Polyesters containing main chain diazo groups and methods for their preparation, post-conversion and degradation

Abstract

The application discloses a polyester containing a diazo group in a main chain and a preparation, post-conversion and degradation method thereof, and belongs to the field of polymer synthesis. The polyester containing the diazo group in the main chain is one of poly-alpha-diazo butyrolactone, poly-alpha-diazo valerolactone and poly-alpha-diazo caprolactone, or is a random copolymer composed of any two of the three aforementioned lactones, and is obtained by using potassium tert-butoxide to initiate ring-opening polymerization of five-, six- or seven-membered ring alpha-diazo lactone monomers under the protection of N2 atmosphere, and by carrying out homopolymerization or random copolymerization in an organic solvent. The polyester containing the diazo group in the main chain can be converted into a new polyester type, such as a polyester containing an alpha, beta-unsaturated double bond structure, a polyester containing a beta-ketone structure in a side chain, a polyester containing a silicon group structure in a side chain and the like, and the poly-alpha-diazo valerolactone can be degraded under the action of an organic base.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of polymer synthesis, and particularly relates to a polyester containing diazo groups in the main chain and a preparation, post-conversion and degradation method thereof. BACKGROUND

[0002] Aliphatic polyesters have been widely concerned in recent years due to their biodegradability. Among them, ring-opening polymerization of cyclic lactones is an important method for synthesizing polyesters. However, due to the structure of the polymer mainly composed of saturated carbon chains, the lack of functional groups limits their application. Therefore, in order to adjust the performance of the polymer, substituents can be introduced into the structural unit of the polyester to broaden its application value.

[0003] At present, the main methods for synthesizing functional polyesters mainly include: (1) the method of protecting the monomer first, then polymerizing, and then deprotecting, which is usually for relatively high reactive groups such as hydroxyl, carboxyl, amino, etc.; (2) the method of direct polymerization, which requires the functional groups on the monomer not to be converted under the ring-opening polymerization conditions of lactones, such as halogen, α-methylene, etc. From the above synthesis route, it can be concluded that for polyesters containing relatively active reactive functional groups, a relatively complicated route is needed for synthesis, and for functional polyesters that can be directly synthesized, due to the stability of the functional groups on the polyester, it is difficult to have a relatively rich post-conversion reaction. How to avoid protection-deprotection, directly prepare functional polyesters containing active functional groups, and realize the post-conversion and degradation recovery process of the polyester is a problem to be solved. SUMMARY

[0004] The purpose of the present application is to provide a polyester containing diazo groups in the main chain and a preparation, post-conversion and degradation method thereof, and other polyesters obtained by post-conversion.

[0005] The technical concept of the present application: diazo compounds are an important class of carbene precursors, which can be efficiently converted through various types of carbene-based organic reactions. If diazo groups are introduced into polyesters, different functional groups can be introduced through post-conversion reactions of the polymer, thereby obtaining a series of polymers with different structures. In order to obtain polyesters containing diazo substituents, diazo groups can be introduced at the α position of lactones, and synthesized by ring-opening polymerization. Diazo compounds are usually converted under acidic, high-temperature and transition metal conditions, and remain stable under low-temperature and alkaline conditions, which are the most common reaction conditions for lactone ring-opening polymerization.

[0006] Based on the above technical concept, the present application provides a ring-opening polymerization reaction of lactones containing α-diazo groups in five-, six- and seven-membered rings, to prepare polyesters containing diazo groups in the main chain, and to realize post-conversion and degradation recovery from the polyester, and to prepare other types of polyesters from the post-conversion of the polyester.

[0007] To achieve the above object, the technical scheme adopted by the present application is as follows:

[0008] In the first aspect, the present application provides a polyester containing diazo groups in the main chain, which is specifically one of the following three lactones: poly-alpha-diazo butyrolactone, poly-alpha-diazo valerolactone, and poly-alpha-diazo caprolactone, or a random copolymer composed of any two of the above three lactones, and the molecular structure formula is as follows:

[0009]

[0010] In the formula, t-BuO represents a tert-butoxy group, and m and n are positive integers; x in formula (I) is 1, 2 or 3, representing poly-alpha-diazo butyrolactone, poly-alpha-diazo valerolactone or poly-alpha-diazo caprolactone; formula (II), (III) and (IV) represent random copolymers.

[0011] In the second aspect, the present application provides a preparation method of a polyester containing diazo groups in the main chain, which comprises the following steps: selecting one or two of alpha-diazo lactone monomers with five, six or seven-membered rings as reactants, using potassium tert-butoxide as a catalyst, and performing homopolymerization or random copolymerization reaction in an organic solvent under the protection of N2 atmosphere to obtain a polyester product containing diazo groups in the main chain, which is specifically one of the following three lactones: poly-alpha-diazo butyrolactone, poly-alpha-diazo valerolactone, and poly-alpha-diazo caprolactone, or a random copolymer composed of any two of the above three lactones;

[0012] The homopolymerization reaction formula is as follows:

[0013]

[0014] The random copolymerization reaction formula is as follows:

[0015]

[0016] In the formula, t-BuOK represents potassium tert-butoxide, and solvent represents an organic solvent; the product of formula (I) is poly-alpha-diazo butyrolactone, poly-alpha-diazo valerolactone or poly-alpha-diazo caprolactone; and the products of formula (II), (III) and (IV) are random copolymers.

[0017] Further, in the homopolymerization reaction, the catalytic amount of potassium tert-butoxide is 2% to 5% of the molar ratio of the alpha-diazo lactone monomer; the organic solvent is tetrahydrofuran, which is pre-treated with metallic sodium under N2 atmosphere, and the amount of the metallic sodium is determined according to the amount of the alpha-diazo lactone monomer; the solution concentration of the alpha-diazo lactone monomer in tetrahydrofuran is 2 mol / L (not limited to this value), and the solution concentration of potassium tert-butoxide in tetrahydrofuran is 1 mol / L (not limited to this value);

[0018] In the random copolymerization reaction, the catalytic amount of potassium tert-butoxide is 5% of the molar ratio of each α-diazo lactone monomer (not limited to this), and 2.5% of the molar ratio of the total α-diazo lactone monomer (not limited to this); the organic solvent is tetrahydrofuran, which is pre-treated with sodium metal under N2 atmosphere, and the amount thereof is determined according to the amount of the α-diazo lactone monomer, the solution concentration of each α-diazo lactone monomer in tetrahydrofuran is 1 mol / L (not limited to this), the solution concentration of the total α-diazo lactone monomer in tetrahydrofuran is 2 mol / L (not limited to this), and the solution concentration of potassium tert-butoxide in tetrahydrofuran is 1 mol / L (not limited to this).

[0019] Further, in the homopolymerization reaction, the reaction time is 5-30 min, and the reaction temperature is -50-25℃, and different reaction temperatures can be selected according to the structure size of the α-diazo lactone monomer;

[0020] In the random copolymerization reaction, the reaction time is 5-10 min, and the reaction temperature is -50--30℃, and different reaction temperatures can be selected according to the structure size of the α-diazo lactone monomer.

[0021] Further, after the homopolymerization or random copolymerization reaction, cooling and post-treatment are performed; the cooling process can use a low-temperature reactor, an ice bath or other cooling methods; the post-treatment includes precipitation and drying; the precipitation process can use dichloromethane as a good solvent and diethyl ether as a poor solvent, and is performed at the polymerization reaction temperature; the drying process can use a vacuum drying box to remove the solvent.

[0022] In a third aspect, the application provides a post-conversion method of a polyester containing a diazo group in the main chain, which comprises the following steps: taking poly-α-diazo valerolactone or poly-α-diazo caprolactone as a reactant, taking rhodium (II) trifluoroacetate dimer as a catalyst, and performing a post-conversion reaction in an organic solvent under the protection of N2 atmosphere to obtain a polyester product containing an α,β-unsaturated double bond with a Z configuration as the main chain, which is specifically poly(Z)-α,β-unsaturated valerolactone or poly(Z)-α,β-unsaturated caprolactone; the reaction formula is as follows:

[0023]

[0024] In the formula, [Rh] represents rhodium (II) trifluoroacetate dimer, solvent represents an organic solvent, the product of formula (I) is poly(Z)-α,β-unsaturated valerolactone, and the product of formula (II) is poly(Z)-α,β-unsaturated caprolactone.

[0025] Further, the catalytic amount of the rhodium (II) trifluoroacetate dimer is at least 1% of the molar ratio of the polyester containing a diazo group in the main chain, and preferably 1%.

[0026] Further, the organic solvent is super-dry dichloromethane, preferably used in an amount determined according to the feeding amount of the main-chain polyester containing diazo group, and the main-chain polyester containing diazo group has a concentration of 0.2 mol / L (not limited to this) in the organic solvent.

[0027] Further, the reaction time of the post-conversion reaction is 30-90 min, and the reaction temperature is room temperature.

[0028] Further, after the post-conversion reaction is completed, the product is subjected to post-treatment, including filtration, concentration, precipitation and drying; the filtration process can be performed under the condition of using a 0.22 μm filter membrane; the concentration process can be performed by using methods such as normal pressure distillation, reduced pressure distillation, for example, vacuum concentration by using a rotary evaporator; the precipitation process can be performed at room temperature by using dichloromethane as a good solvent and diethyl ether or methanol as a poor solvent; and the drying process can be performed by using a vacuum drying box to remove the solvent.

[0029] In a fourth aspect, the present application provides a main-chain polyester containing an α,β-unsaturated double bond with a Z configuration as the main form, specifically poly(Z)-α,β-unsaturated valerolactone or poly(Z)-α,β-unsaturated caprolactone, which is prepared by the post-conversion method described above, and has a molecular structure as shown in the following formula:

[0030]

[0031] In the formula, formula (I) is poly(Z)-α,β-unsaturated valerolactone, and formula (II) is poly(Z)-α,β-unsaturated caprolactone.

[0032] In a fifth aspect, the present application provides a post-conversion method of a main-chain polyester containing a diazo group, which includes the following steps: using poly-α-diazo valerolactone or poly-α-diazo caprolactone and p-bromobenzaldehyde as reactants, using scandium triflate and a chiral ligand as a catalyst, and setting a molecular sieve, and performing a post-conversion reaction in an organic solvent under the protection of N2 atmosphere to obtain a polyester product containing a β-carbonyl structure in the side chain, specifically poly(α-p-bromobenzoyl) valerolactone or poly(α-p-bromobenzoyl) caprolactone; and the reaction formula is as shown in the following formula:

[0033]

[0034] In the formula, formula I is poly-α-diazo valerolactone or poly-α-diazo caprolactone; [Sc] represents scandium triflate, L represents a chiral ligand, MS represents a molecular sieve, and solvent represents an organic solvent; wherein the chiral ligand first reacts with scandium triflate in the reaction, coordinates with scandium, and the coordinated substance catalyzes the reaction to proceed and can control the selectivity of the reaction.

[0035] Further, the catalytic amount of scandium triflate is 3% to 5% molar ratio of the main chain containing diazonium group polyester; the amount of the chiral ligand (trade name: NO-Feng-PDiPPRa; CAS number: 1005495-74-8) is 3% to 5% molar ratio of the main chain containing diazonium group polyester; the amount of the bromobenzaldehyde is 1 to 1.05 equivalent of the main chain containing diazonium group polyester; and the organic solvent is ultradry dichloromethane, the amount of which is determined according to the amount of the main chain containing diazonium group polyester, and the concentration of the main chain containing diazonium group polyester in the organic solvent is 0.2 mol / L (not limited thereto).

[0036] Further, the The molecular sieve is heated and dried under vacuum for not less than 30 min before use, and the amount of the molecular sieve is determined according to the amount of the main chain containing diazonium group polyester, and not less than 5 mg of the molecular sieve is added per 0.2 mmol of the main chain containing diazonium group polyester (not limited thereto). The molecular sieve is heated and dried under vacuum for not less than 30 min before use, and the amount of the molecular sieve is determined according to the amount of the main chain containing diazonium group polyester, and not less than 5 mg of the molecular sieve is added per 0.2 mmol of the main chain containing diazonium group polyester (not limited thereto).

[0037] Further, the reaction time of the post-conversion reaction is 3.5 to 4 h, and the reaction temperature is 0 to 20℃, and different reaction temperatures can be selected according to the structures of different reactants.

[0038] Further, after the post-conversion reaction is completed, cooling and post-treatment are performed, the cooling process can use a low-temperature reactor or other cooling methods; the post-treatment includes filtration, concentration, precipitation and drying; the filtration process can use a 0.22 μm filter membrane; the concentration process can use normal pressure distillation, reduced pressure distillation and the like, for example, vacuum concentration by a rotary evaporator; the precipitation process can use dichloromethane as a good solvent, and diethyl ether or methanol as a poor solvent, and is performed at room temperature; and the drying process can use a vacuum drying box to remove the solvent.

[0039] In a sixth aspect, the present application provides a polyester containing a β-carbonyl structure in a side chain, specifically poly(α-p-bromobenzoyl) valerolactone or poly(α-p-bromobenzoyl) caprolactone, which is prepared by the post-conversion method described above, and the molecular structure formula is as follows:

[0040]

[0041] In the formula, x = 1 or 2.

[0042] In a seventh aspect, the present application provides a post-conversion method of a main-chain polyester containing a diazo group, which comprises the following steps: using poly-alpha-diazo-valerolactone or poly-alpha-diazo-caprolactone and triethylsilane as reactants, using rhodium acetate dimer as a catalyst, and performing a post-conversion reaction in an organic solvent under the protection of N2 atmosphere to obtain a polyester product containing a silicon group structure, which is specifically poly(alpha-triethylsilyl) valerolactone or poly(alpha-triethylsilyl) caprolactone; the reaction formula is as follows:

[0043]

[0044] wherein [Rh] represents rhodium acetate dimer, Et3SiH represents triethylsilane, solvent represents an organic solvent, the product of formula (I) is (alpha-triethylsilyl) valerolactone, and the product of formula (II) is poly(alpha-triethylsilyl) caprolactone.

[0045] Further, the catalytic amount of the rhodium acetate dimer is 1% to 5% of the main-chain polyester containing a diazo group in terms of molar ratio; the amount of the triethylsilane is 20 equivalents of the main-chain polyester containing a diazo group; and the organic solvent is super-dry dichloromethane, the amount of which is determined according to the amount of the main-chain polyester containing a diazo group, and the concentration of the main-chain polyester containing a diazo group in the organic solvent is 0.25 mol / L (not limited thereto).

[0046] Further, the reaction time of the post-conversion reaction is not less than 20 h, and the reaction temperature is -85 to -70℃, preferably -78℃.

[0047] Further, after the post-conversion reaction is completed, the product is subjected to cooling and post-treatment, the cooling process can use a low-temperature reactor or other cooling methods; the post-treatment includes filtration, concentration, separation and purification, and drying; the filtration process can use a 0.22 μm filter membrane; the concentration process can use normal pressure distillation, reduced pressure distillation, etc., such as vacuum concentration by a rotary evaporator; the separation and purification process can use a cycle preparative liquid chromatograph; and the drying process can use a vacuum drying oven.

[0048] In an eighth aspect, the present application provides a polyester containing a silicon group structure in a side chain, which is specifically poly(alpha-triethylsilyl) valerolactone or poly(alpha-triethylsilyl) caprolactone, and is prepared by the above post-conversion method, and the molecular structure formula is as follows:

[0049]

[0050] wherein formula (I) is (alpha-triethylsilyl) valerolactone, and formula (II) is poly(alpha-triethylsilyl) caprolactone.

[0051] In a ninth aspect, a method for post-conversion of a polyester having a main chain containing a diazonium group, comprising the following steps: using poly-alpha-diazobutyrolactone as a reactant, under the protection of N2 atmosphere, under blue light irradiation, and in an organic solvent, to perform a post-conversion reaction to obtain a polyester product containing an alpha, beta-unsaturated double bond structure, i.e., poly-alpha, beta-unsaturated butyrolactone; the reaction formula is as follows:

[0052]

[0053] wherein m, n, and p are positive integers, the wavelength of the blue light is 460-465 nm, and solvent represents an organic solvent.

[0054] Further, the organic solvent is ultradry dichloromethane, and the amount of the solvent is determined according to the amount of the polyester having a main chain containing a diazonium group, and the concentration of the polyester having a main chain containing a diazonium group in the solvent is less than 0.25 mol / L.

[0055] Further, the reaction time of the post-conversion reaction is greater than 20 h, and the reaction temperature is room temperature (10-30℃).

[0056] Further, after the post-conversion reaction is completed, the product is subjected to post-treatment, and the post-treatment comprises concentration, precipitation, and drying; the concentration process can be performed by using methods such as normal pressure distillation, reduced pressure distillation, for example, vacuum concentration by using a rotary evaporator; the precipitation process can be performed by using dichloromethane as a good solvent and diethyl ether as a poor solvent at room temperature; and the drying process can be performed by using a vacuum drying oven to remove the solvent.

[0057] In a tenth aspect, the present application provides a poly-alpha, beta-unsaturated butyrolactone, which is prepared by the post-conversion method described above, and the molecular structure formula is as follows:

[0058]

[0059] wherein m, n, and p are positive integers.

[0060] In an eleventh aspect, the present application provides a method for degradation of a polyester having a main chain containing a diazonium group, comprising the following steps: using poly-alpha-diazopentolactone, an organic base 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and ultradry methanol as a catalyst, under the protection of N2 atmosphere, in an organic solvent, to perform a degradation reaction to obtain an alpha-diazolactone monomer product with a six-membered ring; the reaction formula is as follows:

[0061]

[0062] Wherein, TBD represents an organic base 1,5,7-triazabicyclo[4.4.0]dec-5-ene, MeOH represents super dry methanol, and solvent represents an organic solvent; wherein the organic base can remove the proton of the hydroxyl group at the end of the polymer chain to obtain an alkoxide which can undergo backbiting reaction to generate degradation product six-membered ring lactone; methanol plays the role of chain transfer agent, that is, methanol can undergo ester exchange reaction with the ester group in the polymer chain to increase the number of polymer chains and accelerate the rate of degradation reaction.

[0063] Further, the catalytic amount of the 1,5,7-triazabicyclo[4.4.0]dec-5-ene is 10% to 20% molar ratio of the polyester containing diazo group in the main chain; the catalytic amount of the super dry methanol is 5% to 10% molar ratio of the polyester containing diazo group in the main chain; the organic solvent is tetrahydrofuran which needs to be treated with sodium metal under nitrogen atmosphere, and the amount thereof is determined according to the feeding amount of the polyester containing diazo group in the main chain, and the concentration of the polyester containing diazo group in the main chain in the organic solvent is less than 0.5 mol / L.

[0064] Further, the reaction time of the degradation reaction is greater than 10 h, preferably 12 h, and the reaction temperature is 40 to 50°C; the heating process can adopt oil bath or other heating methods.

[0065] Further, after the completion of the degradation reaction, the monomers obtained by degradation are subjected to post-treatment, which includes filtration, concentration and separation and purification; the filtration process can use a sand core funnel to filter under reduced pressure; the concentration process can adopt methods such as normal pressure distillation, reduced pressure distillation, for example, vacuum concentration by a rotary evaporator; and the purification process is to obtain pure product by thin plate chromatography or column chromatography.

[0066] The beneficial effects of the technical scheme of the present application mainly include:

[0067] 1, the diazo group is a kind of active reaction group, can react under heating, illumination, acidic conditions or with metal, and conversely, how to control the diazo group not to be converted in the reaction process is extremely challenging. The present application first realizes the ring-opening polymerization of three kinds of lactone monomers containing α-diazo group, and the polyester containing diazo group in the main chain can be synthesized quickly by ring-opening polymerization, and the diazo group can be controlled not to be converted in the synthesis process. These synthesized polyesters are new materials with originality prepared by the present application. In the field of polymers, so far, the synthesis of polyester polymer containing diazo group in the main chain has never been reported.

[0068] 2. Ring-opening polymerization of five-membered ring lactones is very difficult (e.g. high monomer concentration, complex catalyst structure), and current methods for synthesizing five-membered ring polyesters require harsh reaction conditions, including bulk polymerization or polymerization at high monomer concentrations of > 5M, low temperature, and the need for complex and expensive catalyst structures. In comparison, the present application innovatively introduces a diazo group to achieve ring-opening polymerization of five-membered ring lactones under conventional conditions, and high conversion ring-opening polymerization can be achieved at a relatively low concentration, and the catalyst is simple and easy to obtain.

[0069] 3. By synthesizing the new polyester material containing a diazo group in the main chain, the present application uses the rich reactivity of the diazo group contained in the structure to achieve post-conversion, and can obtain polyester polymers with diverse structures and difficult to synthesize by other methods in a very short time (e.g. 30 min). For lactones containing α, β-unsaturated double bonds in the six-membered ring, the corresponding polyester containing α, β-unsaturated double bonds with Z structure as the main chain cannot be obtained by direct ring-opening polymerization, but the post-conversion reaction proposed in the present application can achieve the synthesis of such semi-crystalline polymers with high conversion. For polyesters containing β-carbonyl structures in the side chain, such polymers are difficult to synthesize by other methods, and can be easily synthesized by the post-conversion reaction proposed in the present application. For the synthesis of polyesters containing silicon-based structures in the side chain, such polymers are difficult to synthesize by other methods, and can be easily synthesized by the post-conversion reaction proposed in the present application, and the solubility of such polymers in organic solvents can be increased. In the field of polymers, to date, there has been no report on the post-conversion of polyester polymers containing diazo groups in the main chain.

[0070] 4. By post-conversion of polyester containing diazo groups in the main chain, the present application synthesizes new materials such as polyester containing α, β-unsaturated double bond structure with Z structure as the main chain, polyester containing α, β-unsaturated double bond structure, polyester containing β-carbonyl structure in the side chain, and polyester containing silicon-based structure in the side chain. These new materials have new chemical and physical properties, for example, polyester containing β-carbonyl structure in the side chain can react with diamines, and has potential application value for forming dynamic covalent cross-linked structure polymers. These new materials have great potential for contribution to polymer synthesis and the like.

[0071] 5. The polyester containing diazo groups in the main chain synthesized by the present application can be degraded and recycled under relatively mild conditions, and to some extent, the side reactions of the relatively active diazo group can be avoided to achieve ring closure and recycling. DETAILED DESCRIPTION

[0072] In order to make the technical features and advantages or technical effects of the above technical solutions of the present application more obvious and easy to understand, the following examples are used for detailed description.

[0073] Example 1:

[0074] Synthesis of poly-α-diazobutyrolactone

[0075] Into a 10 mL reaction tube, 448 mg (4.0 mmol) of α-diazobutyrolactone was added. The reaction tube was sealed and purged with nitrogen three times. 2 mL of freshly distilled tetrahydrofuran was added. After the reaction was completely dissolved, the reaction bottle was placed in a -40 °C low temperature cold bath. After 20 s, 100 μL of 1 M potassium tert-butoxide tetrahydrofuran solution was added. The reaction was allowed to proceed for 30 min. Then, 60 μL of 4 M acetyl chloride tetrahydrofuran solution was added to quench the reaction. The reaction system was precipitated with ether three times at -40 °C and dried in vacuum to obtain the product poly-α-diazobutyrolactone, which was a red-brown amorphous solid with a yield of 87%. The number average molecular weight was 6.5 kg / mol and the molecular weight distribution coefficient was 1.39 by gel permeation chromatography. The number average molecular weight was 7.3 kg / mol by hydrogen nuclear magnetic resonance spectroscopy. The structure of the product is shown in the following formula:

[0076]

[0077] The nuclear magnetic data thereof are as follows:

[0078] 1 H NMR (400 MHz, CDC13) δ 4.32 (t, J = 5.8 Hz, 2H), 3.80 (t, J = 5.4 Hz, 0.03H, terminal CH2 OH), 2.66 (t, J = 5.8 Hz, 2H), 1.48 (s, 0.14H); 13 C NMR (101 MHz, CDC13) δ 166.36, 63.15, 53.18, 28.26, 23.64.

[0079] Example 2:

[0080] Synthesis of poly-α-diazopentolactone

[0081] Into a 10 mL reaction tube, 490 mg (3.9 mmol) of α-diazopentolactone was added. The reaction tube was sealed and purged with nitrogen three times. 2 mL of freshly distilled tetrahydrofuran was added. After the reaction was completely dissolved, the reaction bottle was placed in a -40 °C low temperature cold bath. After 20 s, 80 μL of 1 M potassium tert-butoxide tetrahydrofuran solution was added. The reaction was allowed to proceed for 20 min. Then, 200 μL of 1 M acetyl chloride tetrahydrofuran solution was added to quench the reaction. The reaction system was precipitated with ether three times at -40 °C and dried in vacuum to obtain the product poly-α-diazopentolactone, which was a yellow powdery solid with a yield of 84%. The number average molecular weight was 10.2 kg / mol and the molecular weight distribution coefficient was 1.11 by gel permeation chromatography. The number average molecular weight was 12.4 kg / mol by hydrogen nuclear magnetic resonance spectroscopy. The structure of the product is shown in the following formula:

[0082]

[0083] Its NMR data are as follows:

[0084] 1 H NMR (400 MHz, CDC13) δ 4.23 (t, J = 6.2 Hz, 2H), 3.69 (t, J = 5.1 Hz, 0.03H, terminal CH2 OH), 2.40 (t, J = 7.3 Hz, 2H), 1.94 - 1.84 (m, 2H), 1.47 (s, 0.10H); 13 C NMR (101 MHz, CDC13) δ 166.97, 63.36, 54.66, 28.32, 26.96, 20.26.

[0085] Example 3:

[0086] Synthesis of poly-α-diazo caprolactone

[0087] Into a 10 mL reaction tube was added 561 mg (4.0 mmol) of α-diazo caprolactone, the reaction tube was sealed and purged with nitrogen three times, 2 mL of freshly distilled tetrahydrofuran was added. After the reaction was completely dissolved, the reaction bottle was placed in a -20 °C low temperature cold bath, then 160 μL of 1 M potassium tert-butoxide tetrahydrofuran solution was added, the reaction was carried out for 25 minutes, then 100 μL of 4 M acetyl chloride tetrahydrofuran solution was added, and the reaction was quenched. The reaction system was precipitated with ether three times at -20 °C, and dried in vacuum to obtain the product poly-α-diazo caprolactone, which was a yellow sticky solid with a yield of 92%. The number average molecular weight was 11.3 kg / mol and the molecular weight distribution coefficient was 1.75 by gel permeation chromatography, and the number average molecular weight was 15.7 kg / mol by nuclear magnetic resonance hydrogen spectrum. The structure of the product is as shown in the following formula:

[0088]

[0089] Its NMR data are as follows:

[0090] 1 H NMR (400 MHz, CDC13) δ 4.19 (t, J = 6.4 Hz, 2H), 3.67 (t, J = 5.5 Hz, 0.04H, terminal CH2 OH), 2.35 (t, J = 7.4 Hz, 2H), 1.78 - 1.66 (m, 2H), 1.65 - 1.53 (m, 2H), 1.47 (s, 0.08H); 13CNMR (101 MHz, CDC13) δ 167.24, 64.11, 55.18, 28.26, 27.91, 24.04, 22.73.

[0091] Example 4:

[0092] Synthesis of random copolymer of α-diazo-β-butyrolactone and α-diazo-γ-butyrolactone

[0093] Into a 5 mL reaction tube was added 44.8 mg (0.40 mmol) of α-diazo-β-butyrolactone and 50.4 mg (0.40 mmol) of α-diazo-γ-butyrolactone. The reaction tube was sealed and purged with nitrogen three times. After the reaction was completely dissolved, the reaction bottle was placed in a -40 °C low temperature cold bath, and 20 μL of 1 M potassium tert-butoxide in tetrahydrofuran was added after 20 s. The reaction was quenched after 10 min by adding 50 μL of 1 M acetyl chloride in tetrahydrofuran. The reaction system was precipitated with ether three times at -40 °C and dried in vacuum to obtain a random copolymer of α-diazo-β-butyrolactone and α-diazo-γ-butyrolactone, which was a yellow amorphous solid. The conversion of α-diazo-β-butyrolactone was 88% and the yield was 85%. The conversion of α-diazo-γ-butyrolactone was 61% and the yield was 59%. The ratio of α-diazo-β-butyrolactone and α-diazo-γ-butyrolactone structural units in the polymer was 59:41. The number average molecular weight was 8.4 kg / mol and the molecular weight distribution coefficient was 1.22 as measured by gel permeation chromatography. The number average molecular weight was 7.4 kg / mol as measured by nuclear magnetic resonance hydrogen spectrum. The product structure is shown in the following formula:

[0094]

[0095] The nuclear magnetic data thereof are as follows:

[0096] 1 H NMR (600 MHz, CDC13) δ 4.35-4.29 (m, 1.18H), 4.26-4.20 (m, 0.82H), 2.70-2.59 (m, 1.18H), 2.47-2.33 (m, 0.82H), 1.94-1.84 (m, 0.82H), 1.49-1.46 (m, 0.14H); 13 C NMR (150 MHz, CDC13) δ 167.6-165.6, 63.7-62.9, 54.51, 53.12, 28.28, 26.91, 23.65, 20.21.

[0097] Example 5:

[0098] Synthesis of random copolymer of α-diazo-β-butyrolactone and α-diazo-γ-butyrolactone

[0099] Into a 5 mL reaction vial was added 44.8 mg (0.40 mmol) of α-diazo butyrolactone and 56.1 mg (0.40 mmol) of α-diazo hexyrolactone. The vial was sealed and purged with nitrogen three times. After the reaction was completely dissolved, the vial was placed in a -40 °C cold bath. After 20 s, 20 μL of 1 M potassium tert-butoxide in tetrahydrofuran was added. The reaction was allowed to proceed for 10 min. After that, 50 μL of 1 M acetyl chloride in tetrahydrofuran was added to quench the reaction. The reaction was precipitated with ether three times at -40 °C and dried under vacuum to give a random copolymer of α-diazo butyrolactone and α-diazo hexyrolactone as a yellow amorphous solid. The conversion of α-diazo butyrolactone was 49% and the yield was 39%. The conversion of α-diazo hexyrolactone was 61% and the yield was 46%. The ratio of α-diazo butyrolactone to α-diazo hexyrolactone in the polymer was 45.5:54.5. The number average molecular weight was 10.5 kg / mol and the molecular weight distribution coefficient was 1.31 by gel permeation chromatography. The number average molecular weight was 7.5 kg / mol by proton nuclear magnetic resonance spectroscopy. The structure of the product is shown below:

[0100]

[0101] The nuclear magnetic resonance data are as follows:

[0102] 1 H NMR (600 MHz, CDC13) δ 4.36 - 4.28 (m, 0.91H), 4.23 - 4.15 (m, 1.09H), 2.69 - 2.61 (m, 0.91H), 2.39 - 2.31 (m, 1.09H), 1.76 - 1.66 (m, 1.09H), 1.64 - 1.54 (m, 1.09H), 1.49 - 1.46 (m, 0.15H); 13 C NMR (150 MHz, CDC13) δ 167.9 - 165.9, 64.7 - 63.9, 63.5 - 62.9, 55.05, 53.16, 28.34, 28.31, 28.1 - 27.9, 24.09, 23.72, 22.81, 22.79.

[0103] Example 6:

[0104] Synthesis of a random copolymer of α-diazo pentyrolactone and α-diazo hexyrolactone

[0105] Into a 5 mL reaction vial was added 50.4 mg (0.40 mmol) of α-diazovalerolactone and 56.1 mg (0.40 mmol) of α-diazohexanolactone. The vial was sealed and purged with nitrogen three times. After the reaction was completely dissolved, the vial was placed in a -40 °C cold bath. After 20 s, 20 μL of 1 M potassium tert-butoxide in tetrahydrofuran was added. The reaction was allowed to proceed for 10 min. After this time, 50 μL of 1 M acetyl chloride in tetrahydrofuran was added and the reaction was quenched. The reaction was precipitated three times with diethyl ether at -40 °C and dried under vacuum to yield a random copolymer of α-diazovalerolactone and α-diazohexanolactone as a yellow amorphous solid. The conversion of α-diazovalerolactone was 89% and the yield was 84%. The conversion of α-diazohexanolactone was greater than 99% and the yield was 97%. The ratio of α-diazovalerolactone to α-diazohexanolactone structural units in the polymer was 46.5:53.5. The number average molecular weight was 14.1 kg / mol and the molecular weight distribution coefficient was 1.35 by gel permeation chromatography. The number average molecular weight was 11.9 kg / mol by proton nuclear magnetic resonance spectroscopy. The structure of the product is shown below:

[0106]

[0107] The nuclear magnetic resonance data are as follows:

[0108] 1 H NMR (600 MHz, CDC13) δ 4.23 (t, J = 6.1 Hz, 0.93H), 4.19 (t, J = 6.4 Hz, 1.07H), 2.40 (t, J = 7.3 Hz, 0.93H), 2.35 (t, J = 7.4 Hz, 1.07H), 1.94 - 1.84 (m, 0.93H), 1.75 - 1.67 (m, 1.07H), 1.62 - 1.54 (m, 1.07H), 1.49 - 1.46 (m, 0.10H); 13 C NMR (150 MHz, CDC13) δ 167.07, 64.16, 63.28, 55.00, 54.56, 28.27, 27.91, 26.91, 24.05, 22.75, 20.22.

[0109] Example 7:

[0110] Synthesis of poly(Z)-α,β-unsaturated valerolactone

[0111] A 25 mL reaction vial was charged with 7.89 mg (0.012 mmol) of rhodium trifluoroacetate dimer, the vial was sealed and purged with nitrogen three times, 2.4 mL of super dry dichloromethane was added, and the reaction was stirred at room temperature for 30 minutes. A 151.3 mg (1.2 mmol) of poly-α-diazopentolactone (number average molecular weight of 10.2 kg / mol, molecular weight distribution index of 1.11) was weighed into a sample vial, dissolved in 3.6 mL of super dry dichloromethane, and added dropwise to the reaction vial. The reaction was allowed to proceed for 1.5 h. After the reaction was complete, the reaction was filtered through a 0.22 μιη filter, concentrated on a rotary evaporator, and then dissolved in dichloromethane, precipitated three times with diethyl ether at room temperature, and dried under vacuum to yield poly(Z)-α,β-unsaturated pentolactone as a gray-green powdery solid in 95% yield. The product had a Z configuration C=C double bond content of 89%. The number average molecular weight was 7.9 kg / mol, and the molecular weight distribution index was 1.58 by gel permeation chromatography. The product structure is shown below:

[0112]

[0113] The NMR data are as follows:

[0114] 1 H NMR (400 MHz, CDC13) δ 6.94 (dt, J = 15.9, 6.9 Hz, 0.11H, trans), 6.27 (dt, J = 11.7, 7.0 Hz, 0.89H, cis), 5.96 - 5.80 (m, 1H), 4.22 (t, J = 6.4 Hz, 2H), 3.10 - 2.96 (m, 1.78H), 2.63 - 2.53 (m, 0.22H), 1.48 (s, 0.09H); 13 C NMR (101 MHz, CDC13) δ 165.87, 145.50, 121.56, 62.79, 28.47.

[0115] Example 8:

[0116] Synthesis of poly(Z)-α,β-unsaturated hexolactone

[0117] A 25 mL reaction vial was charged with 3.95 mg (0.006 mmol) of rhodium trifluoroacetate dimer, the reaction vial was sealed and purged with nitrogen three times, 1.2 mL of super dry dichloromethane was added and the sample was pre-stirred for 30 minutes at room temperature. 84.1 mg (0.60 mmol) of poly-a-diazo caprolactone (number average molecular weight of 11.3 kg / mol, polydispersity index of 1.75) was weighed into a sample vial, dissolved in 1.8 mL of super dry dichloromethane and added dropwise to the reaction vial, the reaction was allowed to proceed for 0.5 h. After the reaction was complete, the reaction mixture was filtered through a 0.22 pm filter, concentrated on a rotary evaporator, dissolved in dichloromethane and precipitated three times with methanol at room temperature and dried under vacuum to yield poly(Z)-a,b-unsaturated caprolactone as a green amorphous solid in 77% yield, the product contained 89% of the Z configured C=C double bond. The number average molecular weight was determined by gel permeation chromatography to be 18.8 kg / mol with a polydispersity index of 1.59. The structure of the product is shown below:

[0118]

[0119] The NMR data are as follows:

[0120] 1 H NMR (400 MHz, CDC13) δ 6.96 (dt, J = 15.4, 6.8 Hz, 0.11H, trans), 6.23 (dt, J = 11.5, 7.4 Hz, 0.89H, cis), 5.90 - 5.70 (m, 1H), 4.13 (t, J = 6.7 Hz, 2H), 2.80 - 2.68 (m, 1.78H), 2.35 - 2.25 (m, 0.22H), 1.87 - 1.77 (m, 2H), 1.48 (s, 0.10H); 13 C NMR (101 MHz, CDC13) δ 166.11, 148.90, 120.40, 63.34, 28.04, 25.57.

[0121] Example 9:

[0122] Synthesis of poly(a-p-bromobenzoyl) valerolactone

[0123] A 5 mL reaction vial was charged with 4.92 mg (0.01 mmol) of scandium triflate, 4.21 mg (0.006 mmol) of chiral ligand (CAS number: 1005495-74-8), 5 mg of The reaction tube was sealed and purged with nitrogen three times, 0.2 mL of super dry dichloromethane was added, and the sample was stirred at 30 °C for 30 min. Then, 25.2 mg (0.20 mmol) of poly-a-diazopivalolactone (number average molecular weight of 10.2 kg / mol, molecular weight distribution coefficient of 1.11) was weighed in a sample bottle and dissolved in 0.8 mL of super dry dichloromethane, and then added dropwise into the reaction bottle. The reaction was carried out for 3.5 h. After the reaction was completed, the reaction solution was filtered with a 0.22 μm filter membrane, concentrated with a rotary evaporator, and then dissolved in dichloromethane, precipitated with methanol twice at room temperature, and precipitated with diethyl ether once, and then dried in vacuum to obtain poly(a-p-bromobenzoyl)valerolactone in the form of a white solid with a yield of 85%. The ratio of hydrogen migration and aryl migration of p-bromobenzaldehyde was 82.7:17.3. The number average molecular weight was 15.4 kg / mol and the molecular weight distribution coefficient was 1.26 as measured by gel permeation chromatography. The structure of the product is shown in the following formula:

[0124]

[0125] The nuclear magnetic resonance data are as follows:

[0126] 1 H NMR (400 MHz, CD2Cl2) δ 9.82-9.72 (m, 0.21H), 7.85-7.74 (m, 2H), 7.68-7.56 (m, 2H), 7.53-7.46 (m, 0.42H), 7.02-6.93 (m, 0.42H), 4.27-3.99 (m, 3.42H), 2.11-1.79 (m, 2.42H), 1.73-1.48 (m, 2.42H).

[0127] Example 10:

[0128] Synthesis of poly(a-p-bromobenzoyl)caprolactone

[0129] Into a 5 mL reaction tube, 4.92 mg (0.01 mmol) of scandium triflate, 4.21 mg (0.006 mmol) of chiral ligand (CAS No.: 1005495-74-8), 5 mg of Molecular sieves and 38.85 mg (0.21 mmol) of p-bromobenzaldehyde, the reaction tube was sealed and nitrogen was exchanged three times, 0.2 mL of super dry dichloromethane was added, and the reaction tube was pre-stirred at 30 °C for 30 min, and then the reaction tube was placed at room temperature. 28.0 mg (0.20 mmol) of poly-α-diazovalerolactone (number average molecular weight of 11.3 kg / mol, molecular weight distribution coefficient of 1.75) was weighed in a sample tube, dissolved with 0.8 mL of super dry dichloromethane, and added dropwise into the reaction tube, and the reaction was carried out for 4 h. After the reaction was completed, it was filtered with a 0.22 μm filter membrane, concentrated with a rotary evaporator, then dissolved with dichloromethane, precipitated with methanol twice at room temperature, and precipitated with diethyl ether once, and vacuum dried to obtain poly(α-p-bromobenzoyl)valerolactone in the form of a white solid with a yield of 93%. The ratio of hydrogen migration and aryl migration of p-bromobenzaldehyde was 81.3:18.7. The number average molecular weight was 12.4 kg / mol and the molecular weight distribution coefficient was 1.69 as measured by gel permeation chromatography. The structure of the product is shown in the following formula:

[0130]

[0131] The nuclear magnetic resonance data are as follows:

[0132] 1 H NMR (400 MHz, CD2Cl2) δ 7.86-7.76 (m, 2H), 7.68-7.56 (m, 2H), 7.46-7.38 (m, 0.46H), 7.18-7.08 (m, 0.46H), 4.20-3.95 (m, 3.46H), 2.05-1.77 (m, 2.46H), 1.61-1.49 (m, 2.46H), 1.30-1.10 (m, 2.46H).

[0133] Example 11:

[0134] Synthesis of poly(α-triethylsilyl)valerolactone

[0135] Into a 10 mL reaction vial, 4.42 mg (0.01 mmol) of rhodium acetate dimer was added, the vial was sealed and purged with nitrogen three times, 0.8 mL of super dry dichloromethane and 465 mg (4.0 mmol) of triethylsilane were added, the sample was stirred at -78 °C for 30 min. In a sample vial, 25.2 mg (0.20 mmol) of poly-α-diazovalerolactone (number average molecular weight of 10.2 kg / mol, molecular weight distribution index of 1.11) was weighed and dissolved in 1.6 mL of super dry dichloromethane, the solution was added to the reaction vial slowly using a peristaltic pump at -78 °C for 4 h, the reaction was continued for another 20 h. After the reaction was completed, the reaction mixture was filtered using a 0.22 μιη filter, concentrated using a rotary evaporator, dissolved in dichloromethane, precipitated in ether at room temperature once, the precipitate was removed, the filtrate was concentrated using a rotary evaporator, dissolved in dichloromethane, purified using a preparative recycle liquid chromatograph, dried in vacuum, poly(α-triethylsilyl)valerolactone was obtained as a green amorphous solid with a yield of 99%, the ratio of diazo conversion to triethylsilyl group was 48%, the rest of the diazo groups dimerized. The number average molecular weight was 17.5 kg / mol, the molecular weight distribution index was 2.17, determined by gel permeation chromatography. The structure of the product is shown in the following formula:

[0136]

[0137] The NMR data are as follows:

[0138] 1 H NMR (400 MHz, CDC13) δ 4.33 - 3.91 (m, 2H), 2.23 - 1.30 (m, 5H), 0.96 (t, J = 7.8 Hz, 4.34H), 0.69 - 0.53 (m, 2.89H).

[0139] Example 12:

[0140] Synthesis of poly(α-triethylsilyl)caprolactone

[0141] Into a 10 mL reaction vial, 4.42 mg (0.01 mmol) of rhodium acetate dimer was added, the vial was sealed and purged with nitrogen three times, 0.8 mL of super dry dichloromethane and 465 mg (4.0 mmol) of triethylsilane were added, the sample was stirred at -78 °C for 30 min. 28.0 mg (0.20 mmol) of poly-α-diazo caprolactone (number average molecular weight of 11.3 kg / mol, polydispersity index of 1.75) was weighed in a sample vial, dissolved in 1.6 mL of super dry dichloromethane, and added dropwise into the reaction vial using a peristaltic pump at -78 °C for 4 h, and the reaction was continued for another 20 h. After the reaction was completed, the sample was filtered using a 0.22 μιη filter, concentrated using a rotary evaporator, dissolved in dichloromethane, precipitated in ether at room temperature once, the precipitate was removed, the filtrate was concentrated using a rotary evaporator, dissolved in dichloromethane, and purified using a preparative recycle liquid chromatograph, dried in vacuum, to give poly(α-triethylsilyl) caprolactone as a green amorphous solid with a yield of 98%, the conversion of diazo group to triethylsilyl group was 39%, and the rest of the sample was dimerized. The number average molecular weight was 23.2 kg / mol, and the polydispersity index was 2.90, as measured by gel permeation chromatography. The structure of the product is shown in the following formula:

[0142]

[0143] The NMR data are as follows:

[0144] 1 H NMR (400 MHz, CDC13) δ 4.25 - 3.95 (m, 2H), 2.11 - 1.15 (m, 7H), 0.95 (t, J = 7.9 Hz, 3.52H), 0.69 - 0.53 (m, 2.35H).

[0145] Example 13:

[0146] Synthesis of poly α, β-unsaturated butyrolactone

[0147] A 10 mL reaction tube was charged with 34.8 mg (0.31 mmol) of poly-α-diazo butyrolactone (number average molecular weight of 6.5 kg / mol, molecular weight distribution index of 1.39), the reaction tube was sealed and purged with nitrogen three times, 1.5 mL of super dry dichloromethane was added, and the reaction was irradiated with blue light (power of 18 w, wavelength of 465 nm) at room temperature for 28 h. After the reaction was completed, the product was concentrated with a rotary evaporator, then dissolved in dichloromethane, precipitated with ether three times at room temperature, and dried in vacuum to obtain poly-α,β-unsaturated butyrolactone in the form of a white amorphous solid with a yield of 99%, wherein the proportion of Z-form C=C double bonds in the product was 28%, the proportion of E-form C=C double bonds was 24%, and the proportion of diazo dimerization was 48%. The number average molecular weight was 8.2 kg / mol, and the molecular weight distribution index was 1.59, as determined by gel permeation chromatography. The structure of the product is shown in the following formula:

[0148]

[0149] The nuclear magnetic resonance data thereof are as follows:

[0150] 1 H NMR (400 MHz, CDCl3) δ 7.09-6.85 (m, 0.46H), 6.42-6.18 (m, 0.54H), 6.14-5.84 (m, 1H), 5.41-5.09 (m, 1.08H), 4.90-4.76 (m, 0.92H), 4.55-3.93 (m, 1.84H), 2.19-2.03 (m, 0.92H), 1.63-1.53 (m, 0.92H).

[0151] Example 14:

[0152] Closed-loop recycling degradation of poly-α-diazo valerolactone

[0153] A 50 mL reaction tube was charged with 201.8 mg (1.60 mmol) of poly-α-diazo valerolactone (number average molecular weight of 9.3 kg / mol, molecular weight distribution index of 1.11), the reaction tube was sealed and purged with nitrogen three times, 2.4 mL of super dry tetrahydrofuran was added, and 6.5 μL (0.16 mmol) of methanol was added. In a glove box, 44.5 mg (0.32 mmol) of 1,5,7-triazabicyclo[4.4.0]dec-5-ene was weighed in a sample bottle, the sample bottle was removed from the glove box, dissolved in 1.6 mL of super dry tetrahydrofuran, and added dropwise to the reaction bottle, and the reaction bottle was moved to a 50°C oil bath for reaction for 12 h. After the reaction was completed, the product was adsorbed on a silica gel column with a Buchner funnel, the filtrate was concentrated with a rotary evaporator, then dissolved in dichloromethane, and the product was separated and purified by preparative column chromatography or thin layer chromatography, and dried to obtain monomeric α-diazo valerolactone in the form of a yellow solid with a yield of 73%. The structure of the product is shown in the following formula:

[0154]

[0155] Its nuclear magnetic data are as follows:

[0156] 1 H NMR (400 MHz, CDCI3) δ 4.31 - 4.23 (m, 2H), 2.80 (t, J = 6.5 Hz, 2H), 2.03 - 1.91 (m, 2H); 13 C NMR (101 MHz, CDCI3) δ 166.44, 68.16, 21.64, 20.12.

[0157] Although the present application has been disclosed with examples as above, it is not intended to limit the present application, and any proper modification or equivalent replacement made by those skilled in the art to the technical solutions of the present application shall be covered within the protection scope of the present application, and the protection scope of the present application is defined by the claims.

Claims

1. A polyester whose main chain contains diazo groups, characterized in that, Specifically, it is one of the three lactones: poly-α-diazobutyrolactone, poly-α-diazopentyl lactone, and poly-α-diazocaprolactone, or a random copolymer composed of any two of the aforementioned three lactones, with the following molecular structure: Wherein, t-BuO represents tert-butoxy, and m and n are positive integers; x = 1, 2 or 3 in formula (I) represents poly-α-diazobutyrolactone, poly-α-diazopentyl lactone or poly-α-diazocaprolactone; formulas (II), (III) and (IV) are random copolymers.

2. A method for preparing a polyester with a main chain containing diazo groups as described in claim 1, characterized in that the step... include: One or two of the five-, six-, and seven-membered ring α-diazo lactone monomers are selected as reactants, and potassium tert-butoxide is used as a catalyst. Under the protection of N2 atmosphere, homopolymerization or random copolymerization reaction is carried out in an organic solvent to obtain polyester products with diazonium groups in the main chain. Specifically, it is one of the three lactones, namely poly-α-diazobutyrolactone, poly-α-diazopentyl lactone, and poly-α-diazocaprolactone, or a random copolymer composed of any two of the aforementioned three lactones. The homopolymerization reaction formula is as follows: The random copolymerization reaction formula is as follows: Wherein, t-BuOK represents potassium tert-butoxide, and solvent represents an organic solvent; the product of formula (I) is poly(α-diazobutyrolactone), poly(α-diazopentylactone), or poly(α-diazocaprolactone); the products of formulas (II), (III), and (IV) are random copolymers.

3. A post-conversion method for a polyester containing diazo groups in its main chain as described in claim 1, characterized in that the step... include: Poly(α-diazocaprolactone) or poly(α-diazocaprolactone) was used as reactants, and rhodium(II) trifluoroacetate dimer was used as a catalyst. Under a nitrogen atmosphere, a post-conversion reaction was carried out in an organic solvent to obtain a polyester product with α,β-unsaturated double bonds in the main chain, primarily in the Z-configuration. Specifically, it was poly(Z)-α,β-unsaturated valerolactone or poly(Z)-α,β-unsaturated caprolactone. The reaction formula is as follows: Wherein, [Rh] represents rhodium(II) trifluoroacetate dimer, solvent represents organic solvent, the product of formula (I) is poly(Z)-α,β-unsaturated valerate, and the product of formula (II) is poly(Z)-α,β-unsaturated caprolactone.

4. A post-conversion method for a polyester containing diazo groups in its main chain as described in claim 1, characterized in that the step... include: Using poly(α-diazopentanolide) or poly(α-diazocaprolactone) and p-bromobenzaldehyde as reactants, scandium trifluoromethanesulfonate and chiral ligands as catalysts, and setting... Molecular sieves, under N2 atmosphere protection, undergo a post-conversion reaction in an organic solvent to yield polyester products with β-carbonyl side chains, specifically poly(α-p-bromobenzoyl)valproate or poly(α-p-bromobenzoyl)caprolactone; the reaction formula is as follows: Wherein, Formula I represents poly-α-diazocaprolactone or poly-α-diazocaprolactone; [Sc] represents scandium trifluoromethanesulfonate, and L represents a chiral ligand. express Molecular sieve; solvent indicates an organic solvent.

5. A polyester with a side chain containing a β-carbonyl structure, characterized in that, Specifically, it is poly(α-p-bromobenzoyl)valproate or poly(α-p-bromobenzoyl)caprolactone, prepared by the post-conversion method described in claim 4, with the following molecular structural formula: Where x = 1 or 2.

6. A post-conversion method for a polyester containing diazo groups in its main chain as described in claim 1, characterized in that the step... include: Using poly(α-diazocaprolactone) or poly(α-diazocaprolactone) and triethylsilane as reactants, and rhodium acetate dimer as catalyst, a post-conversion reaction is carried out in an organic solvent under N2 atmosphere to obtain a polyester product with a silicon-based side chain, specifically poly(α-triethylsilyl)caprolactone or poly(α-triethylsilyl)caprolactone; the reaction formula is as follows: Wherein, [Rh] represents rhodium acetate dimer, Et3SiH represents triethylsilane, solvent represents organic solvent, the product of formula (I) is (α-triethylsilyl)valproic acid lactone, and the product of formula (II) is poly(α-triethylsilyl)caprolactone.

7. A polyester with a silicon-based side chain, characterized in that, Specifically, it is poly(α-triethylsilyl)valproic acid or poly(α-triethylsilyl)caprolactone, prepared by the post-conversion method described in claim 6, with the following molecular structural formula: Wherein, formula (I) is (α-triethylsilyl)valerate, and formula (II) is poly(α-triethylsilyl)caprolactone.

8. A post-conversion method for a polyester containing diazo groups in its main chain as described in claim 1, characterized in that the step... include: Using polyα-diazobutyrolactone as a reactant, a post-conversion reaction was carried out in an organic solvent under N2 atmosphere and blue light irradiation to obtain polyα,β-unsaturated butyrolactone product; the reaction formula is as follows: Where m, n, and p are positive integers, the wavelength of blue light is 460–465 nm, and solvent represents an organic solvent.

9. A poly(α,β-unsaturated butyrolactone) prepared by the post-conversion method according to claim 8, having the following molecular structural formula: in, m, n, p are positive integers.

10. A method for degrading a polyester containing diazo groups in its main chain as described in claim 1, characterized in that the step... include: Poly-α-diazolactone was degraded in an organic solvent under N2 atmosphere using an organic base 1,5,7-triazabicyclo[4.4.0]dec-5-ene and ultra-dry methanol as catalysts to obtain a six-membered ring α-diazolactone monomer product; the reaction formula is as follows: Wherein, TBD represents the organic base 1,5,7-triazabicyclo[4.4.0]dec-5-ene, MeOH represents ultra-dry methanol, and solvent represents an organic solvent.

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