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

Flame-retardant degradable PBS and preparation method thereof Download PDF

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CN113402702B
CN113402702B CN202110794585.9A CN202110794585A CN113402702B CN 113402702 B CN113402702 B CN 113402702B CN 202110794585 A CN202110794585 A CN 202110794585A CN 113402702 B CN113402702 B CN 113402702B
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pbs
butanediol
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succinic acid
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CN113402702A (en
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钟家春
侯洪波
李贤勇
蒲泽军
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Sichuan Xinghuiteng Group Co ltd
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Sichuan University of Science and Engineering
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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 degradable PBS and preparation method thereof
Technical Field
The invention relates to a flame-retardant degradable material and a preparation method thereof, belonging to the technical field of high polymer material processing.
Background
White pollution has become more and more serious since the 21 st century. With the improvement of living standard, people begin to pay more attention to environmental issues. As an indispensable material in our daily life, plastic brings convenience to people and causes serious environmental pollution. Traditional engineering plastics such as PE, PP and PVC are widely applied in daily life. Such as PE plastic bags, are found everywhere in our lives, but because they are not degradable, they are difficult to decompose in nature, thus causing serious pollution to the environment. Environmental problems become more and more serious with the lapse of time. The problem of environmental pollution is urgently solved, and therefore, a new material must be found to replace the conventional engineering plastics.
The biodegradable material is a plastic which can be degraded by bacteria, fungi, algae, enzyme and other natural microorganisms, and is a novel material in the 21 st century. Poly (butylene succinate) (PBS) is an aliphatic polymer with good biodegradability, and can be completely degraded by natural microorganisms or enzymes. The mechanical property of the high molecular weight PBS is similar to that of PE and PP, and the PBS has good heat resistance, chemical corrosion resistance and processability and higher mechanical strength. PBS has received much attention in recent years due to its excellent overall properties, and more researchers have begun to research. At present, the synthesis method of pure PBS mainly adopts a direct esterification method for obtaining PBS by directly polycondensing succinic acid and 1, 4-butanediol.
Pure PBS does not have super-hydrophobic and flame retardant properties, is easily combustible and damaged in the using process, and therefore the using range is influenced to a certain extent. Therefore, the development of flame-retardant, degradable and hydrophobic PBS has very important significance.
Disclosure of Invention
The first purpose of the invention is to provide a novel flame-retardant degradable PBS.
In order to achieve the first object of the invention, the flame-retardant degradable PBS is prepared by the following method:
carrying out polycondensation on succinic acid, tetrafluorosuccinic acid, 2,3, 3-tetrafluoro-1, 4-butanediol and 1, 4-butanediol to obtain PBS (Poly butylenes succinate);
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 molar ratio of the succinic acid to the tetrafluorosuccinic acid to the alcohol acid of the 2,2,3, 3-tetrafluoro-1, 4-butanediol and the 1, 4-butanediol is 1.1-1.5: 1, namely the molar ratio of the 2,2,3, 3-tetrafluoro-1, 4-butanediol and the 1, 4-butanediol to the succinic acid and the tetrafluorosuccinic acid is 1.1-1.5: 1.
In a specific embodiment, the flame-retardant degradable PBS is prepared by the following method: the PBS is obtained by condensation polymerization of succinic acid and 2,2,3, 3-tetrafluoro-1, 4-butanediol.
The molar ratio of the alkyd refers to the molar ratio of hydroxyl groups to carboxyl groups.
In one embodiment, the flame retardant degradable PBS has the following structural formula:
Figure BDA0003162408170000021
Figure BDA0003162408170000022
n is 100 to 180.
In one embodiment, the method comprises:
a. esterification: mixing succinic acid, tetrafluorosuccinic acid, 2,3, 3-tetrafluoro-1, 4-butanediol, 1, 4-butanediol and a catalyst, heating to 120-130 ℃ in a nitrogen or inert gas atmosphere, heating to 150-160 ℃ after a reaction system becomes transparent, and reacting for 1.5-2 hours;
b. polycondensation: after the reaction in the step a is finished, heating to 220-240 ℃, and reacting for 3-3.5 h under the condition that the pressure is 0-200 Pa to obtain the flame-retardant degradable PBS;
preferably, the method also comprises the step b after water produced by the reaction in the step a and a fluorine-containing furan by-product are discharged out of the reaction system.
In one 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 amount of the stannous chloride or stannous octoate is 1 to 1.2 per mill of the total molar amount of succinic acid and tetrafluorosuccinic acid; the dosage of the p-toluenesulfonic acid monohydrate is preferably 1-1.5 per mill of the total molar amount of succinic acid and tetrafluorosuccinic acid.
In a specific embodiment, the limited oxygen index of the flame-retardant degradable PBS is more than 28, preferably 28-31; contact angles of 105-110; the crystallinity is 40 to 43.
The second purpose of the invention is to provide a preparation method of the flame-retardant degradable PBS.
In order to achieve the second object of the invention, the preparation method of the flame-retardant degradable PBS comprises the following steps:
a. esterification: mixing succinic acid, tetrafluorosuccinic acid, 2,3, 3-tetrafluoro-1, 4-butanediol, 1, 4-butanediol and a catalyst, heating to 120-130 ℃ in the atmosphere of nitrogen or inert gas, heating to 150-160 ℃ after a reaction system becomes transparent, and reacting for 1.5-2 h;
b. polycondensation: after the reaction in the step a is finished, heating to 220-240 ℃, and reacting for 3-3.5 h under the condition that the pressure is 0-200 Pa to obtain the flame-retardant degradable PBS;
preferably, the method further comprises the step b after the water and the fluorine-containing furan by-product generated in the step a are discharged out of the reaction system.
In one 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 amount of the stannous chloride or stannous octoate is 1 to 1.2 per mill of the total molar amount of succinic acid and tetrafluorosuccinic acid; the dosage of the p-toluenesulfonic acid monohydrate is preferably 1-1.5 permillage of the total molar amount of the succinic acid and the tetrafluorosuccinic acid.
Has the beneficial effects that:
(1) the PBS of the present invention is hydrophobic and flame retardant.
(2) The PBS of the invention has good biodegradability like pure PBS, which widens the field of biodegradable plastics.
(3) The method has the advantages of simple and controllable process, short reaction time, low energy consumption and good industrial application prospect.
Drawings
FIG. 1 shows the product of the invention1H-NMR chart.
Detailed Description
In order to achieve the first object of the invention, the flame-retardant degradable PBS is prepared by the following method:
carrying out polycondensation on succinic acid, tetrafluorosuccinic acid, 2,3, 3-tetrafluoro-1, 4-butanediol and 1, 4-butanediol to obtain PBS (Poly butylenes succinate);
the molar ratio of the succinic acid to the tetrafluorosuccinic acid to 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 molar ratio of the succinic acid to the tetrafluorosuccinic acid to the alcohol acid of the 2,2,3, 3-tetrafluoro-1, 4-butanediol and the 1, 4-butanediol is 1.1-1.5: 1, namely the molar ratio of the 2,2,3, 3-tetrafluoro-1, 4-butanediol and the 1, 4-butanediol to the succinic acid and the tetrafluorosuccinic acid is 1.1-1.5: 1.
In a specific embodiment, the flame-retardant degradable PBS is prepared by the following method: the PBS is obtained by condensation polymerization of succinic acid and 2,2,3, 3-tetrafluoro-1, 4-butanediol.
The molar ratio of the alkyd refers to the molar ratio of hydroxyl groups to carboxyl groups.
In one embodiment, the flame retardant degradable PBS has the following structural formula:
Figure BDA0003162408170000031
Figure BDA0003162408170000041
Figure BDA0003162408170000042
n is 100 to 180.
In one embodiment, the method comprises:
a. esterification: mixing succinic acid, tetrafluorosuccinic acid, 2,3, 3-tetrafluoro-1, 4-butanediol, 1, 4-butanediol and a catalyst, heating to 120-130 ℃ in a nitrogen or inert gas atmosphere, heating to 150-160 ℃ after a reaction system becomes transparent, and reacting for 1.5-2 hours;
b. and (3) polycondensation: after the reaction in the step a is finished, heating to 220-240 ℃, and reacting for 3-3.5 hours under the condition that the pressure is 0-200 Pa to obtain the flame-retardant degradable PBS;
preferably, the method also comprises the step b after water produced by the reaction in the step a and a fluorine-containing furan by-product are discharged out of the reaction system.
In one 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 amount of the stannous chloride or stannous octoate is 1 to 1.2 per mill of the total molar amount of succinic acid and tetrafluorosuccinic acid; the dosage of the p-toluenesulfonic acid monohydrate is preferably 1-1.5 per mill of the total molar amount of succinic acid and tetrafluorosuccinic acid.
In a specific embodiment, the limiting oxygen index of the flame-retardant degradable PBS is more than 28, preferably 28-31; contact angles of 105-110; the crystallinity is 40 to 43.
The second purpose of the invention is to provide a preparation method of the flame-retardant degradable PBS.
In order to achieve the second object of the invention, the preparation method of the flame-retardant degradable PBS comprises the following steps:
a. esterification: mixing succinic acid, tetrafluorosuccinic acid, 2,3, 3-tetrafluoro-1, 4-butanediol, 1, 4-butanediol and a catalyst, heating to 120-130 ℃ in the atmosphere of nitrogen or inert gas, heating to 150-160 ℃ after a reaction system becomes transparent, and reacting for 1.5-2 h;
b. and (3) polycondensation: after the reaction in the step a is finished, heating to 220-240 ℃, and reacting for 3-3.5 h under the condition that the pressure is 0-200 Pa to obtain the flame-retardant degradable PBS;
preferably, the method further comprises the step b after the water and the fluorine-containing furan by-product generated in the step a are discharged out of the reaction system.
In one embodiment, the catalyst is a composite catalyst comprised of p-toluenesulfonic acid monohydrate and at least one of stannous chloride or stannous octoate.
In a specific embodiment, the amount of the stannous chloride or stannous octoate is 1 to 1.2 permillage of the total molar amount of the succinic acid and the tetrafluorosuccinic acid; the dosage of the p-toluenesulfonic acid monohydrate is preferably 1-1.5 per mill of the total molar amount of succinic acid and tetrafluorosuccinic acid.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the invention to the embodiments described.
Example 1
Adding succinic acid, 2,3, 3-tetrafluoro-1, 4-butanediol and spherical condenser into a reaction system provided with a stirrer, a thermometer, a water separator and a spherical condenser pipe in a nitrogen atmosphereThe catalyst comprises 2mol of succinic acid, wherein the molar ratio of 2,2,3, 3-tetrafluoro-1, 4-butanediol to succinic acid is 1.1: 1, namely 236.18g of succinic acid, 356.58g of 2,2,3, 3-tetrafluoro-1, 4-butanediol, and the dosage of the catalyst is SnCl2·2H2O is 1 per mill mol of succinic acid and p-toluenesulfonic acid monohydrate is 1.5 per mill mol of succinic acid, stirring and reacting are carried out under normal pressure, the temperature is firstly raised to 120 ℃, reactants are melted until the system becomes transparent, then heating is carried out to 150 ℃, esterification reaction is started, water generated in the reaction process and fluorine-containing furan serving as a byproduct are discharged out of the system, the esterification reaction is carried out for 2 hours, and the esterification reaction is finished;
then heating to 230 ℃, carrying out polycondensation reaction under the pressure of 100Pa, and obtaining the product F-PBS-1, F-PBS-1 after reaction for 3 hours1The H-NMR chart is shown in detail in FIG. 1.
It can be seen that the structure of F-PBS-1 is
Figure BDA0003162408170000051
n is 140 to 160.
Example 2
Under the nitrogen atmosphere, adding succinic acid, 2,2,3, 3-tetrafluoro-1, 4-butanediol and a catalyst into a reaction system provided with a stirrer, a thermometer, a water separator and a spherical condenser, wherein the using amount of the succinic acid is 2mol, and the molar ratio of the 2,2,3, 3-tetrafluoro-1, 4-butanediol to the succinic acid is 1.2: 236.18g of 1, namely succinic acid, 388.99g of 2,2,3, 3-tetrafluoro-1, 4-butanediol, and the dosage of the catalyst is SnCl2·2H2O is 1 thousandth mol of succinic acid and p-toluenesulfonic acid monohydrate is 1.5 thousandth mol of succinic acid, stirring and reacting under normal pressure, heating to 120 ℃ at first, melting reactants until the system becomes transparent, heating to 150 ℃, starting esterification reaction, discharging water and by-product fluorine-containing furan generated in the reaction process out of the system, carrying out esterification reaction for 2 hours, and finishing the esterification reaction;
and then heating to 230 ℃, carrying out polycondensation reaction under the pressure of 100Pa, and reacting for 3h to obtain a product F-PBS-2. Wherein n is 140 to 160.
Example 3
In the nitrogen atmosphere, a reaction system provided with a stirrer, a thermometer, a water separator and a spherical condenser pipe is fedAdding succinic acid, 2,2,3, 3-tetrafluoro-1, 4-butanediol and a catalyst, wherein the dosage of the succinic acid is 2mol, and the molar ratio of the 2,2,3, 3-tetrafluoro-1, 4-butanediol to the succinic acid is 1.3: 236.18g of 1, namely succinic acid, 421.41g of 2,2,3, 3-tetrafluoro-1, 4-butanediol, and the dosage of the catalyst is SnCl2·2H2O is 1 per mill mol of succinic acid and p-toluenesulfonic acid monohydrate is 1.5 per mill mol of succinic acid, stirring and reacting are carried out under normal pressure, the temperature is firstly raised to 120 ℃, reactants are melted until the system becomes transparent, then heating is carried out to 150 ℃, esterification reaction is started, water generated in the reaction process and fluorine-containing furan serving as a byproduct are discharged out of the system, the esterification reaction is carried out for 2 hours, and the esterification reaction is finished;
and then heating to 230 ℃, carrying out polycondensation reaction under the pressure of 100Pa, and reacting for 3h to obtain a product F-PBS-3. Wherein n is 140 to 160.
Example 4
Under the nitrogen atmosphere, adding succinic acid, 2,2,3, 3-tetrafluoro-1, 4-butanediol and a catalyst into a reaction system provided with a stirrer, a thermometer, a water separator and a spherical condenser, wherein the using amount of the succinic acid is 2mol, and the molar ratio of the 2,2,3, 3-tetrafluoro-1, 4-butanediol to the succinic acid is 1.4: 1, namely 236.18g of succinic acid, 453.82g of 2,2,3, 3-tetrafluoro-1, 4-butanediol, and the dosage of the catalyst is SnCl2·2H2O is 1 thousandth mol of succinic acid and p-toluenesulfonic acid monohydrate is 1.5 thousandth mol of succinic acid, stirring and reacting under normal pressure, heating to 120 ℃ at first, melting reactants until the system becomes transparent, heating to 150 ℃, starting esterification reaction, discharging water and by-product fluorine-containing furan generated in the reaction process out of the system, carrying out esterification reaction for 2 hours, and finishing the esterification reaction;
and then heating to 230 ℃, carrying out polycondensation reaction under the pressure of 100Pa, and reacting for 3h to obtain a product F-PBS-4. Wherein n is 140 to 160.
Example 5
Under the nitrogen atmosphere, adding succinic acid, 2,2,3, 3-tetrafluoro-1, 4-butanediol and a catalyst into a reaction system provided with a stirrer, a thermometer, a water separator and a spherical condenser, wherein the using amount of the succinic acid is 2mol, and the molar ratio of the 2,2,3, 3-tetrafluoro-1, 4-butanediol to the succinic acid is 1.5:1 i.e. succinic acid 236.18g486.24g of 2,2,3, 3-tetrafluoro-1, 4-butanediol, and the amount of catalyst used is SnCl2·2H2O is 1 per mill mol of succinic acid and p-toluenesulfonic acid monohydrate is 1.5 per mill mol of succinic acid, stirring and reacting are carried out under normal pressure, the temperature is firstly raised to 120 ℃, reactants are melted until the system becomes transparent, then heating is carried out to 150 ℃, esterification reaction is started, water generated in the reaction process and fluorine-containing furan serving as a byproduct are discharged out of the system, the esterification reaction is carried out for 2 hours, and the esterification reaction is finished;
and then heating to 230 ℃, carrying out polycondensation reaction under the pressure of 100Pa, and reacting for 3h to obtain a product F-PBS-5. Wherein n is 140 to 160.
Comparative example 1
Under the nitrogen atmosphere, adding succinic acid, 1, 4-butanediol and a catalyst into a reaction system provided with a stirrer, a thermometer, a water separator and a spherical condenser, wherein the using amount of the succinic acid is 2mol, and the molar ratio of the 1, 4-butanediol to the succinic acid is 1.3: 236.18g of 1, namely succinic acid, 234.31g of 1, 4-butanediol, and the using amount of the catalyst is SnCl2·2H2O is 1 permillage mol of succinic acid and p-toluenesulfonic acid monohydrate is 1.5 permillage mol of succinic acid, stirring and reacting are carried out under normal pressure, the temperature is firstly raised to 120 ℃, reactants are melted until the system becomes transparent, then heating is carried out to 150 ℃, esterification reaction is started, water and by-product tetrahydrofuran generated in the reaction process are discharged out of the system, the esterification reaction lasts for 2 hours, and the esterification reaction is finished;
and then heating to 230 ℃, carrying out polycondensation reaction under the condition of 100Pa, and reacting for 3h to obtain the product of pure PBS.
The fluorine-containing PBS obtained in the embodiments 1 to 5 of the invention has the crystallinity of 42.3, 41.5, 40.6, 40.8 and 42.1 respectively, and has good biodegradability. Comparative example 1 the pure PBS prepared had a crystallinity of 41. The intrinsic viscosity results for examples 1-5 and comparative example 1 are shown in table 1 below:
TABLE 1 intrinsic viscosity of examples 1-5 with neat PBS
Polymer and method of making same Alcohol to acid 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: PBS or PBS/HTPB solution with a concentration of 0.5g/dL was prepared using chloroform as a solvent and measured at 25 ℃ using an Ubbelohde viscometer with an inner diameter of 0.38 mm. The experimental results were calculated by the "one-point method":
Figure RE-GDA0003219820320000071
in the formula, t and t0The flow-out 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 for 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 and method of making same Alcohol to acid 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 with pure PBS are shown in Table 3 below:
TABLE 3 contact Angle test results of examples 1-5 and comparative example 1 pure PBS
Polymer and method of making same Alcohol to acid 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 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 and method of making same Alcohol to acid ratio Degree of crystallization/%)
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 biodegradability of the pure PBS of examples 1-5 and comparative example 1 is shown in table 5 below:
TABLE 5 biodegradability of pure PBS of examples 1-5 and comparative example 1
Polymer and process for producing the same Alcohol to acid ratio Mass/g before burying in soil The mass/g is taken out 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 sample in soil, take out after 30 days, clean, dry and weigh the mass.

Claims (14)

1. The flame-retardant degradable PBS is characterized by being 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 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.
2. The flame-retardant degradable PBS according to claim 1, wherein the flame-retardant degradable PBS is prepared by the following method: the PBS is obtained by condensation polymerization of succinic acid and 2,2,3, 3-tetrafluoro-1, 4-butanediol.
3. The flame-retardant degradable PBS according to claim 1, wherein the flame-retardant degradable PBS has the following structural formula:
Figure FDA0003673772650000011
Figure FDA0003673772650000012
n is 100 to 180.
4. The flame-retardant degradable PBS according to any one of claims 1 to 3, wherein the method comprises:
a. esterification: mixing succinic acid, tetrafluorosuccinic acid, 2,3, 3-tetrafluoro-1, 4-butanediol, 1, 4-butanediol and a catalyst, heating to 120-130 ℃ in the atmosphere of nitrogen or inert gas, heating to 150-160 ℃ after a reaction system becomes transparent, and reacting for 1.5-2 h;
b. and (3) polycondensation: and c, after the reaction in the step a is finished, heating to 220-240 ℃, and reacting for 3-3.5 hours under the condition that the pressure is 0-200 Pa to obtain the flame-retardant degradable PBS.
5. The flame-retardant degradable PBS according to claim 4, wherein the method further comprises the step b after the water produced by the reaction in the step a and the fluorine-containing furan by-product are discharged out of the reaction system.
6. The flame-retardant and degradable PBS according to claim 4, wherein the catalyst is a composite catalyst consisting of at least one of stannous chloride or stannous octoate and p-toluenesulfonic acid monohydrate.
7. The flame-retardant degradable PBS according to claim 6, wherein the amount of the stannous chloride or stannous octoate is 1-1.2 ‰ of the molar total amount of succinic acid and tetrafluorosuccinic acid.
8. The flame-retardant degradable PBS according to claim 7, wherein the p-toluenesulfonic acid monohydrate is used in an amount of 1 to 1.5% o based on the molar total amount of the succinic acid and the tetrafluorosuccinic acid.
9. The flame-retardant degradable PBS according to claim 1 or 2, wherein the flame-retardant degradable PBS has a limiting oxygen index of 28-31; contact angles of 105-110; the crystallinity is 40 to 43.
10. The method for preparing the flame-retardant degradable PBS according to any one of claims 1 to 9, wherein the method comprises the following steps:
a. esterification: mixing succinic acid, tetrafluorosuccinic acid, 2,3, 3-tetrafluoro-1, 4-butanediol, 1, 4-butanediol and a catalyst, heating to 120-130 ℃ in a nitrogen or inert gas atmosphere, heating to 150-160 ℃ after a reaction system becomes transparent, and reacting for 1.5-2 hours;
b. polycondensation: and c, after the reaction in the step a is finished, heating to 220-240 ℃, and reacting for 3-3.5 hours under the condition that the pressure is 0-200 Pa to obtain the flame-retardant degradable PBS.
11. The method for preparing flame-retardant degradable PBS according to claim 10, wherein the method further comprises the step b after water produced by the reaction in the step a and the fluorine-containing furan by-product are discharged out of the reaction system.
12. The method for preparing flame-retardant degradable PBS according to claim 10, wherein the catalyst is a composite catalyst consisting of at least one of stannous chloride or stannous octoate and p-toluenesulfonic acid monohydrate.
13. The preparation method of the flame-retardant degradable PBS according to claim 12, wherein the amount of the stannous chloride or stannous octoate is 1-1.2 ‰ of the molar total amount of succinic acid and tetrafluorosuccinic acid.
14. The method for preparing flame-retardant and degradable PBS according to claim 13, wherein the dosage of the p-toluenesulfonic acid monohydrate is 1-1.5% of the total molar amount of the succinic acid and the tetrafluorosuccinic acid.
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