CN113861395B - Polyester with acetal group in main chain and preparation method thereof - Google Patents
Polyester with acetal group in main chain and preparation method thereof Download PDFInfo
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- CN113861395B CN113861395B CN202111260634.7A CN202111260634A CN113861395B CN 113861395 B CN113861395 B CN 113861395B CN 202111260634 A CN202111260634 A CN 202111260634A CN 113861395 B CN113861395 B CN 113861395B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/56—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds other than from esters thereof
- C08G63/58—Cyclic ethers; Cyclic carbonates; Cyclic sulfites ; Cyclic orthoesters
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- C—CHEMISTRY; METALLURGY
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
- C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
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Abstract
The invention discloses a polyester with acetal group in the main chain, which is prepared by taking cyclic acetal and cyclic anhydride as raw materials and Lewis acid or protonic acid as a catalyst through alternate copolymerization; the polyester is an alternating copolymer structure and has acetal groups in each repeating unit. The invention discloses a polyester with an acetal group in a main chain, which is an alternating copolyester with a definite chain structure and containing the acetal group, and the content of alternating copolyester chain links is higher; and the polyester has excellent degradation performance due to the introduction of a special acetal group in the main chain. The preparation method has the advantages of low raw material cost, simple process, no need of complex post-treatment purification process and contribution to realizing industrialization.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to polyester with acetal groups in main chains and a preparation method thereof.
Background
Polyesters are a common class of polymeric materials, generally classified into aromatic and aliphatic polyesters. Aromatic polyesters, such as polyethylene terephthalate (PET), are widely used in the manufacture of fibers, blow molded bottles and other packaging materials in large quantities due to their good mechanical strength and barrier properties. The aliphatic polyester has the characteristics of good biocompatibility and relative easy hydrolysis, can be degraded into small molecules in the environment, is an environment-friendly high polymer material, is used as a synthetic raw material of various renewable chemicals and a potential substitute of petroleum-based polymers, and has attracted extensive attention in recent years.
The most common method for the industrial synthesis of polyesters is by polycondensation of a dibasic acid or ester with a glycol. However, this method requires removal of small molecular by-products such as water or alcohol, generally requires high temperature and high vacuum reaction conditions, and is energy-intensive in the reaction process and difficult in increasing the molecular weight. Unlike the step-growth polymerization model described above, chain polymerization does not produce small molecule by-products, and polymers of high molecular weight and controlled distribution can be obtained even at low monomer conversion. For example, ring-opening polymerization of cyclic lactones, including five-, six-, seven-, twelve-, and eighteen-membered ring lactones, and ring-opening polymerization of lactides, which have been commercially produced, have been widely studied. In addition to the above processes, catalytic epoxidationThe alternating copolymerization of the compound and cyclic anhydride anion is a method for synthesizing aliphatic polyester by a chain polymerization mode which is currently researched more. By means of alternate copolymerization of two kinds of monomer, over 400 kinds of polyester may be obtained, and the copolymer may be modified to obtain multifunctional aliphatic polyester. However, until the present invention, it has been reported that a polyester having an acetal group in its main chain is synthesized. It has been reported that (Ge-Xia Wang, dan Huang, jun-Hui Ji,
and Frederik R.Wurm.SeaWater-Degradable Polymers-lighting the Marine Plastic polarization.adv.Sci.2021, 8, 2001121), and the development of this class of polyesters is very significant for Marine environmental protection because the acetal group is easily hydrolyzed and thus has a faster hydrolysis response and can be degraded in seawater. Meanwhile, polyester is a very important polymer material due to excellent biodegradability and compatibility. Therefore, the development of acetal group-containing polyesters having a main chain which can be mass-produced is of great significance.
There are documents (Angelika E.Neitzel, thomas J.Haversang, and Marc A.Hillmyer.organic Cationic Ring-Opening Polymerization of a Cyclic molar equivalent ester. Ind.Eng.chem.Res.2016,55,45, 11747) that polyesters containing acetal groups in the main chain are obtained by anionic Ring-Opening Polymerization of 2-methyl-1, 3-dioxan-4-one; the literature (Ryan T.Martin, ludmila P.Camigo and Stephen A.Miller. Marine-degradable polylactic acid. Green chem.,2014,16, 1768) reports the preparation of random, backbone acetal group-containing polyesters by anionic copolymerization of lactide and 1, 3-dioxolan-4-one. In these systems, the raw materials of the monomers are uncommon and expensive, and are difficult to obtain in large quantities, and the applicable range of the monomers is small and difficult to expand.
Disclosure of Invention
In order to solve the problems, the invention discloses a polyester with an acetal group in the main chain, which is an alternating copolyester with a definite chain structure and containing the acetal group, and has higher content of alternating copolyester chain links; and the polyester has excellent degradation performance due to the introduction of a special acetal group in the main chain. The preparation method has the advantages of low raw material cost, simple process, no need of complex post-treatment purification process and contribution to realizing industrialization.
The specific technical scheme is as follows:
a polyester having an acetal group in the main chain:
taking cyclic acetal and cyclic anhydride as raw materials, taking Lewis acid or protonic acid as a catalyst, and preparing the cyclic acetal and the cyclic anhydride after alternating copolymerization;
the polyester is an alternating copolymer structure and has acetal groups in each repeating unit.
After a large number of experimental researches, the invention firstly proposes that cyclic acetal and cyclic anhydride are taken as monomers, lewis acid or protonic acid is taken as a catalyst, and the polyester with the acetal group in the main chain is prepared by a cation alternating copolymerization route, and the polyester has a definite chain structure and an alternating structure.
Preferably:
the cyclic acetal is selected from one or more of five-membered cyclic acetal, six-membered cyclic acetal, seven-membered cyclic acetal and eight-membered cyclic acetal;
the five-membered cyclic acetal is selected from one or more of 1, 3-dioxolane, 2-dimethyl-1, 3-dioxolane, 2-chloromethyl-1, 3-dioxolane, 2-propyl-4-methyl-1, 3-dioxane, 2- (trifluoromethyl) dioxolane, 4-methyl-2-pentyl-1, 3-dioxolane, 2-bromomethyl-1, 3-dioxolane, 2- (2-bromoethyl) -1, 3-dioxane;
the six-membered cyclic acetal is selected from one or more of 1, 3-dioxane, 4-methyl-1, 3-dioxane, glycerol formal, 2- (2-bromoethyl) -1, 3-dioxane, 4-phenyl-1, 3-dioxane;
the seven-membered cyclic acetal is selected from one or more of 1, 3-dioxyheptanes, 2-methylene-1, 3-dioxanes, cis-4, 7-dihydro-1, 3-dioxeps;
the eight-membered cyclic acetal is selected from 1, 3-dioxyoctacyclo and/or 1,3, 6-trioxocane.
The cyclic anhydride is selected from five-membered cyclic anhydride and/or six-membered cyclic anhydride;
the five-membered cyclic anhydride is selected from one or more of maleic anhydride, succinic anhydride, 2, 3-dimethylmaleic anhydride, 2, 3-dichloromaleic anhydride, 2, 3-dibromomaleic anhydride, 2, 3-difluoromaleic anhydride, methylsuccinic anhydride, phthalic anhydride and 3,4,5, 6-tetrahydrophthalic anhydride;
the six-membered cyclic anhydride is selected from one or more of glutaric anhydride, 3-methylglutaric anhydride, 3-dimethylglutaric anhydride, 2-dimethylglutaric anhydride, 3-isobutylglutaric anhydride, hexafluoroglutaric anhydride, 3-tetramethylene glutaric anhydride and 1, 1-cyclohexyl diacetic anhydride.
The above preferred cyclic acetals and cyclic anhydrides are commercially available products, are inexpensive, and are readily available.
Preferably:
the Lewis acid is selected from BF 3 、B(C 6 F 5 ) 3 、SnCl 4 、AlCl 3 、InCl 3 、SbCl 5 、PF 5 、CF 3 SO 3 Et、Ph 3 CPF 6 One or more of;
the protonic acid is selected from HBF 4 、HClO 4 、CF 3 COOH、CF 3 SO 4 H、FSO 4 H. One or more of concentrated sulfuric acid.
In the present invention, the catalyst functions to provide protons to the cyclic acetal to form a cationic center, which in turn initiates the polymerization reaction. Wherein, lewis acid releases protons after reacting with a small amount of proton compounds in the system; and the action of the protonic acid is to release the proton directly. The preferred Lewis acid or protonic acid is a cheaper catalyst, is easily available and can greatly reduce the production cost.
Preferably:
the molar ratio of the cyclic acetal to the cyclic anhydride is 1:0.1 to 10; more preferably 1:0.5 to 10. Within the preferred ranges above, it is possible to ensure simultaneously that the initial concentrations of the two monomers are high, thus ensuring that the polymerization reaction proceeds at a relatively fast rate and is completed in a suitable time; too fast or too slow polymerization is not conducive to control of the copolymerization.
Preferably, the following components:
the molar ratio of the catalyst to the cyclic anhydride is 1:5 to 1000, preferably in the range of catalyst concentration, so that the reaction takes place smoothly and the polymerization reaction can be completed in a suitable time.
Further preferably:
the cyclic acetal is selected from at least one of 1, 3-dioxolane, 1, 3-dioxane, 1, 3-dioxoheptacyclo and 1, 3-dioxooctacyclo;
the cyclic anhydride is selected from at least one of maleic anhydride, glutaric anhydride and succinic anhydride;
the molar ratio of the cyclic acetal to the cyclic anhydride is 1:0.5 to 1.5;
the molar ratio of the catalyst to the cyclic anhydride is 1:50 to 200.
Tests show that the polyester prepared by adopting the preferable monomer types and the mixture ratio of the raw materials has higher molecular weight, and particularly, the content of the chain links of the alternating copolyester in the polyester is higher and is not lower than 90 percent.
Further preferably:
the cyclic acetal is selected from 1, 3-dioxolane and/or 1, 3-dioxane;
the cyclic anhydride is selected from glutaric anhydride.
With further preference for the monomer species, the polyesters produced are of a fully alternating mer structure.
The invention also discloses a preparation method of the polyester with the main chain containing acetal groups, which comprises the steps of adding cyclic acetal, cyclic anhydride, a catalyst and a selectively added solvent into a reaction kettle, and placing the reaction kettle at the temperature of between 0 and 120 ℃ for 0.1 to 12 hours under autogenous pressure.
The above polymerization reaction may be carried out in bulk without a solvent or in solution with a solvent.
If solution polymerization is used, the selectively added solvent is selected from one or more of dichloromethane, chloroform, toluene, trichlorobenzene, o-dichlorobenzene, m-dichlorobenzene and p-dichlorobenzene. Preferred is dichloromethane and/or toluene, and further preferred is toluene in view of industrial use.
After polymerization, the product needs to be subjected to simple post-treatment, specifically:
the crude product was first dissolved in dichloromethane and the polymer precipitated from a methanol/hydrochloric acid mixture, washed repeatedly and dried under vacuum to constant weight.
The polyester with the acetal group in the main chain prepared by the process has the following structural formulas (I-1) to (I-10):
compared with the prior art, the invention has the following beneficial effects:
(1) The invention realizes the cationic copolymerization of the cyclic acetal and the cyclic anhydride monomers for the first time on the basis of mechanism recognition and a large amount of experimental researches, and the polymerization reaction has higher practical value because the two monomer raw materials are easy to prepare, cheap and easy to obtain;
(2) The catalyst system adopted in the invention is commercially cheap and easily available, and the two raw material monomers are combined under the catalytic action of the catalyst to prepare the colorless and transparent polyester with acetal group in the main chain, and complex post-treatment purification steps are not needed;
(3) The polyester with the acetal group-containing main chain prepared by the invention has an ester chain link structure of alternating copolymerization, regular structure and high ester chain link content, and has wide application prospect in the fields of food packaging, biology and electronics; meanwhile, the peculiar acetal group is introduced into the main chain, so that the peculiar degradation performance of the copolymer is maintained.
Drawings
FIG. 1 is a schematic diagram of a synthetic route for preparing a polyester having an acetal group in the main chain according to the present invention;
FIG. 2 is a photograph of a copolymerization product prepared in example 11 1 H NMR spectrum;
FIG. 3 is a photograph of a photograph taken in example 11Of the copolymerization product 13 C NMR spectrum;
FIG. 4 is a photograph of a copolymerization product prepared in example 13 1 H NMR spectrum;
FIG. 5 is a photograph of a copolymerization product prepared in example 13 13 C NMR spectrum.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, but the scope of the present invention is not limited to the following examples.
Example 11,3-Dioxolane/maleic anhydride alternating copolymerization of a polyester containing acetal groups in the main chain
Before the polymerization reaction, 10mL schlecher tube is firstly used for removing water at 110 ℃ for about 2 hours and is cooled to room temperature in a drier; sequentially adding a plurality of masses of BF into a reaction kettle 3 1, 3-dioxolane, maleic anhydride and 1mL toluene. BF (BF) generator 3 The molar ratio of 1, 3-dioxolane/maleic anhydride was 1/400/200. The reaction was carried out at 0 ℃ under autogenous pressure for 4h. After the reaction, the crude product was first dissolved in dichloromethane, and the polymer was precipitated in 100mL of a methanol/hydrochloric acid mixture (5% by mole hydrochloric acid), washed three times again and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
The polyester having an acetal group in its main chain prepared in this example has the following structural formula:
example 24-methyl-2-pentyl-1, 3-dioxolane/maleic anhydride alternating copolymerization to give polyesters containing acetal groups in the main chain
Before the polymerization reaction, 10mL schleck tube is firstly removed of water at 110 ℃ for about 2 hours and is cooled to room temperature in a drier; sequentially adding a plurality of masses of BF into a reaction kettle 3 4-methyl-2-pentyl-1, 3-dioxolane, maleic anhydride and 1mL of toluene. BF 3 The molar ratio of 4-methyl-2-pentyl-1, 3-dioxolane/maleic anhydride is 1/400/200. Reacting at 0 deg.C under autogenous pressureAnd the time is 4 hours. After the reaction, the crude product was first dissolved in dichloromethane and the polymer precipitated in 100mL of a methanol/hydrochloric acid mixture (5% molar hydrochloric acid), washed three times and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
The polyester having an acetal group in its main chain prepared in this example has the following structural formula:
example 32,2-dimethyl-1, 3-dioxolane/maleic anhydride alternately copolymerized into a polyester having an acetal group in the main chain
Before the polymerization reaction, 10mL schleck tube is firstly removed of water at 110 ℃ for about 2 hours and is cooled to room temperature in a drier; sequentially adding a plurality of masses of BF into the reaction kettle 3 2, 2-dimethyl-1, 3-dioxolane, maleic anhydride and 1mL of toluene. BF (BF) generator 3 The molar ratio of 2, 2-dimethyl-1, 3-dioxolane/maleic anhydride was 1/400/200. The reaction was carried out at 0 ℃ under autogenous pressure for 4h. After the reaction, the crude product was first dissolved in dichloromethane, and the polymer was precipitated in 100mL of a methanol/hydrochloric acid mixture (5% by mole hydrochloric acid), washed three times again and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
The polyester having an acetal group in the main chain prepared in this example has the following structural formula:
example 41,3-Dioxolane/2,3-dimethylmaleic anhydride alternating copolymerization to Main chain acetal group-containing polyester
Before the polymerization reaction, 10mL schleck tube is firstly removed of water at 110 ℃ for about 2 hours and is cooled to room temperature in a drier; sequentially adding a plurality of masses of BF into the reaction kettle 3 1, 3-dioxolane, 2,3-Dimethylmaleic anhydride and 1mL of toluene. BF 3 The molar ratio of 1, 3-dioxolane/2, 3-dimethylmaleic anhydride is 1/400/200. The mixture is placed at 0 ℃ and reacted for 4 hours under autogenous pressure. After the reaction, the crude product was first dissolved in dichloromethane and the polymer precipitated in 100mL of a methanol/hydrochloric acid mixture (5% molar hydrochloric acid), washed three times and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
The polyester having an acetal group in its main chain prepared in this example has the following structural formula:
example 51, 3-Dioxolane/2, 3-Difluorometaleic anhydride alternating copolymerization to Synthesis of a polyester containing acetal groups in the Main chain
Before the polymerization reaction, 10mL schlecher tube is firstly used for removing water at 110 ℃ for about 2 hours and is cooled to room temperature in a drier; sequentially adding a plurality of masses of BF into a reaction kettle 3 1, 3-dioxolane, 2, 3-difluoromaleic anhydride and 1mL of toluene. BF 3 The molar ratio of 1, 3-dioxolane/2, 3-difluoromaleic anhydride is 1/400/200. The mixture is placed at 0 ℃ and reacted for 4 hours under autogenous pressure. After the reaction, the crude product was first dissolved in dichloromethane and the polymer precipitated in 100mL of a methanol/hydrochloric acid mixture (5% molar hydrochloric acid), washed three times and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
The polyester having an acetal group in the main chain prepared in this example has the following structural formula:
example 61,3-Dioxolane/maleic anhydride alternating copolymerization to Synthesis of polyester having acetal group in the Main chain
Before the polymerization, 10mL Schlenk tube was dehydrated at 110 ℃ for about 2 hoursAnd cooling to room temperature in a desiccator; sequentially adding a plurality of masses of BF into a reaction kettle 3 1, 3-dioxolane, maleic anhydride and 1mL toluene. BF 3 The molar ratio of 1, 3-dioxolane/maleic anhydride is 1/20/200. The mixture is placed at 0 ℃ and reacted for 12 hours under autogenous pressure. After the reaction, the crude product was first dissolved in dichloromethane and the polymer precipitated in 100mL of a methanol/hydrochloric acid mixture (5% molar hydrochloric acid), washed three times and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
Example 71,3-Dioxolane/maleic anhydride alternating copolymerization to Synthesis of polyester having an acetal group in the Main chain
Before the polymerization reaction, 10mL schlecher tube is firstly used for removing water at 110 ℃ for about 2 hours and is cooled to room temperature in a drier; sequentially adding a plurality of masses of BF into the reaction kettle 3 1, 3-dioxolane, maleic anhydride and 1mL of toluene. BF (BF) generator 3 The molar ratio of 1, 3-dioxolane/maleic anhydride was 1/2000/200. The mixture is placed at 0 ℃ and reacted for 12h under autogenous pressure. After the reaction, the crude product was first dissolved in dichloromethane, and the polymer was precipitated in 100mL of a methanol/hydrochloric acid mixture (5% by mole hydrochloric acid), washed three times again and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
Example 81,3-Dioxolane/maleic anhydride alternating copolymerization to Synthesis of polyester having an acetal group in the Main chain
Before the polymerization reaction, 10mL schlecher tube is firstly used for removing water at 110 ℃ for about 2 hours and is cooled to room temperature in a drier; sequentially adding a plurality of masses of BF into a reaction kettle 3 1, 3-dioxolane, maleic anhydride and 1mL of toluene. BF (BF) generator 3 The molar ratio of 1, 3-dioxolane/maleic anhydride was 1/10/5. The mixture is placed at 0 ℃ and reacted for 4 hours under autogenous pressure. After the reaction, the crude product was first dissolved in dichloromethane, and the polymer was precipitated in 100mL of a methanol/hydrochloric acid mixture (5% by mole hydrochloric acid), washed three times again and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
Example 91,3-Dioxolane/maleic anhydride alternating copolymerization to Synthesis of polyester containing acetal groups in the Main chain
Before the polymerization reaction, 10mL schlecher tube is firstly used for removing water at 110 ℃ for about 2 hours and is cooled to room temperature in a drier; sequentially adding a plurality of masses of BF into a reaction kettle 3 1, 3-dioxolane, maleic anhydride and 1mL toluene. BF (BF) generator 3 The molar ratio of 1, 3-dioxolane/maleic anhydride was 1/2000/1000. The mixture is placed at 0 ℃ and reacted for 12h under autogenous pressure. After the reaction, the crude product was first dissolved in dichloromethane and the polymer precipitated in 100mL of a methanol/hydrochloric acid mixture (5% molar hydrochloric acid), washed three times and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
Example 101,3-Dioxolane/maleic anhydride alternating copolymerization to Synthesis of polyester having acetal group in the Main chain
Before the polymerization reaction, 10mL schlecher tube is firstly used for removing water at 110 ℃ for about 2 hours and is cooled to room temperature in a drier; sequentially adding a plurality of masses of BF into the reaction kettle 3 1, 3-dioxolane, maleic anhydride and 1mL toluene. BF 3 The molar ratio/1, 3-dioxolane/maleic anhydride is 3/100/150. The mixture is placed at 120 ℃ and reacted for 0.1h under autogenous pressure. After the reaction, the crude product was first dissolved in dichloromethane and the polymer precipitated in 100mL of a methanol/hydrochloric acid mixture (5% molar hydrochloric acid), washed three times and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
Example 111, 3-Dioxolane/glutaric anhydride alternating copolymerization to Main chain Acetal group-containing polyester
Before the polymerization reaction, 10mL schlecher tube is firstly used for removing water at 110 ℃ for about 2 hours and is cooled to room temperature in a drier; sequentially adding PF with a plurality of masses into a reaction kettle 5 1, 3-dioxolane, glutaric anhydride and 1mL of toluene. PF (particle Filter) 5 The molar ratio of 1, 3-dioxolane/glutaric anhydride was 1/100/100. The reaction was carried out at 25 ℃ under autogenous pressure for 1h. After the reaction, the crude product is dissolved in dichloromethane and then 1The polymer precipitated out of 00mL of a methanol/hydrochloric acid mixture (5% molar hydrochloric acid), washed three times again and dried to constant weight in vacuo. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
The polyester having an acetal group in the main chain prepared in this example has the following structural formula:
the preparation of the polyester containing acetal groups in the backbone 1 The H NMR spectrum is shown in figure 2, 13 the C NMR spectrum is shown in FIG. 3. As can be seen from the observation of FIG. 2 and FIG. 3, the corresponding peak of the polyether chain segment is not seen in the figure, indicating that the obtained product has a completely alternate chain segment structure.
Example 121, 3-Dioxolane/succinic anhydride alternating copolymerization of polyesters containing acetal groups in the main chain
Before the polymerization reaction, 10mL schleck tube is firstly removed of water at 110 ℃ for about 2 hours and is cooled to room temperature in a drier; adding a plurality of masses of SnCl into the reaction kettle in sequence 4 1, 3-dioxolane, succinic anhydride and 1mL of methylene chloride. SnCl 4 The molar ratio of 1, 3-dioxolane/glutaric anhydride was 1/200/200. The mixture is placed at 80 ℃ and reacted for 2h under autogenous pressure. After the reaction, the crude product was first dissolved in dichloromethane and the polymer precipitated in 100mL of a methanol/hydrochloric acid mixture (5% molar hydrochloric acid), washed three times and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
The polyester having an acetal group in the main chain prepared in this example has the following structural formula:
example 131,3-Dioxane/glutaric anhydride alternating copolymerization to Synthesis of a polyester containing acetal groups in the Main chain
10m before polymerizationL Schlenk tube at 110 ℃ for about 2 hours to remove water and cooling to room temperature in a desiccator; sequentially adding a plurality of masses of CF into the reaction kettle 3 SO 3 Et,1, 3-dioxane, glutaric anhydride. CF 3 SO 3 The Et/1, 3-dioxolane/glutaric anhydride molar ratio was 3/400/600. The mixture is placed at 25 ℃ and reacted under autogenous pressure for 4h. After the reaction, the crude product was first dissolved in dichloromethane and the polymer precipitated in 100mL of a methanol/hydrochloric acid mixture (5% molar hydrochloric acid), washed three times and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
The polyester having an acetal group in its main chain prepared in this example has the following structural formula:
the preparation of the polyester containing acetal groups in the main chain 1 The H NMR spectrum is shown in FIG. 4, 13 the C NMR spectrum is shown in FIG. 5. As can be seen from the observation of FIGS. 4 and 5, no peak corresponding to the polyether chain segment is seen in the figure, indicating that the obtained product has a completely alternating chain segment structure.
Example 141, 3-Dioxohepta/glutaric anhydride alternating copolymerization Synthesis of a polyester containing an acetal group in the Main chain
Before the polymerization reaction, 10mL schleck tube is firstly removed of water at 110 ℃ for about 2 hours and is cooled to room temperature in a drier; sequentially adding a plurality of HBFs with the mass into a reaction kettle 4 1, 3-dioxoheptacyclo, glutaric anhydride. HBF 4 The molar ratio of 1, 3-dioxaheptanes/glutaric anhydride was 1/50/50. The mixture is placed at 25 ℃ and reacted for 2h under autogenous pressure. After the reaction, the crude product was first dissolved in dichloromethane and the polymer precipitated in 100mL of a methanol/hydrochloric acid mixture (5% molar hydrochloric acid), washed three times and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
The polyester having an acetal group in the main chain prepared in this example has the following structural formula:
example 151,3-Dioxooctacyclo/glutaric anhydride alternating copolymerization Synthesis of a polyester containing an acetal group in the Main chain
Before the polymerization reaction, 10mL schleck tube is firstly removed of water at 110 ℃ for about 2 hours and is cooled to room temperature in a drier; sequentially adding a plurality of masses of CF into the reaction kettle 3 COOH,1, 3-dioxyoctacyclo, glutaric anhydride. CF 3 The molar ratio COOH/1, 3-dioxyoctacyclo/glutaric anhydride was 1/100/100. The mixture is placed at 25 ℃ and reacted for 5h under autogenous pressure. After the reaction, the crude product was first dissolved in dichloromethane and the polymer precipitated in 100mL of a methanol/hydrochloric acid mixture (5% molar hydrochloric acid), washed three times and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
The polyester having an acetal group in its main chain prepared in this example has the following structural formula:
TABLE 1
1 M n : number average molecular weight, as determined by gel permeation chromatography; 2 PDI: molecular weight distribution, determined by gel permeation chromatography.
The above description is only a few specific embodiments of the present invention, and it should be noted that many variations and modifications may be made by those skilled in the art, and all variations and modifications that do not exceed the scope of the present invention as defined in the claims should be regarded as the present invention.
Claims (4)
1. A polyester having an acetal group in the main chain, characterized in that:
taking cyclic acetal and cyclic anhydride as raw materials, taking Lewis acid or protonic acid as a catalyst, and carrying out alternating copolymerization to obtain the cyclic acetal and cyclic anhydride;
the cyclic acetal is selected from at least one of 1, 3-dioxolane, 1, 3-dioxane, 1, 3-dioxolane and 1, 3-dioxolane;
the cyclic anhydride is selected from at least one of maleic anhydride, glutaric anhydride and succinic anhydride;
the molar ratio of the cyclic acetal to the cyclic anhydride is 1:0.5 to 1.5;
the molar ratio of the catalyst to the cyclic anhydride is 1:50 to 200;
the polyester is an alternating copolymerization structure, the content of chain links of the alternating copolyester is not less than 90 percent, and each repeating unit has an acetal group.
2. The polyester having an acetal group in the main chain according to claim 1, wherein:
the Lewis acid is selected from BF 3 、B(C 6 F 5 ) 3 、SnCl 4 、AlCl 3 、InCl 3 、SbCl 5 、PF 5 、CF 3 SO 3 Et、Ph 3 CPF 6 One or more of;
the protonic acid is selected from HBF 4 、HClO 4 、CF 3 COOH、CF 3 SO 3 H、FSO 3 H. One or more of concentrated sulfuric acid.
3. A method for preparing the polyester containing acetal groups in the main chain according to any one of claims 1 to 2, wherein the method comprises the following steps:
adding cyclic acetal, cyclic anhydride, a catalyst and a solvent which is selectively added into a reaction kettle, and placing the reaction kettle at the temperature of 0 to 120 ℃ under the autogenous pressure for 0.1 to 12 hours.
4. The method for preparing polyester containing acetal groups in the main chain according to claim 3, wherein the solvent is one or more selected from dichloromethane, chloroform, toluene, trichlorobenzene, o-dichlorobenzene, m-dichlorobenzene, and p-dichlorobenzene.
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