CN104403037B - Topological structure polymer and its preparation method and application - Google Patents
Topological structure polymer and its preparation method and application Download PDFInfo
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Abstract
The invention discloses topological structure polymer and its preparation method and application.The present invention provides topological structure polymer of the one kind as shown in formula 2 or formula 2 '；Wherein, the n represents the degree of polymerization, n=10~250.The preparation method of the topological structure polymer of the present invention is easy to operate, and suitable monomers scope is wide, can remove double thioester groups or xanthate group on polymer, improves the physical and chemical performance and application prospect of polymer.The be stripped of double thioester groups in end or the topological structure polymer of end xanthate group of the present invention has lower molecular weight, narrow molecular weight distribution, compared with the topological structure polymer or linear polymer of traditional high molecular weight, physicochemical properties are more special, for example the solubility in carbon dioxide is higher, the application that close carbon dioxide segment carries out related fields is suitable as, such as carbon dioxide thickener is used to prepare, or it is used to prepare carbon dioxide aqueous emulsion etc..
Description
Technical field
The present invention is specifically related to topological structure polymer and its preparation method and application.
Background technology
Star, the isostructural topological macromolecule of super cladodification, which have, is different from the high molecular special performance of linear chain structure, is one
Class has the new type functional polymeric material of important application prospect in fields such as material modification, nanosecond science and technology and biological medicines,
It is increasingly subject to the attention of people.Such as：The super cladodification of spherical structure, dendroid and star-like macromolecules have relative to linear molecule
There is the polymerized unit density of higher, have ultralow viscosity in the solution, and can utilize with substantial amounts of end group.Starblock
Polymer shows more preferable dissolubility and stronger viscoelasticity than line polymer and can be formed under specific solvent condition
Complicated self assembly pattern.
For a polymer contained compared with complex topology structure, its preparation method can be generally divided into two kinds：One kind be from
Small molecule is set out, and the polymer of specific structure is obtained by the corresponding monomer of living polymerization using suitable reagent, such as uses one
Starlike agent of activity polymerize to obtain star-shape polymer net, but is that reagent is deposited as topological structure core the defects of this method
, when this reagent the property of polymer is adversely affected need remove when, the topological structure of polymer can be with examination
Agent is removed and disappears：Another method is by high molecular weight reactive, and complexity is built using macromolecular chain as construction unit
The polymer of topological structure, such as obtains ring-like polymer by high molecular intramolecular cyclization reaction, is obtained by arm first
To starlike macromolecule etc..Usually all it is essential work either with first method or second method, living polymerization
Tool.Reversible addion-fragmentation chain transfer polymerization, its English full name is Reversible Addition-Fragmentation
Chain Transfer Polymerization, referred to as RAFT, belong to the category of radical polymerization, its monomer model adapted to
Enclose relatively extensively, the monomer for being adapted to RAFT being had been reported at present in document includes phenylethylene, (methyl) esters of acrylic acid and second
Alkenyl pyridines etc..On the other hand, controllable, the living features showed just because of RAFT, can polymerize a monomer
Afterwards, obtained macromolecule is re-used as Macromolecular chain transfer agent and polymerize another monomer under the conditions of RAFT, so as to convenient
Obtain the polymer of the even more blocks of diblock, three block.In addition, if select suitable chain-transferring agent, moreover it is possible to had
There is the polymer of corresponding topological structure.But the polymer that such reaction usually obtains larger number-average molecular weight is relatively easy to, and
It is extremely difficult if obtaining the polymer (if number-average molecular weight is between 800~10000) of low molecular weight, it is rarely seen to have related ends
Report.
The defects of carrying double thioester groups there are reaction product during RAFT radical polymerizations and being not easy to remove, prepares to be follow-up
End group functional macromolecule brings unfavorable factor.For example, prepare the poly- second of end group functional polyvinyl acetate is hydrolyzed
During enol, the conjugation unsaturated aldehyde with xanthan acid end group makes product easily turn yellow.And for example, low molecular weight is being prepared with RAFT methods
During polymer, xanthan acid end group will be unfavorable to properties such as polymer solubility behavior in the solution, self assembly behaviors, especially right
In topological structure polymer, the adverse effect of xanthan acid end group is more serious, and this adverse effect can be found in document [Tong, Y.-
Y.et al.Journal of Polymer Science Part A：Polymer Chemistry 47(18)：4494-4504,
2009；Tan, B.et al.Macromolecules 42 (20)：7945-7952,2009].
The content of the invention
The technical problem to be solved in the present invention is in order to overcome reversible addion-fragmentation chain transfer polymerization in the prior art
Prepared polymer is not easy to reach on low molecular weight (such as number-average molecular weight 500~10000 between) and these polymer
Double thioester group or the xanthate groups contained are not easy to remove so as to bring adverse effect to polymer physical chemistry property
Defect, and provide topological structure polymer and its preparation method and application.The topological structure polymer of the present invention has relatively low
Molecular weight, number-average molecular weight is between 500~10000, narrow molecular weight distribution.The present invention be stripped of the double thioester group in end or
The topological structure polymer of end xanthate group has lower molecular weight, narrow molecular weight distribution, with traditional high molecular weight
Topological structure polymer or linear polymer compare, physicochemical properties are more special, have broad application prospects.This hair
The preparation method of bright topological structure polymer is easy to operate, and suitable monomers scope is wide, can prepare alternating, the nothing of topological structure
The copolymers such as rule, block or grafting, can remove double thioester groups or xanthate group on polymer, improve the thing of polymer
Physicochemical performance and application prospect.The topological structure for being stripped of the double thioester groups in end or end xanthate group of the present invention
Solubility of the polymer in carbon dioxide is higher, is suitable as the application that close carbon dioxide segment carries out related fields, example
Carbon dioxide thickener (this thickener can improve oil recovery) is such as used to prepare, or is used to prepare carbon dioxide water
Lotion etc..The double thioester groups of removal of the present invention or the polymer of xanthate group can be used for carbon dioxide thickener to prepare with
And carbon dioxide aqueous emulsion prepare etc., concrete application method refer to document [Tan, B.and A.I.Cooper,
Functional oligo(vinyl acetate)CO2-philes for solubilization and
Emulsification.J Am Chem Soc, 2005.127 (25)：p.8938-9].
Present invention also offers topological structure polymer of the one kind as shown in formula 2 or formula 2 '；
Wherein, the n represents the degree of polymerization, n=10~250；
Wherein, each " [] " represents a construction unit, is mutually independent between each construction unit, that is,
Say, the Y in each construction unit can be the same or different, and the Z in each construction unit can be the same or different；
Therefore, the Y and Z is independently each that hydrogen or various conventional used in the polymerisation of this area take
The one or more in various substituents on the vinyl monomer in generation；
When construction unit is not single construction unit, according to common sense in the field, represent described such as formula 2 or the institute of formula 2 '
The topological structure polymer shown is copolymer；
The topological structure polymer as shown in Equation 2 is the polymer for having on each molecule three arms；Described
Topological structure polymer as shown in formula 2 ' is the polymer for having on each molecule four arms；Topological structure in the present invention gathers
Compound uses the technique of painting omitted, only draws the structural formula of one of arm, and other arms use waveOmissive representation, the degree of polymerization on each molecule on each arm can be the same or different；
The R1、R2And R3It is independently each hydrogen or C1~C6Alkyl.
Preferably, n=10~100；More preferably, n=10~35.
The R1、R2And R3Each independent preferred hydrogen or C1~C3Alkyl, the C1~C3The preferred methyl of alkyl or
Ethyl.
Preferably, the Y and the Z are independently each hydrogen, C1~C3Alkanoyloxy, cyano group, phenyl and C1~C4
Alkoxy-carbonyl-in one or more, more preferably hydrogen, C1~C3Alkanoyloxy and C1~C4Alkoxy-carbonyl-in one kind
It is or a variety of.The C1~C4Alkoxy-carbonyl-preferred normal-butyl oxygen carbonyl.The C1~C3The preferred acetyl oxygen of alkanoyloxy
Base.
More preferably, in the construction unit described in part, the Y is acetoxyl group and the Z is hydrogen；Remainder
In construction unit, the Y and Z are normal-butyl oxygen carbonyl.
The copolymer can be the various conventional copolymers in this area, preferably random copolymer, alternate copolymer, block
One or more in copolymer and graft copolymer.
The present invention provides topological structure polymer of the one kind as shown in formula 1 or formula 1 '；
Wherein, described n, Y, Z, R1、R2And R3As described above；
Wherein, each " [] " represents a construction unit, is mutually independent between each construction unit, that is,
Say, the Y in each construction unit can be the same or different, and the Z in each construction unit can be the same or different；
Therefore, the Y and Z is independently each that hydrogen or various conventional used in the polymerisation of this area take
The one or more in various substituents on the vinyl monomer in generation；
When construction unit is not single construction unit, according to common sense in the field, represent described such as formula 1 or the institute of formula 1 '
The topological structure polymer shown is copolymer；
The W is carbon or oxygen；
The L is C1~C6Alkyl；
The topological structure polymer as shown in Equation 1 is the polymer for having on each molecule three arms；Described
Topological structure polymer as shown in formula 1 ' is the polymer for having on each molecule four arms；Topological structure in the present invention gathers
Compound uses the technique of painting omitted, only draws the structural formula of one of arm, and other arms use waveOmissive representation, the degree of polymerization on each molecule on each arm can be the same or different；.
Preferably, the W is oxygen；
The preferred methyl of the L, ethyl or propyl group.
Present invention also offers topological structure polymer of the one kind as shown in formula 2 or formula 2 ' to prepare carbon dioxide thickener
Or the application in carbon dioxide aqueous emulsion, wherein, described n, Y, Z, W, L, R1、R2And R3As described above.
Due to the present invention solvability of the topological structure polymer as shown in formula 2 or formula 2 ' in carbon dioxide compared with
It is good, therefore it can be used for the application as close carbon dioxide segment progress related fields, such as be used to prepare carbon dioxide thickening
Agent or carbon dioxide aqueous emulsion etc., wherein carbon dioxide thickener can be used for improving oil recovery, specific application process ginseng
Examine document [Tan, B.and A.I.Cooper, Functional oligo (vinyl acetate) CO2-philes for
Solubilization and emulsification.JAm Chem Soc, 2005.127 (25)：p.8938-9].
Present invention also offers the preparation method of topological structure polymer of the one kind as shown in formula 2 or formula 2 ', it is included such as
Lower step：In solvent, under conditions of 25~150 DEG C, under the conditions of anhydrous and oxygen-free, the topological structure as shown in formula 1 or formula 1 ' is gathered
The double lauroyl of compound, isopropanol and peroxidating carry out the topological structure polymer of removing as follows as shown in formula 1 or formula 1 '
The reaction of the R ' group of upper end；When reaction time is 0~48 small when small (not for 0)；It is corresponding to be made as shown in formula 2 or formula 2 '
Polymer；
Wherein, the R ' group of end is on the topological structure polymer as shown in formula 1 or formula 1 '
Group；
Wherein, described n, Y, Z, W, L, R1、R2And R3As described above；
The topological structure polymer as shown in formula 1 or formula 2 is the polymer for having on each molecule three arms；Institute
The topological structure polymer as shown in formula 1 ' or formula 2 ' stated is the polymer for having on each molecule four arms；In the present invention
Topological structure polymer uses the technique of painting omitted, only draws the structural formula of one of arm, and other arms use waveOmissive representation, the degree of polymerization on each molecule on each arm can be the same or different；.
In the present invention, when the W is carbon, end on the topological structure polymer as shown in formula 1 or formula 1 '
R ' group beAccording to common sense in the field, it is commonly referred to asThis group is double thioester groups, this hair
In bright, in order to simplify expression, described when the W be carbon " is removed into the topological structure polymerization as shown in formula 1 or formula 1 '
The reaction of the R ' group of end on thing " is known as the double thioesters for removing end on the topological structure polymer as shown in formula 1 or formula 1 '
The reaction of group.
In the present invention, when the W is oxygen, end on the topological structure polymer as shown in formula 1 or formula 1 '
R ' group beAccording to common sense in the field, it is commonly referred to asThis group is xanthic acid group, this hair
In bright, in order to simplify expression, described when the W be oxygen " is removed into the topological structure polymerization as shown in formula 1 or formula 1 '
The reaction of the R ' group of end on thing " is known as the xanthic acid for removing end on the topological structure polymer as shown in formula 1 or formula 1 '
The reaction of group.
According to common sense in the field, in the removing as described in the topological structure polymer progress shown in formula 1 or formula 1 '
The R of end on topological structure polymer as shown in formula 1 or formula 1 ', it is described as shown in formula 1 or formula 1 ' during the reaction of group
On topological structure polymer, in addition to the position that end reacts, other positions do not change, that is to say, that reaction
The prepared topological structure polymer as shown in formula 2 or formula 2 ' is except end and described as shown in formula 1 or formula 1 '
Topological structure polymer end structure it is inconsistent outer, what the structure of remainder was all to maintain, that is, correspond.
In the preparation method of the topological structure polymer as shown in formula 2 or formula 2 ', the removing such as formula 1 or
On topological structure polymer shown in formula 1 ' in the reaction of the R ' group of end anhydrous and oxygen-free condition can according to this area this
The method of the conventional various water removal deoxygenations of class reaction is realized, it is preferred to use the reaction vessel of sealing and vacuumizes-lead to protectiveness gas
Body is repeated multiple times to be realized.The preferred nitrogen of the protective gas.
In the preparation method of the topological structure polymer as shown in formula 2 or formula 2 ', the removing such as formula 1 or
Solvent on topological structure polymer shown in formula 1 ' in the reaction of the R ' group of end can be this area conventional institute of such reaction
Various solvents, preferably ether solvent, halogenated hydrocarbon solvent, aromatic hydrocarbon solvent, esters solvent, ketones solvent and amide-type are molten
One or more in agent；The preferred tetrahydrofuran of the ether solvent；The preferred dichloromethane of the halogenated hydrocarbon solvent；Institute
The preferred benzene of aromatic hydrocarbon solvent and/or toluene stated；The esters solvent ethyl acetate；The ketones solvent preferably third
Ketone；The preferred n,N-Dimethylformamide of the amide solvent.
In the preparation method of the topological structure polymer as shown in formula 2 or formula 2 ', the removing such as formula 1 or
On topological structure polymer shown in formula 1 ' in the reaction of the R ' group of end, preferably, the polymer as shown in Equation 1
Molar ratio with the isopropanol is (1: 30)~(3；250).More preferably, the polymer as shown in Equation 1 with it is described
The molar ratio of isopropanol be (1: 20)~(3: 200).
In the preparation method of the topological structure polymer as shown in formula 2 or formula 2 ', the removing such as formula 1 or
On topological structure polymer shown in formula 1 ' in the reaction of the R ' group of end, preferably, the polymer as shown in Equation 1
Molar ratio with the double lauroyl of the peroxidating is 1: (1~6).More preferably, the polymer as shown in Equation 1 with it is described
The molar ratios of the double lauroyl of peroxidating be 1: (1~5).
In the preparation method of the topological structure polymer as shown in formula 2 or formula 2 ', preferably, the isopropyl
The molar ratio of alcohol and the double lauroyl of the peroxidating is (30~83.3): (1~8)；More preferably (20~79): (6~8).
In the preparation method of the topological structure polymer as shown in formula 2 or formula 2 ', the removing such as formula 1 or
Preferably 50 DEG C~100 DEG C of the temperature of the reaction of the R ' group of end, more preferably 60 DEG C on topological structure polymer shown in formula 1 '
~90 DEG C, most preferably 70 DEG C.
In the preparation method of the topological structure polymer as shown in formula 2 or formula 2 ', the removing such as formula 1 or
On topological structure polymer shown in formula 1 ' in the reaction of the R ' group of end, when n is 10~35, the temperature preferably 60 of reaction
DEG C~70 DEG C；When n is 35~100, preferably 70 DEG C~80 DEG C of the temperature of reaction.
In the preparation method of the topological structure polymer as shown in formula 2 or formula 2 ', the removing such as formula 1 or
On topological structure polymer shown in formula 1 ' in the reaction of the R ' group of end, when n is 10~35, the time preferably 0 of reaction
~5 it is small when when small (not for 0)；When n is 35~100, when the time preferably 5~48 of reaction is small.
The preparation method of the topological structure polymer as shown in formula 2 or formula 2 ', it is preferred that in the removing such as
The R ' group of end after reaction, also can further include post processing on topological structure polymer shown in formula 1 or formula 1 '
Operation.The method and condition of the post processing can be the method and condition of the such post-reaction treatment routine in this area, preferably
Ground is：After reaction, it is diluted, adds the solvent of insoluble product to precipitate product, filters, it is dry, you can.Described is dilute
Solvent used is diluted when releasing preferably using reaction.The preferred alkane solvents of solvent of the insoluble product, it is more excellent
Select the n-hexane of n-hexane, most preferably -10~5 DEG C.The drying is preferably dried in vacuo, more preferably in 40~50 DEG C of baking oven
Middle vacuum drying.
Preferably, the preparation method of the topological structure polymer as shown in formula 2 or formula 2 ', further comprise as
Lower step：In solvent, under the conditions of 25 DEG C~150 DEG C, by chain-transferring agent, vinyl monomer and the initiator as shown in formula 3 or formula 4
Carry out Raolical polymerizable under conditions of anhydrous and oxygen-free, the reaction time for 1~48 it is small when, be made described such as formula 1 or formula
Topological structure polymer shown in 1 '；
Wherein, described n, Y, Z, W, L, R1、R2And R3As described above；
The topological structure polymer as shown in formula 1 or formula 2 is the polymer for having on each molecule three arms；Institute
The topological structure polymer as shown in formula 1 ' or formula 2 ' stated is the polymer for having on each molecule four arms；In the present invention
Topological structure polymer uses the technique of painting omitted, only draws the structural formula of one of arm, and other arms use waveOmissive representation, the degree of polymerization on each molecule on each arm can be the same or different；.
It is described when the topological structure polymer as shown in formula 1 or formula 1 ' is copolymer according to common sense in the field
Vinyl monomer must be two or more vinyl monomer.That is, in the Raolical polymerizable
The vinyl monomer is not a kind of single vinyl monomer, but two or more vinyl monomer comes jointly
Participate in polymerisation.In the present invention, in order to simplify expression, in the reaction equation of above-mentioned radical polymerization, only participation polymerization
Monomer is expressed as " vinyl monomer ".
In the preparation method of the topological structure polymer as shown in formula 1 or formula 1 ', the vinyl monomer is excellent
Select vinyl acetate and/or dibutyl maleate；More preferably vinyl acetate.
In the preparation method of the topological structure polymer as shown in formula 1 or formula 1 ', the bar of the anhydrous and oxygen-free
Part can be realized according to the method for the various water removal deoxygenations of this area Raolical polymerizable routine, it is preferred to use the reaction of sealing
Container and vacuumize-lead to that protective gas is repeated multiple times realizes.The preferred nitrogen of the protective gas.
In the preparation method of the topological structure polymer as shown in formula 1 or formula 1 ', the radical polymerization is anti-
Solvent in answering can be the various solvents used in the such reaction routine in this area, preferably ether solvent, halogenated hydrocarbon solvent, aromatic hydrocarbons
One or more in class solvent, esters solvent, ketones solvent and amide solvent；The preferred tetrahydrochysene furan of the ether solvent
Mutter；The preferred dichloromethane of the halogenated hydrocarbon solvent；The preferred benzene of the aromatic hydrocarbon solvent and/or toluene；The esters
Solvent ethyl acetate；The preferred acetone of the ketones solvent；The preferred n,N-Dimethylformamide of the amide solvent.
In the preparation method of the topological structure polymer as shown in formula 1 or formula 1 ', the initiator can be this
The various initiators of field Raolical polymerizable routine, preferably azodiisobutyronitrile, azobisisoheptonitrile and azo diisoamyl
One or more in nitrile.
In the preparation method of the topological structure polymer as shown in formula 1 or formula 1 ', the dosage of the initiator
Can be mole of this area Raolical polymerizable routinely various dosages, the preferably described initiator and the vinyl monomer
Than for 1: (25~100), more preferably 1: (25~60).
It is described such as formula 3 or the institute of formula 4 in the preparation method of the topological structure polymer as shown in formula 1 or formula 1 '
Molar ratio preferably 1 between the chain-transferring agent and vinyl monomer that show: (25~500), more preferably 1: (25~100).
In the preparation method of the topological structure polymer as shown in formula 1 or formula 1 ', the radical polymerization is anti-
Preferably 50~100 DEG C, more preferably 50~80 DEG C of the temperature answered.
In the preparation method of the topological structure polymer as shown in formula 1 or formula 1 ', the radical polymerization is anti-
When the time answered preferably 1~24 is small.
It is described when n is 10~30 in the preparation method of the topological structure polymer as shown in formula 1 or formula 1 '
Raolical polymerizable preferably 50~60 DEG C of temperature；When n is 30~250, the temperature of the Raolical polymerizable
It is preferred that 60~80 DEG C.
In the preparation method of the topological structure polymer as shown in formula 1 or formula 1 ', whennFor 10~30 when, it is described
Raolical polymerizable time preferably 1~3 it is small when；When n is 30~250, the time of the Raolical polymerizable
It is preferred that 3~24 it is small when.
The preparation method of the topological structure polymer as shown in formula 1 or formula 1 ', it is anti-in the radical polymerization
After answering, it is preferred that also can further include the operation of post processing.The method and condition of the post processing can be this area
The method and condition of such post-reaction treatment routine, preferably：After reaction, it is diluted, adds the molten of insoluble product
Agent precipitates product, filters, dry, you can.Solvent used is diluted when the dilution is preferably using reaction.Described
The preferred alkane solvents of solvent of insoluble product, the more preferably n-hexane of n-hexane, most preferably -10~5 DEG C.The drying
It is preferred that being dried in vacuo, more preferably it is dried in vacuo in 30~50 DEG C of baking oven.
Present invention also offers the preparation method of topological structure polymer of the one kind as shown in formula 1 or formula 1 ', it includes such as
Lower step：In solvent, under the conditions of 25 DEG C~150 DEG C, by chain-transferring agent, vinyl monomer and the initiator as shown in formula 3 or formula 4
Raolical polymerizable is carried out under conditions of anhydrous and oxygen-free, when the reaction time is 1~48 small, is made as shown in formula 1 or formula 1 '
Topological structure polymer；
Wherein, described n, Y, Z, W, L, R1、R2And R3As described above；
The vinyl monomer is as described above；
The topological structure polymer as shown in formula 1 or formula 2 is the polymer for having on each molecule three arms；Institute
The topological structure polymer as shown in formula 1 ' or formula 2 ' stated is the polymer for having on each molecule four arms；In the present invention
Topological structure polymer uses the technique of painting omitted, only draws the structural formula of one of arm, and other arms use waveOmissive representation, the degree of polymerization on each molecule on each arm can be the same or different；.
The method and condition of the preparation method of the topological structure polymer as shown in formula 1 or formula 1 ' are as described above.
Present invention also offers a kind of preparation method for the topological structure polymer that degree of polymerization is n, it includes the following steps：
In solvent, under the conditions of 25 DEG C~150 DEG C, by chain-transferring agent, vinyl monomer and the initiator as shown in formula 3 or formula 4 anhydrous
Raolical polymerizable is carried out under conditions of anaerobic, when the reaction time is 1~48 small, the topological structure that the degree of polymerization is n is made and gathers
Compound；
Wherein, described n, W, L, R1、R2And R3As described above.
The degree of polymerization is that the vinyl monomer can be ability in the preparation method of the topological structure polymer of n
One or more in the conventional various vinyl monomers of the such reaction in domain.In the present invention particularly preferred vinyl acetate and/or
Dibutyl maleate；More preferably vinyl acetate.
The degree of polymerization is in the preparation method of the topological structure polymer of n, and the condition of the anhydrous and oxygen-free can be with
According to this area Raolical polymerizable routine various water removal deoxygenations method realize, it is preferred to use the reaction vessel of sealing and
Vacuumize-lead to that protective gas is repeated multiple times realizes.The preferred nitrogen of the protective gas.
The degree of polymerization is in the preparation method of the topological structure polymer of n, in the Raolical polymerizable
Solvent can be the various solvents used in the such reaction routine in this area, and preferably ether solvent, halogenated hydrocarbon solvent, aromatic hydrocarbons are molten
One or more in agent, esters solvent, ketones solvent and amide solvent；The preferred tetrahydrofuran of the ether solvent；Institute
The preferred dichloromethane of halogenated hydrocarbon solvent stated；The preferred benzene of the aromatic hydrocarbon solvent and/or toluene；The esters solvent is excellent
Select ethyl acetate；The preferred acetone of the ketones solvent；The preferred n,N-Dimethylformamide of the amide solvent.
The degree of polymerization is in the preparation method of the topological structure polymer of n, and the initiator can be for this area certainly
By the various initiators of base polymerisation routine, preferably in azodiisobutyronitrile, azobisisoheptonitrile and azobisisovaleronitrile
It is one or more.
The degree of polymerization is in the preparation method of the topological structure polymer of n, and the dosage of the initiator can be this
The molar ratio of the conventional various dosages of field Raolical polymerizable, the preferably described initiator and the vinyl monomer is 1:
(25~100), more preferably 1: (25~60).
The degree of polymerization is the chain as shown in formula 3 or formula 4 in the preparation method of the topological structure polymer of n
Molar ratio preferably 1 between transfer agent and vinyl monomer: (25~500), more preferably 1: (25~100).
The degree of polymerization is the temperature of the Raolical polymerizable in the preparation method of the topological structure polymer of n
Preferably 50~100 DEG C, more preferably 50~80 DEG C of degree.
The degree of polymerization be n topological structure polymer preparation method in, the Raolical polymerizable when
Between preferably 1~24 it is small when.
In preparation method of the degree of polymerization for the topological structure polymer of n, when n is 10~30, the freedom
Preferably 50~60 DEG C of the temperature of base polymerisation；When n is 30~250, the temperature preferably 60 of the Raolical polymerizable
~80 DEG C.
It is described when n is 10~30 in the preparation method of the topological structure polymer as shown in formula 1 or formula 1 '
Raolical polymerizable time preferably 1~3 it is small when；When n is 30~250, the time of the Raolical polymerizable
It is preferred that 3~24 it is small when.
The degree of polymerization is the preparation method of the topological structure polymer of n, is terminated in the Raolical polymerizable
Afterwards, it is preferred that also can further include the operation of post processing.The method and condition of the post processing can be that this area is such anti-
Conventional method and condition should be post-processed, preferably：After reaction, it is diluted, adds the solvent of insoluble product to make production
Thing precipitates, and filters, dry, you can.Solvent used is diluted when the dilution is preferably using reaction.Described is insoluble
The preferred alkane solvents of solvent of product, the more preferably n-hexane of n-hexane, most preferably -10~5 DEG C.The drying is preferably true
Sky is dry, is more preferably dried in vacuo in 30~50 DEG C of baking oven.
Present invention also offers a kind of as obtained by the preparation method for the topological structure polymer that the degree of polymerization is n
The degree of polymerization is the topological structure polymer of n；The n is as described above.
It is opening up for n that the degree of polymerization, which is made, in the preparation method for the topological structure polymer for being n by the degree of polymerization
After flutterring structural polymer, the R ' group that the topological structure polymer that the degree of polymerization is n removes end can be also further prepared
Topological structure polymer, which comprises the following steps：In solvent, under conditions of 25~150 DEG C, anhydrous and oxygen-free condition
Under, the double lauroyl of topological structure polymer, isopropanol and peroxidating that the degree of polymerization is n are carried out removing the polymerization
Spend the reaction of the R ' group of end on the topological structure polymer for n；When reaction time is 0~48 small when small (not for 0)；Accordingly
The degree of polymerization that is made be the topological structure polymer that the topological structure polymer of n removes the R ' group of end；Described
R ' group is as described above.
The above-mentioned degree of polymerization that is made is that the topological structure polymer of n removes the R of end, and the topological structure of group gathers
In the preparation method of compound,
The topological structure of the R ' group that the topological structure polymer removing end that the degree of polymerization is n is made gathers
In the preparation method of compound, the condition of the anhydrous and oxygen-free can be according to the conventional various water removal deoxygenations of the such reaction in this area
Method realize, it is preferred to use the reaction vessel of sealing and vacuumize-lead to that protective gas is repeated multiple times realizes.The guarantor
The shield property preferred nitrogen of gas.
The topological structure of the R ' group that the topological structure polymer removing end that the degree of polymerization is n is made gathers
In the preparation method of compound, the solvent can be this area it is such reaction routine used in various solvents, preferably ether solvent,
One or more in halogenated hydrocarbon solvent, aromatic hydrocarbon solvent, esters solvent, ketones solvent and amide solvent；The ether
The preferred tetrahydrofuran of class solvent；The preferred dichloromethane of the halogenated hydrocarbon solvent；The preferred benzene of the aromatic hydrocarbon solvent and/or
Toluene；The esters solvent ethyl acetate；The preferred acetone of the ketones solvent；The preferred N of the amide solvent,
Dinethylformamide.
The topological structure of the R ' group that the topological structure polymer removing end that the degree of polymerization is n is made gathers
In the preparation method of compound, preferably, the molar ratio for the topological structure polymer and the isopropanol that the degree of polymerization is n
For (1: 30)~(3: 250), mole of the topological structure polymer that the degree of polymerization is n and the double lauroyl of the peroxidating
Than for 1: (1~6)；More preferably, the molar ratio of the topological structure polymer that the degree of polymerization is n and the isopropanol is (1
: 20)~(3: 200), the molar ratio of the topological structure polymer that the degree of polymerization is n and the double lauroyl of the peroxidating are
1: (1~5).
The topological structure of the R ' group that the topological structure polymer removing end that the degree of polymerization is n is made gathers
In the preparation method of compound, preferably, the molar ratio of the double lauroyl of the isopropanol and the peroxidating for (30~
83.3): (1~8)；More preferably (20~79): (6~8).
The topological structure of the R ' group that the topological structure polymer removing end that the degree of polymerization is n is made gathers
In the preparation method of compound, described 25~150 DEG C of condition is preferably 50 DEG C~100 DEG C, more preferably 60 DEG C~90 DEG C,
It is optimal for 70 DEG C.
The topological structure of the R ' group that the topological structure polymer removing end that the degree of polymerization is n is made gathers
In the preparation method of compound, when n is 10~35, preferably 60 DEG C~70 DEG C of described 25~150 DEG C of condition；When n for 35~
When 100, preferably 70 DEG C~80 DEG C of described 25~150 DEG C of condition.
The topological structure of the R ' group that the topological structure polymer removing end that the degree of polymerization is n is made gathers
In the preparation method of compound, when n is 10~35, when the time preferably 0~5 of reaction is small when small (not for 0)；When n is 35~100
When, when the time preferably 5~48 of reaction is small.
The topological structure of the R ' group that the topological structure polymer removing end that the degree of polymerization is n is made gathers
The preparation method of compound, it is preferred that, also can further include the operation of post processing in removing R ' group after reaction.Institute
The method and condition for the post processing stated can be the method and condition of the such post-reaction treatment routine in this area, preferably：Reaction
After, it is diluted, adds the solvent of insoluble product to precipitate product, filters, it is dry, you can.The dilution preferably makes
Solvent used is diluted during with reaction.The preferred alkane solvents of solvent of the insoluble product, more preferably n-hexane,
Most preferably -10~5 DEG C of n-hexane.The drying is preferably dried in vacuo, and more preferably vacuum is done in 40~50 DEG C of baking oven
It is dry.
End is removed by the topological structure polymer that the degree of polymerization is n that is made present invention also offers a kind of
R ' group topological structure polymer preparation method obtained by the degree of polymerization be n topological structure polymer remove
The topological structure polymer of the R ' group of end；The n and the R ' are as described above.
In the present invention, the topological structure polymer is the polymer for having on each molecule three or four arms, this hair
Topological structure polymer in bright uses the technique of painting omitted, only draws the structural formula of one of arm, and other arms use
WaveOmissive representation, the degree of polymerization on each molecule on each arm can be the same or different；.
Room temperature in the present invention refers to environment temperature as 10~30 DEG C.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can be combined, each preferably up to the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is：
1st, topological structure polymer of the invention has lower molecular weight, and number-average molecular weight is divided between 800~10000
Son amount narrowly distributing.
2nd, the preparation method of topological structure polymer of the invention is easy to operate, suitable monomers scope is wide, can prepare and open up
Flutter the structures such as block or the grafting of structure, can remove double thioester groups or xanthate group on polymer, improve polymer
Physical and chemical performance and application prospect.
3rd, of the invention the be stripped of double thioester groups in end or the topological structure polymer of end xanthate group have
Lower molecular weight, narrow molecular weight distribution, compared with the topological structure polymer or linear polymer of traditional high molecular weight, physics
Chemical property is more special, has broad application prospects.
4th, the double thioester groups of removal of the invention or the polymer of xanthate group its dissolving energy in carbon dioxide
The relatively linear non-alternating polymer of power is more excellent, so as to carry out the application of related fields as close carbon dioxide segment, is such as used to make
Standby carbon dioxide thickener or carbon dioxide aqueous emulsion etc., have good application prospect, wherein carbon dioxide thickener can use
In improving oil recovery, document [Tan, B.and A.I.Cooper, Functional oligo (vinyl are specifically referred to
Acetate) CO2-philes for solubilization and emulsification.J Am Chem Soc,
2005.127(25)：p.8938-9].
Brief description of the drawings
Fig. 1 is solubility property test chart of the polymer in carbon dioxide in effect example 1
Fig. 2 is polymer terminal group nucleus magnetic hydrogen spectrum figure before and after the processing in embodiment 4
Fig. 3 is the NMR spectra of four arm topology polyvinyl acetate-poly dibutyl ester copolymer in embodiment 6
Embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
Apply among a scope.The experimental method of actual conditions is not specified in the following example, according to conventional methods and conditions, or according to business
Product specification selects.
Embodiment 1
Step a), take three (methylol) ethane (5.4g), and chloroform (50ml), pyridine (8ml) is in reactor, by reactor
As for 2 bromo propionyl bromide (29.1g) in ice-water bath, is slowly added dropwise, ice-water bath is removed after dripping, seals reactor, at room temperature
48~72h of stirring reaction.Organic phase is washed with 50ml 25vt% dilute hydrochloric acid and 100ml 10wt% sodium bicarbonate solutions, is used in combination
Anhydrous magnesium sulfate dries a few hours.Vacuum distillation obtains white solid powder after removing solvent.
Step b), take the three arm bromination precursor (20g) of product of above-mentioned steps a), chloroform (100ml), excessive ethyl xanthan
72h~96h is reacted in stirring to sour potassium (40g) at room temperature in reactor, filters the ehtyl potassium xanthate of unnecessary suspension, uses 100ml
Chloroform 5 times, vacuum distillation remove solvent.Tri- arm topology xanthates of 8.7g (its structural formula such as the explanation of the present invention is made
Shown in book Chinese style 3, and R1And R2It is methyl).
Embodiment 2
Step a), take pentaerythrite (5.72g), chloroform (50ml), pyridine (8ml) in reactor, by reactor as
In ice-water bath, 2 bromo propionyl bromide (30.0g) is slowly added dropwise, ice-water bath is removed after dripping, seals reactor, stirs at room temperature
React 48~72h.Organic phase is washed with 60ml 25vt% dilute hydrochloric acid and 120ml 10wt% sodium bicarbonate solutions, and with anhydrous
Magnesium sulfate dries a few hours.Vacuum distillation obtains white solid powder after removing solvent.
Step b), the four arm bromination precursor (20g) of product for taking above-mentioned steps a), chloroform (10ml), excessive ethoxy-dithioformic acid
72h-96h is reacted in stirring to potassium (4g) at room temperature in reactor, the ehtyl potassium xanthate of unnecessary suspension is filtered, with 120ml chloroforms
Washing 6 times, vacuum distillation remove solvent.Tetra- arm topology xanthates of 9.2g are made (in the specification of its structural formula such as present invention
Shown in formula 4, and R3For methyl).
Embodiment 3
Take in vinyl acetate (18ml), tetrahydrofuran (4ml), even helium bis-isobutyronitrile (0.6065g) and embodiment 1 and be made
Three arm topology xanthate 1.5g, be uniformly mixed.Reactor is vacuumized before reaction and is passed through drying nitrogen repeatedly for three times, is sealed
Reactor.Reactor is as the stirring reaction 30 minutes of 60 DEG C of constant temperature, and reaction products therefrom 5ml tetrahydrofurans dissolve, in 200ml
Precipitate, filter in ice n-hexane, sediment obtains 2.8g, molecular weight 956, molecular weight distribution is in 40 DEG C of baking oven application of vacuum 48h
1.04 polyvinyl acetate.
Take previous step react synthesized by polyvinyl acetate (2.46mmol), tetrahydrofuran (3ml), isopropanol (6ml) and
The double lauroyl (8mmol) of peroxidating vacuumize in reactor and are passed through drying nitrogen repeatedly for three times, seal reactor.At 70 DEG C
It is lower reaction 6 it is small when, after resulting solution dissolve in 5ml tetrahydrofurans, precipitated in 150ml ice n-hexanes, suction filtration, sediment in
40 DEG C of baking oven application of vacuum 48h obtain 2.1g final products, are molecular weight 712, distribution 1.1 within without the three of xanthan acid end group
Arm topological structure polyvinyl acetate, conversion ratio 25%.
Embodiment 4
Take in vinyl acetate (10ml), tetrahydrofuran (4ml), azodiisobutyronitrile (0.6065g) and embodiment 2 and be made
Four arm topology xanthate 1g, be uniformly mixed.Reactor is vacuumized before reaction and is passed through drying nitrogen repeatedly for three times, sealing is anti-
Answer device.Reactor is as the stirring reaction 30 minutes of 70 DEG C of constant temperature, and reaction products therefrom 5ml tetrahydrofurans dissolve, in 200ml ice
Precipitate, filter in n-hexane, sediment obtains 1.3g, molecular weight 792, molecular weight distribution is in 40 DEG C of baking oven application of vacuum 48h
1.01 polyvinyl acetate.
Take previous step react synthesized by polyvinyl acetate (1.23mmol), tetrahydrofuran (3ml), isopropanol (6ml) and
The double lauroyl (6mmol) of peroxidating vacuumize in reactor and are passed through drying nitrogen repeatedly for three times, seal reactor.At 70 DEG C
Lower reaction 10h, after resulting solution dissolves in 5ml tetrahydrofurans, is precipitated in 100ml ice n-hexanes, is filtered, sediment is in 40
DEG C baking oven application of vacuum 48h obtains final product, is the four arm topological structure polyvinyl acetate without end group, passes through polymer end
Base hydrogen spectrogram comparative analysis before and after the processing, the conversion ratio for removing the reaction of xanthan acid end group are 97%.Product is molecular weight 513,
The four arm topological structure polyvinyl acetate without xanthan acid end group within distribution 1.1.
Embodiment 5
Take in vinyl acetate (10ml), tetrahydrofuran (4ml), azodiisobutyronitrile (0.6065g) and embodiment 2 and be made
Four arm topology xanthate 1.2g, be uniformly mixed.Reactor is vacuumized before reaction and is passed through drying nitrogen repeatedly for three times, is sealed
Reactor.Reactor is dissolved as 80 DEG C of stirring 6 hours of reaction of constant temperature, reaction products therefrom 5ml tetrahydrofurans, in
Precipitate, filter in 200ml ice n-hexanes, sediment is in 40 DEG C of baking oven application of vacuum 48h, and it is molecular weight 10220 to obtain 8.4g, distribution
Polyvinyl acetate within 1.1.
Take previous step react synthesized by polyvinyl acetate (1.23mmol), tetrahydrofuran (3ml), isopropanol (6ml) and
The double lauroyl (6mmol) of peroxidating vacuumize in reactor and are passed through dry helium gas repeatedly for three times, seal reactor.At 70 DEG C
Lower reaction 10h, after resulting solution dissolves in 5ml tetrahydrofurans, is precipitated in 100ml ice n-hexanes, is filtered, sediment is in 40
DEG C baking oven application of vacuum 48h obtains final product, is molecular weight 9800, and four arms without xanthan acid end group within distribution 1.1 are opened up
Flutter structure polyvinyl acetate, conversion ratio 85%.
Embodiment 6
Take vinyl acetate (5ml), dibutyl maleate (5ml), tetrahydrofuran (6ml), azodiisobutyronitrile
Obtained four arm topology xanthate 1.2g, are uniformly mixed in (0.3648g) and embodiment 2.Reactor is vacuumized before reaction
It is passed through drying nitrogen repeatedly for three times, seals reactor.Reactor is as 60 DEG C of stirring 6 hours of reaction of constant temperature, reaction gained production
Thing 5ml tetrahydrofurans dissolve, and are precipitated in 200ml ice n-hexanes, filter, and sediment is obtained in 40 DEG C of baking oven application of vacuum 48h
3.4g, molecular weight 4441, molecular weight distribution are four arm topology polyvinyl acetate-poly dibutyl ester copolymerization within 1.1
Thing, and be alternate copolymer, yield 30%.NMR analyses are carried out to product, NMR spectra is shown in Fig. 3.
Take copolymer (1.23mmol), tetrahydrofuran (3ml), isopropanol (6ml) and peroxidating synthesized by previous step reaction
Double lauroyl (6mmol) vacuumize in reactor and are passed through drying nitrogen repeatedly for three times, seal reactor.Reacted at 70 DEG C
10h, after resulting solution dissolves in 5ml tetrahydrofurans, is precipitated in 100ml ice n-hexanes, is filtered, sediment is in 40 DEG C of baking ovens
Application of vacuum 48h obtains final product, is molecular weight 3982, and molecular weight distribution is four arms without xanthan acid end group within 1.1
The copolymer of topological structure, yield 90%.
Effect example 1
Solubility in the present invention using variable-volume high pressure form kettle characterization polymer in carbon dioxide, in same survey
Try under temperature and quality requirements, solvability of the lower expression material of cloud-point pressure in carbon dioxide is better.
In Fig. 1, what square ■ represented the present invention be free of four arm star polyvinyl acetate of xanthan acid end group, circle ● represents
The four arm star polyvinyl acetate of acid end group containing xanthan of invention, wherein, the polymer representated by square and circle is to correspond
, i.e., the polymer representated by square is the polymer that round representative polymer is formed after xanthan acid end group is sloughed；Just
Synthesized before triangle ▲ represent Tan Bien et al. topological polyvinyl acetate (specific synthetic method refer to document [Tan,
B.and A.I.Cooper, Functional oligo (vinyl acetate) CO2-philes for solubilization
And emulsification.J Am Chem Soc, 2005.127 (25)：p.8938-9])；Up-side down triangleRepresent linear poly-
Vinyl acetate；TiltedlyTriangle represents the linear polyvinyl acetate-poly two synthesized before Hyunsuk Lee et al.
(specific synthetic method refers to document [Lee, H., et al., Synthesis and Phase to butyl ester alternating polymer
Behavior of CO2-Soluble Hydrocarbon Copolymer：Poly(vinyl acetate-alt-dibutyl
Maleate) .Macromolecules, 2010.43 (5)：p.2276-2282]).
It will be noted from fig. 1 that listed polymer molecular weight differs less than 1000 all in the range of 3000-4000.
Cloud point test is carried out at 30 DEG C.All samples are tested under conditions of opposite carbon dioxide quality 0.2%.From Fig. 1
In it can be seen that, the cloud-point pressure without the star-like polyvinyl acetate of xanthan acid end group synthesized in the present invention is
20.5MPa, and the cloud-point pressure of the star-like polyvinyl acetate of acid end group containing xanthan synthesized in the present invention is 26.4MPa,
That is after xanthan acid end group is removed, the cloud-point pressure of star-like polyvinyl acetate is significantly reduced, about 6MPa.The present invention
In synthesized to reduce 8MPa without the more linear polyvinyl acetate cloud-point pressure of the star-like polyvinyl acetate of xanthan acid end group left
The right side, with Tan before must be synthesized by grace et al. topological polyvinyl acetate compared with, cloud-point pressure reduces 5MPa.In shown polymerization
In thing, cloud-point pressure it is minimum be Hyunsuk Lee et al. synthesis linear polyvinyl acetate-poly dibutyl ester alternating
Polymer, about 18.5MPa, in below 20MPa.
In conclusion the star-like polyvinyl acetate without xanthan acid end group synthesized in the present invention can be largely
The upper solubility for improving polymer in carbon dioxide.
Under the monomer unanimous circumstances of polymer, the topology of the double thioester groups of removal of the invention or xanthate group
Its solvability in carbon dioxide of the polymer of structure is more excellent compared with linear polymer, so as to as close carbon dioxide segment
The application of related fields is carried out, is such as used to prepare carbon dioxide thickener or carbon dioxide aqueous emulsion, before having application well
Scape, wherein carbon dioxide thickener can be used for improve oil recovery, specifically refer to document [Tan, B.and A.I.Cooper,
Functional oligo(vinylacetate)CO2-philes for solubilization and
Emulsification.JAm Chem Soc, 2005.127 (25)：p.8938-9].
Claims (11)
- A kind of 1. topological structure polymer as shown in formula 2 or formula 2 '；Wherein, the n represents the degree of polymerization, n=10~250；Wherein, each " [] " represents a construction unit, is mutually independent between each construction unit, that is to say, that each Y in construction unit can be the same or different, and the Z in each construction unit can be the same or different；The Y and Z is independently each hydrogen or the various conventional substituted ethene used in the polymerisation of this area The one or more in various substituents on base monomer；In the structure of the topological structure polymer as shown in formula 2 or formula 2 ', waveRepresent polymerization One arm of thing；The degree of polymerization on each molecule on each arm can be the same or different；The R1、R2And R3It is independently each hydrogen or C1~C6Alkyl.
- 2. the topological structure polymer as shown in formula 2 or formula 2 ' as claimed in claim 1, it is characterised in that：N=10~100；And/or the R1、R2And R3It is independently each hydrogen or C1~C3Alkyl；And/or the Y and the Z are independently each hydrogen, C1~C3Alkanoyloxy, cyano group, phenyl and C1~C4Alcoxyl Base-carbonyl-in one or more.
- 3. the topological structure polymer as shown in formula 2 or formula 2 ' as claimed in claim 2, it is characterised in that：N=10~35；And/or the C1~C3Alkyl is methyl or ethyl；And/or the Y and the Z are independently each hydrogen, C1~C3Alkanoyloxy and C1~C4Alkoxy-carbonyl-in It is one or more.
- 4. the topological structure polymer as shown in formula 2 or formula 2 ' as claimed in claim 3, it is characterised in that：The C1~C4 Alkoxy-carbonyl-it is normal-butyl oxygen carbonyl；And/or the C1~C3Alkanoyloxy is acetoxyl group；And/or in the construction unit described in part, the Y is acetoxyl group and the Z is hydrogen；The structure of remainder In unit, the Y and Z are normal-butyl oxygen carbonyl.
- It is 5. a kind of as the topological structure polymer according to any one of claims 1 to 4 as shown in formula 2 or formula 2 ' is preparing two Application in carbonoxide thickener or carbon dioxide aqueous emulsion.
- 6. the preparation method of a kind of topological structure polymer as shown in formula 2 or formula 2 ', it is characterised in that it includes step as follows Suddenly：In solvent, under conditions of 25~150 DEG C, under the conditions of anhydrous and oxygen-free, will as the topological structure polymer shown in formula 1 or formula 1 ', The double lauroyl of isopropanol and peroxidating carry out removing as follows end on the topological structure polymer as shown in formula 1 or formula 1 ' R ' group reaction；Reaction time for 0~48 it is small when, and for 0 it is small when；It is corresponding to be made poly- as shown in formula 2 or formula 2 ' Compound；Wherein, the R ' group of end is on the topological structure polymer as shown in formula 1 or formula 1 'Group；Wherein, described n, Y, Z, R1、R2And R3Any one of Claims 1 to 4；The W is carbon or oxygen；The L is C1~C6Alkyl；In the structure of the topological structure polymer as shown in formula 1, formula 1 ', formula 2 or formula 2 ', waveRepresent an arm of polymer；The degree of polymerization on each molecule on each arm can be the same or different.
- 7. the preparation method of the topological structure polymer as shown in formula 2 or formula 2 ' as claimed in claim 6, it is characterised in that：In the preparation method of the topological structure polymer as shown in formula 2 or formula 2 ', the removing such as formula 1 or formula 1 ' The condition of anhydrous and oxygen-free is the reaction vessel using sealing in the reaction of the R ' group of end on shown topological structure polymer And vacuumize-lead to that protective gas is repeated multiple times realizes；And/or in the preparation method of the topological structure polymer as shown in formula 2 or formula 2 ', the removing such as formula 1 Or the solvent on the topological structure polymer shown in formula 1 ' in the reaction of the R ' group of end is ether solvent, halogenated hydrocarbon is molten One or more in agent, aromatic hydrocarbon solvent, esters solvent, ketones solvent and amide solvent；And/or in the preparation method of the topological structure polymer as shown in formula 2 or formula 2 ', the removing such as formula 1 Or on the topological structure polymer shown in formula 1 ' in the reaction of the R ' group of end, the polymer as shown in Equation 1 and institute The molar ratio for the isopropanol stated is (1：30)~(3：250)；And/or the molar ratio of the polymer as shown in Equation 1 and the double lauroyl of the peroxidating is 1：(1~6)；And/or in the preparation method of the topological structure polymer as shown in formula 2 or formula 2 ', the removing such as formula 1 Or the temperature of the reaction of the R ' group of end is 50 DEG C~100 DEG C on the topological structure polymer shown in formula 1 '.
- 8. the preparation method of the topological structure polymer as shown in formula 2 or formula 2 ' as claimed in claim 7, it is characterised in that：In the preparation method of the topological structure polymer as shown in formula 2 or formula 2 ', the removing such as formula 1 or formula 1 ' On shown topological structure polymer in the reaction of the R ' group of end, when n is 10~35, the temperature of reaction is 60 DEG C~70 ℃；When n is 35~100, the temperature of reaction is 70 DEG C~80 DEG C；And/or in the preparation method of the topological structure polymer as shown in formula 2 or formula 2 ', the removing such as formula 1 Or on the topological structure polymer shown in formula 1 ' in the reaction of the R ' group of end, when n is 10~35, the time of reaction is 0 ~5 it is small when, and for 0 it is small when；When n is 35~100, when the time of reaction is 5~48 small.
- 9. the preparation method of the topological structure polymer as shown in formula 2 or formula 2 ' as claimed in claim 6, it is characterised in that： The preparation method of the topological structure polymer as shown in formula 2 or formula 2 ', further comprises following steps：In solvent, Under the conditions of 25 DEG C~150 DEG C, by chain-transferring agent, vinyl monomer and the initiator as shown in formula 3 or formula 4 anhydrous and oxygen-free bar Raolical polymerizable is carried out under part, when the reaction time is 1~48 small, the topology knot as shown in formula 1 or formula 1 ' is made Structure polymer；Wherein, described n, Y, Z, W, L, R1、R2And R3With described in claim 6；In the structure of the topological structure polymer as shown in formula 1 or formula 1 ', waveRepresent polymerization One arm of thing；The degree of polymerization on each molecule on each arm can be the same or different.
- 10. the preparation method of the topological structure polymer as shown in formula 2 or formula 2 ' as claimed in claim 9, it is characterised in that：In the preparation method of the topological structure polymer as shown in formula 1 or formula 1 ', the condition of the anhydrous and oxygen-free is Using sealing reaction vessel and vacuumize-lead to that protective gas is repeated multiple times realizes；And/or in the preparation method of the topological structure polymer as shown in formula 1 or formula 1 ', the radical polymerization Solvent in reaction is ether solvent, halogenated hydrocarbon solvent, aromatic hydrocarbon solvent, esters solvent, ketones solvent and amide solvent In one or more；And/or in the preparation method of the topological structure polymer as shown in formula 1 or formula 1 ', the initiator is even One or more in nitrogen bis-isobutyronitrile, azobisisoheptonitrile and azobisisovaleronitrile；And/or in the preparation method of the topological structure polymer as shown in formula 1 or formula 1 ', the use of the initiator The molar ratio measured as the initiator and the vinyl monomer is 1:(25~100)；And/or in the preparation method of the topological structure polymer as shown in formula 1 or formula 1 ', it is described such as formula 3 or formula 4 Molar ratio between shown chain-transferring agent and vinyl monomer is 1：(25~500)；And/or in the preparation method of the topological structure polymer as shown in formula 1 or formula 1 ', the radical polymerization The temperature of reaction is 50~100 DEG C；And/or in the preparation method of the topological structure polymer as shown in formula 1 or formula 1 ', the radical polymerization When the time of reaction is 1~24 small.
- 11. the preparation method of the topological structure polymer as shown in formula 2 or formula 2 ', its feature exist as claimed in claim 10 In：In the preparation method of the topological structure polymer as shown in formula 1 or formula 1 ', when n is 10~30, it is described from It it is 50~60 DEG C by the temperature of base polymerisation；When n is 30~250, the temperature of the Raolical polymerizable for 60~ 80℃；And/or in the preparation method of the topological structure polymer as shown in formula 1 or formula 1 ', when n is 10~30, institute When the time for the Raolical polymerizable stated is 1~3 small；When n is 30~250, the time of the Raolical polymerizable For 3~24 it is small when.
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