CN113402702B - Flame-retardant degradable PBS and preparation method thereof - Google Patents
Flame-retardant degradable PBS and preparation method thereof Download PDFInfo
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000003063 flame retardant Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 112
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000001384 succinic acid Substances 0.000 claims abstract description 42
- YUDUFRYTKFGQCL-UHFFFAOYSA-N 2,2,3,3-tetrafluorobutanedioic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(O)=O YUDUFRYTKFGQCL-UHFFFAOYSA-N 0.000 claims abstract description 34
- CDZXJJOGDCLNKX-UHFFFAOYSA-N 2,2,3,3-tetrafluorobutane-1,4-diol Chemical compound OCC(F)(F)C(F)(F)CO CDZXJJOGDCLNKX-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 29
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims abstract description 28
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 16
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 238000010438 heat treatment Methods 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 30
- 238000005886 esterification reaction Methods 0.000 claims description 25
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 23
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 12
- 239000006227 byproduct Substances 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 239000011737 fluorine Substances 0.000 claims description 12
- 235000011150 stannous chloride Nutrition 0.000 claims description 12
- 239000001119 stannous chloride Substances 0.000 claims description 12
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 12
- 230000032050 esterification Effects 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000012643 polycondensation polymerization Methods 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 9
- 229920000704 biodegradable plastic Polymers 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical group [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- -1 Poly butylenes Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 2
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
- C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6826—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2230/00—Compositions for preparing biodegradable polymers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
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
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:
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:
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.
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":
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.
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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