CN104829765B - A kind of micropore ionization high oil-absorbing resin and preparation method thereof - Google Patents
A kind of micropore ionization high oil-absorbing resin and preparation method thereof Download PDFInfo
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- CN104829765B CN104829765B CN201510216748.XA CN201510216748A CN104829765B CN 104829765 B CN104829765 B CN 104829765B CN 201510216748 A CN201510216748 A CN 201510216748A CN 104829765 B CN104829765 B CN 104829765B
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Abstract
The present invention relates to a kind of micropore ionization high oil-absorbing resin and preparation method thereof, using p-chloromethyl styrene as matrix, with tetraphenyl borate anion and tetraalkylammonium cation as coordination ion group, ionic monomers are obtained by quaternary ammonium reaction, ion-exchange reactions.Again using ionic monomers and methyl acrylic ester as polymerized monomer, butyl acetate is pore-foaming agent, in the presence of initiator, crosslinking agent, and micropore ionization high oil-absorbing resin is prepared using suspension polymerization.The introducing of weak coordination ion group, makes resin in oil-absorbing process, generates the osmotic pressure energy imbalance inside and outside the Coulomb repulsion of electric charge and resin on strand, further increases its oil suction multiplying power and swelling rate to oil product.In addition, prepared ionization resin also has chemical stability high, protect oil performance is good, the features such as mechanical property is strong, has preferable development prospect in processing ocean oil slick and industrial oily waste water etc. field.
Description
Technical field
The present invention relates to functional high polymer material field, and in particular to a kind of micropore ionization high oil-absorbing resin and its system
Preparation Method.
Background technology
In recent years, continuing to develop and progressive with industrial technology, causes environmental problem more serious, particularly greasy dirt
Dye.Such as discharge of oil-polluted water, liquid waste and oil carrier, the oil accident of oil tank, cause the serious dirt of river, ocean
Dye, while the environment and life to the mankind are constituted and greatly threatened.What is occurred in particularly 2010 world wides is multiple great
Crude oil leakage event, because its oil leak amount is big, waste oil spread scope is wide, badly shocked to ocean and environment for human survival subsequent affect
The whole world.Therefore, the research and development of high-capacity oil absorption material turn into a great research topic at this stage.
High oil-absorbing resin is a kind of new functional high molecule material, with excellent oil absorbency.It is by lipophile
The low cross-linking polymer of monomer copolymerization, with three-dimensional netted macromolecular structure.When oils enters inside resin, due to tree
The tridimensional network of fat, makes it be swelled without dissolving, while lipophilic group and oil molecule on macromolecular chain
Solvation, oil molecule is wrapped in the three-dimensional net structure of resin and do not spill over come, so as to realize oil suction and guarantor
Oily effect.Due to unique architectural feature, high oil-absorbing resin has that oil-water selectivity is good, swelling rate is fast, protect oil performance is strong, after
The advantages of handling simple.Therefore high oil-absorbing resin has in terms of environmental protection, Industrial Wastewater Treatment has been widely used.So
And, some problems are still suffered from the research and development of high oil-absorbing resin.Research for example at present both at home and abroad to high oil-absorbing resin
Primary limitation is in terms of response parameter and process conditions are improved, and the naval stores developed is to some organic solvents and vapour
The oil suction multiplying power of the oil products such as oil, diesel oil is relatively low, and swelling rate is slower, generally requires nearly 20 hours and can be only achieved saturation oil absorption,
So it is difficult to meet demand of the market to high-capacity oil absorption material.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is desirable to provide a kind of novel microporous ionization high oil-absorbing
The preparation method of resin, prepared ionization resin has very strong absorbability to organic solvent or oils, with oil suction speed
Rate is fast, protect the features such as oil cut rate is high, mechanical property is strong.This method preparation process is simple, it is easy to operate.
A kind of micropore ionizes high oil-absorbing resin, using p-chloromethyl styrene methyl styrene as matrix, uses tetraphenylboron
Acid anion and tetraalkylammonium cation have been had been introduced in the molecular structure of resin as coordination ion group, by quaternary ammoniated
Reaction, ion-exchange reactions obtain ionic monomers, then using ionic monomers, styrene and methacrylate-based monomer be poly-
Close monomer, butyl acetate is pore-foaming agent, in the presence of initiator, crosslinking agent, is prepared from using suspension polymerization, micropore from
The particle diameter of sonization high oil-absorbing resin is 0.3mm-0.9mm, and micropore size is 50-100um, and specific surface area is 540-580m2/g。
The preparation method of above-mentioned resin, is carried out as steps described below：
Step 1, the preparation of ionic monomers：P-chloromethyl styrene and triethylamine are measured in reaction vessel, is added
Polar organic solvent, is stirred so that it is well mixed, under nitrogen protection, 50 DEG C of isothermal reactions 4-5 hour, general after the completion of reaction
Products therefrom carries out suction filtration, and is put into reaction vessel after being cleaned with acetone, then adds tetraphenylboron sodium thereto and polarity is organic
Solvent, is stirred so that it is well mixed, under nitrogen protection, 25 DEG C of isothermal reactions 5-6 hours, and final product is carried out into suction filtration,
It is placed in after being dried in vacuum drying chamber and preserves after being cleaned with acetone, that is, prepares ionic monomers；
In step 1, the volume ratio of p-chloromethyl styrene and triethylamine is (1：1.5)—(1：2), polar organic solvent
For acetone or ethanol；The quality of tetraphenylboron sodium is 0.5-the 0.6 of p-chloromethyl styrene and triethylamine react product quality
Times；
Step 2, micropore ionizes the preparation of high oil-absorbing resin：Weigh dispersant to be dissolved in distilled water, stir,
Using this solution as aqueous phase, while weighing polymerized monomer, initiator, crosslinking agent and pore-foaming agent, stir, oil is used as using this solution
Phase；Aqueous phase and oil phase are separately added into reaction vessel, mixing speed is 800-900r/min, from 20-25 degrees Celsius of room temperature
80-90 DEG C are warming up to, is reacted 7-9 hours under nitrogen protection, product is carried out suction filtration by reaction after terminating, successively using anhydrous
Ethanol and distillation water washing, are placed in kept dry in vacuum drying chamber, that is, prepare micropore ionization high oil-absorbing resin；
In the step 2, dispersant is composite dispersing agent, and composite dispersing agent composition is hydroxyethyl cellulose and gelatin；
Or gelatin and neopelex；Or hydroxyethyl cellulose and neopelex；Or hydroxy ethyl fiber
Element, gelatin and neopelex；Hydroxyethyl cellulose consumption is 0.25%-the 0.5% of polymerized monomer quality, gelatin
Consumption is the 0.5%-1.0% of polymerized monomer quality, and neopelex consumption is the 0.25%- of polymerized monomer quality
0.5%.
In the step 2, polymerized monomer is made up of ionic monomers, styrene and methacrylate-based monomer, its
Middle methacrylate-based monomer is butyl methacrylate and lauryl methacrylate；Or lauryl methacrylate and
Octadecyl methacrylate；Or butyl methacrylate and octadecyl methacrylate；Or butyl methacrylate, methyl
Dodecyl acrylate and octadecyl methacrylate；In the step 2, in polymerized monomer, ionic monomers are 1-10 matter
Part is measured, styrene monomer is 40-50 mass parts, and the consumption of methacrylate-based monomer is as follows according to component formula：Methyl-prop
Olefin(e) acid butyl ester be 25-35 mass parts, lauryl methacrylate be 15-25 mass parts, octadecyl methacrylate be 10-
15 mass parts, preferred ion monomer is 5-8 mass parts, and styrene monomer is 45-50 mass parts, and butyl methacrylate is
25-30 mass parts, lauryl methacrylate is 15-20 mass parts, and octadecyl methacrylate is 12-15 mass parts.
In the step 2, the volume ratio of the oil phase and aqueous phase is 1：(3—5).
In the step 2, initiator is peroxide or azo, such as benzoyl peroxide or azo two different heptan
Nitrile, consumption is the 2.0%-3.0% of polymerized monomer quality；Crosslinking agent is divinyl hydro carbons, and such as divinylbenzene, consumption is poly-
Close the 1.0%-2.0% of monomer mass；
In the step 2, pore-foaming agent is one kind in ethyl acetate, butyl acetate or normal heptane, and consumption is polymerization
The 30%-50% of monomer mass.
In above-mentioned preparation method, the particle diameter of preparation-obtained micropore ionization high oil-absorbing resin is 0.3mm-0.9mm, micro-
Hole aperture is 50-100um, and specific surface area is 540-580m2/g。
The product of the present invention is tested using infrared spectrum, wave number is 3421cm in (a)-1It is because after the product moisture absorption
- OH the Interference Peaks produced, wave number is in 2935cm in (c)-1、2858cm-1For-CH3、-CH2Stretching vibration absworption peak.1734cm-1
For aliphatic radical-COO- absworption peak, 1468cm-1、1389cm-1The vibration peak belonged to for place on phenyl ring skeleton, 750cm-1For phenyl ring
Out-of-plane bending vibration peak, 1175cm-1For in caused by the stretching vibration of C-N keys.Analyzed with reference to more than, it can be verified that high oil absorption tree
Fat polymerize successfully, and tetraalkylammonium cation and tetraphenyl borate anion have been had been introduced in the molecular structure of resin.
It is an advantage of the current invention that introducing a certain amount of weak coordination ion base on the basis of common high oil-absorbing resin
Group, prepares ionic monomers, then carries out suspension polymerisation and prepare ionization resin, the cycle is short, and process is simple, it is easy to grasp before this
Make.The introducing of weak coordination ion group, makes resin in oil-absorbing process, generates the Coulomb repulsion of electric charge and resin on strand
Inside and outside osmotic pressure energy imbalance, further increases its oil suction multiplying power and swelling rate to oil product.While pore-foaming agent
Add and make it that resin surface is more coarse, number cells increase also substantially increases the oil suction multiplying power and swelling rate of resin.This
Outside, the micropore ion high oil absorption resin prepared by the present invention also has that chemical stability is high, mechanical property is strong, repeatable utilized
Often the features such as.
Brief description of the drawings
Fig. 1 is the scanning electron microscopic picture of micropore ion high oil absorption resin of the present invention.
The infrared spectrogram for the micropore ion high oil absorption resin that Fig. 2 is prepared for the present invention, wherein (a) is to chloromethylbenzene
The quaternary ammoniated product of ethene, (b) is ion exchange product, and (c) ionizes resin for the micropore of polymerization.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, further is made to embodiment of the present invention below
It is described in detail on ground.Embodiment 1
The preparation of ionic monomers：
(1) 9mL p-chloromethyl styrenes and 14mL triethylamines are measured in 250mL three-necked flask, 18mL third is added
Ketone, mixing speed is 500r/min, under nitrogen protection, 50 DEG C of isothermal reactions 4 hours.
(2) product after the completion of reaction is subjected to suction filtration, and be put into there-necked flask after cleaning three times with acetone, added
0.4g tetraphenylboron sodiums and 15mL acetone, mixing speed is 500r/min, under nitrogen protection, 25 DEG C of isothermal reactions 5 hours.
(3) final product is subjected to suction filtration, cleaned with acetone three times, be placed in after being dried in vacuum drying chamber and preserve, that is, make
It is standby go out ionic monomers.
Micropore ionizes the preparation of high oil-absorbing resin：
(1) 0.05g hydroxyethyl celluloses are weighed and 0.10g gelatin is dissolved in 60ml distilled water, are stirred, three mouthfuls are added
In flask.
(2) 0.5g ionic monomers, 9.5g styrene, 6.0g butyl methacrylates, 4.0g methacrylic acids ten are weighed
Diester, 0.4g benzoyl peroxides, 0.2g divinylbenzenes, 6.0g butyl acetates, are added in three-necked flask after mixing.
(3) mixing speed is 900r/min, is to slowly warm up to 85 DEG C, is reacted 7 hours under nitrogen protection.
(4) reacted product is subjected to suction filtration, with absolute ethyl alcohol and distillation water washing three times, be placed in vacuum drying chamber
Kept dry, that is, prepare micropore ionization high oil-absorbing resin.
The micropore ionization high oil-absorbing resin sample prepared in this embodiment understands that sample is to four through oil absorbency test
The oil suction multiplying power of chlorination carbon is 30.24g/g, reaches saturation oil suction time about 3h；Oil suction multiplying power to dichloromethane is
23.57g/g, reaches saturation oil suction time about 2.8h.
Embodiment 2
The preparation of ionic monomers：
(1) 10mL p-chloromethyl styrenes and 16mL triethylamines are measured in 250mL three-necked flask, 19mL third is added
Ketone, mixing speed is 500r/min, under nitrogen protection, 50 DEG C of isothermal reactions 4.5 hours.
(2) product after the completion of reaction is subjected to suction filtration, and be put into there-necked flask after cleaning three times with acetone, added
0.45g tetraphenylboron sodiums and 16mL acetone, mixing speed is 500r/min, under nitrogen protection, 25 DEG C of isothermal reactions 5.5 hours.
(3) final product is subjected to suction filtration, cleaned with acetone three times, be placed in after being dried in vacuum drying chamber and preserve, that is, make
It is standby go out ionic monomers.
Micropore ionizes the preparation of high oil-absorbing resin：
(1) 0.1g hydroxyethyl celluloses are weighed and 0.1g neopelexes are dissolved in 70ml distilled water, stirring is equal
It is even, add in three-necked flask.
(2) 0.8g ionic monomers, 9.2g styrene, 7.0g butyl methacrylates, 3.0g methacrylic acids ten are weighed
Diester, 0.5g benzoyl peroxides, 0.25g divinylbenzenes, 7.0g butyl acetates, are added in three-necked flask after mixing.
(3) mixing speed is 900r/min, is to slowly warm up to 85 DEG C, is reacted 7.5 hours under nitrogen protection.
(4) reacted product is subjected to suction filtration, with absolute ethyl alcohol and distillation water washing three times, be placed in vacuum drying chamber
Kept dry, that is, prepare micropore ionization high oil-absorbing resin.
The micropore ionization high oil-absorbing resin sample prepared in this embodiment understands that sample is to four through oil absorbency test
The oil suction multiplying power of chlorination carbon is 32.51g/g, reaches saturation oil suction time about 2.5h；Oil suction multiplying power to dichloromethane is
25.45g/g, reaches saturation oil suction time about 2.8h.
Embodiment 3
The preparation of ionic monomers：
(1) 11mL p-chloromethyl styrenes and 20mL triethylamines are measured in 250mL three-necked flask, 20mL third is added
Ketone, mixing speed is 500r/min, under nitrogen protection, 50 DEG C of isothermal reactions 5 hours.
(2) product after the completion of reaction is subjected to suction filtration, and be put into there-necked flask after cleaning three times with acetone, added
0.6g tetraphenylboron sodiums and 20mL acetone, mixing speed is 500r/min, under nitrogen protection, 25 DEG C of isothermal reactions 5.5 hours.
(3) final product is subjected to suction filtration, cleaned with acetone three times, be placed in after being dried in vacuum drying chamber and preserve, that is, make
It is standby go out ionic monomers.
Micropore ionizes the preparation of high oil-absorbing resin：
(1) weigh 0.15g gelatin and 0.10g neopelexes are dissolved in 75ml distilled water, stir, add
In three-necked flask.
(2) 1.0g ionic monomers, 9.0g styrene, 5.5g butyl methacrylates, 4.5g methacrylic acids ten are weighed
Diester, 0.6g benzoyl peroxides, 0.3g divinylbenzenes, 7.0g butyl acetates, are added in three-necked flask after mixing.
(3) mixing speed is 900r/min, is to slowly warm up to 85 DEG C, is reacted 8 hours under nitrogen protection.
(4) reacted product is subjected to suction filtration, with absolute ethyl alcohol and distillation water washing three times, be placed in vacuum drying chamber
Kept dry, that is, prepare micropore ionization high oil-absorbing resin.
The micropore ionization high oil-absorbing resin sample prepared in this embodiment understands that sample is to four through oil absorbency test
The oil suction multiplying power of chlorination carbon is 35.86g/g, reaches saturation oil suction time about 1h；Oil suction multiplying power to dichloromethane is
28.38g/g, reaches saturation oil suction time about 1.2h.
Embodiment 4
The preparation of ionic monomers：
(1) 12mL p-chloromethyl styrenes and 20mL triethylamines are measured in 250mL three-necked flask, 25mL third is added
Ketone, mixing speed is 500r/min, under nitrogen protection, 50 DEG C of isothermal reactions 5 hours.
(2) product after the completion of reaction is subjected to suction filtration, and be put into there-necked flask after cleaning three times with acetone, added
0.7g tetraphenylboron sodiums and 25mL acetone, mixing speed is 500r/min, under nitrogen protection, 25 DEG C of isothermal reactions 6 hours.
(3) final product is subjected to suction filtration, cleaned with acetone three times, be placed in after being dried in vacuum drying chamber and preserve, that is, make
It is standby go out ionic monomers.
Micropore ionizes the preparation of high oil-absorbing resin：
(1) 0.05g hydroxyethyl celluloses, 0.10g gelatin and 0.05g neopelexes are weighed and is dissolved in 80ml distillations
In water, stir, add in three-necked flask.
(2) 2.0g ionic monomers, 8.0g styrene, 5.0g butyl methacrylates, 5.0g methacrylic acids ten are weighed
Diester, 0.6g benzoyl peroxides, 0.3g divinylbenzenes, 8.0g butyl acetates, are added in three-necked flask after mixing.
(3) mixing speed is 900r/min, is to slowly warm up to 85 DEG C, is reacted 8 hours under nitrogen protection.
(4) reacted product is subjected to suction filtration, with absolute ethyl alcohol and distillation water washing three times, be placed in vacuum drying chamber
Kept dry, that is, prepare micropore ionization high oil-absorbing resin.
The micropore ionization high oil-absorbing resin sample prepared in this embodiment understands that sample is to four through oil absorbency test
The oil suction multiplying power of chlorination carbon is 34.46g/g, reaches saturation oil suction time about 1.1h；Oil suction multiplying power to dichloromethane is
26.25g/g, reaches saturation oil suction time about 1.4h.
Embodiment 5
The preparation of ionic monomers：
(1) 10mL p-chloromethyl styrenes and 18mL triethylamines are measured in 250mL three-necked flask, 24mL third is added
Ketone, mixing speed is 500r/min, under nitrogen protection, 50 DEG C of isothermal reactions 4.5 hours.
(2) product after the completion of reaction is subjected to suction filtration, and be put into there-necked flask after cleaning three times with acetone, added
0.6g tetraphenylboron sodiums and 20mL acetone, mixing speed is 500r/min, under nitrogen protection, 25 DEG C of isothermal reactions 5.5 hours.
(3) final product is subjected to suction filtration, cleaned with acetone three times, be placed in after being dried in vacuum drying chamber and preserve, that is, make
It is standby go out ionic monomers.
Micropore ionizes the preparation of high oil-absorbing resin：
(1) 0.10g hydroxyethyl celluloses, 0.15g gelatin and 0.05g neopelexes are weighed and is dissolved in 80ml distillations
In water, stir, add in three-necked flask.
(2) 1.5g ionic monomers, 9.0g styrene, 5.5g butyl methacrylates, 4.0g methacrylic acids ten are weighed
Diester, 0.5g benzoyl peroxides, 0.2g divinylbenzenes, 9.0g butyl acetates, are added in three-necked flask after mixing.
(3) mixing speed is 900r/min, is to slowly warm up to 85 DEG C, is reacted 9 hours under nitrogen protection.
(4) reacted product is subjected to suction filtration, with absolute ethyl alcohol and distillation water washing three times, be placed in vacuum drying chamber
Kept dry, that is, prepare micropore ionization high oil-absorbing resin.
The micropore ionization high oil-absorbing resin sample prepared in this embodiment understands that sample is to four through oil absorbency test
The oil suction multiplying power of chlorination carbon is 33.28g/g, reaches saturation oil suction time about 2h；Oil suction multiplying power to dichloromethane is
24.86g/g, reaches saturation oil suction time about 2.3h.
The oil suction multiplying power method of testing of above-mentioned sample is as follows：
The oil suction multiplying power (Q) of high oil-absorbing resin is carried out using following steps.The high oil absorption of certain mass drying is weighed first
Resin, is placed in the beaker of numbering, and enough organic solvents are added in beaker.Sample is stood to 24 at room temperature small
When, make its continuous drip clean to oil droplet drip after taking-up, and weigh rapidly.The oil suction multiplying power of resin can be according to following formula meter
Calculate：
Q=(M2-M1)/M1
M in formula1For the quality before high oil-absorbing resin oil suction, g；M2For the quality after high oil-absorbing resin oil suction, g；Q is oil suction
Multiplying power, g/g.
According to the method described above, different organic solvents are changed and carry out oil suction test, as a result as shown in the table, micropore ionization tree
Oil suction multiplying power of the fat to different organic solvents
The selection that the preparation method and process conditions pointed out according to present invention carry out technological parameter carries out preparation oil suction
Property resin, be able to confirm that tetraalkylammonium cation and tetraphenyl borate anion have had been introduced to resin using examination of infrared spectrum
In molecular structure；When carrying out the test of oil suction multiplying power, as a result become and reveal basically identical with the result of above-described embodiment 1-5, reach
The saturation oil suction time, the oil suction multiplying power for different organic solvents was as follows in 1-3h：3-4g/g of methanol, 3-4.5g/g of acetone,
14-20g/g of dimethylbenzene, 15-21g/g of hexamethylene, 20-38g/g of tetrahydrofuran, 23-30g/g of dichlorotoleune, carbon tetrachloride
30—36g/g。
Exemplary description has been done to the present invention above, it is any simply to repair in the case where not departing from the core of the present invention
Change, deform or other same domains technical staff does not spend the equal replacement of creative work, belong to the protection model of the present invention
Enclose.
Claims (6)
1. a kind of micropore ionizes high oil-absorbing resin, it is characterised in that using tetraphenyl borate anion and tetra-allkylammonium sun from
Son has been had been introduced in the molecular structure of resin as coordination ion group, and 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 540-580m2/ g, is carried out as steps described below：
Step 1, the preparation of ionic monomers：P-chloromethyl styrene and triethylamine are measured in reaction vessel, polarity is added
Organic solvent, is stirred so that it is well mixed, under nitrogen protection, 50 DEG C of isothermal reactions 4-5 hours, by gained after the completion of reaction
Product carries out suction filtration, and is put into reaction vessel after being cleaned with acetone, then adds tetraphenylboron sodium and polar organic solvent thereto,
Stir so that it is well mixed, under nitrogen protection, final product is carried out suction filtration, uses acetone by 25 DEG C of isothermal reactions 5-6 hours
It is placed in after being dried in vacuum drying chamber and preserves after cleaning, that is, prepares ionic monomers；In step 1, p-chloromethyl styrene
Volume ratio with triethylamine is (1：1.5)—(1：2), polar organic solvent is acetone or ethanol；The quality of tetraphenylboron sodium is
0.5-0.6 times of p-chloromethyl styrene and triethylamine react product quality；
Step 2, micropore ionizes the preparation of high oil-absorbing resin：Weigh dispersant to be dissolved in distilled water, stir, with this
Solution is aqueous phase, while weighing polymerized monomer, initiator, crosslinking agent and pore-foaming agent, is stirred, and oil phase is used as using this solution；
Aqueous phase and oil phase are separately added into reaction vessel, mixing speed is 800-900r/min, from 20-25 degrees Celsius of heatings of room temperature
To 80-90 DEG C, react 7-9 hours under nitrogen protection, product is carried out suction filtration by reaction after terminating, and absolute ethyl alcohol is utilized successively
With distillation water washing, kept dry in vacuum drying chamber is placed in, that is, prepares micropore ionization high oil-absorbing resin；
In the step 2, dispersant is composite dispersing agent, and composite dispersing agent composition is hydroxyethyl cellulose and gelatin；Or
Gelatin and neopelex；Or hydroxyethyl cellulose and neopelex；Or it is hydroxyethyl cellulose, bright
Glue and neopelex；Hydroxyethyl cellulose consumption is 0.25%-the 0.5% of polymerized monomer quality, and gelatin consumption is
The 0.5%-1.0% of polymerized monomer quality, neopelex consumption is the 0.25%-0.5% of polymerized monomer quality；
In the step 2, polymerized monomer is made up of ionic monomers, styrene and methacrylate-based monomer, wherein first
Base acrylic ester monomer is butyl methacrylate and lauryl methacrylate；Or lauryl methacrylate and methyl
Octadecyl acrylate；Or butyl methacrylate and octadecyl methacrylate；Or butyl methacrylate, metering system
Dodecyl gallate and octadecyl methacrylate；In the step 2, in polymerized monomer, ionic monomers are 1-10 quality
Part, styrene monomer is 40-50 mass parts, and the consumption of methacrylate-based monomer is as follows according to component formula：Metering system
Acid butyl ester is 25-35 mass parts, and lauryl methacrylate is 15-25 mass parts, and octadecyl methacrylate is 10-15
Mass parts；The volume ratio of the oil phase and aqueous phase is 1：(3—5)；Initiator be benzoyl peroxide or ABVN,
Consumption is the 2.0%-3.0% of polymerized monomer quality；Crosslinking agent is divinylbenzene, and consumption is the 1.0%- of polymerized monomer quality
2.0%；Pore-foaming agent is one kind in ethyl acetate, butyl acetate or normal heptane, and consumption is the 30%- of polymerized monomer quality
50%.
2. a kind of micropore ionization high oil-absorbing resin according to claim 1, it is characterised in that in the step 2,
Preferred ion monomer is 5-8 mass parts, and styrene monomer is 45-50 mass parts, and butyl methacrylate is 25-30 matter
Part is measured, lauryl methacrylate is 15-20 mass parts, and octadecyl methacrylate is 12-15 mass parts.
3. a kind of micropore ionizes the preparation method of high oil-absorbing resin, it is characterised in that carry out as steps described below：
Step 1, the preparation of ionic monomers：P-chloromethyl styrene and triethylamine are measured in reaction vessel, polarity is added
Organic solvent, is stirred so that it is well mixed, under nitrogen protection, 50 DEG C of isothermal reactions 4-5 hours, by gained after the completion of reaction
Product carries out suction filtration, and is put into reaction vessel after being cleaned with acetone, then adds tetraphenylboron sodium and polar organic solvent thereto,
Stir so that it is well mixed, under nitrogen protection, final product is carried out suction filtration, uses acetone by 25 DEG C of isothermal reactions 5-6 hours
It is placed in after being dried in vacuum drying chamber and preserves after cleaning, that is, prepares ionic monomers；In step 1, p-chloromethyl styrene
Volume ratio with triethylamine is (1：1.5)—(1：2), polar organic solvent is acetone or ethanol；The quality of tetraphenylboron sodium is
0.5-0.6 times of p-chloromethyl styrene and triethylamine react product quality；
Step 2, micropore ionizes the preparation of high oil-absorbing resin：Weigh dispersant to be dissolved in distilled water, stir, with this
Solution is aqueous phase, while weighing polymerized monomer, initiator, crosslinking agent and pore-foaming agent, is stirred, and oil phase is used as using this solution；
Aqueous phase and oil phase are separately added into reaction vessel, mixing speed is 800-900r/min, from 20-25 degrees Celsius of heatings of room temperature
To 80-90 DEG C, react 7-9 hours under nitrogen protection, product is carried out suction filtration by reaction after terminating, and absolute ethyl alcohol is utilized successively
With distillation water washing, kept dry in vacuum drying chamber is placed in, that is, prepares micropore ionization high oil-absorbing resin；
In the step 2, dispersant is composite dispersing agent, and composite dispersing agent composition is hydroxyethyl cellulose and gelatin；Or
Gelatin and neopelex；Or hydroxyethyl cellulose and neopelex；Or it is hydroxyethyl cellulose, bright
Glue and neopelex；Hydroxyethyl cellulose consumption is 0.25%-the 0.5% of polymerized monomer quality, and gelatin consumption is
The 0.5%-1.0% of polymerized monomer quality, neopelex consumption is the 0.25%-0.5% of polymerized monomer quality；
In the step 2, polymerized monomer is made up of ionic monomers, styrene and methacrylate-based monomer, wherein first
Base acrylic ester monomer is butyl methacrylate and lauryl methacrylate；Or lauryl methacrylate and methyl
Octadecyl acrylate；Or butyl methacrylate and octadecyl methacrylate；Or butyl methacrylate, metering system
Dodecyl gallate and octadecyl methacrylate；In the step 2, in polymerized monomer, ionic monomers are 1-10 quality
Part, styrene monomer is 40-50 mass parts, and the consumption of methacrylate-based monomer is as follows according to component formula：Metering system
Acid butyl ester is 25-35 mass parts, and lauryl methacrylate is 15-25 mass parts, and octadecyl methacrylate is 10-15
Mass parts；The volume ratio of the oil phase and aqueous phase is 1：(3—5)；Initiator be benzoyl peroxide or ABVN,
Consumption is the 2.0%-3.0% of polymerized monomer quality；Crosslinking agent is divinylbenzene, and consumption is the 1.0%- of polymerized monomer quality
2.0%；Pore-foaming agent is one kind in ethyl acetate, butyl acetate or normal heptane, and consumption is the 30%- of polymerized monomer quality
50%.
4. a kind of micropore according to claim 3 ionizes the preparation method of high oil-absorbing resin, it is characterised in that in institute
State in step 2, preferred ion monomer is 5-8 mass parts, styrene monomer is 45-50 mass parts, butyl methacrylate
For 25-30 mass parts, lauryl methacrylate is 15-20 mass parts, and octadecyl methacrylate is 12-15 mass parts.
5. a kind of micropore ionization high oil-absorbing resin as claimed in claim 1 or 2 is in absorption oils or organic solvent
Application.
6. application according to claim 5, it is characterised in that the saturation oil suction time is reached in 1-3h, for different organic
The oil suction multiplying power of solvent is as follows：3-4g/g of methanol, 3-4.5g/g of acetone, 14-20g/g of dimethylbenzene, 15-21g/g of hexamethylene,
20-38g/g of tetrahydrofuran, 23-30g/g of dichlorotoleune, 30-36g/g of carbon tetrachloride.
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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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| 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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