阻燃可降解pbs及其制备方法

Flame-retardant degradable PBS and preparation method thereof

文档序号：2704 发布日期：2021-09-17 浏览：59次中文

1. The flame-retardant degradable PBS is characterized by being 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.

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:

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 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 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.

5. 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.

6. The flame-retardant degradable PBS according to claim 5, 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; 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.

7. The flame-retardant degradable PBS according to any one of claims 1 to 6, wherein the flame-retardant degradable PBS has a limiting oxygen index of 28 or more, preferably 28 to 31; the contact angle is 105-110; the crystallinity is 40 to 43.

8. The method for preparing the flame-retardant degradable PBS according to any one of claims 1 to 7, wherein the method comprises the following steps:

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.

9. The method for preparing flame-retardant degradable PBS according to claim 8, wherein the catalyst is a composite catalyst consisting of at least one of stannous chloride or stannous octoate and p-toluenesulfonic acid monohydrate.

10. The preparation method of the flame-retardant degradable PBS according to claim 5, wherein the amount of the stannous chloride or stannous octoate is 1-1.2 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.

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 the plastic is an indispensable material in daily life, the 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 over time. The solution to the environmental pollution problem is urgent, and therefore, new materials 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 is mainly a direct esterification method for obtaining PBS by direct polycondensation of 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 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:

n is 100 to 180.

In one embodiment, the method comprises:

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 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; the contact angle is 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:

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.

Has the advantages 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 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:

n is 100 to 180。

In one embodiment, the method comprises:

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 limited oxygen index of the flame-retardant degradable PBS is more than 28, preferably 28-31; the contact angle is 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:

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.

The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.

Example 1

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 1.1: 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 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;

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 3h¹The H-NMR chart is shown in detail in FIG. 1.

As can be seen from the figure, the structure of F-PBS-1 isn is 140 to 160.

Example 2

Atmosphere of nitrogenThen, 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 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 1.2: 1, namely 236.18g of 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

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 1.3: 1, namely 236.18g of succinic acid, 421.41g 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-3. Wherein n is 140 to 160.

Example 4

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 pipe under the atmosphere of nitrogen, wherein the dosage of the succinic acid is 2mol, 2,2,the molar ratio of the 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, namely 236.18g of succinic acid, 486.24g 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-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: 1, i.e. 236.18g of succinic acid, 234.31g of 1, 4-butanediol, SnCl as catalyst₂·2H₂O is 1 thousandth mol of succinic acid and p-toluenesulfonic acid monohydrateStirring the mixture to react at the normal pressure, wherein the temperature is 1.5 thousandth mol of succinic acid, the stirring reaction is carried out at the normal pressure, the temperature is firstly increased to 120 ℃, reactants are melted until a system becomes transparent, then the system is heated to 150 ℃, esterification reaction is started, water and a byproduct tetrahydrofuran generated in the reaction process 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 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":

in the formula, t and t₀Respectively the flow-out time of the polymer solution and the pure solvent; 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	Limit 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 results of the contact angle test of examples 1-5 with pure PBS are shown in Table 3 below:

TABLE 3 contact Angle test results for 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 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 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 method of making 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.

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