CN111606948B - Efficient phosphine-nitrogen flame retardant and preparation method and application thereof - Google Patents
Efficient phosphine-nitrogen flame retardant and preparation method and application thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 107
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 103
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- 238000002156 mixing Methods 0.000 claims description 12
- BIXHPQCUJWTBDQ-UHFFFAOYSA-N 1-[phenyl(piperazin-1-yl)phosphoryl]piperazine Chemical compound C1(=CC=CC=C1)P(N1CCNCC1)(N1CCNCC1)=O BIXHPQCUJWTBDQ-UHFFFAOYSA-N 0.000 claims description 10
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- 229910052698 phosphorus Inorganic materials 0.000 abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 9
- 239000011574 phosphorus Substances 0.000 abstract description 9
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- 230000007062 hydrolysis Effects 0.000 abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 7
- RVZIHXHEDQCEED-UHFFFAOYSA-N n-[bis(dimethylamino)phosphorylimino-bis(dimethylamino)-$l^{5}-phosphanyl]-n-methylmethanamine Chemical compound CN(C)P(=O)(N(C)C)N=P(N(C)C)(N(C)C)N(C)C RVZIHXHEDQCEED-UHFFFAOYSA-N 0.000 description 21
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- QPQGTZMAQRXCJW-UHFFFAOYSA-N [chloro(phenyl)phosphoryl]benzene Chemical compound C=1C=CC=CC=1P(=O)(Cl)C1=CC=CC=C1 QPQGTZMAQRXCJW-UHFFFAOYSA-N 0.000 description 8
- 238000002411 thermogravimetry Methods 0.000 description 8
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
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- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
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- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
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- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
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- 238000001308 synthesis method Methods 0.000 description 1
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- 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
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
- C07F9/6509—Six-membered rings
- C07F9/650952—Six-membered rings having the nitrogen atoms in the positions 1 and 4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
A high-efficiency phosphine-nitrogen flame retardant and a preparation method and application thereof relate to a flame retardant and a preparation method and application thereof. The flame retardant aims to solve the problems of low flame retardant efficiency and low thermal stability of the existing phosphorus-containing flame retardant. The preparation method of the phosphine-nitrogen type flame retardant comprises the following steps: 1. adding anhydrous piperazine, chloroform and triethylamine into a reactor, and stirring; dissolving phenyl phosphoryl dichloride in chloroform, dropwise adding the chloroform into a reactor for reaction, extracting and concentrating to obtain a crude product, and drying to obtain an intermediate; 2. adding the intermediate and chloroform into a reactor, and adding triethylamine; dissolving diphenyl phosphoryl chloride in chloroform, dropwise adding the solution into a reactor, and performing reflux reaction; washing, concentrating and drying to obtain the phosphine-nitrogen flame retardant. The phosphine-nitrogen type flame retardant is applied to flame-retardant modified polylactic acid. The phosphine-nitrogen flame retardant synthesized by the invention has good thermal stability and hydrolysis resistance, and is a high-efficiency phosphine-nitrogen flame retardant integrating gas phase flame retardance and condensed phase flame retardance. The invention is applied to the field of flame retardants.
Description
Technical Field
The invention relates to a flame retardant, a preparation method and application thereof.
Background
The polylactic acid (PLA) has the advantages of wide raw material source, easy processing and forming, excellent mechanical property, excellent biocompatibility and degradability, and the like, and is widely applied to the fields of biological medicine, spinning, packaging, and the like. However, the PLA material is flammable, has high combustion speed and is not easy to extinguish, and meanwhile, a large amount of molten drops are generated, so that the use of the PLA in some fields is limited. Therefore, flame retardant modification of PLA is required.
The halogen-containing flame retardant releases more smoke and toxic gases in the combustion process, and the application of the halogen-containing flame retardant is limited to a certain extent. The inorganic flame retardant is low in price, low in smoke and low in toxicity, but the inorganic flame retardant is often added in a large amount, influences the mechanical and processing performances of the PLA material and has insufficient toughness. In recent years, organic phosphorus flame retardants have been widely used for flame retardant modification of high polymers due to their advantages of low smoke, low toxicity, and the like. With the development of science and technology, products in the fields of electronics and electric appliances are developed towards miniaturization and ultra-thinning, and higher requirements are put forward on flame-retardant polymer materials. The material not only needs to have excellent flame retardant property, but also has excellent properties such as weather resistance, processing, mechanics and the like. Therefore, the flame retardant to be prepared has high flame retardant efficiency for PLA materials, and simultaneously has good thermal stability, hydrolysis resistance and other properties. The existing phosphorus-containing flame retardant for PLA is a compound containing O = P-O bonds, and has the problems of low flame retardant efficiency, unsatisfactory thermal stability, easiness in hydrolysis, difficulty in processing and dispersion and the like.
Disclosure of Invention
The invention aims to solve the problems of low flame retardant efficiency and low thermal stability of the existing phosphorus-containing flame retardant, and provides a high-efficiency phosphine-nitrogen flame retardant, and a preparation method and application thereof.
The phosphine-nitrogen flame retardant is [4,4' - (phenyl phosphoryl) bis (4, 1-dipiperazinyl) ] bis (diphenyl phosphine oxide), and the structural formula is as follows:
the preparation method of the phosphine-nitrogen type flame retardant comprises the following steps:
1. adding anhydrous piperazine and chloroform into an anhydrous and oxygen-free reactor, stirring at the temperature of-6 to-4 ℃ until the piperazine is completely dissolved in the chloroform, then adding triethylamine into the reactor, and fully stirring;
dissolving phenyl phosphoryl dichloride in chloroform to obtain a mixed solution A, then dropwise adding the mixed solution A into a reactor, keeping the temperature of the solution in the reactor at-6 to-4 ℃, continuously keeping the temperature at-6 to-4 ℃ for 30-40 min after the dropwise adding is finished, then raising the reaction temperature to 25-26 ℃, continuously reacting for 2-3 h, directly pouring reactants into water after the reaction is finished, washing away triethylamine hydrochloride, then extracting a lower chloroform layer, and concentrating to obtain a crude product; drying the crude product to obtain a light yellow solid, namely an intermediate phenyl bis (1-piperazinyl) phosphine oxide;
2. adding the intermediate synthesized in the step one and chloroform into a reactor, stirring until the intermediate and the chloroform are dissolved, then adding triethylamine serving as an acid-binding agent, and reducing the reaction temperature to-6 to-4 ℃;
dissolving diphenylphosphinic chloride in chloroform to obtain a mixed solution B, then dropwise adding the mixed solution B into a reactor, keeping the temperature of the solution in the reactor between-6 ℃ and-4 ℃, continuously keeping the temperature between-6 ℃ and-4 ℃ for 30-40 min after the dropwise adding is finished, then raising the reaction temperature to 62-65 ℃, and keeping reflux reaction for 12-14 h;
after the reaction is finished, pouring the reactant into water for washing, removing triethylamine hydrochloride, then separating a lower chloroform layer, concentrating to obtain a light yellow product, and drying to obtain a final product [4,4' - (phenylphosphoryl) bis (1, 4-dipiperazinyl) ] bis (diphenylphosphine oxide), namely the phosphine-nitrogen flame retardant.
Furthermore, in the step one, the mass ratio of the anhydrous piperazine to the chloroform is 1 (8-10), and the molar ratio of the anhydrous piperazine to the triethylamine is 1 (2-2.2).
Furthermore, in the first step, the mass ratio of the phenyl phosphoryl dichloride to the chloroform is 1 (1-1.5).
The phosphine-nitrogen flame retardant is applied to flame-retardant modified polylactic acid.
Further, the specific method of the flame-retardant modified polylactic acid comprises the following steps:
mixing a phosphine-nitrogen flame retardant [4,4' - (phenyl phosphoryl) bis (1, 4-dipiperazino) ] bis (diphenylphosphine oxide) with polylactic acid, heating, melting and blending for 15-20 min, taking out the mixed material, and performing hot press molding to obtain the modified polylactic acid.
Wherein the mass of the phosphine-nitrogen flame retardant is 1 to 6 percent of that of the polylactic acid.
Further, the heating, melting and blending are carried out by a torque rheometer, the temperature of each heating zone is 180 ℃, 180 ℃ and 180 ℃, and the rotating speed is 50r/min.
Further, the hot press molding method comprises the following specific steps: and (3) putting the mixed material on a flat vulcanizing machine, and carrying out hot press molding at 180 ℃ under the pressure of 10 MPa.
The reaction principle of the invention is as follows:
the invention takes phenylphosphoryl dichloride, diphenylphosphine chloride and piperazine as raw materials to prepare the high-efficiency phosphine-nitrogen flame retardant [4,4' - (phenylphosphoryl) bis (4, 1-dipiperazino) ] bis (diphenylphosphine oxide). The synthetic route of the phosphine-nitrogen flame retardant is as follows:
the invention has the beneficial effects that:
the phosphine-nitrogen flame retardant synthesized by the invention contains P-C and P-N bond structures, has good thermal stability and hydrolysis resistance, is a high-efficiency phosphine-nitrogen flame retardant integrating gas phase and condensed phase flame retardance, is light yellow or white powder, and has the synthesis yield of a target product of more than 92 percent. Thermogravimetric analysis tests show that the flame retardant has an initial thermal decomposition temperature of 336.3 ℃, has excellent thermal stability, can meet the processing requirements of most high polymer materials such as PLA and the like, has a char forming amount of 10.4wt% at 800 ℃, and has good char forming performance.
Meanwhile, the flame retardant has good compatibility with a polymer base material, is not easy to migrate and precipitate in the material, can be washed by water, has good water resistance, and overcomes the problems of poor water resistance, easy precipitation and the like of the traditional micromolecular organic phosphorus flame retardant.
Compared with the prior synthesis technology of some phosphorus-containing flame retardants, the synthesis method disclosed by the invention is relatively simple, no catalyst is needed in the synthesis process, the solvent can be recycled, the high-temperature high-pressure reaction is not involved, the energy consumption is low, the synthesis yield of the target product is higher, and the application prospect is better.
When the phosphine-nitrogen flame retardant is added into a PLA material, and the adding amount is only 4wt%, the flame-retardant polylactic acid composite material reaches UL-94V-0 grade in a vertical combustion test, and the Limiting Oxygen Index (LOI) is increased to 29.4 percent from 19.0 percent of a pure PLA material. The flame retardant has excellent flame retardant efficiency on PLA materials, and the influence on the mechanical property, the processing property and the like of the materials is small due to the low addition amount of the flame retardant, so that the high-efficiency flame-retardant polylactic acid material with excellent comprehensive properties is prepared.
Drawings
FIG. 1 is a Fourier Transform Infrared (FTIR) spectrum of an intermediate phenylbis (1-piperazinyl) phosphine oxide;
FIG. 2 is a chart of infrared spectra of the product [4,4' - (phenylphosphoryl) bis (4, 1-dipiperazinyl) ] bis (diphenylphosphine oxide) (PDPO) and the reactant diphenylphosphinic chloride (DPPC);
FIG. 3 is a diagram of PDPO product 13 C NMR spectrum;
FIG. 4 is a diagram of PDPO product 31 A P NMR spectrum;
figure 5 is a DTG and TGA plot of the product PDPO as measured by thermogravimetric analysis.
Detailed Description
The technical solution of the present invention is not limited to the embodiments listed below, and includes any combination of the embodiments.
The first specific implementation way is as follows: the phosphine-nitrogen flame retardant of the embodiment is [4,4' - (phenylphosphoryl) bis (4, 1-dipiperazinyl) ] bis (diphenylphosphine oxide), and has the structural formula:
the compound containing P-C bond has good thermal stability and hydrolysis resistance, and generates phosphorus-containing free radicals during combustion, and the high-efficiency gas-phase flame retardant effect is achieved by quenching the hydrogen free radicals, oxygen free radicals and hydroxyl free radicals which maintain the combustion. Piperazine has good char-forming performance, releases flame-retardant gas during combustion, and plays a role in diluting oxygen and combustible gas. Aiming at the requirements of the fields of electronic appliances and the like on high-performance flame retardants, the embodiment takes phenyl phosphoryl dichloride and diphenyl phosphoryl chloride containing a P-C bond structure and piperazine with excellent char-forming performance as starting raw materials through molecular structure design, and introduces the starting raw materials into the same flame retardant molecular structure through nucleophilic substitution reaction to prepare the phosphine-nitrogen containing flame retardant with excellent comprehensive performance and use the phosphine-nitrogen containing flame retardant in flame retardance of PLA. Solves the problems of low thermal stability, low flame retardant efficiency, easy hydrolysis and the like of the traditional phosphorus-containing flame retardant. The flame retardant has excellent performance in PLA materials and has good application prospect.
The second embodiment is as follows: the preparation method of the phosphine-nitrogen type flame retardant of the embodiment comprises the following steps:
1. adding anhydrous piperazine and chloroform into an anhydrous and oxygen-free reactor, stirring at the temperature of-6 to-4 ℃ until the piperazine is completely dissolved in the chloroform, then adding triethylamine into the reactor, and fully stirring;
dissolving phenyl phosphoryl dichloride in chloroform to obtain a mixed solution A, then dropwise adding the mixed solution A into a reactor, keeping the temperature of the solution in the reactor at-6 to-4 ℃, continuously keeping the temperature at-6 to-4 ℃ for 30 to 40min after the dropwise adding is finished, then raising the reaction temperature to 25 to 26 ℃, continuously reacting for 2 to 3h, directly pouring reactants into water after the reaction is finished, washing away triethylamine hydrochloride, then extracting a lower chloroform layer, and concentrating to obtain a crude product; drying the crude product to obtain a light yellow solid, namely an intermediate phenyl bis (1-piperazinyl) phosphine oxide;
2. adding the intermediate synthesized in the step one and chloroform into a reactor, stirring until the intermediate and the chloroform are dissolved, then adding triethylamine serving as an acid-binding agent, and reducing the reaction temperature to-6 to-4 ℃; wherein chloroform is used as a solvent to dissolve the intermediate;
dissolving diphenylphosphinic chloride in chloroform to obtain a mixed solution B, then dropwise adding the mixed solution B into a reactor, keeping the temperature of the solution in the reactor between-6 ℃ and-4 ℃, continuously keeping the temperature between-6 ℃ and-4 ℃ for 30-40 min after the dropwise adding is finished, then raising the reaction temperature to 62-65 ℃, and keeping reflux reaction for 12-14 h; wherein chloroform is used as a solvent, and diphenyl phosphoryl chloride is dissolved;
after the reaction is finished, pouring the reactant into water for washing, removing triethylamine hydrochloride, then separating a lower chloroform layer, concentrating to obtain a light yellow product, and drying to obtain a final product [4,4' - (phenylphosphoryl) bis (1, 4-dipiperazinyl) ] bis (diphenylphosphine oxide), namely the phosphine-nitrogen flame retardant.
The third concrete implementation mode: the second embodiment is different from the first embodiment in that: in the first step, the mass ratio of the anhydrous piperazine to the chloroform is 1 (8-10), and the molar ratio of the anhydrous piperazine to the triethylamine is 1 (2-2.2). The rest is the same as the second embodiment.
The fourth concrete implementation mode: the second embodiment is different from the first embodiment in that: in the first step, the mass ratio of the phenylphosphoryl dichloride to the chloroform is 1 (1-1.5). The rest is the same as the second embodiment.
The fifth concrete implementation mode: the phosphine-nitrogen flame retardant is applied to the flame-retardant modified polylactic acid.
The sixth specific implementation mode: the fifth embodiment is different from the fifth embodiment in that: the specific method of the flame-retardant modified polylactic acid comprises the following steps:
mixing a phosphine-nitrogen flame retardant [4,4' - (phenyl phosphoryl) bis (1, 4-dipiperazino) ] bis (diphenylphosphine oxide) with polylactic acid, heating, melting and blending for 15-20 min, taking out the mixed material, and performing hot press molding to obtain the modified polylactic acid. The rest is the same as the fifth embodiment.
The seventh embodiment: the sixth embodiment is different from the sixth embodiment in that: the mass of the phosphine-nitrogen flame retardant is 1 to 6 percent of that of the polylactic acid. The rest is the same as the sixth embodiment.
The specific implementation mode eight: the sixth embodiment is different from the specific embodiment in that: the mass of the phosphine-nitrogen flame retardant is 3-4% of that of the polylactic acid. The rest is the same as the sixth embodiment.
The specific implementation method nine: the sixth embodiment is different from the sixth embodiment in that: the heating, melting and blending are carried out by a torque rheometer, the temperature of each heating zone is 180 ℃, 180 ℃ and 180 ℃, and the rotating speed is 50r/min. The rest is the same as the sixth embodiment.
The detailed implementation mode is ten: the sixth embodiment is different from the specific embodiment in that: the hot-press molding method comprises the following steps: and putting the mixed material on a flat vulcanizing machine, and carrying out hot press molding at 180 ℃ under the pressure of 10 MPa. The rest is the same as the sixth embodiment.
The following examples are given to illustrate the present invention, and the following examples are carried out on the premise of the technical solution of the present invention, and give detailed embodiments and specific procedures, but the scope of the present invention is not limited to the following examples.
Example 1:
the phosphine-nitrogen flame retardant of the embodiment is [4,4' - (phenylphosphoryl) bis (4, 1-dipiperazinyl) ] bis (diphenylphosphine oxide), and the synthesis steps are as follows:
the first step is as follows: synthesis of intermediate phenyl bis (1-piperazinyl) phosphine oxide
A500 mL dry five-neck flask was equipped with a stirrer, thermometer, bulb condenser, nitrogen blanketing, constant pressure addition funnel, and ice-salt bath cooler, and was purged repeatedly several times with dry nitrogen to ensure that the reactor was free of water and oxygen.
Then, 17.2g of anhydrous piperazine and 150g of chloroform were added to the five-necked flask, and the solution was kept at about-5 ℃ with an ice salt bath, and the mixture was stirred to completely dissolve the piperazine in the chloroform. Then 20.2g triethylamine was added to the five-necked flask and stirred well. 19.5g of phenylphosphoryl dichloride is weighed, dissolved in 19.5g of chloroform and slowly dripped into a five-mouth bottle by a constant-pressure dropping funnel, the temperature of the solution is kept at about-5 ℃, and after the dripping is finished, the solution is kept for 30min. And then, raising the temperature of the reactant to 25 ℃, continuing to react for 2 hours, pouring the reactant into water after the reaction is finished, washing off triethylamine hydrochloride, and then extracting a lower orange chloroform layer by using a separating funnel. Concentrating by a rotary evaporator to obtain an orange crude product, and drying in a vacuum drying oven at 50 ℃ for 20h to obtain a light yellow solid, namely the intermediate phenyl bis (1-piperazinyl) phosphine oxide, wherein the yield of the intermediate is 96.5%. The synthetic route of the intermediates is shown below.
The second step is that: synthesis of product [4,4' - (phenylphosphoryl) bis (1, 4-dipiperazino) ] bis (diphenylphosphine oxide)
29.6g of the synthesized intermediate phenylbis (1-piperazinyl) phosphine oxide were charged into a 500mL five-necked flask equipped with a stirrer, a thermometer, a bulb-shaped condenser, a nitrogen blanket, a constant pressure dropping funnel, and an ice-salt bath apparatus. Adding 200g of chloroform to dissolve the mixture, adding triethylamine serving as an acid-binding agent, and cooling to-5 ℃. 47.3g of diphenylphosphinic chloride is weighed and dissolved in 47.3g of anhydrous chloroform, and the solution is slowly dripped into a five-mouth bottle through a constant-pressure dropping funnel, the temperature is kept at about-5 ℃, and the solution is kept for 30min after the dripping is finished. Then the reaction was warmed to 62 ℃ and kept under reflux for 12h. After the reaction was completed, the reaction was poured into water to wash, triethylamine hydrochloride was removed, and then the lower chloroform layer was separated by a separatory funnel. The extracted chloroform layer is concentrated by a rotary evaporator to obtain a light yellow product, the light yellow product is dried in a vacuum drying oven at 50 ℃ for 20 hours to obtain a product [4,4' - (phenylphosphoryl) bis (1, 4-dipiperazinyl) ] bis (diphenylphosphine oxide), namely the high-efficiency phosphine-nitrogen flame retardant, the yield is 95.2%, and the synthetic route is shown as follows.
Characterization of the (mono) intermediate Phenylbis (1-piperazinyl) phosphine oxides
The Fourier Transform Infrared (FTIR) spectrum of the intermediate phenylbis (1-piperazinyl) phosphine oxide is shown in FIG. 1. From the FTIR spectrum it can be seen that: 3434cm -1 The strong absorption peak is the expansion vibration absorption peak of N-H of the intermediate; 3055cm -1 The absorption peak of (2) is the stretching vibration of C-H on the benzene ring, 2967cm -1 、2906cm -1 And 2848cm -1 The strong absorption peak is the stretching vibration of C-H on piperazine; 1643cm -1 And 1590cm -1 The absorption peak of (a) is the vibration of the skeleton of the benzene ring; 1437cm -1 And 1206cm -1 The absorption peaks are respectively the stretching vibration absorption peaks of P-C and P = O; furthermore, 1140cm -1 Absorption peak of stretching vibration of newly generated P-N bond and 520cm -1 The disappearance of the left and right P = Cl absorption peaks indicates the successful synthesis of the intermediate phenylbis (1-piperazinyl) phosphine oxide.
Characterization of the (di) product [4,4' - (phenylphosphoryl) bis (1, 4-dipiperazinyl) ] bis (diphenylphosphine oxide) (PDPO)
FIG. 2 is the product [4,4' - (phenylphosphoryl) bis (4, 1-dipiperazinyl)]Infrared spectra of bis (diphenylphosphine oxide) (PDPO) and the reactant diphenylphosphinyl chloride (DPPC), wherein curve a represents PDPO and curve b represents DPPC. As shown by curve a: 3054cm -1 The absorption peak of (A) is on benzene ringC-H stretching vibration, 1650cm -1 And 1589cm -1 The absorption peak of (2) is the skeleton vibration of the benzene ring, 526cm -1 The peak is the absorption peak of the P-Cl expansion vibration. However, in curve b, the newly generated one is located at 2969cm -1 、2904cm -1 And 2852cm -1 The absorption peak is the stretching vibration of C-H on piperazine at 1438cm -1 And 1204cm -1 The absorption peaks at P-C and P-O are obviously enhanced, 1119cm -1 The peak was a stretching vibration peak of the formed P-N, and the absorption peak of the P-Cl bond disappeared.
Of the synthetic product PDPO 13 The C NMR spectrum is shown in FIG. 3, and the peaks at 125.41 to 131.26ppm are assigned to the chemical shifts of C on the phenyl rings of a, b, C, d, e, f identified in the structure, and the peaks at 42.28 and 43.16ppm are the chemical shifts of C atom (g, h) on piperazine in the structure.
FIG. 4 shows the synthesis of product PDPO 31 P NMR spectrum, as can be seen, there are two at 25.14 and 29.56ppm respectively 31 The P peak appears and belongs to P atoms on the phenyl phosphoryl dichloride (b) and the diphenyl phosphoryl chloride (a) respectively, and the test shows that the synthesized product has two phosphine chemical environments.
In combination with FTIR, 13 C NMR and 31 the analysis result of the P NMR spectrogram shows that the synthesized product conforms to the structure of the target product, and the efficient phosphine-nitrogen flame retardant is successfully synthesized.
(III) product PDPO thermogravimetric analysis (TGA) testing
The resulting product was subjected to thermogravimetric analysis (TGA) test and the results are shown in fig. 5, in which curve a represents the DTG curve and curve b represents the TGA curve.
The results of thermogravimetric analysis (TGA) tests show that the phosphine-nitrogen flame retardant synthesized in the embodiment has an initial thermal decomposition temperature of 336.3 ℃ and a residual mass at 800 ℃ of 10.4wt%, which indicates that the synthesized flame retardant has excellent thermal stability and good self-charring performance and can meet the processing temperature requirements of most high molecular materials.
The obtained product is soaked in water at 70 ℃ for 2h, filtered and dried when the product is hot, and the mass loss is 0.68 percent, which shows that the flame retardant has good hydrolysis resistance.
(IV) the performance of the flame-retardant polylactic acid material
1. Preparation of samples
Fully mixing a synthesized product [4,4' - (phenylphosphoryl) bis (1, 4-dipiperazinyl) ] bis (diphenylphosphine oxide) (PDPO) and polylactic acid (PLA)) according to a certain mass ratio by a high-speed stirrer, heating, melting and blending for 15min by a torque rheometer, wherein the temperature of each heating zone is 180, 180 and 180 ℃, and the rotating speed is 50r/min. And taking out the materials after mixing, placing the materials on a flat vulcanizing machine, carrying out hot press molding at 180 ℃ under the pressure of 10MPa, then cutting the materials into standard sample strips, namely the flame-retardant polylactic acid, and carrying out performance test.
2. Flame retardant property test of flame retardant polylactic acid
The flame retardant performance of the flame retardant polylactic acid was characterized by the vertical flame (UL-94) and Limiting Oxygen Index (LOI) tests, the results of which are shown in Table 1. Pure PLA is extremely flammable in air and is associated with a large number of flaming droplets, with an LOI value of 19.0%, which is not rated in the UL-94 test. With the addition of the flame retardant PDPO, the flame retardant property of the polylactic acid is obviously improved. When the addition amount of the PDPO is 4wt%, the PLA/PDPO material smoothly passes through UL-94V-0 level, and the LOI value is as high as 29.4%, which shows that the flame retardant PDPO has excellent flame retardant efficiency on polylactic acid, and a good method is provided for preparing the flame retardant polylactic acid material with excellent comprehensive performance.
Compared with the traditional phosphorus-containing flame retardant, the synthesized phosphine-nitrogen-containing flame retardant PDPO shows high flame retardant rate in the flame-retardant PLA biomass material, and the reasons are as follows: 1) In the molecular structure of PDPO, phosphine and nitrogen are concentrated in one molecule, so that the PDPO can better exert a synergistic effect. 2) PDPO molecules contain a large number of piperazine groups with excellent char-forming performance, and meanwhile, flame-retardant gas is generated in the combustion process, so that the flame-retardant effect of gas phase and condensed phase is realized. 3) The PDPO molecular structure contains a large number of P-C bonds, generates P & PO & lt- & gt in the combustion process, quenches high-energy free radicals such as hydrogen free radicals, oxygen free radicals, hydroxyl free radicals and the like generated in the combustion process of the polymer, and accordingly has a gas phase inhibition effect on the PLA material. Therefore, the flame retardant PDPO shows excellent flame retardant performance in the PLA material, and the aim of the invention is fulfilled.
TABLE 1 vertical burn and limiting oxygen index test data for flame retardant PLA composites
L.D.:Light dripping.
Claims (10)
1. A phosphine-nitrogen flame retardant characterized in that the flame retardant is [4,4' - (phenylphosphoryl) bis (4, 1-dipiperazinyl) ] bis (diphenylphosphine oxide) having the formula:
2. the process for producing a phosphine-nitrogen type flame retardant according to claim 1, characterized by comprising the steps of:
1. adding anhydrous piperazine and chloroform into an anhydrous and oxygen-free reactor, stirring at the temperature of-6 to-4 ℃ until the piperazine is completely dissolved in the chloroform, then adding triethylamine into the reactor, and fully stirring;
dissolving phenyl phosphoryl dichloride in chloroform to obtain a mixed solution A, then dropwise adding the mixed solution A into a reactor, keeping the temperature of the solution in the reactor at-6 to-4 ℃, continuously keeping the temperature at-6 to-4 ℃ for 30 to 40min after the dropwise adding is finished, then raising the reaction temperature to 25 to 26 ℃, continuously reacting for 2 to 3h, directly pouring reactants into water after the reaction is finished, then extracting a lower chloroform layer, and concentrating to obtain a crude product; drying the crude product to obtain a light yellow solid, namely an intermediate phenyl bis (1-piperazinyl) phosphine oxide;
2. adding the intermediate synthesized in the first step and chloroform into a reactor, stirring until the intermediate and the chloroform are dissolved, then adding triethylamine serving as an acid-binding agent, and cooling the reaction temperature to-6 to-4 ℃;
dissolving diphenyl phosphoryl chloride in chloroform to obtain a mixed solution B, then dropwise adding the mixed solution B into a reactor, keeping the temperature of the solution in the reactor between-6 ℃ and-4 ℃, continuously keeping the temperature at between-6 ℃ and-4 ℃ for 30-40 min after the dropwise adding is finished, then raising the reaction temperature to 62-65 ℃, and keeping reflux reaction for 12-14 h;
after the reaction is finished, pouring the reactant into water for washing, then separating the lower chloroform layer, concentrating to obtain a light yellow product, and drying to obtain a final product [4,4' - (phenylphosphoryl) bis (1, 4-dipiperazino) ] bis (diphenylphosphine oxide), namely the phosphine-nitrogen flame retardant.
3. The method for preparing a phosphine-nitrogen type flame retardant according to claim 2, wherein the mass ratio of the anhydrous piperazine to the chloroform in the step one is 1 (8-10), and the molar ratio of the anhydrous piperazine to the triethylamine is 1 (2-2.2).
4. The method for preparing a phosphine-nitrogen type flame retardant according to claim 2, characterized in that the mass ratio of the phenylphosphoryl dichloride and the chloroform in the first step is 1 (1-1.5).
5. Use of the phosphine-nitrogen based flame retardant of claim 1 in flame retardant modified polylactic acid.
6. The use according to claim 5, characterized in that the specific method of the flame retardant modified polylactic acid is as follows:
mixing phosphine-nitrogen flame retardant [4,4' - (phenylphosphoryl) bis (1, 4-dipiperazinyl) ] bis (diphenylphosphine oxide) with polylactic acid, heating, melting and blending for 15-20 min, taking out the mixture, and performing hot press molding to obtain the modified polylactic acid.
7. Use according to claim 6, characterized in that the mass of the phosphine-nitrogen flame retardant is between 1% and 6% of the mass of the polylactic acid.
8. Use according to claim 6, characterized in that the mass of the phosphine-nitrogen flame retardant is between 3% and 4% of the mass of the polylactic acid.
9. The use according to claim 6 or 7, characterized in that the heat melt blending is carried out by a torque rheometer, the temperature of each heating zone being 180 ℃, 180 ℃ and 180 ℃ respectively, the rotation speed being 50r/min.
10. The use according to claim 6 or 7, characterized in that the specific method of hot press forming is: and putting the mixed material on a flat vulcanizing machine, and carrying out hot press molding at 180 ℃ under the pressure of 10 MPa.
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