A bridged cyclic alcohol aliphatic polyester copolymer, its preparation method and application

Abstract

This invention provides a bridged-ring alcohol aliphatic polyester copolymer, its preparation method, and its application, belonging to the field of polyester material preparation technology. This invention introduces the comonomer tricyclodecanediethanol into the aliphatic polyester structure to prepare the bridged-ring alcohol aliphatic polyester copolymer. The bridged-ring structure improves the mechanical, thermal, and gas barrier properties of the bridged-ring alcohol aliphatic polyester copolymer. The bridged-ring alcohol aliphatic polyester copolymer is biodegradable, and its permeability can reach 1.6 × 10⁻⁶. ‑13 (g.cm) 2 The polyester copolymer has an initial decomposition temperature of over 380℃ and exhibits good thermal stability. The bridged cyclic alcohol aliphatic polyester copolymer has high application value in the fields of high mechanical properties and gas barrier biodegradable materials.

Description

Technical Field

[0001] This invention belongs to the field of polyester material preparation technology, specifically relating to a bridged cyclic alcohol aliphatic polyester copolymer, its preparation method, and its application. Background Technology

[0002] Aliphatic polyesters are high-performance polymers with broad application prospects in various materials such as films and sheets. However, the presence of ester groups and flexible linear chains in the structure of aliphatic polyesters results in defects such as poor thermal properties, poor barrier properties, and poor mechanical properties, which limit the application range of aliphatic polyester materials.

[0003] To expand the application fields of aliphatic polyester materials, researchers have carried out a series of enhancement modifications. Existing technologies include introducing rigid-segment monomers such as isosorbide, furan rings, and thiophene rings into the aliphatic polyester molecular chain to improve the polymer's thermal stability and crystallinity; and dispersing inorganic nanoparticles, such as magnesium oxide and zinc oxide, into the aliphatic polyester matrix to obtain nanocomposites with excellent comprehensive properties. However, the above modification methods all employ traditional copolymerization, blending, and compounding to improve the thermal and crystallinity properties of aliphatic polyester materials, and cannot improve their barrier and mechanical properties. Therefore, there is a need to develop an aliphatic polyester that can improve both barrier and thermal properties. Summary of the Invention

[0004] To address some shortcomings in existing technologies, this invention provides a bridged-ring alcohol aliphatic polyester copolymer, its preparation method, and its applications. This invention introduces the comonomer tricyclodecanediethanol into the aliphatic polyester structure to prepare the bridged-ring alcohol aliphatic polyester copolymer. The bridged-ring structure improves the mechanical, thermal, and gas barrier properties of the bridged-ring alcohol aliphatic polyester copolymer. The bridged-ring alcohol aliphatic polyester copolymer is biodegradable, and its permeability can reach 1.6 × 10⁻⁶. -13 (g.cm) 2 The polyester copolymer has an initial decomposition temperature of over 380℃ and exhibits good thermal stability. The bridged cyclic alcohol aliphatic polyester copolymer has high application value in the fields of high mechanical properties and gas barrier biodegradable materials.

[0005] To achieve the above-mentioned technical objectives, the present invention employs the following technical means.

[0006] This invention first provides a bridged cyclic alcohol aliphatic polyester copolymer, the structural formula of which is:

[0007] ;

[0008] Where x represents the molar percentage content of aliphatic polyester units in the bridged cyclic alcohol aliphatic polyester copolymer, x = 70-95%;

[0009] 1-x represents the molar percentage content of tricyclodecanediethanol in the bridged cyclic alcohol aliphatic polyester copolymer, 1-x = 5-30%.

[0010] The present invention also provides a method for preparing the above-mentioned bridged cyclic alcohol aliphatic polyester copolymer, the method comprising:

[0011] (1) In an inert gas environment, aliphatic dicarboxylic acid, 1,4-butanediol and comonomer tricyclodecanediethanol are mixed and esterification reaction is completed under the action of esterification catalyst. After the reaction is completed, the by-products are removed to obtain bridged ring copolyester prepolymer.

[0012] (2) The bridged ring polyester prepolymer is subjected to polycondensation reaction under the action of a polycondensation catalyst, and the bridged ring alcohol aliphatic polyester copolymer is obtained after the reaction is completed.

[0013] Preferably, in step (1), the aliphatic dicarboxylic acid includes any one of oxalic acid, 1,3-malonic acid, 1,4-succinic acid, 1,5-glutaric acid, 1,6-adipic acid, 1,8-octanoic acid, 1,9-azelaic acid, or 1,10-sebacic acid.

[0014] Preferably, in step (1), the esterification catalyst includes one or more of metal oxides, metal carbonates, metal acetates, tin-based organic compounds, or titanium-based organic compounds.

[0015] Preferably, in step (1), the molar ratio of the aliphatic dicarboxylic acid to 1,4-butanediol is 1.2:1;

[0016] The amount of the transesterification catalyst used is 0.1 mol of the amount of aliphatic dicarboxylic acid.

[0017] Preferably, in step (1), the esterification reaction is carried out at 150-190°C for 3-6 hours.

[0018] Preferably, in step (2), the polycondensation catalyst includes one or more of the following: metal oxide, metal carbonate, metal acetate, tin-based organic compound, or titanium-based organic compound.

[0019] Preferably, in step (2), the amount of the polycondensation catalyst is 0.1 mol% of the aliphatic dicarboxylic acid.

[0020] The conditions for the polycondensation reaction are: reaction in a vacuum environment at 220-240℃ and a pressure of less than 200Pa for 5-8 hours.

[0021] Preferably, in the bridged cyclic alcohol aliphatic polyester copolymer, the molar percentage of tricyclodecanediethanol is 5-30%.

[0022] The present invention also provides the application of the above-mentioned bridged cyclic alcohol aliphatic polyester copolymer in the preparation of high gas barrier biodegradable materials or packaging materials.

[0023] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0024] This invention introduces the comonomer tricyclodecanediethanol into the structure of an aliphatic polyester, thereby obtaining a biodegradable bridged-ring alcohol aliphatic polyester copolymer. This invention enhances the thermal, mechanical, and gas barrier properties of aliphatic polyesters by introducing a bridged-ring structure, thus obtaining a bridged-ring alcohol aliphatic polyester copolymer with excellent thermal, gas barrier, and mechanical properties.

[0025] The bridged cyclic alcohol aliphatic polyester copolymer of the present invention has excellent thermal and mechanical properties, and its transmittance can reach 1.6 × 10⁻⁶. -13 (g.cm) 2 The initial decomposition temperature of the polyester copolymer reaches over 380℃, exhibiting good thermal stability. In terms of mechanical properties, its elongation at break reaches 850%, making it highly valuable in the field of high mechanical properties and gas barrier biodegradable materials. It can be used to prepare high gas barrier biodegradable materials or packaging materials.

[0026] The method for preparing bridged cyclic alcohol aliphatic polyester copolymers described in this invention has the advantages of simple operation, readily available raw materials, and easy control of the reaction process and polymer structure, and can be applied on a large scale in industry. Attached Figure Description

[0027] Figure 1 Bridged ring alcohol aliphatic polyester copolymer 1 H-NMR spectrum.

[0028] Figure 2 The diagram shows the mechanical properties of bridged cyclic alcohol aliphatic polyester copolymers. Detailed Implementation

[0029] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, but the scope of protection of the present invention is not limited thereto.

[0030] In the examples below, the structure of the bridged cyclic alcohol aliphatic polyester copolymer was determined by 1H NMR spectroscopy, with CDCl3 as the deuteration reagent, room temperature as the test temperature, and tetramethylsilane as the internal standard. The number-average molecular weight was determined by gel electrophoresis with deuterated chloroform as the standard. The water vapor transmission rate (WVTR) of the film material was measured using the cup method at 38°C and 90%RH according to GB 1037-1988 standard. The static mechanical properties were characterized using a universal testing machine. Test conditions: tensile rate 50 mm / min, room temperature, humidity 40±10.

[0031] Example 1: Preparation of bridged cyclic alcohol aliphatic polyester copolymer

[0032] (1) Under a nitrogen atmosphere, 1,4-butanediol, 1,4-succinic acid, and tricyclodecanediethanol were added to the reactor, such that the molar ratio of 1,4-butanediol to 1,4-succinic acid was 1.2:1, and the molar percentage of tricyclodecanediethanol in the bridged ring alcohol aliphatic polyester copolymer was 5%, 10%, 15%, 20%, 25%, and 30%. Then, tetrabutyl titanate, an esterification catalyst with a total amount of 0.1 mol% of 1,4-succinic acid, was added to the reactor, and the esterification reaction was carried out at 180°C for 4 h to obtain the bridged ring copolyester prepolymer.

[0033] The proportions of tricyclodecanediethanol in the bridged ring copolyester prepolymer are 5%, 10%, 15%, 20%, 25%, and 30%.

[0034] (2) Tetrabutyl titanate, a polycondensation catalyst, was added to the bridged-ring copolyester prepolymers obtained above. The amount of tetrabutyl titanate was 0.1 mol% of the total amount of 1,4-succinic acid. Then, the pressure was reduced to below 200 Pa, and the polycondensation reaction was carried out at 220 °C for 6 h. After the reaction, bridged-ring alcohol aliphatic polyester copolymers with molar fractions of 5%, 10%, 15%, 20%, 25%, and 30% of tricyclodecanediethanol were obtained, which were denoted as PBTCDSn (n=5, 10, 15, 20, 25, 30), respectively.

[0035] The general structural formula of the bridged cyclic alcohol aliphatic polyester copolymer is:

[0036] ;

[0037] Where x represents the molar percentage content of aliphatic polyester units in the bridged cyclic alcohol aliphatic polyester copolymer, x = 70-95%;

[0038] 1-x represents the molar percentage content of tricyclodecanediethanol in the bridged cyclic alcohol aliphatic polyester copolymer, 1-x = 5-30%.

[0039] Tests showed that the transmittance of the prepared bridged cyclic alcohol aliphatic polyester copolymer could reach 1.6 × 10⁻⁶. -13 (g.cm) 2 The initial decomposition temperature of the polyester copolymer reaches over 380℃, exhibiting good thermal stability.

[0040] Figure 1 Bridged ring alcohol aliphatic polyester copolymer 1 The H-NMR spectrum shows that the proton characteristic peaks on tricyclodecanediethanol in the polymer were obtained through a two-step method, and the peak area gradually increases with the increase of its unit content, proving the successful synthesis of aliphatic polyester copolymers containing tricyclodecanediethanol.

[0041] Figure 2 The figure shows the mechanical properties of the bridged cyclic alcohol aliphatic polyester copolymer. As can be seen from the figure, the elongation at break of the bridged cyclic alcohol aliphatic polyester copolymer is as high as 850%, which indicates excellent mechanical properties.

[0042] Example 2: Preparation of bridged cyclic alcohol aliphatic polyester copolymer

[0043] (1) Under a nitrogen atmosphere, 1,4-butanediol, oxalic acid, and tricyclodecanediethanol were added to the reactor, such that the molar ratio of 1,4-butanediol to oxalic acid was 1.2:1, and the molar percentage of tricyclodecanediethanol in the bridged ring alcohol aliphatic polyester copolymer was 5%, 10%, 15%, 20%, 25%, and 30%. Then, tetrabutyl titanate, an esterification catalyst, was added to the reactor at a dosage of 0.1 mol% of the total oxalic acid, and the esterification reaction was carried out at 180°C for 4 h to obtain the bridged ring copolyester prepolymer.

[0044] The proportions of tricyclodecanediethanol in the bridged ring copolyester prepolymer are 5%, 10%, 15%, 20%, 25%, and 30%.

[0045] (2) Add tetrabutyl titanate, a polycondensation catalyst, to the bridged ring copolyester prepolymers obtained above. The amount of tetrabutyl titanate is 0.1 mol% of the total amount of oxalic acid. Then reduce the pressure to below 200 Pa and perform polycondensation reaction at 220 °C for 6 h. After the reaction is completed, bridged ring alcohol aliphatic polyester copolymers with molar fractions of 5%, 10%, 15%, 20%, 25%, and 30% of tricyclodecanediethanol are obtained.

[0046] Example 3: Preparation of bridged cyclic alcohol aliphatic polyester copolymer

[0047] (1) Under a nitrogen atmosphere, 1,4-butanediol, 1,3-malonic acid, and tricyclodecanediethanol were added to the reactor, such that the molar ratio of 1,4-butanediol to 1,3-malonic acid was 1.2:1, and the molar percentage of tricyclodecanediethanol in the bridged ring alcohol aliphatic polyester copolymer was 5%, 10%, 15%, 20%, 25%, and 30%. Then, tetrabutyl titanate, an esterification catalyst, was added to the reactor at a total amount of 0.1 mol% of 1,3-malonic acid, and the esterification reaction was carried out at 180°C for 4 h to obtain the bridged ring copolyester prepolymer.

[0048] The proportions of tricyclodecanediethanol in the bridged ring copolyester prepolymer are 5%, 10%, 15%, 20%, 25%, and 30%.

[0049] (2) Tetrabutyl titanate, a polycondensation catalyst, was added to the bridged ring copolyester prepolymers obtained above. The amount of tetrabutyl titanate was 0.1 mol% of the total amount of 1,3-malonic acid. Then the pressure was reduced to below 200 Pa, and the polycondensation reaction was carried out at 220 °C for 7 h. After the reaction was completed, bridged ring alcohol aliphatic polyester copolymers with molar fractions of 5%, 10%, 15%, 20%, 25%, and 30% of tricyclodecanediethanol were obtained.

[0050] Example 4: Preparation of bridged cyclic alcohol aliphatic polyester copolymer

[0051] (1) Under a nitrogen atmosphere, 1,4-butanediol, 1,5-glutaric acid and tricyclodecanediethanol were added to the reactor together, such that the molar ratio of 1,4-butanediol to 1,5-glutaric acid was 1.2:1, and the molar percentage of tricyclodecanediethanol in the bridged ring alcohol aliphatic polyester copolymer was 5%, 10%, 15%, 20%, 25%, and 30%. Then, tetrabutyl titanate, an esterification catalyst with a total amount of 0.1 mol% of 1,5-glutaric acid, was added to the reactor, and the esterification reaction was carried out at 180°C for 4 h to obtain the bridged ring copolyester prepolymer.

[0052] The proportions of tricyclodecanediethanol in the bridged ring copolyester prepolymer are 5%, 10%, 15%, 20%, 25%, and 30%.

[0053] (2) Tetrabutyl titanate, a polycondensation catalyst, was added to the bridged ring copolyester prepolymers obtained above. The amount of tetrabutyl titanate was 0.1 mol% of the total amount of 1,5-glutaric acid. Then the pressure was reduced to below 200 Pa, and the polycondensation reaction was carried out at 220 °C for 6 h. After the reaction was completed, bridged ring alcohol aliphatic polyester copolymers with molar fractions of 5%, 10%, 15%, 20%, 25%, and 30% of tricyclodecanediethanol were obtained.

[0054] Example 5: Preparation of bridged cyclic alcohol aliphatic polyester copolymer

[0055] (1) Under a nitrogen atmosphere, 1,4-butanediol, 1,8-octanoic acid and tricyclodecanediethanol were added to the reactor together, such that the molar ratio of 1,4-butanediol to 1,8-octanoic acid was 1.2:1, and the molar percentage of tricyclodecanediethanol in the bridged ring alcohol aliphatic polyester copolymer was 5%, 10%, 15%, 20%, 25%, and 30%. Then, tetrabutyl titanate, an esterification catalyst with a total amount of 0.1 mol% of 1,8-octanoic acid, was added to the reactor, and the esterification reaction was carried out at 180°C for 4 h to obtain the bridged ring copolyester prepolymer.

[0056] The proportions of tricyclodecanediethanol in the bridged ring copolyester prepolymer are 5%, 10%, 15%, 20%, 25%, and 30%.

[0057] (2) Tetrabutyl titanate, a polycondensation catalyst, was added to the bridged ring copolyester prepolymers obtained above. The amount of tetrabutyl titanate was 0.1 mol% of the total amount of 1,8-octanoic acid. Then the pressure was reduced to below 200 Pa, and the polycondensation reaction was carried out at 220 °C for 7 h. After the reaction was completed, bridged ring alcohol aliphatic polyester copolymers with molar fractions of 5%, 10%, 15%, 20%, 25%, and 30% of tricyclodecanediethanol were obtained.

[0058] Example 6: Preparation of bridged cyclic alcohol aliphatic polyester copolymer

[0059] (1) Under a nitrogen atmosphere, 1,4-butanediol, 1,9-azelic acid and tricyclodecanediethanol were added to the reactor together, such that the molar ratio of 1,4-butanediol to 1,9-azelic acid was 1.2:1, and the molar percentage of tricyclodecanediethanol in the bridged ring alcohol aliphatic polyester copolymer was 5%, 10%, 15%, 20%, 25%, and 30%. Then, tetrabutyl titanate, an esterification catalyst with a total amount of 0.1 mol% of 1,9-azelic acid, was added to the reactor, and the esterification reaction was carried out at 180°C for 4 h to obtain the bridged ring copolyester prepolymer.

[0060] The proportions of tricyclodecanediethanol in the bridged ring copolyester prepolymer are 5%, 10%, 15%, 20%, 25%, and 30%.

[0061] (2) Tetrabutyl titanate, a polycondensation catalyst, was added to the bridged ring copolyester prepolymers obtained above. The amount of tetrabutyl titanate was 0.1 mol% of the total amount of 1,9-azelaic acid. Then the pressure was reduced to below 200 Pa, and the polycondensation reaction was carried out at 220 °C for 7 h. After the reaction was completed, bridged ring alcohol aliphatic polyester copolymers with molar fractions of 5%, 10%, 15%, 20%, 25%, and 30% of tricyclodecanediethanol were obtained.

[0062] Example 7: Preparation of bridged cyclic alcohol aliphatic polyester copolymer

[0063] (1) Under a nitrogen atmosphere, 1,4-butanediol, 1,10-sebacic acid and tricyclodecanediethanol were added to the reactor together, such that the molar ratio of 1,4-butanediol to 1,10-sebacic acid was 1.2:1, and the molar percentage of tricyclodecanediethanol in the bridged ring alcohol aliphatic polyester copolymer was 5%, 10%, 15%, 20%, 25%, and 30%. Then, tetrabutyl titanate, an esterification catalyst, was added to the reactor at a total amount of 0.1 mol% of 1,10-sebacic acid, and the esterification reaction was carried out at 180°C for 4 h to obtain the bridged ring copolyester prepolymer.

[0064] The proportions of tricyclodecanediethanol in the bridged ring copolyester prepolymer are 5%, 10%, 15%, 20%, 25%, and 30%.

[0065] (2) Tetrabutyl titanate, a polycondensation catalyst, was added to the bridged ring copolyester prepolymers obtained above. The amount of tetrabutyl titanate was 0.1 mol% of the total amount of 1,10-sebaceous acid. Then the pressure was reduced to below 200 Pa, and the polycondensation reaction was carried out at 220 °C for 8 h. After the reaction was completed, bridged ring alcohol aliphatic polyester copolymers with molar fractions of 5%, 10%, 15%, 20%, 25%, and 30% of tricyclodecanediethanol were obtained.

[0066] In summary, the bridged-ring alcohol aliphatic polyester copolymer of the present invention possesses excellent thermal and mechanical properties, and its transmittance can reach 1.6 × 10⁻⁶. -13 (g.cm) 2 The initial decomposition temperature of the polyester copolymer reaches over 380℃, exhibiting good thermal stability. In terms of mechanical properties, its elongation at break reaches 850%, making it highly valuable in the field of high mechanical properties and gas barrier biodegradable materials. It can be used to prepare high gas barrier biodegradable materials or packaging materials.

[0067] The embodiments described above are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments. Any obvious improvements, substitutions or modifications that can be made by those skilled in the art without departing from the essence of the present invention shall fall within the protection scope of the present invention.

Claims

1. A method for preparing a bridged cyclic alcohol aliphatic polyester copolymer, characterized in that, The preparation method includes: (1) 1,4-Butanediol, 1,4-butanediol and the comonomer tricyclodecanediethanol were mixed in an inert gas environment and the esterification reaction was completed under the action of an esterification catalyst. After the reaction was completed, the by-products were removed to obtain the bridged ring copolyester prepolymer. The molar ratio of 1,4-succinic acid to 1,4-butanediol is 1.2:1; The amount of the esterification catalyst used is 0.1 mol% of the amount of 1,4-succinic acid. The esterification reaction is carried out at 150-190°C for 3-6 hours. (2) The bridged ring polyester prepolymer is subjected to polycondensation reaction under the action of a polycondensation catalyst, and the bridged ring alcohol aliphatic polyester copolymer is obtained after the reaction is completed. The amount of the polycondensation catalyst used is 0.1 mol% of the aliphatic dicarboxylic acid. The conditions for the polycondensation reaction are: reaction at 220-240℃ and in a vacuum environment with a pressure of less than 200Pa for 5-8 hours; In the bridged cyclic alcohol aliphatic polyester copolymer, the molar percentage of tricyclodecanediethanol is 5-30%.

2. The method for preparing the bridged cyclic alcohol aliphatic polyester copolymer according to claim 1, characterized in that, In step (1), the esterification catalyst includes one or more of the following: metal oxide, metal carbonate, metal acetate, tin-based organic compound or titanium-based organic compound.

3. The method for preparing the bridged cyclic alcohol aliphatic polyester copolymer according to claim 1, characterized in that, In step (2), the polycondensation catalyst includes one or more of the following: metal oxide, metal carbonate, metal acetate, tin-based organic compound, or titanium-based organic compound.

4. The bridged cyclic alcohol aliphatic polyester copolymer prepared by the method according to any one of claims 1 to 3, characterized in that, The structural formula of the bridged cyclic alcohol aliphatic polyester copolymer is: ； Where x represents the molar percentage content of aliphatic polyester units in the bridged cyclic alcohol aliphatic polyester copolymer, x = 70-95%; 1-x represents the molar percentage content of tricyclodecanediethanol in the bridged cyclic alcohol aliphatic polyester copolymer, 1-x = 5-30%.

5. The application of the bridged cyclic alcohol aliphatic polyester copolymer of claim 4 in the preparation of high gas barrier biodegradable materials or packaging materials.

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