CN113307963B - Method for synthesizing glycidyl linear polymer - Google Patents

Method for synthesizing glycidyl linear polymer Download PDF

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CN113307963B
CN113307963B CN202110635845.8A CN202110635845A CN113307963B CN 113307963 B CN113307963 B CN 113307963B CN 202110635845 A CN202110635845 A CN 202110635845A CN 113307963 B CN113307963 B CN 113307963B
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赵俊鹏
刘珊
张广照
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South China University of Technology SCUT
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
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    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
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Abstract

The invention provides a method for synthesizing a glycidyl linear polymer, which takes glycidyl ester as a monomer, protects hydroxyl in a carboxylic ester form, avoids the occurrence of additional chain transfer reaction of the hydroxyl on the glycidyl monomer in the polymerization process, and obtains linear polyglycidyl with definite structure, controllable molecular weight and narrow dispersity through alkaline alcoholysis deprotection after the polymerization is finished. The chiral monomer is used as a raw material, and the obtained polyglycidyl ester and linear polyglycidyl have good stereoregularity and regioregularity. After alkaline alcoholysis of the random copolymerization product of the glycidyl ester and other non-glycidyl ester monomers, the nearly random distribution of free hydroxyl groups (or other functional groups) on the side chain of the copolymer can be realized, and a plurality of reaction sites are provided for modification after polymerization. When the polymerization reaction is block copolymerization, a glycidyl amphipathic or amphiphilic block copolymer can be obtained, and the application of the copolymer in the aspect of controllable drug release is facilitated.

Description

Method for synthesizing glycidyl linear polymer
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to a method for synthesizing a glycidyl linear polymer.
Background
Polyethylene glycol (PEG, also known as polyethylene oxide) has excellent water solubility and biocompatibility, is widely used in many fields such as food, health, medicine, chemical industry, and the like, and is recognized by the U.S. food and drug administration. The PEG is covalently linked with the surface, drugs or biomolecules through chemical modification, namely PEGylation (PEGylation), so that the solubility of the modified substance can be obviously improved, the half-life period can be prolonged, the immunogenicity and antigenicity can be reduced, the toxicity can be reduced, and the like. The strategy becomes an effective method for solving the problems of short half-life, strong immunogenicity and the like in clinical application of protein and polypeptide biopharmaceuticals. However, PEG also suffers from a number of disadvantages during use, mainly represented by low linear PEG functionality, containing at most only two modifiable end-group sites; PEG oligomer with smaller molecular weight (up to 400g/mol) shows certain nephrotoxicity in the process of organism metabolism; PEG-modified protein drugs may cause a portion of the body to produce the corresponding antibody. Common solutions to the above problems include the development of methods for the synthesis of multifunctional PEG, introducing modifiable functional groups on the PEG backbone; performing biological optimization, and establishing an optimal PEG modification method; at the same time, a potential alternative to PEG is sought that is expected to retain the superior properties of the original PEG polymer, but also to overcome the limitations present in PEG applications. In recent years, polyglycidols have attracted attention because they have an ether linkage backbone structure (-R-O-R-) similar to PEG, and each structural unit carries a free hydroxyl group. Compared with PEG, the polyglycidyl has better water solubility and biocompatibility, has antifouling property which is comparable with that of PEG, and becomes an important potential polymer for supplementing or even replacing related applications of PEG. In addition, abundant hydroxyl groups on the main chain of the polyglycidyl can be converted into functional groups with higher activity, such as carboxyl, azido, allyl or thiol, and the like through organic substitution reaction, so that the application of the polyglycidyl in the biomedical field, such as biomolecule encapsulation, storage, transportation and the like, is promoted.
The hyperbranched polyglycidyl (hbPG) can be directly prepared by anion ring-opening multi-branching polymerization of a glycidol monomer. However, the structure of the products obtained is generally difficult to control, in particular when the molecular weight is relatively high, both the distribution of the branching points and the chain length of the branches are not controllable. In contrast, linear polyglycidyl glycerol (linPG) has a definite structure and a controllable molecular weight, and has been studied in biomedicine and pharmaceutical fields. However, only oligo-diglycerol and triglycerol are currently commercialized, and the commercial products often contain impurities having a cyclic or branched structure. The synthesis of hbPG can be completed by a one-step method, while the synthesis route of linPG usually needs a two-step method, so the synthesis process is more complicated, and large-scale industrial scale-up tests of hbPG are to be researched. The synthesis of linPG in the laboratory generally requires the pre-protection of the hydroxyl group of the glycidyl monomer, and the removal of the protecting group after the polymerization is complete, releasing the hydroxyl group. The commonly used glycidyl monomers containing a protective group mainly comprise trimethylsilyl glycidyl ether (TMSGE), ethoxyethyl glycidyl ether (EEGE) and tert-butyl glycidyl ether (TMSGE)tBGE), Allyl Glycidyl Ether (AGE) and the like, which can resist the strong alkaline condition required by the polymerization of epoxy monomers, and can release hydroxyl after the polymerization is completed and is hydrolyzed under the acidic condition, so that the linPG is obtained. Among them, EEGE monomers containing acetal protecting groups are favored in the laboratory because they can be deprotected under mild acidic conditions.
The acidic hydrolysis of the polyglycidyl ether derivatives is not an effective method for synthesizing linPG, but has the following disadvantages. Firstly, ether protecting groups such as silyl ether, alkyl ether and the like can be removed under a strong acidic condition which is likely to cause the degradation of a polyether main chain, and the weak acidic condition is only suitable for acetal protecting groups, and the monomer needs to be additionally synthesized; secondly, strong acid in the system may have esterification reaction with hydroxyl generated by hydrolysis, so that the hydrolysis reaction process is difficult to control; in addition, the acidic catalyst is easy to remain in the product, is difficult to remove from the polyglycidyl molecule, and has adverse effects on the subsequent drying process of the product, such as dehydration of intermolecular hydroxyl groups to form ether bonds, thereby reducing the quality of the finished product.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. To this end, the first aspect of the present invention provides a method for synthesizing a linear glycidyl polymer, which can prevent the hydroxyl groups on the glycidyl monomer from undergoing an additional chain transfer reaction during the polymerization reaction to obtain linear polyglycidyl.
According to a first aspect of the present invention, there is provided a method for synthesizing a glycidyl linear polymer, comprising the steps of:
s1: in an inert atmosphere, adding a catalytic initiation system into an epoxy monomer containing at least one ester bond functionalization to perform polymerization reaction, so as to obtain a glycidyl ester based polymer;
s2: dissolving the polymer prepared by S1 in an alcohol solution, adding soda ash for alcoholysis reaction to obtain a glycidyl linear polymer;
the catalytic initiation system comprises a hydroxyl compound and a metal-free Lewis acid-base pair; the metal-free Lewis acid-base pair comprises an organic base and an alkyl boron.
In some embodiments of the invention, when the epoxy monomer is a glycidyl ester monomer, the linear polymer is a linear polyglycidyl.
In some preferred embodiments of the present invention, when the epoxy monomers are glycidyl ester monomers and non-glycidyl ester monomers and the polymerization reaction is a hybrid copolymerization, the linear polymer is a glycidyl polyether random copolymer.
In some more preferred embodiments of the present invention, when the epoxy monomers are glycidyl ester monomers and non-glycidyl ester monomers and the polymerization reaction is a block copolymerization, the linear polymer is a glycidyl polyether block copolymer.
In some more preferred embodiments of the present invention, the glycidyl ester monomer is selected from a glycidyl ester of a fatty acid having 2 to 18 carbon atoms, and the glycidyl ester of a fatty acid is selected from any one of (1) a glycidyl ester of rac-straight-chain fatty acid, (2) a glycidyl ester of R-straight-chain fatty acid, and (3) a glycidyl ester of S-straight-chain fatty acid; the specific structural formula is as follows:
Figure BDA0003105133020000031
in some more preferred embodiments of the present invention, the non-glycidyl ester monomer includes, but is not limited to, any one of (1) ethylene oxide, (2) linear alkyl ethylene oxide (alkyl carbon number 1 to 20), (3) linear alkyl glycidyl ether (alkyl carbon number 1 to 16), (4) isopropyl glycidyl ether, (5) tert-butyl glycidyl ether, (6) 2-ethylhexyl glycidyl ether, (7) phenyl glycidyl ether, (8) benzyl glycidyl ether, (9) allyl glycidyl ether, (10) propargyl glycidyl ether, and (11) glycidyl methacrylate. The specific structural formula is as follows:
Figure BDA0003105133020000032
in some more preferred embodiments of the present invention, the hydroxyl compound includes, but is not limited to (1) methanol and linear alkyl alcohol, (2) isopropanol, (3) 2-butanol, (4) t-butanol, (5) phenol and 1-phenyl linear alkyl alcohol, (6) allyl alcohol and linear terminal alkene 1-ol, (7) 2-allyloxyethanol, (8) 3-methyl-3-buten-1-ol, (9) propargyl alcohol, (10) cholesterol, (11) menthol, (12) 5-ethyl-1, 3-dioxane-5-methanol, (13) 3-dimethylamino-1-propanol, (14) linear perfluorool, (15) betulin, (16) water, (17) n-alkyl glycol, (18) p-xylene glycol, (19) glycerol, and mixtures thereof, (20)1,1, 1-tris (hydroxymethyl) propane, (21) pentaerythritol, (22) sorbitol, (23) dipentaerythritol, (24) tripentaerythritol, (25) glucose, (26) sucrose, (27) a copolymer of ethylene and vinyl alcohol, and (28) 5-norbornene-2-methanol. The carbon atom number of the straight chain alkyl alcohol is 2-18; the alkyl carbon atom number of the 1-phenyl linear alkyl alcohol is 1-10; the saturated carbon atom number of the straight chain terminal alkene 1-alcohol is 2-10; the number of carbon atoms of the straight-chain perfluoroalcohol is 2-12; the carbon atom number of the n-alkyl diol is 1-18, and the specific structural formula is as follows:
Figure BDA0003105133020000041
in some more preferred embodiments of the invention, the organic bases include, but are not limited to, tertiary amines (DABCO), amidines (DBN, DBU), and phosphazene bases (BEMP,tBuP1,tBuP2,EtP2,tBuP4) And the like. The specific structural formula is as follows:
Figure BDA0003105133020000042
in some more preferred embodiments of the present invention, the alkyl boron includes, but is not limited to, triisopropyl borane (T)iPrB) and other tri (linear) alkylboranes (TAB; carbon chain length from 1 to 8). The specific structural formula is as follows:
Figure BDA0003105133020000043
in some more preferred embodiments of the present invention, the molar ratio of the hydroxy compound, the organic base, and the boron alkyl is 1: (0.01-3): (0.01-5).
In some more preferred embodiments of the invention, the amount of the Lewis acid-base pair used may be adjusted according to the designed molecular weight and the desired reaction time.
In some more preferred embodiments of the present invention, the molar ratio of the boron alkyl to the organic base is (0.2 to 5): 1.
in some more preferred embodiments of the present invention, the concentration of the epoxy monomer in the catalytic initiation system is (3-10) mol/L.
In some more preferred embodiments of the present invention, the polymerization reaction is carried out in bulk or in a solvent selected from any one of benzene, toluene, tetrahydrofuran, 2-methyltetrahydrofuran, acetone, ethyl acetate, γ -butyrolactone.
In some more preferred embodiments of the present invention, the temperature of the polymerization reaction is room temperature, and the reaction time is 8 to 96 hours; the room temperature is 20-30 ℃.
In some more preferred embodiments of the present invention, in S2, the alcohol solution is selected from any one of methanol, ethanol, n-propanol, isopropanol, and n-butanol.
In some more preferred embodiments of the present invention, in S2, the soda ash is one selected from potassium hydroxide, sodium hydroxide, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (TBD) or 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU).
In some more preferred embodiments of the present invention, the temperature of the alcoholysis reaction is from 25 ℃ to 60 ℃ and the alcoholysis time is from 4h to 48 h.
The beneficial effects of the invention are as follows:
1. in the synthetic method, glycidyl ester is used as a monomer, hydroxyl is protected in a carboxylic ester form, so that the hydroxyl on the glycidyl ester monomer is prevented from generating additional chain transfer reaction in the polymerization reaction process, and alkaline alcoholysis deprotection is performed after the polymerization is completed, so that the linear polyglycidyl with a definite structure, controllable molecular weight and narrow dispersity is obtained. In the traditional preparation of the polyglycidyl oil, the ring opening polymerization of the anions of the glycidol is directly carried out, only the hyperbranched polyglycidyl oil can be obtained, and the structure and the molecular weight of the product are generally difficult to control.
2. In the method of the invention, the polymerization reaction and the alcoholysis reaction have selectivity: the ring-opening polymerization of the glycidyl ester can be efficiently and controllably carried out in a metal-free Lewis acid-base pair catalytic system without destructive reactions such as ester exchange and the like, so that the carboxylic ester structure is completely reserved after the polymerization; the alkaline alcoholysis only acts on the side group of the polyglycidyl ester, and has no adverse effect on the main chain structure.
3. The glycidyl ester monomer adopted by the invention, such as R-glycidyl butyrate and S-glycidyl butyrate, has wide commercial sources and lower price or is relatively simple and convenient to synthesize, and provides convenient conditions for synthesizing stereoregular linear polyglycidyl glycerol.
4. The metal-free Lewis acid-base pair catalytic system adopted by the invention has regioselectivity on the polymerization of the chiral glycidyl ester monomer. In the ring opening process, the growing tail end of the active chain selectively attacks methylene carbon atoms with lower upper resistance on the monomer, and the head-tail connection of the polymer structure is realized. Meanwhile, the process does not involve the configuration inversion of chiral carbon, so that a series of linear polyglycidyl glycerol with good stereoregularity and regioregularity can be conveniently synthesized.
5. Compared with the acid hydrolysis of glycidyl ether polymers, the alkaline alcoholysis is more favorable for industrial production (such as the alcoholysis of polyvinyl acetate to synthesize polyvinyl alcohol). The invention realizes the controllable ring-opening polymerization of the glycidyl ester monomer, and the combination of the process and the alkaline alcoholysis is favorable for realizing the batch synthesis of (stereoregularity) linear polyglycidyl.
6. Different hydroxyl compound initiators are selected according to requirements, and glycidyl polymers with various topological structure characteristics such as end group functionalization, block, star and grafting can be conveniently synthesized.
7. In the method, after alkaline alcoholysis is carried out on a random copolymerization product of glycidyl ester and other non-glycidyl ester monomers, a glycidyl ester structure can be introduced into a polyether main chain, so that the water solubility of the copolymer can be improved, modifiable sites of the copolymer can be increased, and the application range can be enlarged.
8. In the method, after alkaline alcoholysis is carried out on the block copolymerization product of the glycidyl ester and other non-glycidyl ester monomers, a glycidyl amphiphilic or amphiphilic copolymer can be obtained, and the application of the copolymer in the aspect of controllable drug release is facilitated.
9. Ester bonds are easy to generate ester exchange reaction in a classical catalytic system of epoxy monomers, ester group functionalized epoxy monomers are used as raw materials, carboxylic ester is successfully introduced into polyether chain side groups, the ester exchange reaction of polymer side chains is fully inhibited, and then the controllable synthesis of linear polyglycidyl is realized through alkaline alcoholysis. The method breaks through the limitation that the synthesis of the traditional linear polyglycidyl depends on the ring-opening polymerization and the acidic hydrolysis of glycidyl ether monomers, so that the synthesis conditions of the linear polyglycidyl are more suitable for the process requirements of mass production.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is a drawing showing the preparation of poly (glycidyl R-butyrate) in example 1113C NMR spectrum.
FIG. 2 is a diagram of the alcoholysis product of poly (R-glycidyl butyrate) -poly (S-glycidol) in example 1113C NMR spectrum.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
In the embodiment of the invention, the conversion rate of the glycidyl ester monomer and the structural characteristics of the polymer are measured by a Bruker AV400 liquid nuclear magnetic resonance instrument, the solvent is deuterated chloroform, and the polyglycidyl is deuterated dimethyl sulfoxide (DMSO-d)8) Is a solvent. The molecular weight and molecular weight dispersity of the polymerized product are measured by volume exclusion chromatography (SEC), and the instrument adopts a Waters 1515 type pump and HR-2, HR-4 and HR-6 series chromatographic columns, takes N, N-Dimethylformamide (DMF) as a mobile phase, has a column temperature of 50 ℃ and a flow rate of 1mL/min, and takes a series of polyethylene oxide standard samples as a calibration curve. The following examples are all formulas describing the fractionsAre molar components.
Example 1
This example realizes the synthesis of an alpha-benzyl-omega-hydroxy linear polyglycidyl. S1: performing ring-opening polymerization of rac-glycidyl acetate in a body by taking benzyl alcohol as an initiator and metal-free Lewis acid-base pairs as catalysts; s2: alkaline alcoholysis, which comprises the following specific steps:
1 part (mole part) of benzyl alcohol, 30 parts of rac-glycidyl acetate, 0.05 part of trimethylborane and 0.01 part oftBuP1Then the mixture is added into a dry glass reactor in sequence and stirred uniformly (wherein the initial concentration of the monomer is 9.7mol/L), and the mixture is reacted for 24 hours at room temperature.1H NMR gave 100% monomer conversion, SEC gave a molecular weight of 5.6kg/mol as the crude product, and a dispersity of 1.14.
The resulting polymer was dissolved in methanol (polymer concentration: 0.1g/mL), 1.5 parts of NaOH was added, and the reaction was carried out at room temperature for 4 hours. After the alcoholysis reaction is finished, concentrating the reaction solution, adding THF for reverse precipitation, collecting the precipitate, and drying to obtain the catalyst.1The degree of hydrolysis of the ester groups was 100% by H NMR, and the molecular weight of the crude product was 3.0kg/mol, dispersity 1.16 by SEC. The molar ratio of the hydroxyl compound, the organic base and the boron alkyl in this example was 1: 0.01: 0.05.
example 2
In this example, the amount of Lewis acid-base pair used in example 1 was varied, and the molar ratio of the hydroxy compound, organic base and boron alkyl in the catalytic initiation system was 1: 1: 2, adding 1 part of phosphazene basetBuP1And 2 parts of trimethylborane, the polymerization time of the monomers is shortened to 8 hours, and the rest is kept unchanged. After the polymerization reaction in the first step is finished,1h NMR gave 100% monomer conversion, SEC gave a molecular weight of 5.8kg/mol as the crude product, and a dispersity of 1.16. After the alcoholysis reaction in the second step is finished,1the conversion of the ester groups was determined to be 100% by H NMR, and the molecular weight of the crude product was 3.0kg/mol, determined by SEC, with a dispersity of 1.14.
Example 3
This example varied the amount of Lewis acid base used in example 1 to provide a molar ratio of hydroxyl compound, organic base and boron alkyl of 1 in the catalytic initiation system: 3: 0.6, in particular adding 3 parts of phosphazene basetBuP1And 0.6 part of trimethylborane, and the polymerization time is prolonged to 48 hours, and the rest is kept unchanged. After the polymerization reaction in the first step is finished,1h NMR gave 100% monomer conversion, SEC gave a molecular weight of 5.8kg/mol as the crude product, and a dispersity of 1.15. After the alcoholysis reaction in the second step is finished,1the transesterification rate was 100% by H NMR, the molecular weight of the crude product was 3.0kg/mol by SEC, and the dispersity was 1.14.
Example 4
This example replaces the organic base of example 1 with the tertiary amine DABCO, extending the polymerization time to 48h, the rest remaining unchanged. After the polymerization reaction in the first step is finished,1h NMR gave 100% monomer conversion, SEC gave a molecular weight of 5.8kg/mol as the crude product, and a dispersity of 1.16. After the alcoholysis reaction in the second step is finished,1the conversion of the ester groups was determined to be 100% by H NMR, and the molecular weight of the crude product was 3.0kg/mol, determined by SEC, with a dispersity of 1.15.
Example 5
This example changed the organic base from example 1 to DBU, the rest remaining unchanged. After the polymerization reaction in the first step is finished,1the monomer conversion was 100% by HNMR and the molecular weight of the crude product was 5.7kg/mol by SEC with a dispersity of 1.16. After the alcoholysis reaction in the second step is finished,1the transesterification rate was 100% by H NMR, the molecular weight of the crude product was 3.1kg/mol by SEC, and the dispersity was 1.16.
Example 6
In this example, trimethylboron in example 1 was replaced with triisopropylborane, and the polymerization time was prolonged to 48 hours, and the rest was kept unchanged. After the polymerization reaction in the first step is finished,1h NMR gave 100% monomer conversion, SEC gave a molecular weight of 5.6kg/mol as the crude product, and a dispersity of 1.18. After the alcoholysis reaction in the second step is finished,1the transesterification rate was 100% by H NMR, the molecular weight of the crude product was 3.3kg/mol by SEC, and the dispersity was 1.13.
Example 7
This example increased the mole fraction of rac-glycidyl acetate in example 2 to 200 parts, maintaining the hydroxyl groups in the systemThe molar ratio of the compound, the organic base and the boron alkyl is 1: 1: 2, prolonging the polymerization reaction time to 96 hours; and (3) increasing the mol fraction of NaOH in the second alcoholysis reaction to 10 parts, increasing the alcoholysis temperature to 45 ℃, and keeping the rest unchanged. After the polymerization reaction in the first step is finished,1h NMR gave 100% monomer conversion, SEC gave a crude molecular weight of 12.3kg/mol with a dispersity of 1.12. After the alcoholysis reaction in the second step is finished,1the conversion of the ester groups was 100% by H NMR and the molecular weight of the crude product was 6.7kg/mol by SEC with a dispersity of 1.15.
Example 8
In this example, THF was added to adjust the initial polymerization concentration of glycidyl acetate in example 1 to 3mol/L, and the polymerization time was prolonged to 72 hours, with the remainder being unchanged. After the polymerization reaction in the first step is finished,1h NMR gave 100% monomer conversion, SEC gave a molecular weight of 5.7kg/mol as the crude product, and a dispersity of 1.13. After the alcoholysis reaction in the second step is finished,1the conversion of the ester groups was determined to be 100% by H NMR, and the molecular weight of the crude product was 3.3kg/mol, determined by SEC, with a dispersity of 1.15.
Example 9
In this example, toluene was added to adjust the initial polymerization concentration of glycidyl acetate in example 1 to 7mol/L, and the polymerization time was prolonged to 36 hours, and the remainder was kept constant. After the polymerization reaction in the first step is finished,1h NMR gave 100% monomer conversion, SEC gave a molecular weight of 5.6kg/mol as the crude product, and a dispersity of 1.13. After the alcoholysis reaction in the second step is finished,1the conversion of the ester groups was determined to be 100% by H NMR, and the molecular weight of the crude product was 3.1kg/mol, determined by SEC, with a dispersity of 1.15.
Example 10
In this example, the rac-glycidyl acetate monomer in example 2 was replaced by glycidyl stearate, the polymerization time in the first step was extended to 96h, and the alcoholysis reaction time in the second step was extended to 48 h. After the polymerization reaction in the first step is finished,1the monomer conversion was 100% by H NMR, the molecular weight of the crude product was 8.9kg/mol by SEC, and the dispersity was 1.14. After the alcoholysis reaction in the second step is finished,1the conversion of the ester groups was 100% by H NMR and the molecular weight of the crude product was 3.1kg/mol by SEC,the dispersity was 1.15.
Example 11
This example replaces the glycidyl acetate monomer of example 1 with glycidyl R-butyrate. After the polymerization reaction in the first step is finished,1h NMR gave 100% monomer conversion, SEC gave a molecular weight of 5.0kg/mol as the crude product, and a dispersity of 1.12. As shown in fig. 1, from the polymerization product13Methylene, methine and side chain alpha-methylene of a polyether main chain on a C NMR spectrogram are known, and the obtained poly (R-glycidyl butyrate) has good stereoregularity, wherein the tacticity is [ mm [ -mm ]]Percent is 97%. The result shows that the ring opening process of the epoxy does not involve the configuration inversion of chiral carbon, and during the polymerization reaction, the active chain end selectively attacks the methylene carbon atom of the monomer to realize the head-tail connection of the polymer structure, so that the catalytic system has regioselectivity for the polymerization of the glycidyl ester monomer. After the alcoholysis reaction in the second step is finished,1the conversion of the ester groups was determined to be 100% by H NMR, and the molecular weight of the crude product was 3.0kg/mol by SEC with a dispersity of 1.18. Likewise, as shown in FIG. 2, from alcoholysis products13The [ mm ] of poly (R-glycidol) was found in the C NMR spectrum]The percent is 97 percent, which indicates that the alcoholysis product follows the stereo configuration of the original poly (R-glycidyl butyrate), i.e. the alcoholysis process has no influence on the stereoregularity of the polymer, and indicates that the linear polyglycidyl with the stereoregularity is successfully synthesized.
Example 12
This example synthesizes a three-arm linear polyglycidyl ester by replacing the initiator in example 7 with benzyl alcohol by 1,1, 1-tris (hydroxymethyl) propane. In the second step, the alcoholysis temperature is increased to 60 ℃, and the rest conditions are kept unchanged. After the polymerization reaction in the first step is finished,1h NMR gave 100% monomer conversion, SEC gave a crude molecular weight of 11.2kg/mol with a dispersity of 1.12. After the alcoholysis reaction in the second step is finished,1the conversion of the ester groups was 100% by H NMR and the molecular weight of the crude product was 5.8kg/mol by SEC with a dispersity of 1.19.
Example 13
This example replaces the initiator benzyl alcohol of example 1 with 5-norbornene-2-methanol, andto form alpha-norbornenyl-omega-hydroxyl linear polyglycidyl. After the polymerization reaction in the first step is finished,1the monomer conversion was 100% by H NMR, the molecular weight of the crude product was 5.8kg/mol by SEC, and the dispersity was 1.13. After the alcoholysis reaction in the second step is finished,1the conversion of the ester groups was determined to be 100% by H NMR, and the molecular weight of the crude product was 3.0kg/mol by SEC with a dispersity of 1.18.
The carbon-carbon double bond on the polymer chain can be subjected to post-modification, post-polymerization and hydrogenation reaction, and the application of the polymer is expanded. This example conveniently synthesizes end-functionalized linear polyglycidyl esters by selecting a double bond-functionalized hydroxyl initiator.
Example 14
This example replaces the catalyst used in the basic alcoholysis of example 1 with NaOH by 1, 8-diazabicyclo [5.4.0]Undec-7-ene (DBU), the alcoholysis time was extended to 12h, the rest was unchanged. After the polymerization reaction in the first step is finished,1h NMR gave 100% monomer conversion, SEC gave a molecular weight of 5.9kg/mol as the crude product, and a dispersity of 1.12. After the alcoholysis reaction in the second step is finished,1the conversion of the ester groups was determined to be 100% by H NMR, and the molecular weight of the crude product was 3.1kg/mol, determined by SEC, with a dispersity of 1.18.
Compared with inorganic bases such as NaOH and KOH, the organic base has better solubility in organic solvents and wide application range. 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (TBD) and the like are common basic catalysts in the fields of organic chemistry and high molecular chemistry, and the feasibility of catalyzing the efficient alcoholysis of carboxylic ester by using organic weak base is verified in the embodiment.
Example 15
This example synthesizes a-benzyl- ω -hydroxypoly (glycidol-co-propylene oxide) random copolymer. S1: performing ring-opening polymerization of rac-Glycidyl Butyrate (GBE) and Propylene Oxide (PO) in a body by using benzyl alcohol as an initiator and metal-free Lewis acid-base pairs as catalysts; s2: and (3) alkaline alcoholysis. The specific operation is as follows:
1 part (mole part) of benzyl alcohol, 50 parts of GBE, 50 parts of PO, 0.3 part of trimethylborane and 0.1 part of trimethylborane are added in an inert atmospheretBuP1Sequentially adding into a dry glass reactor and stirring uniformly ([ GEB)]0＝4.8mol/L，[PO]04.8mol/L), and reacting at room temperature for 18 h.1The H NMR gave 100% conversion of both monomers, and the SEC gave a crude molecular weight of 10.5kg/mol with a dispersity of 1.09. Kinetic studies of the copolymerization reaction revealed that the conversion rates of the two monomers were relatively close throughout the polymerization. From this, we conclude that the resulting copolymer is a random copolymer.
The polymer was dissolved in methanol (polymer concentration: 0.1g/mL), 2.5 parts of DBU was added, and the reaction was carried out at room temperature for 8 hours. After the alcoholysis reaction is finished, adding a small amount of acetic acid to neutralize the reaction solution. The reaction solution was diluted with dichloromethane, and added with neutral alumina, stirred, and filtered. Collecting the filtrate, and spin-drying.1The degree of hydrolysis of the ester groups was 100% by H NMR and the molecular weight of the crude product was 6.3kg/mol, dispersity 1.08 by SEC.
Through random copolymerization and alkaline alcoholysis of GBE and PO, a structural unit (such as a glycidol structure) with high hydrophilicity is introduced to a PPO main chain, so that the hydrophilicity of PPO is improved, modifiable sites on the PPO main chain are increased, and the application range of PPO is widened.
Example 16
This example synthesizes a random copolymer of α -benzyl- ω -hydroxy poly (glycidyl-co-allyl glycidyl ether) by replacing the epoxy monomer copolymerized with GBE in example 15 with Allyl Glycidyl Ether (AGE). The feeding ratio of the comonomer is 20 parts of GBE and 80 parts of AGE, the copolymerization time is 36h, and the rest is kept unchanged. After the polymerization reaction in the first step is finished,1the H NMR gave 100% conversion of both monomers, and the SEC gave a crude molecular weight of 12.6kg/mol with a dispersity of 1.17. After the alcoholysis reaction in the second step is finished,1h NMR shows that the hydrolysis degree of the ester group is 100 percent, and the allyl structure on the main chain and the side chain of the polymer is not influenced. The crude product has a molecular weight of 8.4kg/mol, determined by SEC, and a dispersity of 1.16.
Random copolymerization and basic hydrolysis of GBE and AGE in this example achieve near random distribution of double bonds and hydroxyl functional groups on the polymer side chain, providing a variety of possible combinations for post-polymerization modification reactions.
Example 17
This example synthesizes an α -benzyl- ω -hydroxy poly (glycidol-b-propylene oxide) block copolymer. S1: performing continuous ring-opening polymerization of rac-Glycidyl Butyrate (GBE) and Ethylene Oxide (EO) in a body by using benzyl alcohol as an initiator and metal-free Lewis acid-base pairs as catalysts; s2: and (3) alkaline alcoholysis. The specific operation is as follows:
1 part of benzyl alcohol, 1.5 parts of trimethylborane and 0.5 part of phosphazene base are reacted under an inert atmospheretBuP1And a proper amount of THF are sequentially added into a dry glass reactor and uniformly stirred. The reactor was connected to a vacuum line, and part of the gas in the bottle was vented and cooled with an ice-water bath. 70 parts of dry EO (where [ EO ] is distilled off at-20 ℃]010mol/L), the glass reactor was sealed and reacted at room temperature for 1.5 h.1H NMR gave 100% EO conversion, SEC gave the crude product a molecular weight of 3.0kg/mol and a dispersity of 1.08. The reaction flask was transferred into a glove box, and 70 parts of GBE (GBE [ GBE ] was added thereto]05.3 mol/L). The reaction flask was heated until the reaction solution was homogeneous, slowly cooled to room temperature, and stirred for 24 h.1The GBE conversion was determined to be 100% by H NMR, the molecular weight of the crude product was determined to be 13.0kg/mol by SEC, and the dispersity was 1.16.
The polymer was dissolved in methanol (polymer concentration: 0.1g/mL), 3.5 parts of DBU was added, and the reaction was carried out at room temperature for 8 hours. After the alcoholysis reaction is finished, adding a small amount of acetic acid to neutralize the reaction solution. The reaction solution was diluted with dichloromethane, and added with neutral alumina, stirred, and filtered. Collecting the filtrate, and spin-drying.1The degree of hydrolysis of the ester groups was 100% by H NMR and the molecular weight of the crude product was 6.8kg/mol, dispersity 1.15 by SEC.
Due to the hydrophobicity of the butyrate groups, the resulting block copolymerization product of GBE and EO is an amphiphilic copolymer. After the side butyrate group is alcoholyzed, the free hydroxyl group is exposed, and at the moment, the polymer is converted into the amphiphilic copolymer from the amphipathy.
Example 18
This example replaces the ethylene oxide monomer of example 17 with t-butylGlycidyl Ether (BGE), and the rest are kept unchanged, and alpha-benzyl-omega-hydroxy poly (glycidyl-b-tert-butyl glycidyl ether) block copolymer is synthesized. After the polymerization reaction in the first step is finished,1the conversions of both GBE and BGE reached 100% by H NMR, the molecular weight of the crude product was 16.8kg/mol by SEC, and the degree of dispersion was 1.14. After the alcoholysis reaction in the second step is finished,1h NMR determined that the degree of hydrolysis of the ester groups was 100% and the tertiary butyl ether structure in the polymer backbone as well as in the side chains was unaffected. The crude product had a molecular weight of 7.9kg/mol, dispersity of 1.18 by SEC.
This example demonstrates the feasibility of converting a block copolymer consisting of GBE and BGE from hydrophobic to amphiphilic by alkaline alcoholysis of the comonomer GBE.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the embodiments, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.

Claims (12)

1. A method of synthesizing a glycidyl linear polymer characterized by: the method comprises the following steps:
s1: in an inert atmosphere, adding a catalytic initiation system into an epoxy monomer containing at least one ester bond functionalization to perform polymerization reaction, so as to obtain a glycidyl ester based polymer;
s2: dissolving the polymer prepared by S1 in an alcohol solution, adding soda ash for alcoholysis reaction to obtain a glycidyl linear polymer;
the catalytic initiation system comprises a hydroxyl compound and a metal-free Lewis acid-base pair; the metal-free Lewis acid-base pair comprises an organic base and an alkyl boron.
2. The method for synthesizing a glycidyl linear polymer according to claim 1, characterized in that: when the epoxy monomer is a glycidyl ester monomer, the linear polymer is linear polyglycidyl.
3. The method for synthesizing a glycidyl linear polymer according to claim 1, characterized in that: when the epoxy monomer is a glycidyl ester monomer and a non-glycidyl ester monomer and the polymerization reaction is mixed copolymerization, the linear polymer is a glycidyl polyether random copolymer.
4. The method for synthesizing a glycidyl linear polymer according to claim 1, characterized in that: when the epoxy monomer is a glycidyl ester monomer and a non-glycidyl ester monomer and the polymerization reaction is block copolymerization, the linear polymer is a glycidyl polyether block copolymer.
5. The method for synthesizing a glycidyl linear polymer according to any of claims 2 to 4, characterized in that: the glycidyl ester monomer is selected from fatty acid glycidyl ester with the fatty acid carbon atom number of 2-18.
6. The method for synthesizing a glycidyl linear polymer according to claim 3 or 4, characterized in that: the non-glycidyl ester monomer comprises any one of ethylene oxide, linear alkyl ethylene oxide with alkyl carbon number of 1-20, linear alkyl glycidyl ether with alkyl carbon number of 1-16, isopropyl glycidyl ether, tert-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, allyl glycidyl ether and propargyl glycidyl ether.
7. The method for synthesizing a glycidyl linear polymer according to claim 1, characterized in that: the hydroxyl compound includes methanol, linear alkyl alcohol having 2-18 carbon atoms, isopropanol, 2-butanol, tert-butanol, phenol, 1-phenyl linear alkyl alcohol having 1-10 carbon atoms in the alkyl group, allyl alcohol, linear terminal alkene 1-alcohol having 2-10 saturated carbon atoms, 2-allyloxyethanol, 3-methyl-3-butene-1-ol, propargyl alcohol, cholesterol, menthol, 5-ethyl-1, 3-dioxane-5-methanol, 3-dimethylamino-1-propanol, linear perfluoroalcohol having 2-12 carbon atoms, betulin, water, n-alkylene glycol having 1-18 carbon atoms, p-xylene glycol, glycerol, 1,1, 1-tris (hydroxymethyl) propane, pentaerythritol, sorbitol, and mixtures thereof, Any one of dipentaerythritol, tripentaerythritol, glucose, sucrose, ethylene-vinyl alcohol copolymer and 5-norbornene-2-methanol.
8. The method for synthesizing a glycidyl linear polymer according to claim 1, characterized in that: the organic base comprises any one of tertiary amine, amidine and phosphazene base.
9. The method for synthesizing a glycidyl linear polymer according to claim 1, characterized in that: the alkyl boron includes any one of triisopropyl borane and other tri-linear alkyl boranes with carbon chain lengths from 1 to 8.
10. The method for synthesizing a glycidyl linear polymer according to claim 1, characterized in that: the molar ratio of the hydroxyl compound, the organic base and the boron alkyl is 1: (0.01-3): (0.01-5).
11. The method for synthesizing a glycidyl linear polymer according to claim 1, characterized in that: the concentration of the epoxy monomer in the catalytic initiation system is (3-10) mol/L.
12. The method for synthesizing a glycidyl linear polymer according to claim 1, characterized in that: the polymerization reaction is carried out in a bulk or in a solvent, and the solvent is any one of benzene, toluene, tetrahydrofuran, 2-methyltetrahydrofuran, acetone, ethyl acetate and gamma-butyrolactone.
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