CN104761930A - Modified nanometer silica functional monomer for oil-displacement polymer - Google Patents

Modified nanometer silica functional monomer for oil-displacement polymer Download PDF

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CN104761930A
CN104761930A CN201510018173.0A CN201510018173A CN104761930A CN 104761930 A CN104761930 A CN 104761930A CN 201510018173 A CN201510018173 A CN 201510018173A CN 104761930 A CN104761930 A CN 104761930A
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nano
meter sio
amino
modified
carbon
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赖南君
吴涛
叶仲斌
张艳
刘艳勤
张琴
冯泓萍
冯静
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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 silica functional monomer for an oil-displacement polymer. A preparation method of the modified nanometer silica functional monomer comprises the following steps that 1, nanometer SiO2 and an aminosilane coupling agent undergo a reaction to produce amino-modified nanometer SiO2, and the content of amino groups on the surface of the nanometer SiO2 is controlled by control of a use amount of the aminosilane coupling agent, and 2, an excess amount of a modifier containing carbon-carbon double bonds and the amino-modified nanometer SiO2 undergo a reaction to produce a carbon-carbon double bond-modified nanometer SiO2 monomer with reaction activity. The modified nanometer silica functional monomer for an oil-displacement polymer can quantificationally graft carbon-carbon double bonds with reaction activity to the surface of the nanometer SiO2 according to demands and is convenient for control of the content of the grafted carbon-carbon double bonds by control of a use amount of the aminosilane coupling agent.

Description

For the modified manometer silicon dioxide function monomer of flooding polymers
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 manometer silicon dioxide function monomer for flooding polymers.
Background technology
Nano silicon is a kind of nano-powder material that the output of large-scale industrial production in the world is at present the highest.Special microparticle surfaces Rotating fields and electronic energy level structure create the performance that common nanoparticle does not have.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, and the property such as unusual mechanics, electromagnetism, optics, calorifics and chemistry of having, be used to all conglomeraties such as biology, medicine, chemical industry, material, electronics, machinery, the energy, national defence; Especially all have a wide range of applications in fields such as polymer composite, electronic package material, plastics, coating, pigment, rubber, pottery, sizing agent, makeup, support of the catalyst and anti-biotic materials.
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.Nano-meter SiO_2 2surface modifying method have esterification reaction method, modification by coupling, surfactant method, graftomer method etc.In the prior art, 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.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, can with carboxyl (-COOH), isocyanate group (-NCO) etc. can with the functional group of hydroxyl reaction.
Usually the silane coupling agent containing carbon-carbon double bond is utilized to modify nano silicon in prior art, but the carbon-carbon double bond of silica sphere is difficult to quantitative mensuration, and the reaction contained between the silane coupling agent of carbon-carbon double bond and silicon-dioxide is difficult to fully react completely, and be subject to the impact of many factors, therefore the modification degree of silica sphere carbon-carbon double bond is difficult to accurately control, but silica surface modified degree, the performance of proportionlity on matrix material of such as unmodified hydroxyl and carbon-carbon double bond has remarkably influenced, therefore be necessary very much to develop a kind of Nano-meter SiO_2 2surface modification degree carries out the method for fixing quantity.
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 manometer silicon dioxide function monomer for flooding polymers.
To achieve these goals, present invention employs following technical scheme:
For a modified manometer silicon dioxide function monomer for flooding polymers, described monomer is prepared by following methods: (1) utilizes Nano-meter SiO_2 2amino modified Nano-meter SiO_2 is obtained by reacting with amino silicane coupling agent 2, and control Nano-meter SiO_2 by the addition controlling amino silicane coupling agent 2the content of surface amino groups; (2) properties-correcting agent of excessive carbon-carbon double bonds 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, step (2) comprises following operation: the properties-correcting agent 1. adding carbon-carbon double bonds in a second organic solvent, and stirring and dissolving obtains mixing solutions completely; 2. at amino modified Nano-meter SiO_2 2in add the second organic solvent and stir and obtain dispersion liquid; 3. be then added to operating the dispersant liquid drop that 2. obtains in the mixing solutions that 1. operation obtain, then stirring reaction is complete, 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 (1), Nano-meter SiO_2 is utilized 2react in the first organic solvent with amino silicane coupling agent.
Wherein, described amino silicane coupling agent is at least one in γ-aminopropyltrimethoxysilane, γ-aminopropyl triethoxysilane, phenylaminomethyl triethoxyl silane, phenylaminomethyl Trimethoxy silane, N-β (aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N-β (aminoethyl)-γ-aminopropyltriethoxy diethoxy silane and N-β (aminoethyl)-γ-aminopropyl triethoxysilane.
Wherein, the properties-correcting agent of described carbon-carbon double bonds is maleic anhydride, vinylformic acid or acrylate.
Wherein, described first organic solvent is selected from least one in anhydrous dimethyl benzene, propyl carbinol, petroleum naphtha, Virahol, methylcyclohexanone, dimethylcyclohexanon, trimethylcyclohexanone, isophorone, ritalin or vinyl acetic monomer.
Wherein, described second organic solvent is selected from least one in DMF, N,N-dimethylacetamide and N-Methyl pyrrolidone.
Wherein, hydrochloric acid-ethanol nonaqueous titrations is utilized to confirm amino modified Nano-meter SiO_2 in step (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 step (1) reaction 2the content of surface amino groups.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, 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.
Embodiment 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 titration apparatus; 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), measurement result 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 1nano-meter SiO_2 2the adsorbed hydroxyl content
Nano-meter SiO_2 2the mensuration of modified surface amino groups
Utilize γ-aminopropyl triethoxysilane to Nano-meter SiO_2 2modifying surface, 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.
Hydrochloric acid-ethanol nonaqueous titrations can be used after reaction to measure Nano-meter SiO_2 2surface institute connect amino content.Titration principle and the operation steps of the method are as follows: Nano-meter SiO_2 2modified through γ-aminopropyl triethoxysilane, 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 γ-aminopropyl triethoxysilane 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.
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 γ-aminopropyl triethoxysilane and 80mL anhydrous dimethyl benzene, stirring reaction 48h at the temperature arranged.After reaction terminates, decompression steams unreacted γ-aminopropyl triethoxysilane and anhydrous dimethyl benzene, 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.When temperature of reaction is lower, Nano-meter SiO_2 2surface amino groups content increases along with the rising of temperature; But continue to raise temperature of reaction, Nano-meter SiO_2 when temperature of reaction is elevated to 75.0 DEG C or more 2the amino content on surface does not continue to increase, and γ-aminopropyl triethoxysilane and Nano-meter SiO_2 75 DEG C or more times are described 2the reaction of surface hydroxyl is more complete.As preferably, consider volatilization and the speed of reaction of solvent, described temperature of reaction is preferably 75 ~ 100 DEG C, further, is preferably 80 ~ 90 DEG C.
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 γ-aminopropyl triethoxysilane and 80mL anhydrous dimethyl benzene, at 75.0 DEG C, react different time.After reaction terminates, decompression steams unreacted γ-aminopropyl triethoxysilane and anhydrous dimethyl benzene, 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.Make properties-correcting agent with γ-aminopropyl triethoxysilane, when being 12h when reacted, continue 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.
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 anhydrous dimethyl benzene at 80.0 DEG C with γ-aminopropyl triethoxysilane, 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 γ-aminopropyl triethoxysilane and the 16mL anhydrous dimethyl benzene of different amount, at 80.0 DEG C, reacts 12h.By reaction product vacuum-drying 24h at 80.0 DEG C after reaction terminates.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.Modified Nano-meter SiO_2 can be controlled by the dosage controlling γ-aminopropyl triethoxysilane 2the content of surface amino groups.Along with the increase of γ-aminopropyl triethoxysilane dosage, the linear increase of amino content, the corresponding increase of modification degree.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 γ-aminopropyl triethoxysilane is modified 2, add 20mL N,N-dimethylacetamide (DMA) and make solvent, dropped to by above-mentioned solution at 20.0 DEG C in the solution containing 0.4g ethyl acrylate and 20mLDMA, time for adding is 3h; At 75.0 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.
Show to adopt the method for the present embodiment at Nano-meter SiO_2 by thermogravimetric analysis and Infrared spectroscopy 2surface has connected the carbon-carbon double bond with reactive behavior.
Embodiment 2
Utilize phenylaminomethyl triethoxyl silane to substitute γ-aminopropyl triethoxysilane as different from Example 1, can obtain at Nano-meter SiO_2 equally 2surface has connected the carbon-carbon double bond with reactive behavior, and the addition of modification degree and phenylaminomethyl triethoxyl silane is linear, can control modification degree easily by the addition controlling phenylaminomethyl triethoxyl silane.
Embodiment 3
Propyl carbinol, petroleum naphtha, Virahol, methylcyclohexanone, dimethylcyclohexanon, trimethylcyclohexanone, isophorone, ritalin, vinyl acetic monomer is utilized to substitute anhydrous dimethyl benzene wherein as there being agent solvent as different from Example 1.Can obtain at Nano-meter SiO_2 equally 2surface has connected the carbon-carbon double bond with reactive behavior, and the addition of modification degree and phenylaminomethyl triethoxyl silane is linear, can control modification degree easily by the addition controlling amino silicane coupling agent.
Embodiment 4
Maleic anhydride, methyl acrylate, ethyl propenoate, butyl acrylate, ethyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, glycidyl acrylate, hydroxyethyl methylacrylate, Rocryl 410, glycidyl methacrylate or a-cyanoacrylate is utilized to substitute methacrylic acid-2-ethylhexyl as different from Example 1.Can obtain at Nano-meter SiO_2 equally 2surface has connected the carbon-carbon double bond with reactive behavior, and the addition of modification degree and phenylaminomethyl triethoxyl silane is linear, can control modification degree easily by the addition controlling amino silicane coupling agent.

Claims (9)

1., for a modified manometer silicon dioxide function monomer for flooding polymers, it is characterized in that described monomer is prepared by following methods: (1) utilizes Nano-meter SiO_2 2amino modified Nano-meter SiO_2 is obtained by reacting with amino silicane coupling agent 2, and control Nano-meter SiO_2 by the addition controlling amino silicane coupling agent 2the content of surface amino groups; (2) properties-correcting agent of excessive carbon-carbon double bonds 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. modified manometer silicon dioxide function monomer according to claim 1, is characterized in that: step (2) comprises following operation: the properties-correcting agent 1. adding carbon-carbon double bonds in a second organic solvent, and stirring and dissolving obtains mixing solutions completely; 2. at amino modified Nano-meter SiO_2 2in add the second organic solvent and stir and obtain dispersion liquid; 3. be then added to operating the dispersant liquid drop that 2. obtains in the mixing solutions that 1. operation obtain, then stirring reaction is complete, 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. modified manometer silicon dioxide function monomer according to claim 1, is characterized in that: in step (1), utilize Nano-meter SiO_2 2react in the first organic solvent with amino silicane coupling agent.
4. modified manometer silicon dioxide function monomer according to claim 1, is characterized in that: described amino silicane coupling agent is at least one in γ-aminopropyltrimethoxysilane, γ-aminopropyl triethoxysilane, phenylaminomethyl triethoxyl silane, phenylaminomethyl Trimethoxy silane, N-β (aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N-β (aminoethyl)-γ-aminopropyltriethoxy diethoxy silane and N-β (aminoethyl)-γ-aminopropyl triethoxysilane.
5. modified manometer silicon dioxide function monomer according to claim 1, is characterized in that: the properties-correcting agent of described carbon-carbon double bonds is maleic anhydride, vinylformic acid or acrylate.
6. modified manometer silicon dioxide function monomer according to claim 3, is characterized in that: described first organic solvent is selected from least one in anhydrous dimethyl benzene, propyl carbinol, petroleum naphtha, Virahol, methylcyclohexanone, dimethylcyclohexanon, trimethylcyclohexanone, isophorone, ritalin or vinyl acetic monomer.
7. modified manometer silicon dioxide function monomer according to claim 2, is characterized in that: described second organic solvent is selected from least one in DMF, N,N-dimethylacetamide and N-Methyl pyrrolidone.
8. modified manometer silicon dioxide function monomer according to claim 1, is characterized in that: utilize hydrochloric acid-ethanol nonaqueous titrations to confirm amino modified Nano-meter SiO_2 in step (2) 2the amino on surface reacts completely.
9. modified manometer silicon dioxide function monomer according to claim 1, 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 step (1) reaction 2the content of surface amino groups.
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CN115286316A (en) * 2022-08-05 2022-11-04 中建西部建设北方有限公司 Recycled concrete of gold tailings and waste rubber and preparation method thereof
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Application publication date: 20150708