtained with reactivity
Carbon-carbon double bond modified Nano SiO2Monomer.
Wherein, in step (2) including following operation：1. maleic acid is added in DMF solution
Acid anhydride, stirring and dissolving obtain mixed solution completely；2. in amino modified Nano-meter SiO_22Middle addition DMF stirring
Dispersion liquid is obtained uniformly；3. and then by the dispersant liquid drop that 2. operation obtains it is added in the mixed solution that 1. operation obtains, Ran Hou
60～80 DEG C of stirring reactions completely, the product for obtaining through washing, filter, be dried after can obtain and described there is reactivity
Carbon-carbon double bond modified Nano SiO2Monomer.
Wherein, amino modified Nano-meter SiO_2 is confirmed using hydrochloric acid-ethanol non-aqueous titration in step (2)2The ammonia on surface
Base reaction is complete.
Wherein, using Grignard reagent titration measuring Nano-meter SiO_2 before the reaction of step (1)2Surface hydroxyl quantity, and
Nano-meter SiO_2 is determined using hydrochloric acid-ethanol non-aqueous titration after reacting2The content of surface amino groups.
Wherein, in step (1), the 3- aminopropyl triethoxysilanes and Nano-meter SiO_22Mass ratio be 1: 5～20.
Wherein, in step (2), the maleic anhydride and amino modified Nano-meter SiO_22Mass ratio be 1: 1～
4。
Compared with prior art, the modified Nano SiO for the copolymer displacement of reservoir oil of the present invention2Monomer has and following has
Beneficial effect：
Modified Nano SiO for the copolymer displacement of reservoir oil of the present invention2Monomer, not only can as needed in nanometer
SiO2There is in the grafting that surface can be quantitative the carbon-carbon double bond of reactivity, and amino can be contained conveniently by control
Silane coupler amount come control be grafted on carbon-carbon double bond content.
Description of the drawings
Fig. 1 is Nano-meter SiO_22The structural representation of the chemical constitution on surface.
Fig. 2 is Nano-meter SiO_22The measure device of surface hydroxyl quantity.
Fig. 3 is silane coupler KH540 additions and Nano-meter SiO_22The graph of a relation of surface modification degree.
Fig. 4 is maleic anhydride and Nano-meter SiO_22The reaction schematic diagram of surface amino groups.
Fig. 5 is SiO2- KH540 and SiO2The thermogravimetric curve figure of-KH540-MA.
Fig. 6 is SiO2- KH540 and SiO2The infrared spectrum of-KH540-MA.
Fig. 7 is SiO2The hydrogen spectrum of-KH540.
Fig. 8 is SiO2The hydrogen spectrum of-KH540-MA.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, it is below in conjunction with drawings and Examples, right
The present invention is described in further detail.It should be appreciated that specific embodiment described herein is only intended to illustrate the present invention
Technical scheme, be not used to limit invention protection domain.
1. Nano-meter SiO_2 is determined2Surface hydroxyl quantity
Using Grignard reagent titration measuring Nano-meter SiO_22The operating procedure of surface hydroxyl quantity is as follows：1. connect Fig. 1
Shown titration appratuss；2. dry toluene is added to equipped with Nano-meter SiO_22Bottle,suction in, to dispersed sample；By five oxidations
Two phosphorus exsiccators open (eudiometer cut out), are dried 10min to the pipeline of titration appratuss, are then shut off exsiccator, to bottle,suction
In rapidly join the CH being stored in constant pressure funnel3MgCl；3. the gas for generating is collected using drainage with eudiometer,
Until reaction is complete；4. blank experiment：Measure is added without Nano-meter SiO_22Amount V of Shi Shengcheng gasesK.Nano-meter SiO_2 is calculated by formula 12Table
The quantity of face silicon hydroxyl：
Formula 1
In formula：N- Nano-meter SiO_2s2The quantity of surface hydroxyl, individual/m2；P- atmospheric pressures, Pa；V- generates the volume of gas, m3；
VK- blank experiment generates the volume of gas, m3；NA- Avogadro's number, individual/mol；R- gas constants, (m3·Pa)/(K·
mol)；T- experimental temperatures, K；The specific surface area of S- samples, m2/g；The quality of m- samples, g.
According to Nano-meter SiO_2 used by above-mentioned determination of experimental method paper2The quantity of surface hydroxyl, Grignard reagent used are methyl
Magnesium chloride (3mol/L, is stored in tetrahydrofuran, Shanghai Jing Chun biochemical technologies limited company), measurement result such as table 1.Take
The meansigma methodss of 4 groups of parallel laboratory tests, obtain Nano-meter SiO_22The adsorbed hydroxyl content is 1.1223mmol/g.
1 Nano-meter SiO_2 of table2The adsorbed hydroxyl content
2. Nano-meter SiO_22The measure of modified surface amino groups
In numerous Nano-meter SiO_2s2In modifying agent, the application of silane coupler is more, and reaction condition is more ripe.If used
Silane coupler with some specific groups, both can successfully with Nano-meter SiO_22Reaction, can also be special by determining these
The content of different organo-functional group is calculating Nano-meter SiO_22The modified degree in surface.Inventor has found 3- ammonia by substantial amounts of research
Base propyl trimethoxy silicane (KH540) is to Nano-meter SiO_22Modifying surface, is because 3- TSL 8330s
Under certain condition can be with Nano-meter SiO_22Surface hydroxyl quantitative response, so can just be calculated by the content for determining amino
Nano-meter SiO_22The modified degree in surface.
Nano-meter SiO_2 is determined with hydrochloric acid-ethanol non-aqueous titration2The content of the connect amino in surface.The titration principle of the method
And operating procedure is as follows：Nano-meter SiO_22Jing 3- TSL 8330s are modified, the amine-based basic that its surface carries compared with
It is weak, it is impossible to amino content is accurately titrated in water.Using thymol blue as indicator, under non-aqueous conditions, rubbed with known
You then can accurately titrate amino content by the hydrochloric acid-ethanol solution of concentration.The chemical equation of drop reaction is as follows：
The concentrated hydrochloric acid of 10mL mass concentrations about 36% is added in 500mL dehydrated alcohol, is uniformly mixed.Accurately claim
0.3g natrium carbonicum calcinatums are taken, is dissolved in 30mL deionized waters, add 5 to drip bromocresol green-C.I. 13020. mixing that mass concentration is 1%
Indicator solution, with the hydrochloric acid prepared-ethanol solution titration, color is that kermesinus is titration end-point by green transition, while entering
Line blank test.The molar concentration of hydrochloric acid-ethanol solution is calculated by formula 2：
Formula 2
In formula：C- hydrochloric acid-ethanol solution molar concentration, mol/L；M- natrium carbonicum calcinatum quality, g；V- sample consumption hydrochloric acid-
The volume of ethanol solution, mL；V0- blank sample consumes the volume of hydrochloric acid-ethanol solution, mL.
The modified Nano-meter SiO_2 of a certain amount of 3- TSL 8330s is weighed accurately2Sample, add 20～
30mL dehydrated alcohol, after sample dispersion is uniform, adds 5 to drip the thymol blue solution that mass concentration is 1%, with known mole
The titration of the hydrochloric acid of concentration-ethanol solution, is titration end-point when color from light yellow is changed into pink, while carrying out blank experiment.
Modified Nano SiO is calculated using formula 32The content of surface amino groups.
Formula 3
In formula：CN- Nano-meter SiO_22Surface amino groups content, mmol/g；M- Nano-meter SiO_2s2Quality, g；C- hydrochloric acid-ethanol solution
Molar concentration, mol/L；V- modified Nano SiO2Consume the volume of hydrochloric acid-ethanol solution, mL；V0- blank experiment consumption hydrochloric acid-
The volume of ethanol solution, mL.
Impact of the solvent to modification degree
Solvent has important impact to modified-reaction.The solvent for being used first has to disperse reactant well,
Secondly the polarity of solvent will be conducive to reaction to carry out.Experimental selection solvents of 5 kinds of reagents as modified-reaction, according to polarity
Strong and weak sequence is as follows：Water ＞ methanol ＞ ether ＞ toluene ＞ hexamethylene.
(1) key instrument and medicine
Round-bottomed flask, serpentine condenser, stirrer, heat-collecting magnetic stirring device, water-bath, Rotary Evaporators, conical flask；
Water is deionized water；Methanol, ether, toluene, hexamethylene (analyzing pure, Chengdu Ke Long chemical reagents factory) are removed using front first drying
The a small amount of moisture for containing；3- TSL 8330s (99%, Shanghai Jing Chun biochemical technologies limited company)；Clean
Round-bottomed flask and serpentine condenser afterwards is vacuum dried 24h at 110.0 DEG C.
(2) experimental procedure
Weigh 5g Nano-meter SiO_2s2(being dried 8h at 110.0 DEG C using front), adds 1g 3- TSL 8330s
With 80mL solvents, flow back at 110.0 DEG C, stirring reaction 48h.After reaction terminates, decompression steams unreacted 3- aminopropyls
Trimethoxy silane and solvent, product are vacuum dried 24h at 110.0 DEG C.Determined using hydrochloric acid-ethanol non-aqueous titration
The amino content on modified product surface, further according to Nano-meter SiO_2 before modified2The adsorbed hydroxyl content, can calculate Nano-meter SiO_22Surface changes
Property degree.
(3) experimental result and analysis
The modified product of 0.5g or so is weighed in 100mL conical flasks, 20mL dehydrated alcohol is added, is added 5 drop quality
Concentration is that 1% thymol blue solution makees indicator, is 8.8236 × 10 with molar concentration-3Hydrochloric acid-the ethanol solution of mol/L
Titration modified Nano SiO2The content of surface amino groups, measurement result are shown in Table 2.Grignard reagent method measures Nano-meter SiO_2 used2Surface
Hydroxy radical content is 1.1223mmol/g, and according to reaction principle, 1mol 3- TSL 8330s can be with the silicon of 3mol
Hydroxyl reaction.As shown in Table 2, toluene as during solvent closer to theoretical value 0.3741mmol/g.
2 solvent of table is to Nano-meter SiO_22The impact of surface amino groups content
Impact of the reaction temperature to modification degree
Weigh 5g Nano-meter SiO_2s2(being dried 8h at 110.0 DEG C using front), adds 1g 3- TSL 8330s
With 80mL toluene, stirring reaction 48h at a temperature of the setting.After reaction terminates, decompression steams unreacted 3- aminopropyls three
Methoxy silane and toluene, product are vacuum dried 24h at corresponding temperature.Surveyed using hydrochloric acid-ethanol non-aqueous titration
Determine the amino content of its surface, calculate Nano-meter SiO_22Surface modification degree, the results are shown in Table 3.As shown in Table 3, in reaction temperature
When relatively low, Nano-meter SiO_22Surface amino groups content increases with the rising of temperature；But when reaction temperature is increased to 80.0 DEG C,
Measure modified Nano-meter SiO_22Surface amino groups content is 0.3537mmol/g, continues to rise high reaction temperature, Nano-meter SiO_22The ammonia on surface
Base content does not continue increase, illustrates 3- TSL 8330s and Nano-meter SiO_2 at 80.0 DEG C2Surface hydroxyl it is anti-
Should be more complete.
3 reaction temperature of table is to Nano-meter SiO_22The impact of surface amino groups content
Impact of the response time to modification degree
Weigh 5g Nano-meter SiO_2s2(Nano-meter SiO_228h is dried using front at 110.0 DEG C), add 1g 3- aminopropyl front threes
TMOS and 80mL toluene, react different time at 80.0 DEG C.After reaction terminates, decompression steams unreacted 3- amino
Propyl trimethoxy silicane and toluene, product are vacuum dried 24h at 80.0 DEG C.Using hydrochloric acid-ethanol non-aqueous titration
The amino content on modified product surface is determined, and calculates Nano-meter SiO_22Conducting modification of surface hydroxy group degree, measurement result are shown in Table 4.By
Table 4 understands that the response time has a certain degree of impact to modified-reaction.It is modified with 3- TSL 8330s
Agent, when reacted between for 12h when, measure modified Nano-meter SiO_22Surface amino groups content is 0.3535mmol/g, continues to extend
Response time, Nano-meter SiO_22The amino content on surface is not significantly increased, and illustrates that the response time should be controlled in 12h or so.
4 response time of table is to Nano-meter SiO_22The impact of surface amino groups content
Impact of the feed molar ratio to modification degree
Found by above-mentioned experimental result, Nano-meter SiO_22Made with toluene at 80.0 DEG C with 3- TSL 8330s
More thoroughly, the response time can be controlled in 12h or so to solvent reaction ratio.So control Nano-meter SiO_22Surface modification degree, Ke Yitong
Cross control feed molar ratio to realize.Weigh 1g Nano-meter SiO_2s2(being dried 8h at 110.0 DEG C using front), adds different amounts of 3- amino
Propyl trimethoxy silicane and 16mL toluene, react 12h at 80.0 DEG C.After reaction terminates, decompression steams unreacted 3- ammonia
Base propyl trimethoxy silicane and toluene, product are vacuum dried 24h at 80.0 DEG C.Using hydrochloric acid-ethanol nonaquepous tration
Method determines the amino content of its surface, calculates Nano-meter SiO_22Conducting modification of surface hydroxy group degree, as a result as shown in Figure 3.Can by Fig. 3
Know, modified Nano-meter SiO_2 can be controlled by controlling the dosage of 3- TSL 8330s2The content of surface amino groups.
As the increase of 3- TSL 8330 dosages, amino content gradually increase, modification degree accordingly increases.When 3- ammonia
When the dosage of base propyl trimethoxy silicane is 0.1345g, modified Nano-meter SiO_22Surface amino groups content 0.3586mmol/g,
Modification degree is 96%.These results suggest that the condition by controlling modified-reaction, it is possible to achieve to Nano-meter SiO_22Surface hydroxyl
It is controllable modified.
Nano-meter SiO_22The introducing of surface double-bond
Weigh the modified Nano-meter SiO_2 of 1g 3- TSL 8330s2, add 20mL N, N- dimethyl formyls
Amine (DMF) makees solvent, drops to above-mentioned solution molten containing 0.4g maleic anhydrides and 20mL DMF at 20.0 DEG C
In liquid, time for adding is 3h；12h is reacted at 70.0 DEG C after dripping, product is washed with deionized, then at 70.0 DEG C
Vacuum drying 24h.Product surface is determined using hydrochloric acid-ethanol non-aqueous titration there is no amino, and illustrate that second step is anti-
Should carry out completely.Maleic anhydride and Nano-meter SiO_22The reaction of surface amino groups is as shown in Figure 4.
The sign of modified product
Thermogravimetric analysiss
(1) key instrument
449 F3 type simultaneous synthesis thermal analyzers of STA, German Nai Chi companies；The infrared tablet machine of FW-5 types, the rich day victory in Tianjin
Up to development in science and technology company limited.
(2) laboratory sample
Sample for thermogravimetric analysiss is by the completely modified product (SiO of 3- TSL 8330s2-
) and SiO KH5402Product (the SiO that-KH540 is reacted completely with excessive maleic anhydride2-KH540-MA)。
(3) experimental technique
1. balance is first corrected before thermogravimetric analysiss；2. sample is vacuum dried into 24h at 70.0 DEG C, with infrared tablet machine pressure
Piece；3. load the sample strip of compacting, it is desirable to uniform and thin；4. determination sample weight loss at different temperatures.
(4) result and analysis
Nano-meter SiO_2 is determined respectively using simultaneous synthesis thermal analyzer2Through silane coupler 3- aminopropyl trimethoxies
Modified product (the SiO of base silane (KH540)2- KH540) and SiO2The product of-KH540 and maleic anhydride
(SiO2- KH540-MA) thermogravimetric curve, as shown in Figure 5.From thermogravimetric curve, as temperature is raised, SiO2- KH540 and
SiO2The weight loss of-KH540-MA gradually increases, and illustrates Nano-meter SiO_22The Organic substance on surface constantly decomposes as temperature is raised, this
Can confirm in Nano-meter SiO_22Surface has connected Organic substance.Temperature from be increased to 150.0 DEG C for 40.0 DEG C when, this stage is mainly
Sample surfaces adsorb the weightlessness of water, SiO2The corresponding weight losses of-KH540 are 0.2%, SiO2The corresponding weight losses of-KH540-MA are
0.8%, both weight loss differences 0.6%, this is primarily due to SiO2- KH540 and SiO2- KH540-MA surface naturies are different,
Surface adsorption water content is different.High-temperature, SiO are risen further2The weight loss of-KH540-MA gradually increases, this be mainly because
For SiO2- KH540-MA is SiO2The product of-KH540 and maleic anhydride, its surface contain more organic components,
At the same temperature as the decomposition of Organic substance makes mass loss degree bigger.After temperature is increased to 900.0 DEG C, SiO2-KH540
And SiO2The weight loss of-KH540-MA is respectively 9.8% and 6.2%, both weight loss differences 3.6%, is deducting because adsorbing water
After the weight loss for causing, SiO2- KH540 and SiO2The actual weight loss difference about 3.0% of-KH540-MA.SiO2-KH540
And SiO2The theoretical value difference 3.2% of-KH540-MA surface organic matter contents, it is known that measured value differs less with theoretical value.It is logical
Cross thermogravimetric analysiss and confirm modified product SiO2- KH540-MA and SiO2- KH540 contains a certain amount of Organic substance, according to both
Weight loss data tentatively can judge to have obtained target modified product.In order to further characterize modified product SiO2- KH540 and SiO2-
The structure of KH540-MA, in addition it is also necessary to combine first characterizing method such as infrared spectrum and nuclear magnetic resonance, NMR.
Infrared spectrum analysiss
(1) key instrument and reagent
WQF-520 type infrared spectrometers, Beijing Ruili Analytical Instrument Co., Ltd；The infrared tablet machine of FW-5 types, Tianjin are won
Its victory is up to development in science and technology company limited；DZF-6500 type vacuum drying ovens, Shanghai Qi Xin scientific instrument company limited；Potassium bromide
(KBr, spectroscopic pure), Chengdu Ke Long chemical reagents factory.
(2) experimental technique
The modified product for obtaining is vacuum dried into 48h at 70.0 DEG C；A small amount of dried KBr is taken, infrared tabletting is used
Machine tabletting；IR spectrum scanning, acquisition instrument background are carried out with WQF-520 types infrared spectrometer；A small amount of dried sample is taken,
Add KBr mix homogeneously, the mass ratio of KBr and sample is 50: 1 or so；The infrared tabletting machines of the KBr added with sample；
The sample strip for making is carried out into IR spectrum scanning with WQF-520 types infrared spectrometer.
(3) result and analysis
Nano-meter SiO_22Product obtained by silane coupler 3- TSL 8330s (KH540) is modified
(SiO2- KH540) and SiO2Product (the SiO of-KH540 and maleic anhydride2- KH540-MA) infrared spectrum such as
Shown in Fig. 6.By Nano-meter SiO_22Infrared spectrum understand, in 3451.5cm-1And 1625.4cm-1Neighbouring absworption peak is hydrone
Absworption peak；1103.6cm-1Asymmetric stretching vibration peak of the neighbouring absworption peak for Si-O-Si, 804.2cm-1Neighbouring absworption peak
For the symmetrical stretching vibration peak of Si-O-Si, these absworption peaks are Nano-meter SiO_22Characteristic peak.By SiO2The infrared spectrum of-KH540
Understand, in 3394.6cm-1Neighbouring absworption peak is the stretching vibration peak of-NH, in 2924.7cm-1Neighbouring absworption peak is-CH2's
Characteristic absorption peak, is also clearly present Nano-meter SiO_2 in addition on infrared spectrum2Characteristic peak.Result above shows, Nano-meter SiO_22With silicon
Alkane coupling agent KH540 there occurs reaction, in Nano-meter SiO_22Surface has connected amino.By SiO2The infrared spectrum of-KH540-MA can
Know, in 2931.4cm-1Neighbouring absworption peak is-CH2Characteristic absorption peak, new absworption peak is occurred in that on infrared spectrum,
1707.3cm-1Characteristic absorption peak of the neighbouring absworption peak for carbonyl, in 1580.2cm-1Neighbouring absworption peak is carbon-carbon double bond
Characteristic absorption peak.Additionally, SiO is also clearly present on infrared spectrum2Characteristic peak.Result above shows, Nano-meter SiO_22The hydroxyl on surface
Base is reacted with KH540, in Nano-meter SiO_22Surface has connected amino；Nano-meter SiO_22The amino on surface again with maleic acid
Acid anhydride reacts, in Nano-meter SiO_22Surface has connected the carbon-carbon double bond with reactivity.
Nuclear magnetic resonance spectroscopy
(1) instrument and reagent
200 nuclear magnetic resonance spectrometers of Bruker AC-E, Bruker Biospin companies of Switzerland；Nuclear magnetic tube, U.S. WILMAD
LAB GLASS companies；DZF-6500 type vacuum drying ovens, 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 70.0 DEG C of vacuum drying oven and is dried 24h；2. a certain amount of modified product for obtaining
Product are added in nuclear magnetic tube；3. to addition SiO2Deuterated acetone is added in the nuclear magnetic tube of-KH540, to addition SiO2-KH540-MA
Nuclear magnetic tube in add deuterated dimethyl sulfoxide；4. the hydrogen spectrum of product is scanned with 200 nuclear magnetic resonance spectrometers of Bruker AC-E, is swept
Frequency is retouched for 200Hz.
(3) experimental result and analysis
SiO2The hydrogen spectrum of-KH540 is as shown in Figure 7.0.89ppm is-CH2-CH2-CH2-NH2The chemical shift of proton,
1.91ppm is-CH2-CH2-CH2-NH2The chemical shift of proton, 2.22ppm are-CH2-CH2-CH2-NH2The chemical shift of proton,
2.83ppm is-CH2-CH2-CH2-NH2The chemical shift of proton, by SiO2Knowable to the hydrogen spectrum of-KH540, Nano-meter SiO_22By silane idol
Connection agent KH540 is successfully modified, so as in Nano-meter SiO_22Surface introduces amino.SiO2The hydrogen spectrum of-KH540-MA is as shown in Figure 8.
0.87ppm is-CH2-CH2-CH2The chemical shift of-NH- protons, 1.99ppm are-CH2-CH2-CH2The chemical potential of-NH- protons
Move, 2.67ppm is-CH2-CH2-CH2The chemical shift of-NH- protons, chemistry of the 6.68ppm for-NH-C (O)-CH=CH- protons
Displacement, chemical shifts of the 7.22ppm for-NH-C (O)-CH=CH- protons, by SiO2Knowable to the hydrogen spectrum of-KH540-MA, nanometer
SiO2Modified, the Nano-meter SiO_2 by silane coupler KH5402The amino that surface introduces is reacted with maleic anhydride, so as to
In Nano-meter SiO_22Surface introduces the carbon-carbon double bond that may participate in polyreaction.
Claims (5)
1. a kind of modified Nano SiO for the copolymer displacement of reservoir oil2Monomer, it is characterised in that the monomer is prepared into by following methods
Arrive：(1) utilize Nano-meter SiO_22With 3- aminopropyl triethoxysilanes in 80～100 DEG C of anhydrous toluene solution, reaction 12h with
On obtain amino modified Nano-meter SiO_22, and by controlling the addition of 3- aminopropyl triethoxysilanes controlling Nano-meter SiO_22
The content of surface amino groups；(2) using excessive maleic anhydride and amino modified Nano-meter SiO_22Reaction is obtained with reaction
The carbon-carbon double bond modified Nano SiO of activity2Monomer；Step (2) is including following operation：1. in DMF solution
Maleic anhydride, stirring and dissolving is added to obtain mixed solution completely；2. in amino modified Nano-meter SiO_22Middle addition N, N- bis-
Methylformamide is uniformly mixing to obtain dispersion liquid；3. and then by the dispersant liquid drop that 2. operation obtains it is added to the mixing that 1. operation obtains
In solution, then in 60～80 DEG C of stirring reactions completely, the product for obtaining can obtain described through washing, filtration, after being dried
Carbon-carbon double bond modified Nano SiO with reactivity2Monomer.
2. the modified Nano SiO for the copolymer displacement of reservoir oil according to claim 12Monomer, it is characterised in that：In step (2)
Middle utilization hydrochloric acid-ethanol non-aqueous titration confirms amino modified Nano-meter SiO_22The amino reaction on surface is complete.
3. the modified Nano SiO for the copolymer displacement of reservoir oil according to claim 12Monomer, it is characterised in that：In step (1)
Reaction before utilize Grignard reagent titration measuring Nano-meter SiO_22Surface hydroxyl quantity, and hydrochloric acid-second is utilized after reacting
Alcohol non-aqueous titration determines Nano-meter SiO_22The content of surface amino groups.
4. the modified Nano SiO for the copolymer displacement of reservoir oil according to claim 12Monomer, it is characterised in that：In step (1)
In, the 3- aminopropyl triethoxysilanes and Nano-meter SiO_22Mass ratio be 1: 5～20.
5. the modified Nano SiO for the copolymer displacement of reservoir oil according to claim 12Monomer, it is characterised in that：In step (2)
In, the maleic anhydride and amino modified Nano-meter SiO_22Mass ratio be 1: 1～4.
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| 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 |
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| 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 |
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