CN1757658A - Method for preparing high oil absorption resin - Google Patents
Method for preparing high oil absorption resin Download PDFInfo
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- CN1757658A CN1757658A CN 200410064893 CN200410064893A CN1757658A CN 1757658 A CN1757658 A CN 1757658A CN 200410064893 CN200410064893 CN 200410064893 CN 200410064893 A CN200410064893 A CN 200410064893A CN 1757658 A CN1757658 A CN 1757658A
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Abstract
A process for preparing the resin with high oil absorptivity from styrene and long-chain olefin monomer CnH2n, where n is equal to or greater than 4, includes such steps as preparing the low-cross-linked polystryrene or styrene copolymer, immersing it in solvent or long-chain olefin monomer or their mixture, and alkylating reaction. Its advantages are high content of gel and oil absorptivity, and low cost.
Description
One technical field
The present invention relates to a kind of preparation method's of functional polymer, particularly a kind of high oil absorbing resin preparation method.
Two background technologies
High oil absorbing resin is a kind of threedirection polymerization resin with low three-dimensional netted chemically crosslinked structure.Compare with traditional oil absorption material; high oil absorbing resin has that the oil suction kind is many, oil number is big, the profit selectivity is good, it is convenient to reclaim, oil-retaining is strong, plurality of advantages such as oil-proof, easy storage transportation during pressurized; so be widely used in industries such as environment protection, rubber, agricultural chemicals and papermaking; as various oil-treatment agents, base material, mist of oil filtering material, rubber modifier and paper with additive etc., as absorb the oil pollution thing that leak into the sea because of the oil tanker accident with high oil absorbing resin.
According to the difference of monomeric species, high oil absorbing resin is mainly two big classes: the one, and alkyl-acrylates resin, alkyl-acrylates high oil absorbing resin mainly adopt alkyl ester to contain the long alkyl chain length ester of the vinylformic acid monomer of carbon number 〉=8.Announced the long alkyl chain length ester of vinylformic acid high oil absorbing resin as the flat 05-15777 of Japanese Patent, flat 05-32708 peace 05-209017 etc.The 2nd, olefine kind resin, olefine kind resin are that (molecular formula is C to employing long-chain olefin class monomer
nH
2n) or chain alkyl styrene monomer etc. be the high oil absorbing resin of principal monomer preparation.Comparatively ideal is to adopt the chain alkyl styrene monomer.Announced the high oil absorbing resin that adopts the preparation of ring-alkylated styrenes monomer as the clear 45-27081 of Japanese Patent, flat 05-9243 has announced the high oil absorbing resin that adopts the preparation of long-chain alpha-olefin monomer.
At present, the research of olefines high oil absorbing resin is seldom studied at most and the high oil absorbing resin that obtained to a certain degree to use mainly is the alkyl-acrylates high oil absorbing resin.The monomeric synthetic yield of the long alkyl chain length ester of vinylformic acid is low, and the monomer cost is very high, and the monomeric polymerization yield rate of the long alkyl chain length ester of vinylformic acid is also not really high simultaneously, so the price of its high oil absorbing resin is high.Simultaneously, owing to have the ester group polar group in the molecular structure, not too high to the oil absorption of nonpolar oil product, and oil suction body rigidity is not so good, is the sposh shape, is unfavorable for actual use and recycling.Therefore the widespread use of alkyl-acrylates high oil absorbing resin is promoted and has been subjected to very big restriction.
Olefine kind resin is a non-polar resin, and is therefore strong with the affinity of nonpolar oil product, than alkyl-acrylates resin height, is the high oil absorbing resin that a class oil absorption can be very good, gets a good chance of obtaining widespread use to the oil absorbency of nonpolar oil product.But the monomeric polymerizing power of long-chain olefin class is difficult for making the high high oil absorbing resin of gel content than alkyl-acrylates difference, therefore often can not get the good high oil absorbing resin of oil absorptiveness; Simultaneously, do not have rigid element in the molecular structure, the molecular chain flexibility is too big, and the resin rigidity is low, so its oil suction body is the sposh shape, the actual use and the recycling inconvenience.Chain alkyl styrene type high oil absorbing resin is the comparatively ideal high oil absorbing resin of a class, because it belongs to non-polar resin, simultaneously on the molecular structure inflexible phenyl ring is arranged, so its high oil absorbing resin can have good oil absorptiveness, and the oil suction body is not the sposh shape.But chain alkyl styrene monomer preparation difficulty is simultaneously also poor than the alkyl-acrylates polymerizing power.
Three summary of the invention
The object of the present invention is to provide a kind of preparation method of high oil absorbing resin, overcome because long-chain olefin class monomer polymerization ability and transformation efficiency is low when homopolymerization or copolymerization high oil absorbing resin, gel content is low, and the low problem of apparent oil absorbency, thereby improving long-chain olefin class conversion of monomer is the productive rate of high oil absorbing resin and obtains high gel content, make the high oil absorbing resin of preparation have good oil absorptiveness, and having suitable hard and soft property, the oil suction body is not the sposh shape.
The technical scheme that realizes the object of the invention is: a kind of preparation method of high oil absorbing resin may further comprise the steps:
(1) adopting vinylbenzene and linking agent is that raw material monomer prepares the low cross-linking polystyrene;
(2) adopt long-chain olefin class monomer or solvent and the monomeric mixture swelling of long-chain olefin class low cross-linking polystyrene, and carry out alkylated reaction, long-chain olefin class monomer is linked on the benzene lateral group of low cross-linking polystyrene molecule by alkylated reaction, makes vinylbenzene-long-chain olefin type high oil absorbing resin.
The preparation method of another kind of high oil absorbing resin may further comprise the steps:
(1) mixture of one or more in employing alkyl-acrylates monomer, vinyl ester monomer, vinyl ethers monomer and the vinyl monomer except that vinylbenzene, long-chain olefin class monomer and vinylchlorid is with vinylbenzene and linking agent copolymerization low cross-linking styrene type multipolymer;
(2) adopt long-chain olefin class monomer, perhaps solvent and the monomeric mixture swelling of long-chain olefin class low cross-linking styrene type multipolymer, and carry out alkylated reaction, long-chain olefin class monomer is linked on the benzene lateral group of low cross-linking styrene type copolymer molecule by alkylated reaction, makes vinylbenzene-long-chain olefin type high oil absorbing resin.
Also have a kind of preparation method of oil-absorbing resin, may further comprise the steps:
(1) adopting vinylbenzene, long-chain olefin class monomer and linking agent is that raw material monomer prepares low cross-linking styrene type multipolymer; Perhaps adopt one or more the mixture in alkyl-acrylates monomer, vinyl ester monomer, vinyl ethers monomer and the vinyl monomer except that vinylbenzene, long-chain olefin class monomer and vinylchlorid, with vinylbenzene, long-chain olefin class monomer and linking agent copolymerization low cross-linking styrene type multipolymer;
(2) adopt solvent, perhaps long-chain olefin class monomer, perhaps solvent and the monomeric mixture swelling of long-chain olefin class low cross-linking styrene type multipolymer, and carry out alkylated reaction, long-chain olefin class monomer is linked on the benzene lateral group of low cross-linking styrene type copolymer molecule by alkylated reaction, makes vinylbenzene-long-chain olefin type high oil absorbing resin.
The process of swelling low cross-linking polystyrene of the present invention or low cross-linking styrene type multipolymer with carry out alkylated reaction, the process that long-chain olefin class monomer is linked into by alkylated reaction on the benzene lateral group of low cross-linking polystyrene or low cross-linking styrene type copolymer molecule can proceed step by step, and promptly first swelling is carried out alkylated reaction then.
The process of swelling low cross-linking polystyrene of the present invention or low cross-linking styrene type multipolymer with carry out alkylated reaction, the process that long-chain olefin class monomer is linked into by alkylated reaction on the benzene lateral group of low cross-linking polystyrene or low cross-linking styrene type copolymer molecule also can be carried out synchronously.
The present invention can adopt suspension polymerization when preparing low cross-linking polystyrene and low cross-linking styrene type multipolymer, adopts general suspension dispersive agent and general suspension polymerization radical initiator in described suspension polymerization.
When the present invention prepares low cross-linking polystyrene and low cross-linking styrene type multipolymer, can adopt diene hydro carbons monomer as linking agent, the mole dosage of linking agent is 0.5%～3.5%.
The dispersion medium that can adopt when solvent that can adopt during swelling of the present invention and alkylated reaction is alkylation solvent or rudimentary saturated fatty hydrocarbon solvent.
It is in the low cross-linking polystyrene of raw material monomer preparation that the present invention adopts vinylbenzene and linking agent, and the ratio of the unitary total moles of vinylbenzene chain link that all molecules contained is 0.5～1.5: 1 in the monomeric total moles of swollen long-chain olefin class and the low cross-linking polystyrene.
The present invention adopts one or more the mixture in alkyl-acrylates monomer, vinyl ester monomer, vinyl ethers monomer and the vinyl monomer except that vinylbenzene, long-chain olefin class monomer and vinylchlorid, in the low cross-linking styrene type multipolymer of vinylbenzene and linking agent copolymerization, the ratio of the unitary total moles of vinylbenzene chain link that all molecules contained is 0.5～1.5: 1 in the monomeric total moles of swollen long-chain olefin class and such low cross-linking styrene type multipolymer.
It is that raw material monomer is when preparing low cross-linking styrene type multipolymer that the present invention adopts vinylbenzene, long-chain olefin class monomer and linking agent, perhaps adopt one or more the mixture in alkyl-acrylates monomer, vinyl ester monomer, vinyl ethers monomer and the vinyl monomer except that vinylbenzene, long-chain olefin class monomer and vinylchlorid, during with vinylbenzene, long-chain olefin class monomer and linking agent copolymerization low cross-linking styrene type multipolymer, it is 0.001%～75% that long-chain olefin class monomer accounts for all monomeric quality consumption branch rates.The long-chain olefin class monomer that can adopt during such low cross-linking styrene type multipolymer of swelling of the present invention is identical with the long-chain olefin class monomer that adopts when preparing such low cross-linking styrene type multipolymer, also can be different.The ratio that enters the unitary total moles of vinylbenzene chain link that all molecules contained in the monomeric total moles of long-chain olefin class and such low cross-linking styrene type multipolymer in such low cross-linking styrene type multipolymer by swelling process among the present invention is 0～1.5: 1.Simultaneously, the ratio of the unitary total moles of vinylbenzene chain link that all molecules contained is lower than 2.0: 1 in the total moles of swollen long-chain olefin class monomer in such low cross-linking styrene type multipolymer of the present invention (comprising not polymerization long-chain olefin class monomer residual when swelling enters long-chain olefin class monomer in such low cross-linking styrene type multipolymer and copolymerization) and such low cross-linking styrene type multipolymer.
When swelling low cross-linking polystyrene of the present invention or low cross-linking styrene type multipolymer, except that adopting solvent and/or long-chain olefin class monomer to carry out the swelling, can also add one or more the mixture in alkyl-acrylates monomer, vinyl ester monomer, vinyl ethers monomer and the vinyl monomer except that vinylbenzene, long-chain olefin class monomer and vinylchlorid.
When carrying out alkylated reaction, use alkylation catalysts such as aluminum trichloride (anhydrous), hydrofluoric acid.The adding mode of alkylation catalyst of the present invention can be, employed solvent when alkylation catalyst is dissolved in swelling, perhaps long-chain olefin class monomer, perhaps in solvent and the monomeric mixture of long-chain olefin class, when swelling low cross-linking polystyrene or low cross-linking styrene type multipolymer, alkylation catalyst is introduced in the swelling body of low cross-linking polystyrene or low cross-linking styrene type multipolymer.The adding mode of alkylation catalyst of the present invention also can be after swelling low cross-linking polystyrene or low cross-linking styrene type multipolymer, alkylation catalyst to be added in the alkylation reaction system.
The total mass of employed whole vinylbenzene and long-chain olefin class monomer shared branch rate in employed all monomeric total masses is 50%～100% in vinylbenzene of the present invention-long-chain olefin type high oil absorbing resin preparation process, obtains oil absorption and cost performance preferably to guarantee high oil absorbing resin.
The long-chain olefin class monomer that the present invention uses is that molecular formula is C
nH
2nThe one-component monoolefine, n 〉=4; Or molecular formula is C
nH
2nBut the mixture of the polycomponent monoolefine that n is different; Or be C with the molecular formula
nH
2nMonoolefine be main polycomponent monoolefine monomer mixture; Or be C with the molecular formula
nH
2nBut the polycomponent monoolefine mixture that n is different is main monoolefine monomer mixture.
Compared with prior art, the present invention has remarkable advantage: the present invention prepares low cross-linking polystyrene or low cross-linking styrene type multipolymer earlier, pass through alkylated reaction then, can in high oil absorbing resin, introduce more long flexible chain alkyl side chain effectively, the vinylbenzene that makes-long-chain olefin type high oil absorbing resin gel content height, oil absorbency height have similar structure and the performance of poly-chain alkyl styrene type high oil absorbing resin.Vinylbenzene of the present invention-long-chain olefin type high oil absorbing resin both can have good oil absorptiveness, had certain rigid again simultaneously, and the oil suction body is not the sposh shape, and speed of oil absorption is fast especially, is convenient to actual use and recycling.Principal monomer benzene feedstock ethene and the monomeric price of long-chain olefin class that the present invention uses are much lower than the alkyl-acrylates raw material monomer, also low than vinyl ester monomer and vinyl ethers monomer raw material, therefore vinylbenzene-long-chain olefin type high oil absorbing resin the price of preparation is low, is expected to have bigger marketing application prospect.Principal feature of the present invention is the method by alkylated reaction, long-chain olefin class monomer (comprising not polymerization long-chain olefin class monomer residual when swelling enters long-chain olefin class monomer in low cross-linking polystyrene or the low cross-linking styrene type multipolymer and copolymerization) is inserted on the benzene lateral group of vinylbenzene chain link, make productive rate height, long-chain olefin class monomer conversion height, i.e. the gel content height of resin of the vinylbenzene-long-chain olefin type high oil absorbing resin for preparing.
Four embodiments
The present invention adopts vinylbenzene and long-chain olefin class monomer, and (molecular formula is C
nH
2n, n 〉=4) and be principal monomer feedstock production high oil absorbing resin.The cost of material of vinylbenzene and long-chain monoolefine is all very low, is again non-polar monomer, and therefore the high oil absorbing resin of preparation can satisfy the low and good requirement of oil absorptiveness of cost.But the high oil absorbing resin of its preparation will have good oil absorptiveness, must overcome because of long-chain olefin class monomer polymerization ability to cause the not high problem of high oil absorbing resin gel content.The present invention has investigated the performance of high oil absorbing resin by gel content and oil absorbency index.Gel content be meant part (comprise unreacted monomer in the high oil absorbing resin, be not connected into the macromole of three-dimensional netted body etc.) that high oil absorbing resin fully extracted, will not be connected into three-dimensional netted body with good solvent fully wash-out remove the percentage of the remaining quality in back.Gel content has reflected the integrated degree of the three-dimensional netted body of high oil absorbing resin and the productive rate of high oil absorbing resin (being the transformation efficiency that conversion of monomer becomes polymkeric substance).Oil absorbency is meant that high oil absorbing resin is immersed in the oil suction physique amount that forms when reaching the oil suction balance in the specific oil product and the ratio of high oil absorbing resin initial mass.The oil absorption of oil absorbency reflection resin, oil absorbency show more greatly that the oil absorption of resin is stronger.
The present invention at first prepares low cross-linking polystyrene or preparation low cross-linking styrene type multipolymer.Be raw material monomer with vinylbenzene and linking agent during preparation low cross-linking polystyrene.And during preparation low cross-linking styrene type multipolymer, can adopt one or more the mixture in alkyl-acrylates monomer, vinyl ester monomer, vinyl ethers monomer and the vinyl monomer except that vinylbenzene, long-chain olefin class monomer and vinylchlorid, and vinylbenzene and linking agent are raw material monomer; Can be raw material monomer also with vinylbenzene, long-chain olefin class monomer and linking agent; Also can adopt one or more the mixture in alkyl-acrylates monomer, vinyl ester monomer, vinyl ethers monomer and the vinyl monomer except that vinylbenzene, long-chain olefin class monomer and vinylchlorid, and vinylbenzene, long-chain olefin class monomer and linking agent are raw material monomer.Product to preparation carries out swelling then, promptly adopt long-chain olefin class monomer or solvent and the monomeric mixture swelling of long-chain olefin class low cross-linking polystyrene, perhaps adopt solvent, long-chain olefin class monomer or solvent and the monomeric mixture swelling of long-chain olefin class low cross-linking styrene type multipolymer, and carry out alkylated reaction, promptly long-chain olefin class monomer is linked into by alkylated reaction on the benzene lateral group of low cross-linking polystyrene molecule and makes vinylbenzene-long-chain olefin type high oil absorbing resin, perhaps long-chain olefin class monomer is linked into by alkylated reaction on the benzene lateral group of low cross-linking styrene type copolymer molecule and makes vinylbenzene-long-chain olefin type high oil absorbing resin.
The present invention carries out the swollen purpose to low cross-linking polystyrene or low cross-linking styrene type multipolymer, is alkylation catalyst can be introduced in low cross-linking polystyrene or the low cross-linking styrene type multipolymer, so that alkylated reaction can carry out; Can introduce to replenish in long-chain olefin class monomer or the low cross-linking styrene type multipolymer to the low cross-linking polystyrene by swelling process simultaneously and introduce long-chain olefin class monomer.
The process of swelling low cross-linking polystyrene of the present invention or low cross-linking styrene type multipolymer with carry out alkylated reaction, the process that long-chain olefin class monomer is linked into by alkylated reaction on the benzene lateral group of low cross-linking polystyrene or low cross-linking styrene type copolymer molecule can proceed step by step, promptly elder generation's swelling low cross-linking polystyrene or low cross-linking styrene type multipolymer under the temperature lower than alkylated reaction temperature is warming up to the temperature that alkylated reaction can take place then and carries out alkylated reaction.
The process of swelling low cross-linking polystyrene of the present invention or low cross-linking styrene type multipolymer with carry out alkylated reaction, the process that long-chain olefin class monomer is linked into by alkylated reaction on the benzene lateral group of low cross-linking polystyrene or low cross-linking styrene type copolymer molecule also can be carried out synchronously.Employed solvent when alkylation catalyst is dissolved in swelling, perhaps long-chain olefin class monomer, perhaps in solvent and the monomeric mixture of long-chain olefin class, carry out alkylated reaction at following swelling low cross-linking polystyrene of alkylated reaction temperature or low cross-linking styrene type multipolymer limit.
Adopt suspension polymerization when the present invention prepares low cross-linking polystyrene and low cross-linking styrene type multipolymer, general dispersion agent when wherein suspension dispersive agent can adopt the styrene suspension copolymerization is as polyvinyl alcohol, gelatin, calcium phosphate powder etc.
When the present invention prepares low cross-linking polystyrene and low cross-linking styrene type multipolymer, adopt diene hydro carbons monomer, as Vinylstyrene, diacrylate second diester etc., as linking agent.The mole dosage of linking agent should be moderate, and its mole dosage scope is advisable with 0.5%～3.5%.The long-chain olefin class monomer difference of using, the preferable mole dosage of linking agent is slightly variant.
When the present invention prepared low cross-linking polystyrene and low cross-linking styrene type multipolymer, initiator can adopt general suspension polymerization radical initiator, as organic superoxide, Diisopropyl azodicarboxylate etc.
The present invention is adopting vinylbenzene, when long-chain olefin class monomer and linking agent suspension polymerization low cross-linking vinylbenzene-long-chain olefin type multipolymer, perhaps adopt the alkyl-acrylates monomer, the vinyl ester monomer, vinyl ethers monomer and remove vinylbenzene, the mixture of one or more in the vinyl monomer outside long-chain olefin class monomer and the vinylchlorid, with vinylbenzene, when long-chain olefin class monomer and linking agent copolymerization low cross-linking vinylbenzene-long-chain olefin type multipolymer, the monomeric quality consumption of long-chain olefin class divides the rate can not be too high, should guarantee that suspension polymerization makes low cross-linking vinylbenzene-long-chain olefin type multipolymer in pelletized form.If the quality consumption divides rate too high, because the monomeric polymerizing power of long-chain olefin class is poor, monomeric total conversion rate is too low during polymerization, and too much unpolymerized long-chain olefin class monomer swell makes multipolymer be sposh in low cross-linking vinylbenzene-long-chain olefin type multipolymer; Or since the long-chain olefin class monomer of polymerizing power difference to the excess dilution of other polymerisable monomers and linking agent, cause to form more complete three-dimensional netted body, the macromole that aggregates into is become liquid state by too much unpolymerized long-chain olefin class monomer dissolving, thereby can't obtain low cross-linking vinylbenzene-long-chain olefin type copolymer pellet, also just can't finally make vinylbenzene-long-chain olefin type high oil absorbing resin.Therefore, when preparing such low cross-linking styrene type multipolymer, it is good with 0.001%～75% that long-chain olefin class monomer accounts for all monomeric quality consumption branch rates.
The solvent that adopts during swelling is alkylation solvent or rudimentary saturated fatty hydrocarbon solvent.Alkylation solvent such as oil of mirbane, dithiocarbonic anhydride, tetracol phenixin, Nitromethane 99Min., nitroethane, nitropropane, chloroform, ethylene dichloride, trichloroethane, tetrachloroethane, chlorobenzene, rudimentary saturated fatty hydrocarbon solvent such as pentane, 2-methylbutane, hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, heptane isomers, sherwood oil.In addition, also can adopt pentamethylene and methylcyclopentane.For the ease of adopting the distillatory method to slough solvent behind the alkylated reaction, be good to select the lower or close solvent of boiling point for use with alkylation temperature.
In the low cross-linking polystyrene in the monomeric total moles of swollen long-chain olefin class and the low cross-linking polystyrene ratio of the unitary total moles of vinylbenzene chain link that all molecules contained with 0.5～1.5: 1 for good.If swollen long-chain olefin class amount of monomer is too low in the low cross-linking polystyrene, the long flexible chain monoolefine of introducing in the vinylbenzene that then makes-long-chain olefin type high oil absorbing resin very little, the oil absorbency of the high oil absorbing resin that makes is low.Simultaneously, because alkylated reaction is balanced reaction, level of response is lower than 100%, therefore in order in the low cross-linking polystyrene, to introduce more long-chain olefin class monomer by alkylated reaction, can adopt long-chain olefin class monomer consumption slightly excessive way relatively, the monomeric total moles of swollen long-chain olefin class can be than the unitary total moles height of the vinylbenzene chain link that all molecules contained in the low cross-linking polystyrene in the low cross-linking polystyrene promptly of the present invention.But can not be excessive too many, otherwise because of there are not enough benzene lateral group access positions in the low cross-linking polystyrene, the long-chain olefin class monomer of final residue in resin is more, and the gel content of high oil absorbing resin and oil absorbency are lower on the contrary.
Long-chain olefin class monomer when the long-chain olefin class monomer that adopts during swelling low cross-linking vinylbenzene-long-chain monoolefine multipolymer can be with copolymerization low cross-linking vinylbenzene-long-chain olefin type multipolymer is identical, also can be different.But during copolymerization low cross-linking vinylbenzene-long-chain olefin type multipolymer, long-chain olefin class monomer is good with alpha-olefin, because the polymerizing power of alpha-olefin is stronger, transformation efficiency during copolymerization is higher, so that the long-chain olefin class monomer of introducing main chain in the high oil absorbing resin that finally makes is many, and oil absorptiveness is good.During swelling low cross-linking vinylbenzene-long-chain olefin type multipolymer, the ratio of introducing the unitary total moles of vinylbenzene chain link that all molecules contained in the monomeric total moles of long-chain olefin class and the low cross-linking vinylbenzene-long-chain olefin type multipolymer in low cross-linking vinylbenzene-long-chain olefin type multipolymer by swelling is with 0～1.5: 1 for good.
In not using the monomeric low cross-linking styrene type of long-chain olefin class multipolymer swollen long-chain olefin class amount of monomer can not be too low can not be too high, the ratio of the unitary total moles of vinylbenzene chain link that all molecules contained is with 0.5～1.5 in the monomeric total moles of swollen long-chain olefin class and the low cross-linking styrene type multipolymer: 1 for good.And the upper limit of the ratio of the unitary total moles of vinylbenzene chain link that all molecules contained can be relative higher in the monomeric total moles of swollen long-chain olefin class (unpolymerized long-chain olefin class monomer when comprising the long-chain olefin class monomer that enters by swelling in low cross-linking vinylbenzene-long-chain olefin type multipolymer and preparation low cross-linking vinylbenzene-long-chain olefin type multipolymer) and the low cross-linking vinylbenzene-long-chain olefin type multipolymer in low cross-linking vinylbenzene-long-chain olefin type multipolymer, and to be lower than .2.0: 1 is good.
When swelling low cross-linking polystyrene of the present invention or low cross-linking styrene type multipolymer, except that adopting solvent and/or long-chain olefin class monomer to carry out the swelling, can also add one or more the mixture in alkyl-acrylates monomer, vinyl ester monomer, vinyl ethers monomer and the vinyl monomer except that vinylbenzene, long-chain olefin class monomer and vinylchlorid.But in order in vinylbenzene-long-chain olefin type high oil absorbing resin, to introduce alkyl-acrylates monomer, vinyl ester monomer, vinyl ethers monomer and the vinyl monomer except that vinylbenzene, long-chain olefin class monomer and vinylchlorid, preferably directly adding copolymerization system and participate in copolymerization when copolymerization, is not the best approach and adopt the method that adds again by alkylated reaction they are introduced in the high oil absorbing resin structure after the copolymerization.
When carrying out alkylated reaction, use alkylation catalysts such as aluminum trichloride (anhydrous), hydrofluoric acid, can use alkylation solvent and rudimentary saturated fatty hydrocarbon solvent to be dispersion medium.The adding mode of alkylation catalyst can be, employed solvent when alkylation catalyst is dissolved in swelling, perhaps long-chain olefin class monomer, perhaps in solvent and the monomeric mixture of long-chain olefin class, when swelling low cross-linking polystyrene or low cross-linking styrene type multipolymer, alkylation catalyst is introduced in the swelling body of low cross-linking polystyrene or low cross-linking styrene type multipolymer; Also can be after swelling low cross-linking polystyrene or low cross-linking styrene type multipolymer, alkylation catalyst is added in the alkylation reaction system, in the dispersion medium that adopts such as alkylation catalyst can be dissolved in alkylated reaction the time, alkylation catalyst constantly enters in the swelling body and catalytic alkylation reaction by spreading in the process of carrying out alkylated reaction like this.
The total mass of employed whole vinylbenzene and long-chain olefin class monomer shared branch rate in employed all monomeric total masses is in 50%～100% in vinylbenzene of the present invention-long-chain olefin type high oil absorbing resin preparation process, to guarantee that high oil absorbing resin has oil absorption and cost performance preferably simultaneously.Certainly; outside this scope; adopt technical scheme of the present invention also can obtain the high oil absorbing resin of better oil absorption; just the high oil absorbing resin cost can be higher; therefore outside this scope, adopt the vinylbenzene-long-chain olefin type high oil absorbing resin of technical scheme preparation of the present invention also to belong to protection domain of the present invention.
The long-chain olefin class monomer that the present invention uses is that molecular formula is C
nH
2nThe monoolefine of (n 〉=4) is as heptene, octene, dodecylene, cetene, vaccenic acid etc.It can be that molecular formula is C
nH
2nThe one-component monoolefine of (n 〉=4) also can be that molecular formula is C
nH
2nThe mixture of the polycomponent monoolefine that (n 〉=4) but n are different can also be to be C with the molecular formula
nH
2nThe long-chain monoolefine of (n 〉=4) is main and mixes the polycomponent monoolefine monomer mixture of other alkene (as one or more the mixture in alkyl-acrylates monomer, vinyl ester monomer, vinyl ethers monomer and the vinyl monomer except that vinylbenzene, long-chain olefin class monomer, vinylchlorid), can also be to be C with the molecular formula
nH
2nThe mixture of the polycomponent long-chain monoolefine that (n 〉=4) but n are different is main and mixes the polycomponent monoolefine monomer mixture of other alkene.
The best-of-breed technology scheme that the present invention prepares vinylbenzene-long-chain olefin type high oil absorbing resin is: at first adopt copolymerization low cross-linking vinylbenzene-long-chain olefin type multipolymers such as long-chain olefin class monomer and vinylbenzene and linking agent, adopt solvent then, perhaps long-chain olefin class monomer, perhaps behind solvent and the monomeric mixture swelling of the long-chain olefin class low cross-linking vinylbenzene-long-chain olefin type multipolymer, carry out alkylated reaction.When if the quality consumption branch rate of long-chain olefin class monomer in vinylbenzene-long-chain olefin type high oil absorbing resin is not very high (as being lower than 75%), when being preferably in copolymerization low cross-linking vinylbenzene-long-chain olefin type multipolymer long-chain olefin class monomer all added copolymerization system and carry out copolymerization (just only using solvent during swelling low cross-linking vinylbenzene-long-chain olefin type multipolymer), although the monomeric polymerizing power of long-chain olefin class is poor, but the long-chain olefin class monomer that major part is still arranged in the process of copolymerization enters in the three-dimensional network body main chain, and residual not polymerization long-chain olefin class monomer is linked on the benzene lateral group of low cross-linking styrene type copolymer molecule by follow-up alkylated reaction at last again during copolymerization, the structure of the final like this vinylbenzene that obtains-long-chain olefin type high oil absorbing resin is better and gel content is high, thereby the oil absorbency height.If the quality consumption of long-chain olefin class monomer in vinylbenzene-long-chain olefin type high oil absorbing resin divides rate when very high (as greater than 75%), when copolymerization low cross-linking vinylbenzene-long-chain olefin type multipolymer, long-chain olefin class monomer all can not be added copolymerization system and carry out copolymerization, because like this, can't obtain low cross-linking vinylbenzene-long-chain olefin type copolymer pellet during copolymerization.At this moment, can add copolymerization system to most long-chain olefin class monomer when the copolymerization low cross-linking vinylbenzene-long-chain olefin type multipolymer and carry out copolymerization, and the long-chain olefin class monomer of small portion restock swelling when swelling low cross-linking vinylbenzene-long-chain olefin type multipolymer enters low cross-linking vinylbenzene-long-chain olefin type multipolymer, alkylation process essence is that not polymerization long-chain olefin class monomer residual during with preparation low cross-linking vinylbenzene-long-chain olefin type multipolymer and back replenish the long-chain olefin class monomer that swelling enters low cross-linking vinylbenzene-long-chain olefin type multipolymer and be linked in the lump on the benzene lateral group of low cross-linking vinylbenzene-long-chain olefin type copolymer molecule, although long-chain olefin class monomer divides rate very high at the quality consumption of vinylbenzene-long-chain olefin type high oil absorbing resin like this, but still have high gel content by the vinylbenzene-long-chain olefin type high oil absorbing resin that makes behind the alkylated reaction, and correspondingly have a good oil absorption.
Need to prove: for the vinylbenzene-long-chain olefin type high oil absorbing resin that makes preparation has good oil absorption, the present invention mentions, in the low cross-linking polystyrene in the monomeric total moles of swollen long-chain olefin class and the low cross-linking polystyrene ratio of the unitary total moles of vinylbenzene chain link that all molecules contained with 0.5～1.5: 1 for good; Perhaps in not using the monomeric low cross-linking styrene type of long-chain olefin class multipolymer in the monomeric total moles of swollen long-chain olefin class and the low cross-linking styrene type multipolymer ratio of the unitary total moles of vinylbenzene chain link that all molecules contained with 0.5～1.5: 1 for good; Perhaps in low cross-linking vinylbenzene-long-chain olefin type multipolymer in the monomeric total moles of swollen long-chain olefin class (when comprising the long-chain olefin class monomer that enters by swelling in low cross-linking vinylbenzene-long-chain olefin type multipolymer and preparation low cross-linking vinylbenzene-long-chain olefin type multipolymer residual not polymerization long-chain olefin class monomer) and the low cross-linking vinylbenzene-long-chain olefin type multipolymer ratio of the unitary total moles of vinylbenzene chain link that all molecules contained to be lower than 2.0: 1 for good.Even but when exceeding this scope; adopt the vinylbenzene-long-chain olefin type high oil absorbing resin of technical solution of the present invention preparation; although its oil absorption is poorer than the vinylbenzene-long-chain olefin type high oil absorbing resin in mentioning scope; but same have higher relatively gel content, relative better oil absorption and cost performance relatively preferably than the vinylbenzene-long-chain olefin type high oil absorbing resin that adopts prior art for preparing; have practical value equally, therefore also belong to protection domain of the present invention.
Embodiment 1
In the reactor that agitator, reflux exchanger, thermometer and feeder are housed, add concentration and be 1% calcium phosphate powder dispersant solution 15mL, concentration and be 1% polyvinyl alcohol solution 10mL and water 75mL, disperse 15min in stirring at room, add the oil-phase solution that mixes by 0.75g dibenzoyl peroxide, 0.75g Vinylstyrene and 50g vinylbenzene then while stirring, logical nitrogen deoxygenation, be warming up to 80 ℃ of reaction 8h behind the dispersed with stirring 15min, be warming up to 95 ℃ of slaking 6h then.After question response finished, with the product cooled and filtered, and with hot wash repeatedly, the product oven dry with obtaining got low cross-linking polystyrene resin particle.
In the reactor that agitator, reflux exchanger, thermometer and feeder are housed, add anhydrous tetracol phenixin of 200mL purified and 5.0g aluminum trichloride (anhydrous), after 30 ℃ of stirring and dissolving, add the anhydrous α of 60g-dodecylene stirring and evenly mixing, add prepared dry low cross-linking polystyrene resin particle again.Treat low cross-linking polystyrene resin particle under 30 ℃ by swelling after, be warming up to 75 ℃ of alkylated reaction 3h, in reactor, add 200mL water then, stir 0.5h, suction filtration adds the resin particle that leaches thermal distillation at last and removes tetracol phenixin and dry then, promptly obtains high oil absorbing resin.
Embodiment 2
In the reactor that agitator, reflux exchanger, thermometer and feeder are housed, add concentration and be 1% calcium phosphate powder dispersant solution 15mL, concentration and be 1% polyvinyl alcohol solution 10mL and water 75mL, disperse 15min in stirring at room, add the oil-phase solution that mixes by 0.75g dibenzoyl peroxide, 0.75g Vinylstyrene, 30g vinylbenzene and 20g α-dodecylene then while stirring, logical nitrogen deoxygenation, be warming up to 80 ℃ of reaction 8h behind the dispersed with stirring 15min, be warming up to 95 ℃ of slaking 6h then.After question response finished, with the product cooled and filtered, and with hot wash repeatedly, the product oven dry with obtaining got low cross-linking styrene type copolymer resin particle.
In the reactor that agitator, reflux exchanger, thermometer and feeder are housed, add anhydrous tetracol phenixin of 200mL purified and 5.0g aluminum trichloride (anhydrous), after 40 ℃ of stirring and dissolving, add prepared dry low cross-linking styrene type copolymer resin particle and carry out swelling.Treat low cross-linking styrene type copolymer resin particle under 40 ℃ by swelling after, be warming up to 75 ℃ of alkylated reactions 3 hours, in reactor, add 200mL water then, stir 0.5h, suction filtration then, at last the resin particle that leaches is added thermal distillation and remove tetracol phenixin and dry, promptly obtain high oil absorbing resin.
Embodiment 3
In the reactor that agitator, reflux exchanger, thermometer and feeder are housed, add concentration and be 1% calcium phosphate powder dispersant solution 15mL, concentration and be 1% polyvinyl alcohol solution 10mL and water 75mL, disperse 15min in stirring at room, add the oil-phase solution that mixes by 0.75g dibenzoyl peroxide, 0.75g Vinylstyrene, 35g vinylbenzene and 15g α-dodecylene then while stirring, logical nitrogen deoxygenation, be warming up to 80 ℃ of reaction 8h behind the dispersed with stirring 15min, be warming up to 95 ℃ of slaking 6h then.After question response finished, with the product cooled and filtered, and with hot wash repeatedly, the product oven dry with obtaining got low cross-linking styrene type copolymer resin particle.
In the reactor that agitator, reflux exchanger, thermometer and feeder are housed, add anhydrous tetracol phenixin of 200mL purified and 5.0g aluminum trichloride (anhydrous), after 40 ℃ of stirring and dissolving, add the anhydrous α-dodecylene of 40g, stirring and evenly mixing, and then add prepared dry low cross-linking styrene type copolymer resin particle.Treat low cross-linking styrene type copolymer resin particle under 40 ℃ by swelling after, be warming up to 75 ℃ of alkylated reactions 3 hours, in reactor, add 200mL water then, stir 0.5h, suction filtration then, at last the resin particle that leaches is added thermal distillation and remove tetracol phenixin and dry, promptly obtain high oil absorbing resin.
Embodiment 4
In the reactor that agitator, reflux exchanger, thermometer and feeder are housed, add concentration and be 1% calcium phosphate powder dispersant solution 15mL, concentration and be 1% polyvinyl alcohol solution 10mL and water 75mL, disperse 15min in stirring at room, add the oil-phase solution that mixes by 0.75g dibenzoyl peroxide, 0.75g Vinylstyrene, 35g vinylbenzene and 15g α-dodecylene then while stirring, logical nitrogen deoxygenation, be warming up to 80 ℃ of reaction 8h after stirring 15min, be warming up to 95 ℃ of slaking 6h then.After question response finished, with the product cooled and filtered, and with hot wash repeatedly, the product oven dry with obtaining got low cross-linking styrene type copolymer resin particle.
In the reactor that agitator, reflux exchanger, thermometer and feeder are housed, add the anhydrous oil of mirbane of 200mL, 5.0g aluminum trichloride (anhydrous), after 40 ℃ of following stirring and dissolving, add the anhydrous α-C of 40g
16～18Alkene, stirring and evenly mixing, and then add prepared dry low cross-linking styrene type copolymer resin particle.Be warming up to 75 ℃, limit swelling low cross-linking styrene type copolymer resin particulate limit alkylated reaction 4 hours simultaneously under agitation, water and ethanol agitator treating resin particle repeatedly washes out aluminum trichloride (anhydrous) and oil of mirbane then, with the resin particle drying, promptly obtain high oil absorbing resin at last.
Embodiment 5
In the reactor that agitator, reflux exchanger, thermometer and feeder are housed, add concentration and be 1% calcium phosphate powder dispersant solution 15mL, concentration and be 1% polyvinyl alcohol solution 10mL and water 75mL, disperse 15min in stirring at room, add the oil-phase solution that mixes by 0.75g dibenzoyl peroxide, 0.75g Vinylstyrene and 50g vinylbenzene then while stirring, logical nitrogen deoxygenation, be warming up to 80 ℃ of reaction 8h behind the dispersed with stirring 15min, be warming up to 95 ℃ of slaking 6h then.After question response finished, with the product cooled and filtered, and with hot wash repeatedly, the product oven dry with obtaining obtained low cross-linking polystyrene resin particle.
Agitator is equipped with in the dry low cross-linking polystyrene resin particle and the anhydrous α of the 60g-dodecylene adding that make, reflux exchanger, in the reactor of thermometer and feeder, 75 ℃ are stirred swelling down, after treating that low cross-linking polystyrene resin particle is by swelling, add refining dry oil ether (60～90 ℃ of boiling points) the solution 200mL that contains the 10.0g aluminum trichloride (anhydrous), temperature control is at 75 ℃ of alkylated reaction 4h while stirring, in reactor, add 200mL water then, stir 0.5h, suction filtration then, at last the resin particle that leaches is added thermal distillation and remove sherwood oil and dry, promptly obtain high oil absorbing resin.
Embodiment 6
In the reactor that agitator, reflux exchanger, thermometer and feeder are housed, add concentration and be 1% calcium phosphate powder dispersant solution 15mL, concentration and be 1% polyvinyl alcohol solution 10mL and water 75mL, disperse 15min in stirring at room, add the oil-phase solution that mixes by 0.75g dibenzoyl peroxide, 0.75g Vinylstyrene, 15g vinylbenzene, 10g α-dodecylene and 25g α-octene then while stirring, logical nitrogen deoxygenation, be warming up to 80 ℃ of reaction 8h behind the dispersed with stirring 15min, be warming up to 95 ℃ of slaking 6h then.After question response finished, with the product cooled and filtered, and with hot wash repeatedly, the product oven dry with obtaining got low cross-linking styrene type copolymer resin particle.
In the reactor that agitator, reflux exchanger, thermometer and feeder are housed, add anhydrous tetracol phenixin of 200mL purified and 5.0g aluminum trichloride (anhydrous), after 40 ℃ of stirring and dissolving, add prepared dry low cross-linking styrene type copolymer resin particle 50 ℃ of following swellings.After treating that low cross-linking styrene type copolymer resin particle is by swelling, be warming up to 75 ℃ of alkylated reactions 3 hours, in reactor, add 200mL water then, stir 0.5h, suction filtration adds the resin particle that leaches thermal distillation at last and removes tetracol phenixin and dry then, promptly obtains high oil absorbing resin.
Embodiment 7-9
Solvent that uses when preparation process, initiator and suspension system and their consumption, alkylation catalyst and consumption thereof, swelling and consumption thereof are all identical with embodiment 1.Difference from Example 1 is: cinnamic quality consumption was 50g when polymerization prepared low cross-linking polystyrene resin particle among the embodiment 7, and the quality consumption of Vinylstyrene is 0.75g, had also used α-C during swelling except that using solvent
16～18Alkene, quality consumption are 60g; Cinnamic quality consumption was 50g when polymerization prepared low cross-linking polystyrene resin particle among the embodiment 8, and the quality consumption of Vinylstyrene is 0.75g, had also used α-octene during swelling except that using solvent, and the quality consumption is 60g; Cinnamic quality consumption was 50g when polymerization prepared low cross-linking polystyrene resin particle among the embodiment 9, and the quality consumption of Vinylstyrene is 1.8g, had also used α-dodecylene during swelling except that using solvent, and the quality consumption is 60g.
Embodiment 10-14
Solvent that uses when preparation process, initiator and suspension system and their consumption, alkylation catalyst and consumption thereof, swelling and consumption thereof are all identical with embodiment 2, do not use monomer during swelling.Difference from Example 2 is:
Cinnamic quality consumption was 25g when polymerization prepared low cross-linking styrene type copolymer resin particle among the embodiment 10, and the quality consumption of α-dodecylene is 25g, and the quality consumption of Vinylstyrene is 1.2g; Cinnamic quality consumption was 25g when polymerization prepared low cross-linking styrene type copolymer resin particle among the embodiment 11, and the quality consumption of α-dodecylene is 25g, and the quality consumption of Vinylstyrene is 0.5g; Cinnamic quality consumption was 40g when polymerization prepared low cross-linking styrene type copolymer resin particle among the embodiment 12, and the quality consumption of α-dodecylene is 10g, and the quality consumption of Vinylstyrene is 0.75g; Cinnamic quality consumption was 30g when polymerization prepared low cross-linking styrene type copolymer resin particle among the embodiment 13, α-C
16～18The quality consumption of alkene is 20g, and the quality consumption of Vinylstyrene is 0.75g; Cinnamic quality consumption was 20g when polymerization prepared low cross-linking styrene type copolymer resin particle among the embodiment 14, and the quality consumption of dodecylene is 15g, and the quality consumption of tetradecyl acrylate is 15g, and the quality consumption of Vinylstyrene is 0.75g.
Embodiment 15-17
Solvent that uses when preparation process, initiator and suspension system and their consumption, alkylation catalyst and consumption thereof, swelling and consumption thereof are all identical with embodiment 3.Difference from Example 3 is: cinnamic quality consumption was 30g when polymerization prepared low cross-linking styrene type copolymer resin particle among the embodiment 15, α-C
16～18The quality consumption of alkene is 20g, and the quality consumption of Vinylstyrene is 0.75g, has also used α-dodecylene and α-octene during swelling except that using solvent, and their quality consumption is respectively 10g and 25g.Cinnamic quality consumption was 20g when polymerization prepared low cross-linking styrene type copolymer resin particle among the embodiment 16, the quality consumption of α-dodecylene is 5g, the quality consumption of tetradecyl acrylate is 25g, the quality consumption of Vinylstyrene is 0.75g, also used α-dodecylene and vinyl acetate during swelling except that using solvent, their quality consumption is respectively 20g and 10g.Cinnamic quality consumption was 20g when polymerization prepared low cross-linking styrene type copolymer resin particle among the embodiment 17, the quality consumption of tetradecyl acrylate is 30g, the quality consumption of Vinylstyrene is 0.75g, has also used α-dodecylene during swelling except that using solvent, and the quality consumption is 30g.
Comparative example 1
In the reactor that agitator, reflux exchanger, thermometer and feeder are housed, add concentration and be 1% calcium phosphate powder dispersant solution 15mL, concentration and be 1% polyvinyl alcohol solution 10mL and water 75mL, disperse 15min in stirring at room, add the oil-phase solution that mixes by 0.75g dibenzoyl peroxide, 0.75g Vinylstyrene, 30g vinylbenzene and 20g α-dodecylene then while stirring, logical nitrogen deoxygenation, be warming up to 80 ℃ of reaction 8h after stirring 15min, be warming up to 95 ℃ of slaking 6h then.After question response finished, with the product cooled and filtered, and with hot wash repeatedly, the product oven dry with obtaining was high oil absorbing resin.
Comparative example 2-6
Preparation process, initiator and suspension system and their consumption thereof are identical with comparative example 1.With comparative example 1 difference be: the quality consumption of monomer styrene, α-dodecylene and the Vinylstyrene of preparation high oil absorbing resin is respectively 40g, 10g and 0.75g in the comparative example 2; The quality consumption of monomer styrene, α-dodecylene and the Vinylstyrene of preparation high oil absorbing resin is respectively 20g, 30g and 0.5g in the comparative example 3; The monomer of preparation high oil absorbing resin is vinylbenzene, α-C in the comparative example 4
16～18Alkene and Vinylstyrene, their quality consumption is respectively 30g, 20g and 0.75g; The monomer of preparation high oil absorbing resin is vinylbenzene, α-octene and Vinylstyrene in the comparative example 5, and their quality consumption is respectively 30g, 20g and 0.75g; The monomer of preparation high oil absorbing resin is vinylbenzene, α-dodecylene, tetradecyl acrylate and Vinylstyrene in the comparative example 6, and their quality consumption is respectively 20g, 15g, 15g and 0.75g.
The resins prescription and the performance of each embodiment and comparative example see Table.
The resins prescription and the performance table of table embodiment and comparative example
| The resins prescription | Resin property | ||||||
| Vinylbenzene quality consumption (gram) during polymerization | Comonomer kind of using during polymerization and quality consumption (gram) thereof | Vinylstyrene quality consumption (gram) during polymerization | Monomeric species that uses during swelling and quality consumption (gram) thereof | The gel content of resin (%) | Resin is to the oil absorbency (doubly) of toluene | Resin is to the oil absorbency (doubly) of chloroform | |
| Embodiment 1 | 50 | 0 | 0.75 | 60 ① | 73.5 | 9.8 | 16.2 |
| Embodiment 2 | 30 | 20 ① | 0.75 | 0 | 87.2 | 11.8 | 27.8 |
| Embodiment 3 | 35 | 15 ① | 0.75 | 40 ① | 83.3 | 14.2 | 30.8 |
| Embodiment 4 | 35 | 15 ① | 0.75 | 40 ② | 80.2 | 16.5 | 36.7 |
| Embodiment 5 | 50 | 0 | 0.75 | 60 ① | 72.5 | 9.2 | 15.6 |
| Embodiment 6 | 15 | 10 ①+25 ③ | 0.75 | 0 | 86.4 | 10.5 | 21.6 |
| Embodiment 7 | 50 | 0 | 0.75 | 60 ② | 69.6 | 11.2 | 19.5 |
| Embodiment 8 | 50 | 0 | 0.75 | 60 ③ | 78.6 | 8.6 | 13.6 |
| Embodiment 9 | 50 | 0 | 1.8 | 60 ① | 85.6 | 6.8 | 10.1 |
| Embodiment 10 | 25 | 25 ① | 1.2 | 0 | 90.5 | 9.5 | 20.6 |
| Embodiment 11 | 25 | 25 ① | 0.5 | 0 | 77.6 | 10.1 | 23.2 |
| Embodiment 12 | 40 | 10 ① | 0.75 | 0 | 90.2 | 8.5 | 20.9 |
| Embodiment 13 | 30 | 20 ② | 0.75 | 0 | 83.2 | 13.2 | 31.2 |
| Embodiment 14 | 20 | 15 ①+15 ④ | 0.75 | 89.2 | 10.2 | 20.3 | |
| Embodiment 15 | 30 | 20 ② | 0.75 | 10 ①+25 ③ | 81.2 | 16.2 | 36.1 |
| Embodiment 16 | 20 | 5 ①+25 ④ | 0.75 | 20 ①+10 ⑤ | 76.2 | 12.2 | 25.3 |
| Embodiment 17 | 20 | 30 ④ | 0.75 | 30 ① | 79.3 | 13.6 | 29.1 |
| Comparative example 1 | 30 | 20 ① | 0.75 | 46.8 | 4.6 | 12.8 | |
| Comparative example 2 | 40 | 10 ① | 0.75 | 70.2 | 6.0 | 14.6 | |
| Comparative example 3 | 20 | 30 ① | 0.5 | 32.5 | 3.4 | 9.6 | |
| Comparative example 4 | 30 | 20 ② | 0.75 | 41.5 | 5.6 | 14.8 | |
| Comparative example 5 | 30 | 20 ③ | 0.75 | 58.6 | 4.6 | 12.2 | |
| Comparative example 6 | 20 | 15 ①+15 ④ | 0.75 | 60.2 | 6.1 | 14.1 | |
Annotate:
1.Be α-dodecylene;
2.Be α-C
16～18Alkene;
3.Be α-octene;
4.Be tetradecyl acrylate;
5.Be vinyl acetate.
Claims (15)
1. the preparation method of a high oil absorbing resin is characterized in that may further comprise the steps:
(1) adopting vinylbenzene and linking agent is that raw material monomer prepares the low cross-linking polystyrene;
(2) adopt long-chain olefin class monomer or solvent and the monomeric mixture swelling of long-chain olefin class low cross-linking polystyrene, and carry out alkylated reaction, long-chain olefin class monomer is linked on the benzene lateral group of low cross-linking polystyrene molecule by alkylated reaction, makes vinylbenzene-long-chain olefin type high oil absorbing resin.
2. the preparation method of a high oil absorbing resin is characterized in that may further comprise the steps:
(1) mixture of one or more in employing alkyl-acrylates monomer, vinyl ester monomer, vinyl ethers monomer and the vinyl monomer except that vinylbenzene, long-chain olefin class monomer and vinylchlorid is with vinylbenzene and linking agent copolymerization low cross-linking styrene type multipolymer;
(2) adopt long-chain olefin class monomer, perhaps solvent and the monomeric mixture swelling of long-chain olefin class low cross-linking styrene type multipolymer, and carry out alkylated reaction, long-chain olefin class monomer is linked on the benzene lateral group of low cross-linking styrene type copolymer molecule by alkylated reaction, makes vinylbenzene-long-chain olefin type high oil absorbing resin.
3. the preparation method of a high oil absorbing resin is characterized in that may further comprise the steps:
(1) adopting vinylbenzene, long-chain olefin class monomer and linking agent is that raw material monomer prepares low cross-linking styrene type multipolymer; Perhaps adopt one or more the mixture in alkyl-acrylates monomer, vinyl ester monomer, vinyl ethers monomer and the vinyl monomer except that vinylbenzene, long-chain olefin class monomer and vinylchlorid, with vinylbenzene, long-chain olefin class monomer and linking agent copolymerization low cross-linking styrene type multipolymer;
(2) adopt solvent, perhaps long-chain olefin class monomer, perhaps solvent and the monomeric mixture swelling of long-chain olefin class low cross-linking styrene type multipolymer, and carry out alkylated reaction, long-chain olefin class monomer is linked on the benzene lateral group of low cross-linking styrene type copolymer molecule by alkylated reaction, makes vinylbenzene-long-chain olefin type high oil absorbing resin.
4. according to the preparation method of claim 1,2 or 3 described high oil absorbing resins, it is characterized in that: the process of swelling low cross-linking polystyrene or low cross-linking styrene type multipolymer with carry out alkylated reaction, long-chain olefin class monomer is linked into the process proceed step by step on the benzene lateral group of low cross-linking polystyrene or low cross-linking styrene type copolymer molecule by alkylated reaction, promptly first swelling is carried out alkylated reaction then.
5. according to the preparation method of claim 1,2 or 3 described high oil absorbing resins, it is characterized in that: the process of swelling low cross-linking polystyrene or low cross-linking styrene type multipolymer with carry out alkylated reaction, the process that long-chain olefin class monomer is linked into by alkylated reaction on the benzene lateral group of low cross-linking polystyrene or low cross-linking styrene type copolymer molecule is carried out synchronously.
6. according to the preparation method of claim 1,2 or 3 described high oil absorbing resins, it is characterized in that: adopt suspension polymerization when preparation low cross-linking polystyrene or low cross-linking styrene type multipolymer, in described suspension polymerization, adopt general suspension dispersive agent and general suspension polymerization radical initiator.
7. according to the preparation method of claim 1,2 or 3 described high oil absorbing resins, it is characterized in that: when preparation low cross-linking polystyrene and low cross-linking styrene type multipolymer, adopt diene hydro carbons monomer as linking agent, the mole dosage of linking agent is 0.5%～3.5%.
8. according to the preparation method of claim 1,2 or 3 described high oil absorbing resins, it is characterized in that: the dispersion medium that adopts when solvent that adopts during swelling and alkylated reaction is alkylation solvent or rudimentary saturated fatty hydrocarbon solvent.
9. the preparation method of high oil absorbing resin according to claim 1 is characterized in that: in the low cross-linking polystyrene in the monomeric total moles of swollen long-chain olefin class and the low cross-linking polystyrene ratio of the unitary total moles of vinylbenzene chain link that all molecules contained be 0.5～1.5: 1.
10. the preparation method of high oil absorbing resin according to claim 2 is characterized in that: in the low cross-linking styrene type multipolymer in the monomeric total moles of swollen long-chain olefin class and the low cross-linking styrene type multipolymer ratio of the unitary total moles of vinylbenzene chain link that all molecules contained be 0.5～1.5: 1.
11. the preparation method of high oil absorbing resin according to claim 3 is characterized in that: during preparation low cross-linking styrene type multipolymer, it is 0.001%～75% that long-chain olefin class monomer accounts for all monomeric mass fractions.
12. the preparation method of high oil absorbing resin according to claim 3 is characterized in that: the long-chain olefin class monomer that adopts during swelling low cross-linking styrene type multipolymer is identical or different with the long-chain olefin class monomer that adopts when preparing low cross-linking styrene type multipolymer.
13. the preparation method of high oil absorbing resin according to claim 3 is characterized in that: the ratio that enters the unitary total moles of vinylbenzene chain link that all molecules contained in the monomeric total moles of long-chain olefin class and the low cross-linking styrene type multipolymer in the low cross-linking styrene type multipolymer by swelling process is 0～1.5: 1.
14. the preparation method according to claim 1,2 or 3 described high oil absorbing resins is characterized in that: summation shared branch rate in employed all monomeric total masses of the quality of employed whole vinylbenzene and long-chain olefin class monomer is 50%～100% in preparation vinylbenzene-long-chain olefin type high oil absorbing resin process.
15. the preparation method according to each described high oil absorbing resin in the claim 1,2,3,9,10,11,12,13 is characterized in that: long-chain olefin class monomer is that molecular formula is C
nH
2nThe one-component monoolefine, n 〉=4; Or molecular formula is C
nH
2nBut the mixture of the polycomponent monoolefine that n is different; Or to contain molecular formula be C
nH
2nThe polycomponent monoolefine monomer mixture of monoolefine; Or to contain molecular formula be C
nH
2nBut the monoolefine monomer mixture of the polycomponent monoolefine mixture that n is different.
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| CN101235118B (en) * | 2007-11-30 | 2010-10-06 | 华南理工大学 | Method for preparing oil smoke absorbing material by microwave |
| CN101914180A (en) * | 2010-07-13 | 2010-12-15 | 中国人民解放军空军油料研究所 | Preparation method of high oil-absorption resin |
| CN102875717A (en) * | 2011-08-26 | 2013-01-16 | 中化化工科学技术研究总院 | Synthetic resin, and preparation method and application thereof |
| CN104693380A (en) * | 2014-07-03 | 2015-06-10 | 中国科学院西北高原生物研究所 | High oil absorption resin and preparation method thereof |
| CN108948312A (en) * | 2018-08-06 | 2018-12-07 | 山东非金属材料研究所 | A kind of cinnamic acrylic ester oil suction swelling elastomer |
Family Cites Families (3)
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| JPS5094092A (en) * | 1973-12-25 | 1975-07-26 | ||
| AU9133401A (en) * | 2000-11-28 | 2002-05-30 | Rohm And Haas Company | Hydrophobic absorbing polymers and process |
| CN1164630C (en) * | 2001-06-28 | 2004-09-01 | 复旦大学 | Method of preparing high oil-absorbing resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235118B (en) * | 2007-11-30 | 2010-10-06 | 华南理工大学 | Method for preparing oil smoke absorbing material by microwave |
| CN101914180A (en) * | 2010-07-13 | 2010-12-15 | 中国人民解放军空军油料研究所 | Preparation method of high oil-absorption resin |
| CN101914180B (en) * | 2010-07-13 | 2012-06-13 | 中国人民解放军空军油料研究所 | Preparation method of high oil-absorption resin |
| CN102875717A (en) * | 2011-08-26 | 2013-01-16 | 中化化工科学技术研究总院 | Synthetic resin, and preparation method and application thereof |
| CN104693380A (en) * | 2014-07-03 | 2015-06-10 | 中国科学院西北高原生物研究所 | High oil absorption resin and preparation method thereof |
| CN104693380B (en) * | 2014-07-03 | 2018-02-27 | 中国科学院西北高原生物研究所 | A kind of high oil-absorbing resin and preparation method thereof |
| CN108948312A (en) * | 2018-08-06 | 2018-12-07 | 山东非金属材料研究所 | A kind of cinnamic acrylic ester oil suction swelling elastomer |
| CN108948312B (en) * | 2018-08-06 | 2021-06-04 | 山东非金属材料研究所 | Styrene-acrylate oil-absorbing swelling elastomer |
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| CN1320013C (en) | 2007-06-06 |
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