CN112225895A - Flame-retardant aromatic polyoxadiazole polymer and preparation method thereof - Google Patents
Flame-retardant aromatic polyoxadiazole polymer and preparation method thereof Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 44
- 239000003063 flame retardant Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 34
- TVOZCMWRGNCDIY-UHFFFAOYSA-N 4-[4-[[1-(4-carboxyphenyl)piperidin-4-yl]-phenylphosphoryl]piperidin-1-yl]benzoic acid Chemical compound C1(=CC=CC=C1)P(=O)(C1CCN(CC1)C1=CC=C(C(=O)O)C=C1)C1CCN(CC1)C1=CC=C(C(=O)O)C=C1 TVOZCMWRGNCDIY-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 18
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012493 hydrazine sulfate Substances 0.000 claims abstract description 15
- 229910000377 hydrazine sulfate Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 8
- 239000011550 stock solution Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000000835 fiber Substances 0.000 claims description 17
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 9
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 9
- 239000005711 Benzoic acid Substances 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 235000010233 benzoic acid Nutrition 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- XDCLOVOOEKUJBK-UHFFFAOYSA-N 4-piperidin-1-ium-4-ylbenzoate Chemical compound C1=CC(C(=O)O)=CC=C1C1CCNCC1 XDCLOVOOEKUJBK-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- -1 (phenylphosphoryl) bis (piperidine-4, 1-diyl) Chemical group 0.000 claims description 2
- 238000004587 chromatography analysis Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 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 abstract description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 9
- 239000011574 phosphorus Substances 0.000 abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 239000007833 carbon precursor Substances 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000012772 electrical insulation material Substances 0.000 abstract 1
- 238000009987 spinning Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006210 cyclodehydration reaction Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/08—Polyhydrazides; Polytriazoles; Polyaminotriazoles; Polyoxadiazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/59—Hydrogenated pyridine rings
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
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- Health & Medical Sciences (AREA)
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- Medicinal Chemistry (AREA)
- Textile Engineering (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a flame-retardant aromatic polyoxadiazole polymer and a preparation method thereof, wherein the flame-retardant aromatic polyoxadiazole polymer comprises the following steps: preparing 4,4' - ((phenylphosphoryl) bis (piperidine-4, 1-diyl)) dibenzoic acid serving as a third monomer, and performing polycondensation and cyclization with hydrazine sulfate and terephthalic acid to prepare a polymer stock solution; the 4,4' - ((phenylphosphoryl) bis (piperidine-4, 1-diyl)) dibenzoic acid has the following structure:
according to the invention, the phosphorus flame-retardant elements are introduced into the polymer molecular chain, so that the in-situ synergistic effect of the phosphorus and nitrogen flame-retardant elements can be exerted, the flame retardance of polyoxadiazole is improved, and the flame-retardant aromatic polyoxadiazole polymer prepared by the method has good spinnability and can be prepared into high-temperature-resistant aromatic polyoxadiazoleFiber and film materials, in turn, are used in the fields of honeycomb materials, electrical insulation materials, or carbon precursors, among others.
Description
Technical Field
The invention belongs to the technical field of flame-retardant polymer materials, and particularly relates to a flame-retardant aromatic polyoxadiazole polymer and a preparation method thereof.
Background
Aromatic Polyoxadiazole (POD) is a high-performance polymer with outstanding high-temperature stability and containing benzene rings and oxadiazole rings on a molecular chain, and like other aromatic heterocyclic polymers, POD has excellent fiber forming property and film forming property, can be prepared into high-temperature-resistant fibers and thin-film materials, and is further used in the fields of honeycomb structure materials, electric insulating materials, carbon precursors and the like.
POD has excellent thermal stability, the thermal decomposition temperature reaches over 500 ℃, but the Limiting Oxygen Index (LOI) is only 25 percent, and the POD is still inflammable in air. Therefore, in order to meet the corresponding use requirements, there is a need to further improve the flame retardancy of POD, and at present, blending methods and copolymerization methods are mainly used. The blending method is to blend POD and some aromatic copolyamides or flame retardants to prepare corresponding materials, which affects the use of the materials, and the flame retardant effect is difficult to last. The copolymerization method is to introduce a compound containing a flame-retardant element into a macromolecular chain of POD as a comonomer, and the flame retardant is combined on the macromolecular chain, so that the flame-retardant effect is durable, and the influence on the service performance of the POD is not great. CN 111410740 a discloses that the obtained polyoxadiazole is sulfonated by using terephthalic acid substituted by halogen elements (fluorine, bromine) as comonomer to load flame retardant metal, and aromatic polyoxadiazole with good flame retardant effect is obtained. Although the halogen-based brominated flame retardant has good flame retardant property, toxic gaseous hydrogen halide can be released in the combustion process, so that the environmental pollution is caused; in contrast, the phosphorus and nitrogen flame retardant is not easy to release corrosive gas in the combustion process, has good smoke suppression performance and has more application potential in preparing flame retardant polymers. Few reports on the preparation of the phosphorus-containing polyoxadiazole by a copolymerization method exist in the prior art.
Disclosure of Invention
The invention aims to provide a flame-retardant aromatic polyoxadiazole polymer, which is prepared by designing and synthesizing a phosphorus-containing diacid monomer as a comonomer, copolymerizing the phosphorus-containing diacid monomer with terephthalic acid and hydrazine sulfate in fuming sulfuric acid, and then carrying out cyclization reaction.
The invention also aims to provide a preparation method of the flame-retardant aromatic polyoxadiazole polymer.
A flame retardant aromatic polyoxadiazole polymer having the structural formula:
in the formula, m and n are integers.
The reaction flow and the preparation method of the flame-retardant aromatic polyoxadiazole polymer are as follows:
1. preparation of 4,4' - ((phenylphosphoryl) bis (piperidine-4, 1-diyl)) dibenzoic acid
Weighing phenylphosphonic dichloride, triethylamine and a solvent, putting into a reaction kettle, dripping 4- (piperidine-4-yl) benzoic acid solution in an ice bath, removing the ice bath after dripping, moving to an oil bath for heating, heating to 60-80 ℃, refluxing for 4-6 h, finishing the reaction, and obtaining 4,4'-4,4' - ((phenylphosphoryl) bis (piperidine-4, 1-diyl)) dibenzoic acid through reduced pressure distillation, suction filtration and chromatography, wherein the molecular structure of the formula (II) is as follows:
the solvent may be chloroform, toluene, acetonitrile.
The feeding molar ratio of the 4- (piperidine-4-yl) benzoic acid to the phenylphosphonic dichloride to the triethylamine is 2-2.2: 1: 1.
Preferably, the reaction temperature is 80 ℃.
Preferably, the reaction time is 4 h.
2. Polycondensation and cyclization reaction
Polymerization reaction: weighing hydrazine sulfate, terephthalic acid and 4,4' - ((phenylphosphoryl) bis (piperidine-4, 1-diyl)) dibenzoic acid, putting the weighed materials into a reaction kettle, adding fuming sulfuric acid, heating to the prepolymerization temperature of 60-100 ℃, and reacting for 2-4 hours; and further heating to 100-130 ℃ for polycondensation, reacting for 5-8 h, and adding a certain amount of benzoic acid for end capping to obtain the polyhydrazide.
Cyclization reaction: and continuously raising the temperature of the reaction system to 120-170 ℃ for cyclization, and finishing the reaction after reacting for 3-5 hours to obtain a stock solution.
The oleum is SO310-50% of fuming sulfuric acid.
The feeding molar ratio of the fuming sulfuric acid, the hydrazine sulfate, the terephthalic acid and the 4,4' - ((phenylphosphoryl) bis (piperidine-4, 1-diyl)) dibenzoic acid is 5-8: 1-1.4: 0.80-0.95: 0.2-0.05, wherein the molar amount of the fuming sulfuric acid is the SO contained in the fuming sulfuric acid3Calculating the molar weight.
The feeding molar weight of the benzoic acid is 0.5-2% of the molar weight of the terephthalic acid.
3. Spinning
Filtering the stock solution prepared in the step 2, and removing free SO by vacuum defoaming3The spinning solution is conveyed to a spinning box body by a hydraulic pump with the conveying pressure of 0.6MPa, metered by a metering pump, enters a spinning assembly, is extruded from a spinneret orifice, and enters a 20 wt% sulfuric acid solution with the temperature of 35-40 ℃ for solidification and forming to obtain a nascent strand. And then the polyoxadiazole fiber is obtained after hot bath stretching, bundling, alkali washing, water washing and drying.
The invention has the following advantages and beneficial effects:
(1) according to the invention, the synthesized third monomer participates in copolymerization, so that the in-situ synergistic flame retardance of phosphorus and nitrogen flame retardant elements can be exerted, the flame retardance of polyoxadiazole is improved, and the problems of timeliness, durability and the like of the flame retardance are fundamentally solved.
(2) The polymerization method is simple, and the cyclization effect and the flame retardant property of the polymer are controllable.
(3) The polymer stock solution prepared by the invention has low apparent viscosity, good fluidity and spinnability.
Drawings
FIG. 1 is a scheme showing the preparation of 4,4' - ((phenylphosphoryl) bis (piperidine-4, 1-diyl)) dibenzoic acid1H-NMR spectrum.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which are not intended to limit the present invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
The test of the invention comprises the following steps:
intrinsic viscosity number: measured using an Ubbelohde viscometer.
Elemental analysis: the samples were tested for P element content using a German Elmentar variao EL element analyzer.
Fineness test: cutting the fiber with a fiber cutter, drying with an infrared moisture dryer for 30min, balancing for 20min, weighing with JN-B torsion balance, and calculating titer.
Limiting Oxygen Index (LOI): the test is carried out according to the national standard GB/T2406-1993 and the test is carried out by using a LOI-1045G05 type limiting oxygen index determinator.
And (3) testing thermal stability: a Q600 thermal analyzer manufactured by American TA is adopted, the sample dosage is 6-8 mg, the temperature rise rate is 10 ℃/min under the nitrogen atmosphere, and the scanning temperature is 100-800 ℃.
Fiber tensile test: the tensile strength, elongation at break and initial modulus of the monofilaments were measured using a model YG001A fiber electronic Strength Meter.
And (3) testing cyclization rate: the cyclization ratio of POD fiber was calculated by TGA method (Q600 type thermal analyzer), and the sample was dried in a drying oven at 100 ℃ under vacuum for 48 hours to a constant volume in N2Measuring the cyclodehydration weight loss of a sample at 200-400 ℃ in atmosphere
The cyclization ratio was calculated using the following formula:
example 1
Preparation of 4,4' - ((phenylphosphoryl) bis (piperidine-4, 1-diyl)) dibenzoic acid
21.62g (0.11mol) of phenylphosphonyl dichloride, 11.22g (0.11mol) of triethylamine and 100mL of dry chloroform are added into a reaction flask provided with a reflux condenser tube, a constant pressure dropping funnel and a stirrer, and stirred to be fully dissolved and mixed; weighing 50.08g (0.24mol) of 4- (piperidine-4-yl) benzoic acid, dissolving in 200mL of chloroform, placing in a constant-pressure dropping funnel, beginning to drop into a reaction bottle under ice bath, moving the reaction bottle into an oil bath pot after dropping within 1h, heating to 80 ℃, refluxing for 4h, distilling under reduced pressure to remove the solvent, performing suction filtration on triethylamine hydrochloride, taking filtrate, taking dichloromethane as an eluent, and purifying by silica gel column chromatography to obtain 4,4' - ((phenylphosphoryl) bis (piperidine-4, 1-diyl)) dibenzoic acid, wherein the yield is 78.62%.
Process for preparing 4,4' - ((phenylphosphoryl) bis (piperidin-4, 1-diyl)) dibenzoic acid1The H-NMR spectrum is shown in figure 1. The spectra were determined using a BrukeraV-400 NMR spectrometer using DMSO as the solvent (TMS internal standard).
Example 2
Preparation of polyoxadiazole Polymer, oleum (as SO)3Calculated), hydrazine sulfate, terephthalic acid and 4,4' - ((phenylphosphoryl) bis (piperidine-4, 1-diyl)) dibenzoic acid in a molar ratio of 8:1.4:0.80:0.2, wherein the number is A1, and the specific reaction process is as follows:
192.96g of oleum (50 wt%) (SO) were weighed out31.21mol), 27.44g (0.21mol) of hydrazine sulfate, 20.02g (0.12mol) of terephthalic acid, 16.04g (0.03mol) of 4,4' - ((phenylphosphoryl) bis (piperidine-4, 1-diyl)) dibenzoic acid are put into a reaction kettle to be uniformly stirred and mixed, the temperature is raised to the prepolymerization temperature of 80 ℃ for reaction for 4h, then the temperature is raised to the polycondensation temperature of 130 ℃ for continuous reaction for 8h, 0.3g (2.46mmol) of benzoic acid is added for end capping, the temperature is raised to 170 ℃ for further cyclization, and the reaction is finished after 5h, so that a polymer stock solution A1 is obtained.
Example 3
Preparation of polyoxadiazole Polymer, oleum (as SO)3Calculated), hydrazine sulfate, terephthalic acid and 4,4' - ((phenylphosphoryl) bis (piperidine-4, 1-diyl)) dibenzoic acid in a molar ratio of 8:1.2:0.85:0.15, wherein the number is A2, and the specific reaction process is as follows:
177.42g of oleum (50 wt%) (SO) were weighed out31.11mol) of hydrazine sulfate, 21.63g (0.17mol) of hydrazine sulfate, 19.56g (0.12mol) of terephthalic acid, 11.07g (0.02mol) of 4,4' - ((phenylphosphoryl) bis (piperidine-4, 1-diyl)) dibenzoic acid, the prepolymerization temperature is 100 ℃, and the reaction is carried out for 2 hours; the polycondensation temperature is 130 ℃, the reaction is continued for 6h, and 0.29g (2.3mmol) of benzoic acid is added for end capping; the cyclization reaction temperature was 150 ℃ and the reaction was terminated after 5 hours to obtain a polymer dope A2.
Example 4
Preparation of polyoxadiazole Polymer, oleum (as SO)3Calculated), hydrazine sulfate, terephthalic acid and 4,4' - ((phenylphosphoryl) bis (piperidine-4, 1-diyl)) dibenzoic acid in a molar ratio of 6:1.3:0.9:0.1, wherein the number is A3, and the specific reaction process is as follows:
215.47g of smoke were weighed outSulfuric acid (30 wt%) (SO3A molar weight of 0.81mol), 22.76g (0.17mol) of hydrazine sulfate, 20.12g (0.12mol) of terephthalic acid, 7.17g (0.01mol) of 4,4' - ((phenylphosphoryl) bis (piperidine-4, 1-diyl)) dibenzoic acid, a prepolymerization temperature of 60 ℃ and a reaction time of 4 hours; the polycondensation temperature is 120 ℃, the reaction is continued for 8 hours, and 0.3g (2.42mmol) of benzoic acid is added for end capping; the cyclization reaction temperature was 120 ℃ and the reaction was completed after 5 hours to obtain a polymer dope A3.
Example 5
Preparation of polyoxadiazole Polymer, oleum (as SO)3Calculated), hydrazine sulfate, terephthalic acid and 4,4' - ((phenylphosphoryl) bis (piperidine-4, 1-diyl)) dibenzoic acid in a molar ratio of 5:1:0.95:0.05, wherein the number is A4, and the specific reaction process is as follows:
168.67g of oleum (30 wt%) (SO) were weighed out3A molar mass of 0.63mol), 16.45g (0.13mol) of hydrazine sulfate, 19.95g (0.12mol) of terephthalic acid, 3.37g (6.32mmol) of 4,4' - ((phenylphosphoryl) bis (piperidine-4, 1-diyl)) dibenzoic acid, a prepolymerization temperature of 60 ℃ and a reaction time of 4 hours; the polycondensation temperature is 100 ℃, the reaction is continued for 6 hours, and 0.29g (2.4mmol) of benzoic acid is added for end capping; the cyclization reaction temperature was 140 ℃ and the reaction was completed after 3 hours to obtain a polymer dope A4.
Example 6
Preparation of polyoxadiazole fibers
Filtering the obtained polymer stock solution, and vacuum defoaming to remove free SO3The spinning solution is conveyed to a spinning box body by a hydraulic pump with the conveying pressure of 0.6MPa, metered by a metering pump, enters a spinning assembly, is extruded from a spinneret orifice, and enters a 35 ℃ coagulating bath for forming to obtain a nascent strand silk. The spinning temperature is kept at 60-70 ℃, the rotating speed of a metering pump is 15rpm, the diameter of a spinneret orifice is 0.06mm, and the extrusion speed is 20 m/min.
And (3) stretching the nascent filaments in a steam bath (at 90-100 ℃), bundling, and then performing alkali washing, water washing and drying to obtain the finished fiber. Wherein the stretching ratio is 5 times, the stretching ratio is 1.5 times, the alkali liquor concentration of alkali washing is 3 wt%, and the drying is carried out in a hot air drying oven at the temperature of 200-300 ℃.
The polymer stock solutions prepared in examples 2 to 5 were molded in different coagulation baths to prepare fibers, and the performance tests thereof are shown in table 1.
TABLE 1
As can be seen from Table 1, the limiting oxygen index of the flame-retardant aromatic polyoxadiazole polymer is greatly improved compared with that of POD fibers without phosphorus, and the LOI is 34-38%. As can be seen from the comparison of the data in the table, the molecular chain structure of the polymer is changed due to the addition of the phosphorus-containing unit, the crystal region is reduced, and the thermal stability of the polymer is reduced, but the reduction amplitude is not large as a whole. The cyclization rate is reduced along with the reduction of the regularity of the molecular structure of the polymer, and has influence on various properties of the fiber, such as mechanical property and thermal stability. In conclusion, the polyoxadiazole fiber prepared by introducing 4,4' - ((phenylphosphoryl) bis (piperidine-4, 1-diyl)) dibenzoic acid copolymerization can improve the flame retardant property of the fiber, has little influence on the thermal stability and mechanical property of the fiber, and has good application prospect.
Claims (9)
1. A flame retardant aromatic polyoxadiazole polymer and method of making the same, wherein the flame retardant aromatic polyoxadiazole polymer has the structure of formula (I):
in the formula, m and n are integers.
2. The flame-retardant aromatic polyoxadiazole polymer and the preparation method thereof are characterized by comprising the following steps of:
(1) preparation of 4,4' - ((phenylphosphoryl) bis (piperidine-4, 1-diyl)) dibenzoic acid
Weighing phenylphosphonic dichloride, triethylamine and a solvent, putting into a reaction kettle, dripping 4- (piperidine-4-yl) benzoic acid solution in an ice bath, removing the ice bath after dripping, moving to an oil bath for heating, heating to 60-80 ℃, refluxing for 4-6 h, finishing the reaction, and obtaining 4,4'-4,4' - ((phenylphosphoryl) bis (piperidine-4, 1-diyl)) dibenzoic acid through reduced pressure distillation, suction filtration and chromatography, wherein the molecular structure of the formula (II) is as follows:
(2) polycondensation and cyclization reaction
The method comprises a prepolymerization stage, a final polymerization stage and a cyclization stage.
A prepolymerization stage: weighing hydrazine sulfate, terephthalic acid and 4,4' - ((phenylphosphoryl) bis (piperidine-4, 1-diyl)) dibenzoic acid, putting the weighed materials into a reaction kettle, adding fuming sulfuric acid, heating to the prepolymerization temperature of 60-100 ℃, and reacting for 2-4 hours;
and (3) final polymerization stage: heating the reaction kettle to 100-130 ℃, keeping the temperature for reaction for 5-8 h, and adding a certain amount of benzoic acid for end capping to obtain polyhydrazide;
a cyclization stage: and continuously raising the temperature of the reaction kettle to 120-170 ℃ for cyclization, and finishing the reaction after 3-5 h to obtain a polymer stock solution.
3. The flame retardant aromatic polyoxadiazole polymer of claim 2, wherein the resulting polymer dope can be wet spun to produce finished fibers.
4. The flame retardant aromatic polyoxadiazole polymer of claim 2 and the method of making the same, wherein: the solvent of the step (1) can be chloroform, toluene and acetonitrile.
5. The flame retardant aromatic polyoxadiazole polymer of claim 2 and the method of making the same, wherein: the feeding molar ratio of the 4- (piperidine-4-yl) benzoic acid, the phenylphosphonic dichloride and the triethylamine in the step (1) is 2-2.2: 1: 1.
6. The flame retardant aromatic polyoxadiazole polymer of claim 2 and the method of making the same, wherein: the reaction temperature in the step (1) is preferably 80 ℃, and the reaction time is preferably 4 h.
7. The flame retardant aromatic polyoxadiazole polymer of claim 2 and the method of making the same, wherein: the oleum of step (2) is SO310-50% of fuming sulfuric acid.
8. The flame retardant aromatic polyoxadiazole polymer of claim 2 and the method of making the same, wherein: the feeding molar ratio of the fuming sulfuric acid, the hydrazine sulfate, the terephthalic acid and the 4,4' - ((phenylphosphoryl) bis (piperidine-4, 1-diyl)) dibenzoic acid in the step (2) is 5-8: 1-1.4: 0.80-0.95: 0.2-0.05, wherein the molar amount of the fuming sulfuric acid is the amount of SO contained in the fuming sulfuric acid3Calculating the molar weight; the feeding molar weight of the benzoic acid is 0.5-2% of the molar weight of the terephthalic acid.
9. The flame retardant aromatic polyoxadiazole polymer according to any one of claims 1 to 8, wherein: the titer of the flame-retardant aromatic polyoxadiazole polymer is 2-3 dtex, the limiting oxygen index is 30-38%, and the initial decomposition temperature is not less than 480 ℃.
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