CN104031181A - Catalytic system for atom transfer radical polymerization reaction and application thereof - Google Patents
Catalytic system for atom transfer radical polymerization reaction and application thereof Download PDFInfo
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- CN104031181A CN104031181A CN201410256173.XA CN201410256173A CN104031181A CN 104031181 A CN104031181 A CN 104031181A CN 201410256173 A CN201410256173 A CN 201410256173A CN 104031181 A CN104031181 A CN 104031181A
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Abstract
The invention discloses a catalytic system for atom transfer radical polymerization reaction and application thereof. According to the catalytic system, a 1, 3, 5, 7-tetra-azatricyclo [3.3.1.1] decane compound is used as an atom transfer radical polymerization reaction accelerant. In a polymerization system of atom transfer radical polymerization of methyl acrylate (MA), methyl methacrylate (MMA) and styrene (St) of a three-catalyst system including CuBr/pentamethyl diethylenetriamine (PMDETA), CuBr/ tetra[(2-pyridyl) methyl] ethylenediamine (TPEN) and CuBr/tri[2-(dimethylamino) ethyl] amine (Me6TREN) added with the accelerant, the reaction activity of the transition metal catalyst is significantly improved without losing the control on the polymerization reaction, and the polymerization rate of the reaction is increased, so that the consumption of the catalyst is significantly reduced, and the systems can substantially meet the requirements of industrialized large-scale production.
Description
Technical field
The invention belongs to polymkeric substance preparation field, be specifically related to catalyst system and the application thereof of a kind for atom transition free radical polymerization reaction.
Background technology
Atom transfer radical polymerization (ATRP) is a kind of " activity "/controllable free-radical polymerisation of transition metal complex catalysis.At present, ATRP technology be used to prepare that various structures are clear and definite, the complicated macromole such as random, the block of narrow molecular weight distributions, grafting, ring-type, hyperbranched, dendroid, cross-linked structure.But, it is to be solved that ATRP still has a defect to have, because rate of polymerization is slow thereby catalyzer usage quantity is larger, the usage quantity phase 1:1 mol ratio at once of conventional amount used and initiator, makes the content of catalyzer in conventional forward ATRP system at least reach 2000-10000ppm.
In addition, general high molecular polymer system viscosity is larger, removing or reclaim catalyzer quite bothers, conventionally need to use the processing such as a large amount of organic solvent washings, extraction, precipitation, classification, not only greatly increase the production cost of ATRP technique, also brought the problem of plurality of heavy metal catalyst residue environmental pollution thereupon.This makes many polymkeric substance only can synthesize and but can not adapt to large-scale industrial production requirement in use for laboratory ATRP technology at present.Therefore, exploitation ATRP promotor, to strengthen catalyst activity and then to improve polymerization rate, is reduced catalyzer usage quantity, alleviates production cost, and ATRP technological direction industrial applications tool is of great significance.
Publication number is that the Chinese patent application of CN1183107A discloses a kind of polymerization process based on atom transfer radical polymerization, this polymerization process is using monovalence copper as catalyzer, using dipyridyl as part, using alkylogen as initiator, " activity " or the controlled radical polymerization of the monomer that vinylbenzene, (methyl) acrylate and other can free crowd are realized.But this polyreaction exists the too high shortcoming of catalyst levels, has both increased cost, causes again the heavy-metal residual in polymerisate, be difficult to realize industrially scalable application.
Summary of the invention
The invention provides a kind of catalyst system for atom transition free radical polymerization reaction and application thereof, when this catalyst system is applied to atom transition free radical polymerization reaction, improve rate of polymerization, reduce the consumption of catalyzer, under optimal situation, can make catalyst levels be reduced to 1% of conventional amount used.
For a catalyst system for atom transition free radical polymerization reaction, comprise CuBr, part and promotor;
Described promotor is 1,3,5,7-, tetra-aza-tricycles [3.3.1.1] decane;
The mol ratio of described CuBr, part and promotor is 1:0.5～2:1～50.
It is the main speed control step of rate of polymerization for the reduction activation of high valence state transition-metal catalyst in ATRP polymerization process, catalyst system of the present invention is by adding specific promotor, accelerate this reduction activation step, both improved rate of polymerization, reduced again the consumption of catalyzer.
As preferably, the mol ratio of described CuBr, part and promotor is 1:1:5～25.Experimental result shows, the catalyzer of this concentration can be when catalyst content be very low, ensures that polyreaction carries out effectively.
As preferably, described part is pentamethyl-diethylenetriamine, four [(2-pyridyl) methyl] quadrol or three [2-(dimethylamino) ethyl] amine.
The present invention also provides a kind of atom transition free radical polymerization reaction of described catalyst system catalysis, using 2-isobutyl ethyl bromide as initiator, under the effect of described CuBr, part and promotor, polymerization single polymerization monomer generation atom transition free radical polymerization reaction, obtains polymerisate.
By add specific promotor in this atom transition free radical polymerization reaction, both improve rate of polymerization, reduce again the consumption of catalyzer, the molecular weight that simultaneously do not change atom transfer radical polymerization is controlled, the living polymerization feature of narrow molecular weight distributions
As preferably, described polymerization single polymerization monomer is methyl acrylate, methyl methacrylate or vinylbenzene.
As further preferred, described polymerization single polymerization monomer is methyl acrylate, and the mol ratio of described 2-isobutyl ethyl bromide and described methyl acrylate is 1～2:100.
As preferably, the mol ratio of described CuBr and described methyl acrylate is 0.01～0.02:100
As preferably, the temperature of described atom transition free radical polymerization reaction is 60～80 DEG C.
The present invention adopts 1,3,5,7-tetra-aza-tricycles [3.3.1.1] decane compound is as atom transfer radical polymerization promotor, at CuBr/ pentamethyl-diethylenetriamine (PMDETA), CuBr/ tetra-[(2-pyridyl) methyl] quadrol (TPEN) and CuBr/ tri-[2-(dimethylamino) ethyl] amine (Me
6tREN) in the polyreaction of three kinds of catalyst system, significantly shorten the reaction times of the ATRP of methyl acrylate (MA), methyl methacrylate (MMA) and vinylbenzene (St), and obtained that structure is clear and definite, molecular weight is controlled, the polymkeric substance of narrow distribution.The content of its transition-metal catalyst has been reduced to tens of ppm orders of magnitude, makes the large-scale industrial production of these systems become possibility.
Brief description of the drawings
Fig. 1 represents the promotor of adding in embodiment 1 impact on ATRP reaction;
Fig. 2 represents the graph of molecular weight distribution of the product that embodiment 1 obtains;
Fig. 3 represents the promotor of adding in embodiment 2 impact on ATRP reaction;
Fig. 4 represents the promotor of adding in embodiment 3 impact on ATRP reaction.
Embodiment
Embodiment 1
At 70 DEG C, taking EBiB (2-isobutyl ethyl bromide) as initiator, taking CuBr/PMDETA as catalyzer, under the condition that the mol ratio of fixing MA/EBiB/CuBr/PMDETA is 100:1:0.01:0.01, carried out the ATRP reaction of MA, promotor represents as Fig. 1 the ATRP promoter action of MA.
Fig. 1 show when the concentration of catalyzer be initiator concentration while being only 1% (mol ratio), monomer conversion only 18.8% after the ATRP of MA reaction 10h in blank system.But in the time adding promotor in system, under the same terms, the polymerization rate of MA significantly improves.Data show that 5 times to the promotor of CuBr molar mass, can make the monomer conversion of the ATRP of MA reach 88.8% after reaction 10h.And within the specific limits, while increasing accelerator content, polymerization rate also can increase.As shown in the figure, the ATRP monomer conversion of the highest MA of making reaches 97.2% after reaction 3h.Visible, in the ATRP of the MA that is catalyst system at CuBr/PMDETA, even if catalyst levels is reduced to 1% of conventional amount used in the ATRP of MA, the existence of promotor obviously can improve the speed of reaction of the ATRP of MA.
Fig. 2 show molecular weight that promotor exists resulting polymers in the ATRP of lower MA along with the increase of monomer conversion linear increase and with theoretical molecular Mn, theo (dotted line) coincide better.And, the narrower (M of molecular weight distribution of resulting polymers
w/ M
n≤ 1.3).Visible, promotor exists the ATRP of lower MA to meet the essential characteristic of living polymerization.
Embodiment 2
At 70 DEG C, same taking EBiB as initiator, changing CuBr/TPEN is catalyzer, and the mol ratio of fixing MA/EBiB/CuBr/TPEN is 100:1:0.01:0.01, has carried out the ATRP reaction of MA, shown in promoter action Fig. 2 of the ATRP of promotor to MA.
Fig. 3 data show, in the time that the concentration of catalyzer is only 1% (mol ratio) of initiator concentration, in blank system, after the ATRP of MA reaction 6h, monomer conversion is 26.6%.But in the time adding promotor, under the same terms, the polymerization rate of MA obviously improves.Add 5 times to the promotor of CuBr molar mass, can make the monomer conversion of the ATRP of MA reach 90.2% after reaction 6h.Visible, in the ATRP of the MA that is catalyst system at CuBr/TPEN, even if catalyst levels is reduced to 1% of conventional amount used in the ATRP of MA, the existence of promotor obviously can improve the speed of reaction of the ATRP of MA.
Embodiment 3
At 70 DEG C, taking EBiB as initiator, CuBr/Me
6tREN is catalyst system, fixing MA/EBiB/CuBr/Me
6the mol ratio of TREN is 100:1:0.01:0.01, has carried out the ATRP reaction of MA, promotor to the ATRP promoter action of MA as shown in Figure 3:
As can be seen from Figure 3, when 1% (mol ratio) that the concentration of catalyzer is initiator concentration, in blank system, the monomer conversion of the ATRP of MA is after reaction 10h only 23.5%.Under promotor exists, under the same terms, the polymerization rate of MA improves obviously.Add 5 times to the promotor of CuBr molar mass, can make the ATRP monomer conversion of MA reach 84.5% after reaction 10h.The same accelerator level polymerization rate that increases also can increase.As shown above, the ATRP monomer conversion of the highest MA of making reaches 99.4% after reaction 6h.Visible, at CuBr/Me
6tREN is in the ATRP of MA of catalyst system, even if catalyst levels is reduced to 1% of conventional amount used in the ATRP of MA, the existence of promotor obviously can improve the speed of reaction of the ATRP of MA.
Embodiment 4
At 70 DEG C, taking EBiB as initiator, CuBr/Me
6tREN is catalyst system, fixing MA/EBiB/CuBr/Me
6the mol ratio of TREN is 100:1:0.05:0.05, has carried out the ATRP reaction of MMA.Result shows, when 5% (mol ratio) that the concentration of catalyzer is initiator concentration, the monomer conversion that does not add the ATRP of MMA in the blank system of promotor is only 15.0% after reaction 10h.And in the time adding 25 times of promotor to CuBr molar mass in system, make the monomer conversion of the ATRP of MMA reach 68.9%, molecular weight distribution M after reaction 10h
w/ M
n≤ 1.47.Visible, at CuBr/Me
6tREN is in the ATRP of MMA of catalyst system, even if catalyst levels is reduced to 5% of catalyzer usual amounts in the ATRP of MMA, the existence of promotor obviously can improve the speed of reaction of the ATRP of MMA.
Embodiment 5
At 70 DEG C, taking EBiB as initiator, CuBr/Me
6tREN is catalyst system, fixing St/EBiB/CuBr/Me
6the mol ratio of TREN is 100:1:0.05:0.05, has carried out the ATRP reaction of St.Result shows, when 5% (mol ratio) that the concentration of catalyzer is initiator concentration, the monomer conversion that does not add the ATRP of St in the blank system of promotor is only 8.0% after reaction 18h.And in the time adding 25 times of promotor to CuBr molar mass in system, make the monomer conversion of the ATRP of St reach 66.4%, molecular weight distribution M after reaction 18h
w/ M
n≤ 1.35.Visible, at CuBr/Me
6tREN is in the ATRP of St of catalyst system, even if catalyst levels is reduced to 5% of catalyzer usual amounts in the ATRP of St, the existence of promotor obviously can improve the speed of reaction of the ATRP of St.
Claims (8)
1. for a catalyst system for atom transition free radical polymerization reaction, it is characterized in that, comprise CuBr, part and promotor;
Described promotor is 1,3,5,7-, tetra-aza-tricycles [3.3.1.1] decane;
The mol ratio of described CuBr, part and promotor is 1:0.5～2:1～50.
2. the catalyst system for atom transition free radical polymerization reaction according to claim 1, is characterized in that, the mol ratio of described CuBr, part and promotor is 1:1:5～25.
3. the catalyst system for atom transition free radical polymerization reaction according to claim 1 and 2, it is characterized in that, described part is pentamethyl-diethylenetriamine, four [(2-pyridyl) methyl] quadrol or three [2-(dimethylamino) ethyl] amine.
4. the atom transition free radical polymerization reaction of the catalyst system catalysis as described in claim 1～3 any one, it is characterized in that, using 2-isobutyl ethyl bromide as initiator, under the acting in conjunction of described CuBr, part and promotor, polymerization single polymerization monomer generation atom transition free radical polymerization reaction, obtains polymerisate.
5. the atom transition free radical polymerization reaction of catalyst system catalysis according to claim 4, is characterized in that, described polymerization single polymerization monomer is methyl acrylate, methyl methacrylate or vinylbenzene.
6. the atom transition free radical polymerization reaction of catalyst system catalysis according to claim 5, is characterized in that, described polymerization single polymerization monomer is methyl acrylate, and the mol ratio of described 2-isobutyl ethyl bromide and described methyl acrylate is 1～2:100.
7. the atom transition free radical polymerization reaction of catalyst system catalysis according to claim 6, is characterized in that, the mol ratio of described CuBr and described methyl acrylate is 0.01～0.02:100.
8. the atom transition free radical polymerization reaction of catalyst system catalysis according to claim 4, is characterized in that, the temperature of described atom transition free radical polymerization reaction is 60～80 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409894A (en) * | 2017-02-09 | 2018-08-17 | 浙江工业大学 | The method that transition metal nanoparticles are catalyzed polymerization of vinyl monomer reaction |
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| CN103682433A (en) * | 2012-09-26 | 2014-03-26 | 中国科学院研究生院 | Multi-arm star-shaped block polymer based electrolyte and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824127A (en) * | 2010-04-01 | 2010-09-08 | 江西科技师范学院 | Method for preparing crosslinkable segmented copolymer by utilizing active free radical soap-free emulsion polymerization and prepared compound thereof |
| CN103682433A (en) * | 2012-09-26 | 2014-03-26 | 中国科学院研究生院 | Multi-arm star-shaped block polymer based electrolyte and preparation method thereof |
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| 袁照: ""原子转移自由基聚合促进剂的研究"", 《中国优秀硕士学位论文全文数据库（电子期刊）,工程科技Ⅰ辑》, no. 3, 31 March 2014 (2014-03-31), pages 59 - 66 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409894A (en) * | 2017-02-09 | 2018-08-17 | 浙江工业大学 | The method that transition metal nanoparticles are catalyzed polymerization of vinyl monomer reaction |
| CN108409894B (en) * | 2017-02-09 | 2020-12-25 | 浙江工业大学 | Method for catalyzing vinyl monomer polymerization reaction by transition metal nanoparticles |
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