CN109880097B - Polymerization method for preparing block copolymer by inserting alkyl thioether into bis (tri) thioester end-group polymer under base catalysis - Google Patents

Polymerization method for preparing block copolymer by inserting alkyl thioether into bis (tri) thioester end-group polymer under base catalysis Download PDF

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CN109880097B
CN109880097B CN201910069149.8A CN201910069149A CN109880097B CN 109880097 B CN109880097 B CN 109880097B CN 201910069149 A CN201910069149 A CN 201910069149A CN 109880097 B CN109880097 B CN 109880097B
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polymer
thioester
template
integer
monomer
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CN109880097A (en
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宗立率
希布莱德·范德扎赫
永井篤志
蹇锡高
王锦艳
唐慕
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Dalian University of Technology
Technische Universiteit Delft
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Technische Universiteit Delft
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Abstract

A polymerization method for preparing block copolymer by inserting alkyl thioether into bis (tri) thioester end group polymer under the action of base cocatalyst includes adding organic base as cocatalyst, and combining it with reported phase transfer catalyst, such as tetraphenylphosphine chloride and tetraphenylamine chloride to form catalyst system for catalyzing insertion polymerization of template compound or polymer containing thioester end group and cyclic thioether monomer to obtain high-molecular-weight homopolymer or block copolymer. The polymerization method has the beneficial effects that: for the insertion reaction initiated by the template compound, the monomer conversion rate is improved to more than 80 percent; the insertion polymerization can also be successfully carried out when the molecular weight of the template polymer is higher than 2500g/mol, and the monomer conversion is higher than 80%. The block polymer synthesized by the method has a special phase topological structure, can greatly improve the amorphous state of the polymer, and has wide application prospect in the fields of self-healing materials, intelligent materials, self-assembly, biological macromolecules, drug slow release and the like.

Description

Polymerization method for preparing block copolymer by inserting alkyl thioether into bis (tri) thioester end-group polymer under base catalysis
Technical Field
The invention belongs to the technical field of block polymer material preparation, relates to a polymerization method, and particularly relates to a polymerization method for preparing a block copolymer by inserting alkyl thioether into a bis (tri) thioester end-group polymer under the action of an alkali cocatalyst.
Background
The polyalkyl sulfide is a high molecular polymer with peculiar performance, and has good biocompatibility and chain flexibility. The glass transition temperature is close to-50 ℃, and the copolymer can be used as a blending resin element and a copolymerization component for improving the biocompatibility and amorphous state of the commercial high polymer.
The compatibility of the multiphase resin can not be accurately regulated and controlled due to the blending of the resin, so that a good modification effect is achieved. Therefore, the alkyl sulfide structural unit is introduced by adopting a copolymerization method so as to improve the comprehensive performance of the polymer. Balzer et al prepared styrene-alkyl sulfide block copolymers (Macromolecules 2013,46(18),7406-7414.) using alkyllithium as a catalyst by anionic copolymerization. However, since the lithium alkyls are expensive and too reactive, the reaction needs to be carried out at a low temperature with absolute water and oxygen free, which brings certain difficulties to the application. Nagai et al have reported the catalytic synthesis of block copolymeric styrene and copolymeric vinylamine using a phase transfer catalyst, tetraphenylphosphine halide, as the catalyst, but the report only applied the polymerization process to oligomers with molecular weights below 2500g/mol, so the product molecular weight was below 4000g/mol, the monomer conversion was below 50%, and it was not known whether it could be used to prepare high molecular weight polymers, and had no technical value for further applications (Macromolecules 2007,40(23),8129 plus 8131.). The inventors found that no matter what phase transfer catalyst, catalyst content, reaction temperature and organic solvent system is used, insertion polymerization cannot be successfully initiated due to low end group content and embedding effect when the molecular weight of the oligomer is higher than 2500g/mol when the process described by Atsushi et al is used for preparing the high molecular weight alkyl thioether block copolymer, indicating that the polymerization method cannot be popularized and applied to the preparation of high molecular weight materials.
On the basis of exploring the research, by analyzing the reaction mechanism, organic weak base such as 4-Dimethylaminopyridine (DMAP) or 1, 8-diazabicycloundec-7-ene (DBU) and the like is added as a cocatalyst (the addition amount is 0.1-100 eq, preferably 0.2-1.0 eq), so that the insertion polymerization reaction can be effectively realized, a high-molecular-weight homo (co) polymer is prepared, and the conversion rate of the alkyl thioether monomer is more than 80%. The polymerization process not only gives the possibility of high molecular weight polymerization reaction to occur, but also polymerization reaction efficiency and economy.
Disclosure of Invention
The invention provides a preparation method of homo (co) polyalkyl sulfide. The method can be carried out under mild reaction conditions (the reaction temperature is 40-90 ℃, and the requirements on water and oxygen are not strict), has higher atom utilization and economy, expands the application range of the polyalkyl sulfide, and can be applied to the fields of self-healing materials, intelligent materials, self-assembly, biological macromolecules, drug sustained release and the like.
The technical scheme of the invention is as follows:
a polymerization method for preparing a block copolymer by inserting alkyl thioether into a bis (tri) thioester end-group polymer with base catalysis comprises the following steps:
sequentially adding a template compound or polymer containing a thioester end group, a phase transfer catalyst, an organic base, an episulfide monomer and an organic solvent into a reactor, wherein the molar ratio of the template compound or polymer containing the thioester end group, the phase transfer catalyst, the organic base and the organic solvent is 1: 0.01-10: 0.01-10: 0.1 to 100; the mol number of the cyclic thioether monomer depends on the molecular weight of the designed block copolymer, and the mol ratio of the cyclic thioether monomer to the sulfide compound or the polymer is 10-1000: 1, preferably 20 to 300: 1; using liquid nitrogen and a vacuum pump, performing three freezing and vacuum operations to completely remove air in the reactor and then sealing; heating to 40-90 ℃ for reaction for 6-72 hours, then settling the reaction solution in methanol, centrifugally washing for three times, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain a homo (co) polymer for use;
the thioester-terminated template compound or polymer has the following general structural formula:
bis-thioester template compound:
Figure GDA0002821862100000031
trithioester template compound:
Figure GDA0002821862100000032
R1and R'2The same or different;
bis-thioester template polymer:
Figure GDA0002821862100000033
Figure GDA0002821862100000034
trithioester template polymer:
Figure GDA0002821862100000041
R1and R'2The same or different;
R3-R10＝H，or CnH2n+1，n＝1，2，3...
R3～R10the same or different;
M1and M2The structure represents a structural unit of the polymer, and the structure contained in the structure is independently selected without any relevant limitation; m1And M2One of which may be zero, but not both; m1And M2When the value of the first is zero, the polymer is a homopolymer; when all the components are not zero, the copolymer is obtained; in the category, the template polymer comprises common styrene, acrylate, acrylamide, acetate and acrylonitrile homo-or copolymer and the like.
The phase transfer catalyst has the following structural general formula:
Figure GDA0002821862100000042
the phase transfer catalyst includes, but is not limited to, the above structure.
The organic base comprises the following structural formula:
Figure GDA0002821862100000051
the base catalyst comprises the above three structural organic bases, but is not limited to these three structural organic bases.
The cyclic thioether monomer can comprise the following structural general formula:
Figure GDA0002821862100000052
the cyclic sulfide monomer comprises the above structure, but is not limited to the above structure, and the core structural feature of the cyclic sulfide monomer is that the cyclic sulfide monomer comprises a cyclic sulfide structure.
The organic solvent used comprises: chloroform, N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethylsulfoxide and the like may be used alone or in combination of two or more.
The chemical reagents are all obtained from the market except the episulfide monomer with a special structure.
The invention has the beneficial effects that:
(1) the catalyst system does not need harsh anhydrous and oxygen-free environment in the reaction preparation stage, and only needs to vacuumize the air in the system before reaction.
(2) For polymers of high molecular weight (>2500g/mol), the insertion reaction can be successfully carried out with monomer conversions above 80%.
(3) The prepared block copolymer has the characteristic of soft and hard segment double-chain segment, the molecular weight can reach 20000-100000 g/mol, the mechanical property is obviously improved, the amorphous state of the polymer is obviously modified, and the glass transition temperature can be as low as-50 ℃.
(4) The invention converts the insertion reaction from chemical concept to applicable technology, and potential application fields comprise self-healing materials, intelligent materials, self-assembly, biological macromolecules, drug slow release and the like.
Drawings
FIG. 1 is a comparison of gel chromatograms of polymers before and after intercalation, where a is a template polystyrene; b inserting the polymerization product without adding an alkali promoter; c insertion of the polymerization product base cocatalyst is added.
FIG. 2 is a graph comparing the monomer conversion of polymerization reactions before and after an insertion reaction (monomer conversion was measured by H-NMR of the reaction stock solution), wherein a insertion polymerization is carried out without addition of an alkali cocatalyst; b insertion of the polymerization product with addition of a base cocatalyst.
FIG. 3 is a DSC of the polymerization product before and after the insertion reaction, wherein a is styrene as a template; b insertion into the polymerization product (block polystyrene-alkyl sulfide).
FIG. 4 is a TGA comparison of the polymerization product before and after the insertion reaction, wherein a is styrene as a template; b insertion into the polymerization product (block polystyrene-alkyl sulfide).
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1
For example, a PMCT synthesis reaction formula, a template compound BMSE0.0122g containing thioester end groups, a phase transfer catalyst tetraphenylphosphonium chloride TPPC0.0381g, an organic base DMAP0.3660g, an episulfide monomer 0.8126mL and an organic solvent NMP0.2mL are sequentially added into a 10mL Schlenk reactor, and after uniform stirring, liquid nitrogen and a vacuum pump are used for carrying out three times of freezing and vacuum operation to completely remove air in the reactor and then sealing. And (3) heating to 70 ℃ for reaction for 6 hours, settling the reaction solution in methanol, centrifuging and washing for three times, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the pink viscous homopolymer PMCT. The glass transition temperature (DSC) was-68 ℃, the number average molecular weight was 11.6KDa by GPC, and the reaction conversion was 83%.
Figure GDA0002821862100000061
PMCT synthetic reaction formula
Example 2
As shown in the synthesis of PS-co-MCT, 0.48g of template polystyrene (A-PS) containing thioester internal end groups, 0.094g of phase transfer catalyst tetraphenylphosphonium bromide TPPB0.094g, organic base DMAP0.0122g, 1.05mL of cyclic thioether monomer MCT and organic solvent DMSO 4ML are sequentially added into a 20mL Schlenk reactor. Three freezing, vacuum operations were performed using liquid nitrogen and a vacuum pump to completely remove the air from the reactor and seal. After the temperature is raised to 60 ℃ and the reaction is carried out for 12 hours, the reaction solution is settled in methanol, centrifuged and washed for three times, and the mixture is placed in a vacuum oven to be dried for 24 hours at 60 ℃ to obtain the yellow copolymer PS-co-MCT. The glass transition temperature (DSC) was-40 ℃, the number average molecular weight was 15.2KDa by GPC, and the reaction conversion was 87%.
Figure GDA0002821862100000071
Reaction formula for synthesizing PS-co-MCT
Example 3
For example, in the reaction formula of PBMA-co-BCT synthesis, a 10mL Schlenk reactor is sequentially added with a template polymer B-PBMA 0.5177g containing thioester end groups, a phase transfer catalyst TBNB 0.0074g of tetra-tert-butyl nitrogen bromide, and an organic base Et3N0.0240 g, episulfide monomer BCT 3.6480g and organic solvent NMP 2mL, stirring well, using liquid nitrogen and vacuum pump, performing three times of freezing and vacuum operation to completely remove the air in the reactor, and sealing. And (3) heating to 50 ℃ for reaction for 48 hours, settling the reaction solution in methanol, centrifuging and washing for three times, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain pink viscous copolymer PBMA-co-BCT. The glass transition temperature (DSC) was-39 ℃, the number average molecular weight was 19.8KDa by GPC, and the reaction conversion was 85%.
Figure GDA0002821862100000081
PBMA-co-BCT synthesis reaction formula
Example 4
As shown in the reaction formula of PMMA-co-BA-co-FCT, 3.70g of a template polymer having a thioester end group (polymethyl methacrylate-butyl acrylate copolymer, PMMA-co-BA, MMA: BA ═ 3:1, Mn ═ 37.0KDa, Tg ═ 63 ℃) was sequentially added to a 100mL reactor, 1.12g of a phase transfer catalyst tetraphenyl nitrogen iodide TPNI, 1.52g of an organic base DBU, 12.36g of a cyclic thioether monomer, and 20mL of an organic solvent DMAc. Three freezing, vacuum operations were performed using liquid nitrogen and a vacuum pump to completely remove the air from the reactor and seal. And heating to 60 ℃ for reaction for 72 hours, settling the reaction solution in methanol, centrifuging and washing for three times, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain a light yellow copolymer PMMA-co-BA-co-FCT. The glass transition temperature (DSC) was-38 ℃, the number average molecular weight was 73.2KDa by GPC, and the reaction conversion was 83%.
Figure GDA0002821862100000082
Reaction formula of PMMA-co-BA-co-FCT
Example 5
For example, a reaction formula of PS-co-MCT, a 10mL Schlenk reactor is sequentially added with template polymer B-PS 0.9342g containing thioester end groups, phase transfer catalyst tetra-tert-butyl phosphine chloride 0.0324g, organic base DBU 0.0430g, episulfide monomer MCT 1.8683g and organic solvent NMP 4mL, stirred uniformly, and then frozen and vacuumized for three times by using liquid nitrogen and a vacuum pump to completely remove air in the reactor and then sealed. And (3) heating to 50 ℃ for reaction for 72 hours, settling the reaction solution in methanol, centrifugally washing for three times, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain pink viscous copolymer PBMA-co-BCT. The glass transition temperature (DSC) was-41 ℃, the number average molecular weight was 20.2KDa by GPC, and the reaction conversion was 81%.
Figure GDA0002821862100000091
Reaction formula of PS-co-MCT.

Claims (3)

1. A polymerization process for preparing a block copolymer by inserting an alkyl sulfide into a di-or trithioester end-group polymer with the aid of a base, characterized by the following steps:
sequentially adding a template compound or polymer containing a thioester end group, a phase transfer catalyst, an organic base, an episulfide monomer and an organic solvent into a reactor, wherein the molar ratio of the template compound or polymer containing the thioester end group, the phase transfer catalyst, the organic base and the organic solvent is 1: 0.01-10: 0.01-10: 0.1 to 100; the mol number of the cyclic thioether monomer depends on the molecular weight of the designed block copolymer, and the mol ratio of the cyclic thioether monomer to the thioester compound or the polymer is 10-1000: 1; using liquid nitrogen and a vacuum pump, performing three freezing and vacuum operations to completely remove air in the reactor and then sealing; heating to 40-90 ℃ for reaction for 6-72 hours, then settling the reaction solution in methanol, centrifugally washing for three times, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain a homopolymer or a copolymer for later use;
the thioester-terminated template compound or polymer has the following general structural formula:
bis-thioester template compound:
Figure FDA0002821862090000011
Figure FDA0002821862090000012
or CnH2n+1N is an integer of 1 or more
Figure FDA0002821862090000013
Trithioester template compound:
Figure FDA0002821862090000014
Figure FDA0002821862090000015
or CnH2n+1N is an integer of 1 or more;
R1and R'2The same or different;
bis-thioester template polymer:
Figure FDA0002821862090000021
Figure FDA0002821862090000022
or CnH2n+1N is an integer of 1 or more
Figure FDA0002821862090000023
R3-R10H, or CnH2n+1N is an integer of 1 or more;
trithioester template polymer:
Figure FDA0002821862090000024
Figure FDA0002821862090000025
or CnH2n+1N is an integer of 1 or more
R1And R'2The same or different;
R3-R10h, or CnH2n+1N is an integer of 1 or more
R3～R10The same or different;
M1and M2The same or different;
the phase transfer catalyst has the following structural general formula:
Figure FDA0002821862090000031
X＝F、Cl、Br、I
Figure FDA0002821862090000032
or CnH2n+1(ii) a n is an integer of 1 or more
R11～R14The same or different;
the organic base comprises the following structural formula:
Figure FDA0002821862090000033
the episulfide monomer comprises the following structural general formula:
Figure FDA0002821862090000034
M1and M2The structure represents a structural unit of the polymer, and the structure contained in the structure is independently selected without any relevant limitation; m1And M2One of which may be zero, but not both; m1And M2When the value of the first is zero, the polymer is a homopolymer; when none of them is zero, the copolymer is obtained.
2. The polymerization process according to claim 1, wherein the organic solvent used is one or a mixture of two or more of chloroform, N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide and dimethylsulfoxide.
3. The polymerization process according to claim 1 or 2, wherein the molar ratio of the episulfide monomer to the thioester compound or polymer is 20 to 300: 1.
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Publication number Priority date Publication date Assignee Title
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JP2008231349A (en) * 2007-03-23 2008-10-02 Univ Kanagawa Cyclic polysulfide compound and method for producing the same
US20100184899A1 (en) * 2008-04-24 2010-07-22 Prc-Desoto International, Inc. Thioethers, methods for their preparation, and compositions including such thioethers
CN108904446A (en) * 2018-06-11 2018-11-30 中山大学 A kind of preparation method and application of the medicament-carried nano micelle of artery plaque microenvironment response

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1896120A (en) * 2006-06-29 2007-01-17 四川大学 Preparation of polyarylphenyl resin by phase-transferring catalyst
JP2008231349A (en) * 2007-03-23 2008-10-02 Univ Kanagawa Cyclic polysulfide compound and method for producing the same
US20100184899A1 (en) * 2008-04-24 2010-07-22 Prc-Desoto International, Inc. Thioethers, methods for their preparation, and compositions including such thioethers
CN108904446A (en) * 2018-06-11 2018-11-30 中山大学 A kind of preparation method and application of the medicament-carried nano micelle of artery plaque microenvironment response

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Title
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