CN113402702B - Flame-retardant degradable PBS and preparation method thereof - Google Patents

Abstract

The invention relates to flame-retardant degradable PBS and a preparation method thereof, belonging to the technical field of high polymer material processing. The flame-retardant degradable PBS is prepared by the following method: performing polycondensation on succinic acid, tetrafluorosuccinic acid, 2,3, 3-tetrafluoro-1, 4-butanediol and 1, 4-butanediol to obtain PBS; the molar ratio of the succinic acid to the tetrafluorosuccinic acid to the alcohol acid of the 2,2,3, 3-tetrafluoro-1, 4-butanediol to the 1, 4-butanediol is 1.1-1.5: 1, and the molar ratio of the tetrafluorosuccinic acid to the 2,2,3, 3-tetrafluoro-1, 4-butanediol is not 0 at the same time. The PBS has hydrophobicity and flame retardance, has good biodegradability as the pure PBS, and widens the field of biodegradable plastics. The method has the advantages of simple and controllable process, short reaction time, low energy consumption and good industrial application prospect.

Description

Flame retardant and degradable PBS and preparation method thereof

technical field

The invention relates to a flame retardant and degradable and a preparation method thereof, belonging to the technical field of polymer material processing.

Background technique

Since entering the 21st century, white pollution has become more and more serious. With the improvement of living standards, people have begun to pay more and more attention to environmental issues. As an indispensable material in our daily life, plastic not only brings convenience to people, but also causes serious environmental pollution. Traditional engineering plastics such as PE, PP, PVC have been widely used in our daily life. For example, PE plastic bags can be seen everywhere in our lives, but because they are not degradable, they are difficult to decompose in nature, so they have brought serious pollution to the environment. As time goes by, environmental problems become more and more serious. Solving the problem of environmental pollution is imminent, therefore, it is necessary to find new materials to replace traditional engineering plastics.

Biodegradable material refers to a plastic that can be degraded by natural microorganisms such as bacteria, fungi, algae, enzymes, etc. It is a new type of material in the 21st century. Polybutadiene succinate (PBS) is an aliphatic polymer with good biodegradability, which can be completely degraded by natural microorganisms or enzymes. The mechanical properties of high molecular weight PBS are similar to PE and PP, with good heat resistance, chemical resistance and processability, and high mechanical strength. Due to its excellent comprehensive properties, PBS has received extensive attention in recent years, and more and more researchers have begun to study it. At present, the synthesis method of pure PBS is mainly the direct esterification method of obtaining PBS by the direct polycondensation of succinic acid and 1,4-butanediol.

Pure PBS does not have super-hydrophobicity and flame retardancy, and is flammable and easily damaged during use, which affects the scope of use. Therefore, the development of flame-retardant, degradable, and hydrophobic PBS is of great significance.

SUMMARY OF THE INVENTION

The first object of the present invention is to provide a new flame-retardant and degradable PBS.

In order to achieve the first object of the present invention, the flame-retardant and degradable PBS of the present invention is prepared by the following method:

PBS is obtained by polycondensation with succinic acid, tetrafluorosuccinic acid, 2,2,3,3-tetrafluoro-1,4-butanediol and 1,4-butanediol;

The alkyd molar ratio of succinic acid, tetrafluorosuccinic acid, 2,2,3,3-tetrafluoro-1,4-butanediol and 1,4-butanediol is 1.1-1.5:1, And tetrafluorosuccinic acid and 2,2,3,3-tetrafluoro-1,4-butanediol are not 0 at the same time.

The alkyd molar ratio of succinic acid, tetrafluorosuccinic acid, 2,2,3,3-tetrafluoro-1,4-butanediol and 1,4-butanediol is 1.1-1.5:1, That is, the molar ratio of 2,2,3,3-tetrafluoro-1,4-butanediol and 1,4-butanediol to succinic acid and tetrafluorosuccinic acid is 1.1 to 1.5:1.

In a specific embodiment, the flame-retardant and degradable PBS is prepared by the following method: PBS is obtained by polycondensation of succinic acid and 2,2,3,3-tetrafluoro-1,4-butanediol.

The alkyd molar ratio refers to the molar ratio of hydroxyl groups to carboxyl groups.

In a specific embodiment, the structural formula of the flame-retardant and degradable PBS is as follows:

n为100～180。

n is 100-180.

In a specific embodiment, the method includes:

a. Esterification: Mix succinic acid, tetrafluorosuccinic acid, 2,2,3,3-tetrafluoro-1,4-butanediol, 1,4-butanediol, catalyst, under nitrogen or inert The temperature is raised to 120-130°C under a gas atmosphere, and the reaction system is heated to 150-160°C for 1.5-2h after the reaction system becomes transparent;

b. Polycondensation: after the reaction in step a, the temperature is raised to 220-240°C, and the pressure is 0-200Pa for 3-3.5 hours to obtain flame-retardant and degradable PBS;

Preferably, it also includes first discharging the water and fluorine-containing furan by-products produced in the reaction of step a out of the reaction system, and then performing step b.

In a specific embodiment, the catalyst is a composite catalyst composed of at least one of stannous chloride or stannous octoate and p-toluenesulfonic acid monohydrate.

In a specific embodiment, the dosage of the stannous chloride or stannous octoate is 1-1.2‰ of the total molar amount of succinic acid and tetrafluorosuccinic acid; the dosage of the p-toluenesulfonic acid monohydrate It is preferably 1 to 1.5‰ of the total molar amount of succinic acid and tetrafluorosuccinic acid.

In a specific embodiment, the limiting oxygen index of the flame-retardant and degradable PBS is above 28, preferably 28-31; the contact angle is 105-110; the crystallinity is 40-43.

The second object of the present invention is to provide a method for preparing the above-mentioned flame-retardant and degradable PBS.

In order to achieve the second object of the present invention, the preparation method of the flame-retardant and degradable PBS includes:

a. Esterification: Mix succinic acid, tetrafluorosuccinic acid, 2,2,3,3-tetrafluoro-1,4-butanediol, 1,4-butanediol, catalyst, under nitrogen or inert The temperature is raised to 120-130°C under a gas atmosphere, and the reaction system is heated to 150-160°C for 1.5-2h after the reaction system becomes transparent;

b. Polycondensation: after the reaction in step a, the temperature is raised to 220 to 240 ° C, and the pressure is 0 to 200 Pa to react for 3 to 3.5 hours to obtain flame-retardant and degradable PBS;

Preferably, it also includes first discharging the water and fluorine-containing furan by-products produced in the reaction of step a out of the reaction system, and then performing step b.

In a specific embodiment, the catalyst is a composite catalyst composed of at least one of stannous chloride or stannous octoate and p-toluenesulfonic acid monohydrate.

In a specific embodiment, the dosage of the stannous chloride or stannous octoate is 1-1.2‰ of the total molar amount of succinic acid and tetrafluorosuccinic acid; the dosage of the p-toluenesulfonic acid monohydrate It is preferably 1 to 1.5‰ of the total molar amount of succinic acid and tetrafluorosuccinic acid.

Beneficial effects:

(1) The PBS of the present invention has hydrophobicity and flame retardancy.

(2) The PBS of the present invention has good biodegradability like pure PBS, which broadens the field of biodegradable plastics.

(3) The process of the invention is simple and controllable, the reaction time is short, the energy consumption is low, and the invention has a good prospect of industrial application.

Description of drawings

Figure 1 is the ¹ H-NMR chart of the product of the present invention.

Detailed ways

In order to achieve the first object of the present invention, the flame-retardant and degradable PBS of the present invention is prepared by the following method:

PBS is obtained by polycondensation with succinic acid, tetrafluorosuccinic acid, 2,2,3,3-tetrafluoro-1,4-butanediol and 1,4-butanediol;

The alkyd molar ratio of succinic acid, tetrafluorosuccinic acid, 2,2,3,3-tetrafluoro-1,4-butanediol and 1,4-butanediol is 1.1-1.5:1, And tetrafluorosuccinic acid and 2,2,3,3-tetrafluoro-1,4-butanediol are not 0 at the same time.

The alkyd molar ratio of succinic acid, tetrafluorosuccinic acid, 2,2,3,3-tetrafluoro-1,4-butanediol and 1,4-butanediol is 1.1-1.5:1, That is, the molar ratio of 2,2,3,3-tetrafluoro-1,4-butanediol and 1,4-butanediol to succinic acid and tetrafluorosuccinic acid is 1.1 to 1.5:1.

In a specific embodiment, the flame-retardant and degradable PBS is prepared by the following method: PBS is obtained by polycondensation of succinic acid and 2,2,3,3-tetrafluoro-1,4-butanediol.

The alkyd molar ratio refers to the molar ratio of hydroxyl groups to carboxyl groups.

In a specific embodiment, the structural formula of the flame-retardant and degradable PBS is as follows:

n为100～180。

n is 100-180.

In a specific embodiment, the method includes:

a. Esterification: Mix succinic acid, tetrafluorosuccinic acid, 2,2,3,3-tetrafluoro-1,4-butanediol, 1,4-butanediol, catalyst, under nitrogen or inert The temperature is raised to 120-130°C under a gas atmosphere, and the reaction system is heated to 150-160°C for 1.5-2h after the reaction system becomes transparent;

b. Polycondensation: after the reaction in step a, the temperature is raised to 220-240°C, and the pressure is 0-200Pa for 3-3.5 hours to obtain flame-retardant and degradable PBS;

Preferably, it also includes first discharging the water and fluorine-containing furan by-products produced in the reaction of step a out of the reaction system, and then performing step b.

In a specific embodiment, the catalyst is a composite catalyst composed of at least one of stannous chloride or stannous octoate and p-toluenesulfonic acid monohydrate.

In a specific embodiment, the dosage of the stannous chloride or stannous octoate is 1-1.2‰ of the total molar amount of succinic acid and tetrafluorosuccinic acid; the dosage of the p-toluenesulfonic acid monohydrate It is preferably 1 to 1.5‰ of the total molar amount of succinic acid and tetrafluorosuccinic acid.

In a specific embodiment, the limiting oxygen index of the flame-retardant and degradable PBS is above 28, preferably 28-31; the contact angle is 105-110; the crystallinity is 40-43.

The second object of the present invention is to provide a method for preparing the above-mentioned flame-retardant and degradable PBS.

In order to achieve the second object of the present invention, the preparation method of the flame-retardant and degradable PBS includes:

a. Esterification: Mix succinic acid, tetrafluorosuccinic acid, 2,2,3,3-tetrafluoro-1,4-butanediol, 1,4-butanediol, catalyst, under nitrogen or inert The temperature is raised to 120-130°C under a gas atmosphere, and the reaction system is heated to 150-160°C for 1.5-2h after the reaction system becomes transparent;

b. Polycondensation: after the reaction in step a, the temperature is raised to 220-240°C, and the pressure is 0-200Pa for 3-3.5 hours to obtain flame-retardant and degradable PBS;

Preferably, it also includes first discharging the water and fluorine-containing furan by-products produced in the reaction of step a out of the reaction system, and then performing step b.

In a specific embodiment, the catalyst is a composite catalyst composed of at least one of stannous chloride or stannous octoate and p-toluenesulfonic acid monohydrate.

In a specific embodiment, the dosage of the stannous chloride or stannous octoate is 1-1.2‰ of the total molar amount of succinic acid and tetrafluorosuccinic acid; the dosage of the p-toluenesulfonic acid monohydrate It is preferably 1 to 1.5‰ of the total molar amount of succinic acid and tetrafluorosuccinic acid.

The specific embodiments of the present invention will be further described below in conjunction with the examples, and therefore the present invention is not limited to the scope of the described examples.

Example 1

Under a nitrogen atmosphere, succinic acid, 2,2,3,3-tetrafluoro-1,4-butanediol and a catalyst were put into a reaction system equipped with a stirrer, a thermometer, a water separator and a spherical condenser, wherein The dosage of succinic acid is 2mol, the molar ratio of 2,2,3,3-tetrafluoro-1,4-butanediol to succinic acid is 1.1:1, that is, succinic acid is 236.18g, 2,2,3 ,3-tetrafluoro-1,4-butanediol is 356.58g, the catalyst dosage is SnCl ₂ ·2H ₂ O is 1‰mol of succinic acid and p-toluenesulfonic acid monohydrate is 1.5‰mol of succinic acid , the reaction is stirred under normal pressure, the temperature is first raised to 120 ° C, the reactant is melted until the system becomes transparent, and then heated to 150 ° C to start the esterification reaction, the water and by-product fluorine-containing furan generated during the reaction process are discharged from the system, and the esterification Reaction 2h, esterification reaction finishes;

Then the temperature was raised to 230°C, and the polycondensation reaction was carried out under the pressure of 100Pa. After the reaction for 3 hours, the product F-PBS- ¹ was obtained.

n为140～160。It can be seen from the figure that the structure of F-PBS-1 is

n is 140-160.

Example 2

Under nitrogen atmosphere, put succinic acid, 2,2,3,3-tetrafluoro-1,4-butanediol and catalyst into the reaction system equipped with stirrer, thermometer, water separator and spherical condenser, among which butane The amount of diacid is 2mol, and the molar ratio of 2,2,3,3-tetrafluoro-1,4-butanediol to succinic acid is 1.2:1, that is, succinic acid is 236.18g, 2,2,3, 3-tetrafluoro-1,4-butanediol is 388.99g, the catalyst dosage is SnCl ₂ ·2H ₂ O is 1‰mol of succinic acid and p-toluenesulfonic acid monohydrate is 1.5‰mol of succinic acid, The reaction was stirred under normal pressure, the temperature was first raised to 120°C, the reactants were melted until the system became transparent, and then heated to 150°C to start the esterification reaction. 2h, the esterification reaction ends;

Then, the temperature was raised to 230° C. and the polycondensation reaction was carried out under the condition of a pressure of 100 Pa. After the reaction for 3 hours, the product F-PBS-2 was obtained. Among them, n is 140～160.

Example 3

Under nitrogen atmosphere, put succinic acid, 2,2,3,3-tetrafluoro-1,4-butanediol and catalyst into the reaction system equipped with stirrer, thermometer, water separator and spherical condenser, among which butane The amount of diacid is 2mol, the molar ratio of 2,2,3,3-tetrafluoro-1,4-butanediol to succinic acid is 1.3:1, that is, succinic acid is 236.18g, 2,2,3, 3-tetrafluoro-1,4-butanediol is 421.41g, the catalyst dosage is SnCl ₂ ·2H ₂ O is 1‰mol of succinic acid and p-toluenesulfonic acid monohydrate is 1.5‰mol of succinic acid, The reaction was stirred under normal pressure, the temperature was first raised to 120°C, the reactants were melted until the system became transparent, and then heated to 150°C to start the esterification reaction. 2h, the esterification reaction ends;

Then, the temperature was raised to 230° C., and the polycondensation reaction was carried out under the condition of a pressure of 100 Pa. After the reaction for 3 hours, the product F-PBS-3 was obtained. Among them, n is 140～160.

Example 4

Under nitrogen atmosphere, put succinic acid, 2,2,3,3-tetrafluoro-1,4-butanediol and catalyst into the reaction system equipped with stirrer, thermometer, water separator and spherical condenser, among which butane The amount of diacid is 2mol, and the molar ratio of 2,2,3,3-tetrafluoro-1,4-butanediol to succinic acid is 1.4:1, that is, succinic acid is 236.18g, 2,2,3, 3-tetrafluoro-1,4-butanediol is 453.82g, the catalyst dosage is SnCl ₂ ·2H ₂ O is 1‰mol of succinic acid and p-toluenesulfonic acid monohydrate is 1.5‰mol of succinic acid, The reaction was stirred under normal pressure, the temperature was first raised to 120°C, the reactants were melted until the system became transparent, and then heated to 150°C to start the esterification reaction. 2h, the esterification reaction ends;

Then, the temperature was raised to 230° C., and the polycondensation reaction was carried out under the condition of a pressure of 100 Pa. After the reaction for 3 hours, the product F-PBS-4 was obtained. Among them, n is 140～160.

Example 5

Under nitrogen atmosphere, put succinic acid, 2,2,3,3-tetrafluoro-1,4-butanediol and catalyst into the reaction system equipped with stirrer, thermometer, water separator and spherical condenser, among which butane The amount of diacid is 2mol, and the molar ratio of 2,2,3,3-tetrafluoro-1,4-butanediol to succinic acid is 1.5:1, that is, succinic acid is 236.18g, 2,2,3, 3-tetrafluoro-1,4-butanediol is 486.24g, the catalyst dosage is SnCl ₂ ·2H ₂ O is 1‰mol of succinic acid and p-toluenesulfonic acid monohydrate is 1.5‰mol of succinic acid, The reaction was stirred under normal pressure, the temperature was first raised to 120°C, the reactants were melted until the system became transparent, and then heated to 150°C to start the esterification reaction. 2h, the esterification reaction ends;

Then the temperature was raised to 230°C, and the polycondensation reaction was carried out under the condition of a pressure of 100Pa. After the reaction for 3 hours, the product F-PBS-5 was obtained. Among them, n is 140～160.

Comparative Example 1

Under nitrogen atmosphere, put succinic acid, 1,4-butanediol and catalyst into the reaction system equipped with stirrer, thermometer, water separator and spherical condenser, wherein the consumption of succinic acid is 2mol, 1,4- The molar ratio of butanediol and succinic acid is 1.3:1, that is, succinic acid is 236.18g, 1,4-butanediol is 234.31g, and the catalyst dosage is SnCl ₂ ·2H ₂ O is 1‰mol of succinic acid and p-toluenesulfonic acid monohydrate is 1.5‰mol of succinic acid, and the reaction is stirred under normal pressure. The temperature first rises to 120 ° C, the reactant melts until the system becomes transparent, and then heated to 150 ° C to start the esterification reaction, the reaction The water and by-product tetrahydrofuran generated in the process are discharged from the system, and the esterification reaction is 2h, and the esterification reaction ends;

Then the temperature was raised to 230° C., and the polycondensation reaction was carried out under the condition of a pressure of 100 Pa. After the reaction for 3 hours, the product pure PBS was obtained.

The crystallinity of the fluorine-containing PBS obtained in Examples 1-5 of the present invention are 42.3, 41.5, 40.6, 40.8, and 42.1, respectively, and have good biodegradability. The crystallinity of pure PBS prepared in Comparative Example 1 was 41. The intrinsic viscosity results of Examples 1-5 and Comparative Example 1 are shown in Table 1 below:

Table 1 Intrinsic Viscosity of Examples 1-5 and Pure PBS

polymer Alkyd ratio [η]/dL/g PBS 1.3:1 1.03 F-PBS-1 1.1:1 0.64 F-PBS-2 1.2:1 0.68 F-PBS-3 1.3:1 0.78 F-PBS-4 1.4:1 0.86 F-PBS-5 1.5:1 0.80

The above intrinsic viscosity test: use chloroform as a solvent to prepare a PBS or PBS/HTPB solution with a concentration of 0.5g/dL, and use an Ubbelohde viscometer with an inner diameter of 0.38mm to measure at 25°C. The experimental results are calculated using the "one-point method":

In the formula, t and t ₀ are the outflow time of the polymer solution and the pure solvent, respectively; C is the concentration of the polymer solution.

The pure PBS limiting oxygen index results of Examples 1-5 and Comparative Example 1 are shown in Table 2 below:

Table 2 Limiting oxygen index of pure PBS of Examples 1-5 and Comparative Example 1

polymer Alkyd ratio Limiting Oxygen Index (LOI) % PBS 1.3:1 20.5 F-PBS-1 1.1:1 29.2 F-PBS-2 1.2:1 28.8 F-PBS-3 1.3:1 29.6 F-PBS-4 1.4:1 30.2 F-PBS-5 1.5:1 29.7

The contact angle test results of Examples 1-5 and pure PBS are shown in Table 3 below:

The contact angle test result of table 3 embodiment 1-5 and comparative example 1 pure PBS

polymer Alkyd ratio Contact angle (°) PBS 1.3:1 91.5 F-PBS-1 1.1:1 105.3 F-PBS-2 1.2:1 106.2 F-PBS-3 1.3:1 108.8 F-PBS-4 1.4:1 109.6 F-PBS-5 1.5:1 107.5

The crystallinity of the pure PBS of Examples 1-5 and Comparative Example 1 is shown in Table 4 below:

Table 4 Crystallinity of pure PBS of Examples 1-5 and Comparative Example 1

polymer Alkyd ratio Crystallinity/% PBS 1.3:1 41 F-PBS-1 1.1:1 42.3 F-PBS-2 1.2:1 41.5 F-PBS-3 1.3:1 40.6 F-PBS-4 1.4:1 40.8 F-PBS-5 1.5:1 42.1

The biodegradation properties of the pure PBS of Examples 1-5 and Comparative Example 1 are shown in Table 5 below:

Table 5 Biodegradation properties of pure PBS of Examples 1-5 and Comparative Example 1

polymer Alkyd ratio Mass before burying in soil/g Take out mass/g after 30 days PBS 1.3:1 10.0 9.53 F-PBS-1 1.1:1 10.0 9.56 F-PBS-2 1.2:1 10.0 9.51 F-PBS-3 1.3:1 10.0 9.53 F-PBS-4 1.4:1 10.0 9.48 F-PBS-5 1.5:1 10.0 9.53

The biodegradation performance test is to bury 10g of the sample in the soil, take it out after 30 days, wash it, dry it, and weigh it.

Claims (14)

1. flame retardant degradable PBS, is characterized in that, described flame retardant degradable PBS adopts following method to prepare: PBS is obtained by polycondensation with succinic acid, tetrafluorosuccinic acid, 2,2,3,3-tetrafluoro-1,4-butanediol and 1,4-butanediol; The alkyd molar ratio of succinic acid, tetrafluorosuccinic acid, 2,2,3,3-tetrafluoro-1,4-butanediol and 1,4-butanediol is 1.1-1.5:1, And tetrafluorosuccinic acid and 2,2,3,3-tetrafluoro-1,4-butanediol are not 0 at the same time. 2. The flame-retardant and degradable PBS according to claim 1, wherein the flame-retardant and degradable PBS is prepared by the following method: with succinic acid, 2,2,3,3-tetrafluoro-1, 4-Butanediol was polycondensed to obtain PBS. 3. fire-retardant degradable PBS according to claim 1, is characterized in that, the structural formula of described fire-retardant and degradable PBS is as follows:

n is 100-180. 4. The flame-retardant and degradable PBS according to any one of claims 1 to 3, wherein the method comprises: a. Esterification: Mix succinic acid, tetrafluorosuccinic acid, 2,2,3,3-tetrafluoro-1,4-butanediol, 1,4-butanediol, catalyst, under nitrogen or inert The temperature is raised to 120-130°C under a gas atmosphere, and the reaction system is heated to 150-160°C for 1.5-2h after the reaction system becomes transparent; b. Polycondensation: after the reaction in step a, the temperature is raised to 220-240° C. and the pressure is 0-200 Pa to react for 3-3.5 hours to obtain flame-retardant and degradable PBS. 5 . The flame-retardant and degradable PBS according to claim 4 , wherein the method further comprises first discharging the water and fluorine-containing furan by-products produced by the reaction of step a from the reaction system and then performing step b. 6 . 6 . The flame-retardant and degradable PBS according to claim 4 , wherein the catalyst is a composite catalyst composed of at least one of stannous chloride or stannous octoate and p-toluenesulfonic acid monohydrate. 7 . 7 . The flame-retardant and degradable PBS according to claim 6 , wherein the amount of stannous chloride or stannous octoate is 1-1.2‰ of the total molar amount of succinic acid and tetrafluorosuccinic acid. 8 . 8 . The flame-retardant and degradable PBS according to claim 7 , wherein the amount of the p-toluenesulfonic acid monohydrate is 1-1.5‰ of the total molar amount of succinic acid and tetrafluorosuccinic acid. 9 . 9 . The flame-retardant and degradable PBS according to claim 1 or 2 , wherein the limiting oxygen index of the flame-retardant and degradable PBS is 28-31; the contact angle is 105-110; and the crystallinity is 40-43. 10 . 10. The method for preparing flame-retardant and degradable PBS according to any one of claims 1 to 9, wherein the method comprises: a. Esterification: Mix succinic acid, tetrafluorosuccinic acid, 2,2,3,3-tetrafluoro-1,4-butanediol, 1,4-butanediol, catalyst, under nitrogen or inert The temperature is raised to 120-130°C under a gas atmosphere, and the reaction system is heated to 150-160°C for 1.5-2h after the reaction system becomes transparent; b. Polycondensation: after the reaction in step a, the temperature is raised to 220-240° C. and the pressure is 0-200 Pa to react for 3-3.5 hours to obtain flame-retardant and degradable PBS. 11. The preparation method of flame-retardant and degradable PBS according to claim 10, characterized in that, the method further comprises performing step b after first discharging the water and the fluorine-containing furan by-product produced in the reaction of step a from the reaction system. . 12. The preparation method of flame-retardant degradable PBS according to claim 10, wherein the catalyst is a composite of at least one of stannous chloride or stannous octoate and p-toluenesulfonic acid monohydrate. catalyst. 13. The preparation method of flame-retardant and degradable PBS according to claim 12, wherein the consumption of the stannous chloride or stannous octoate is 1～10% of the total molar amount of succinic acid and tetrafluorosuccinic acid. 1.2‰. 14 . The method for preparing flame-retardant and degradable PBS according to claim 13 , wherein the amount of the p-toluenesulfonic acid monohydrate is 1-1.5 of the total molar amount of succinic acid and tetrafluorosuccinic acid. 15 . ‰.

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