CN106008797A - Polyacrylonitrile gradient copolymer and controllable synthesis method thereof - Google Patents
Polyacrylonitrile gradient copolymer and controllable synthesis method thereof Download PDFInfo
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- CN106008797A CN106008797A CN201610516919.5A CN201610516919A CN106008797A CN 106008797 A CN106008797 A CN 106008797A CN 201610516919 A CN201610516919 A CN 201610516919A CN 106008797 A CN106008797 A CN 106008797A
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- polyacrylonitrile
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
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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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/50—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkaline earth metals, zinc, cadmium, mercury, copper or silver
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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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/80—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from iron group metals or platinum group metals
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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
- C08F2438/00—Living radical polymerisation
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract
The invention provides a polyacrylonitrile gradient copolymer and a controllable synthesis method thereof. The method is characterized in that the process is simple, applicable monomers are wide in range, and the synthesis efficiency is high. The controllable synthesis method comprises the following steps of putting an acrylonitrile monomer, a comonomer, a ligand, an initiator and a zero-valent metal catalyst into solvent; performing a polymerization reaction on the acrylonitrile monomer, the comonomer and the initiator at the temperature of 25 to 100DEG C, and controlling the molecular weight of the obtained polyacrylonitrile gradient copolymer by adjusting the reaction time. The Mw-to-Mn ratio of the polyacrylonitrile gradient copolymer obtained by synthesis is small, which shows that the molecular weight is narrow in distribution and high in purity; an actual molecular weight of the obtained polymer is consistent with a theoretical molecular weight.
Description
Technical field
The present invention relates to macromolecule synthesising technology field, particularly relate to a kind of polyacrylonitrile gradient copolymer
Controllable synthesis method.
Background technology
Owing to " active "/controllable free-radical can be to the structure of polymer, molecular weight, molecule
Amount distribution is designed, thus by scientist's extensive concern.Study hotter mainly including at present
The polymerization of atom transfer radical polymerization, reversible addion-fragmentation chain transfer and zero-valent metal are catalyzed
Controllable free-radical polymerisation.For first two polymerization, zero-valent metal especially zeroth order
" active " controllable free-radical polymerisation of copper catalysis has that response speed is fast, reaction condition gentle with
And the feature of good economy performance, thus by wide coverage.
Secondly, the character of polymer is had the biggest by the sequence distribution of repeating unit of copolymer
Impact, thus scientists constantly promotes polymer by the control being distributed unit sequence
Performance.And forming along with the chain growth of copolymer can constantly become due to gradient polymer
Change, thus many excellent performances can be brought to polymer.
It is known that acrylonitrile obtains extensively on synthetic fibers, synthetic rubber and synthetic resin
General application, thus the performance of research polyacrylonitrile gradient copolymer is particularly important.Close at present
Report great majority in synthesis polyacrylonitrile gradient copolymer are all based on living free radical polymerization
Polymerization, atom transfer radical polymerization and the method for reversible addion-fragmentation chain transfer polymerization.
And " active " controllable free-radical polymerisation being catalyzed by zerovalent copper builds polyacrylonitrile gradient altogether
The method of polymers so far it is not yet reported that.
In view of drawbacks described above, the design people's the most in addition research and innovation, pass through to founding one
" the active "/controllable free-radical polymerisation of zerovalent copper catalysis builds polyacrylonitrile gradient copolymer
Synthetic method so that it is have more the value in industry.
Summary of the invention
For solving above-mentioned technical problem, it is an object of the invention to provide a kind of polyacrylonitrile gradient altogether
Polymers and controllable synthesis method thereof, the method technique is simple, suitable monomers scope is wide, synthesis effect
Rate is high.
The controllable synthesis method of the polyacrylonitrile gradient copolymer of the present invention, comprises the following steps:
Monomers acrylonitrile, comonomer, initiator, zero-valent metal catalyst and zero-valent metal are urged
The part of agent is placed in solvent, at 25-100 DEG C, and described monomers acrylonitrile and comonomer
Carry out polyreaction, and by adjusting the polyacrylonitrile gradient copolymer that response time control obtains
Molecular weight.
Further, described zero-valent metal catalyst is zerovalent copper or Zero-valent Iron catalyst.
Further, described monomers acrylonitrile, comonomer, part, initiator and zeroth order gold
The mol ratio of metal catalyst is 100-300:100:1-3:1-3:1-3.
Further, described comonomer and solvent volume are than for 100:50-200.
Further, described comonomer is methyl methacrylate and derivant, acrylic acid
One or more in methyl ester and derivant thereof and Styrene and its derivatives, as shown in Figure 1.
Further, described initiator be alpha-chloro vinylbenzene, alpha-brominated vinylbenzene, benzyl chloride,
Benzyl bromide a-bromotoluene, α-chloro-propionicacid ethyl ester, ethyl α bromopropionate, alpha-brominated ethyl isobutyrate, α-chloroethene
One or more in nitrile, α-chloroethyl nitrile and 1-phenylethyl bromine.
Further, described part be pentamethyl-diethylenetriamine, hexamethyl trien,
Diethylenetriamine, N, N, N', N'-tetra-(2-picolyl) ethylenediamine, three (2-pyridylmethyl) amine,
Three (2-amino-ethyl) amine, 1,10-phenanthroline, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclododecane four
One or more in decane and 2,2'-bipyridyl.
Further, described solvent is dimethyl sulfoxide, DMF and N, N-bis-
One or more in methylacetamide.
The polyacrylonitrile gradient copolymer of the present invention, the molecule of described polyacrylonitrile gradient copolymer
Amount breadth coefficient is Mw/Mn=1.10-1.60
By such scheme, the invention have the advantages that
The invention provides the controllable synthesis method of a kind of polyacrylonitrile gradient copolymer, successfully lead to
" the active "/controllable free-radical polymerisation crossing zerovalent copper catalysis has synthesized polyacrylonitrile gradient copolymerization
Thing, has relative to prior art that reaction condition is gentle, suitable copolymerization monomer scope wide, reaction
Speed is fast, yield advantages of higher, it is adaptable to industrialized production；The polyacrylonitrile ladder that synthesis obtains
The M of degree copolymerw/MnRatio is little, shows narrow molecular weight distribution, and purity is high, resulting polymers
Actual molecular weight be consistent with theoretical molecular.
Described above is only the general introduction of technical solution of the present invention, in order to better understand this
Bright technological means, and can be practiced according to the content of description, below with the present invention relatively
Good embodiment and coordinate accompanying drawing describe in detail as after.
Accompanying drawing explanation
Fig. 1 is the molecular structure of comonomer in the present invention；
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of the polymer of embodiment 1 in the present invention；
When Fig. 3 is embodiment 1 and embodiment 2 copolymerization in the present invention monomer conversion and molecular weight with
And the graph of a relation between molecular weight distribution；
Fig. 4 is the SEC of the different polyacrylonitrile gradient copolymers that embodiment 1 obtains in the present invention
Elution curve figure；
Fig. 5 is the SEC of the different polyacrylonitrile gradient copolymers that embodiment 2 obtains in the present invention
Elution curve figure；
Fig. 6 is the composition relation with conversion ratio of the copolymer in the present invention obtained by embodiment 1
Figure；
Fig. 7 is the structural representation obtaining polyacrylonitrile gradient copolymer.
Detailed description of the invention
Below in conjunction with the accompanying drawings and embodiment, the detailed description of the invention of the present invention is made the most in detail
Describe.Following example are used for illustrating the present invention, but are not limited to the scope of the present invention.
Embodiment 1
Successively by acrylonitrile 0.75mL (11.2mmol), comonomer 1 methyl methacrylate
Ester 0.6mL (5.6mmol), catalyst copper powder 7.2mg (0.112mmol), initiator 2-
Ethyl bromide 20.2mg (0.112mmol), part 2,2-bipyridyl 17.5mg (0.112
And solvent dimethyl sulfoxide 1mL joins in reaction vessel mmol), add stirrer, pass through
After the freezing of 3 standards-inflation cycle of bleeding-thaw, tube sealing under a shielding gas.By tube sealing
After ampoule bottle be placed in agitator, react after certain time at 25 DEG C, take out tube sealing,
Open tube sealing, with a small amount of solvent dissolve after pour in a large amount of precipitant, overnight place after sucking filtration,
Drying and i.e. can get polyacrylonitrile gradient copolymer, its structural representation is as shown in Figure 7.
Polyacrylonitrile gradient copolymer is tested as follows sign:
Nucleus magnetic hydrogen spectrum figure as shown in Figure 2, can find repetitive acrylonitrile and first from figure
The proton peak of base acrylic acid methyl ester., illustrates that two kinds of monomers are successfully accessed in polymer chain；Such as figure
Shown in 3, when carrying out acrylonitrile and methyl methacrylate copolymer conversion ratio and molecular weight and
Graph of a relation between molecular weight distribution, as can be seen from the figure the molecular weight of polymer is along with conversion
The increase of rate and increase, and molecular weight distribution is relatively low；Polyacrylonitrile gradient as shown in Figure 4 is altogether
The SEC elution curve figure of polymers, find from figure its elution curve all in Unimodal Distribution, this
A little data all show that polymerization process is " active "/controlled；Fig. 6 is obtained copolymer
The graph of a relation of composition and conversion ratio, as can be seen from the figure along with the increase of conversion ratio, copolymerization
In thing, the unit number of acrylonitrile is on the increase, and the unit number of methyl methacrylate constantly subtracts
Few, this also illustrates that the polymer obtained is polyacrylonitrile gradient copolymer, and its structural representation is such as
Shown in Fig. 7.
Embodiment 2
Successively by acrylonitrile 0.75mL (11.2mmol), comonomer 1 methyl methacrylate
Ester 0.6mL (5.6mmol), catalyst copper powder 7.2mg (0.112mmol), initiator 2-
Ethyl bromide 20.2mg (0.112mmol), part 2,2-bipyridyl 17.5mg (0.112
Mmol) and solvent DMF 1mL joins in reaction vessel, addition is stirred
Mix son, after the freezing-inflation cycle of bleeding-thaw of 3 standards, seal under a shielding gas
Pipe.Ampoule bottle after tube sealing is placed in agitator, after reacting certain time at 25 DEG C,
Take out tube sealing, open tube sealing, pour in a large amount of precipitant after dissolving with a small amount of solvent, overnight put
Postpone sucking filtration, drying i.e. can get polyacrylonitrile gradient copolymer.
Polyacrylonitrile gradient copolymer is tested as follows sign:
As it is shown on figure 3, when carrying out acrylonitrile and methyl methacrylate copolymer conversion ratio with point
Graph of a relation between son amount and molecular weight distribution, the as can be seen from the figure molecular weight of polymer
Increase along with the increase of conversion ratio, and molecular weight distribution is relatively low；Fig. 5 is for obtaining polyacrylonitrile
The SEC elution curve figure of gradient copolymer, finds that from figure its elution curve is all in unimodal point
Cloth, these data all show that polymerization process is " active "/controlled.
To sum up, present invention success " active "/controllable free-radical based on zero-valent metal catalysis gathers
Conjunction constructs polyacrylonitrile gradient copolymer, and the method response speed is fast, and reaction condition is gentle.
The above is only the preferred embodiment of the present invention, is not limited to the present invention, should
When pointing out, for those skilled in the art, without departing from the technology of the present invention
On the premise of principle, it is also possible to make some improvement and modification, these improve and modification also should regard
For protection scope of the present invention.
Claims (9)
1. the synthetic method of a polyacrylonitrile gradient copolymer, it is characterised in that include following step
Rapid: by monomers acrylonitrile, comonomer, initiator, zero-valent metal catalyst and described zero
The part of valency metallic catalyst is placed in solvent, carries out polyreaction, obtain at 25-100 DEG C
Polyacrylonitrile gradient copolymer.
Synthetic method the most according to claim 1, it is characterised in that: described zero-valent metal is urged
Agent is copper or ferrum.
Synthetic method the most according to claim 1 and 2, it is characterised in that: described monomer third
The mol ratio of alkene nitrile, comonomer, part, initiator and zero-valent metal catalyst is 100-300:
100:1-3:1-3:1-3。
Synthetic method the most according to claim 1, it is characterised in that: described comonomer with
Solvent volume is than for 100:50-200.
Synthetic method the most according to claim 1, it is characterised in that: described comonomer is
Methyl methacrylate and derivant, acrylic acid methyl ester. and derivant thereof and styrene and spread out
One or more in biology.
Synthetic method the most according to claim 1, it is characterised in that: described initiator be α-
Chlorobenzene ethane, alpha-brominated vinylbenzene, benzyl chloride, benzyl bromide a-bromotoluene, α-chloro-propionicacid ethyl ester, α-bromine
Ethyl propionate, alpha-brominated ethyl isobutyrate, α-chloroacetonitrile, α-chloroethyl nitrile and 1-phenylethyl bromine
In one or more.
Synthetic method the most according to claim 1, it is characterised in that: described part is five first
Base diethylenetriamine, hexamethyl trien, diethylenetriamine, N, N, N', N'-tetra-(2-
Picolyl) ethylenediamine, three (2-pyridylmethyl) amine, three (2-amino-ethyl) amine, 1,10-be luxuriant and rich with fragrance
In sieve quinoline, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclododecane four decane and 2,2'-bipyridyl one
Plant or several.
Synthetic method the most according to claim 1, it is characterised in that: described solvent is diformazan
One or more in sulfoxide, N,N-dimethylformamide and DMAC N,N' dimethyl acetamide.
9. the polyacrylonitrile gradient copolymer that the synthetic method as described in claim 1-8 is arbitrary obtains,
It is characterized in that: the molecular weight distribution index of described polyacrylonitrile gradient copolymer
Mw/Mn=1.10-1.60.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1206424A (en) * | 1995-11-15 | 1999-01-27 | 卡内基梅隆大学 | Improved processes based on atom (or group) transfer fadical polymerization and novel (CO) polymers having useful structure and properties |
| CN102177183A (en) * | 2008-08-12 | 2011-09-07 | 阿肯马法国公司 | Method for synthesizing amphiphilic gradient copolymers soluble in an alkaline medium |
| CN102863597A (en) * | 2012-10-12 | 2013-01-09 | 浙江大学 | V-shaped gradient copolymer and preparation process thereof |
| CN104870485A (en) * | 2012-12-18 | 2015-08-26 | 汉高知识产权控股有限责任公司 | Process of controlled radical polymerization of branched polyacrylates |
-
2016
- 2016-07-04 CN CN201610516919.5A patent/CN106008797A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1206424A (en) * | 1995-11-15 | 1999-01-27 | 卡内基梅隆大学 | Improved processes based on atom (or group) transfer fadical polymerization and novel (CO) polymers having useful structure and properties |
| CN102177183A (en) * | 2008-08-12 | 2011-09-07 | 阿肯马法国公司 | Method for synthesizing amphiphilic gradient copolymers soluble in an alkaline medium |
| CN102863597A (en) * | 2012-10-12 | 2013-01-09 | 浙江大学 | V-shaped gradient copolymer and preparation process thereof |
| CN104870485A (en) * | 2012-12-18 | 2015-08-26 | 汉高知识产权控股有限责任公司 | Process of controlled radical polymerization of branched polyacrylates |
Non-Patent Citations (1)
| Title |
|---|
| 高金龙: ""SET-LRP"共聚合研究", 《中国优秀硕士学位论文全文数据库 工程科技 I辑》 * |
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