CN105175393B - A kind of compound, preparation method, a kind of oil-absorbing resin and its synthetic method - Google Patents
A kind of compound, preparation method, a kind of oil-absorbing resin and its synthetic method Download PDFInfo
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- CN105175393B CN105175393B CN201510483238.9A CN201510483238A CN105175393B CN 105175393 B CN105175393 B CN 105175393B CN 201510483238 A CN201510483238 A CN 201510483238A CN 105175393 B CN105175393 B CN 105175393B
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- 229920005989 resin Polymers 0.000 title claims abstract description 52
- 239000011347 resin Substances 0.000 title claims abstract description 52
- 150000001875 compounds Chemical class 0.000 title claims abstract description 32
- 238000010189 synthetic method Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- -1 alkyl chain methacrylates Chemical class 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 11
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 3
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 3
- 229940068984 polyvinyl alcohol Drugs 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 22
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 abstract description 6
- QHEMLDKHONPLFI-UHFFFAOYSA-N 9-(2-ethylhexyl)-3-nitrocarbazole Chemical compound C(C)C(CN1C2=CC=CC=C2C=2C=C(C=CC12)[N+](=O)[O-])CCCC QHEMLDKHONPLFI-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 239000003921 oil Substances 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 14
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 229960001866 silicon dioxide Drugs 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- SAXNQWFLHXTRDI-UHFFFAOYSA-N 9-(2-ethylhexyl)carbazole Chemical compound C1=CC=C2N(CC(CC)CCCC)C3=CC=CC=C3C2=C1 SAXNQWFLHXTRDI-UHFFFAOYSA-N 0.000 description 3
- QMJXKSGNSFFGSD-UHFFFAOYSA-N C(C)C(CC=1C=C2C=3C=CC=CC=3NC2=CC=1)CCCC Chemical compound C(C)C(CC=1C=C2C=3C=CC=CC=3NC2=CC=1)CCCC QMJXKSGNSFFGSD-UHFFFAOYSA-N 0.000 description 3
- FMVJKXLKNMXVCA-UHFFFAOYSA-N CCCCC(CC)CC1=CC2=C(C=C1)NC3=C2C=C(C=C3)[N+](=O)[O-] Chemical compound CCCCC(CC)CC1=CC2=C(C=C1)NC3=C2C=C(C=C3)[N+](=O)[O-] FMVJKXLKNMXVCA-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ZZPNDIHOQDQVNU-UHFFFAOYSA-N 2-hydroxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC1(C)OB(O)OC1(C)C ZZPNDIHOQDQVNU-UHFFFAOYSA-N 0.000 description 2
- SUTWPJHCRAITLU-UHFFFAOYSA-N 6-aminohexan-1-ol Chemical compound NCCCCCCO SUTWPJHCRAITLU-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000005417 food ingredient Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000013324 preserved food Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011175 product filtration Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F120/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention provides a kind of compounds with formula (I) structure, present invention also provides the preparation methods of the compound, it include: by 6- (9- (2- ethylhexyl) -6- nitro -9H- carbazole -3- alcohol radical) -2- (6- hydroxyethyl) -1H- benzisoquinoline -1,3 (2H)-diketone are reacted with methacrylic chloride, obtain the compound with formula (I) structure.Present invention also provides a kind of synthetic methods of oil-absorbing resin, comprising: reacts described or prepared compound, acrylate, initiator with crosslinking agent, obtains oil-absorbing resin.Since the side chain of compound provided by the present application is the monomer with rigid conjugated backbone, its oil-absorbing resin for being used to synthesize is acted on due to the strength support of rigid backbone, make that change in shape does not occur before and after the oil-absorbing resin oil suction of synthesis, to maintain the stability of intensity, reusing is higher.
Description
Technical field
The present invention relates to oil-absorbing resin technical field more particularly to a kind of compound, preparation method, a kind of oil-absorbing resins
And its synthetic method.
Background technique
Resin type adsorbent material can based on oil pollutant type design, synthesis have with oil pollutant it is preferable affine
Property polymer architecture, therefore its structure design on have flexibility, while the absorption principle of polymeric resin type adsorbent with
Activated carbon adsorption makes a big difference, therefore improves a lot in its adsorption capacity.Moreover, resin type adsorbent material is using
It can easily be regenerated later, realize the recycling of adsorbent material and the recycling of organic matter, therefore in oil-containing
Waste water dis posal field has broad application prospects.Research and development has absorption speed to the oiliness pollutant such as crude oil, product oil
The novel tree epoxy-type adsorbent material for the advantages that degree is fast, adsorbance is high, Oil keeping is good, adsorptive selectivity is good, high mechanical strength is especially
It is important.
However, resin type oil absorption material still cannot be widely used at present, the main reason is that mechanical strength of resin is low, it is existing
The monomer of Choice of Resin is all some monomers containing flexible chain, therefore main chain in resin and side chain are all made of flexible chain
's；After flexible chain and adsorbed fry dried food ingredients give birth to sufficient solvation after resin adsorption saturation, strand is fully extended, this
When resin at gel or at flowing shape colloid, as the candle of thawing, make post-processing become difficult, reduce resin
Practicability, the requirement of resin tolerance adsorption-desorption process repeatedly when being unable to satisfy oily waste water disposition at all, let alone and
Equipment is resistant to powerful mechanical force when being used in combination.Although some researchers have reported that adding a certain amount of filler in resin
Its structure is supported to keep the resin shape after oil suction, but it is using sacrificial resin oil absorbing effect as cost.Therefore it studies and opens
Still it is able to maintain the resin of higher-strength after hair oil suction, is to make the widely used key of oil-absorbing resin.
Summary of the invention
Present invention solves the technical problem that being to provide a kind of synthetic method of oil-absorbing resin, the oil suction tree of the application synthesis
It can intensity with higher after rouge oil suction.
In view of this, this application provides a kind of compounds with formula (I) structure:
Wherein, n is 2~15.
Preferably, the n is 5~10.
Present invention also provides the preparation methods of the compound described in above scheme, comprising:
By 4- (9- (2- ethylhexyl) -6- nitro -9H- carbazole) -2- (6- hydroxyethyl) -1H- benzisoquinoline -1,3
(2H)-diketone is reacted with methacrylic chloride, obtains the compound with formula (I) structure；
Wherein, n is 2~15.
Present invention also provides a kind of synthetic methods of oil-absorbing resin, comprising the following steps:
It will be described in above scheme or compound prepared by above scheme, acrylate, initiator and crosslinking agent carry out
Reaction, obtains oil-absorbing resin.
Preferably, the initiator is azo-bis-isobutyl cyanide, and the additive amount of the initiator is the compound
0.1wt%~0.3wt%.
Preferably, the crosslinking agent is divinylbenzene, and the additive amount of the crosslinking agent is less than or equal to the compound
1wt%.
Preferably, it is described reaction carried out in water and dispersing agent, the dispersing agent be polyvinyl alcohol, polyethylene glycol 200 or
Polyethylene glycol 400, the additive amount of the dispersing agent are 0.3wt%~1.0wt% of the compound.
Preferably, the mass ratio of the acrylate and the compound is (5~10): 1.
Preferably, the acrylate is long alkyl chain methacrylates.
Present invention also provides the oil-absorbing resins prepared by above scheme.
The application has synthesized a kind of compound with formula (I) structure first, is a kind of side chain for rigid conjugated backbone
Monomer.Monomer provided by the present application with conjugated backbone is conjugated rigid backbone after being copolymerized with acrylic ester monomer
Play the role of strength support in polymer architecture, so that shape of the synthesized resin before and after oil suction is not changed, still
It is able to maintain higher intensity.
Detailed description of the invention
Fig. 1 is the absorption multiplying power datagram after oil-absorbing resin provided by the invention regenerates 100 times；
Fig. 2 is that oil-absorbing resin of the present invention inhales the structure chart after toluene.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
The embodiment of the invention discloses a kind of compounds with formula (I) structure:
Wherein, n is 2~15.
This application provides a kind of compounds with rigid conjugated backbone, are used to synthesize oil-absorbing resin, due to monomer
In conjugation rigid backbone have the function of strength support in polymer architecture, therefore the oil-absorbing resin of the application synthesis is being inhaled
Oily front and back shape does not change, to keep the intensity of oil-absorbing resin constant.
N is preferably 5~10 in herein described compound.
Present invention also provides the preparation methods of the compound with formula (I) structure, comprising:
By 4- (9- (2- ethylhexyl)-6- nitro-9H- carbazole)-2- (6- hydroxyhexane base) benzisoquinoline-1-1H-,
3 (2H)-diketone are reacted with methacrylic chloride, obtain the compound with formula (I) structure.
In the above process, 4- (9- (2- ethylhexyl) -6- nitro -9H- carbazole) -2- (6- hydroxyhexane the base) -1H-
Benzisoquinoline -1,3 (2H)-diketone and the methacrylic chloride are happens is that substitution reaction.It is described during reaction
4- (9- (2- ethylhexyl) -6- nitro -9H- carbazole) -2- (6- hydroxyhexane base) -1H- benzisoquinoline -1,3 (2H)-diketone
It is dissolved in tetrahydrofuran and triethylamine first, the methacrylic chloride is dissolved in tetrahydrofuran, is then again carried out the two anti-
It answers, and has obtained the compound with formula (I) structure.4- (9- (2- the ethylhexyl) -6- nitro -9H- carbazole) -2- (6-
Hydroxyhexane base) -1H- benzisoquinoline -1,3 (2H)-diketone preparation method is prepared according to following processes:
Carbazole is reacted with the bromo- 2- ethylhexyl of 1-, obtains 9- (2- ethylhexyl) -9H- carbazole；
9- (2- ethylhexyl) -9H- carbazole is reacted with bromosuccinimide, obtains the bromo- 9- of 3- (2- ethylhexyl) -
9H- carbazole；
The bromo- 9- of 3- (2- ethylhexyl) -9H- carbazole is reacted with fuming nitric aicd, obtains the bromo- 9- of 3- (2- ethylhexyl) -
6- nitro -9H- carbazole；
Bromo- 1, the 8- naphthalene anhydride of 4- is reacted with 6- amino-hexanol, obtains the bromo- 1H- benzo isoquinoline of 2- (6- hydroxyhexane base) -6-
Quinoline -1,3 (2H)-diketone；
By the bromo- 1H- benzisoquinoline -1,3 (2H) of 2- (6- hydroxyhexane base) -6--diketone, connection boric acid pinacol ester and second
Sour potassium reacts under the effect of the catalyst, and obtaining 2- (6- hydroxyhexane base) -6-, (4,4,5,5- tetramethyls -1,3,2- bis- dislike boron
Alkane -2- base) -1H- benzisoquinoline -1,3 (2H)-diketone；
By 2- (6- hydroxyhexane base) -6- (4,4,5,5- tetramethyl -1,3,2- two dislikes borine -2- base) -1H- benzo isoquinoline
Quinoline -1,3 (2H)-diketone and the bromo- 9- of 3- (2- ethylhexyl) -6- nitro -9H- carbazole reaction, obtain 2- (6- hydroxyhexane base) -
6- (9- (2- ethylhexyl) -6- nitro -9H- carbazole) -1H- benzisoquinoline -1,3 (2H)-diketone.
In above-mentioned preparation 2- (6- hydroxyhexane base) -6- (9- (2- ethylhexyl) -6- nitro -9H- carbazole) -1H- benzo
During isoquinolin -1,3 (2H)-diketone, solvent involved in above-mentioned reaction and catalyst is known to those skilled in the art
, the application is without particularly limiting.
Present invention also provides the synthetic methods of oil-absorbing resin, comprising the following steps:
It will be described in above scheme or compound prepared by above scheme, long alkyl chain methacrylates, initiator and friendship
Connection agent is reacted, and oil-absorbing resin is obtained.
During above-mentioned synthesis oil-absorbing resin, the application is by by above-mentioned monomer and acrylic acid with conjugated backbone
Ester carries out copolyreaction, has obtained copolymer oil-absorbing resin.
In above process, the acrylate is copolymerized with monomer, increase the oil suction multiplying power of target product with
Processing performance.Herein described acrylate is preferably long alkyl chain methacrylates, the long alkyl chain methacrylates with it is described
The mass ratio of monomer is preferably (5~10): 1.
The initiator decomposes generate free radicals at high temperature, and the free radical especially generated causes monomer and polymerization occurs instead
It answers, forms oil-absorbing resin.Herein described initiator is preferably azo-bis-isobutyl cyanide, and dosage is the 0.1wt% of the monomer
~0.3wt%.
The crosslinking agent, which can make to form chemical bond after monomer polymerization between the linear polymer chain of formation, connects into sky
Between reticular structure, effect be to make to be formed by the organic matter object that polymer oil-absorbing resin will not be adsorbed in oil-absorbing process
It is dissolved.Herein described crosslinking agent is preferably divinylbenzene, and dosage is less than the 1wt% of the monomer.
The above-mentioned reaction of the application is carried out in water with dispersing agent, and the dispersing agent is preferably polyvinyl alcohol, polyethylene glycol 200
Or polyethylene glycol 400.The dispersing agent can stablize reaction system during the reaction, prevent in reaction process occur agglomeration and
Implode.The additive amount of the dispersing agent is preferably 0.3wt%~1.0wt% of the monomer.
The present invention is directed the status of existing resinae monolithic flexible face, having synthesized a kind of side chain is rigid conjugated backbone
Monomer, be copolymerized with acrylic ester monomer, obtained oil-absorbing resin, since the conjugation rigid backbone in monomer is polymerizeing
Play the role of strength support in object structure, so that oil-absorbing resin is not changed in oil suction front-end geometry, therefore oil-absorbing resin exists
Intensity has not been changed after oil suction.
For a further understanding of the present invention, below with reference to embodiment to compound provided by the invention, preparation method with
The process of synthesis oil-absorbing resin is described in detail, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
The preparation of 9- (2- ethylhexyl) -9H- carbazole: carbazole (4.0g, 23.9mmol), N, N-METHYLFORMAMIDE (DMF,
30mL), potassium hydroxide powder (2.53g, 0.5mol) is added in 200 milliliters of round-bottomed flask, stirs 30min；The bromo- 2- second of 1-
Base hexyl (4.86g, 25.19mmol) is dissolved in 10 milliliters of DMF and instills in above-mentioned mixed solution, stirs 12h at normal temperature；
Reaction solution pours into 400 ml deionized waters, and magnesium sulfate is dry after being extracted with methylene chloride, uses silicagel column after being evaporated methylene chloride
It separates (methylene chloride and petroleum ether 25:1 volume ratio), obtains product 5.16g, 77% yield).1H NMR (400MHz, CDCl3)δ
8.11 (d, J=7.7Hz, 2H), 7.52-7.45 (m, 2H), 7.40 (d, J=7.3Hz, 2H), 7.30~7.20 (m, 2H),
4.23-4.13 (m, 2H), 2.16-2.02 (m, 1H), 1.47-1.22 (m, 8H), 0.92 (t, J=7.5Hz, 3H), 0.87 (t, J
=7.2Hz, 3H).
The preparation of the bromo- 9- of 3- (2- ethylhexyl) -9H- carbazole: product 1 is added in 100 milliliters of round-bottomed flask
(5.16g, 18.47mmol) and 50 milliliters of chloroform maintains the temperature under 0 DEG C and dark condition and is stirred to react 30min, rear to be added
Bromosuccinimide (NBS, 3.29g, 18.47mmol) is simultaneously stirred overnight.After being evaporated chloroform, 150 milliliters of ether dissolutions are added,
And three times with saturated common salt water washing, filtering is evaporated to obtain product 2 (4.88g, 74% yield) after anhydrous magnesium sulfate is dry.
1HNMR (400MHz, CDCl3) δ 8.12 (d, J=1.8Hz, 1H), 7.97 (d, J=7.7Hz, 1H), 7.45 (dd, J=8.7,
1.9Hz, 1H), 7.40 (d, J=8.1Hz, 1H), 7.31 (d, J=8.2Hz, 1H), 7.22-7.13 (m, 3H), 4.06 (dd, J=
7.5,2.6Hz, 2H), 2.03-1.86 (m, 1H), 1.36-1.12 (m, 8H), 0.83 (t, J=7.4Hz, 3H), 0.78 (t, J=
7.1Hz, 3H).
The preparation of the bromo- 9- of 3- (2- ethylhexyl) -6- nitro -9H- carbazole: product 2 (4.88g, 13.6mmol) and 100 millis
It rises glacial acetic acid to be added in 250 milliliters of round-bottomed flasks, 1.6 milliliters of fuming nitric aicds and 30 milliliters of acetic acid volume mixing is then added dropwise
It after solution, reacts three hours, product 3 (4.46g, 81% yield) i.e. is dried after product filtration washing.1HNMR (400MHz,
CDCl3) δ (ppm): 8.96 (s, 1H), 8.39 (d, J=9.1Hz, 1H), 8.26 (s, 1H), 7.63 (d, J=8.7Hz, 1H),
7.36 (dd, J=26.5,8.9Hz, 2H), 4.19 (d, J=7.5Hz, 2H), 2.02 (s, 1H), 1.42-1.16 (m, 8H), 0.88
(dt, J=13.6,7.1Hz, 6H).
The bromo- 1H- benzisoquinoline -1,3 (2H) of 2- (6- hydroxyhexane base) -6--diketone preparation: bromo- 1, the 8- naphthalene anhydride of 4-
(2g, 7mmol), 6- amino-hexanol (1.2g, 10mmol) and 100 milliliters of ethyl alcohol, which are added in round-bottomed flask, to flow back 12 hours for 90 DEG C,
Mixed liquor with ethyl acetate and methylene chloride 1:1 volume ratio solvent crosses silicagel column after being evaporated, and obtaining product 4, (1.95g, 74% produces
Rate).1HNMR (400MHz, CDCl3) δ (ppm): 8.65 (d, J=7.2Hz, 1H), 8.56 (d, J=8.3Hz, 1H), 8.40 (d,
J=7.9Hz, 1H), 8.03 (d, J=7.8Hz, 1H), 7.84 (t, J=7.9Hz, 1H), 4.17 (t, J=7.5Hz, 2H), 3.64
(t, J=6.5Hz, 2H), 1.75-1.72 (m, 2H), 1.58-1.45 (m, 6H).
2- (6- hydroxyhexane base) -6- (4,4,5,5- tetramethyl -1,3,2- two dislikes borine -2- base) -1H- benzo isoquinoline
Quinoline -1,3 (2H)-diketone preparation: product 4 (1.51g, 4mmol), connection boric acid pinacol ester (1.52g, 6mmol), potassium acetate
(1.17g, 11.88mmol) and 50 milliliters of toluene are added in round-bottomed flask, stir 30 minutes under nitrogen atmosphere, catalyst is added
pd(dppf)Cl270 DEG C are warming up to after (0.29g, 0.4mmol) to react 16 hours.It is evaporated after reaction solution is cooled to room temperature with two
The solvent of chloromethanes and ethyl acetate volume ratio 15:1 cross silicagel column, obtain product 5 (1.46g, 86% yield).1H NMR
(400MHz, CDCl3) δ (ppm): 9.11 (d, J=8.4Hz, 1H), 8.59 (d, J=7.1Hz, 1H), 8.55 (d, J=7.1Hz,
1H), 8.29 (d, J=7.2Hz, 1H), 7.77 (t, J=7.8Hz, 1H), 4.18 (t, J=7.3Hz, 2H), 3.64 (t, J=
6.4Hz, 2H), 1.75 (d, J=6.4Hz, 4H), 1.45 (s, 12H), 1.29-1.23 (m, 4H).
2- (6- hydroxyhexane base) -6- (9- (2- ethylhexyl) -6- nitro -9H- carbazole) -1H- benzisoquinoline -1,3
The preparation of (2H)-diketone: after product 5 (1.0g, 2.4mmol) and product 3 (0.81g, 2mmol) are added in round-bottomed flask, first
20mL toluene, 20mL water, 8mL ethyl alcohol and potassium carbonate (0.55g, 4mmol) are added afterwards, stirs 30 minutes, adds under nitrogen atmosphere
Enter catalyst pd (pph3)470 DEG C are warming up to after (93mg, 0.08mmol) to stir 24 hours；It is used after reaction solution is cooled to room temperature
Methylene chloride extract and dried, filtered with anhydrous magnesium sulfate be evaporated after use methylene chloride and ethyl acetate volume ratio 15:1 solvent
Silicagel column is crossed, product 6 (1.04g, 84% yield) is obtained.1HNMR (400MHz, CDCl3) δ (ppm): 9.05 (s, 1H), 8.67
(dd, J=11.6,7.4Hz, 2H), 8.43 (d, J=9.1Hz, 1H), 8.35 (d, J=8.4Hz, 1H), 8.30 (s, 1H), 7.81
(d, J=7.5Hz, 1H), 7.80-7.66 (m, 2H), 7.62 (d, J=8.4Hz, 1H), 7.48 (d, J=9.1Hz, 1H), 4.31
(d, J=7.7Hz, 2H), 4.24 (t, J=7.4Hz, 2H), 3.66 (t, J=6.5Hz, 2H), 2.13 (s, 1H), 1.80 (s,
2H), 1.62 (s, 2H), 1.50-1.23 (m, 12H), 0.98 (t, J=7.3Hz, 3H), 0.88 (t, J=6.9Hz, 3H).
Subject monomers synthesis: product 6 (1.2g, 1.87mmol), 40mL tetrahydrofuran and triethylamine (4.11g,
It 39.27mmol) is added in round-bottomed flask, is cooled to 0 DEG C and stirs 30 minutes, methacrylic chloride (2.15g) and 20mL tetra-
The mixed solution of hydrogen furans is slowly added drop-wise in above-mentioned mixed solution, and is stirred to react 12h at normal temperature, is used after 20mL water is added
Methylene chloride extracts reaction solution, and dried, filtered with anhydrous magnesium sulfate be evaporated after with ethyl acetate and petroleum ether volume ratio 1:5
Solvent crosses silicagel column, obtains final goal monomer 1.4g.1H NMR (400MHz, CDCl3) δ (ppm): 9.05 (s, 1H), 8.68
(dd, J=11.3,7.4Hz, 2H), 8.44 (d, J=9.1Hz, 1H), 8.36 (d, J=8.5Hz, 1H), 8.31 (s, 1H), 7.82
(d, J=7.6Hz, 1H), 7.76-7.67 (m, 2H), 7.63 (d, J=8.5Hz, 1H), 7.48 (d, J=9.0Hz, 1H), 6.10
(s, 1H), 5.54 (s, 1H), 4.32 (d, J=6.6Hz, 2H), 4.24 (t, J=7.5Hz, 2H), 4.15 (t, J=6.4Hz,
2H), 2.13 (s, 1H), 1.95 (d, J=8.7Hz, 3H), 1.81 (s, 2H), 1.72 (s, 2H), 1.50-1.21 (m, 12H),
0.99 (t, J=7.3Hz, 3H), 0.89 (t, J=6.9Hz, 3H).
Embodiment 2
The polyethylene of dispersing agent alcohol of water and 1g is added in reaction flask, is stirred at 40 DEG C cold after making polyvinyl alcohol solvent
But, monomer 10g, the 0.3~1.0g initiator azo two synthesized in long alkyl chain methacrylates 90g and embodiment 1 is added
After the cross-linker divinylbenzene of isobutyl cyanogen and 0.3~1.0g, react under nitrogen protection a few hours, cold filtration, with 60~
Drying obtains 85g oil-absorbing resin after 80 DEG C of water washing.
The experimental results showed that when the content of monomer of the invention in the copolymer is between 8~12%, products obtained therefrom
Oil suction multiplying power highest inhales toluene up to 12~15 times of own wt, and passing through after oil-absorbing resin adsorption saturation can be again after desorbing
Raw, the oil suction multiplying power of resin is still 92% or more of initial adsorption multiplying power after regenerating 100 times, and is inhaled after Reusability 100 times
Resin shape after oil saturation does not still occur to collapse and change, and plays good humidification, said effect institute as shown in Figure 1, Figure 2
Show, Fig. 1 is the absorption multiplying power datagram after oil-absorbing resin provided in this embodiment regenerates 100 times, as shown in Fig. 2, Fig. 2 is this hair
The shape graph of material after bright oil-absorbing resin absorption toluene.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (9)
1. the compound that one kind has formula (I) structure:
Wherein, n is 2~15.
2. compound according to claim 1, which is characterized in that the n is 5~10.
3. a kind of synthetic method of oil-absorbing resin, comprising the following steps:
Compound, acrylate described in claim 1~2, initiator are reacted with crosslinking agent, obtain oil-absorbing resin.
4. synthetic method according to claim 3, which is characterized in that the initiator is azo-bis-isobutyl cyanide, described to draw
The additive amount for sending out agent is 0.1wt%~0.3wt% of the compound.
5. synthetic method according to claim 3, which is characterized in that the crosslinking agent is divinylbenzene, the crosslinking
The additive amount of agent is less than or equal to the 1wt% of the compound.
6. synthetic method according to claim 3, which is characterized in that the reaction carries out in water and dispersing agent, described
Dispersing agent is polyvinyl alcohol, polyethylene glycol 200 or polyethylene glycol 400, and the additive amount of the dispersing agent is the compound
0.3wt%~1.0wt%.
7. synthetic method according to claim 3, which is characterized in that the mass ratio of the acrylate and the compound
For (5~10): 1.
8. synthetic method according to claim 3, which is characterized in that the acrylate is long alkyl chain methacrylates.
9. oil-absorbing resin prepared by any one of claim 3~8.
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|---|---|---|---|---|
| CN1324876A (en) * | 2001-06-28 | 2001-12-05 | 复旦大学 | Method of preparing high oil-absorbing resin |
| CN101838372A (en) * | 2010-04-23 | 2010-09-22 | 苏州天立蓝环保科技有限公司 | Method for preparing fast oil-absorption material |
| CN104667888A (en) * | 2015-01-29 | 2015-06-03 | 苏州大学 | Photosensitive polymer modified adsorbing material and preparation method and application of photosensitive polymer modified adsorbing material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1324876A (en) * | 2001-06-28 | 2001-12-05 | 复旦大学 | Method of preparing high oil-absorbing resin |
| CN101838372A (en) * | 2010-04-23 | 2010-09-22 | 苏州天立蓝环保科技有限公司 | Method for preparing fast oil-absorption material |
| CN104667888A (en) * | 2015-01-29 | 2015-06-03 | 苏州大学 | Photosensitive polymer modified adsorbing material and preparation method and application of photosensitive polymer modified adsorbing material |
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