CN104829765A - Microporous ionized resin with high oil absorption performance and preparation method thereof - Google Patents
Microporous ionized resin with high oil absorption performance and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a microporous ionized resin with high oil absorption performance and a preparation method thereof. The preparation method comprises the following steps: with chloromethylstyrene as a substrate and tetra phenylboric acid anion and tetraalkylammonium cation as coordination ionic groups, carrying out quaterization reaction and ion exchange reaction so as to obtain ionized monomer; and with the ionized monomer and metacrylate as polymerization monomer and butyl acetate as a pore forming agent, preparing the microporous ionized resin with high oil absorption performance via suspension polymerization under the action of an initiator and a cross-linking agent. According to the invention, due to introduction of the weak coordination ionic groups, the phenomena of electrostatic repulsion of charges on a molecular chain and imbalanced osmotic pressure in and out of the resin occur in the process of oil absorption of the resin, so the oil absorption rate and speed of the resin to oil products are further improved; moreover, the prepared ionized resin has the characteristics of high chemical stability, good oil retention performance, strong mechanical properties, etc. and has good development prospects in fields like marine floating oil and industrial oil-containing waste water.
Description
Technical field
The present invention relates to functional high polymer material field, be specifically related to a kind of micropore ionization high oil-absorbing resin and preparation method thereof.
Background technology
In recent years, along with development and the progress of industrial technology, cause environmental problem more serious, particularly oil pollution.The oil accident of the discharge of such as oily(waste)water, liquid waste and oil carrier, oil tank, causes the severe contamination of river, ocean, forms simultaneously threaten greatly the environment of the mankind and life.The repeatedly great crude oil leakage event particularly occurred in world wide in 2010, because its leakage of oil amount is large, waste oil spread scope is wide, badly shock the whole world to ocean and environment for human survival subsequent affect.Therefore, the research and development of high-capacity oil absorption material have become present stage one great research topic.
High oil absorbing resin is a kind of novel functional high molecule material, has excellent oil absorptiveness.It is by the low cross-linking polymkeric substance of lipophilicity monomer copolymerization, has three-dimensional netted macromolecular structure.When oils enters resin inside, due to the tridimensional network of resin, it is made to occur swelling and can not dissolve, lipophilic group simultaneously on macromolecular chain and the solvation of oil molecule, oil molecule is wrapped in the three-dimensional net structure of resin and does not overflow, thus realize oil suction and protect oily effect.Due to the constitutional features of uniqueness, high oil absorbing resin has the advantages such as oil-water selectivity is good, swelling rate fast, Oil keeping energy is strong, aftertreatment is simple.Therefore high oil absorbing resin tool in environment protection, Industrial Wastewater Treatment etc. has been widely used.But, in the research and development of high oil absorbing resin, still there are some problems.Such as the domestic and international research primary limitation to high oil absorbing resin is improving in reaction parameter and processing condition etc. at present, the oil suction multiplying power of the rosin products developed to some organic solvents and the oil product such as gasoline, diesel oil is lower, swelling rate is slower, general needs just can reach capacity oil number for nearly 20 hours, are difficult to like this meet the demand of market to high-capacity oil absorption material.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, aim to provide a kind of preparation method of novel microporous ionization high oil-absorbing resin, prepared ionization resin has very strong receptivity to organic solvent or oils, have swelling rate fast, protect the features such as oily rate is high, mechanical property is strong.The method preparation process is simple, easy handling.
A kind of micropore ionization high oil-absorbing resin, with p-chloromethyl styrene vinyl toluene for matrix, be incorporated in the molecular structure of resin by tetraphenyl borate negatively charged ion and tetraalkylammonium cation as coordination ion group, pass through quaternary ammonium reaction, ion exchange reaction obtains ionic monomers, again with ionic monomers, vinylbenzene and methacrylate-based monomer are polymerization single polymerization monomer, butylacetate is pore-creating agent, at initiator, under the effect of linking agent, employing suspension polymerization is prepared from, the particle diameter of micropore ionization high oil absorbing resin is 0.3mm-0.9mm, micropore size is 50-100um, specific surface area is 540-580m
2/ g.
The preparation method of above-mentioned resin, carries out according to following step:
Step 1, the preparation of ionic monomers: measure p-chloromethyl styrene and triethylamine in reaction vessel, add polar organic solvent again, stir to make it mix, under nitrogen protection, 50 DEG C of isothermal reaction 4-5 hour, after having reacted, products therefrom is carried out suction filtration, and put into reaction vessel with after acetone cleaning, add sodium tetraphenylborate and polar organic solvent wherein again, stir to make it mix, under nitrogen protection, 25 DEG C of isothermal reaction 5-6 hour, final product is carried out suction filtration, dry rear preservation in vacuum drying oven is placed on acetone cleaning, namely ionic monomers is prepared,
In step 1, the volume ratio of p-chloromethyl styrene and triethylamine is (1:1.5)-(1:2), and polar organic solvent is acetone or ethanol; The quality of sodium tetraphenylborate is 0.5-0.6 times of p-chloromethyl styrene and triethylamine reaction product quality;
Step 2, the preparation of micropore ionization high oil-absorbing resin: take dispersion agent and be dissolved in distilled water, stir, with this solution for aqueous phase, takes polymerization single polymerization monomer, initiator, linking agent and pore-creating agent simultaneously, stirs, using this solution as oil phase; Aqueous phase and oil phase are added in reaction vessel respectively, stirring velocity is 800-900r/min, 80-90 DEG C are warming up to from room temperature 20-25 degrees Celsius, react 7-9 hour under nitrogen protection, after reaction terminates, product is carried out suction filtration, utilize dehydrated alcohol and distilled water wash successively, be placed in vacuum drying oven kept dry, namely prepare micropore ionization high oil-absorbing resin;
In described step 2, dispersion agent is composite dispersing agent, and composite dispersing agent consists of Natvosol and gelatin; Or gelatin and Sodium dodecylbenzene sulfonate; Or Natvosol and Sodium dodecylbenzene sulfonate; Or Natvosol, gelatin and Sodium dodecylbenzene sulfonate; Natvosol consumption is 0.25%-0.5% of polymerization single polymerization monomer quality, and gelatin consumption is the 0.5%-1.0% of polymerization single polymerization monomer quality, and Sodium dodecylbenzene sulfonate consumption is the 0.25%-0.5% of polymerization single polymerization monomer quality.
In described step 2, polymerization single polymerization monomer is made up of ionic monomers, vinylbenzene and methacrylate-based monomer, and wherein methacrylate-based monomer is butyl methacrylate and lauryl methacrylate, or lauryl methacrylate and stearyl methacrylate, or butyl methacrylate and stearyl methacrylate, or butyl methacrylate, lauryl methacrylate and stearyl methacrylate, in described step 2, in polymerization single polymerization monomer, ionic monomers is 1-10 mass parts, styrene monomer is 40-50 mass parts, the consumption of methacrylate-based monomer is as follows according to component formula: butyl methacrylate is 25-35 mass parts, lauryl methacrylate is 15-25 mass parts, stearyl methacrylate is 10-15 mass parts, preferred ion monomer is 5-8 mass parts, styrene monomer is 45-50 mass parts, butyl methacrylate is 25-30 mass parts, lauryl methacrylate is 15-20 mass parts, stearyl methacrylate is 12-15 mass parts.
In described step 2, the volume ratio of described oil phase and aqueous phase is 1:(3-5).
In described step 2, initiator is peroxide or azo, such as benzoyl peroxide or 2,2'-Azobis(2,4-dimethylvaleronitrile), and consumption is the 2.0%-3.0% of polymerization single polymerization monomer quality; Linking agent is divinyl hydro carbons, and as Vinylstyrene, consumption is the 1.0%-2.0% of polymerization single polymerization monomer quality;
In described step 2, pore-creating agent is the one in ethyl acetate, butylacetate or normal heptane, and consumption is the 30%-50% of polymerization single polymerization monomer quality.
In above-mentioned preparation method, the particle diameter of preparation-obtained micropore ionization high oil absorbing resin is 0.3mm-0.9mm, and micropore size is 50-100um, and specific surface area is 540-580m
2/ g.
Utilize infrared spectra to test product of the present invention, in (a), wave number is 3421cm
-1that in (c), wave number is at 2935cm because the-OH Interference Peaks produced after the product moisture absorption
-1, 2858cm
-1for-CH
3,-CH
2stretching vibration absorption peak.1734cm
-1for the absorption peak of fat base-COO-, 1468cm
-1, 1389cm
-1for place belongs to the vibration peak on phenyl ring skeleton, 750cm
-1for the out-of-plane deformation vibration peak of phenyl ring, 1175cm
-1for what cause in the stretching vibration of C-N key.Analyze in conjunction with above, susceptible of proof high oil absorbing resin is polymerized successfully, and tetraalkylammonium cation and tetraphenyl borate negatively charged ion have been incorporated in the molecular structure of resin.
The invention has the advantages that, the basis of common high oil absorbing resin introduces a certain amount of weak coordination ion group, prepared ionic monomers before this, then carry out suspension polymerization and prepare ionization resin, the cycle is short, and process is simple, easy handling.The introducing of weak coordination ion group, makes resin in oil-absorbing process, creates the osmotic pressure energy imbalance inside and outside the Coulomb repulsion of electric charge on molecular chain and resin, further increases it to the oil suction multiplying power of oil product and swelling rate.Make resin surface more coarse adding of pore-creating agent, number cells increases, and also substantially increases oil suction multiplying power and the swelling rate of resin simultaneously.In addition, the micropore ion height oil suction resin prepared by the present invention also has that chemical stability is high, mechanical property is strong, can reuse the feature such as often.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscopic picture of micropore ion height oil suction resin of the present invention.
Fig. 2 is the infrared spectrogram of micropore ion height oil suction resin prepared by the present invention, wherein (a) the quaternary ammoniated product that is p-chloromethyl styrene, and (b) is ion exchange product, and (c) is the micropore ionization resin of polymerization.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly, below embodiment of the present invention is described further in detail.Embodiment 1
The preparation of ionic monomers:
(1) measure 9mL p-chloromethyl styrene and 14mL triethylamine in the there-necked flask of 250mL, then add 18mL acetone, stirring velocity is 500r/min, under nitrogen protection, and 50 DEG C of isothermal reactions 4 hours.
(2) product after having reacted is carried out suction filtration, and put into there-necked flask after cleaning three times with acetone, then add 0.4g sodium tetraphenylborate and 15mL acetone, stirring velocity is 500r/min, under nitrogen protection, and 25 DEG C of isothermal reactions 5 hours.
(3) final product is carried out suction filtration, clean three times with acetone, be placed in the dry rear preservation of vacuum drying oven, namely prepare ionic monomers.
The preparation of micropore ionization high oil-absorbing resin:
(1) take 0.05g Natvosol and 0.10g gelatin is dissolved in 60ml distilled water, stir, add in there-necked flask.
(2) take 0.5g ionic monomers, 9.5g vinylbenzene, 6.0g butyl methacrylate, 4.0g lauryl methacrylate, 0.4g benzoyl peroxide, 0.2g Vinylstyrene, 6.0g butylacetate, add in there-necked flask after mixing.
(3) stirring velocity is 900r/min, is slowly warming up to 85 DEG C, reacts 7 hours under nitrogen protection.
(4) reacted product is carried out suction filtration, with dehydrated alcohol and distilled water wash three times, be placed in vacuum drying oven kept dry, namely prepare micropore ionization high oil-absorbing resin.
The micropore ionization high oil-absorbing resin sample prepared in this embodiment is known through oil absorptiveness test, and the oil suction multiplying power of sample to tetracol phenixin is 30.24g/g, and the oil suction time that reaches capacity is about 3h; Be 23.57g/g to the oil suction multiplying power of methylene dichloride, the oil suction time that reaches capacity is about 2.8h.
Embodiment 2
The preparation of ionic monomers:
(1) measure 10mL p-chloromethyl styrene and 16mL triethylamine in the there-necked flask of 250mL, then add 19mL acetone, stirring velocity is 500r/min, under nitrogen protection, and 50 DEG C of isothermal reactions 4.5 hours.
(2) product after having reacted is carried out suction filtration, and put into there-necked flask after cleaning three times with acetone, then add 0.45g sodium tetraphenylborate and 16mL acetone, stirring velocity is 500r/min, under nitrogen protection, and 25 DEG C of isothermal reactions 5.5 hours.
(3) final product is carried out suction filtration, clean three times with acetone, be placed in the dry rear preservation of vacuum drying oven, namely prepare ionic monomers.
The preparation of micropore ionization high oil-absorbing resin:
(1) take 0.1g Natvosol and 0.1g Sodium dodecylbenzene sulfonate is dissolved in 70ml distilled water, stir, add in there-necked flask.
(2) take 0.8g ionic monomers, 9.2g vinylbenzene, 7.0g butyl methacrylate, 3.0g lauryl methacrylate, 0.5g benzoyl peroxide, 0.25g Vinylstyrene, 7.0g butylacetate, add in there-necked flask after mixing.
(3) stirring velocity is 900r/min, is slowly warming up to 85 DEG C, reacts 7.5 hours under nitrogen protection.
(4) reacted product is carried out suction filtration, with dehydrated alcohol and distilled water wash three times, be placed in vacuum drying oven kept dry, namely prepare micropore ionization high oil-absorbing resin.
The micropore ionization high oil-absorbing resin sample prepared in this embodiment is known through oil absorptiveness test, and the oil suction multiplying power of sample to tetracol phenixin is 32.51g/g, and the oil suction time that reaches capacity is about 2.5h; Be 25.45g/g to the oil suction multiplying power of methylene dichloride, the oil suction time that reaches capacity is about 2.8h.
Embodiment 3
The preparation of ionic monomers:
(1) measure 11mL p-chloromethyl styrene and 20mL triethylamine in the there-necked flask of 250mL, then add 20mL acetone, stirring velocity is 500r/min, under nitrogen protection, and 50 DEG C of isothermal reactions 5 hours.
(2) product after having reacted is carried out suction filtration, and put into there-necked flask after cleaning three times with acetone, then add 0.6g sodium tetraphenylborate and 20mL acetone, stirring velocity is 500r/min, under nitrogen protection, and 25 DEG C of isothermal reactions 5.5 hours.
(3) final product is carried out suction filtration, clean three times with acetone, be placed in the dry rear preservation of vacuum drying oven, namely prepare ionic monomers.
The preparation of micropore ionization high oil-absorbing resin:
(1) take 0.15g gelatin and 0.10g Sodium dodecylbenzene sulfonate is dissolved in 75ml distilled water, stir, add in there-necked flask.
(2) take 1.0g ionic monomers, 9.0g vinylbenzene, 5.5g butyl methacrylate, 4.5g lauryl methacrylate, 0.6g benzoyl peroxide, 0.3g Vinylstyrene, 7.0g butylacetate, add in there-necked flask after mixing.
(3) stirring velocity is 900r/min, is slowly warming up to 85 DEG C, reacts 8 hours under nitrogen protection.
(4) reacted product is carried out suction filtration, with dehydrated alcohol and distilled water wash three times, be placed in vacuum drying oven kept dry, namely prepare micropore ionization high oil-absorbing resin.
The micropore ionization high oil-absorbing resin sample prepared in this embodiment is known through oil absorptiveness test, and the oil suction multiplying power of sample to tetracol phenixin is 35.86g/g, and the oil suction time that reaches capacity is about 1h; Be 28.38g/g to the oil suction multiplying power of methylene dichloride, the oil suction time that reaches capacity is about 1.2h.
Embodiment 4
The preparation of ionic monomers:
(1) measure 12mL p-chloromethyl styrene and 20mL triethylamine in the there-necked flask of 250mL, then add 25mL acetone, stirring velocity is 500r/min, under nitrogen protection, and 50 DEG C of isothermal reactions 5 hours.
(2) product after having reacted is carried out suction filtration, and put into there-necked flask after cleaning three times with acetone, then add 0.7g sodium tetraphenylborate and 25mL acetone, stirring velocity is 500r/min, under nitrogen protection, and 25 DEG C of isothermal reactions 6 hours.
(3) final product is carried out suction filtration, clean three times with acetone, be placed in the dry rear preservation of vacuum drying oven, namely prepare ionic monomers.
The preparation of micropore ionization high oil-absorbing resin:
(1) take 0.05g Natvosol, 0.10g gelatin and 0.05g Sodium dodecylbenzene sulfonate to be dissolved in 80ml distilled water, stir, add in there-necked flask.
(2) take 2.0g ionic monomers, 8.0g vinylbenzene, 5.0g butyl methacrylate, 5.0g lauryl methacrylate, 0.6g benzoyl peroxide, 0.3g Vinylstyrene, 8.0g butylacetate, add in there-necked flask after mixing.
(3) stirring velocity is 900r/min, is slowly warming up to 85 DEG C, reacts 8 hours under nitrogen protection.
(4) reacted product is carried out suction filtration, with dehydrated alcohol and distilled water wash three times, be placed in vacuum drying oven kept dry, namely prepare micropore ionization high oil-absorbing resin.
The micropore ionization high oil-absorbing resin sample prepared in this embodiment is known through oil absorptiveness test, and the oil suction multiplying power of sample to tetracol phenixin is 34.46g/g, and the oil suction time that reaches capacity is about 1.1h; Be 26.25g/g to the oil suction multiplying power of methylene dichloride, the oil suction time that reaches capacity is about 1.4h.
Embodiment 5
The preparation of ionic monomers:
(1) measure 10mL p-chloromethyl styrene and 18mL triethylamine in the there-necked flask of 250mL, then add 24mL acetone, stirring velocity is 500r/min, under nitrogen protection, and 50 DEG C of isothermal reactions 4.5 hours.
(2) product after having reacted is carried out suction filtration, and put into there-necked flask after cleaning three times with acetone, then add 0.6g sodium tetraphenylborate and 20mL acetone, stirring velocity is 500r/min, under nitrogen protection, and 25 DEG C of isothermal reactions 5.5 hours.
(3) final product is carried out suction filtration, clean three times with acetone, be placed in the dry rear preservation of vacuum drying oven, namely prepare ionic monomers.
The preparation of micropore ionization high oil-absorbing resin:
(1) take 0.10g Natvosol, 0.15g gelatin and 0.05g Sodium dodecylbenzene sulfonate to be dissolved in 80ml distilled water, stir, add in there-necked flask.
(2) take 1.5g ionic monomers, 9.0g vinylbenzene, 5.5g butyl methacrylate, 4.0g lauryl methacrylate, 0.5g benzoyl peroxide, 0.2g Vinylstyrene, 9.0g butylacetate, add in there-necked flask after mixing.
(3) stirring velocity is 900r/min, is slowly warming up to 85 DEG C, reacts 9 hours under nitrogen protection.
(4) reacted product is carried out suction filtration, with dehydrated alcohol and distilled water wash three times, be placed in vacuum drying oven kept dry, namely prepare micropore ionization high oil-absorbing resin.
The micropore ionization high oil-absorbing resin sample prepared in this embodiment is known through oil absorptiveness test, and the oil suction multiplying power of sample to tetracol phenixin is 33.28g/g, and the oil suction time that reaches capacity is about 2h; Be 24.86g/g to the oil suction multiplying power of methylene dichloride, the oil suction time that reaches capacity is about 2.3h.
The oil suction multiplying power testing method of above-mentioned sample is as follows:
The oil suction multiplying power (Q) of high oil absorbing resin adopts following steps to carry out.First take the high oil absorbing resin of certain mass drying, be placed in the beaker of numbering, in beaker, add enough organic solvents.Sample is at room temperature left standstill 24 hours, makes it drip continuously after taking-up to drop down to drip to oil droplet to drop down clean, and to weigh rapidly.The oil suction multiplying power of resin can calculate according to formula below:
Q＝(M
2-M
1)/M
1
M in formula
1for the quality before high oil absorbing resin oil suction, g; M
2for the quality after high oil absorbing resin oil suction, g; Q is oil suction multiplying power, g/g.
According to the method described above, change different organic solvents and carry out oil suction test, result is as shown in the table, and micropore ionization resin is to the oil suction multiplying power of different organic solvents
The selection that the preparation method pointed out according to content of the present invention and processing condition carry out processing parameter is prepared oil absorption resin, and tetraalkylammonium cation and tetraphenyl borate negatively charged ion have been incorporated in the molecular structure of resin to utilize examination of infrared spectrum to be confirmed; When carrying out the test of oil suction multiplying power, result is cashed out with the result of above-described embodiment 1-5 basically identical, reach capacity the oil suction time at 1-3h, oil suction multiplying power for different organic solvents is as follows: methyl alcohol 3-4g/g, acetone 3-4.5g/g, dimethylbenzene 14-20g/g, hexanaphthene 15-21g/g, tetrahydrofuran (THF) 20-38g/g, toluene dichloride 23-30g/g, tetracol phenixin 30-36g/g.
Above to invention has been exemplary description, when not departing from core of the present invention, any simple amendment, distortion or other same domains technician do not spend the equal replacement of creative work, all belong to protection scope of the present invention.
Claims (6)
1. a micropore ionization high oil-absorbing resin, it is characterized in that, tetraphenyl borate negatively charged ion and tetraalkylammonium cation is adopted to be incorporated in the molecular structure of resin as coordination ion group, the particle diameter of micropore ionization high oil absorbing resin is 0.3mm-0.9mm, micropore size is 50-100um, and specific surface area is 540-580m
2/ g, carries out according to following step:
Step 1, the preparation of ionic monomers: measure p-chloromethyl styrene and triethylamine in reaction vessel, add polar organic solvent again, stir to make it mix, under nitrogen protection, 50 DEG C of isothermal reaction 4-5 hour, after having reacted, products therefrom is carried out suction filtration, and put into reaction vessel with after acetone cleaning, add sodium tetraphenylborate and polar organic solvent wherein again, stir to make it mix, under nitrogen protection, 25 DEG C of isothermal reaction 5-6 hour, final product is carried out suction filtration, dry rear preservation in vacuum drying oven is placed on acetone cleaning, namely ionic monomers is prepared, in step 1, the volume ratio of p-chloromethyl styrene and triethylamine is (1:1.5)-(1:2), and polar organic solvent is acetone or ethanol, the quality of sodium tetraphenylborate is 0.5-0.6 times of p-chloromethyl styrene and triethylamine reaction product quality,
Step 2, the preparation of micropore ionization high oil-absorbing resin: take dispersion agent and be dissolved in distilled water, stir, with this solution for aqueous phase, takes polymerization single polymerization monomer, initiator, linking agent and pore-creating agent simultaneously, stirs, using this solution as oil phase; Aqueous phase and oil phase are added in reaction vessel respectively, stirring velocity is 800-900r/min, 80-90 DEG C are warming up to from room temperature 20-25 degrees Celsius, react 7-9 hour under nitrogen protection, after reaction terminates, product is carried out suction filtration, utilize dehydrated alcohol and distilled water wash successively, be placed in vacuum drying oven kept dry, namely prepare micropore ionization high oil-absorbing resin;
In described step 2, dispersion agent is composite dispersing agent, and composite dispersing agent consists of Natvosol and gelatin; Or gelatin and Sodium dodecylbenzene sulfonate; Or Natvosol and Sodium dodecylbenzene sulfonate; Or Natvosol, gelatin and Sodium dodecylbenzene sulfonate; Natvosol consumption is 0.25%-0.5% of polymerization single polymerization monomer quality, and gelatin consumption is the 0.5%-1.0% of polymerization single polymerization monomer quality, and Sodium dodecylbenzene sulfonate consumption is the 0.25%-0.5% of polymerization single polymerization monomer quality;
In described step 2, polymerization single polymerization monomer is made up of ionic monomers, vinylbenzene and methacrylate-based monomer, and wherein methacrylate-based monomer is butyl methacrylate and lauryl methacrylate; Or lauryl methacrylate and stearyl methacrylate; Or butyl methacrylate and stearyl methacrylate; Or butyl methacrylate, lauryl methacrylate and stearyl methacrylate; In described step 2, in polymerization single polymerization monomer, ionic monomers is 1-10 mass parts, styrene monomer is 40-50 mass parts, the consumption of methacrylate-based monomer is as follows according to component formula: butyl methacrylate is 25-35 mass parts, lauryl methacrylate is 15-25 mass parts, and stearyl methacrylate is 10-15 mass parts; The volume ratio of described oil phase and aqueous phase is 1:(3-5); Initiator is benzoyl peroxide or 2,2'-Azobis(2,4-dimethylvaleronitrile), and consumption is the 2.0%-3.0% of polymerization single polymerization monomer quality; Linking agent is Vinylstyrene, and consumption is the 1.0%-2.0% of polymerization single polymerization monomer quality; Pore-creating agent is the one in ethyl acetate, butylacetate or normal heptane, and consumption is the 30%-50% of polymerization single polymerization monomer quality.
2. a kind of micropore ionization high oil-absorbing resin according to claim 1, it is characterized in that, in described step 2, preferred ion monomer is 5-8 mass parts, styrene monomer is 45-50 mass parts, butyl methacrylate is 25-30 mass parts, and lauryl methacrylate is 15-20 mass parts, and stearyl methacrylate is 12-15 mass parts.
3. a preparation method for micropore ionization high oil-absorbing resin, is characterized in that, carries out according to following step:
Step 1, the preparation of ionic monomers: measure p-chloromethyl styrene and triethylamine in reaction vessel, add polar organic solvent again, stir to make it mix, under nitrogen protection, 50 DEG C of isothermal reaction 4-5 hour, after having reacted, products therefrom is carried out suction filtration, and put into reaction vessel with after acetone cleaning, add sodium tetraphenylborate and polar organic solvent wherein again, stir to make it mix, under nitrogen protection, 25 DEG C of isothermal reaction 5-6 hour, final product is carried out suction filtration, dry rear preservation in vacuum drying oven is placed on acetone cleaning, namely ionic monomers is prepared, in step 1, the volume ratio of p-chloromethyl styrene and triethylamine is (1:1.5)-(1:2), and polar organic solvent is acetone or ethanol, the quality of sodium tetraphenylborate is 0.5-0.6 times of p-chloromethyl styrene and triethylamine reaction product quality,
Step 2, the preparation of micropore ionization high oil-absorbing resin: take dispersion agent and be dissolved in distilled water, stir, with this solution for aqueous phase, takes polymerization single polymerization monomer, initiator, linking agent and pore-creating agent simultaneously, stirs, using this solution as oil phase; Aqueous phase and oil phase are added in reaction vessel respectively, stirring velocity is 800-900r/min, 80-90 DEG C are warming up to from room temperature 20-25 degrees Celsius, react 7-9 hour under nitrogen protection, after reaction terminates, product is carried out suction filtration, utilize dehydrated alcohol and distilled water wash successively, be placed in vacuum drying oven kept dry, namely prepare micropore ionization high oil-absorbing resin;
In described step 2, dispersion agent is composite dispersing agent, and composite dispersing agent consists of Natvosol and gelatin; Or gelatin and Sodium dodecylbenzene sulfonate; Or Natvosol and Sodium dodecylbenzene sulfonate; Or Natvosol, gelatin and Sodium dodecylbenzene sulfonate; Natvosol consumption is 0.25%-0.5% of polymerization single polymerization monomer quality, and gelatin consumption is the 0.5%-1.0% of polymerization single polymerization monomer quality, and Sodium dodecylbenzene sulfonate consumption is the 0.25%-0.5% of polymerization single polymerization monomer quality;
In described step 2, polymerization single polymerization monomer is made up of ionic monomers, vinylbenzene and methacrylate-based monomer, and wherein methacrylate-based monomer is butyl methacrylate and lauryl methacrylate; Or lauryl methacrylate and stearyl methacrylate; Or butyl methacrylate and stearyl methacrylate; Or butyl methacrylate, lauryl methacrylate and stearyl methacrylate; In described step 2, in polymerization single polymerization monomer, ionic monomers is 1-10 mass parts, styrene monomer is 40-50 mass parts, the consumption of methacrylate-based monomer is as follows according to component formula: butyl methacrylate is 25-35 mass parts, lauryl methacrylate is 15-25 mass parts, and stearyl methacrylate is 10-15 mass parts; The volume ratio of described oil phase and aqueous phase is 1:(3-5); Initiator is benzoyl peroxide or 2,2'-Azobis(2,4-dimethylvaleronitrile), and consumption is the 2.0%-3.0% of polymerization single polymerization monomer quality; Linking agent is Vinylstyrene, and consumption is the 1.0%-2.0% of polymerization single polymerization monomer quality; Pore-creating agent is the one in ethyl acetate, butylacetate or normal heptane, and consumption is the 30%-50% of polymerization single polymerization monomer quality.
4. the preparation method of a kind of micropore ionization high oil-absorbing resin according to claim 3, it is characterized in that, in described step 2, preferred ion monomer is 5-8 mass parts, styrene monomer is 45-50 mass parts, butyl methacrylate is 25-30 mass parts, and lauryl methacrylate is 15-20 mass parts, and stearyl methacrylate is 12-15 mass parts.
5. the application of a kind of micropore ionization high oil-absorbing resin as claimed in claim 1 or 2 in absorption oils or organic solvent.
6. application according to claim 5, it is characterized in that, reach capacity the oil suction time at 1-3h, oil suction multiplying power for different organic solvents is as follows: methyl alcohol 3-4g/g, acetone 3-4.5g/g, dimethylbenzene 14-20g/g, hexanaphthene 15-21g/g, tetrahydrofuran (THF) 20-38g/g, toluene dichloride 23-30g/g, tetracol phenixin 30-36g/g.
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| CN114316099A (en) * | 2022-01-18 | 2022-04-12 | 西南石油大学 | Water purifying agent containing boric acid ester for treating oilfield produced water through dynamic covalent bond and application of water purifying agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101845215A (en) * | 2010-04-02 | 2010-09-29 | 中国科学技术大学 | Preparation method based on brominated polyphenylether blending of hybrid anion exchange membrane |
| CN102643384A (en) * | 2012-04-28 | 2012-08-22 | 天津大学 | Polymethacrylate high oil-absorbing polyelectrolyte resin and preparation method thereof |
| CN104277170A (en) * | 2013-07-12 | 2015-01-14 | 天津大学 | Ternary porous high oil-absorption polyelectrolyte resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101845215A (en) * | 2010-04-02 | 2010-09-29 | 中国科学技术大学 | Preparation method based on brominated polyphenylether blending of hybrid anion exchange membrane |
| CN102643384A (en) * | 2012-04-28 | 2012-08-22 | 天津大学 | Polymethacrylate high oil-absorbing polyelectrolyte resin and preparation method thereof |
| CN104277170A (en) * | 2013-07-12 | 2015-01-14 | 天津大学 | Ternary porous high oil-absorption polyelectrolyte resin and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316099A (en) * | 2022-01-18 | 2022-04-12 | 西南石油大学 | Water purifying agent containing boric acid ester for treating oilfield produced water through dynamic covalent bond and application of water purifying agent |
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