CN106883362B - Copolymer, intermediate and preparation method thereof, purposes - Google Patents
Copolymer, intermediate and preparation method thereof, purposes Download PDFInfo
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- CN106883362B CN106883362B CN201710173928.3A CN201710173928A CN106883362B CN 106883362 B CN106883362 B CN 106883362B CN 201710173928 A CN201710173928 A CN 201710173928A CN 106883362 B CN106883362 B CN 106883362B
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- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers 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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/12—Esters of phenols or saturated alcohols
- C08F222/14—Esters having no free carboxylic acid groups, e.g. dialkyl maleates or fumarates
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- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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- 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
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
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- 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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/02—Low molecular weight, e.g. <100,000 Da.
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Abstract
The invention discloses a kind of copolymers, intermediate and preparation method thereof, purposes.The copolymer provided by the invention as shown in formula 1* have lower molecular weight (number-average molecular weight < 8000g/mol), molecular weight distribution in controlled range (PD < 1.6), environmentally friendly, degradable and cost is relatively low；Thus the CO of copolymer building2/ aqueous emulsion emulsifying effectiveness is good, has higher CO2There is preferable stability again while volume fraction.
Description
Technical field
The present invention relates to copolymers, intermediate and preparation method thereof, purposes.
Background technique
CO2It can be applied to nano material preparation, extraction as the lotion that two kinds on the earth the most abundant resources are formed with water
The fields such as separation and biological medicine engineering, are especially concerned in terms of improving oil recovery factor.CO2It is a kind of solvability
Poor solvent, based on existing document report analyze, with preferable emulsifying effectiveness surfactant be mainly it is fluorine-containing with
And siliceous surfactant (when being embodied in dispersed phase integral rate, lotion building pressure and emulsion-stabilizing of emulsifying effectiveness
Between aspect)；Wherein good lotion effect is that dispersed phase integral rate is high (> 74%), and lotion building pressure is lower and lotion is steady
It fixes time length, but because its toxicity is big, expensive, not degradable and pollution fails due to environment the shortcomings that by large-scale use；
And with the environmental-friendly hydrocarbon class surfactant of commercialization, such as: the surfactant SAM185, DOW USA of PPG Industries Inc.
Surfactant B -70-4600, the surfactant L-61 of BSF etc., there is the emulsion system CO of building2Volume fraction is not
Higher than 70% and stablize time shorter deficiency.For this purpose, the hydrocarbon class surfactant of design and synthetic environment close friend, structure
Build phase CO in the good height of stability2/ emulsion system will be more meaningful.
Most close CO in polymer of the report discovery at present containing only C, H, O2Property is polyvinyl acetate (PVAc), and
The oligomeric vinylacetate (OVAc) of lower molecular weight has better solubility.Wang et al. is in quantum-mechanical effects mould
On the basis of quasi-, also turn out PVAc be in polymer containing only C, H, O with CO2The highest polymer of compatibility, is specifically detailed in text
Offer [Y.Wang, L.Hong, I.C.Kim, I.H.Paik, J.M.Crosthwaite, A.D.Hamilton, M.Thies,
E.Beckman,R.M.Enick,K.Johnson,D.Tapriyal.Design and evaluation of non-
fluorous CO2-soluble polymers.Journal of Physical Chemistry B,2009,113:14971–
14980].But research is found: if using PVAc as parent CO2The surface modification PVA c-b-PDMAEMA being prepared is held, though it can
To construct CO2The lotion of volume dispersion rate higher (80%), but it is shorter to stablize the time.
Therefore, numerous researchers are dedicated to finding or synthesizing a kind of surfactant, can effectively emulsify CO2-H2O
System, to prepare CO2The higher stable C/W type lotion of volume fraction, but do not obtain ideal effect.
Summary of the invention
The technical problem to be solved by the present invention is in order to overcome in the prior art using PVAc as parent CO2What end was prepared
The emulsion system CO of surfactant polyvinyl acetate-b- polymethylacrylic acid dimethylaminoethyl building2Volume fraction is steady
It fixes time shorter defect, and a kind of copolymer as shown in formula 1*, intermediate is provided and preparation method thereof, purposes.This is total
Polymers have lower molecular weight number-average molecular weight < 8000g/mol, molecular weight distribution in controlled range (PD < 1.6), to environment
It is friendly, degradable and cost is relatively low；Thus the CO of copolymer building2/ aqueous emulsion emulsifying effectiveness is good, has higher CO2Volume point
There is preferable stability again while rate.
The present invention provides one kind copolymers as shown in formula 1*:
Number-average molecular weight < 8000g/mol of copolymer shown in the formula 1*；N=1~100, such as 3~30, then
Such as n=5~16；M=1~100, such as 5~40, then such as m=10~22.
One structure list of representation according to common sense in the field, in copolymer shown in the formula 1*, in each " () "
Member, each structural unit are independent from each other；The n and m indicates the degree of polymerization, and the corresponding structural unit of the n is parent CO2
End, the corresponding structural unit of the m are parent H2The end O.
One of the preferred random copolymer of the copolymer, alternate copolymer, block copolymer and graft copolymer or
It is a variety of, further preferred block copolymer.
The present invention provides a kind of preparation methods of polymer shown in formula 1*, and it includes following steps: anhydrous nothing
Under the conditions of oxygen, in organic solvent, under the action of catalyst and ligand, by compound shown in polymer shown in formula 2* and formula 3 into
Row ATRP reaction；
Wherein, one structural unit of representation in each " () ", each structural unit are independent from each other；It is described
N indicate the degree of polymerization, n=1~100, such as 3~30, then such as n=5~16.
In the present invention, the ATRP reaction refers to atom transition free radical polymerization reaction, and operation can refer to this field should
The routine operation of class reaction, following operation specifically preferred according to the invention and method:
In the preparation method of the copolymer, the anhydrous and oxygen-free condition in the ATRP reaction can be by reactant point
Son screens out the reaction vessel of water process and sealing and is repeated as many times realization by vacuumizing-leading to protective gas；The guarantor
The shield property preferred nitrogen of gas.
In the preparation method of the copolymer, organic solvent in the described ATRP reaction can such reaction of this field
Conventional solvents, such as fragrant ether solvent (such as methyl phenyl ethers anisole).
In the preparation method of the copolymer, in the ATRP reaction, the catalyst can such be anti-for this field
The custom catalysts answered, such as stannous chloride and/or cuprous bromide.
In the preparation method of the copolymer, in the ATRP reaction, the ligand can such be anti-for this field
The common ligand answered, such as N, N, N, N, N- five methyl diethylentriamine and/or 1, Isosorbide-5-Nitrae, 7,10,10- hexamethyl Sanya second
Urotropine.
In the preparation method of the copolymer, in the ATRP reaction, polymer shown in the formula 2* and institute
The molar ratio for stating 3 compound represented of formula can be the conventional amount used ratio of such reaction of this field, such as (1:40)~(1:70), then
Such as 1:60.
In the preparation method of the copolymer, in the described ATRP reaction, compound shown in the formula 3 and described
The molar ratio of catalyst can be the conventional amount used ratio of such reaction of this field, such as (1:0.5)~(1:2), then such as (1:1).
In the copolymer preparation method, in the described ATRP reaction, polymer shown in the formula 2* with it is described
The molar ratio of ligand can be the conventional amount used ratio of such reaction of this field, such as (1:0.5)~(1:2), then such as (1:2).
In the preparation method of the copolymer, in the described ATRP reaction, compound shown in the formula 3 and described
The mass ratio of organic solvent can be the conventional amount used ratio of such reaction of this field, such as (1:0.67)~(1:1.5), then such as 1:
1。
In the preparation method of the copolymer, the ATRP reaction temperature can refer to the routine of such reaction of this field
Temperature, such as 50~80 DEG C, then such as 55 DEG C.
In the preparation method of the copolymer, in the ATRP reaction, the reaction time can refer to this field, and such is anti-
The reaction time answered, such as 2~8 hours, then such as 3h~5.5h.
In the preparation method of the copolymer, the ATRP after reaction, also can further include post-processing behaviour
Make.
The post-processing approach and condition can be the method and condition of the such post-reaction treatment routine in this field.Preferably
, it after reaction, is extracted, precipitates and/or dry；The solvent when extraction can be selected the dissolution compound 1*'s
Solvent；Such as tetrahydrofuran；
It is described to be precipitated as precipitating product the extraction phase solubilizer being obtained by extraction, supernatant liquor is outwelled, precipitating is taken
Object；Solvent when the described precipitating can be used the solvent for not dissolving the compound 1*, preferably -10 DEG C~0 DEG C just oneself
Alkane.
The drying is preferably dried in vacuo, and more preferable 45~60 DEG C of vacuum drying oven is dried.
The preparation method of the copolymer, also may include following steps: in solvent, by chain-transferring agent as shown in Equation 5,
Vinyl monomer and initiator carry out RAFT polymerization reaction under conditions of anhydrous and oxygen-free, are made described and gather as shown in formula 2*
Close object；The vinyl monomer is Vinyl Acetate Monomer and dibutyl maleate monomer；
In the present invention, the RAFT polymerization reaction refers to that Invertible ideal reacts, and operation can refer to
The routine operation of such reaction of this field, following operation specifically preferred according to the invention and method:
Anhydrous and oxygen-free condition in the RAFT polymerization reaction can be by screening out water process and excellent to reactant molecule
It selects the reaction vessel of sealing and is repeated as many times realization by vacuumizing-leading to protective gas；The preferred nitrogen of the protective gas
Gas.
In the RAFT polymerization reaction, the solvent can be various solvents used in the such reaction routine in this field,
Such as esters solvent (such as ethyl acetate).
In the RAFT polymerization reaction, the initiator can be various the drawing of this field Raolical polymerizable routine
Send out agent, such as azodiisobutyronitrile.
The RAFT polymeric reaction temperature can refer to the ordinary temperature of such reaction of this field, such as 60~80 DEG C, then
Such as 70 DEG C.
The RAFT polymerization reaction reaction time can refer to the reaction time of such reaction of this field, such as 24~48 is small
When.
In the RAFT polymerization reaction, the molar ratio of the chain-transferring agent and the vinyl monomer can be ability
The conventional amount used ratio of such reaction of domain, such as (1:20)~(1:150), then such as (1:30)~(1:110)；The acetic acid second
The molar ratio of allyl ester monomer and dibutyl maleate monomer is preferably (1:1).
In the RAFT polymerization reaction, preferably, the molar ratio of the chain-transferring agent and the initiator can be
The conventional amount used ratio of such reaction of this field, such as (1:0.1)~(1:0.4), then such as (1:0.1)~(1:0.2).
In the RAFT polymerization reaction, the vinyl monomer and the solvent quality ratio can refer to this field and be somebody's turn to do
The conventional amount used ratio of class reaction, such as 4:1.
After the RAFT polymerization reaction, post-processing operation also can further include.The post-processing approach and
Condition can be the method and condition of the such post-reaction treatment routine in this field, preferably, after reaction, being extracted, precipitate
And/or it is dry；The solvent when extraction can use the solvent for dissolving the compound 2*, such as ethyl acetate；It is described to be precipitated as
It precipitates product the extraction phase solubilizer being obtained by extraction, outwells supernatant liquor, taking precipitate；When the described precipitating
Solvent can be the solvent for not dissolving the compound 2*, such as preferably -10 DEG C~0 DEG C of n-hexane；The drying is preferred
Vacuum drying, more preferable 45~60 DEG C of vacuum drying oven are dried.
The present invention also provides the polymer as shown in formula 2*:
Number-average molecular weight < 6000g/mol of copolymer shown in the formula 2*；N=1~100, such as 3~30, then
Such as n=5~16.
Wherein, one structural unit of representation in each " () ", each structural unit are independent from each other；It is described
N indicate the degree of polymerization.
The polymer is one of random copolymer, alternate copolymer, block copolymer and graft copolymer or more
Kind, preferred block copolymer.
Polymer shown in the formula 2* is the intermediate of copolymer shown in the preparation formula 1*.
The present invention also provides a kind of preparation methods of polymer as shown in formula 2*, comprise the following steps:, will in solvent
Chain-transferring agent, vinyl monomer and initiator as shown in Equation 5 carries out RAFT polymerization reaction under conditions of anhydrous and oxygen-free, i.e.,
It can；The vinyl monomer is Vinyl Acetate Monomer and dibutyl maleate monomer；
In the present invention, the RAFT reaction refers to that Invertible ideal reacts, and operation can refer to ability
The routine operation of such reaction of domain, following operation specifically preferred according to the invention and method:
Anhydrous and oxygen-free condition in the RAFT polymerization reaction can be by screening out water process and excellent to reactant molecule
It selects the reaction vessel of sealing and is repeated as many times realization by vacuumizing-leading to protective gas；The preferred nitrogen of the protective gas
Gas.
In the RAFT polymerization reaction, the solvent can be various solvents used in the such reaction routine in this field,
Such as esters solvent (such as ethyl acetate).
In the RAFT polymerization reaction, the initiator can be various the drawing of this field Raolical polymerizable routine
Send out agent, such as azodiisobutyronitrile.
The RAFT polymeric reaction temperature can refer to the ordinary temperature of such reaction of this field, such as 60~80 DEG C, then
Such as 70 DEG C.
The RAFT polymerization reaction reaction time can refer to the reaction time of such reaction of this field, such as 24~48 is small
When.
In the RAFT polymerization reaction, the molar ratio of the chain-transferring agent and the vinyl monomer can be ability
The conventional amount used ratio of such reaction of domain, such as (1:20)~(1:150), then such as (1:30)~(1:110)；The acetic acid second
The molar ratio of allyl ester monomer and dibutyl maleate monomer is preferably (1:1).
In the RAFT polymerization reaction, preferably, the molar ratio ratio of the chain-transferring agent and the initiator can
For the conventional amount used ratio of such reaction of this field, such as (1:0.1)~(1:0.4)；Such as (1:0.1)~(1:0.2) again.
In the RAFT polymerization reaction, the vinyl monomer and the solvent quality ratio can refer to this field and be somebody's turn to do
The conventional amount used ratio of class reaction, such as (4:1).
After the RAFT polymerization reaction, post-processing operation also can further include.The post-processing approach and
Condition can be the method and condition of the such post-reaction treatment routine in this field, preferably, after reaction, being extracted, precipitate
And/or it is dry；The solvent when extraction can use the solvent for dissolving the compound 2*, such as ethyl acetate；It is described to be precipitated as
It precipitates product the extraction phase solubilizer being obtained by extraction, outwells supernatant liquor, taking precipitate；When the described precipitating
Solvent can be the solvent for not dissolving the compound 2*, such as preferably -10 DEG C~0 DEG C of n-hexane；The drying is preferred
Vacuum drying, more preferable 45~60 DEG C of vacuum drying oven are dried.
The present invention also provides copolymers shown in a kind of formula 1* to construct CO in high-pressure emulsification device2The side of/aqueous emulsion
Method comprising following steps: in high-pressure emulsification device, copolymer shown in formula 1* is mixed with deionized water, is filled with titanium dioxide
Carbon, stirring.
The preferred high pressure form kettle of high-pressure emulsification device, further preferred sapphire form.
This field conventional-volume, such as 10~40ml, then such as 37.49ml can be used in the high-pressure emulsification device volume.
It is described be filled with carbon dioxide the carbon dioxide of purity 99%~100% can be selected for example be using purity
99.95% carbon dioxide, the pressure for being filled with carbon dioxide can be 0~30MPa, such as 20MPa.
Copolymer shown in the formula 1* constructs CO in high-pressure emulsification device2The method of/aqueous emulsion can be in temperature
It is operated at 0~60 DEG C, such as 15~35 DEG C, then such as 25 DEG C.
It is added in stirrer cooperation external high pressure gear pump drive runner and follows in the preferred high-pressure emulsification device of the stirring
Ring；The mixing time can be 30min~60min, such as 45min.
CO is constructed in high-pressure emulsification device in the copolymer as shown in formula 1*2It is described in the method for/aqueous emulsion
CO2/ aqueous emulsion forms the volume fraction of the preferred dispersed phase carbon dioxide of effect (with phase CO in building height2/ aqueous emulsion is mesh
Mark), lotion formed need pressure carbon dioxide or CO2The characterizing methods such as/aqueous emulsion stability.
CO is constructed in high-pressure emulsification device in the copolymer as shown in formula 1*2It is described in the method for/aqueous emulsion
Carbon dioxide and the volume ratio of deionized water can be to construct CO in this field2Conventional ratio in the method for/aqueous emulsion, such as
(5:5)~(9:1), then such as (7:3)~(8:2).
CO is constructed in high-pressure emulsification device in the copolymer as shown in formula 1*2It is described in the method for/aqueous emulsion
Surfactant and deionized water mass ratio can for this field construct CO2Conventional ratio in the method for/aqueous emulsion, such as
(0.2:100)~(5:100), then such as (3:100)~(5:100).
The present invention also provides copolymers shown in formula 1* in building CO2Application in/aqueous emulsion.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that:
(1) surfactant of the invention is environmentally friendly, degradable and cost is relatively low；
(2) CO of surfactant of the invention building2/ aqueous emulsion CO2Volume fraction is high；It is long to stablize the time.
(3) amphiphilic surfactant's preparation method of the invention is easy to operate, poly- using Reversible Addition Fragmentation Chain Transfer
It closes (RAFT) to synthesize with atom transfer radical polymerization (ATRP) method, by adjusting water-wet side and parent CO2The degree of polymerization ratio at end
To adjust hydrophilic/parent CO2It balances (HCB).
Detailed description of the invention
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of polyvinyl acetate-alt- poly dibutyl ester in embodiment 3: wherein a-q is represented
In embodiment 3 in compound 2* each hydrogen ownership.
Fig. 2 is polyvinyl acetate-alt- poly dibutyl ester-b- polymethylacrylic acid dimethylamino in embodiment 3
The nucleus magnetic hydrogen spectrum figure of ethyl ester: wherein a-n represents the ownership of each hydrogen in compound 1* in embodiment 3.
Fig. 3 is the polyvinyl acetate-alt- poly dibutyl ester-b- polymethylacrylic acid diformazan ammonia in embodiment 3
The CO of base ethyl ester building2/ aqueous emulsion (before demulsification/demulsification after)
Fig. 4 is the CO of polyvinyl acetate-b- polymethylacrylic acid dimethylaminoethyl building2/ aqueous emulsion (before demulsification/
After demulsification)
Fig. 5 is the CO of Commercial surfactants TMN-6 building2/ aqueous emulsion (before demulsification/demulsification after)
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
Analysis test method is as follows:
Hydrogen nuclear magnetic resonance spectrum analysis
The structure that polymer is characterized using nuclear magnetic resonance spectroscopy (1H NMR), using deuterated chloroform as solvent, tetramethyl
Silane is measured with Bruker AV spectroscope 400MHz at room temperature as internal standard compound.
Gel permeation chromatograph analysis
The molecular weight of polymer is measured using 1100 gel permeation chromatograph of Agilent (GPC, U.S. Agilent) and is divided
Son amount distribution, using differential refraction detector and chromatographic column (5 μm of PL gel), using THF as mobile phase, flow 1.0ml/min,
Test temperature is 30 DEG C.
Embodiment 1
Step a), it takes ethylene glycol (3.10g), triethylamine (5.06g) and tetrahydrofuran (50ml) are in reactor, sealing
Reactor vacuumizes the oxygen in logical argon gas removing reactor.2- bromine propionyl is slowly added dropwise into mixture under the conditions of ice-water bath
Bromine (10.79g), drips and moves back ice-water bath, is stirred to react at room temperature for 24 hours.The salt that reaction generates is removed by suction filtration under vacuum, uses
Deionized water (3 × 50ml) washs organic phase three times, takes lower layer's organic phase anhydrous magnesium sulfate dry a few hours.Vacuum distillation removes
Weak yellow liquid is obtained after removing solvent, that is, compound 7 as follows is prepared；
Step b), take compound 7 (4.69g) obtained in above-mentioned steps a), excessive ehtyl potassium xanthate (5.17g) and
Acetone (60ml) seals reactor, vacuumizes the oxygen in logical argon gas removing system, be stirred to react down at room temperature in reactor
12h.The salt that reaction generates is removed by suction filtration under vacuum, washs organic phase three times with distilled water (3 × 50ml), takes lower layer's organic phase nothing
Water magnesium sulfate dries a few hours.Vacuum distillation obtains yellow oily liquid after removing solvent, that is, chemical combination as follows is prepared
Object 8；
Step c), compound 8 (4.23g) obtained in above-mentioned steps b), triethylamine (1.80g) and methylene chloride are taken
(50ml) seals reactor, vacuumizes the oxygen in logical argon gas removing system in reactor.Slowly to mixed under the conditions of ice-water bath
It closes in object and 2 bromo propionyl bromide (3.83g) is added dropwise, drip and move back ice-water bath, be stirred to react at room temperature for 24 hours.With 10% chlorination
Ammonium salt solution (3 × 50ml), 5%NaHCO3Solution (3 × 50ml), deionized water (3 × 50ml) wash organic phase, and with anhydrous sulphur
Sour magnesium dry a few hours.Vacuum distillation obtains 6.30g difunctional RAFT reagent S- (1- methyl -4- hydroxyl second after removing solvent
Acetoacetic ester) O- ethyl dithiocarbonates, i.e., compound shown in formula 5 as follows, yield 87%, purity 98%.
Embodiment 2
A), RAFT reagent S- obtained in Example 1 (1- methyl -4- hydroxyl ethyl acetate) O- ethyl dithiocarbonic acids
Ester (1.00g, 0.0027mol), vinylacetate (4.62g, 0.054mol), dibutyl maleate (12.24g, 0.054mol),
Azodiisobutyronitrile (0.044g, 0.00027mol) and ethyl acetate (4.22g) seal reactor in reactor, take out true
The logical argon gas of the sky oxygen in removing system in triplicate.48h is stirred to react at 70 DEG C.Obtained organic phase is reacted in ice n-hexane
The polymer of middle precipitating, precipitating is dissolved with ethyl acetate, is precipitated in ice n-hexane, and rear taking precipitate is placed in vacuum baking in triplicate
48h is dried in case, obtains the i.e. compound 2* of polymer poly vinylacetate-alt- poly dibutyl ester that molecular weight is 2257
(degree of polymerization 6), yield 81%, purity 96%.
Embodiment 3
A), RAFT reagent S- obtained in Example 1 (1- methyl -4- hydroxyl ethyl acetate) O- ethyl dithiocarbonic acids
Ester (1.00g, 0.0027mol), vinylacetate (3.46g, 0.040mol), dibutyl maleate (9.18g, 0.040mol),
Azodiisobutyronitrile (0.044g, 0.00027mol) and ethyl acetate (3.16g) seal reactor in reactor, take out true
The logical argon gas of the sky oxygen in removing system in triplicate.48h is stirred to react at 70 DEG C.Obtained organic phase is reacted in ice n-hexane
The polymer of middle precipitating, precipitating is dissolved with ethyl acetate, is precipitated in ice n-hexane, and rear taking precipitate is placed in vacuum baking in triplicate
48h is dried in case, obtains the polymer poly vinylacetate-alt- poly dibutyl ester i.e. compound that molecular weight is 1943
2*, the degree of polymerization 5, yield 80%.
The structure of compound 2* is as follows, is identified by nucleus magnetic hydrogen spectrum, and wherein the ownership of hydrogen is shown in attached drawing 1.
The hydrogen modal data of compound 2*:
1H NMR(400MHz,CDCl3)δ(ppm):0.93(m,CH 3-CH2),1.18(d,CH 3-CH),1.25(t,3H,
CH 3-CH2-O),1.40(m,CH3-CH 2),1.61(s,CH2-CH 2-CH2),1.84(t,CH 3-CH-Br),2.05(m,CH 3-C,
CH-CH 2-S),2.26(d,CH-CH3),2.78(t,C-CH),4.06(s,CH2-CH 2-O),4.40(d,CH2-CH 2-O,C-CH-
Br),4.62(t,CH3-CH 2-O),5.06(s,CH2-CH-O),6.58(s,CH2-CH-O)
B), the polyvinyl acetate-alt- poly dibutyl ester (0.50g) that the n for taking previous step to react is 5, first
Base acrylic acid dimethylamine ethyl ester (2.43g) and methyl phenyl ethers anisole (2.43g) seal reactor in reactor, in the item of logical argon gas
Under part, be added (N, N, N ', N ', N "-pentamethyl-diethylenetriamine) (0.089g) and stannous chloride (0.025g), vacuumize logical argon
Oxygen in gas removing system, is stirred to react 3.0h at 55 DEG C.Obtained organic phase is reacted to precipitate in ice n-hexane, precipitating
Polymer is first dissolved with tetrahydrofuran, then is precipitated with ice n-hexane, is placed in vacuum drying oven dries 48h in triplicate, divided
Amphiphilic polymer polyvinyl acetate-alt- poly dibutyl ester-b- polymethylacrylic acid diformazan the ammonia that son amount is 3515
Base ethyl ester, that is, compound 1*, yield 80%, n 5, m 10.
The structure of compound 1* is as follows, is identified by nucleus magnetic hydrogen spectrum, and wherein the ownership of hydrogen is shown in attached drawing 2.
The hydrogen modal data of compound 1*:
1H NMR(400MHz,CDCl3)δ(ppm):0.93(t,CH 3-CH2),1.05(s,CH 3-C),1.35(m,CH3-
CH 2),1.61(s,CH2-CH 2-CH2),1.95(m,CH-CH 2-S,CH 3-C,CH-CH 2-C),2.29(t,CH 3-N,CH 3-CH),
2.57(t,CH2-CH 2-N),2.78(t,C-CH),4.06(t,CH2-CH 2-O),5.06(s,CH2-CH-O)。
Embodiment 4
A), RAFT reagent S- obtained in Example 1 (1- methyl -4- hydroxyl ethyl acetate) O- ethyl dithiocarbonic acids
Ester (1.00g, 0.0027mol), vinylacetate (6.92g, 0.080mol), dibutyl maleate (18.36g, 0.080mol),
Azodiisobutyronitrile (0.044g, 0.00027mol) and ethyl acetate (6.32g) seal reactor in reactor, take out true
The logical argon gas of the sky oxygen in removing system in triplicate.48h is stirred to react at 70 DEG C.Obtained organic phase is reacted in ice n-hexane
The polymer of middle precipitating, precipitating is dissolved with ethyl acetate, is precipitated in ice n-hexane, and rear taking precipitate is placed in vacuum baking in triplicate
48h is dried in case, obtains the polymer poly vinylacetate-alt- poly dibutyl ester i.e. compound that molecular weight is 2887
2*, the degree of polymerization 8, yield 89%.
B), the polyvinyl acetate-alt- poly dibutyl ester (0.36g) that the n for taking previous step to react is 8, first
Base acrylic acid dimethylamine ethyl ester (1.18g) and methyl phenyl ethers anisole (1.18g) seal reactor in reactor, in the item of logical argon gas
Under part, be added (N, N, N ', N ', N "-pentamethyl-diethylenetriamine) (0.043g) and stannous chloride (0.012g), vacuumize logical argon
Oxygen in gas removing system, is stirred to react 5.5h at 55 DEG C.Obtained organic phase is reacted to precipitate in ice n-hexane, precipitating
Polymer is first dissolved with tetrahydrofuran, then is precipitated with ice n-hexane, is placed in vacuum drying oven dries 48h in triplicate, divided
Amphiphilic polymer polyvinyl acetate-alt- poly dibutyl ester-b- polymethylacrylic acid diformazan the ammonia that son amount is 5715
Base ethyl ester, that is, compound 1*, yield 79%.N is 8, m 22.
Embodiment 5
A) RAFT reagent S- obtained in Example 1 (1- methyl -4- hydroxyl ethyl acetate) O- ethyl dithiocarbonic acids
Ester (1.00g, 0.0027mol), vinylacetate (9.23g, 0.11mol), dibutyl maleate (24.48g, 0.11mol) are even
Nitrogen bis-isobutyronitrile (0.066g, 0.00040mol) and ethyl acetate (8.43g) seal reactor, vacuumize in reactor
The logical argon gas oxygen in removing system in triplicate.48h is stirred to react at 70 DEG C.Obtained organic phase is reacted in ice n-hexane
Precipitating, the polymer of precipitating are dissolved with ethyl acetate, are precipitated in ice n-hexane, and rear taking precipitate is placed in vacuum drying oven in triplicate
Middle drying 48h obtains the polymer poly vinylacetate-alt- poly i.e. compound 2* of dibutyl ester that molecular weight is 4141,
The degree of polymerization is 12, yield 87%.
B) polyvinyl acetate-alt- poly dibutyl ester (0.80g) that the n for taking previous step to react is 12, first
Base acrylic acid dimethylamine ethyl ester (1.82g) and methyl phenyl ethers anisole (1.82g) seal reactor in reactor, in the item of logical argon gas
Under part, be added (N, N, N ', N ', N "-pentamethyl-diethylenetriamine) (0.067g) and stannous chloride (0.019g), vacuumize logical argon
Oxygen in gas removing system, is stirred to react 4.0h at 55 DEG C.Obtained organic phase is reacted to precipitate in ice n-hexane, precipitating
Polymer is first dissolved with tetrahydrofuran, then is precipitated with ice n-hexane, is placed in vacuum drying oven dries 48h in triplicate, divided
Amphiphilic polymer polyvinyl acetate-alt- poly dibutyl ester-b- polymethylacrylic acid diformazan the ammonia that son amount is 6814
Base ethyl ester, that is, compound 1*, yield 83%, n 12, m 17.
Embodiment 6
RAFT reagent S- obtained in Example 1 (1- methyl -4- hydroxyl ethyl acetate) O- ethyl dithiocarbonates
(1.00g, 0.0027mol), vinylacetate (12.69g, 0.15mol), dibutyl maleate (33.66g, 0.054mol) are even
Nitrogen bis-isobutyronitrile (0.088g, 0.00054mol) and ethyl acetate (11.59g) seal reactor, vacuumize in reactor
The logical argon gas oxygen in removing system in triplicate.48h is stirred to react at 70 DEG C.Obtained organic phase is reacted in ice n-hexane
Precipitating, the polymer of precipitating are dissolved with ethyl acetate, are precipitated in ice n-hexane, and rear taking precipitate is placed in vacuum drying oven in triplicate
Middle drying 48h obtains the polymer poly vinylacetate-alt- poly i.e. compound 2* of dibutyl ester that molecular weight is 5402,
Polymerization degree n is 16, yield 92%.
Comparative example 1
A), RAFT reagent S- obtained in Example 1 (1- methyl -4- hydroxyl ethyl acetate) O- ethyl dithiocarbonic acids
Ester (0.30g), vinylacetate (4.85g), azodiisobutyronitrile (0.053g) and ethyl acetate (1.21g) are in reactor
In, reactor is sealed, under conditions of logical argon gas, the oxygen in logical argon gas removing system is vacuumized, is stirred to react at 70 DEG C
13h.It reacts obtained organic phase to precipitate in ice n-hexane, the polymer of precipitating is dissolved with ethyl acetate, heavy in ice n-hexane
It forms sediment, rear taking precipitate is placed in vacuum drying oven drying 48h in triplicate, obtains the polyvinyl acetate that molecular weight is 1750, such as
Compound shown in following formula 2, yield 85%；Polymerization degree n=16.
B), the polyvinyl acetate (0.40g) for taking previous step to react, dimethylaminoethyl methacrylate (2.16g),
And methyl phenyl ethers anisole (2.16g) seals reactor in reactor, under conditions of logical argon gas, be added (N, N, N ', N ', N "-five
Methyl diethylenetriamine) (0.079g) and stannous chloride (0.023g), the oxygen in logical argon gas removing system is vacuumized, at 55 DEG C
It is stirred to react 5h.It reacts obtained organic phase to precipitate in ice n-hexane, the polymer of precipitating is first dissolved with tetrahydrofuran, then is used
Ice n-hexane precipitating, is placed in vacuum drying oven dries 48h in triplicate, obtains the polymer poly vinyl acetate that molecular weight is 4423
Ester-b- polymethylacrylic acid dimethylaminoethyl, the compound as shown in following formula 1, yield 78%.N=16, m=17
Effect example 1
A), the polyvinyl acetate-alt- poly dibutyl ester-b- polymethylacrylic acid two synthesized in Example 3
The hydrochloric acid (two drops) that methylamino ethyl ester (0.23g, the 3wt% of water), deionized water (7.48g) and concentration are 1mol/L is in high pressure
In form kettle, controlled at 25 DEG C, form kettle is sealed.It is filled with high-purity (99.95%) carbon dioxide emulsifier unit body of 20MPa
Product is 37.49ml, and the volume for being filled with water is 37.49*1/5=7.50ml, and 25 DEG C of density being lauched are 997.3g/cm3, water is added
Quality be 7.48g, CO2Volume be 37.49*4/5=29.99ml.It drives in runner and flows under the action of high-pressure gear pump
Body circulation, in addition fluid acutely disturbs under the action of magnetic stirring apparatus in kettle, and stirring 45min or so after closing stirring, passes through
For sapphire form observation kettle it can be found that stable emulsion can be formed, volume dispersion rate is 80%, and stablizing the time is 5.5h.
Effect example 2
A), the polyvinyl acetate-alt- poly dibutyl ester-b- polymethylacrylic acid two synthesized in Example 3
The hydrochloric acid (two drops) that methylamino ethyl ester (0.45g, the 4wt% of water), deionized water (11.22g) and concentration are 1mol/L is in height
It presses in form kettle, emulsifier unit volume is 37.49ml, controlled at 25 DEG C, seals form kettle.It is filled with the high-purity of 20MPa
(99.95%) carbon dioxide, the volume for being filled with carbon dioxide is 26.24ml, and the volume of water is 11.25ml, in high-pressure gear pump
Under the action of drive runner in fluid circulation, in addition fluid acutely disturbs under the action of magnetic stirring apparatus in kettle, stir 45min
Kettle after closing stirring, is observed by sapphire form it can be found that stable emulsion can be formed in left and right, and volume dispersion rate is 70%,
Stablizing the time is 4.6h.
Effect example 3
A), the polyvinyl acetate-alt- poly dibutyl ester-b- polymethylacrylic acid two synthesized in Example 5
The hydrochloric acid (two drops) that methylamino ethyl ester (0.23g, the 3wt% of water), deionized water (7.48g) and concentration are 1mol/L is in high pressure
In form kettle, controlled at 25 DEG C, form kettle is sealed.It is filled with high-purity (99.95%) carbon dioxide emulsifier unit body of 20MPa
Product is 37.49ml, and the volume for being filled with water is 37.49*1/5=7.50ml, and 25 DEG C of density being lauched are 997.3g/cm3, water is added
Quality be 7.48g, CO2Volume be 37.49*4/5=29.99ml.It drives in runner and flows under the action of high-pressure gear pump
Body circulation, in addition fluid acutely disturbs under the action of magnetic stirring apparatus in kettle, and stirring 45min or so after closing stirring, passes through
For sapphire form observation kettle it can be found that stable emulsion can be formed, volume dispersion rate is 80%, and stablizing the time is 18h.
Effect example 4
A), the polyvinyl acetate-alt- poly dibutyl ester-b- polymethylacrylic acid two synthesized in Example 4
The hydrochloric acid (two drops) that methylamino ethyl ester (0.23g, the 3wt% of water), deionized water (7.48g) and concentration are 1mol/L is in high pressure
In form kettle, controlled at 25 DEG C, form kettle is sealed.It is filled with high-purity (99.95%) carbon dioxide emulsifier unit body of 20MPa
Product is 37.49ml, and the volume for being filled with water is 37.49*1/5=7.50ml, and 25 DEG C of density being lauched are 997.3g/cm3, water is added
Quality be 7.48g, CO2Volume be 37.49*4/5=29.99ml.It drives in runner and flows under the action of high-pressure gear pump
Body circulation, in addition fluid acutely disturbs under the action of magnetic stirring apparatus in kettle, and stirring 45min or so after closing stirring, passes through
For sapphire form observation kettle it can be found that stable emulsion can be formed, volume dispersion rate is 80%, and stablizing the time is 48h.
Contrast on effect example 1
Take synthesized in comparative example embodiment 1 polyvinyl acetate-b- polymethylacrylic acid dimethylaminoethyl (0.23g,
The 3wt% of water), the hydrochloric acid (two drops) that deionized water (7.48g) and concentration are 1mol/L is in high pressure form kettle, emulsifier unit
Volume is 37.49mL, controlled at 25 DEG C, seals form kettle.It is filled with high-purity (99.95%) carbon dioxide of 20MPa, CO2
Volume be 29.99mL, the volume of water is 7.50mL.Fluid circulation in runner is driven under the action of high-pressure gear pump, in addition
Fluid acutely disturbs under the action of magnetic stirring apparatus in kettle, and stirring 45min or so closes stirring, seen by sapphire form
Kettle is examined it can be found that stable emulsion can be formed, volume dispersion rate is 80%, and stablizing the time is 2.2h.
Contrast on effect example 2
Take Commercial surfactants TMN-6 (0.37g, the 5wt% of water), deionized water (7.48g) in high pressure form kettle,
Emulsifier unit volume is 37.49mL, controlled at 25 DEG C, seals form kettle.It is filled with high-purity (99.95%) dioxy of 20MPa
Change carbon, CO2Volume be 29.99ml, the volume of water is 7.50mL.Fluid in runner is driven to follow under the action of high-pressure gear pump
Ring, in addition fluid acutely disturbs under the action of magnetic stirring apparatus in kettle, and stirring 45min or so is observed by sapphire form
Lotion formational situation in kettle and in runner, closes stirring, can form stable emulsion, volume dispersion rate is 80%, stablizes the time
No more than half an hour.
Partial data in said effect embodiment see the table below:
Pass through dispersed phase (CO in the present invention2) volume fraction, the lotion building indexs such as pressure and emulsion-stabilizing time
Characterize CO2The effect of/aqueous emulsion.CO2Volume fraction higher (height in phase), lotion building pressure is lower and the emulsion-stabilizing time
It is longer, indicate that the lotion effect of surfactant building is better.
By Fig. 3 it can be seen that, by polyvinyl acetate-alt- poly dibutyl ester-b- polymethylacrylic acid diformazan ammonia
Base ethyl ester can construct phase CO in stable height2/ aqueous emulsion, CO2Volume fraction can reach 80%, emulsion-stabilizing after stirring stops
Time can reach 48h.
By Fig. 4 it can be seen that, by polyvinyl acetate-b- polymethylacrylic acid dimethylaminoethyl construct CO2/ water and milk
Liquid, CO2Volume fraction maximum can reach 80%.2.2 small layereds (demulsification) after stirring stops.
Fig. 5 can see, and stable CO can be constructed by Commercial surfactants2/ aqueous emulsion, CO2Volume fraction maximum can
Reach 80%.But stablize the time no more than half an hour.
In conclusion amphiphilic surfactant shown in the formula 1* synthesized in the present invention can largely improve institute
The CO of building2The stabilization time of lotion, and energy can be improved in the addition of the stability of/aqueous emulsion, i.e. poly dibutyl ester-segment
The stable emulsion of phase in building height.In addition, as hydrocarbon class surfactant, compared to fluorine-containing and siliceous surfactant
Have the advantages that environmental-friendly, degradable and low in cost.
Claims (12)
1. copolymer shown in formula 1*:
Number-average molecular weight < 8000g/mol of copolymer shown in the formula 1*；N=1~100；M=1~100.
2. polymer shown in formula 1* as described in claim 1, it is characterised in that: n=3~30.
3. polymer shown in formula 1* as claimed in claim 2, it is characterised in that: n=5~16.
4. polymer shown in formula 1* as claimed in any one of claims 1-3, it is characterised in that: m=5~40.
5. polymer shown in formula 1* as claimed in claim 4, it is characterised in that: m=10~22.
6. the preparation method of polymer shown in formula 1* according to any one of claims 1 to 5, which is characterized in that comprising with
Lower step: under the conditions of anhydrous and oxygen-free, in organic solvent, under the action of catalyst and ligand, by polymer shown in formula 2* and formula 3
Shown compound carries out ATRP reaction；
7. preparation method as claimed in claim 6, which is characterized in that the organic solvent in the ATRP reaction is aromatic ether
Class solvent；And/or the catalyst is stannous chloride and/or cuprous bromide；And/or the ligand is N, N, N, N, N-
Five methyl diethylentriamine and/or 1,1,4,7,10,10- hexamethyl trien；And/or shown in the formula 2*
Polymer and 3 compound represented of formula molar ratio be 1:40~1:70；And/or compound shown in the formula 3 with
The molar ratio of the catalyst is 1:0.5~1:2；And/or polymer shown in the formula 2* and the ligand rub
You are than being 1:0.5~1:2；And/or the mass ratio of compound shown in the formula 3 and the organic solvent be 1:0.67~
1:1.5；And/or the ATRP reaction temperature is 50~80 DEG C；And/or the ATRP reaction time is 2~8 hours.
8. preparation method as claimed in claim 7, which is characterized in that the organic solvent in the ATRP reaction is benzene first
Ether；And/or the molar ratio of polymer shown in the formula 2* and 3 compound represented of formula is 1:60；And/or it is described
Formula 3 shown in the molar ratio of compound and the catalyst be 1:1；And/or polymer shown in the formula 2* with it is described
Ligand molar ratio be 1:2；And/or the mass ratio of compound shown in the formula 3 and the organic solvent is 1:1；
And/or the ATRP reaction temperature is 55 DEG C；And/or the ATRP reaction time is 3 hours~5.5 hours.
9. preparation method as claimed in claim 7, which is characterized in that also comprise the following steps:, will be as shown in Equation 5 in solvent
Chain-transferring agent, vinyl monomer and initiator RAFT polymerization reaction is carried out under conditions of anhydrous and oxygen-free, be made it is described as
Polymer shown in formula 2*；The vinyl monomer is Vinyl Acetate Monomer and dibutyl maleate monomer；
10. preparation method as claimed in claim 9, which is characterized in that in the RAFT polymerization reaction, the solvent is
Esters solvent；And/or the initiator is azodiisobutyronitrile；And/or the RAFT polymeric reaction temperature be 60~
80℃；And/or the RAFT polymerization reaction reaction time is 24~48 hours；And/or the chain-transferring agent with it is described
Vinyl monomer molar ratio be 1:20~1:150；And/or the Vinyl Acetate Monomer and dibutyl maleate list
The molar ratio of body is 1:1；And/or the molar ratio of the chain-transferring agent and the initiator is 1:0.1~1:0.4；With/
Or, the vinyl monomer and the solvent quality ratio are 4:1.
11. preparation method as claimed in claim 10, which is characterized in that in the RAFT polymerization reaction, the solvent
For ethyl acetate；And/or the RAFT polymeric reaction temperature is 70 DEG C；And/or the chain-transferring agent and the second
The molar ratio of alkenyl monomer is 1:30~1:110；And/or the molar ratio of the chain-transferring agent and the initiator is 1:
0.1~1:0.2.
12. copolymer shown in formula 1* according to any one of claims 1 to 5 is in building CO2Application in/aqueous emulsion.
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Non-Patent Citations (4)
| Title |
|---|
| Synthesis and Phase Behavior of CO2-Soluble Hydrocarbon Copolymer: Poly(vinyl acetate-alt-dibutyl maleate);Hyunsuk Lee，等;《Macromoleculars》;20100204;第43卷(第5期);第2278右栏第2-3段，第2278页图3，第2279页表3 |
| Synthesis of a CO2-philic poly(vinyl acetate)-based cationic amphiphilic surfactant by RAFT/ATRP and its application in preparing monolithic materials;Zhang Shoucun;《Green Chemistry》;20140716;第16卷(第9期);第4406-4412页 |
| Synthesis of poly(vinyl acetate) block copolymers by successive RAFT and ATRP with a bromoxanthate iniferter;Renaud Nicolay，等;《Chemical Communications》;20080918;第5336页图1，第5336页右栏第2段，第5337页左栏倒数第一段 |
| 醋酸乙烯酯类亲二氧化碳碳氢聚合物的合成及其应用;张守村;《中国博士学位论文全文数据库工程科技Ⅰ辑（月刊）》;20150215(第02期);B014-20 |
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