CN116693730A - Method for removing polymer terminal thioester group - Google Patents
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- CN116693730A CN116693730A CN202310748428.3A CN202310748428A CN116693730A CN 116693730 A CN116693730 A CN 116693730A CN 202310748428 A CN202310748428 A CN 202310748428A CN 116693730 A CN116693730 A CN 116693730A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 167
- 150000007970 thio esters Chemical group 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 42
- 150000003254 radicals Chemical class 0.000 claims abstract description 47
- 239000003999 initiator Substances 0.000 claims abstract description 43
- 239000006259 organic additive Substances 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 239000005416 organic matter Substances 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 9
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 9
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- 239000012989 trithiocarbonate Substances 0.000 claims description 8
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- 150000001875 compounds Chemical class 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
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- 150000002576 ketones Chemical class 0.000 claims description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
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- 238000010526 radical polymerization reaction Methods 0.000 description 5
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- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 3
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- 125000003396 thiol group Chemical class [H]S* 0.000 description 3
- JAMNSIXSLVPNLC-UHFFFAOYSA-N (4-ethenylphenyl) acetate Chemical compound CC(=O)OC1=CC=C(C=C)C=C1 JAMNSIXSLVPNLC-UHFFFAOYSA-N 0.000 description 2
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- FMEBJQQRPGHVOR-UHFFFAOYSA-N (1-ethylcyclopentyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1(CC)CCCC1 FMEBJQQRPGHVOR-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- FMFHUEMLVAIBFI-UHFFFAOYSA-N 2-phenylethenyl acetate Chemical compound CC(=O)OC=CC1=CC=CC=C1 FMFHUEMLVAIBFI-UHFFFAOYSA-N 0.000 description 1
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 1
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical group [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
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- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
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Classifications
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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
- C08F8/42—Introducing metal atoms or metal-containing groups
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a method for removing a polymer terminal thioester group, which comprises the following steps: providing a polymer, wherein the end of the polymer contains a thioester group; the polymer, the organic solvent, the free radical initiator and the metal organic additive are mixed and fully reacted, so that the thioester group at the tail end of the polymer is removed, wherein the metal organic additive is a hydrogenated metal organic matter. According to the method for removing the thioester groups at the tail ends of the polymers, disclosed by the invention, on the basis of removing the thioester groups at the tail ends of the polymers by a traditional free radical coupling method, the metal-organic additive with excellent capability of providing hydrogen atoms is added into the system, so that the metal-organic additive can be effectively combined with polymer free radicals generated after the thioester removal process, the broadening of the molecular weight distribution of the polymers due to the coupling termination effect of the polymer free radicals is avoided, and the fact that the molecular weight distribution of the polymers is kept unchanged while the thioester groups at the tail ends of the polymers are removed is ensured.
Description
Technical Field
The invention relates to the field of synthesis and modification of high polymer materials, in particular to a method for removing a polymer terminal thioester group.
Background
The Road et al, institute of CSIRO, australia, 1998, invented a reversible addition fragmentation chain transfer (RAFT) free radical polymerization process for the synthesis of functional polymers with monodispersity of molecular weight distribution. Polymers prepared by RAFT polymerization exhibit excellent unique high molecular properties compared to conventional radical polymers due to the monodispersity of their molecular weight distribution, and have attracted wide interest in academia and industry. Compared with the traditional anionic polymerization and other active free radical polymerization methods for preparing the molecular weight distribution monodisperse polymer, the RAFT polymerization method has mild reaction conditions, does not need to be carried out under the harsh anhydrous and anaerobic conditions, does not need to add a metal catalyst, has wide controllable molecular weight range (1000-100000), and is applicable to most vinyl monomers, so the RAFT polymerization method is recognized as the active free radical polymerization method with the most industrialized prospect from the past. Specifically, the RAFT polymerization can realize the monodispersity of the molecular weight distribution of the obtained polymer by only adding a thioester chain transfer agent based on the traditional free radical polymerization. The polymer prepared contains a thioester group at the end. It is well known that thioester groups appear yellow in color and have malodorous off-flavors resembling thiol molecules. Moreover, the thioester group at the end of the polymer is unstable at high temperature and is easily degraded, thereby affecting the performance of the polymer. How to effectively remove the thioester groups at the ends of polymers prepared by RAFT polymerization has thus become a great industrial problem limiting the use of RAFT polymerization.
Chemically amplified photoresist is a critical material for the core of semiconductor chip fabrication. Photoresists typically comprise polymeric film forming resins, photoacid generators, surfactants, solvents, and the like, and as photolithography techniques continue to improve to produce finer electronic devices, the structure of the polymers in the photoresist components also continues to change. The polymers used have evolved from early phenolic resins (G/I line) to current poly-p-hydroxystyrene (KrF) and methacrylate polymers (ArF). It is well known that the molecular weight distribution of polymeric film-forming resins has a significant impact on the performance of photoresists. Literature reports: the lithographic dissolution properties of the photoresist are closely related to the molecular weight distribution of the polymers in the system (Ito H.; macromolecules,1998,31,1024-1031), and polymers with narrow molecular weight distribution can greatly improve lithographic resolution and reduce lithographic dimension edge roughness (Line edge roughness). Thus, how to synthesize polymeric film-forming resins for photoresists with narrow molecular weight distribution, which are of controllable composition, has attracted attention from researchers.
RAFT polymerization has been reported to synthesize narrow molecular weight distribution photoresist film forming resins, with molecular weight distribution monodispersity (PD < 1.2) of the synthesized methacrylate polymers, which can significantly improve photoresist resolution and reduce photoresist feature size edge roughness in 193nm lithography tests. However, the methacrylate polymer solution prepared by RAFT polymerization exhibits yellow color due to the terminal disulfate groups, and during the film formation of the photoresist, the polymer terminal disulfate groups are unstable and thermally decomposed at high temperature, thereby affecting the performance of the photoresist film.
The results of the studies published so far show that: the general method for removing the thioester group at the end of the polymer prepared by RAFT polymerization comprises a nucleophilic reagent and a free radical coupling method, wherein the general nucleophilic reagent comprises strong alkali, primary amine, secondary amine and the like, and the nucleophilic reagent attacks sulfur carbon atoms to convert the end of the polymer into sulfhydryl groups, and the method has mild conditions, but amine nucleophilic reagent also easily breaks up anhydride, ester group and other functional groups on the side chain of the polymer, and in addition, the generated sulfhydryl groups are unstable and are easily oxidized into oversulfur bonds, so that the molecular weight distribution of the obtained monodisperse polymer is widened. The free radical coupling method is a method that by adding an initiator, free radicals generated by thermal decomposition of the initiator are rapidly added into a thioester bond at the tail end of a polymer, and the thioester group is removed from the tail end of the polymer due to relatively strong leaving capability of the polymer chain, and the generated free radicals of the polymer chain are combined with excessive free radicals in a system to terminate, so that a stable polymer capped by an initiator fragment is generated. The existing free radical initiator comprises a common azo initiator and a peroxide initiator, the reaction condition for removing the thioester group by a free radical coupling method is mild, however, the process has a plurality of side reactions, the system is not easy to separate, the high molecular chain free radicals are easy to generate coupling termination reaction, and the molecular weight distribution of the polymer obtained after removing the thioester group is obviously widened (PD is more than 1.8). Therefore, the molecular weight distribution of the RAFT polymer is different from that of the traditional free radical polymerization method, and the advantage of monodispersion of the molecular weight distribution of the polymer prepared by RAFT polymerization is lost. Ultraviolet light is also reported to be useful in removing thioester functionalities from the ends of polymers prepared by RAFT polymerization. However, this method has a long reaction time and incomplete reaction, and the resulting mixture has some thioester functional groups removed.
In summary, how to remove the thioester groups at the end of the polymer produced by RAFT polymerization while still maintaining the monodispersity of the molecular weight distribution of the resulting polymer has become a popular problem for RAFT polymerization industry applications.
Disclosure of Invention
Based on this, it is necessary to provide a method for removing a polymer terminal thioester group that can solve the above-mentioned problems.
A method for removing a polymer terminal thioester group comprising the steps of:
providing a polymer having a thioester group at the terminus of the polymer;
and mixing the polymer, an organic solvent, a free radical initiator and a metal organic additive, and then fully reacting to remove the thioester group at the tail end of the polymer, wherein the metal organic additive is a hydrogenated metal organic matter.
In one embodiment, the metal organic additive is a compound having the structural formula:
wherein R is 1 Is methyl, ethyl, propyl, n-butyl, tert-butyl or phenyl, R 2 Is methyl, ethyl, propyl, n-butyl, tert-butyl or phenyl, R 3 Methyl, ethyl, propyl, n-butyl, tert-butyl or phenyl, M is Sn or Ge.
In one embodiment, the metal organic additive is at least one of the compounds having the following structural formula:
in one embodiment, in the operation of fully reacting the polymer, the organic solvent, the free radical initiator, and the metal organic additive after mixing, the molar ratio of the metal organic additive to the polymer is 1 to 10:1.
in one embodiment, in the operation of fully reacting the polymer, the organic solvent, the free radical initiator, and the metal organic additive after mixing, the molar ratio of the metal organic additive to the polymer is from 2.5 to 4.5:1.
in one embodiment, in the operation of fully reacting the polymer, the organic solvent, the free radical initiator and the metal organic additive after mixing, the mass ratio of the polymer, the organic solvent, the free radical initiator and the metal organic additive is 5 to 50: 50-90: 0.1 to 1:1 to 10.
In one embodiment, the reaction time is 4 hours to 40 hours and the reaction temperature is 20 ℃ to 80 ℃ in the operation of fully reacting the polymer, the organic solvent, the free radical initiator and the metal organic additive after mixing.
In one embodiment, the polymer is a RAFT polymerized polymer;
the thioester group is at least one of an aromatic dithiocarboxylic ester, an aliphatic dithiocarboxylic ester, a trithiocarbonate and a dithiocarbamate.
In one embodiment, the polymer is a styrenic polymer or an acrylate polymer.
In one embodiment, the radical initiator is an azo-based initiator or a peroxide-based radical initiator;
the organic solvent is at least one of benzene, ketone, ethyl acetate, tetrahydrofuran, ether and chloroform.
According to the method for removing the thioester groups at the tail ends of the polymers, disclosed by the invention, on the basis of removing the thioester groups at the tail ends of the polymers by a traditional free radical coupling method, the metal-organic additive with excellent capability of providing hydrogen atoms is added into the system, so that the metal-organic additive can be effectively combined with polymer free radicals generated after the thioester removal process, the broadening of the molecular weight distribution of the polymers due to the coupling termination effect of the polymer free radicals is avoided, and the fact that the molecular weight distribution of the polymers is kept unchanged while the thioester groups at the tail ends of the polymers are removed is ensured.
In combination with the description of the specific examples, the method for removing the terminal thioester group of the polymer can remove the terminal thioester group of the polymer prepared by RAFT polymerization, and still maintain the monodispersity of the molecular weight distribution of the obtained polymer.
In addition, compared with the prior conventional technology for removing the thioester group by free radical coupling, the method for removing the end thioester group of the polymer has good effect on removing the aromatic dithiocarboxylic ester, the aliphatic dithiocarboxylic ester, the trithiocarbonate and the dithiocarbamic ester, and the addition of the organic metal additive can ensure that the molecular weight distribution of the thioester is unchanged before and after the removal of the thioester, so the method has good industrial application value.
According to the method for removing the terminal thioester groups of the polymer, the obtained polymer with the terminal thioester groups removed is colorless and stable, and compared with the polymer before the thioester groups are removed, the molecular weight distribution of the polymer is unchanged, and the monodispersity (the molecular weight distribution PD < 1.1) is still maintained.
The invention effectively solves the problem that the removal of the thioester group at the tail end of the polymer leads to the remarkable widening of the molecular weight distribution of the polymer, greatly expands the industrial application range of the polymer prepared by RAFT polymerization, and particularly has wide application prospect in the field of monodisperse film-forming resins for photoresist.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that all directional indicators (such as up, down, left, right, front, and rear … …) in the embodiments of the present invention are merely used to explain the relative positional relationship between the members, the movement condition, etc. in a specific posture, and if the specific posture is changed, the directional indicators are correspondingly changed.
Furthermore, the description of "first," "second," etc. in this disclosure is for descriptive purposes only and is not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
The invention discloses a method for removing a polymer terminal thioester group, which comprises the following steps:
s10, providing a polymer, wherein the tail end of the polymer contains a thioester group.
In general, the polymer may be a polymer prepared by RAFT polymerisation.
Preferably, in the present embodiment, the polymer is a styrene polymer or an acrylate polymer.
Preferably, the thioester group is at least one of an aromatic dithiocarboxylic ester, an aliphatic dithiocarboxylic ester, a trithiocarbonate and a dithiocarbamate.
And S20, mixing the polymer obtained in the step S10, an organic solvent, a free radical initiator and a metal organic additive, and then fully reacting so that the thioester group at the tail end of the polymer is removed.
Wherein the metal organic additive is a hydrogenated metal organic. The hydrogenated metallo-organic compound has excellent ability to provide hydrogen atoms.
Preferably, in this embodiment, the metal organic additive is a compound having the following structural formula:
wherein R is 1 Is methyl, ethyl, propyl, n-butyl, tert-butyl or phenyl, R 2 Is methyl, ethyl, propyl, n-butyl, tert-butyl or phenyl, R 3 Methyl, ethyl, propyl, n-butyl, tert-butyl or phenyl, M is Sn or Ge.
More preferably, in this embodiment, the metal organic additive is at least one of the compounds having the following structural formula:
preferably, in S20, the molar ratio of the metal organic additive to the polymer is 1 to 10:1.
more preferably, in S20, the molar ratio of the metal organic additive to the polymer is 2.5 to 4.5:1.
preferably, in S20, the mass ratio of the polymer, the organic solvent, the radical initiator and the metal organic additive is 5 to 50: 50-90: 0.1 to 1:1 to 10.
More preferably, in S20, the mass ratio of the polymer, the organic solvent, the radical initiator and the metal organic additive is 10:40:0.5:1.5.
preferably, in S20, the reaction time is 4-40 h, and the reaction temperature is 20-80 ℃.
Preferably, in S20, the reaction time is 8 hours and the reaction temperature is 70 ℃.
In this embodiment, the radical initiator may be an azo-based initiator or a peroxide-based radical initiator.
In particular, the free radical initiator may be dilauroyl peroxide.
In this embodiment, the organic solvent may be at least one of benzene, ketone, ethyl acetate, tetrahydrofuran, ether, and chloroform.
In the present embodiment, S20 needs to be performed in a protective gas atmosphere.
According to the method for removing the thioester groups at the tail ends of the polymers, disclosed by the invention, on the basis of removing the thioester groups at the tail ends of the polymers by a traditional free radical coupling method, the metal-organic additive with excellent capability of providing hydrogen atoms is added into the system, so that the metal-organic additive can be effectively combined with polymer free radicals generated after the thioester removal process, the broadening of the molecular weight distribution of the polymers due to the coupling termination effect of the polymer free radicals is avoided, and the fact that the molecular weight distribution of the polymers is kept unchanged while the thioester groups at the tail ends of the polymers are removed is ensured.
In combination with the description of the specific examples, the method for removing the terminal thioester group of the polymer can remove the terminal thioester group of the polymer prepared by RAFT polymerization, and still maintain the monodispersity of the molecular weight distribution of the obtained polymer.
In addition, compared with the prior conventional technology for removing the thioester group by free radical coupling, the method for removing the end thioester group of the polymer has good effect on removing the aromatic dithiocarboxylic ester, the aliphatic dithiocarboxylic ester, the trithiocarbonate and the dithiocarbamic ester, and the addition of the organic metal additive can ensure that the molecular weight distribution of the thioester is unchanged before and after the removal of the thioester, so the method has good industrial application value.
According to the method for removing the terminal thioester groups of the polymer, the obtained polymer with the terminal thioester groups removed is colorless and stable, and compared with the polymer before the thioester groups are removed, the molecular weight distribution of the polymer is unchanged, and the monodispersity (the molecular weight distribution PD < 1.1) is still maintained.
The invention effectively solves the problem that the removal of the thioester group at the tail end of the polymer leads to the remarkable widening of the molecular weight distribution of the polymer, greatly expands the industrial application range of the polymer prepared by RAFT polymerization, and particularly has wide application prospect in the field of monodisperse film-forming resins for photoresist.
The following are specific examples.
In a specific embodiment, the para-acetoxystyrene monomer is purchased from Henan Carde chemical Co., ltd, tetrahydrofuran is purchased from Anhuizhen technologies Co., ltd, the trithiocarbonate is purchased from Anhuizhen technologies Co., ltd, the initiator AIBN is purchased from Henan Carde chemical Co., ltd, n-hexane is purchased from Henan Carde chemical Co., ltd, the 1-ethyl methyl methacrylate monomer is purchased from Anhui Hirshine Co., ltd, the free radical initiator dilauroyl peroxide is purchased from Anhui Hirshine Co., ltd, the tri-n-butyl tin hydride is purchased from Anhui Hirshine Co., ltd, and the triethylgermanium hydride is purchased from Anhui Hirshine Co., ltd.
Example 1: RAFT polymerization to synthesize polyacetoxy styrene polymer with narrow molecular weight distribution
A5000 mL three-necked flask polymerization reactor equipped with an electric stirrer, condenser, thermometer, stirring controller, temperature controller, heating mantle and nitrogen protection device was assembled in a fume hood. To a three-necked flask were added 1620 g of p-acetoxystyrene monomer, 2000 g of tetrahydrofuran solvent, 157 g of trithiocarbonate, and the mixture was stirred under nitrogen and heated to the reflux temperature (67 ℃ C.). Initiator AIBN 1.6 g was added and the reaction temperature was maintained at 67 degrees Celsius with continued stirring for 20 hours and heating was stopped when the polymerization conversion reached the target. After the solution cooled to room temperature, the polymerization reaction solution was slowly dropped into 10 times volume of n-hexane solvent, stirring was continued for 30 minutes, stirring was stopped, the polymer was precipitated at the bottom of the vessel, the upper n-hexane solvent was removed, new n-hexane solvent was added, stirring was continued, and the above operation was repeated 2 to 3 times to remove unreacted monomers and initiator. After drying in vacuo, a pale yellow solid polymer was obtained.
As determined by GPC: number average molecular weight 5269; weight average molecular weight: 5532; molecular weight distribution: 1.05. the weighed polymer yield was 92%.
Example 2: RAFT polymerization to synthesize polymethacrylate polymer with narrow molecular weight distribution
A5000 mL three-necked flask polymerization reactor equipped with an electric stirrer, condenser, thermometer, stirring controller, temperature controller, heating mantle and nitrogen protection device was assembled in a fume hood. To a three-necked flask was added 1820 g of 1-ethyl cyclopentylmethacrylate monomer, 2100 g of tetrahydrofuran solvent, 143 g of trithiocarbonate, and the mixture was stirred under nitrogen and heated to the reflux temperature (67 ℃). Initiator AIBN 2.4 g was added and the reaction temperature was maintained at 67 degrees Celsius and stirring was continued for 18 hours, and heating was stopped when the polymerization conversion reached the target. After the solution cooled to room temperature, the polymerization reaction solution was slowly dropped into 10 times volume of methanol solvent, stirring was continued for 30 minutes, stirring was stopped, the polymer was precipitated at the bottom of the vessel, the upper n-hexane solvent was removed, new n-hexane solvent was added, stirring was continued, and the above operation was repeated 2 to 3 times to remove unreacted monomers and initiator. After drying in vacuo, a pale yellow solid polymer was obtained.
As determined by GPC: number average molecular weight 6431; weight average molecular weight: 6945; molecular weight distribution: 1.08. the weighed polymer yield was 93%.
Example 3: removal of Polyacetoxystyrene Polymer terminal thioester group by addition of Trin-butyl tin hydride
In a three-necked flask, 549 g of the polyacetyl-styrene polymer prepared in example 1, 1456 g of tetrahydrofuran were added, and the radical initiator dilauroyl peroxide 457 g and the tri-n-butyltin hydride 35.6 g were sequentially added, and the mixed solution was stirred under nitrogen protection and heated to the reflux temperature (67 ℃ C.). The reaction temperature was maintained at 67 degrees celsius and stirring was continued for 10 hours, the color of the solution gradually turned clear and colorless, and heating was stopped. After the solution had cooled to room temperature, the UV-Vis test showed complete disappearance of the characteristic absorption peak of the sulfate at 320nm indicating complete detachment of the thioester groups from the polymer ends.
GPC determination: a polymer after removal of the thioester groups, having a number average molecular weight of 5369; weight average molecular weight: 5690; molecular weight distribution: 1.06.
example 4: removal of terminal thioester groups of polymethacrylate polymers by addition of tri-n-butyltin hydride
In a three-necked flask, 512 g of the polymethacrylate polymer prepared in example 2 and 1154 g of tetrahydrofuran were added, 84 g of dilauryl peroxide and 36.1 g of tri-n-butyltin hydride as radical initiators were added in sequence, and the mixed solution was stirred under nitrogen protection and heated to a solution reflux temperature (67 ℃). The reaction temperature was maintained at 67 degrees celsius and stirring was continued for 10 hours, the color of the solution gradually turned clear and colorless, and heating was stopped. After the solution had cooled to room temperature, the UV-Vis test showed complete disappearance of the characteristic absorption peak of the sulfate at 320nm indicating complete detachment of the thioester groups from the polymer ends. GPC determination: a polymer after removal of the thioester groups, having a number average molecular weight of 6369; weight average molecular weight: 6815; molecular weight distribution: 1.07.
example 5: removal of polyacetoxy styrene Polymer terminal thioester groups by addition of triethylgermanium hydride
In a three-necked flask, 512 g of the polyacetyl-styrene polymer prepared in example 1 and 1256 g of tetrahydrofuran were added, 72g of dilauroyl peroxide and 25.6 g of triethylgermanium hydride as radical initiators were added in this order, and the mixed solution was stirred under nitrogen protection and heated to a solution reflux temperature (67 ℃ C.). The reaction temperature was maintained at 67 degrees celsius and stirring was continued for 7 hours, the color of the solution gradually turned clear and colorless, and heating was stopped. After the solution had cooled to room temperature, the UV-Vis test showed complete disappearance of the characteristic absorption peak of the sulfate at 320nm indicating complete detachment of the thioester groups from the polymer ends.
GPC determination: a polymer after removal of the thioester groups, having a number average molecular weight of 5241; weight average molecular weight: 5576; molecular weight distribution: 1.06.
example 6: removal of terminal thioester groups of polymethacrylate polymers by adding triethylgermanium hydride
In a three-necked flask, 508 g of the polymethacrylate polymer prepared in example 2 and 1108 g of tetrahydrofuran were added, 67 g of dilauroyl peroxide and 31.1 g of triethylgermanium hydride as free radical initiator were added in sequence, and the mixed solution was stirred under nitrogen protection and heated to the reflux temperature (67 ℃ C.). The reaction temperature was maintained at 67 degrees celsius and stirring was continued for 10 hours, the color of the solution gradually turned clear and colorless, and heating was stopped. After the solution had cooled to room temperature, the UV-Vis test showed complete disappearance of the characteristic absorption peak of the sulfate at 320nm indicating complete detachment of the thioester groups from the polymer ends.
GPC determination: a polymer after removal of the thioester groups, having a number average molecular weight of 6245; weight average molecular weight: 6615; molecular weight distribution: 1.07.
comparative example 1: removal of the terminal thioester groups of the Poly (acetoxystyrene) polymer by conventional methods
In a three-necked flask, 515 g of the polyacetoxy styrene polymer prepared in example 1, 1523 g of tetrahydrofuran, under nitrogen protection, were added, and the mixed solution was stirred and heated to the reflux temperature (67 ℃ C.). 65 g of dilauroyl peroxide as an initiator is added, the reaction temperature is kept at 67 ℃, stirring is continued for 6 hours, the color of the solution is gradually changed into transparent and colorless, and heating is stopped. After the solution had cooled to room temperature, the UV-Vis test showed complete disappearance of the characteristic absorption peak of the sulfate at 320nm, indicating complete detachment of the thioester groups from the polymer ends.
GPC determination: a polymer after removal of thioester groups, having a number average molecular weight of 8673; weight average molecular weight: 15392; molecular weight distribution: 1.75.
comparative example 2: conventional methods remove the terminal thioester groups of polymethacrylate polymers
In a three-necked flask, 529 g of the polymethacrylate polymer prepared in example 2, 1329 g of tetrahydrofuran were added, and the mixed solution was stirred under nitrogen protection and heated to a solution reflux temperature (67 ℃). 356 g of dilauroyl peroxide as an initiator was added, the reaction temperature was kept at 67℃and stirring was continued for 8 hours, the color of the solution was gradually changed to transparent and colorless, and the heating was stopped. After the solution had cooled to room temperature, the UV-Vis test showed complete disappearance of the characteristic absorption peak of the sulfate at 320nm indicating complete detachment of the thioester groups from the polymer ends.
GPC determination: a polymer after removal of the thioester groups, having a number average molecular weight 7251; weight average molecular weight: 13487; molecular weight distribution: 1.86.
the above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the claims. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. A method for removing a terminal thioester group of a polymer, comprising the steps of:
providing a polymer having a thioester group at the terminus of the polymer;
and mixing the polymer, an organic solvent, a free radical initiator and a metal organic additive, and then fully reacting to remove the thioester group at the tail end of the polymer, wherein the metal organic additive is a hydrogenated metal organic matter.
2. The method of claim 1, wherein the metal organic additive is a compound having the following structural formula:
wherein R is 1 Is methyl, ethyl, propyl, n-butyl, tert-butyl or phenyl, R 2 Is methyl, ethyl, propyl, n-butyl, tert-butyl or phenyl, R 3 Methyl, ethyl, propyl, n-butyl, tert-butyl or phenyl, M is SnOr Ge.
3. The method of claim 1, wherein the metal organic additive is at least one of the following compounds:
4. the method for removing a terminal thioester group of a polymer according to claim 1, wherein in the step of mixing the polymer, the organic solvent, the radical initiator and the metal-organic additive and then sufficiently reacting, the molar ratio of the metal-organic additive to the polymer is 1 to 10:1.
5. the method for removing a terminal thioester group from a polymer according to claim 4, wherein the molar ratio of the metal-organic additive to the polymer is 2.5 to 4.5:1.
6. the method for removing a terminal thioester group of a polymer according to any one of claims 1 to 5, wherein in the operation of mixing the polymer, the organic solvent, the radical initiator and the metal-organic additive and then sufficiently reacting, the mass ratio of the polymer, the organic solvent, the radical initiator and the metal-organic additive is 5 to 50: 50-90: 0.1 to 1:1 to 10.
7. The method for removing a terminal thioester group of a polymer according to claim 6, wherein the reaction time is 4 to 40 hours and the reaction temperature is 20 to 80 ℃ in the operation of mixing the polymer, the organic solvent, the radical initiator and the metal organic additive and then sufficiently reacting.
8. The method for removing a terminal thioester group of a polymer according to claim 7, wherein the polymer is a polymer produced by RAFT polymerization;
the thioester group is at least one of an aromatic dithiocarboxylic ester, an aliphatic dithiocarboxylic ester, a trithiocarbonate and a dithiocarbamate.
9. The method for removing a terminal thioester group of a polymer according to claim 8, wherein the polymer is a styrene-based polymer or an acrylate-based polymer.
10. The method for removing a terminal thioester group of a polymer according to claim 9, wherein the radical initiator is an azo-type initiator or a peroxide-type radical initiator;
the organic solvent is at least one of benzene, ketone, ethyl acetate, tetrahydrofuran, ether and chloroform.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100137548A1 (en) * | 2007-02-23 | 2010-06-03 | Commonwealth Scientific And Industrial Research Organisation | Process for transforming the end groups of polymers |
| CN103242466A (en) * | 2013-05-22 | 2013-08-14 | 苏州大学 | Method for removing terminal thiocarbonyl of RAFT (reversible addition-fragmentation chain transfer) polymer at room temperature |
| CN104105718A (en) * | 2011-12-14 | 2014-10-15 | 联邦科学和工业研究组织 | RAFT polymers |
| CN104513326A (en) * | 2013-09-27 | 2015-04-15 | 中国石油天然气股份有限公司 | Reversible addition-fragmentation chain transfer reagent and preparation and application thereof |
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|---|---|---|---|---|
| US20100137548A1 (en) * | 2007-02-23 | 2010-06-03 | Commonwealth Scientific And Industrial Research Organisation | Process for transforming the end groups of polymers |
| CN104105718A (en) * | 2011-12-14 | 2014-10-15 | 联邦科学和工业研究组织 | RAFT polymers |
| CN103242466A (en) * | 2013-05-22 | 2013-08-14 | 苏州大学 | Method for removing terminal thiocarbonyl of RAFT (reversible addition-fragmentation chain transfer) polymer at room temperature |
| CN104513326A (en) * | 2013-09-27 | 2015-04-15 | 中国石油天然气股份有限公司 | Reversible addition-fragmentation chain transfer reagent and preparation and application thereof |
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