CN104610083B - Branch skeleton monomer that one is core with 2,4-diacetyl-3-(4-bromophenyl) ethyl glutarate and preparation method thereof and application - Google Patents
Branch skeleton monomer that one is core with 2,4-diacetyl-3-(4-bromophenyl) ethyl glutarate and preparation method thereof and application Download PDFInfo
- Publication number
- CN104610083B CN104610083B CN201510065283.2A CN201510065283A CN104610083B CN 104610083 B CN104610083 B CN 104610083B CN 201510065283 A CN201510065283 A CN 201510065283A CN 104610083 B CN104610083 B CN 104610083B
- Authority
- CN
- China
- Prior art keywords
- product
- reaction
- generation product
- generation
- core
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides the branch skeleton monomer that one is core with 2,4-diacetyl-3-(4-bromophenyl) ethyl glutarate, molecular formula is as shown in I; The preparation method of described resin matrix monomer is also provided, first adopt 2, modification is carried out in 4-diacetyl-3-(4-bromophenyl) ethyl glutarate and aliphatic diamine mixing, make reaction core, alternate grafting on reaction core again, generate successively 0.5 generation product, 1 generation product, 1.5 generation product, 2 generation product and 2.5 generation product, finally generate 3 generation product, i.e. branch skeleton monomer of the present invention; Wherein in preparation half in the process for product, employing methyl acrylate is reactant; In the process of the whole generation reaction of preparation, employing aliphatic diamine is reactant. The resin matrix monomer that the present invention makes has rigid structure main chain, thereby has good anti-salt property and heat endurance, is applied in effect in oil field displacement of reservoir oil polymer and promotes to some extent.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of with 2,4-diacetyl-3-(4-bromophenyl) ethyl glutarateFor branch skeleton monomer of core and preparation method thereof and application.
Background technology
Dendritic macromole (Dendrimer) is the novel synthetic macromolecule of a class of 20th century the mid-80 appearance, and it hasHeight geometrical symmetry structure, surface has a large amount of functional groups and controlled internal cavities simultaneously, be a class three-dimensional, canTo control, to design the Novel polymer of bulk of molecule, shape, 26S Proteasome Structure and Function group from molecular level. TreeThe large molecular proportion tradition of shape macromolecule has better monodispersity, amorphism and dissolubility, and mutually twines due to intermolecularKnot is few, and viscosity pole is low, has its end and can import a large amount of various features such as reactivity or functional groups. Only based on theseSpecial structure and character feature, scientists utilizes molecular design theory that the functional group with difference in functionality is introduced to large molecule masterChain or side chain, become the macromolecular material with photosensitive function, magnetic function or conducting function, in large molecule, introducesThe group of response type, makes various polymer reactants, polymer catalyst, is used as sustained release agent and polymer drug pharmaceutically,Become the study hotspot in field.
Dendritic macromole has special morphosis, and its synthetic method is different from linear macromolecule. From exploitation tree in 1985Since dendritic macromolecules, the dendritic macromole of various structures is synthesized. Accurately control the growth of strand in space,Taking suitable synthetic method is the key of synthesizing. The synthetic method of the dendritic macromole having worked out at present, mainly contains to be sent outArching pushing, convergence method, disperse convergence share method etc.
(1) disperse method
What Tomalia and Newkome worked out disperses synthetic route. What is called is dispersed synthetic method, from dendritic macromoleCentral point starts, and outside expansion is step by step synthesized. The first synthetic incipient nucleus of the method, then centered by incipient nucleus byWalk grafting outward, originally only have an active growth point to develop into the next generation and can generate two or three and there is same activityGrowth point.
Disperse synthetic method and place outside very conveniently for introducing functional group, but shortcoming is also clearly, and reaction increases progressionLarger, required reactive functionality number is more, and sterically hindered have certain influence to the reaction of introducing branching unit, easily makesThereby not exclusively allowing molecule produce defect, reaction of propagation affects productive rate. React completely if make, need more harsh reaction conditionWith excessive reagent, so the purifying of product has again certain difficulty.
(2) convergence method
Frechet and Miller etc. have and have worked out new synthetic route after the method for dispersing--convergence synthetic method. Convergence synthetic method be withThe method that the method for dispersing is corresponding, this method, from the peripheral limb part of required synthetic dendritic macromole, is inwardly carried out anti-Should.
Restrain synthetic method and be with respect to the advantage of the method for dispersing, the reaction nodes of every generation reaction is limited, thereby can obtainThe product of higher single degree of scatter, the easier purifying of product and the sign that synthesize than the method for dispersing simultaneously. But shortcoming is, withThe continuous increase of algebraically, the sterically hindered also increase accordingly that central point reactive group is suffered, easily hinders the further of reactionCarry out, make its synthetic macromolecular structure large be not as synthetic as what disperse synthetic method.
(3) disperse convergence share method
This method combines the advantage of first two method. Generally first making the dendroid that is called " hypernucleus " in low generation by the method for dispersing divides greatlySon, then with the synthetic algebraically needing of convergence method be called " monomer of branching " fan-shaped dendrimer, then by the " list of branchingBody " receive on " hypernucleus ".
Kawaguch usesSiMe3 is transformed into hydrogen (H) as a kind of monomer, willEt2N-N=N-changes over iodine (I) as another kind of monomer, and both slough HI at reaction, can obtain the dendroid of polyphenylacetylene skeletonLarge molecule.
At present, synthetic main employing of dendritic macromole dispersed to method synthesis mode both at home and abroad, but with regard to dendrimer structure, in the time that main chain and side chain are all shorter linear flexible chain, because being curling shape on linear chain tool flexibility space, to wholeIndividual molecule, end participates in the functional group of reaction because steric effect is reacted and can be decreased, and may cause ultimate yieldLower. And along with the continuous increase of algebraically, the degree that participates in reaction is also more difficult, known be used in the branch in oil fieldThe high energy of large molecule is to three generations, and pure chemistry synthetic on, during industry is synthetic, also can only arrive ten generations just again difficulty continue to have reacted.
Due to the dendrimer networks structure in the special ball-type space of dendritic, it should have reasonable anti-shear ability,Can solve the requirement of polymer flooding to polymer oil-displacing agent anti-shear performance. But the dendritic macromole of application is due to knot at presentSterically hindered large on structure, linear chain reaction is more difficult, thereby molecular weight is low, and therefore the viscosity of dendritic is with respect to oilThe viscosity of the desired polymer of the field displacement of reservoir oil is still aobvious less. Therefore, if dendritic is applied in the displacement of reservoir oil of oil field,The viscosity that improves dendritic, making it to meet the displacement of reservoir oil is the most important condition with requiring, good salt-resistant temperature performance and strongerFluidity control ability be crucial. And the main chain and the side chain that are applied at present the dendritic polymers in oil field are linear flexible chain mostlyStructure, puies forward the anti-shearing heat resistance of high capability of anti-salt limited.
Summary of the invention
For prior art above shortcomings, the object of this invention is to provide a kind of have rigid structure main chain with 2,4-bis-Acetyl group-3-(4-bromophenyl) ethyl glutarate (Diethyl2,4-diacetyl-3-(4-bromophenyl) pentanedioate) isBranch skeleton monomer of core and preparation method thereof.
The present invention also provides the application of above-mentioned branch skeleton monomer.
Realize above-mentioned purpose, the present invention adopts following technical scheme: a kind of with 2,4-diacetyl-3-(4-bromophenyl) glutaric acid twoEthyl ester is the branch skeleton monomer of core, and molecular formula is as shown in I:
The preparation method of the described branch skeleton monomer that is core with 2,4-diacetyl-3-(4-bromophenyl) ethyl glutarate, comprisesFollowing steps:
1) 2,4-diacetyl-3-(4-bromophenyl) ethyl glutarate and aliphatic diamine are mixed, at ice-water bath magnetic stirring apparatusMiddle lucifuge reaction 24～25 hours, after reaction finishes, removes reaction dissolvent with rotary evaporator decompression distillation, and adds methyl alcoholRepeatedly revolve steaming, obtain glassy yellow solid, be i.e. the peripheral reaction core with functional group that can grafting; Wherein, aliphatic diamine bothAs solvent again as reactant, 2,4-diacetyl-3-(4-bromophenyl) ethyl glutarate and participate in the aliphatic diamine that reactsMol ratio be 1:2～3;
2) using step 1) gained reaction core is abundant as dissolution with solvents with methyl alcohol, with constant voltage separatory funnel in the solution of reaction coreDrip methyl acrylate, at normal temperatures with magnetic stirring apparatus reaction 24～25 hours, after reaction finishes, rotation for purification by liquid extractionEvaporimeter decompression distillation, and add methyl alcohol repeatedly to revolve steaming, obtains yellow solid, 0.5 generation product; Wherein 0 generation product and propyleneThe mol ratio of acid methyl esters is 1～1.5:3～4.5;
3) by step 2) gained 0.5 generation product continues that to make dissolution with solvents with methyl alcohol abundant, drips aliphatic with constant voltage separatory funnelDiamines, with magnetic stirring apparatus reaction 24～25 hours, after reaction finishes, purification by liquid extraction reduced pressure with rotary evaporator at normal temperaturesDistillation, and adds methyl alcohol repeatedly to revolve steaming, obtains yellow solid, 1 generation product; Wherein, 0.5 generation product and aliphatic diamineMol ratio is 1～1.2:6-8;
4) alternately generate successively 1.5 generations, 2 generations and 2.5 generation product, finally generate 3 generation product, i.e. product shown in formula I; Wherein,Prepare each generation when product, all previous generation product is made to dissolution with solvents with methyl alcohol abundant, drip with constant voltage separatory funnel in molar ratioReactant, reacts with magnetic stirring apparatus at normal temperatures, after reaction finishes, and purification by liquid extraction rotary evaporator decompression distillation,And add methyl alcohol repeatedly to revolve steaming, obtain each generation product; Described reactant, in the process in preparation half for product, is acrylic acidMethyl esters; In the process of the whole generation reaction of preparation, it is aliphatic diamine;
Wherein, 1.5 generations of preparation are when product, 1 generation product and the mol ratio of methyl acrylate be 1～1.5:8～12, the reaction time is 36～37Hour, obtain faint yellow solid, 1.5 generation product;
Prepared for 2 generations when product, 1.5 generation product and the mol ratio of aliphatic diamine be 1～1.2:10～12, the reaction time is 36～37Hour, obtain yellow solid, 2 generation product;
Prepared for 2.5 generations when product, 2 generation product and the mol ratio of methyl acrylate be 1～1.5:16～20, the reaction time is 48～49Hour, obtain buff solid, 2.5 generation product;
Prepared for 3 generations when product, 2.5 generation product and the mol ratio of aliphatic diamine be 1～1.2:18～20, the reaction time is 48～49Hour, obtain brown color coagulation, 3 generation product.
Above-mentioned resin matrix monomer, the application in oil field displacement of reservoir oil polymer.
Compared to existing technology, the present invention has following beneficial effect:
1, the present invention carries out modification with the little molecule with rigid structure, participates in the synthetic of dendrimer, makes dendrimerCenter main chain be no longer flexible chain but the little molecule of rigid structure, and then improved the anti-salt anti-shear performance of dendrimer.
2, the large molecule of dendritic network monomer that the present invention makes has rigid structure, and its performance is just by center main chain rigidity structureAnd Side Chain Flexibility chain embodies jointly, and rigid structure has impact to whole large molecule and even polymer. Increase strand rigidity,Can stop it under high salinity, chain to occur curling, improve the anti-salt property of polymer, the heat that can increase macromolecular chain is simultaneously steadyQualitative, make its aqueous solution can at high temperature keep higher viscosity. Even in ageing process with molecule chain break, because of rigidityThe steric effect of group, molecular motion resistance is large, and it is also less that the apparent viscosity of polymer solution reduces amplitude.
3, branch skeleton monomer unimolecule the present invention being made is applied in oil field displacement of reservoir oil polymer, divides with the polymer of rigiditySon has toughening effect to the polymeric matrix of rigidity. Kurauchi and Inoue etc. have proposed " cold for the toughness reinforcing phenomenon of rigid moleculeMachine drawing reason ": in the time that polymer is subject to External Force Acting, the compression stress that dispersed phase particles is subject to producing perpendicular to stress directionEffect, in the time that this compression stress is enough large, can there is fragility-ductility transmition in the dispersed phase particles of rigidity, or cause decentralized photo grainThe son surrender of matrix around (or simultaneously occurring), and in deformation process, absorb a large amount of energy, thus it is anti-that polymer is shownThe ability of shearing.
What 4, branch skeleton monomer of the present invention adopted is centered by rigid structure, and the branch skeleton monomer making is by infrared checking,Proof modification is successful, has obtained having the branch skeleton monomer at such rigid structure center.
5, preparation technology of the present invention is simple to operation, and along with the continuous increase of algebraically, does not occur the problem that is difficult to react.
Brief description of the drawings
Fig. 1 is the present invention's 3 generation rigid macromolecule infrared spectrum;
Fig. 2 is synthesis step schematic diagram of the present invention;
Fig. 3 is rigid macromolecule ball-and-stick model figure of the present invention;
Fig. 4 is rigid macromolecule spherical model figure of the present invention.
Detailed description of the invention
Below in conjunction with specific embodiments and the drawings, the present invention is described in further detail, in embodiment, if no special instructions, adoptsWith raw material be common commercially available prod.
The branch skeleton monomer that one is core with 2,4-diacetyl-3-(4-bromophenyl) ethyl glutarate, as molecular formula I.
The branch skeleton monomer unimolecule that the present invention is made is applied in oil field displacement of reservoir oil polymer, with the polymer molecule of rigidityPolymeric matrix to rigidity has toughening effect. Kurauchi and Inoue etc. have proposed " cold for the toughness reinforcing phenomenon of rigid moleculeMachine drawing reason ":, in the time that polymer is subject to External Force Acting, the compression that dispersed phase particles is subject to producing perpendicular to stress direction shouldThe effect of power, in the time that this compression stress is enough large, can there is fragility-ductility transmition in the dispersed phase particles of rigidity, or cause dispersionThe phase particle surrender of matrix around (or simultaneously occurring), and in deformation process, absorb a large amount of energy, thus make polymer tableReveal shear-stable ability.
The branch skeleton method for preparing monomer that the present invention is core with 2,4-diacetyl-3-(4-bromophenyl) ethyl glutarate, ginsengSee embodiment 1-5.
Embodiment 1: the preparation of the little molecular reaction core of rigidity, comprises the steps:
Take 1 gram of 2,4-diacetyl-3-(4-bromophenyl) ethyl glutarate, be dissolved in 4.4 grams of ethylenediamines, wherein, second twoAmine is not only as solvent but also as reactant, 2,4-diacetyl-3-(4-bromophenyl) ethyl glutarate and participate in the ethylenediamine reactingMol ratio be 1:2.5; Lucifuge is reacted 24～25 hours with the long rotor of 2.5cm in ice-water bath on magnetic stirring apparatus, anti-After should finishing, with the distillation of rotary evaporation pressure reducer, then add 15 grams of methyl alcohol, repeatedly revolve and steam to obtain glassy yellow solid, anti-Answer core.
Embodiment 2: the reaction core that adopts embodiment 1 to make carries out subsequent reactions, and concrete steps are as follows:
Glassy yellow solid reaction core is made to dissolution with solvents with methyl alcohol abundant, with constant voltage separatory funnel dropping methyl acrylate, oftenUnder temperature, with magnetic stirring apparatus reaction 24～25 hours, after reaction finishes, purification by liquid extraction was used rotary evaporator decompression distillation again, andAdd methyl alcohol repeatedly to revolve to steam to obtain yellow solid, 0.5 generation product, wherein react the mol ratio 1.5:3 of core and methyl acrylate;
It is abundant that gained 0.5 generation product continues to make dissolution with solvents with methyl alcohol, with constant voltage separatory funnel dropping ethylenediamine, at normal temperaturesWith magnetic stirring apparatus reaction 24～25 hours, after reaction finishes, purification by liquid extraction was used rotary evaporator decompression distillation again, and addsMethyl alcohol repeatedly revolve steam 1 generation yellow solid product; Wherein 0.5 generation product and the mol ratio 1.2:6 of ethylenediamine;
By 1 generation yellow solid product to make dissolution with solvents with methyl alcohol abundant, drip methyl acrylate with constant voltage separatory funnel, oftenUnder temperature, with magnetic stirring apparatus reaction 36～37 hours, after reaction finishes, purification by liquid extraction was used rotary evaporator decompression distillation again, andAdd methyl alcohol repeatedly to revolve to steam 1.5 generation faint yellow solid; Wherein 1 generation product and the mol ratio 1.5:8 of methyl acrylate;
It is abundant that gained 1.5 generation product continues to make dissolution with solvents with methyl alcohol, with constant voltage separatory funnel dropping ethylenediamine, at normal temperaturesWith magnetic stirring apparatus reaction 36～37 hours, after reaction finishes, purification by liquid extraction was used rotary evaporator decompression distillation again, and addsMethyl alcohol repeatedly revolve steam 2 generation yellow solid product, wherein 1.5 generation product and the mol ratio 1.2:10 of ethylenediamine;
By 2 generation yellow solid product to make dissolution with solvents with methyl alcohol abundant, drip methyl acrylate with constant voltage separatory funnel, oftenUnder temperature, with magnetic stirring apparatus reaction 48～49 hours, after reaction finishes, purification by liquid extraction was used rotary evaporator decompression distillation again, andAdd methyl alcohol repeatedly to revolve to steam 2.5 generation buff solid, wherein 2 generation product and the mol ratio 1.5:16 of methyl acrylate;
It is abundant that gained 2.5 generation product continues to make dissolution with solvents with methyl alcohol, with constant voltage separatory funnel dropping ethylenediamine, at normal temperaturesWith magnetic stirring apparatus reaction 48～49 hours, after reaction finishes, purification by liquid extraction was used rotary evaporator decompression distillation again, and addsMethyl alcohol repeatedly revolve steam 3 generation brown color coagulation, wherein 2.5 generation product and the mol ratio of ethylenediamine be 1.2:18.
To the three generations's molecular reaction core making, by infrared detection, as shown in Figure 1, general, primary amine groups exists spectrogram3500-3200cm-1Have two absworption peaks, secondary amine is at 3400cm-1In scope, only have a nitrogen hydrogen absworption peak, and3070cm-1Near have flexible frequency multiplication peak in weak nitrogen hydrogen face, its fundamental frequency is about 1570-1510cm-1. 3342cm in spectrogram-1For the overlap peak of the N-H stretching vibration absworption peak of corresponding primary amine groups N-H stretching vibration absworption peak and secondary amine; 2946cm-1For methylene-CH2-stretching vibration absworption peak, 1574cm-1Place is the N-H fundamental frequency peak of secondary amine; 1480cm-1、1319cm-1For methyl flexural vibrations absworption peak, methylene scissors flexural vibrations absworption peak; 686cm-1There are a wider absorption band, correspondence in placeIn the out-of-plane bending vibration absworption peak of primary amine and secondary amine, wherein 3091cm-1、1478cm-1It is the principal character absworption peak of phenyl ring;Prove that the peripheral group of the reaction core making has the functional group of the reaction of participating in, and illustrates modification success.
Fig. 2 is the synthesis step schematic diagram of above-mentioned reaction, synthesize 3 generation product, ball-and-stick model as shown in Figure 3, ball-typeModel as shown in Figure 4.
Embodiment 3: the reaction core that adopts embodiment 1 to make carries out subsequent reactions, and concrete steps are as follows:
Glassy yellow solid reaction core is made to dissolution with solvents with methyl alcohol abundant, with constant voltage separatory funnel dropping methyl acrylate, oftenUnder temperature, with magnetic stirring apparatus reaction 24～25 hours, after reaction finishes, purification by liquid extraction was used rotary evaporator decompression distillation again, andAdd methyl alcohol repeatedly to revolve to steam to obtain yellow solid, this be 0.5 generation product, wherein react the mol ratio 1:4.5 of core and methyl acrylate;
It is abundant that gained 0.5 generation product continues to make dissolution with solvents with methyl alcohol, with constant voltage separatory funnel dropping ethylenediamine, at normal temperaturesWith magnetic stirring apparatus reaction 24～25 hours, after reaction finishes, purification by liquid extraction was used rotary evaporator decompression distillation again, and addsMethyl alcohol repeatedly revolve steam 1 generation yellow solid product, wherein 0.5 generation product and the mol ratio 1:8 of ethylenediamine;
By 1 generation yellow solid product to make dissolution with solvents with methyl alcohol abundant, drip methyl acrylate with constant voltage separatory funnel, oftenUnder temperature, with magnetic stirring apparatus reaction 36～37 hours, after reaction finishes, purification by liquid extraction was used rotary evaporator decompression distillation again, andAdd methyl alcohol repeatedly to revolve to steam 1.5 generation faint yellow solid, wherein 1 generation product and the mol ratio 1:12 of methyl acrylate;
It is abundant that gained 1.5 generation product continues to make dissolution with solvents with methyl alcohol, with constant voltage separatory funnel dropping ethylenediamine, at normal temperaturesWith magnetic stirring apparatus reaction 36～37 hours, after reaction finishes, purification by liquid extraction was used rotary evaporator decompression distillation again, and addsMethyl alcohol repeatedly revolve steam 2 generation yellow solid product, wherein 1.5 generation product and the mol ratio 1:12 of ethylenediamine;
By 2 generation yellow solid product to make dissolution with solvents with methyl alcohol abundant, drip methyl acrylate with constant voltage separatory funnel, oftenUnder temperature, with magnetic stirring apparatus reaction 48～49 hours, after reaction finishes, purification by liquid extraction was used rotary evaporator decompression distillation again, andAdd methyl alcohol repeatedly to revolve to steam 2.5 generation buff solid, wherein 2 generation product and the mol ratio 1:20 of methyl acrylate;
It is abundant that gained 2.5 generation product continues to make dissolution with solvents with methyl alcohol, with constant voltage separatory funnel dropping ethylenediamine, at normal temperaturesWith magnetic stirring apparatus reaction 48～49 hours, after reaction finishes, purification by liquid extraction was used rotary evaporator decompression distillation again, and addsMethyl alcohol repeatedly revolve steam 3 generation brown color coagulation, wherein 2.5 generation product and the mol ratio 1:20 of ethylenediamine.
Embodiment 4: the reaction core that adopts embodiment 1 to make carries out subsequent reactions, and concrete steps are as follows:
Glassy yellow solid reaction core is made to dissolution with solvents with methyl alcohol abundant, with constant voltage separatory funnel dropping methyl acrylate, oftenUnder temperature, with magnetic stirring apparatus reaction 24～25 hours, after reaction finishes, purification by liquid extraction was used rotary evaporator decompression distillation again, andAdd methyl alcohol repeatedly to revolve to steam to obtain yellow solid, this be 0.5 generation product, wherein react the mol ratio 1:3.5 of core and methyl acrylate;
It is abundant that gained 0.5 generation product continues to make dissolution with solvents with methyl alcohol, with constant voltage separatory funnel dropping aliphatic diamine ethylenediamine,With magnetic stirring apparatus reaction 24～25 hours, after reaction finishes, purification by liquid extraction was used rotary evaporator decompression distillation more at normal temperatures,And add methyl alcohol repeatedly to revolve to steam 1 generation yellow solid product, wherein 0.5 generation product and the mol ratio 1:5 of ethylenediamine;
By 1 generation yellow solid product to make dissolution with solvents with methyl alcohol abundant, drip methyl acrylate with constant voltage separatory funnel, oftenUnder temperature, with magnetic stirring apparatus reaction 36～37 hours, after reaction finishes, purification by liquid extraction was used rotary evaporator decompression distillation again, andAdd methyl alcohol repeatedly to revolve to steam 1.5 generation faint yellow solid, wherein 1 generation product and the mol ratio 1:10 of methyl acrylate;
It is abundant that gained 1.5 generation product continues to make dissolution with solvents with methyl alcohol, with constant voltage separatory funnel dropping ethylenediamine, at normal temperaturesWith magnetic stirring apparatus reaction 36～37 hours, after reaction finishes, purification by liquid extraction was used rotary evaporator decompression distillation again, and addsMethyl alcohol repeatedly revolve steam 2 generation yellow solid product, wherein 1.5 generation product and the mol ratio 1:11 of ethylenediamine;
By 2 generation yellow solid product to make dissolution with solvents with methyl alcohol abundant, drip methyl acrylate with constant voltage separatory funnel, oftenUnder temperature, with magnetic stirring apparatus reaction 48～49 hours, after reaction finishes, purification by liquid extraction was used rotary evaporator decompression distillation again, andAdd methyl alcohol repeatedly to revolve to steam 2.5 generation buff solid, wherein 2 generation product and the mol ratio 1:18 of methyl acrylate;
It is abundant that gained 2.5 generation product continues to make dissolution with solvents with methyl alcohol, with constant voltage separatory funnel dropping ethylenediamine, at normal temperaturesWith magnetic stirring apparatus reaction 48～49 hours, after reaction finishes, purification by liquid extraction was used rotary evaporator decompression distillation again, and addsMethyl alcohol repeatedly revolve steam 3 generation brown color coagulation, wherein 2.5 generation product and the mol ratio 1:19 of ethylenediamine.
Finally explanation, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although with reference to better realityExecute example the present invention is had been described in detail, those of ordinary skill in the art should be appreciated that can be to technical side of the present inventionCase is modified or is equal to replacement, and does not depart from aim and the scope of technical solution of the present invention, and it all should be encompassed in the present inventionClaim scope in the middle of.
Claims (4)
1. the branch skeleton monomer that is core with 2,4-diacetyl-3-(4-bromophenyl) ethyl glutarate, is characterized in that,Molecular formula is as shown in I:
In described formula I, the value of n is 2,3 or 4.
2. the branch skeleton list that is core with 2,4-diacetyl-3-(4-bromophenyl) ethyl glutarate as claimed in claim 1The preparation method of body, is characterized in that, comprises the steps:
1) 2,4-diacetyl-3-(4-bromophenyl) ethyl glutarate and aliphatic diamine are mixed, at ice-water bath magnetic stirring apparatusMiddle lucifuge reaction 24～25 hours, after reaction finishes, removes reaction dissolvent with rotary evaporator decompression distillation, and adds methyl alcoholRepeatedly revolve steaming, obtain glassy yellow solid, be i.e. the peripheral reaction core with functional group that can grafting; Wherein, aliphatic diamine bothAs solvent again as reactant, 2,4-diacetyl-3-(4-bromophenyl) ethyl glutarate and participate in the aliphatic diamine that reactsMol ratio be 1:2～3;
2) using step 1) gained reaction core is abundant as dissolution with solvents with methyl alcohol, with constant voltage separatory funnel in the solution of reaction coreDrip methyl acrylate, at normal temperatures with magnetic stirring apparatus reaction 24～25 hours, after reaction finishes, rotation for purification by liquid extractionEvaporimeter decompression distillation, and add methyl alcohol repeatedly to revolve steaming, obtains yellow solid, 0.5 generation product; Wherein 0 generation product and propyleneThe mol ratio of acid methyl esters is 1～1.5:3～4.5;
3) by step 2) gained 0.5 generation product continues that to make dissolution with solvents with methyl alcohol abundant, drips aliphatic with constant voltage separatory funnelDiamines, with magnetic stirring apparatus reaction 24～25 hours, after reaction finishes, purification by liquid extraction reduced pressure with rotary evaporator at normal temperaturesDistillation, and adds methyl alcohol repeatedly to revolve steaming, obtains yellow solid, 1 generation product; Wherein, 0.5 generation product and aliphatic diamineMol ratio is 1～1.2:6-8;
4) alternately generate successively 1.5 generations, 2 generations and 2.5 generation product, finally generate 3 generation product, i.e. product shown in formula I; Wherein,Prepare each generation when product, all previous generation product is made to dissolution with solvents with methyl alcohol abundant, drip with constant voltage separatory funnel in molar ratioReactant, reacts with magnetic stirring apparatus at normal temperatures, after reaction finishes, and purification by liquid extraction rotary evaporator decompression distillation,And add methyl alcohol repeatedly to revolve steaming, obtain each generation product; Described reactant, in the process in preparation half for product, is acrylic acidMethyl esters; In the process of the whole generation reaction of preparation, it is aliphatic diamine;
Wherein, 1.5 generations of preparation are when product, 1 generation product and the mol ratio of methyl acrylate be 1～1.5:8～12, the reaction time is 36～37Hour, obtain faint yellow solid, 1.5 generation product;
Prepared for 2 generations when product, 1.5 generation product and the mol ratio of aliphatic diamine be 1～1.2:10～12, the reaction time is 36～37Hour, obtain yellow solid, 2 generation product;
Prepared for 2.5 generations when product, 2 generation product and the mol ratio of methyl acrylate be 1～1.5:16～20, the reaction time is 48～49Hour, obtain buff solid, 2.5 generation product;
Prepared for 3 generations when product, 2.5 generation product and the mol ratio of aliphatic diamine be 1～1.2:18～20, the reaction time is 48～49Hour, obtain brown color coagulation, 3 generation product.
3. the branch skeleton monomer that is core with 2,4-diacetyl-3-(4-bromophenyl) ethyl glutarate according to claim 2Preparation method, it is characterized in that, described aliphatic diamine is ethylenediamine, 1,3-propane diamine or Putriscine.
4. the branch skeleton list that is core with 2,4-diacetyl-3-(4-bromophenyl) ethyl glutarate as claimed in claim 1The application of body, is characterized in that, the application in oil field displacement of reservoir oil polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510065283.2A CN104610083B (en) | 2015-02-06 | 2015-02-06 | Branch skeleton monomer that one is core with 2,4-diacetyl-3-(4-bromophenyl) ethyl glutarate and preparation method thereof and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510065283.2A CN104610083B (en) | 2015-02-06 | 2015-02-06 | Branch skeleton monomer that one is core with 2,4-diacetyl-3-(4-bromophenyl) ethyl glutarate and preparation method thereof and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104610083A CN104610083A (en) | 2015-05-13 |
| CN104610083B true CN104610083B (en) | 2016-05-04 |
Family
ID=53144774
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510065283.2A Expired - Fee Related CN104610083B (en) | 2015-02-06 | 2015-02-06 | Branch skeleton monomer that one is core with 2,4-diacetyl-3-(4-bromophenyl) ethyl glutarate and preparation method thereof and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104610083B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114149338B (en) * | 2021-09-13 | 2023-04-07 | 中国科学院化学研究所 | Preparation method and application of amphiphilic dendritic molecule |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4561501A (en) * | 1983-06-28 | 1985-12-31 | Phillips Petroleum Company | Surfactant oil recovery systems and recovery of oil therewith |
| CN104250380A (en) * | 2013-06-25 | 2014-12-31 | 中国石油化工股份有限公司 | Dendritic polymer, dendritic polymer monomer, and preparation methods and application of two |
| CN104311755A (en) * | 2014-10-30 | 2015-01-28 | 孙安顺 | Salt-resistant polymer for oil displacement of oil field and preparation method thereof |
-
2015
- 2015-02-06 CN CN201510065283.2A patent/CN104610083B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4561501A (en) * | 1983-06-28 | 1985-12-31 | Phillips Petroleum Company | Surfactant oil recovery systems and recovery of oil therewith |
| CN104250380A (en) * | 2013-06-25 | 2014-12-31 | 中国石油化工股份有限公司 | Dendritic polymer, dendritic polymer monomer, and preparation methods and application of two |
| CN104311755A (en) * | 2014-10-30 | 2015-01-28 | 孙安顺 | Salt-resistant polymer for oil displacement of oil field and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 树枝状分子驱油剂的合成和评价;郑性能 等;《新疆石油地质》;20091031;第30卷(第5期);第637-640页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104610083A (en) | 2015-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102167817B (en) | Preparation method of polyamino acid and polyamino acid nano-hydrogel | |
| CN104558323B (en) | A kind of highly-water-soluble nano-hexagonal boron nitride and the preparation method of polymer composite aquogel thereof | |
| CN101747491B (en) | Fast thickening vinyl ester resin as well as preparation method and application thereof | |
| CN105367806B (en) | A kind of new polyrotaxane and preparation method thereof | |
| CN105884987A (en) | Bi-sulfonate interface initiator and preparing method thereof | |
| Yang et al. | Two tandem multicomponent reactions for the synthesis of sequence-defined polymers | |
| CN101323662B (en) | Biodegradable hyper branched aliphatic polyamide fiber daiamid and preparation thereof | |
| CN101412792A (en) | Method for synthesizing bead form polymeric acylating reagent | |
| CN104610083B (en) | Branch skeleton monomer that one is core with 2,4-diacetyl-3-(4-bromophenyl) ethyl glutarate and preparation method thereof and application | |
| CN101440150A (en) | Hyperbranched aqueous polyurethane and preparation thereof | |
| CN102557099A (en) | Method for preparing calcite phase and/or vaterite phase calcium carbonate | |
| CN107652443B (en) | Hyperbranched poly (ester-amine) with functional groups on surface and inside and preparation method thereof | |
| CN110437426A (en) | A kind of scopiform copolymer and preparation method thereof | |
| CN107286351A (en) | A kind of end amino superbranching polyester and preparation method thereof and epoxy resin modification agent | |
| CN111040184B (en) | Polyethylene glycol monomethyl ether-polybutadiene-polyethylene glycol monomethyl ether triblock copolymer and preparation method thereof | |
| CN102924725A (en) | Polyamino acid/chitosan composite material and preparation method thereof | |
| CN106700528A (en) | Supramolecular assembly and preparation method and morphological control method thereof | |
| CN106242954A (en) | The polyetheramine preparation method of low molecular polyether polyhydric alcohol | |
| CN109503827A (en) | A method of the catalyst of polypeptide is prepared for amino acid ring inner-acid anhydride ring-opening polymerisation and utilizes the catalyst preparation polypeptide | |
| CN103755844A (en) | Method for preparing polyisobutylene succinic acid triethanolamine ester | |
| CN109053997A (en) | A kind of aliphatic hyperbranched epoxy resin and preparation method thereof | |
| Kong et al. | Preparation of dendrimer-like copolymers based on polystyrene and poly (l-lactide) and formation of hollow microspheres | |
| CN103044697A (en) | Method for preparing microphase structural latex film | |
| CN103232363B (en) | The continuous production method of polyamide-amide | |
| CN103965384A (en) | Preparation method of polymethyl methacrylate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160504 Termination date: 20180206 |