CN110052250A - A kind of high oil-absorbing resin and preparation method thereof - Google Patents
A kind of high oil-absorbing resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of high oil-absorbing resins and preparation method thereof, belong to high oil-absorbing resin field.The present invention adds cationic additive, promote strand mutually to stretch, further expand the reticular structure of resin, more oil molecules is promoted to enter inside it, the ion dissociated away simultaneously moves in subrange can make to generate certain osmotic pressure inside and outside resin network structure, improve swelling rate；The cross-linking monomer of preparation, promote the oil suction multiplying power of oil-absorbing resin, rigid unitary styrene and soft chain segment monomer methacrylic acid butyl ester etc. is added simultaneously to improve the mechanical performance of the network structure of water-absorbing resin, mechanical strength and toughness are increased to the strand of resin, increase endurance quality；The crosslinking agent of addition improves oil absorbency and simultaneously maintains the preferable structural form of oil-absorbing resin, so that in more the entrances structure of grease molecules, raising oil absorption.The present invention solves the problems, such as that the oil suction multiplying power of current oil-absorbing resin is low and swelling rate is slow.
Description
Technical field
The invention belongs to high oil-absorbing resin technical field, in particular to a kind of high oil-absorbing resin and preparation method thereof.
Background technique
High oil-absorbing resin (Super Oil-Absorbable Resin, abbreviation SOAR) is that a kind of new type functional is high
Molecular material is a kind of general name with the high molecular polymer compared with high oil-absorbing energy.High oil-absorbing resin is to develop in recent years
A kind of novel high polymer material for waste oil disposal, have the self swelling type functional polymer material of absorption and absorption concurrently
Material has oil suction multiplying power height, and absorbable oil types are more, and oil-water selectivity is high, and Oil keeping is good under pressure condition, can not only replace
In generation, traditional oil absorption material was used for waste oil disposal, and was suitable for the processing of spillage over water oil, recycled oil slick.It is opened in petroleum
It adopts, in transportational process, frequent occurrence oily substance incident of leakage, the petroleum pollution floated on water body in large is difficult with general
Logical chemically or physically method is removed, meanwhile, petroleum pollution is gradually oxidized generation one under strong illumination effect
The jelly substance of kind sepia causes more serious secondary chemical substance dirty including some toxic phenols chemical substances
Dye.Simultaneously as the high oil-absorbing resin function used in water surface oil pollutant process field is relatively simple, to petroleum wastewater
The absorbability for contaminating object is limited, and about 6-10 times, and absorption rate is slower.It on the other hand, in daily life also can be frequent
The problem of encountering oil stain, such as kitchen.Kitchen is last line of defense of food safety, keeps kitchen tools, ground, metope without spot,
Clean food can just be made.But often occurring the case where greasy dirt on the kitchen tools in kitchen, table top, main component is to plant
Object oil and animal oil, oxidation reaction has occurred in these greases at high temperature, if do not cleaned out in time, it will and other oil
Dirt is mingled with together, is formed as the sticky grease paint, moreover over time, and greasy dirt is more and more viscous, so that after
Continuous cleaning is more difficult, while also more breeding a large amount of bacterium, mould.It can be seen that wiped in time using oil absorption material,
Absorbing the greasy dirt on kitchen kitchen tools or table top is extremely necessary for the physical and mental health of family life health even household.
However, the greasy dirt commonly used rag cleaning in daily life, absorb kitchen, absorption energy of the one side rag to greasy dirt
Power is limited, causes to wring out after washing repeatedly and gives wiping again, even if being wiped repeatedly in this way, is still difficult to clean, this is
Due to washing after wet rag have moisture, and water and oil it is incompatible caused by；On the other hand, the rag for having wiped greasy dirt needs
It is cleaned with cleaning agent, such as soap, dish washing liquid, causes cleaning process cumbersome and time-consuming, this is for now allegro
Seem extremely inconvenient for office worker.Based on aforementioned reason, high oil-absorbing resin and include the kitchen of the high oil-absorbing resin
Room cleaning article is seasonable and gives birth to.But there is lipophilic poor, suctions for the high oil-absorbing resin of the prior art, kitchen cleaning product
The disadvantage that oily multiplying power is low and swelling rate is slow.
Summary of the invention
The technical problems to be solved by the invention: for the oil suction multiplying power of current oil-absorbing resin is low and swelling rate is slow
Problem provides a kind of high oil-absorbing resin and preparation method thereof.
In order to solve the above technical problems, the present invention is using technical solution as described below:
A kind of high oil-absorbing resin, including anionic additive, cationic additive, cross-linking monomer, crosslinking agent.
The anionic additive are as follows: take 1- hexyl -3- methyl imidazolium tetrafluoroborate 5 ~ 10:2 in mass ratio ~ 5:3 ~ 7
Be added sodium tetraphenylborate, 4-(1H- imidazoles -2- base) phenylboric acid mixing to get.
The cationic additive the preparation method comprises the following steps:
(1) it takes p-chloromethyl styrene 1 ~ 4:10 in mass ratio ~ 15 that acetone is added to be stirred, adds p-chloromethyl styrene
The triethylamine that 1 ~ 1.5 times of quality is stirred, and is evaporated under reduced pressure, and filtering takes filter residue to be dried in vacuo, obtains vacuum drying object；
(2) it takes melamine 2 ~ 5:40 in mass ratio ~ 50 that anhydrous pyridine is added, is passed through nitrogen protection, is stirred, obtain mixed liquor
A takes hexachlorocyclotriph,sphazene 1 ~ 5:5 in mass ratio ~ 10 that anhydrous pyridine is added, and three second of hexachlorocyclotriph,sphazene quality 5 ~ 10% are added
Amine and the toluene of hexachlorocyclotriph,sphazene quality 10 ~ 15% are stirred, and obtain mixed liquor b, and 2 ~ 5:5 ~ 8 in mass ratio mixed liquor b is taken to add
Enter mixed liquor a to be stirred, filter, take filter residue a to be evaporated under reduced pressure, obtain vacuum distillation object, takes vacuum distillation object in mass ratio 5 ~ 10:
3 ~ 7 are added vacuum drying object mixing to get cationic additive.
The cross-linking monomer the preparation method comprises the following steps: alcohol additive 50 ~ 80:1 in mass ratio ~ 3:0.5 ~ 1 is taken to be added to toluene
Sulfonic acid, hydroquinone are stirred, and the methacrylic acid that 1 ~ 3 times of alcohol additive quality is added is stirred, and are cooled to room temperature, and are adjusted
PH to 7 ~ 7.5 is saved, mixture is obtained, according to the mass fraction, takes 5 ~ 10 parts of mixtures, 4 ~ 7 parts of styrene, 2 ~ 5 parts of methacrylic acids
Butyl ester, 10 ~ 15 parts of modified cyclodextrin mixing are to get cross-linking monomer.
The alcohol additive are as follows: take laruyl alcohol 2 ~ 5:1 in mass ratio ~ 3 be added myristyl alcohol mixing to get.
The modified cyclodextrin are as follows: take beta-cyclodextrin 1 ~ 3:40 in mass ratio ~ 50 that N,N-dimethylformamide stirring is added
Mixing, the Anhydrous potassium carbonate for adding beta-cyclodextrin quality 3 ~ 7% are stirred, and obtain stirring mixture, take stirring mixture by matter
Dimethyl carbonate is added than 30 ~ 40:3 ~ 7 in amount, and in 80 ~ 85 DEG C of 5 ~ 9h of heat preservation, centrifugation takes supernatant rotary evaporation, is concentrated under reduced pressure,
Concentrate is obtained, takes concentrate 2 ~ 5:10 in mass ratio ~ 20 that acetone is added, is stood, filtering takes filter residue and drying to paste to get modified ring
Essence.
The crosslinking agent the preparation method comprises the following steps: according to the mass fraction, taking 5 ~ 10 parts of γ-methacryloxypropyl front three
Oxysilane, 20 ~ 40 parts of deionized waters, 3 ~ 6 parts of triethylamines, 60 ~ 80 parts of stirring solvent mixing, vacuum distillation are washed through ether,
Take washing residue 4 ~ 7:3 in mass ratio ~ 5 that the mixing of 1,4-butanediol diacrylate is added to get crosslinking agent.
The solvent are as follows: take tetrahydrofuran 2 ~ 5:1 in mass ratio ~ 3 be added hexahydrotoluene mixing to get.
The preparation method includes the following steps: to take anionic additive 1 ~ 5:10 in mass ratio ~ 20 that acetone is added, add
The cationic additive of anionic additive quality 60 ~ 70% is stirred, and must stir mixture a, takes cross-linking monomer in mass ratio
Stirring mixture a is added in 4 ~ 9:3 ~ 5, and the crosslinking agent of cross-linking monomer quality 5 ~ 10% is added, is passed through nitrogen protection, is stirred, obtain
Matrix object takes matrix object 100 ~ 120:1 in mass ratio ~ 3 that azodiisobutyronitrile is added and is cooled in 50 ~ 55 DEG C of 10 ~ 12h of heat preservation
Room temperature is to get high oil-absorbing resin.
The present invention is compared with other methods, and advantageous effects are:
(1) cationic additive that the present invention adds is to carry out quaternization reaction with triethylamine with p-chloromethyl styrene to obtain,
And the substance containing phosphine nitrile group reacted with melamine with raw materials such as hexachlorocyclotriph,sphazenes is assisted, add anion addition
Agent makes it constitute one kind and matches using 1- hexyl -3- methyl imidazolium tetrafluoroborate, sodium tetraphenylborate etc. as oleophylic anion
Position ion pair, zwitterion swap reaction, and the lipophilic monomer that the ionic group that can be dissociated is formed in oil-absorbing resin is added,
The Van der Waals force that the lipophilic group and oil molecule of its inside configuration generate, oil molecule, which enters, can occur solvation in resin,
Make resin that swelling occur without dissolving, on the other hand the ion of dissociation can be attached to around strand, will form between charge quiet
Electric repulsion promotes strand mutually to stretch, and further expands the reticular structure of resin, and more oil molecules is promoted to enter in it
Portion, while the ion dissociated away moves in subrange and can make to generate certain osmotic pressure inside and outside resin network structure, into
One step promotes oil molecule to enter, and improves swelling rate；
(2) cross-linking monomer prepared by the present invention is that Anhydrous potassium carbonate catalysis is added, pastes to β-ring using beta-cyclodextrin as raw material first
The esterification modification of essence occurs Infectious disease with beta-cyclodextrin and reacts, and is allowed to equal oleophylic generate with double bond structure and inside and outside
Surface-active macromonomer, oil molecule can be wrapped up when oil molecule enters in oil-absorbing resin, promote the oil suction times of oil-absorbing resin
Rate preferably be stored in the network structure of oil-absorbing resin to the grease of sucking, at the same be added rigid unitary styrene and
Soft chain segment monomer methacrylic acid butyl ester etc. improves the mechanical performance of the network structure of water-absorbing resin, to the molecule of resin
Chain increases mechanical strength and toughness, and that improves resin uses the time, increases endurance quality；
(3) crosslinking agent that the present invention finally adds is using γ-methacryloxypropyl trimethoxy silane as raw material, through water
Solution reaction, then dehydration condensation generate the oligosiloxane for having double bond, so that the crosslink density of resin increases, are formed preferable
Three-dimensional cross-linked reticular structure, improve oil absorbency simultaneously maintain the preferable structural form of oil-absorbing resin, not will increase molecule segment
The influence of elastic contractile force, so that improving oil absorption in the more entrance structure of grease molecules.
Specific embodiment
Cationic additive the preparation method comprises the following steps:
(1) it takes p-chloromethyl styrene 1 ~ 4:10 in mass ratio ~ 15 that acetone is added, is stirred 20 ~ 30min in 30 ~ 40 DEG C, then
1 ~ 1.5 times of p-chloromethyl styrene quality of triethylamine is added, is warming up to 40 ~ 50 DEG C and is stirred 4 ~ 7h, is evaporated under reduced pressure, mistake
Filter, takes filter residue to be dried in vacuo, obtains vacuum drying object；
(2) it takes melamine 2 ~ 5:40 in mass ratio ~ 50 that anhydrous pyridine is added, is passed through nitrogen protection, is stirred in -4 ~ 1 DEG C
20 ~ 40min obtains mixed liquor a, takes hexachlorocyclotriph,sphazene 1 ~ 5:5 in mass ratio ~ 10 that anhydrous pyridine is added, and three phosphorus of chlordene ring is added
The triethylamine of nitrile quality 5 ~ 10% and the toluene of hexachlorocyclotriph,sphazene quality 10 ~ 15%, are stirred 20 ~ 30min, obtain mixed liquor b,
Take mixed liquor b 2 ~ 5:5 in mass ratio ~ 8 that mixed liquor a is added, be warming up to 100 ~ 120 DEG C be stirred 18 ~ for 24 hours, filtering takes filter residue
A vacuum distillation, obtains vacuum distillation object, takes vacuum distillation object 5 ~ 10:3 in mass ratio ~ 7 that vacuum drying object mixing is added to get sun
Ionic additive.
Anionic additive are as follows: 1- hexyl -3- methyl imidazolium tetrafluoroborate 5 ~ 10:2 in mass ratio ~ 5:3 ~ 7 is taken to be added
Sodium tetraphenylborate, 4-(1H- imidazoles -2- base) phenylboric acid mixing to get.
Cyclodextrin are as follows: take beta-cyclodextrin 1 ~ 3:40 in mass ratio ~ 50 that n,N-Dimethylformamide is added, it is stirred 20 ~
30min adds the Anhydrous potassium carbonate of beta-cyclodextrin quality 3 ~ 7%, is warming up to 70 ~ 80 DEG C and is stirred 30 ~ 50min, must stir
Mixture takes stirring mixture 30 ~ 40:3 in mass ratio ~ 7 that dimethyl carbonate is added, and in 80 ~ 85 DEG C of 5 ~ 9h of heat preservation, centrifugation is taken
Supernatant rotary evaporation, be concentrated under reduced pressure, obtain concentrate, take concentrate 2 ~ 5:10 in mass ratio ~ 20 be added acetone, stand 30 ~
60min, filtering, takes filter residue and drying to get cyclodextrin.
Alcohol additive are as follows: take laruyl alcohol 2 ~ 5:1 in mass ratio ~ 3 be added myristyl alcohol mixing to get.
Cross-linking monomer the preparation method comprises the following steps: take alcohol additive 50 ~ 80:1 in mass ratio ~ 3:0.5 ~ 1 be added p-methyl benzenesulfonic acid,
Hydroquinone is warming up to 80 ~ 100 DEG C and is stirred 30 ~ 40min, the methacrylic acid of 1 ~ 3 times of alcohol additive quality is added, in
120 ~ 130 DEG C are stirred 3 ~ 5h, are cooled to room temperature, and adjust pH to 7 ~ 7.5, obtain mixture, according to the mass fraction, take 5 ~ 10 parts
Mixture, 4 ~ 7 parts of styrene, 2 ~ 5 parts of butyl methacrylates, 10 ~ 15 parts of cyclodextrin mixing are to get cross-linking monomer.
Solvent are as follows: take tetrahydrofuran 2 ~ 5:1 in mass ratio ~ 3 be added hexahydrotoluene mixing to get.
Crosslinking agent the preparation method comprises the following steps: according to the mass fraction, taking 5 ~ 10 parts of γ-methacryloxypropyl trimethoxy
Silane, 20 ~ 40 parts of deionized waters, 3 ~ 6 parts of triethylamines, the mixing of 60 ~ 80 parts of solvents, it is stirred 18 in 40 ~ 45 DEG C ~ for 24 hours, decompression
Distillation, washed through ether, take washing residue 4 ~ 7:3 in mass ratio ~ 5 be added 1,4-butanediol diacrylate mixing to get
Crosslinking agent.
A kind of preparation method of high oil-absorbing resin, includes the following steps:
It takes anionic additive 1 ~ 5:10 in mass ratio ~ 20 that acetone is added, adds the sun of anionic additive quality 60 ~ 70%
Ionic additive is stirred 6 ~ 8h in 20 ~ 25 DEG C, must stir mixture a, and cross-linking monomer 4 ~ 9:3 in mass ratio ~ 5 is taken to be added
Mixture a is stirred, the crosslinking agent of cross-linking monomer quality 5 ~ 10% is added, is passed through nitrogen protection, it is stirred 20 in 50 ~ 55 DEG C ~
30min obtains matrix object, take matrix object 100 ~ 120:1 in mass ratio ~ 3 be added azodiisobutyronitrile, in 50 ~ 55 DEG C keep the temperature 10 ~
12h is cooled to room temperature to get high oil-absorbing resin.
Cationic additive the preparation method comprises the following steps:
(1) it takes p-chloromethyl styrene 1:10 in mass ratio that acetone is added, is stirred 20min in 30 DEG C, adds to chloromethane
The triethylamine of 1 times of base styrene quality is warming up to 40 DEG C and is stirred 4h, is evaporated under reduced pressure, and filtering takes filter residue to be dried in vacuo, obtains
It is dried in vacuo object；
(2) it takes melamine 2:40 in mass ratio that anhydrous pyridine is added, is passed through nitrogen protection, is stirred 20min in -4 DEG C, obtains
Mixed liquor a takes hexachlorocyclotriph,sphazene 1:5 in mass ratio that anhydrous pyridine is added, and the triethylamine of hexachlorocyclotriph,sphazene quality 5% is added
With the toluene of hexachlorocyclotriph,sphazene quality 10%, it is stirred 20min, obtains mixed liquor b, mixed liquor b 2:5 in mass ratio is taken to be added
Mixed liquor a is warming up to 100 DEG C and is stirred 18h, and filtering takes filter residue a to be evaporated under reduced pressure, obtains vacuum distillation object, take vacuum distillation object
Vacuum drying object mixing is added to get cationic additive in 5:3 in mass ratio.
Anionic additive are as follows: take 1- hexyl -3- methyl imidazolium tetrafluoroborate 5:2:3 in mass ratio that tetraphenyl boron is added
Sour sodium, 4-(1H- imidazoles -2- base) phenylboric acid mixing to get.
Cyclodextrin are as follows: it takes beta-cyclodextrin 1:40 in mass ratio that n,N-Dimethylformamide is added, is stirred 20min, then
The Anhydrous potassium carbonate of beta-cyclodextrin quality 3% is added, is warming up to 70 DEG C and is stirred 30min, obtain stirring mixture, takes stirring mixed
It closes object 30:3 in mass ratio and dimethyl carbonate is added, in 80 DEG C of heat preservation 5h, centrifugation takes supernatant rotary evaporation, is concentrated under reduced pressure, obtains
Concentrate takes concentrate 2:10 in mass ratio that acetone is added, and stands 30min, and filtering takes filter residue and drying to get cyclodextrin.
Alcohol additive are as follows: take laruyl alcohol 2:1 in mass ratio be added myristyl alcohol mixing to get.
Cross-linking monomer the preparation method comprises the following steps: take alcohol additive 50:1:0.5 in mass ratio be added p-methyl benzenesulfonic acid, to benzene two
Phenol is warming up to 80 DEG C and is stirred 30min, the methacrylic acid of 1 times of alcohol additive quality is added, is stirred 3h in 120 DEG C,
It is cooled to room temperature, adjusts pH to 7, obtain mixture, according to the mass fraction, take 5 parts of mixtures, 4 parts of styrene, 2 parts of metering systems
Acid butyl ester, 10 parts of cyclodextrin mixing are to get cross-linking monomer.
Solvent are as follows: take tetrahydrofuran 2:1 in mass ratio be added hexahydrotoluene mixing to get.
Crosslinking agent the preparation method comprises the following steps: according to the mass fraction, taking 5 parts of γ-methacryloxypropyl trimethoxy silicon
Alkane, 20 parts of deionized waters, 3 parts of triethylamines, 60 parts of solvent mixing, are stirred 18h in 40 DEG C, are evaporated under reduced pressure, wash through ether,
Take washing residue 4:3 in mass ratio that the mixing of 1,4-butanediol diacrylate is added to get crosslinking agent.
A kind of preparation method of high oil-absorbing resin, includes the following steps:
It takes anionic additive 1:10 in mass ratio that acetone is added, adds the cation addition of anionic additive quality 60%
Agent is stirred 6h in 20 DEG C, must stir mixture a, takes cross-linking monomer 4:3 in mass ratio that stirring mixture a is added, is added and hands over
The crosslinking agent of receipts or other documents in duplicate weight 5%, is passed through nitrogen protection, is stirred 20min in 50 DEG C, obtains matrix object, takes matrix object by quality
Azodiisobutyronitrile is added than 100:1 to be cooled to room temperature in 50 DEG C of heat preservation 10h to get high oil-absorbing resin.
Cationic additive the preparation method comprises the following steps:
(1) it takes p-chloromethyl styrene 4:15 in mass ratio that acetone is added, is stirred 30min in 40 DEG C, adds to chloromethane
The triethylamine of 1.5 times of base styrene quality is warming up to 50 DEG C and is stirred 7h, is evaporated under reduced pressure, and filtering takes filter residue to be dried in vacuo,
Object must be dried in vacuo；
(2) it takes melamine 5:50 in mass ratio that anhydrous pyridine is added, is passed through nitrogen protection, is stirred 40min in 1 DEG C, obtains
Mixed liquor a takes hexachlorocyclotriph,sphazene 5:10 in mass ratio that anhydrous pyridine is added, and three second of hexachlorocyclotriph,sphazene quality 10% are added
The toluene of amine and hexachlorocyclotriph,sphazene quality 15%, is stirred 30min, obtains mixed liquor b, and mixed liquor b 5:8 in mass ratio is taken to add
Enter mixed liquor a, be warming up to 120 DEG C and be stirred for 24 hours, filtering takes filter residue a to be evaporated under reduced pressure, obtains vacuum distillation object, take vacuum distillation
Vacuum drying object mixing is added to get cationic additive in object 10:7 in mass ratio.
Anionic additive are as follows: take 1- hexyl -3- methyl imidazolium tetrafluoroborate 10:5:7 in mass ratio that tetraphenyl is added
Boratex, 4-(1H- imidazoles -2- base) phenylboric acid mixing to get.
Cyclodextrin are as follows: it takes beta-cyclodextrin 3:50 in mass ratio that n,N-Dimethylformamide is added, is stirred 30min, then
The Anhydrous potassium carbonate of beta-cyclodextrin quality 7% is added, is warming up to 80 DEG C and is stirred 50min, obtain stirring mixture, takes stirring mixed
It closes object 40:7 in mass ratio and dimethyl carbonate is added, in 85 DEG C of heat preservation 9h, centrifugation takes supernatant rotary evaporation, is concentrated under reduced pressure, obtains
Concentrate takes concentrate 5:20 in mass ratio that acetone is added, and stands 60min, and filtering takes filter residue and drying to get cyclodextrin.
Alcohol additive are as follows: take laruyl alcohol 5:3 in mass ratio be added myristyl alcohol mixing to get.
Cross-linking monomer the preparation method comprises the following steps: take alcohol additive 80:3:1 in mass ratio be added p-methyl benzenesulfonic acid, hydroquinone,
It is warming up to 100 DEG C and is stirred 40min, the methacrylic acid of 3 times of alcohol additive quality is added, is stirred 5h in 130 DEG C, it is cold
But to room temperature, pH to 7.5 is adjusted, mixture is obtained, according to the mass fraction, takes 10 parts of mixtures, 7 parts of styrene, 5 parts of metering systems
Acid butyl ester, 15 parts of cyclodextrin mixing are to get cross-linking monomer.
Solvent are as follows: take tetrahydrofuran 5:3 in mass ratio be added hexahydrotoluene mixing to get.
Crosslinking agent the preparation method comprises the following steps: according to the mass fraction, taking 10 parts of γ-methacryloxypropyl trimethoxy silicon
Alkane, 40 parts of deionized waters, 6 parts of triethylamines, 80 parts of solvent mixing, are stirred for 24 hours in 45 DEG C, and vacuum distillation is washed through ether,
Take washing residue 7:5 in mass ratio that the mixing of 1,4-butanediol diacrylate is added to get crosslinking agent.
A kind of preparation method of high oil-absorbing resin includes the following steps: that anionic additive 5:20 in mass ratio is taken to be added
Acetone adds the cationic additive of anionic additive quality 70%, is stirred 8h in 25 DEG C, must stir mixture a,
It takes cross-linking monomer 9:5 in mass ratio that stirring mixture a is added, the crosslinking agent of cross-linking monomer quality 10% is added, be passed through nitrogen guarantor
Shield, is stirred 30min in 55 DEG C, obtains matrix object, takes matrix object 120:3 in mass ratio that azodiisobutyronitrile is added, in 55 DEG C
12h is kept the temperature, is cooled to room temperature to get high oil-absorbing resin.
Cationic additive the preparation method comprises the following steps:
(1) it takes p-chloromethyl styrene 2:13 in mass ratio that acetone is added, is stirred 25min in 35 DEG C, adds to chloromethane
The triethylamine of 1.2 times of base styrene quality is warming up to 45 DEG C and is stirred 6h, is evaporated under reduced pressure, and filtering takes filter residue to be dried in vacuo,
Object must be dried in vacuo；
(2) it takes melamine 3:45 in mass ratio that anhydrous pyridine is added, is passed through nitrogen protection, is stirred 30min in -2 DEG C, obtains
Mixed liquor a takes hexachlorocyclotriph,sphazene 3:7 in mass ratio that anhydrous pyridine is added, and the triethylamine of hexachlorocyclotriph,sphazene quality 7% is added
With the toluene of hexachlorocyclotriph,sphazene quality 13%, it is stirred 25min, obtains mixed liquor b, mixed liquor b 3:7 in mass ratio is taken to be added
Mixed liquor a is warming up to 110 DEG C and is stirred 22h, and filtering takes filter residue a to be evaporated under reduced pressure, obtains vacuum distillation object, take vacuum distillation object
Vacuum drying object mixing is added to get cationic additive in 7:4 in mass ratio.
Anionic additive are as follows: take 1- hexyl -3- methyl imidazolium tetrafluoroborate 7:3:4 in mass ratio that tetraphenyl boron is added
Sour sodium, 4-(1H- imidazoles -2- base) phenylboric acid mixing to get.
Cyclodextrin are as follows: it takes beta-cyclodextrin 2:45 in mass ratio that n,N-Dimethylformamide is added, is stirred 25min, then
The Anhydrous potassium carbonate of beta-cyclodextrin quality 4% is added, is warming up to 75 DEG C and is stirred 40min, obtain stirring mixture, takes stirring mixed
It closes object 35:4 in mass ratio and dimethyl carbonate is added, in 83 DEG C of heat preservation 7h, centrifugation takes supernatant rotary evaporation, is concentrated under reduced pressure, obtains
Concentrate takes concentrate 3:16 in mass ratio that acetone is added, and stands 40min, and filtering takes filter residue and drying to get cyclodextrin.
Alcohol additive are as follows: take laruyl alcohol 3:2 in mass ratio be added myristyl alcohol mixing to get.
Cross-linking monomer the preparation method comprises the following steps: take alcohol additive 70:2:0.7 in mass ratio be added p-methyl benzenesulfonic acid, to benzene two
Phenol is warming up to 90 DEG C and is stirred 35min, the methacrylic acid of 2 times of alcohol additive quality is added, is stirred 4h in 125 DEG C,
It is cooled to room temperature, adjusts pH to 7.3, obtain mixture, according to the mass fraction, take 7 parts of mixtures, 5 parts of styrene, 3 parts of methyl-props
Olefin(e) acid butyl ester, 13 parts of cyclodextrin mixing are to get cross-linking monomer.
Solvent are as follows: take tetrahydrofuran 3:2 in mass ratio be added hexahydrotoluene mixing to get.
Crosslinking agent the preparation method comprises the following steps: according to the mass fraction, taking 7 parts of γ-methacryloxypropyl trimethoxy silicon
Alkane, 30 parts of deionized waters, 5 parts of triethylamines, 70 parts of solvent mixing, are stirred 20h in 42 DEG C, are evaporated under reduced pressure, wash through ether,
Take washing residue 5:4 in mass ratio that the mixing of 1,4-butanediol diacrylate is added to get crosslinking agent.
A kind of preparation method of high oil-absorbing resin includes the following steps: that anionic additive 3:13 in mass ratio is taken to be added
Acetone adds the cationic additive of anionic additive quality 65%, is stirred 7h in 22 DEG C, must stir mixture a,
It takes cross-linking monomer 5:4 in mass ratio that stirring mixture a is added, the crosslinking agent of cross-linking monomer quality 7% is added, is passed through nitrogen protection,
It is stirred 25min in 52 DEG C, obtains matrix object, takes matrix object 110:2 in mass ratio that azodiisobutyronitrile is added, is kept the temperature in 53 DEG C
11h is cooled to room temperature to get high oil-absorbing resin.
Comparative example 1: it is essentially identical with the preparation method of embodiment 2, it has only the difference is that lacking anionic additive.
Comparative example 2: it is essentially identical with the preparation method of embodiment 2, it has only the difference is that lacking cationic additive.
Comparative example 3: it is essentially identical with the preparation method of embodiment 2, it has only the difference is that lacking cross-linking monomer.
Comparative example 4: it is essentially identical with the preparation method of embodiment 2, it has only the difference is that lacking crosslinking agent.
Comparative example 5: the high oil-absorbing resin of Shanghai City company production.
The high oil-absorbing resin that above-described embodiment is prepared with comparative example is detected, oil suction multiplying power: using kerosene as test
Oil product accurately weighs suitable dry resin in 80 mesh Nylon Bags, is put into the 500ml beaker for filling enough oil products to be absorbed
In, 4h is stood under room temperature and is taken out, and is stood drip 5min, is dried weighing afterwards spontaneously for Nylon Bag surface with filter paper.Oil suction times
The calculation formula of rate are as follows: oil suction multiplying power G(g.g-1)=(W2-W1-W0)/W0, wherein G is the absorbency of resin, and W2 is tree
Gross mass g after rouge and Nylon Bag saturation oil suction；W1 is the quality g after Nylon Bag oil suction saturation；W0 dry tree before being oil suction
The quality g of rouge；It protects oil cut rate: measuring guarantor's oil cut rate by the way of centrifugation, be put into centrifuge and have reached saturation oil suction and standard
The oil absorption material of quality is really weighed, 3min is then centrifuged with the revolving speed of 1000r/min with centrifuge, centrifugation takes out oil suction after stopping
Resin simultaneously weighs.It is as follows to protect oil cut rate calculation formula: R=(W4-W3)/(W2-W1-W0) * 100%, wherein R is guarantor's oil of resin
Rate, W4 are the resin for being saturated oil suction and the gross mass g after Nylon Bag centrifugation；W2 is the quality after the Nylon Bag centrifugation of oil suction saturation
g；W1 is the quality g after Nylon Bag oil suction saturation；The quality g of dry resin before W0 is oil suction；Swelling rate test:
Rate of liquid aspiration will be different oil absorption resin in section in different times, using the oil suction of natural filtration method measurement product
Rate.Quantitative dry resin is accurately weighed in the Nylon Bag of 80 mesh, is immersed in the beaker equipped with enough oil products to be measured, resin
Constantly swelling at room temperature, takes out every 2.5h, stands 5min, blots surface oil content with filter paper, weighs, and record obtains not in this way
With the absorbency of time, obtain that the results are shown in Table 1.
Table 1:
In summary, high oil-absorbing resin effect of the invention is more preferable as can be seen from Table 1, is worth of widely use, it is described above only
For preferred mode of the invention, it is not intended to limit the invention, it is all within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of high oil-absorbing resin, which is characterized in that including anionic additive, cationic additive, cross-linking monomer, crosslinking
Agent.
2. high oil-absorbing resin according to claim 1, which is characterized in that the anionic additive are as follows: take 1- hexyl -3-
Sodium tetraphenylborate, 4-(1H- imidazoles -2- base is added in methyl imidazolium tetrafluoroborate 5 ~ 10:2 in mass ratio ~ 5:3 ~ 7) phenyl boron
Acid-mixed close to get.
3. high oil-absorbing resin according to claim 1, which is characterized in that the cationic additive the preparation method comprises the following steps:
(1) it takes p-chloromethyl styrene 1 ~ 4:10 in mass ratio ~ 15 that acetone is added to be stirred, adds p-chloromethyl styrene
The triethylamine that 1 ~ 1.5 times of quality is stirred, and is evaporated under reduced pressure, and filtering takes filter residue to be dried in vacuo, obtains vacuum drying object；
(2) it takes melamine 2 ~ 5:40 in mass ratio ~ 50 that anhydrous pyridine is added, is passed through nitrogen protection, is stirred, obtain mixed liquor
A takes hexachlorocyclotriph,sphazene 1 ~ 5:5 in mass ratio ~ 10 that anhydrous pyridine is added, and three second of hexachlorocyclotriph,sphazene quality 5 ~ 10% are added
Amine and the toluene of hexachlorocyclotriph,sphazene quality 10 ~ 15% are stirred, and obtain mixed liquor b, and 2 ~ 5:5 ~ 8 in mass ratio mixed liquor b is taken to add
Enter mixed liquor a to be stirred, filter, take filter residue a to be evaporated under reduced pressure, obtain vacuum distillation object, takes vacuum distillation object in mass ratio 5 ~ 10:
3 ~ 7 are added vacuum drying object mixing to get cationic additive.
4. high oil-absorbing resin according to claim 1, which is characterized in that the cross-linking monomer the preparation method comprises the following steps: taking alcohol
P-methyl benzenesulfonic acid is added in additive 50 ~ 80:1 in mass ratio ~ 3:0.5 ~ 1, hydroquinone is stirred, and alcohol additive quality is added
1 ~ 3 times of methacrylic acid is stirred, and is cooled to room temperature, and is adjusted pH to 7 ~ 7.5, is obtained mixture, according to the mass fraction, take 5 ~
10 parts of mixtures, 4 ~ 7 parts of styrene, 2 ~ 5 parts of butyl methacrylates, 10 ~ 15 parts of modified cyclodextrin mixing are single to get crosslinking
Body.
5. high oil-absorbing resin according to claim 4, which is characterized in that the alcohol additive are as follows: take laruyl alcohol by quality
Than 2 ~ 5:1 ~ 3 be added myristyl alcohol mixing to get.
6. high oil-absorbing resin according to claim 4, which is characterized in that the modified cyclodextrin are as follows: take beta-cyclodextrin by
1 ~ 3:40 of mass ratio ~ 50 is added n,N-Dimethylformamide and is stirred, and adds the Carbon Dioxide of beta-cyclodextrin quality 3 ~ 7%
Potassium is stirred, and obtains stirring mixture, takes stirring mixture 30 ~ 40:3 in mass ratio ~ 7 that dimethyl carbonate is added, in 80 ~ 85 DEG C
5 ~ 9h is kept the temperature, centrifugation takes supernatant rotary evaporation, is concentrated under reduced pressure, obtains concentrate, and concentrate 2 ~ 5:10 ~ 20 in mass ratio is taken to add
Enter acetone, stand, filtering takes filter residue and drying to get modified cyclodextrin.
7. high oil-absorbing resin according to claim 1, which is characterized in that the crosslinking agent the preparation method comprises the following steps: press quality
Number meter, take 5 ~ 10 parts of γ-methacryloxypropyl trimethoxy silanes, 20 ~ 40 parts of deionized waters, 3 ~ 6 parts of triethylamines,
60 ~ 80 parts of stirring solvent mixing, vacuum distillation are washed through ether, take washing residue 4 ~ 7:3 in mass ratio ~ 5 that Isosorbide-5-Nitrae-fourth is added
Omega-diol diacrylate mixes to get crosslinking agent.
8. high oil-absorbing resin according to claim 7, which is characterized in that the solvent are as follows: take tetrahydrofuran in mass ratio 2
~ 5:1 ~ 3 be added hexahydrotoluene mixing to get.
9. a kind of preparation method of the high oil-absorbing resin as described in claim 1 ~ 8 any one, which is characterized in that the preparation side
Method includes the following steps: to take anionic additive 1 ~ 5:10 in mass ratio ~ 20 that acetone is added, and adds anionic additive quality
60 ~ 70% cationic additive is stirred, and must stir mixture a, takes cross-linking monomer 4 ~ 9:3 in mass ratio ~ 5 that stirring is added
Mixture a is added the crosslinking agent of cross-linking monomer quality 5 ~ 10%, is passed through nitrogen protection, is stirred, obtain matrix object, take matrix object
100 ~ 120:1 in mass ratio ~ 3 is added azodiisobutyronitrile and is cooled to room temperature in 50 ~ 55 DEG C of 10 ~ 12h of heat preservation to get high oil absorption
Resin.
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| CN110882678A (en) * | 2019-12-05 | 2020-03-17 | 广东海纳新材料科技有限公司 | Preparation method of modified waste hydrophobic fiber oil absorption material |
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