A novel fatty polycarbonate material and a preparation method and application thereof

Abstract

The application belongs to the technical field of material chemistry, and particularly relates to a novel fatty polycarbonate material and a preparation method and application thereof. The application uses epoxy halogenated alkane and epoxy cyclohexane as epoxy monomers, introduces chemical modification compared with traditional PCHC, uses epoxy halogenated alkane compared with existing chemical modification methods, improves the thermal stability, temperature resistance and mechanical properties of the material, overcomes the defects of existing similar materials, and expands the application scenarios of the material. At the same time, the application also provides a good reaction site for further performance improvement and functional derivation of the ternary polyester, and has a good development prospect. Meanwhile, a novel double-metal cobalt catalyst with a quaternary ammonium group is used as a polymerization catalyst in the synthesis process of the application, and the double-metal synergistic catalysis process can be well realized, and the catalytic system is simple and easy to recycle and reuse.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of material chemistry, and particularly relates to a novel aliphatic polycarbonate material and a preparation method and application thereof. BACKGROUND

[0002] Aliphatic polycarbonate material is a kind of material directly prepared by using greenhouse gas carbon dioxide as raw material. The material is one of effective ways to fix and utilize carbon dioxide, and has good development prospect. The first developed aliphatic polycarbonate is polypropylene carbonate (PPC), which is a degradable material synthesized by using carbon dioxide and propylene oxide as raw materials. The prepared PPC has a molecular weight of 20,000-100,000, and has good flexibility and biodegradability. However, due to the open-chain isopropyl structure of the PPC molecular main chain, the molecular flexibility leads to a glass transition temperature (T g ) of less than 40℃, and a thermal decomposition temperature of generally less than 220℃, thereby causing certain limitations to the popularization and application of the PPC.

[0003] In order to improve the temperature application window of the aliphatic polycarbonate, people use epoxy cyclohexane with a rigid six-membered ring structure to replace propylene oxide for alternative copolymerization to prepare a novel aliphatic polycarbonate, and continuously conduct in-depth research. Patents CN201711037217.X and CN201711037215.0 use carbon dioxide and epoxy cyclohexane as monomer raw materials, and use an organic zinc complex as a catalyst to prepare poly(cyclohexylene carbonate) (PCHC) with a molecular weight of more than 20,000. Compared with the traditional PPC, the glass transition temperature of the PCHC polyester can reach more than 110℃, and the thermal decomposition temperature can reach more than 280℃, thereby greatly widening the temperature use window of the aliphatic polycarbonate. However, the material has certain defects in the mechanical properties. Due to the existence of the six-membered alicyclic structure in the polyester main chain, the molecular structure is rigid but has insufficient toughness, and the material is hard and brittle at room temperature, and has poor impact resistance. In view of the situation, many researchers use the method of physical blending to improve the mechanical properties of the PCHC. Patent CN202011040246.3 adds nano-silicon dioxide, sheet structure wollastonite nano material and glass fiber and other auxiliary ingredients, and melts and blends to prepare an organic-inorganic composite material, which can improve the tensile strength of the PCHC to a certain extent, but the preparation process of the material is relatively complex. Patent [CN202211016329.8] adds polyolefin elastomer POE and related additives, and modifies by melting and blending, which can improve the elongation at break of the PCHC to a certain extent, but the compatibility of POE with the PCHC is poor, and if the formula is unreasonable or the operation is improper, phase separation phenomenon is easy to occur.

[0004] Physical modification operation is complex and limited to the degree of performance improvement, compared with chemical modification method which is modified from the molecular level, its effect is usually more significant. Patent CN 202111307477.0 uses methyl acryloyl chloride and its oxides as modification reagents to end-cap low molecular weight PCHC, reduce the content of terminal hydroxyl group, weaken the intermolecular hydrogen chloride effect, so as to reduce the crystallinity and increase the toughness of the material. Li Xiang et al. of Northeast Normal University copolymerize lactide as the third component and obtain a terpolymer, but due to the large difference in properties between lactide and epoxy cyclohexane, the activation mode is different, so a binary or even ternary catalyst system is required, the catalysis is complex and the structure regulation of the chain segment is difficult.

[0005] Therefore, how to improve the thermal performance, strength and comprehensive performance such as gas barrier of polycarbonate materials in a simple and efficient way while maintaining the advantages of polycarbonate polymers, and promote the development of related products, is a technical problem that needs to be solved by the technical personnel in the field at present. SUMMARY

[0006] In order to solve the problems existing in the prior art, one of the purposes of the present application is to provide a new fatty polycarbonate material with relatively better thermal stability, temperature resistance and mechanical properties.

[0007] The second purpose of the present application is to provide a preparation method of a new fatty polycarbonate material, which uses a self-synthesized catalyst to improve the reaction efficiency, and the catalyst is easy to recover, and the polymerization reaction is simple and efficient.

[0008] The third purpose of the present application is to provide an application of a new fatty polycarbonate material in preparing degradable products.

[0009] In order to achieve the above purposes, the technical scheme adopted by the present application is as follows:

[0010] A new fatty polycarbonate material is prepared by polymerization of carbon dioxide, epoxy cyclohexane and epoxy halogenated alkane monomers under the action of a catalyst.

[0011] Optionally, the molar amount ratio of the epoxy cyclohexane to the epoxy halogenated alkane monomer is 1:0.5-2.0.

[0012] As a preferred, in the specific embodiment of the present application, the epoxy halogenated alkane monomer is epoxy chloropropane.

[0013] Optionally, the total molar amount of the epoxy cyclohexane and the epoxy chloropropane is the amount of the epoxy monomer; the molar amount ratio of the carbon dioxide to the epoxy monomer is 0.5-1.5:1.

[0014] Optionally, the number average molecular weight of the material is 14000-30000.

[0015] As preferred, the material has a general structure shown in formula (V): Wherein m:n=0.5~2.0:1.

[0016] The present application uses epoxy halogenated alkane and epoxy cyclohexane as epoxy monomers, compared with traditional PCHC and existing chemical modification, creatively uses epoxy halogenated alkane, embeds halogenated carbonate chain segment in the structure to improve the thermal stability, temperature resistance and mechanical properties of the material, overcomes the defects of existing similar materials, and expands the application scenarios of the material. Meanwhile, the present application also provides a good reaction site for further performance improvement and functional derivation of the ternary polyester, and has a good development prospect.

[0017] As preferred, in the specific embodiment of the present application, the catalyst is a double-metal cobalt catalyst with a quaternary ammonium group; preferably, the catalyst has a general structure shown in formula (VI): Wherein X is a coordination negative ion group; epoxy

[0018] Preferably, X is selected from 2,4-dinitrophenoxide, 3,5-bistrifluoromethylphenoxide or trichloroacetate ion.

[0019] The total molar amount of epoxy cyclohexane and epoxy chloropropane is used as the amount of epoxy monomer; the molar amount ratio of the catalyst to the epoxy monomer is 1:2000-4000.

[0020] The present application uses a new type of double-metal cobalt catalyst with a quaternary ammonium group as a polymerization catalyst, which has the structural characteristics of electrophilic-nucleophilic bifunctional property and two catalytically active centers, can well realize the double-metal synergistic catalysis process, and has high catalytic activity. The catalyst can be used alone, and the catalytic system is simple and easy to recycle and reuse. The structural characteristics are that the two mononuclear cobalt structures are connected by a biphenyl hard connection to keep the distance between the catalytically active centers relatively fixed. The central metal is Co(III) cation, which has moderate acidity, can ensure good electrophilic interaction with monomers, and after the reaction is completed, the polyester chain can also be relatively easily dissociated from the Co(III) active center, realizing good chain transfer and being beneficial to the narrow distribution of polyester molecular weight. The quaternary ammonium group is a tetra-n-butylammonium structure, which has large steric hindrance and weak electrostatic force between the counter ion, so that the counter ion has strong nucleophilic effect. The axial coordination ions are all negative ion groups with strong electron-withdrawing ability, such as 2,4-dinitrophenoxide, 3,5-bistrifluoromethylphenoxide and trichloroacetate ion, so that the cobalt atom can be stabilized in the Co(III) oxidation state and maintain high electrophilic ability.

[0021] The preparation method of the new fatty carbonate material comprises the following steps: dissolving and mixing cyclohexene oxide, epoxy halogenated alkane and a catalyst under nitrogen protection, filling carbon dioxide, stirring and heating, separating and purifying the reaction product after the reaction is completed to obtain the new fatty carbonate material.

[0022] As preferred, in the specific embodiment of the present application, the filling of carbon dioxide specifically comprises firstly filling carbon dioxide to 80% of the set pressure, stirring and heating to the reaction temperature, and then supplementally filling carbon dioxide to 100% of the set pressure.

[0023] It also comprises controlling the reaction conversion rate to 50% by timing reaction, stopping the reaction, reducing to room temperature, releasing the residual carbon dioxide, and then separating and purifying the reaction product.

[0024] Preferably, the separation and purification comprises evaporating the unreacted epoxy alkane under reduced pressure to recover the raw material, adding dichloromethane and 1M hydrochloric acid into the residual liquid after cooling, slowly stirring until dissolved and uniform, then adding methanol under stirring to precipitate, aging, filtering to obtain the light yellow crude product, then dissolving the crude product in dichloromethane, precipitating again with methanol, repeating the process for 2-3 times, washing and drying, and the process is completed.

[0025] Preferably, the reaction pressure is 2.0-4.0 MPa, and the reaction temperature is 25-45℃.

[0026] Preferably, it also comprises firstly preparing the bimetallic cobalt catalyst with a quaternary ammonium group. BRIEF DESCRIPTION OF DRAWINGS

[0027] In order to more clearly illustrate the technical solutions of the embodiments of the present application or the prior art, the drawings needed in the embodiments or the prior art description will be briefly introduced as follows. Obviously, the drawings in the following description are only embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor on the basis of the provided drawings.

[0028] Figure 1 The 1H-NMR spectrum of the intermediate compound I in the synthesis of the catalyst;

[0029] Figure 2 The 1H-NMR spectrum of the intermediate compound II in the synthesis of the catalyst;

[0030] Figure 3 The 1H-NMR spectrum of the intermediate compound III in the synthesis of the catalyst;

[0031] Figure 4 The 1H-NMR spectrum of the refined product prepared in Example 1;

[0032] Figure 5 GPC chromatogram of the purified product prepared for Example 1;

[0033] Figure 6 Molecular weight fitting results of the purified product prepared for Example 1;

[0034] Figure 7 Thermogravimetric curve of the purified product prepared for Example 1;

[0035] Figure 8 Differential thermogravimetric curve of the purified product prepared for Example 1;

[0036] Figure 9 Differential scanning calorimetric curve of the purified product prepared for Example 1. DETAILED DESCRIPTION

[0037] The above content of the present application is further illustrated in detail by the following examples, but this should not be understood as the scope of the above subject matter of the present application being limited to the following examples only, and any technology realized based on the above content of the present application falls within the scope of the present application.

[0038] The raw materials used in the following examples are all commercially available, wherein the epoxycyclohexane is purchased from Shenma Nylon Chemical Co., Ltd., and the epoxchloropropane is purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd., both of which are of analytical purity, and are distilled after being sufficiently dried by calcium hydride and stored in a sealed container for standby use.

[0039] The catalyst used in the following examples is a general structure represented by formula (VI): wherein X is a coordination negative ion group; wherein X is selected from 2,4-dinitrophenoxide, 3,5-bistrifluoromethylphenoxide or trichloroacetate ion.

[0040] The synthesis reaction process thereof is represented by formula (VII):

[0041]

[0042] The specific synthesis process thereof is:

[0043] (1) Preparation of compound I

[0044] A 100ml round-bottom flask equipped with a magnetic stir bar was placed in a low-temperature cooling solution and stirred. The temperature was controlled below 0℃. The condensation product of 3,3'-diformyl-4,4'-biphenyl (24g, 0.1mol), cyclohexanediamine hydrochloride, and salicylaldehyde (48.5g, 0.2mol) was dissolved in 300ml of purified dichloromethane. Triethylamine (55ml, 0.4mmol) and an appropriate amount of 5A molecular sieve were added. After reacting at room temperature for 24h, the solution was filtered, and the filter cake was washed with dichloromethane (50ml × 5). The filtrate was collected and distilled under reduced pressure to obtain the crude product. The crude product was purified by column chromatography (dry loading; silica gel column; developing solvent: petroleum ether / ethyl acetate = 10 / 1) to obtain a golden yellow powder compound I. Its 1H-NMR characterization results are as follows: Figure 1 As shown, the yield was 55.02g, with a yield of approximately 85.6%.

[0045] (2) Preparation of Compound II

[0046] Take 32.14 g (0.05 mol) of purified compound I, add 200 mL of dichloromethane, then add 14.41 g (0.11 mol) of anhydrous AlCl3, and stir at room temperature to dissolve. Then add 50 mL of dichloromethane solution containing 14.10 g of chlorobutyryl chloride, and absorb the escaping HCl tail gas with dilute alkaline solution. After the addition is complete, continue the reaction for 2.5 hours to stop the reaction. Add 100 mL of ice-water mixture to the reaction solution and stir vigorously to decompose the complex. Then transfer to a separatory funnel, allow to stand and separate into layers. Wash the separated organic liquid phase successively with deionized water, 5% NaOH solution, and then wash with water until neutral. Evaporate and concentrate, cool and crystallize to obtain crude acylated intermediate, which is purified with dichloromethane to obtain 34.30 g of pure product, with a yield of about 80.0%.

[0047] The above acylated compound was dissolved in 200 mL of anhydrous ethanol and 8.0 g of palladium on carbon catalyst. Hydrogen gas was introduced, and the reaction was carried out at 25°C for 24 hours, after which the reaction was terminated. The reaction solution was concentrated to half its volume by rotary evaporation, allowed to cool naturally, and a white solid precipitated. This solid was filtered, washed with alcohol, and dried to give 28.24 g of compound II. Its 1H-NMR characterization results are as follows: Figure 2 As shown, the yield is approximately 85.1%.

[0048] (3) Preparation of compound III

[0049] Compound II (16.59 g, 0.02 mol), tri-n-butylamine (9.28 g, 0.05 mol), a small amount of KI, and 150 mL of anhydrous ethanol were added to the reactor. The mixture was stirred and refluxed for 24 hours before the reaction was stopped. The mixture was concentrated under reduced pressure, cooled, and crystallized, resulting in a pale yellow solid. The crude product was dissolved again by heating with an appropriate amount of anhydrous ethanol, allowed to cool naturally to room temperature, crystallized, filtered, and dried to obtain 21.95 g of quaternary ammonium compound, with a yield of approximately 92.5%.

[0050] The quaternary ammonium compound was dissolved in 100 mL of anhydrous dichloromethane under nitrogen protection, and 100 mL of a methanol solution dissolving 7.08 g of cobalt acetate was slowly added under stirring conditions, and a red precipitate was constantly separated. After the addition was completed, the reaction was stopped after 1 hour of continuous stirring. After standing for 0.5 hours, the precipitate was completely separated. Filtration, washing the filter cake with an appropriate amount of methanol 3 times, and vacuum drying, a brick red solid powder compound III was obtained, and the 1H-NMR characterization results are shown in Figure 3 The yield was 22.83 g,

[0051] The yield was 94.9%.

[0052] (4) Preparation of compounds IVa-c

[0053] 0.01 mol of compound III and 0.03 mol of anhydrous LiCl were added to the reactor, and then 80 mL of anhydrous dichloromethane was added and stirred to dissolve. The O2 flow rate was adjusted, and the oxidation was carried out at room temperature until it turned dark green, and then the oxygen was turned off. The organic phase was washed with saturated NaHCO3 solution and water until it was neutral, dried with anhydrous Na2SO4, and then the drying agent was filtered out. Then 0.042 mol of AgBF4 was added and reacted in the dark for 12 hours, and then the insoluble material was filtered out. Then 0.05 mmol of 2,4-dinitrophenol sodium or 3,5-bistrifluoromethyl phenol sodium or sodium trichloroacetate was added, and the reaction was continued for 24 hours with vigorous stirring. The material was taken out, the inorganic salt was filtered out, the filtrate was washed with saturated NaHCO3 solution and deionized water until it was neutral, concentrated and crystallized, and dark green or dark green solid powder IVa-c was obtained, with a yield of 88.9%, 85.2% and 81.4% respectively, and was dried and stored for use.

[0054] Example 1

[0055] This example provides a new type of synthetic process of fatty polycarbonate material, and the synthetic process route is shown in the following formula (VIII):

[0056] (VIII), and the specific synthetic process operation process is as follows:

[0057] (1) Preparation of epoxy mixture: the epoxy cyclohexane and halogenated epoxy propyl mixture were weighed according to the molar amount ratio and mixed uniformly;

[0058] (2) A certain amount of dry catalyst was weighed in a flask under a dry nitrogen atmosphere, and then the epoxy mixture: catalyst = 2000:1 molar ratio was added to the epoxy mixture prepared in step (1) and stirred to dissolve;

[0059] (3) The reactor is pre-dried in vacuum, then filled with low-pressure nitrogen for protection, then the material in step (2) is transferred into the reactor by a syringe, and then sealed, placed in a heating jacket, then filled with 0.8 times the set pressure of carbon dioxide, and then stirred and heated, until the temperature reaches the set temperature, and then the carbon dioxide is supplemented to the set pressure and the timing is started, and when the reaction conversion rate reaches about 50%, the reaction is stopped (this is to avoid the solidification of the reaction system due to deep reaction, which is inferred by the pressure gauge), and then the temperature is lowered to room temperature, and then the remaining carbon dioxide is slowly released, and then the reactor is opened, and then a small amount of liquid is first sucked by a syringe for reaction process analysis, and then the remaining material is subjected to subsequent separation and purification;

[0060] (4) The material is extracted and placed in a flask, and then unreacted alkylene oxide is distilled off under reduced pressure for raw material recovery, and then a proper amount of dichloromethane and a few drops of 1M hydrochloric acid are added to the residual liquid after cooling, and then slowly stirred until dissolved uniformly, and then added to excess methanol for precipitation under stirring, and then aged, filtered, and then a light yellow crude product is obtained. Then the crude product is dissolved in a small amount of dichloromethane, and then precipitated with methanol again, and then the process is repeated for 2-3 times, and then washed and dried, and then a refined white CO2 / CHO / ECH ternary polyester product is obtained, which is the new fatty polycarbonate material.

[0061] The set epoxy monomer material ratio, catalyst dosage, reaction time, temperature and reaction product analysis results in the synthesis of the new fatty polycarbonate material according to various embodiments of the present application are shown in Table 1 below:

[0062] Table 1

[0063]

[0064] Note: n(epoxide):n(catalyst) = 2000, carbon dioxide pressure 3.0 MPa; TOF: catalyst conversion frequency

[0065] Comparative Example 1

[0066] This comparative example provides a fatty polycarbonate material, which is different from Example 1 in that the epoxy chloropropane monomer ECH is omitted, and a CO2 / CHO binary polymer is prepared by polymerization in the same way as Example 1.

[0067] Comparative Example 2

[0068] This comparative example provides a fatty polycarbonate material, which is different from Example 1 in that epoxy propane is used instead of epoxy chloropropane, and a CO2 / CHO / PPO ternary polymer is prepared by polymerization in the same way as Example 1.

[0069] Comparative Example 3

[0070] This comparative example provides an aliphatic polycarbonate material, which differs from Example 1 in that the epoxy cyclohexane monomer CHO is omitted, and the CO2 / ECH binary polymer is prepared by polymerization using the same method as in Example 1.

[0071] Test case

[0072] 1. Performance Characterization and Comparison:

[0073] (1) Structural characterization: The product obtained in Example 1 of this invention was subjected to... 1 1H NMR, molecular weight and distribution analysis:

[0074] The product prepared in Example 1 was analyzed, and its proton nuclear magnetic resonance spectrum was as follows. Figure 4 As shown in the figure, the multiplets between chemical shifts 1.19 and 2.16 represent the four methylene peaks on the cyclohexyl group, the peak at 3.72 represents the chloromethyl peak, the peak at 4.38 represents the two methine peaks in the ring, the peak at 4.51 represents the methylene peak in the ECH segment connected to the carbonate portion, and the peak at chemical shift 5.12 represents the methine peak in the ECH segment. This indicates that the sample has a ternary polyester structure. Simultaneously, very small peaks appear at chemical shifts 3.2-3.6, which are peaks representing a very small amount of polyether structure in the main chain, indicating that the main chain is essentially an alternating copolymer polyester structure with good chemical selectivity in the reaction.

[0075] Molecular weight and distribution were determined using high-temperature gel permeation chromatography (TPC). The mobile phase was anhydrous tetrahydrofuran, and the flow rate was 1.00 ml / min. Polystyrene was selected as the standard sample (used to determine the molecular weight of polyester).

[0076] like Figure 5 The GPC chromatogram of the product in Example 1 shows that the prepared CO2 / CHO / ECH terpolymer sample has a relatively wide peak duration of 2 minutes. Figure 6 As shown, after molecular weight fitting, the number-average molecular weight of the sample was 21.3 kg / mol, the weight-average molecular weight was 34.6 kg / mol, and the polydispersity index (PDI) was approximately 1.62. This is because, compared to binary polyesters, ternary polyester reaction systems contain three components, increasing the disorder of the reaction and the random termination factors encountered during chain growth, thus leading to increased differences in molecular chain size. Therefore, the PDI is larger than the approximately 1.2–1.3 distribution coefficient of binary copolymerization.

[0077] (2) Performance comparison:

[0078] ① Thermal stability: such as Figure 7The thermogravimetric analysis (TGA) diagram of the product in Example 1 shows that the sample initially exhibited a slow, slight decrease in mass, attributed to a small amount of residual volatile solvent from the sample preparation process. Decomposition began at 294°C, reaching its maximum rate of weight loss around 300°C. Furthermore, the decomposition temperature was concentrated within a relatively narrow temperature range, indicating that the ternary polymer has a relatively homogeneous composition. This conclusion can also be drawn from… Figure 8 As verified in the differential weight loss graph, a sharp thermal decomposition peak appeared in the sample at 299℃.

[0079] Compared to the thermal decomposition peak temperature of around 280℃ for the CO2 / CHO / PPO ternary polymer provided in Comparative Example 2, this is nearly 20℃ higher, indicating that the thermal stability of the obtained polymer is improved to a certain extent after the third monomer is changed to epichlorohydrin.

[0080] ② DSC detection of changes in the aggregation state of samples during heating, from Figure 9 As can be seen, the glass transition temperature of the product of Example 1 of this invention is approximately 68.2°C, which is significantly higher than the glass transition temperature of 42°C of the CO2 / ECH copolymer with a comparable molecular weight provided in Comparative Example 3. This is because the CHO monomer introduces a rigid six-membered ring structure into the polyester backbone, increasing the rigidity of the chain while reducing the flexibility of the molecular chain. This strengthens the intermolecular interaction forces, making it less likely for molecules to slide against each other, thus significantly increasing the glass transition temperature.

[0081] For random copolymerized ternary polyesters, the glass transition temperature can be measured. The glass transition temperature is an important performance indicator for structural materials, reflecting their temperature tolerance. Currently, mass-produced polypropylene carbonate (PPC) products have a glass transition temperature of only around 40°C, which is relatively low for a structural material, limiting its application to some extent. Therefore, a higher glass transition temperature is an important requirement for this type of new material. The novel material provided by this invention has positive significance in expanding the temperature operating window of this material.

[0082] ③Mechanical properties:

[0083] First, the material was made into thin film samples using a Babyplast 6 / 10P miniature injection molding machine from Cronoplast SL for performance testing. Tensile strength and elongation at break were tested using a TSE04B universal testing machine according to the standard GB / 1040.3-2006. The light transmittance of the samples was tested using a UV-2401PC ultraviolet spectrophotometer according to the standard GB / T 2410-2008.

[0084] The samples prepared from the products of Example 1, Example 4, Example 5, Example 6, Example 7, Comparative Examples 1-3 were tested according to the above test method, and the test results are shown in Table 2:

[0085] Table 2

[0086]

[0087]

[0088] Note: sample thickness 0.50mm, tensile rate 100mm / min

[0089] As shown by the test results in Table 2 above, the novel fatty polycarbonate material provided by the present application has a tensile strength comparable to that of the conventional binary polymer material CO2 / CHO (Comparative Example 1), but has a higher elongation at break and significantly enhanced mechanical toughness; has a higher tensile strength than the binary polymer CO2 / ECH (Comparative Example 3), and has a substantially improved mechanical strength; and has a certain degree of improved tensile strength compared to the existing ternary polymer CO2 / CHO / PPO (Comparative Example 2) due to the increased intermolecular force caused by the polar carbon-chlorine bond.

[0090] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application, and not to limit them; although the present application has been described in detail with reference to the foregoing examples, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing examples, or make equivalent replacements to some of the technical features; and such modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A fatty polycarbonate material, characterized by, The fatty polycarbonate material is prepared by polymerization of carbon dioxide, epoxycyclohexane and epoxide haloalkane monomers under the action of a catalyst; the ester chain content of the fatty polycarbonate material is 95% or 97% or 98% or 99%; the molar ratio of the epoxycyclohexane to the epoxide haloalkane monomer is 1:0.5-2.0, the epoxide haloalkane monomer is epoxide chloropropane; the catalyst is a bimetallic cobalt catalyst with a quaternary ammonium group, having a general structure shown in formula (VI): (VI), wherein X is a coordinating anion group selected from 2,4-dinitrophenoxide, 3,5-bistrifluoromethylphenoxide or trichloroacetate.

2. The fatty polycarbonate material of claim 1, wherein, The total molar amount of the epoxycyclohexane and the epoxide chloropropane is used as the amount of the epoxy monomer; the molar ratio of the carbon dioxide to the epoxy monomer is 0.5-1.5:

1.

3. The fatty polycarbonate material of claim 2, wherein, The number average molecular weight of the material ranges from 14000 to 30000.

4. The fatty polycarbonate material of claim 2, wherein, The material has a general structure shown in formula (V): (V), wherein m: n=0.5~2.0：1。 5. The fatty polycarbonate material of claim 1, wherein, The total molar amount of the epoxycyclohexane and the epoxide chloropropane is used as the amount of the epoxy monomer; the molar ratio of the catalyst to the epoxy monomer is 1:2000-4000.

6. A process for the preparation of a fatty polycarbonate material as claimed in any one of claims 1 to 5, characterized in that, The fatty polycarbonate material is prepared by dissolving and mixing the epoxycyclohexane, the epoxide haloalkane and the catalyst uniformly under nitrogen protection, charging carbon dioxide, stirring and heating, and separating and purifying the reaction product after the reaction is completed.

7. The method of claim 6, wherein the fatty polycarbonate material is prepared by the process comprising: reacting a fatty acid with a carbonate source to form a fatty polycarbonate material; and purifying the fatty polycarbonate material. The charging of the carbon dioxide specifically includes first charging carbon dioxide to a set pressure of 80%, stirring and heating to the reaction temperature, and then supplementally charging carbon dioxide to a set pressure of 100%. It also includes controlling the reaction conversion rate to 50% by timing, stopping the reaction, reducing to room temperature, releasing the remaining carbon dioxide, and then separating and purifying the reaction product.

8. The method of claim 6, wherein the fatty polycarbonate material is prepared by the process comprising: reacting a fatty acid with a carbonate source to form a fatty polycarbonate material. The separation and purification includes evaporating the unreacted epoxide alkane under reduced pressure to recover the raw material, adding dichloromethane and 1M hydrochloric acid to the residual liquid after cooling, slowly stirring until dissolved uniformly, then adding methanol under stirring to precipitate, aging, filtering, obtaining a light yellow crude product, then dissolving the crude product in dichloromethane, precipitating again with methanol, repeating the process 2-3 times, washing and drying, and the process is completed.

9. The method for preparing the aliphatic polycarbonate material as described in claim 6, characterized in that, The reaction pressure is 2.0-4.0MPa; the reaction temperature is 25-45℃.

10. The method for preparing the aliphatic polycarbonate material as described in claim 6, characterized in that, It also includes first preparing the bimetallic cobalt catalyst with a quaternary ammonium group according to claim 1.

11. Use of the fatty polycarbonate material according to any one of claims 1-5 in the preparation of a degradable material product.

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