CN102453296B - High oil absorption resin with semi-interpenetrating polymer network structure and its preparation method - Google Patents
High oil absorption resin with semi-interpenetrating polymer network structure and its preparation method Download PDFInfo
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Abstract
The invention discloses high oil absorption resin with a semi-interpenetrating polymer network structure and its preparation method. The high oil absorption resin comprises the following ingredients: 100 parts of oil absorption monomer, 2-20 parts of styrene, 0.1-1 part of cross-linking agent, 0.3-3 parts of dispersant, 0.1-1 part of initiator, 5-30 parts of pore forming agent and 2-20 parts of semi-interpenetrating polymer network structure agent. The preparation method comprises the following steps: a, dissolving the dispersant in deionized water; b, dissolving the semi-interpenetrating polymer network structure agent in the short chain acrylic acid ester monomer, mixing with long chain alkyl ester monomer, the initiator, the cross-linking agent, styrene and the pore forming agent in the dispersant of the step a; c, heating the mixture, stirring , reacting, slaking to stop the reaction; d, washing, pump filtering, drying to obtain the product. The high oil absorption resin has the advantages of high oil absorption multiplying power, fast oil absorption rate and good oil absorption reversibility.
Description
Technical field
The present invention relates to petrochemical industry, say further, relate to a kind of high oil absorbing resin that contains half interpenetrating network structure and preparation method thereof.
Background technology
High oil-absorbing resin is a kind of threedirection polymerization resin with low three-dimensional netted chemically crosslinked structure, and adsorbable various oil products can be used for environmental protection and other aspects, are development in recent years new functional macromolecule material rapidly.High oil absorbing resin is to realize the oil suction purpose by the Van der Waals force that produces between oleophilic group and oil molecule, its oil suction mechanism is the solvation process of polymer segment, so change the network structure of oil-absorbing resin, improving the interaction force between lipophilic group and the oil molecule, is the key of improving the resin oil absorptiveness.
At present, the high oil absorbing resin of developing the esters of acrylic acid high oil absorbing resin arranged substantially, olefines high oil absorbing resin and natural or prepare three kinds of macromolecule modified preparation high oil absorbing resins etc., though wherein the olefines high oil absorbing resin is more superior to the affinity performance of oil product, but the higher olefins source is less, price is too expensive, and natural or preparation modification though to prepare its raw material sources of high oil absorbing resin comparatively extensive, price is comparatively cheap, but intensity is too low after the resin oil suction, the oil suction reversibility is poor, be unfavorable for recycling, so adopt the acrylic acid or the like material to prepare high oil absorbing resin more.
But, the acrylic acid or the like material high oil absorbing resin of now preparing both at home and abroad, it is single chemically crosslinked, and side chain generally all has chain alkyl, its effect is to increase kerosene, gasoline, the receptivity of long-chain non-polar oil product such as machine oil, but chemically crosslinked makes molecular chain be subjected to very strong constraint in the preparation process, has influenced the expansion of resin three-dimensional network, makes that the oil suction multiplying power of resin is not high, the suction reversibility of draining the oil is poor, and side group is chain alkyl, has increased the sterically hindered of oil-absorbing resin, has reduced effective oil suction volume of resin network structure.The Dow Chemical Co. (US) 2030 Dow Center, Abbott Road, Midland, Michigan 48640, at first succeeded in developing a kind of nonpolar high oil absorbing resin in 1966; Japan was also studied after the seventies in last century, the long alkyl chain length ester of vinylformic acid high oil absorbing resin is disclosed as the flat 05-15777 of Japanese Patent, flat 05-32708 peace 05-209017 etc., Chinese patent (publication number: CN1869090) disclose a kind of high oil absorbing resin, be monomer with rubber and ring-alkylated styrenes, be linking agent with divinylbenzene, glycol diacrylate class material, a kind of high oil absorbing resin that contains the part semi-intercrossing network that adopted suspension polymerization, reversibility is not good but oil suction speed and suction are drained the oil.
Summary of the invention
For solving problems of the prior art, the invention discloses a kind of high oil absorbing resin that contains half interpenetrating network structure and preparation method thereof, can improve effective oil suction volume of resin and the network structure of improving oil-absorbing resin, increase oil suction multiplying power and the oil suction speed of oil-absorbing resin.
One of purpose of the present invention provides a kind of high oil absorbing resin that contains half interpenetrating network structure.
Comprise following component:
Oil suction monomer 100 weight parts
Vinylbenzene 2～20 weight parts
Linking agent 0.1～1 weight part
Dispersion agent 0.3～3 weight part
Initiator 0.1～1 weight part
Pore-creating agent 5～30 weight parts
Half interpenetrating network structure agent 2～20 weight parts
Described oil suction monomer comprises chain alkyl esters monomer and short chain acrylates class monomer mixture, and wherein the chain alkyl esters monomer is: one or more in vinylformic acid 12 (14,16,18) ester, methacrylic acid 12 (14,16, the 18) ester; Short chain acrylates class monomer is: one or more in vinylformic acid first (second, fourth) ester, methyl methacrylate (second, the fourth) ester;
Using the chain alkyl esters monomer among the present invention is in order to introduce the long-chain side group to increase it to kerosene in oil-absorbing resin, gasoline, the receptivity of long-chain non-polar oil product such as machine oil, using short chain acrylates class monomer is in order to introduce the short chain side group in oil-absorbing resin, to increase it to benzene, toluene, dimethylbenzene, the absorption of short chain polarity oil products such as trichloromethane, vinylbenzene then can increase the rigidity of oil-absorbing resin, makes to keep after its oil suction certain intensity can improve speed of oil absorption and be convenient to actual use and recycling.
Described linking agent is one or more in diene class or the vinylformic acid diol-lipid, preferred divinylbenzene, one or more in N-N-methylene-bisacrylamide, glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, the Diethylene Glycol dimethacrylate;
Described dispersion agent is one or more in polyvinyl alcohol, gelatin, the methylcellulose gum;
Described initiator is radical initiator, at least a in preferred benzoyl peroxide, Diisopropyl azodicarboxylate or the 2,2'-Azobis(2,4-dimethylvaleronitrile);
Described pore-creating agent is trichloromethane, butanone, ethyl acetate, two or more in the primary isoamyl alcohol; The adding of pore-creating agent mainly be make do not react, volatile small organic molecule is at the inner micropore that forms some amount of resin, can increase effective oil suction volume of resin, improves oil suction multiplying power and the oil suction speed of resin.
Described half interpenetrating network structure agent is one or more in natural rubber, isoprene-isobutylene rubber, ethylene-propylene rubber(EPR), the acrylic elastomer.The introducing of half interpenetrating network structure agent mainly is because the high oil absorbing resin oil-absorbing process is the stretching process of three-dimensional molecular net, chemically crosslinked is covalent linkage, bond energy is bigger, molecular chain is subjected to crosslinked constraint, therefore resin oil suction space is restricted, cause its oil suction multiplying power low, the semi-intercrossing network effect forms cross-linking zone by entanglement or the interactional microcell of macromolecular chain mostly, than a little less than the chemically crosslinked many. in extensive chemical is crosslinked, add weak relatively semi-intercrossing network, can form a kind of existing certain skeleton truly, be easy to the loose three-dimensional molecular web frame that stretches again, reach and reduce molecular network space potential barrier purpose, low to solve resin oil suction multiplying power, the drain the oil problem of reversibility difference of suction.
The above component deionized water dissolving, the common consumption of deionized water is 100～500 weight parts.
Two of purpose of the present invention provides a kind of described preparation method who contains the high oil absorbing resin of half interpenetrating network structure.
Comprise following steps:
A, dispersion agent is dissolved in deionized water fully;
After b, elder generation are dissolved in short chain acrylates class monomer with the half interpenetrating network structure agent, mix by described parts by weight with chain alkyl esters monomer, initiator, linking agent, vinylbenzene, pore-creating agent again, join after the mixing in the dispersant solution of step a, stir and make its even dispersion;
C, mixed system is warming up to 70～75 ℃, constant temperature is stirred to and mixes, and is warmed up to 80～85 ℃ then, the complete post curing of question response, stopped reaction;
Make the described high oil absorbing resin that contains half interpenetrating network structure after d, washing, suction filtration, the oven dry.
Among the above step c, priority condition is: described constant temperature churning time is 30～60 minutes, and the reaction times is 4～7 hours; Be warmed up to 90 ℃ of slakings, the curing time is 1 hour.
Concrete operations are as follows:
Having agitator, thermometer, add deionized water and dispersion agent in the reactor of prolong, heat up and stir, after treating that dispersion agent fully dissolves, add mix monomer (wherein the half interpenetrating network structure agent is dissolved in short chain acrylates class monomer in advance), initiator, linking agent, vinylbenzene, the mixture of pore-creating agent, 70～75 ℃ of dispersed with stirring half an hour, continue to be warmed up to 80～85 ℃, reacted 4～7 hours, be warmed up to 90 ℃ of slakings stopped reaction after 1 hour at last, with product with 60～70 ℃ of hot washes for several times, adopt common water distilling apparatus to utilize wet distillation to steam residual monomer and pore-creating agent then, decompress filter (B and vacuum cycle water pump), vacuum-drying (vacuum drying oven) can obtain high oil absorbing resin.
Because the present invention has improved the spacial framework of described high oil absorbing resin, improved the rigidity of resin.Make the high oil absorbing resin of making have than higher oil suction multiplying power with than oil suction speed faster, the oil suction reversibility is good, has good recycling performance.
Embodiment
Below in conjunction with embodiment, further specify the present invention.
The mensuration of oil suction multiplying power: the oil suction multiplying power comprises volume oil suction multiplying power and quality oil suction multiplying power, and the present invention adopts quality oil suction multiplying power, and the mensuration process of oil suction multiplying power is as follows:
Take by weighing the 0.5g high oil absorbing resin, wrap in the 200 order nylon net bags, put in 100 milliliters of flat bottom beakers, add excessive oil product, treat that oil suction reaches capacity after, take out nylon net bag, aloft drip and drop down 5 minutes, accurately weigh, empty Nylon Bag also immerses in the flat bottom beaker, deduct its oil suction quality, calculate the oil suction multiplying power of resin according to following formula:
Oil suction multiplying power (g/g)=A/B
A: resin quality before sample quality after the oil suction-Nylon Bag oil suction quality-oil suction
B: resin quality before the oil suction
The mensuration of secondary oil suction multiplying power
Resin after an oil suction is saturated is dried to constant weight under 60 ℃, take by weighing its quality, repeats the mensuration process of oil suction multiplying power then, calculates the secondary oil suction multiplying power of resin according to following formula:
Secondary oil suction multiplying power (g/g)=C/D
C: resin oven dry back quality after sample quality after the secondary oil suction-Nylon Bag oil suction quality-oil suction
D: resin oven dry back quality after the oil suction
In embodiment and the Comparative Examples raw materials used be commercially available.
Embodiment 1
Having agitator, prolong, in the 250ml there-necked flask of thermometer, add 300 parts of deionized waters (in weight part, the back together), 0.5 part of polyvinyl alcohol is warmed up to 70 ℃ in oil bath, constant temperature 30 minutes, after the dispersion agent dissolving, add 60 parts of stearyl methacrylates, 40 parts of butyl acrylates (be dissolved in the butyl acrylate isoprene-isobutylene rubber 3.3 parts), 0.5 part of benzoyl peroxide, 0.6 part of divinylbenzene, 10 parts of vinylbenzene, 5 parts of butanone, 5 parts of ethyl acetate, be warming up to 75 ℃, stirred 40 minutes fast, be warmed up to 80 ℃ then, rotating speed is reduced to about 400-420 rev/min, reacted about 5 hours, be warmed up to 90 ℃ of slakings stopped reaction after 1 hour at last, with product with hot wash for several times, wet distillation steams residual monomer and pore-creating agent then, the suction filtration oven dry can obtain high oil absorbing resin, the resin particle diameter is about 1mm after measured, and degree of crosslinking is 58%, and this resin is as follows to the absorption multiplying power of different oil products:
Oil product oil suction multiplying power (g/g) secondary oil absorbency (g/g)
Benzene 22 20
Dimethylbenzene 27 24
Trichloromethane 35 30
Gasoline 16 14
Diesel oil 14 11
Embodiment 2
Having agitator, prolong, in the 250ml there-necked flask of thermometer, add 333 parts of deionized waters, 0.53 part of polyvinyl alcohol, in oil bath, be warmed up to 70 ℃, constant temperature 30 minutes, after the dispersion agent dissolving, add 53.3 parts of methacrylic acid hexadecyl esters, 46.7 parts of butyl methacrylate (be dissolved in the butyl methacrylate isoprene-isobutylene rubber 5 parts), 13.3 parts of vinylbenzene, 5 parts of butanone, 5 parts of ethyl acetate, 0.57 part of divinylbenzene, Diisopropyl azodicarboxylate 0.5, stirred 30 minutes fast, be warmed up to 80 ℃ then, rotating speed is reduced to about 400-420 rev/min, reacted about 5 hours, be warmed up to 90 ℃ of slakings stopped reaction after 1 hour at last, with product with hot wash for several times, wet distillation steams residual monomer and pore-creating agent then, the suction filtration oven dry can obtain high oil absorbing resin, the resin particle diameter is about 1mm after measured, and degree of crosslinking is 58%, and this resin is as follows to the absorption multiplying power of different oil products:
Oil product oil suction multiplying power (g/g) secondary oil absorbency (g/g)
Benzene 21 18
Dimethylbenzene 27 24
Trichloromethane 35 29
Gasoline 15 13
Diesel oil 14 10
Embodiment 3
Having agitator, prolong, in the 250ml there-necked flask of thermometer, add 300 parts of deionized waters, 1 part in gelatin is warmed up to 70 ℃ in oil bath, constant temperature 30 minutes, after the dispersion agent dissolving, add 53.3 parts of methacrylic acid 14 esters, 46.7 parts of Jia Jibingxisuanyizhis, 6.7 parts of vinylbenzene, 9.3 parts of ethyl acetate, 3 parts of trichloromethanes, 1 part of primary isoamyl alcohol, 3.3 parts in ethylene-propylene rubber(EPR) (being dissolved in the Jia Jibingxisuanyizhi earlier), 0.6 part of N-N-methylene-bisacrylamide, 0.5 part of Diisopropyl azodicarboxylate is warming up to 75 ℃, stirs fast 60 minutes, be warmed up to 85 ℃ then, rotating speed is reduced to about 400-420 rev/min, reacted about 6 hours, be warmed up to 90 ℃ of slakings stopped reaction after 1 hour at last, with product with hot wash for several times, wet distillation steams residual monomer and pore-creating agent then, and the suction filtration oven dry can obtain high oil absorbing resin, and the resin particle diameter is about 1.1mm after measured, degree of crosslinking is 59%, and this resin is as follows to the absorption multiplying power of different oil products:
Oil product oil suction multiplying power (g/g) secondary oil absorbency (g/g)
Benzene 19 16
Dimethylbenzene 25 21
Trichloromethane 31 25
Gasoline 14 12
Diesel oil 12 10
Embodiment 4
Having agitator, prolong, in the 250ml there-necked flask of thermometer, add 300 parts of deionized waters, 1 part in gelatin, in oil bath, be warmed up to 70 ℃, constant temperature 30 minutes after the dispersion agent dissolving, adds 20 parts of Process Conditions of Cetane Acrylate, 80 parts of butyl acrylates, 4 parts of vinylbenzene, 2 parts of trichloromethanes, 3 parts of primary isoamyl alcohol, 10 parts in ethylene-propylene rubber(EPR) (being dissolved in the butyl acrylate), 0.6 part of glycol diacrylate, 0.5 part of 2,2'-Azobis(2,4-dimethylvaleronitrile) is warming up to 75 ℃, stirs fast 60 minutes, be warmed up to 80 ℃ then, rotating speed is reduced to about 400-420 rev/min, reacted about 7 hours, be warmed up to 90 ℃ of slakings stopped reaction after 1 hour at last, with product with hot wash for several times, wet distillation steams residual monomer and pore-creating agent then, and the suction filtration oven dry can obtain high oil absorbing resin, and the resin particle diameter is about 1mm after measured, degree of crosslinking is 58%, and this resin is as follows to the absorption multiplying power of different oil products:
Oil product oil suction multiplying power (g/g) secondary oil absorbency (g/g)
Benzene 20 18
Dimethylbenzene 26 24
Trichloromethane 33 28
Gasoline 14 12
Diesel oil 12 9
Embodiment 5
Having agitator, prolong, in the 250ml there-necked flask of thermometer, add 300 parts of deionized waters (in weight part, the back together), 0.5 part of polyvinyl alcohol is warmed up to 70 ℃ in oil bath, constant temperature 30 minutes, after the dispersion agent dissolving, add 60 parts of stearyl methacrylates, 40 parts of butyl acrylates (be dissolved in the butyl acrylate isoprene-isobutylene rubber 10 parts), 0.3 part of benzoyl peroxide, 0.3 part of divinylbenzene, 4 parts of vinylbenzene, 2 parts of butanone, 3 parts of ethyl acetate, be warming up to 75 ℃, stirred 40 minutes fast, be warmed up to 80 ℃ then, rotating speed is reduced to about 420 rev/mins, reacted about 5 hours, be warmed up to 90 ℃ of slakings stopped reaction after 1 hour at last, with product with hot wash for several times, wet distillation steams residual monomer and pore-creating agent then, the suction filtration oven dry can obtain high oil absorbing resin, the resin particle diameter is about 1mm after measured, and degree of crosslinking is 47%, and this resin is as follows to the absorption multiplying power of different oil products:
Oil product oil suction multiplying power (g/g) secondary oil absorbency (g/g)
Benzene 20 17
Dimethylbenzene 23 20
Trichloromethane 27 22
Gasoline 13 10
Diesel oil 10 8
Embodiment 6
Having agitator, prolong, in the 250ml there-necked flask of thermometer, add 400 parts of deionized waters, 2 parts of polyvinyl alcohol, in oil bath, be warmed up to 70 ℃, constant temperature 30 minutes, after the dispersion agent dissolving, add 15 parts of methacrylic acid hexadecyl esters, 85 parts of butyl methacrylate (be dissolved in the butyl methacrylate acrylic rubber 15 parts), 8 parts of vinylbenzene, 15 parts of butanone, 5 parts of ethyl acetate, 0.1 part of divinylbenzene, Diisopropyl azodicarboxylate 0.1, stirred 30 minutes fast, be warmed up to 75 ℃ then, rotating speed is reduced to about 400 rev/mins, reacted about 5 hours, be warmed up to 90 ℃ of slakings stopped reaction after 1 hour at last, with product with hot wash for several times, wet distillation steams residual monomer and pore-creating agent then, the suction filtration oven dry can obtain high oil absorbing resin, the resin particle diameter is about 1mm after measured, and degree of crosslinking is 38%, and this resin is as follows to the absorption multiplying power of different oil products:
Oil product oil suction multiplying power (g/g) secondary oil absorbency (g/g)
Benzene 15 12
Dimethylbenzene 18 14
Trichloromethane 21 16
Gasoline 10 8
Diesel oil 86
Embodiment 7
Having agitator, prolong, in the 250ml there-necked flask of thermometer, add 400 parts of deionized waters, 2 parts of methylcellulose gum are warmed up to 70 ℃ in oil bath, constant temperature 30 minutes, after the dispersion agent dissolving, add 5 parts of methacrylic acid 14 esters, 95 parts of Jia Jibingxisuanyizhis, 2 parts of vinylbenzene, 10 parts of ethyl acetate, 10 parts of trichloromethanes, 10 parts of primary isoamyl alcohol, 20 parts in ethylene-propylene rubber(EPR) (being dissolved in the Jia Jibingxisuanyizhi earlier), 0.8 part of N-N-methylene-bisacrylamide, 0.8 part of Diisopropyl azodicarboxylate is warming up to 80 ℃, stirs fast 60 minutes, be warmed up to 85 ℃ then, rotating speed is reduced to about 400 rev/mins, reacted about 5 hours, be warmed up to 90 ℃ of slakings stopped reaction after 1 hour at last, with product with hot wash for several times, wet distillation steams residual monomer and pore-creating agent then, and the suction filtration oven dry can obtain high oil absorbing resin, and the resin particle diameter is about 1.2mm after measured, degree of crosslinking is 72%, and this resin is as follows to the absorption multiplying power of different oil products:
Oil product oil suction multiplying power (g/g) secondary oil absorbency (g/g)
Benzene 17 15
Dimethylbenzene 20 16
Trichloromethane 28 21
Gasoline 98
Diesel oil 76
Embodiment 8
Having agitator, prolong, in the 250ml there-necked flask of thermometer, add 400 parts of deionized waters, 3 parts of polyvinyl alcohol, in oil bath, be warmed up to 70 ℃, constant temperature 30 minutes after the dispersion agent dissolving, adds 80 parts of Process Conditions of Cetane Acrylate, 20 parts of butyl acrylates, 20 parts of vinylbenzene, 7 parts of trichloromethanes, 8 parts of primary isoamyl alcohol, 2 parts of natural rubbers (being dissolved in the butyl acrylate), 1 part of glycol diacrylate, 1 part of 2,2'-Azobis(2,4-dimethylvaleronitrile) is warming up to 75 ℃, stirs fast 60 minutes, be warmed up to 80 ℃ then, rotating speed is reduced to about 400-420 rev/min, reacted about 7 hours, be warmed up to 90 ℃ of slakings stopped reaction after 1 hour at last, with product with hot wash for several times, wet distillation steams residual monomer and pore-creating agent then, and the suction filtration oven dry can obtain high oil absorbing resin, and the resin particle diameter is about 1.2mm after measured, degree of crosslinking is 84%, and this resin is as follows to the absorption multiplying power of different oil products:
Oil product oil suction multiplying power (g/g) secondary oil absorbency (g/g)
Benzene 22 19
Dimethylbenzene 27 25
Trichloromethane 33 26
Gasoline 16 13
Diesel oil 13 10
Below list three groups of Comparative Examples, compare with embodiment 1, wherein do not add pore-creating agent in the Comparative Examples 1 and introduce the half interpenetrating network structure agent, add pore-creating agent in the Comparative Examples 2 and do not introduced the half interpenetrating network structure agent, introduce the half interpenetrating network structure agent in the Comparative Examples 3 and do not add pore-creating agent, specific as follows:
Comparative Examples 1
Having agitator, prolong, in the 250ml there-necked flask of thermometer, add 300 parts of deionized waters, 0.5 part of polyvinyl alcohol is warmed up to 70 ℃ in oil bath, constant temperature 30 minutes, after the dispersion agent dissolving, add 60 parts of stearyl methacrylates, 40 parts of butyl acrylates, 10 parts of vinylbenzene, 0.6 part of divinylbenzene, 0.5 part of benzoyl peroxide is warming up to 75 ℃, stirs fast 40 minutes, be warmed up to 80 ℃ then, rotating speed is reduced to about 400-420 rev/min, reacted about 5 hours, be warmed up to 90 ℃ of slakings stopped reaction after 1 hour at last, with product with hot wash for several times, wet distillation steams residual monomer and pore-creating agent then, and the suction filtration oven dry can obtain high oil absorbing resin, and the resin particle diameter is about 0.8mm after measured, degree of crosslinking is 62%, and this resin is as follows to the absorption multiplying power of different oil products:
Oil product oil suction multiplying power (g/g) secondary oil absorbency (g/g)
Benzene 14 9
Dimethylbenzene 17 12
Trichloromethane 21 10
Gasoline 10 6
Diesel oil 84
Comparative Examples 2
Having agitator, prolong, in the 250ml there-necked flask of thermometer, add 300 parts of deionized waters, 0.5 part of polyvinyl alcohol, in oil bath, be warmed up to 70 ℃, constant temperature 30 minutes after the dispersion agent dissolving, adds 60 parts of stearyl methacrylates, 40 parts of butyl acrylates, 10 parts of vinylbenzene, 5 parts of butanone, 5 parts of ethyl acetate, 0.6 part of divinylbenzene, 0.5 part of benzoyl peroxide is warming up to 75 ℃, stirs fast 30 minutes, be warmed up to 80 ℃ then, rotating speed is reduced to about 400-420 rev/min, reacted about 5 hours, be warmed up to 90 ℃ of slakings stopped reaction after 1 hour at last, with product with hot wash for several times, wet distillation steams residual monomer and pore-creating agent then, and the suction filtration oven dry can obtain high oil absorbing resin, and the resin particle diameter is about 0.9mm after measured, degree of crosslinking is 62%, and this resin is as follows to the absorption multiplying power of different oil products:
Oil product oil suction multiplying power (g/g) secondary oil absorbency (g/g)
Benzene 15 10
Dimethylbenzene 20 12
Trichloromethane 25 16
Gasoline 12 7
Diesel oil 95
Comparative Examples 3
Having agitator, prolong, in the 250ml there-necked flask of thermometer, add 300 parts of deionized waters (in weight part, the back together), 0.5 part of polyvinyl alcohol, in oil bath, be warmed up to 70 ℃, constant temperature 30 minutes after the dispersion agent dissolving, adds 60 parts of stearyl methacrylates, 40 parts of butyl acrylates (be dissolved in the butyl acrylate isoprene-isobutylene rubber 3.3 parts), 0.5 part of benzoyl peroxide, 0.6 part of divinylbenzene, 10 parts of vinylbenzene, be warming up to 75 ℃, stirred 40 minutes fast, be warmed up to 80 ℃ then, rotating speed is reduced to about 400-420 rev/min, reacted about 5 hours, be warmed up to 90 ℃ of slakings stopped reaction after 1 hour at last, with product with hot wash for several times, wet distillation steams residual monomer then, the suction filtration oven dry can obtain high oil absorbing resin, the resin particle diameter is about 1mm after measured, and degree of crosslinking is 61%, and this resin is as follows to the absorption multiplying power of different oil products:
Oil product oil suction multiplying power (g/g) secondary oil absorbency (g/g)
Benzene 13 11
Dimethylbenzene 19 13
Trichloromethane 21 15
Gasoline 11 9
Diesel oil 96
Data by embodiment and Comparative Examples as can be seen, the high oil absorbing resin of embodiment 1 preparation to the oil suction multiplying power of different oil products and secondary oil absorbency apparently higher than Comparative Examples 1～3.High oil absorbing resin of the present invention has than higher oil suction multiplying power with than oil suction speed faster, and the oil suction reversibility is good, has good recycling performance.
Claims (7)
1. high oil absorbing resin that contains half interpenetrating network structure is characterized in that:
Described high oil absorbing resin is got by the feedstock production that comprises following component:
Oil suction monomer 100 weight parts
Vinylbenzene 2～20 weight parts
Linking agent 0.1～1 weight part
Dispersion agent 0.3～3 weight part
Initiator 0.1～1 weight part
Pore-creating agent 5～30 weight parts
Half interpenetrating network structure agent 2～20 weight parts
Described oil suction monomer is the mixture of chain alkyl esters monomer and short chain acrylates class monomer, and wherein the chain alkyl esters monomer is: one or more in dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, octadecyl acrylate, methacrylic dodecyl gallate, methacrylic acid 14 esters, methacrylic acid hexadecyl ester, the stearyl methacrylate; Short chain acrylates class monomer is: one or more in methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, the butyl methacrylate;
Described linking agent is one or more in diene class or the vinylformic acid diol-lipid;
Described dispersion agent is one or more in polyvinyl alcohol, gelatin, the methylcellulose gum;
Described initiator is radical initiator;
Described pore-creating agent is trichloromethane, butanone, ethyl acetate, two or more in the primary isoamyl alcohol;
Described half interpenetrating network structure agent is one or more in natural rubber, isoprene-isobutylene rubber, ethylene-propylene rubber(EPR), the acrylic elastomer.
2. a kind of high oil absorbing resin that contains half interpenetrating network structure as claimed in claim 1 is characterized in that:
Described linking agent is divinylbenzene, one or more in N-N-methylene-bisacrylamide, glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, the Diethylene Glycol dimethacrylate.
3. a kind of high oil absorbing resin that contains half interpenetrating network structure as claimed in claim 1 is characterized in that:
Described initiator is at least a in benzoyl peroxide, Diisopropyl azodicarboxylate or the 2,2'-Azobis(2,4-dimethylvaleronitrile).
4. one kind prepares as the described method that contains the high oil absorbing resin of half interpenetrating network structure of one of claim 1～3, comprises following steps:
A, dispersion agent is dissolved in deionized water fully;
After b, elder generation are dissolved in short chain acrylates class monomer with the half interpenetrating network structure agent, mix by described parts by weight with chain alkyl esters monomer, initiator, linking agent, vinylbenzene, pore-creating agent again, join after the mixing in the dispersant solution of step a, stir and make its even dispersion;
C, mixed system is warming up to 70～75 ℃, constant temperature is stirred to and mixes, and is warmed up to 80～85 ℃ then, the complete post curing of question response, stopped reaction;
Make the described high oil absorbing resin that contains half interpenetrating network structure after d, washing, suction filtration, the oven dry.
5. one kind prepares the method that contains the high oil absorbing resin of half interpenetrating network structure as claimed in claim 4, it is characterized in that:
Among the described step c, the constant temperature churning time is 30～60 minutes, and the reaction times is 4～7 hours.
6. one kind prepares the method that contains the high oil absorbing resin of half interpenetrating network structure as claimed in claim 5, it is characterized in that:
Among the described step c, be warmed up to 90 ℃ of slakings, the curing time is 1 hour.
7. one kind prepares as the described method that contains the high oil absorbing resin of half interpenetrating network structure of one of claim 4～6, it is characterized in that:
The consumption of deionized water is 100 weight parts in described oil suction monomer among the described step a, is 100～500 weight parts.
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| CN 201010517906 CN102453296B (en) | 2010-10-25 | 2010-10-25 | High oil absorption resin with semi-interpenetrating polymer network structure and its preparation method |
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| CN 201010517906 CN102453296B (en) | 2010-10-25 | 2010-10-25 | High oil absorption resin with semi-interpenetrating polymer network structure and its preparation method |
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| CN113896829B (en) * | 2021-09-30 | 2023-08-22 | 青岛汇智领先新材料科技有限公司 | High-oil-absorption resin capable of rapidly absorbing oil and preparation method thereof |
| CN114438614B (en) * | 2021-12-25 | 2023-12-22 | 江苏集萃先进纤维材料研究所有限公司 | Preparation method and product of warm regenerated cellulose fiber |
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