CN106366229A - Synthetic method of polycyclic branched polymer - Google Patents
Synthetic method of polycyclic branched polymer Download PDFInfo
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- CN106366229A CN106366229A CN201610803687.1A CN201610803687A CN106366229A CN 106366229 A CN106366229 A CN 106366229A CN 201610803687 A CN201610803687 A CN 201610803687A CN 106366229 A CN106366229 A CN 106366229A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/48—Isomerisation; Cyclisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2810/00—Chemical modification of a polymer
- C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority
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Abstract
The invention discloses a synthetic method of a polycyclic branched polymer. The invention adopts the technical scheme that the synthetic method comprises the following steps: firstly synthesizing an initiator monomer (BiBEM) and then initiating styrene polymerization through a synthetic branched monomer initiator; preparing branched polystyrene (BPS) through typical atom transfer radical polymerization (ATRP) by taking cuprous bromide (CuBr) as a catalyst and 2-2'dipyridyl (bpy) as a ligand; further obtaining branched polystyrene (BPS) with higher molecular weight and branching degree by performing settling classification on the prepared branched polystyrene; finally, enabling a polymer intra-molecular chain end to generate coupling reaction through an atom transfer radical cyclization (ATRC) method and synthesizing the branched polymer containing a polycyclic structure. Compared with other polymers with topological structures, the cyclic polymer disclosed by the invention has special properties, including viscosity, glass transition temperature, self-assembly properties, surface properties and the like. While the advantages of the cyclic polymer are absorbed, the polycyclic branched polymer synthesized by the synthetic method disclosed by the invention overcomes the defect that the synthesis of the cyclic polymer is only limited to the reaction among polymers with low-molecular weights.
Description
Technical field
Present document relates to the preparation of macromolecular material, develop a kind of synthetic method containing multi-ring branched polymer.
Background technology
In nature, some natural macromolecular materials, such as dna, polysaccharide, peptide and polypeptide etc., it is cyclic polymer,
Play very important effect in vital movement, which results in the extensive interest of researcher.In recent years, with scientific and technological
Development and the lifting of research meanses, people conduct in-depth research to cyclic polymer, the preparation of artificial cyclic polymer with
One of person's research direction that application becomes polymer science.Compared with linear polymer, cyclic polymer has unique advantage, in structure
There is not any end group, form stronger rigid molecule chain, its conformational entropy is less, and the unit on strand has equivalent materialization
Performance, shows higher glass transition temperature (tg), density and refraction index, less hydrodynamic radius, characteristic glue
The characteristic such as degree and mobile coefficient of friction.It is easy to there is intermolecular side reaction, intramolecular in synthesis of cyclic polymer process
Annulation activity is poor, prepares high-purity cyclic polymer and brings greatly difficult and challenge, therefore, the past adopts mostly
Anion or ring-opening polymerisation are obtained with other reaction combined methods, but reaction condition is relatively harsh.In recent years, with " active "/
The development of controllable free-radical polymerisation and the introducing of highly effective reaction, open the new method preparing cyclic polymer, greatly enrich
The type of cyclic polymer, the new material having property for research and development provides and supplements and develop.2006, laurent
Et al. make use of atom transfer radical polymerization (atrp) method to prepare end group polystyrene containing alkynyl, by Hydrazoic acid,sodium salt first
Terminal-modified to α-bromine prepare the huge legendary turtle claw type polymer that end group contains alkynes and azido, " click " chemical method under the conditions of extremely dilute
Intramolecular cyclization, prepares efficient annular polystyrene.Liu Shiyong seminar prepares the temperature of uniqueness using similar method
Quick property ring-type is poly- (n- N-isopropylacrylamide).Zhu Xiu woods seminar is employed atrp and is prepared with " click " chemical combination method
The cyclic polymer (cyclic-pvbcz) of carbazolyl-containing group, compared with corresponding linear polymer, shows excellent fluorescence
And chemical property.Cyclomethicones acrylic acid methyl ester. and its block copolymer are also reported in succession.In addition, atrp is even with free radical
Conjunction terminates cyclization combination, RAFT (raft) is polymerized and " click " chemical combination, Terminal Acetylenes coupling cyclization,
" diels-alder " addition cyclization, raft polymerization are combined with mercaptan-alkene or aldehyde addition, NO free radical polymerization is even with free radical
Synthesis ring Assembled lamp method is widely used in the preparation and application of cyclic polymer.
Deepen continuously with research, the preparation of monocyclic polymer tends to ripe, starts to containing ring-type complex topology structure
Macromolecular material develops.Hong Chunyan et al. adopts atrp and " click " chemical combination method to prepare controlled side chain containing polycyclic
The comb-shaped polymer of structure, its branching density reaches 20%, additionally, this seminar reports 8 font cyclic polymers, after cyclisation
Polymer fluorescent performance is obviously improved.Chen Yongming et al. prepares 8 words using atom transferred free radical coupling cyclization (atrcc) method
Type cyclic polymer, the fracture transition that ironically bicyclic polymer can pass through-s-s- is monocyclic polymer.Additionally, more
The structure of complicated band topology is reported in succession, such as sun flower pattern, ring-type brush-type, Margarita serial type, the polymer such as petal-shaped.But it is existing
The report being related to cyclic polymer is limited only to low-molecular weight polymer, relevant high molecular cyclic polymer pertinent literature and
Patent is not reported.
It provided herein is the synthetic method containing polycyclic branched polymer, with cyclic branched polystyrene (cyclic-
bps).
For realizing the technical solution used in the present invention it is
(1) preparation of initiator monomer (bibem)
Hydroxyethyl methylacrylate (hema), pyridine (py) and ch is added in 250ml single port bottle2cl2, will be alpha-brominated
Isobutyl acylbromide and ch2cl2It is configured to mixed solution, is stirred vigorously under the conditions of 0 DEG C, be slowly dropped in single port bottle, completion of dropwise addition
React 5h afterwards.After reaction stops, mixed solution is filtered in the aqueous hydrochloric acid solution pour into 5% and stirs, take off a layer liquid.Use respectively
5% hydrochloric acid solution, 5% sodium bicarbonate aqueous solution and solution washing, washing separates organic faciess several times afterwards, adds anhydrous sodium sulfate
It is dried, vacuum distillation obtains methacrylic acid (α-bromine Isobutanovloxyethvl) ester (bibem).
(2) preparation of branched polystyrene (bps)
To synthesize bibem as initiator, styrene is monomer (st), 2-2 ' bipyridyl (bpy), and cuprous bromide (cubr) is
Catalyst, methyl phenyl ethers anisole is solvent.Typical atrp polymerization: by branched monomer, styrene, 2-2’Bipyridyl, methyl phenyl ethers anisole is added to
In the polymerization bottle of 100ml, cubr is added to continue evacuation after evacuation deoxygenation 40min, polymerization bottle is placed in oil after finishing by deoxygenation
In bath, 80 DEG C of reaction 48h terminate.Polymer is passed through alkali alumina pillar in ethanol with after oxolane (thf) dissolving
Precipitation.Sucking filtration obtains polymer and places oven for drying to constant weight.
(3) classification of sedimentation obtains molecular weight and the higher polystyrene (bps) of the degree of branching
The branched polymer of above-mentioned synthesis is dissolved in substantial amounts of oxolane (thf), under agitation slowly to poly-
Deca ethanol in polymer solution, until system goes to micro- rate of addition slowing down ethanol in vain further.Stand liquid, collect polymerization
Thing, places oven for drying to constant weight, has both obtained molecular weight and the higher polystyrene (bps) of the degree of branching
(2) preparation of branched polymer containing polycyclic (cyclic-bps)
1. the selection of catalyst system and catalyzing
With the higher me of activity6Tren is part, and cuprous bromide (cubr) is catalyst, is made in the presence of Nanometer Copper and urges
Change system.Reaction need to be carried out under extremely dilute oxygen free condition, by me6Tren, cubr, cu are dissolved in 200ml oxolane (thf), and
Logical argon deoxygenation 3h.
2. the enforcement of course of reaction
10mg bps is dissolved in after 20ml thf deoxygenation, in catalyst system and catalyzing before being slowly expelled to by syringe pump, reaction
24h terminates, that is, obtain cyclic-bps.
The cyclic polymer advantage that the present invention prepares is:
1. building-up process is relatively easy efficiently first, and course of reaction does not have side reaction to produce.
2. the cyclic polymer invented herein has special property with respect to the polymer of other topological structure, including viscous
Degree, glass transition temperature, self-assembly property and surface nature etc..While drawing the advantage of cyclic polymer, close herein
The synthesis of cyclic polymer before the cyclic polymer becoming overcomes is limited only to the reaction between low-molecular weight polymer.
Brief description
Fig. 1 is initiator monomer (bibem) of the present invention, branched polystyrene and the branched polyphenyl second containing polycyclic
The synthetic route of alkene.
Fig. 2 is the nuclear magnetic spectrogram of branched polystyrene as herein described (bps).
It can be seen that bibem goes out peak position in hydrogen spectrogram and ratio is consistent with theory in Fig. 2.
Fig. 3 is branched polystyrene as herein described (bps) and branched polystyrene containing polycyclic (cyclic-bps) gpc
Curve chart.
Fig. 3 can be seen that bps and cyclic-bps peak type and pdi do not have significant change, illustrates do not have in course of reaction
There is intermolecular coupling reaction.
It is embodied as:
Embodiment 1
The preparation of initiator monomer (bibem).
Hydroxyethyl methylacrylate (hema), pyridine (py) and ch is added in 250ml single port bottle2cl2, will be alpha-brominated
Isobutyl acylbromide and ch2cl2It is configured to mixed solution, is stirred vigorously under the conditions of 0 DEG C, be slowly dropped in single port bottle, completion of dropwise addition
React 5h afterwards.After reaction stops, mixed solution is filtered in the aqueous hydrochloric acid solution pour into 5% and stirs, take off a layer liquid.Use respectively
5% hydrochloric acid solution, 5% sodium bicarbonate aqueous solution and solution washing, washing separates organic faciess several times afterwards, adds anhydrous sodium sulfate
It is dried, vacuum distillation obtains methacrylic acid (α-bromine Isobutanovloxyethvl) ester (bibem).
Embodiment 2
1. the preparation of branched polystyrene (bps).
Typical atrp reaction experiment is as follows, and with styrene (st) as monomer, the bibem of synthesis is initiator monomer, with
Cuprous bromide (cubr) and part 2-2 ' bipyridyl (bpy) constitute catalyst system and catalyzing, with methyl phenyl ethers anisole as solvent.Concrete operation is such as
Under: first solvent methyl phenyl ethers anisole is added in the polymerisation bottle of 100ml, then the branched monomer bibem after good, part by weighing
Bpy is added in reaction bulb, rapidly joins catalyst cubr after stirring evacuation 40min under condition of ice bath, continues logical argon
Gas evacuation 40min, reaction bulb is placed in reaction 48h in 85 DEG C of oil bath pans.After reaction terminates, product parlkaline is aoxidized
Aluminum pillar is added drop-wise in dehydrated alcohol and is settled out polymer.Polymer is taken out by centrifugation and places vacuum drying oven to constant weight, obtain
To branched polystyrene (bps).
2. molecular weight and the higher branched polystyrene (bps) of the degree of branching are obtained by classification of sedimentation
The bps preparing before is dissolved in oxolane, ethanol is slowly dropped under agitation four dissolved with bps
In hydrogen tetrahydrofuran solution, until there being micro polymer to separate out, slow down rate of addition further.The polymer overnight stand that will separate out
Collect and obtain molecular weight and the higher branched polystyrene (bps) of the degree of branching.
Embodiment 3
The preparation of branched polymer containing polycyclic (cyclic-bps)
Add 200ml oxolane in the there-necked flask of 500ml, be simultaneously introduced me6Tren, cubr, cu, then lead to argon
It is to slowly warm up to 75 DEG C after gas deoxygenation 3h, after balance 30min, will be dissolved with bps (10mg) tetrahydrofuran solution by syringe pump
(25ml) slowly it is expelled in there-necked flask (0.8ml/h).After reaction 24h terminates, first pass through alkali alumina pillar and remove copper
Salt, then resulting polymers are finally precipitated out, that is, obtain product (cyclic-bps) by revolving removing thf in methyl alcohol.
Synthetic method containing polycyclic branched polymer provided by the present invention is it is not limited to retouching in above-described embodiment
State method, foregoing description method is merely exemplary, nonrestrictive.The authority of the present invention is defined in the claims, and is based on
Those skilled in the art the technology with the present invention that method obtains such as can change, recombinate, at this according to the present invention
Within bright rights protection scope.
Claims (1)
1. one kind contains multi-ring branched polymer preparation method, and its feature is as follows:
1st, the synthesis (bibem) of initiator monomer methacrylic acid (2- bromine Isobutanovloxyethvl) ester
Hydroxyethyl methylacrylate (hema), pyridine (py) and ch is added in 250ml single port bottle2cl2, by alpha-brominated isobutyl
Acylbromide and ch2cl2It is configured to mixed solution, is stirred vigorously under the conditions of 0 DEG C, be slowly dropped in single port bottle, anti-after completion of dropwise addition
Answer 5h.After reaction stops, mixed solution is filtered in the aqueous hydrochloric acid solution pour into 5% and stirs, take off a layer liquid.Respectively with 5%
Hydrochloric acid solution, 5% sodium bicarbonate aqueous solution and solution washing, washing separates organic faciess several times afterwards, adds anhydrous sodium sulfate to do
Dry, vacuum distillation obtains methacrylic acid (α-bromine Isobutanovloxyethvl) ester (bibem).
2nd, the preparation of branched polystyrene (bps)
Typical atrp reaction experiment is as follows, and with styrene (st) as monomer, the bibem of synthesis is initiator monomer, with bromination
Cuprous (cubr) and part 2-2 ' bipyridyl (bpy) constitute catalyst system and catalyzing, with methyl phenyl ethers anisole as solvent.Concrete operation is as follows:
First solvent methyl phenyl ethers anisole is added in the polymerisation bottle of 100ml, then by the branched monomer bibem after weighing well, part bpy adds
Enter in reaction bulb, after stirring evacuation 40min under condition of ice bath, rapidly join catalyst cubr, continue logical argon and take out very
Empty 40min, reaction bulb is placed in reaction 48h in 85 DEG C of oil bath pans.After reaction terminates, by product parlkaline aluminium oxide pillar
It is added drop-wise in dehydrated alcohol and be settled out polymer.Polymer is taken out by centrifugation and places vacuum drying oven to constant weight, obtain branched
Polystyrene bps.
3rd, molecular weight and the higher branched polystyrene (bps) of the degree of branching are obtained by classification of sedimentation
The bps preparing before is dissolved in oxolane, ethanol is slowly dropped under agitation the tetrahydrochysene furan dissolved with bps
Muttering in solution, until there being micro polymer to separate out, slowing down rate of addition further.The polymer overnight stand separating out is collected
Obtain molecular weight and the higher branched polystyrene (bps) of the degree of branching.
4th, the preparation of branched polymer containing polycyclic (cycilic-bps)
Add 200ml oxolane in the there-necked flask of 500ml, be simultaneously introduced me6Tren, cubr, cu, then lead to argon and remove
It is to slowly warm up to 75 DEG C after oxygen 3h, after balance 30min, will be dissolved with bps (10mg) tetrahydrofuran solution (25ml) by syringe pump
Slowly it is expelled in there-necked flask (0.8ml/h).After reaction 24h terminates, first pass through alkali alumina pillar and remove mantoquita, then
Revolving removes thf, is finally precipitated out resulting polymers in methyl alcohol, that is, obtains product (cyclic-bps).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107163178A (en) * | 2017-05-23 | 2017-09-15 | 常州大学 | A kind of quick method for preparing hyperbranched poly acrylic resin under normal temperature |
| CN114671770A (en) * | 2021-12-04 | 2022-06-28 | 青岛科技大学 | Production method of 4,4' -diaminodiphenyl ether |
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| CN103214606A (en) * | 2013-04-28 | 2013-07-24 | 苏州大学 | Preparation method of cyclic polyvinyl acetate |
| CN104151483A (en) * | 2014-06-04 | 2014-11-19 | 常州大学 | Preparation method of hydroxyl-terminated hyperbranched polyacrylate |
| CN104961847A (en) * | 2015-07-14 | 2015-10-07 | 湘潭大学 | Synthesis method of annular rigid liquid crystal polymer |
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2016
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103214606A (en) * | 2013-04-28 | 2013-07-24 | 苏州大学 | Preparation method of cyclic polyvinyl acetate |
| CN104151483A (en) * | 2014-06-04 | 2014-11-19 | 常州大学 | Preparation method of hydroxyl-terminated hyperbranched polyacrylate |
| CN104961847A (en) * | 2015-07-14 | 2015-10-07 | 湘潭大学 | Synthesis method of annular rigid liquid crystal polymer |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163178A (en) * | 2017-05-23 | 2017-09-15 | 常州大学 | A kind of quick method for preparing hyperbranched poly acrylic resin under normal temperature |
| CN114671770A (en) * | 2021-12-04 | 2022-06-28 | 青岛科技大学 | Production method of 4,4' -diaminodiphenyl ether |
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