CN106243442A - The material containing benzene is had the compositions of high filtration - Google Patents

The material containing benzene is had the compositions of high filtration Download PDF

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Publication number
CN106243442A
CN106243442A CN201610605620.7A CN201610605620A CN106243442A CN 106243442 A CN106243442 A CN 106243442A CN 201610605620 A CN201610605620 A CN 201610605620A CN 106243442 A CN106243442 A CN 106243442A
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diluent
compositions described
compositions
silicon dioxide
aromatic compound
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CN106243442B (en
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张勇
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SHANGHAI SUPERHIGH ENGINEERING PLASTIC Co Ltd
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SHANGHAI SUPERHIGH ENGINEERING PLASTIC Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/32—Hydrocarbons, e.g. oil
    • C02F2101/322—Volatile compounds, e.g. benzene
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/20—Prevention of biofouling
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/068—Ultra high molecular weight polyethylene

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Filtering Materials (AREA)

Abstract

The present invention provides a kind of compositions to the material containing benzene with high filtration, and it is prepared raw material and includes at least: ultra-high molecular weight polyethylene；Silicon dioxide；4 vinylphenylboronic acid；Brominated aromatic compound；Mesitylene phenol；Diluent.

Description

The material containing benzene is had the compositions of high filtration
Technical field
The invention belongs to ultra-high molecular weight polyethylene filtering material field, particularly to the material containing benzene, there is high filtration Filter combination.
Background technology
The bright only 60 years history of filtering material technology, industrial applications is the most also with regard to about 20 years, but it is recognized For being one of the most promising science and technology.At present, before filtering material technology receives in the world, institute is not Some attention, " who has grasped filtering material technology, and who has just grasped future of chemical industry " has obtained everybody and has been widely recognized as.
As a kind of polyethylene kind thermoplastic engineering plastic, ultra-high molecular weight polyethylene has unrivaled comprehensive Can, such as: lower temperature resistance, wearability, impact resistance, chemical stability etc..In view of ultra-high molecular weight polyethylene has superiority Can, utilize it to prepare poromerics and be always, with separation process, the target that educational circles is studied for filtering.At present, described supra polymer Weight northylen is widely used in filtration art, such as: the process of dirty water pollutant: sanitary sewage, trade effluent；Air pollutes The process of gas: PM2.5, industrial waste gas, vehicle exhaust；The field such as interception of microorganism in water.
For the problems referred to above, the present invention provides a kind of and can have the strongest to the microorganism in containing benezene material and waste water The filter combination of interdiction capability, and present invention also offers a kind of filtering material, described filtering material with filter combination is Stock prepares.
Summary of the invention
In order to solve the problems referred to above, the present invention provides a kind of compositions to the material containing benzene with high filtration, and it is at least Comprise:
Solvent: ultra-high molecular weight polyethylene；
Hole-forming component: be prepared into by silicon dioxide, 4-vinylphenylboronic acid, brominated aromatic compound and mesitylene phenol Arrive；
Solvent: diluent.
As a kind of embodiment, the weight average molecular weight of described ultra-high molecular weight polyethylene is 2,500,000-400 ten thousand.
As a kind of embodiment, described brominated aromatic compound is the nitrogenous quasi-aromatic compound of bromo.
As a kind of embodiment, described brominated aromatic compound is bromo imidazoles, bromo s-triazine or brominated pyrimidine.
As a kind of embodiment, described diluent be dissolubility be 7.5-7.8J1/2/cm3/2The first diluent and molten Xie Du is 8.5-9.0J1/2/cm3/2The mixture of the second diluent.
As a kind of embodiment, described first diluent is the one in paraffin oil, decahydronaphthalene, naphthane, diphenyl ether Or it is multiple.
As a kind of embodiment, described second diluent is second benzene,toluene,xylene, metacetone, n-butyl acetate In one.
As a kind of embodiment, described silicon dioxide is that particle diameter is the silicon dioxide of 100-300nm and particle diameter is The mixture of the silicon dioxide of 400nm-800nm.
Described compositions, it is used for preparing filtering material.
A kind of filtering material, it prepares by described compositions.
Accompanying drawing explanation
Fig. 1: the liquid chromatogram of containing benezene material in stock solution；
Fig. 2: the liquid chromatogram of containing benezene material in filtrate；
The nucleus magnetic hydrogen spectrum of Fig. 3: material (1)
Fig. 4-Fig. 6: the embodiment of the filtering material that filterability compositions prepares
Detailed description of the invention
Participate in the election of the detailed description being preferable to carry out method of the invention below and the embodiment that includes can be more easily understood this Bright content.Unless otherwise defined, all technology used herein and scientific terminology have common with art of the present invention The identical implication that technical staff is generally understood that.When there is contradiction, it is as the criterion with the definition in this specification.
Term as used herein " by ... preparation " and " comprising " synonym.Term used herein " comprises ", " including ", " have ", " containing " or its other deformation any, it is intended that cover the including of non-exclusionism.Such as, the combination of listed elements is comprised Thing, step, method, goods or device are not necessarily solely those key elements, but can include other not expressly listed key element or The key element that this kind of compositions, step, method, goods or device are intrinsic.
Conjunction " Consists of " gets rid of any key element, step or component do not pointed out.If in claim, this Phrase will make claim be closed so that it is does not comprise the material in addition to the material that those describe, but relative often Except rule impurity.When being rather than immediately following during phrase " Consists of " occurs in the clause of claim main body after theme, It is only limited to the key element described in this clause；Other key element is not excluded outside as overall described claim.
Equivalent, concentration or other value or parameter are excellent with scope, preferred scope or a series of upper limit preferred value and lower limit During the Range Representation that choosing value limits, this is appreciated that and specifically discloses by any range limit or preferred value and any scope All scopes that arbitrary pairing of lower limit or preferred value is formed, regardless of whether whether this scope separately discloses.Such as, when open During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to 5 ", " 1 to 3 and 5 " etc..When numerical range is described in this article, unless otherwise indicated, otherwise this scope is intended to include its end Value and all integers within the range and mark.
Singulative includes that plural number discusses object, unless the context clearly dictates otherwise." optional " or " arbitrarily A kind of " refer to that the item described thereafter or event may or may not occur, and this description include situation that event occurs with The situation that event does not occurs.
Approximation term in specification and claims is used for modifying quantity, represents that the present invention is not limited to this concrete Quantity, also includes close to this quantity acceptable without causing the part of the correction of the change of relevant basic function.Phase Answer, modify a numerical value with " about ", " about " etc., mean and the invention is not restricted to this exact numerical.In some example, approximation Term likely corresponds to measure the precision of the instrument of numerical value.In present specification and claims, scope limits permissible Combination and/or exchange, these scopes include all subranges contained therebetween if not stated otherwise.
Additionally, indefinite article " a kind of " before key element of the present invention or component and " one " are to key element or the quantitative requirement of component (i.e. occurrence number) unrestriction.Therefore " one " or " a kind of " should be read as including one or at least one, and odd number The key element of form or component also include plural form, unless the obvious purport of described quantity refers to singulative.
" polymer " means the polymerizable compound prepared by the monomer by being polymerized identical or different type.Generic term " polymer " comprises term " homopolymer ", " copolymer ", " terpolymer " and " copolymer ".
" copolymer " means the polymer prepared by polymerization at least two different monomers.Generic term " copolymer " includes (it is general with term " terpolymer " for term " copolymer " (it is typically in order to refer to the polymer prepared by two kinds of different monomers) In order to refer to the polymer prepared by three kinds of different monomers).It also comprises the polymerization manufactured by polymerization four or more kinds of monomers Thing." blend " mean two or more polymer by physics or the method for chemistry jointly mix and the polymerization that formed Thing.
In order to solve the problems referred to above, the present invention provides a kind of compositions to the material containing benzene with high filtration, and it is at least Comprise:
Solvent: ultra-high molecular weight polyethylene；
Hole-forming component: be prepared into by silicon dioxide, 4-vinylphenylboronic acid, brominated aromatic compound and mesitylene phenol Arrive；
Solvent: diluent.
Ultra-high molecular weight polyethylene:
In the present invention, described polyethylene is the mixing of the polyethylene of different molecular weight.
The weight average molecular weight (Mw) of heretofore described polyethylene is 2,500,000-400 ten thousand, more preferably 2,500,000-350 Ten thousand, more preferably 250-320 ten thousand.
In the present invention, the weight average molecular weight of described polyethylene is 5.0 × 104Above～less than 4.0 × 105。
If described polyethylene overall weight to be set to 100 percentage by weights, the then weight average molecular weight poly-second more than 2,500,000 The content of alkene is preferably below 60.0 percentage by weights.If this content is above-mentioned preferred scope, then will not cause pressure during molding Rising, productivity is the best.Additionally, the lower limit of this content there is no particular restriction, but from maintain mechanical strength and maintain height From the standpoint of fusion temperature, more than especially preferably 30.0 percentage by weights.
The homopolymer of ethylene is not only by polyethylene, it is also possible to be the copolymer containing other alpha-olefins a small amount of.As ethylene Other alpha-olefins in addition, can enumerate propylene, butene-1, hexene-1, amylene-1,4-methylpentene-1, octene, vinyl acetate Ester, methyl methacrylate, styrene etc..
As a kind of embodiment, heretofore described compositions, except this polyolefin of polyethylene, it is also possible to include Polypropylene.
Described polyacrylic weight average molecular weight is preferably greater than 60,000-50 ten thousand.
As polypropylene, being possible not only to is homopolymer, it is also possible to be the block copolymerization comprising other alpha-olefins or alkadienes Thing and/or random copolymer.As the alpha-olefin that other alkene, optimal ethylene or carbon number are 4～8.Former as carbon Subnumber is the alpha-olefin of 4～8, include, for example 1-butylene, 1-hexene, 4-methyl-1-pentene etc..The carbon number of alkadienes is excellent Elect 4～14 as.As the alkadienes that carbon number is 4～14, include, for example butadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadinene etc..If propylene copolymer is set to 100 molar percentages, then the containing ratio of other alkene or alkadienes is the least In 10 molar percentages.
If described polyethylene overall weight is set to 100 percentage by weights, the most polyacrylic content is preferably less than 5.0 weights Amount percentage ratio.Polyacrylic upper content limit is preferably 3.5 percentage by weights.Polyacrylic content lower limit is preferably 0.5 weight hundred Proportion by subtraction, more preferably 1 percentage by weight.If polyacrylic content is within the above range, then oxidative resistance, filtering material uniform Property and intensity can improve.
It addition, this weight average molecular weight is to pass through: prepare the chloroformic solution that polyolefinic concentration is 0.5 mass %, use height Effect liquid phase chromatogram is measured, with the weight average molecular weight measured under the same conditions known to polystyrene compare, thus The value calculated.It addition, condition determination is as follows.
Post: GPC post
Column temperature: 40 DEG C
Eluent: chloroform
Flow velocity: 1ml/ minute
Melt flow rate (MFR) (MFR, the list that the mobility of resin is such as measured by the method utilizing JIS7210:1999 to specify Position: g/10min) represent.
Heretofore described polyolefin can prepare with any method known to those skilled in the art.Such as Prepare the copolymer of ethylene and propylene.
Ethylene and propylene mix in advance in proportion in air accumulator.It is aggregated in equipped with slotting bill kept on file body canal, outtake tube Carry out with in the tubular type there-necked flask of mechanical agitation 100ml.First polymerization bottle evacuation, logical monomer are replaced twice the most continuously, connect Vacuum and bake bottle 5 minutes.By reactor as in water bath with thermostatic control, once add normal heptane, promoter, external electron donor, lead to Enter gaseous mixture continuous bubbling, after monomer reaches dissolution equilibrium, add major catalyst and cause polymerization.Polymerization uses acidifying after terminating Ethanol terminates reaction, and polymer, through filtering, washs, is dried under vacuum to constant weight, weighs at 60 DEG C.
Silicon dioxide:
Silicon dioxide: heretofore described silicon dioxide is that particle diameter is the silicon dioxide of 100-300nm and particle diameter is The mixture of the silicon dioxide of 400nm-800nm.
The silicon dioxide of different-grain diameter can be commercially available, it is also possible to is synthesis.
The synthetic method of the silicon dioxide of described 100-300nm: with high-pressure emulsification method to containing hydrophobic organic compound, Pressurization implemented by the mixed liquor of surfactant and water solvent, thus formed and comprise the emulsion that emulsifying is dripped, wherein said breast Change and drip containing described hydrophobic organic compound；Silica source is added to described emulsion, drips surface shape in described emulsifying Become there is the housing department wrapping silica containing meso-hole structure, and make to have described housing department and compound dioxy that described emulsifying is dripped Silicon carbide particle separates out, and the inner side being positioned at compared with described housing department is dripped in wherein said emulsifying；From described dioxide composite silicon grain Remove described emulsifying to drip.
(hydrophobic organic compound)
So-called hydrophobic organic compound refers to low relative to the dissolubility of water, and forms separated material with water.Dredge Aqueous organic compounds can disperse the most in the presence of surfactants, preferably at an example as surfactant Can disperse in the presence of quaternary ammonium salt.
As hydrophobic organic compound, such as, can enumerate hydrocarbon compound, ester compounds, carbon number are 6～22 The oil preparation such as fatty acid and silicone oil.
As hydrocarbon compound, alkane that carbon number is 5～18 can be enumerated, carbon number be 5～18 cycloalkane, Liquid Paraffin or liquid petrolatum, squalane, Squalene, perhydro-squalene, trimethylbenzene, dimethylbenzene, benzene etc.
As ester compounds, the oils such as glyceride that can enumerate the fatty acid that carbon number is 6～22, the most permissible Enumerate trilaurin, triolein, tripalmitin, glycerol tristearate Oleum Gossypii semen, almond oil, castor Oleum Sesami, American Avocado Tree oil, Jojoba oil, olive oil or grain germ oil etc..
It addition, as ester compounds, can enumerate the fatty acid that carbon number is 4～22 is 1～22 with carbon number Monohydric alcohol or the condensation substance of the polyhydric alcohol in addition to glycerol, specifically can enumerate isopropyl myristate, Palmic acid isopropyl Ester, butyl stearate, lauric acid hexyl ester, Palmic acid 2-octyl group ester in the last of the ten Heavenly stems, ODM etc..
As the fatty acid that carbon number is 6～22, capric acid, lauric acid, myristic acid, Palmic acid, tristearin can be enumerated Acid, behenic acid, oleic acid, linoleic acid, linolenic acid or isostearic acid etc..
As silicone oil, can enumerate by fatty acid and aliphatic alcohol or polyoxyalkylene-modified polysiloxanes, fluorosilicone, Perfluor silicone oil etc..
These hydrophobic organic compounds can be used alone, or mixes two or more use with arbitrary proportion.
(water solvent)
The water solvent used in an example as the manufacture method in the present invention, can enumerate such as water or The mixed solvent etc. that person is made up of water and water-miscible organic solvent, but from the viewpoint of the stability that emulsifying is dripped, water system is molten Agent is the most only made up of water.As water, such as distilled water, ion exchange water, ultra-pure water etc. can be enumerated.Organic as water solublity Solvent, can enumerate methanol, ethanol, acetone, 1-propanol and 2-propanol etc..Water-miscible organic solvent is comprised in water solvent In the case of, from the viewpoint of the stability that emulsifying is dripped, the content of the water-miscible organic solvent in water solvent is preferably 0.1 ～50 weight %, more preferably 1～40 weight %, particularly preferably 1～30 weight %.
(surfactant)
The surfactant used in an example as the manufacture method in the present invention, from improving, hydrophobicity is organic From the viewpoint of the utilization rate of compound, preferably quaternary surfactant, such as butyl trimethyl ammonium chloride, hexyl front three Ammonium chloride, octyltrimethylammonium chloride, decyl trimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride, CPC Ammonium chloride, hexadecyltrimethylammonium chloride, octadecyl trimethyl ammonium chloride, butyl trimethylammonium bromide, hexyl front three Base ammonium bromide, octyl trimethyl ammonium bromide, DTAB, Dodecyl trimethyl ammonium chloride, CPC Base ammonium bromide, cetyl trimethylammonium bromide, Cetyltrimethylammonium bromide.
(silica source)
As silica source, preferably generated the material of silanol compound, preferably tetramethoxy-silicane, tetrem by hydrolysis TMOS, phenyl triethoxysilane, 1,1,1-trifluoro propyl triethoxysilane, more preferably tetramethoxy-silicane.This A little silica source can be used alone, or mixes two or more use with arbitrary ratio.
Described particle diameter be the silicon dioxide of 400-500nm be commercially available, be purchased from Shanghai and jump the river limited public affairs of titanium white heavy chemicals Department.
4-vinylphenylboronic acid；Brominated aromatic compound；Mesitylene phenol:
In the present invention, described 4-vinylphenylboronic acid, brominated aromatic compound and mesitylene phenol synthesize.
Preparation method is as follows:
(1), weigh 0.1mol 4-vinylphenylboronic acid be placed in 250mL round-bottomed flask, add 0.11mol bromo fragrance Compounds of group, 0.003mol tetrakis triphenylphosphine palladium, 0.15mol potassium carbonate, after mix homogeneously add 30mL oxolane and 15mL water.Being heated to reflux 15h, reaction is cooled to room temperature after terminating, and filters, and collects filtrate.With ethyl acetate and petroleum ether volume As fixing phase, after employing column chromatography purifies, with chloroform and Diethyl ether recrystallization, to obtain final product as flowing phase, silica gel than for 1:10 Material (1)；
(2), silicon dioxide is placed in round-bottomed flask, adds the salpeter solution of a certain amount of 5%, stirring, water-bath backflow 24h, product distilled water is washed till neutrality, puts into and is dried 12h in 60 DEG C of baking ovens；
(3), the silicon dioxide activated and 160mL toluene, 4.7mL KH-570,1mL triethylamine are put in three-necked bottle, Ultrasonic vibration 5min, N2The lower heating in water bath of protection is stirred at reflux 24h.After filtration after toluene, acetone, methanol cyclic washing, in It is vacuum dried 24 hours at 80 DEG C, obtains material (2)；
(4), by the mesitylene phenol of 0.25mmol, material (1), material (2), at benzoyl peroxide as initiator, live Property calcium phosphate and anhydrous sodium sulfate as dispersant in the case of, at normal temperatures after magnetic agitation 6h, be placed in water-bath reaction 6h； Then with methanol/acetic acid solution eluting, material (3) can be prepared.
The nucleus magnetic hydrogen spectrum of described material (1) is as it is shown on figure 3, solvent is DMSO, and chemical shift is: 5.18 (d, 1H)；5.61 (d,1H)；6.63(t,1H)；7.22-7.48(m,9H).
Described brominated aromatic compound be protium on aromatic compound by bromo element to replacing.
Described aromatic compound is preferably aromatic heterocyclic compounds.
Described aromatic compound, such as, can enumerate the virtue that the ring of monocycle or more than 2 condenses the condensed ring of formation Fragrant compounds of group, more specifically can enumerate the looped carbon number of structure is the aromatic series of 6-14, such as: benzene, naphthalene, anthracene, From the perspective of dissolubility, preferably benzene.
As aromatic heterocyclic compounds, such as can enumerate containing in nitrogen-atoms, oxygen atom and sulphur atom extremely The monocycle aromatic heterocyclic compounds of 5 yuan or 6 yuan of few 1 atom, it is the bicyclo-that condenses of 3～8 rings or three rings and contains There is the heteroatomic condensed ring aromatic heterocyclic compounds of at least 1 in nitrogen-atoms, oxygen atom and sulphur atom etc., more specifically For, can enumerate furan, thiophene, purine, pyrroles, imidazoles, pyrazoles, oxazole, isoxazole, thiazole, isothiazole, thiadiazoles, three Azoles, tetrazolium, pyridine, pyridazine, pyrimidine, pyrazine, triazine, benzofuran, benzothiophene, benzothiazole, benzothiazole, iso-indoles, Indole, indazole, benzimidazole, benzotriazole, azoles pyrimidine, thiazole pyrimidine, pyrrolopyridine, pyrrolopyrimidine, imidazoles And pyridine, purine, quinoline, isoquinolin, 2，3-benzodiazine, quinazoline, quinoxaline, naphthyridine etc..
Described aromatic compound is preferably nitrogenous aromatic heterocyclic compounds.
One or more in imidazoles, pyrimidine, 1,3,5-triazine of described nitrogenous aromatic heterocyclic compounds.
Diluent:
In the present invention, described diluent be dissolubility be 7.5-7.8J1/2/cm3/2The first diluent and dissolubility be 8.5-9.0Jl1/2/cm3/2The mixture of the second diluent.
Solubility parameter is measured:
The method of testing of solubility parameter is the acetone dilution of polyester sample 10g taking 0.5 gram: by two parts of testing samples It is placed in 20 degree of cleansing bath tubs, a with normal hexane titration, a with deionized water titration, until becoming cloudy.Solubility parameter meter Calculation formula is as follows:
Wherein:
φ ml drips to the volume fraction of normal hexane during terminal,
φ mh drips to the volume fraction of deionized water during terminal,
T (Hexane) drips to the volume of normal hexane during terminal,
T (water) drips to the volume of deionized water during terminal,
V m l = V ( H e x a n e ) * V g φ m l * V g + ( 1 - φ m l ) * V ( h e x a n e )
V m l = V ( w a t e r ) * V g φ m h * V g + ( 1 - φ m h ) * V ( w a t e r )
Vml normal hexane drips to the molal volume of mixed solvent during terminal,
Vmh deionized water drips to the molal volume of mixed solvent during terminal,
The molal volume of V (hexane) normal hexane,
The molal volume of V (water) deionized water,
The molal volume of Vg good solvent acetone,
δ m l = φ m l * δ 2 ( H e x a n e ) + ( 1 - φ m l ) δ 2 g
δ m h = φ m h * δ 2 ( w a t e r ) + ( 1 - φ m h ) δ 2 g
The solvent degree parameter of δ g solvent acetone
δ ml normal hexane drips to the solubility parameter of mixed solvent during terminal,
δ mh deionized water drips to the solubility parameter of mixed solvent during terminal,
The solubility parameter of δ (Hexane) normal hexane
The solubility parameter of δ (water) deionized water.
Dissolubility is 7.5-7.8J1/2/cm3/2The first diluent can be selected from paraffin oil, decahydronaphthalene, naphthane, hexichol One or more in ether.
One or more in paraffin oil, decahydronaphthalene of described first diluent.
Described second diluent is the one in second benzene,toluene,xylene, metacetone, n-butyl acetate；Described second Diluent is the one in ethylbenzene, toluene, n-butyl acetate.
In the present invention, the weight ratio of described first diluent and the second diluent is (80-90): (10-20).
In the present invention, the described compositions to the material containing benzene with high filtration, it is used for preparing filtering material.
Described filtering material can serve as gas or the filter of liquid or solid and separates material, battery use and capacitor Dividing plate, or their part.For example, it is possible to as liquid separation material, solid separation material, gas separation material or he A part use.
Specifically, can enumerate: bag filter, dust removal filter, air conditioner filter, the filter (air of automobile Depurator, oil cleaner, indoor purifying filter, exogenous QI filter by suction etc.) etc..Furthermore, it is possible to as circuit substrate, electricity The electromagnetic wave such as pond dividing plate, electromagnetic wave shielding or electromagnetic wave absorb control material, electrolysis condenser, advanced low-k materials, Padded coaming, ink imaging film, reagent paper, insulant, heat-barrier material, cell culture medium material, lonizing radiation cover bed course to be used The baseplate material that material, oil absorption material etc. are extensively utilizes.
Third aspect present invention provides a kind of method preparing described filtering material.
Described method can use any method well known by persons skilled in the art to prepare.
Sintering process: sintering process is a kind of relatively simple method preparing polymer microporous material, it can be summarized as follows: The polymer powder of a certain size granule is compressed, the most at high temperature calcines.Calcining heat depends on selected material Character, different calcined material temperature is not quite similar.In calcination process, intergranular interface disappears, and forms microcellular structure, Pore size depends on the distribution of powder particle size and granular size.
Track etch method: track etch method is the high energy grain making filtering material or thin slice accept to be perpendicular to filtering material direction Son radiation, under the effect of radiating particle, polymer suffers damage and forms track；Subsequently, by this filtering material immerse acid or In alkaline solution, the polymeric material at result track is corroded and obtains having the uniform cylindrical of narrow pore-size distribution Hole.During track etch method prepares polymer micro filtering material, the length of filtering material raying time determined Filtering material number of perforations, the length of etch period determines pore size.And the selection of filtering material depends primarily on and can obtain Filtering material thickness and the radiant intensity that used.
Phase transition method: phase transition method is to make polymer be changed into two phases or multinomial state from equal phase with certain control method Process, this solidification process is often as a homogeneous phase solution and is changed into two liquid (liquid-liquid layering) and causes.? When split-phase reaches to a certain degree, liquid phase (polymer-rich phase) solidification that wherein polymer concentration is high, define solid body.Another The liquid phase (solvent-rich phase) that polymer concentration is low is by rich in polymers solidifying and then terminates its growth.Phase transition method mainly includes non- Solvent causes phase separation method and thermally induced phase separation.
Thermally induced phase separation is that polymer and high boiling point, the diluent of low-molecular-weight are at high temperature formed homogeneous phase solution, Occurring liquid-liquid or solid-liquid phase to separate when reducing temperature, finally removing diluent prepares polymer micro filtering material.Permitted Polycrystalline or polymer with strong hydrogen bonding effect, at room temperature dissolubility is low, it is difficult to find suitable solvent, therefore can not use When traditional phase separation method makes micropore filter material generally profit in this way, the chemical stability of these materials And Heat stability is good, good mechanical performance, cheap.Thermally induced phase separation prepares micropore filter material, has widened polymer The range of application of filtering material.
In the present invention, concrete preparation process is:
(1), by material (3), ultra-high molecular weight polyethylene, silicon dioxide and diluent according to certain proportioning, uniformly mix Closing, at 70-90 DEG C, heat is blended 0.5 hour；
(2), blend is placed in mould, at keeping 180-200 DEG C after a few hours, cooling, the demoulding, to obtain final product.
In the present invention, when the concentration of described polymer is 10-40wt%, the porosity of obtained filtering material is higher.
In the present invention, in described waste water containing benzene material can be enumerated as benzene,toluene,xylene, phenol, chlorobenzene, dichloro-benzenes, Perchlorobenzene, phthalate, pentachlorophenol etc..
Beneficial effect
In the present invention, the addition of described material (1) can improve the filtering material of ultra-high molecular weight polyethylene formation to useless The filterability of water pollutant, in nitrogenous heterocyclic compound, the atomic radius of nitrogen is less than carbon, and electronegativity is higher, adds Cloud density on aromatic rings, is particular enable to improve the filterability containing benzene material, and particularly, present inventor is unexpected Find, when the lone pair electrons on nitrogen-atoms on heterocyclic compound are positioned at aromatic rings plane, the beneficially accumulation of aromatic rings, also Being conducive to the filtration containing polar group pollutant on phenyl ring, the filtration for chlorobenzene, dichloro-benzenes has particularly preferred effect.With Time, the filtering material that filterability compositions provided by the present invention prepares has the strongest rejection to microorganism.
An aspect of of the present present invention provides described high filtration compositions, on the other hand additionally provides by described filtration combination The filtering material that thing prepares.Described filtering material can exist in any form, such as composite block structure, spiral-winding Plate or the filter medium of folded sheet, also or screen plate, filter membrane, filter bag, or the sieve containing these filter mediums Select device etc..
The filtering material that the present invention prepares, can be widely used for the various field needing filtering material, such as: gas is led The filtration in territory: the filtration of waste gas in PM2.5 in industrial waste gas, vehicle exhaust, air, burning；
Field of sewage: sanitary wastewater, industrial wastewater, Metallurgical Waste Water, Shui Kuang, steel-making waste water, laboratory waste water, scientific research institutions Waste water, surface active agent wastewater；
Microorganism field: microbiological interception.
Below by embodiment, the present invention is specifically described.Be necessary it is pointed out here that, following example are only used In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field Some nonessential improvement and adjustment that content according to the invention described above is made, still fall within protection scope of the present invention.
It addition, illustrate without other, raw materials used is all commercially available.
Wherein:
The preparation method of material (1): weigh 0.1mol 4-vinylphenylboronic acid and be placed in 250mL round-bottomed flask, add 0.11mol brominated aromatic compound, 0.003mol tetrakis triphenylphosphine palladium, 0.15mol potassium carbonate, add after mix homogeneously 30mL oxolane and 15mL water.Being heated to reflux 15h, reaction is cooled to room temperature after terminating, and filters, and collects filtrate.With acetic acid second Ester and petroleum ether volume ratio are 1:10 as flowing phase, and silica gel is as fixing phase, after using column chromatography to purify, by chloroform and second Ether recrystallization, obtains material (1)
A1: brominated aromatic compound is bromobenzene
A2: brominated aromatic compound is pyridine bromide
A3: brominated aromatic compound is bromo imidazoles
A4: brominated aromatic compound is bromo 1,3,5-triazine
The preparation method of material (2): be placed in round-bottomed flask by silicon dioxide, adds the salpeter solution of a certain amount of 5%, stirs Mix, water-bath refluxes 24h, and product distilled water is washed till neutrality, puts into and is dried 12h in 60 DEG C of baking ovens；The silicon dioxide that will have activated Put in three-necked bottle with 160mL toluene, 4.7mL KH-570,1mL triethylamine, ultrasonic vibration 5min, N2The lower heating in water bath of protection It is stirred at reflux 24h.After filtration after toluene, acetone, methanol cyclic washing, it is vacuum dried 24 hours at 80 DEG C, obtains material (2)；
B1: general silica
B2: silicon dioxide particle diameter is 100-150nm
B3: silicon dioxide particle diameter is 100-150nm and particle diameter is the blend of 400-500nm, and ratio is 1:2；
The preparation method of material (3): by the mesitylene phenol of 0.25mmol, 0.50mmol material (1), 1.0mmol material (2), benzoyl peroxide as initiator, active calcium phosphate and anhydrous sodium sulfate as dispersant in the case of, at room temperature After lower magnetic agitation 6h, it is placed in water-bath reaction 6h；Then with methanol/acetic acid solution eluting, material (3) can be prepared.
C1:A1+B1
C2:A1+B2
C3:A1+B3
C4:A2+B3
C5:A3+B3
C6:A3+B3+ mesitylene phenol
C7:A4+B3+ mesitylene phenol
Diluent:
D1: decahydronaphthalene
D2: n-butyl acetate
D3:50 weight portion decahydronaphthalene+50 parts by weight acetic acid N-butyl
D4:85 weight portion decahydronaphthalene+15 parts by weight acetic acid N-butyl
Ultra-high molecular weight polyethylene
E1: weight average molecular weight is 3,000,000
E2: weight average molecular weight is 500,000
E3:50 weight portion E1+50 weight portion E2
E4:90 weight portion E1+10 weight portion E2
In the present invention, the weight part ratio of described ultra-high molecular weight polyethylene, material (3) and diluent is (35-55): (8- 15): 100
Wherein, the weight portion of described ultra-high molecular weight polyethylene is the arbitrary number between 35-55, such as 35,36,37, 38, any one in 39,40,41,42,43,44,45,46,47,48,49,50,51,52,53,54,55；
The weight portion of described material (3) you be the arbitrary number between 8-15, such as in 8,9,10,11,12,13,14,15 Any one.
By heretofore described filter combination, it is prepared as filter membrane, is further tested.
Test:
(1) porosity (Ak)
Dry film is immersed in absolute alcohol and takes out after 10 hours, with filter paper, the ethanol on film surface is wiped dry doubling and weighs.AkTable Reach formula as follows:
A k = ( W 0 - W ) ρ ρW 0 + ( ρ - ρ ‾ ) W
W is dry film quality, and W0 is the quality of wet film, and ρ is the density of polymer,Density for ethanol.
(2) strainability of containing benezene material is tested
Containing benezene material and distilled water are mixed, measures the concentration C of containing benezene material in original liquid1, use the present invention In film to be measured carry out filtering 6 hours, measure the concentration C of containing benezene material in filtrate2, calculate rejection=(C1-C2)/C1× 100%, calculate the concentration of containing benezene material in liquid with the peak area of liquid chromatograph.
The condition of liquid chromatograph is: eluent is oxolane/water=80:20；Flow velocity is 1mL/min, and injection rate is 10 μ L；Detection wavelength is 230nm.
In figure, appearance time about 5.390 be chlorobenzene；Appearance time about 6.950 be benzene.
Data above is it can be seen that compared with the product not used containing material 3 and mixed diluent 1, prepared by the present invention Material possessing higher porosity and to containing benezene material rejection, be thus provided that the Advantageous Effects of the present invention.
Aforesaid example is merely illustrative, for explaining some features of the feature of the disclosure.Appended claim It is intended to the widest scope that requirement it is contemplated that, and embodiments as presented herein is only according to all possible embodiment The explanation of embodiment of selection of combination.Therefore, the purpose of applicant is that appended claim is not by the explanation present invention The selectional restriction of example of feature.And the progress in science and technology will be formed due to language performance inaccurate reason and not The possible equivalent or the son that are presently considered are replaced, and these changes also should be interpreted in the conceived case by appended Claim covers.

Claims (10)

1. pair material Han benzene has the compositions of high filtration, and it includes at least:
Solvent: ultra-high molecular weight polyethylene；
Hole-forming component: prepared by silicon dioxide, 4-vinylphenylboronic acid, brominated aromatic compound and mesitylene phenol；
Solvent: diluent.
2. the compositions described in claim 1, the weight average molecular weight of described ultra-high molecular weight polyethylene is 2,500,000-400 ten thousand.
3. the compositions described in claim 1, described brominated aromatic compound is the nitrogenous quasi-aromatic compound of bromo.
4. the compositions described in claim 1, described brominated aromatic compound is that bromo imidazoles, bromo s-triazine or bromo are phonetic Pyridine.
5. the compositions described in claim 1, described diluent be dissolubility be 7.5-7.8J1/2/cm3/2The first diluent and Dissolubility is 8.5-9.0J1/2/cm3/2The mixture of the second diluent.
6. the compositions described in claim 1, described first diluent is in paraffin oil, decahydronaphthalene, naphthane, diphenyl ether Plant or multiple.
7. the compositions described in claim 1, described second diluent be second benzene,toluene,xylene, metacetone, acetic acid just One in butyl ester.
8. the compositions described in claim 1, described silicon dioxide is that particle diameter is the silicon dioxide of 100-300nm and particle diameter is The mixture of the silicon dioxide of 400nm-800nm.
9. the compositions described in claim 1, it is used for preparing filtering material.
10. the compositions described in claim 1, it is used for air filtration, sewage disposal, microbiological interception field.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006102762A1 (en) * 2005-04-01 2006-10-05 Mcmaster University Glucose responsive microgels
CN101244377A (en) * 2008-03-18 2008-08-20 西北大学 Polymer absorbing agent and preparation thereof
JP2012046596A (en) * 2010-08-25 2012-03-08 Tokyo Metropolitan Univ Polymer gel, method for producing the same, treating agent for cleaning water, and treating method for cleaning water
CN102553546A (en) * 2012-01-18 2012-07-11 中国人民解放军63971部队 High-molecule adsorption material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006102762A1 (en) * 2005-04-01 2006-10-05 Mcmaster University Glucose responsive microgels
CN101244377A (en) * 2008-03-18 2008-08-20 西北大学 Polymer absorbing agent and preparation thereof
JP2012046596A (en) * 2010-08-25 2012-03-08 Tokyo Metropolitan Univ Polymer gel, method for producing the same, treating agent for cleaning water, and treating method for cleaning water
CN102553546A (en) * 2012-01-18 2012-07-11 中国人民解放军63971部队 High-molecule adsorption material

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