CN115232362A - Preparation method of efficient phosphorus flame retardant - Google Patents
Preparation method of efficient phosphorus flame retardant Download PDFInfo
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- CN115232362A CN115232362A CN202210798636.XA CN202210798636A CN115232362A CN 115232362 A CN115232362 A CN 115232362A CN 202210798636 A CN202210798636 A CN 202210798636A CN 115232362 A CN115232362 A CN 115232362A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 49
- 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 47
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 26
- 239000011574 phosphorus Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 101
- 238000003756 stirring Methods 0.000 claims description 33
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 23
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 230000008878 coupling Effects 0.000 claims description 9
- 238000010168 coupling process Methods 0.000 claims description 9
- 238000005859 coupling reaction Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 230000005587 bubbling Effects 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000004888 barrier function Effects 0.000 abstract description 3
- 238000003763 carbonization Methods 0.000 abstract description 3
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- 230000001276 controlling effect Effects 0.000 abstract 1
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- 230000001105 regulatory effect Effects 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 8
- 230000002572 peristaltic effect Effects 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
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- 238000003889 chemical engineering Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- -1 small molecule halogen Chemical class 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- ZTTFLCGNQCKBRY-UHFFFAOYSA-N O=C1c2ccccc2-c2ccccc2P1=O Chemical compound O=C1c2ccccc2-c2ccccc2P1=O ZTTFLCGNQCKBRY-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
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- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/14—Carbides
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- 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
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
-
- 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
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of a high-efficiency phosphorus flame retardant, which combines the physical barrier effect and the catalytic carbonization of MXene two-dimensional material to isolate the heat and gas exchange between a polymer material and a flame area, and prepares a novel high-efficiency phosphorus flame retardant through chemical covalent grafting; the invention uses a chemical covalent modification method, and prepares a novel flame retardant by finely designing, regulating and controlling a flame retardant molecular structure grafted on the MXene surface and a connection mode and performing molecular level compounding on a two-dimensional material MXene and DPP.
Description
Technical Field
The invention belongs to the technical field of chemistry and chemical engineering, and particularly relates to a preparation method of a high-efficiency phosphorus flame retardant with good flame retardant performance and thermal stability.
Background
With the continuous development of chemical engineering and polymer science, polymer materials are almost ubiquitous, and great progress is brought to the modern society. Unfortunately, the inherent flammability of most polymers makes them susceptible to fire after ignition, resulting in irreparable loss of life, property and culture. Thus, polymers with fire-fighting properties are beginning to receive more attention and choice.
The addition of small molecule halogen or phosphorus containing flame retardants to polymer matrices is currently the most common method of improving fire safety. These flame retardants can polymerize during polymerizationThe compound is decomposed in advance before the decomposition temperature to release free radicals containing phosphorus/halogen, thereby effectively capturing H and OH to play a gas phase flame retardant role. But the initial thermal decomposition temperature (T) of the flame-retardant polymer due to premature decomposition of these flame retardants 5％ ) Greatly reducing the cost. At the same time, the plasticizing effect of small molecules can also lead to the glass transition temperature (T) of the polymer g ) And decreases. Therefore, this essentially results in an inevitable contradiction between flame retardancy and heat resistance. It is noteworthy that small molecule flame retardants not only destroy the mechanical properties of the polymer material due to poor compatibility with the macromolecular chains, but also gradually migrate into the surrounding environment during long-term use, resulting in poor flame retardant durability and creating environmental problems, i.e., small molecule flame retardants present bioaccumulation and toxicity. In view of all of these, the preparation of environmentally friendly and high performance flame retardants is highly desirable.
Compared with small molecules, the macromolecular flame retardant has the advantages of good thermal stability, good compatibility with polymers, almost no biological accumulation and the like, and represents one of green development directions of polymer additives.
Disclosure of Invention
The invention provides a preparation method of a high-efficiency phosphorus flame retardant, which is characterized in that high-molecular phosphorus flame retardant is combined with the physical barrier effect and the catalytic carbonization of MXene two-dimensional material, the heat and gas exchange between a polymer material and a flame area is isolated, a novel high-efficiency phosphorus flame retardant is prepared through chemical covalent grafting, and the two-dimensional material MXene and a long-chain phosphaphenanthrene flame retardant (DPP) are subjected to molecular level compounding to obtain the novel flame retardant.
A preparation method of a high-efficiency phosphorus flame retardant comprises the following steps:
(1) Mixing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with a silane coupling agent, heating to 180-220 ℃ under the protection of nitrogen, and reacting for 6-8h under the condition of vigorous stirring;
(2) Cooling the reactant in the step (1) to 50-60 ℃, adding an ethanol solution A, stirring for reaction for 30 minutes, carrying out reduced pressure distillation, and drying at normal temperature to obtain a DOPO coupling silane coupling agent intermediate compound;
(3) Ultrasonically dispersing MXene in dimethyl sulfoxide, magnetically stirring for 48 hours, centrifugally collecting sediments, and carrying out vacuum drying in a vacuum drying oven to obtain pretreated MXene powder;
(4) Adding DOPO to a silane coupling agent intermediate compound into the ethanol solution B, and stirring at the temperature of 50-70 ℃ at the speed of 300rpm for 1h to obtain a solution A;
(5) And (2) placing the pretreated MXene powder in an ethanol solution B, performing ultrasonic treatment for 10-30min, adding the ethanol solution B, stirring under nitrogen bubbling, dropwise adding the solution A by using a peristaltic pump, heating, stirring and reacting for 2-4h after dropwise adding is finished to obtain a solution B, centrifuging the solution B, washing for 3 times by using the ethanol solution B, and performing freeze drying to obtain the high-efficiency phosphorus flame retardant DPP-MXene.
The silane coupling agent in the step (1) is one or the mixture of more than two of gamma-glycidoxypropyltrimethoxysilane, gamma-aminopropyltriethoxysilane and aminopropyltrimethoxysilane.
The molar ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the silane coupling agent in the step (1) is 1:1-1.5.
The rotating speed of the violent stirring condition in the step (1) is 300r/min.
The ethanol solution A in the step (2) is obtained by mixing ethanol and ultrapure water according to the mass ratio of 1:2, and the adding amount of the ethanol solution A is 1.5-2 times of the volume of the reactant.
The temperature of the reduced pressure distillation in the step (2) is 60-70 ℃, and the pressure is 0.07Mpa.
Step (3), the mass volume ratio g of MXene to dimethyl sulfoxide is 1: mL, and the ultrasonic dispersion time is 30-60min; the magnetic stirring speed is 15rpm; the centrifugal speed is 15000rpm, and the centrifugal time is 120min; the vacuum drying temperature is 40-60 deg.C, and the drying time is 72-96h.
The ethanol solution B in the step (4) is obtained by mixing absolute ethanol and ultrapure water according to the volume ratio of 9:1; the mass volume ratio g: mL of the DOPO coupling silane coupling agent intermediate compound to the ethanol solution B is 1.
The mass volume ratio g of the MXene powder pretreated in the step (5) to the ethanol solution B is 1: mL, and the mass volume ratio of the MXene powder to the ethanol solution B is equal to that of the ethanol solution B in the two times; the stirring speed was 200rpm and the temperature was 25-35 ℃ while stirring with nitrogen bubbling.
The mass ratio of DOPO coupling silane coupling agent intermediate compound in the liquid A dripped in the step (5) to the pre-treated MXene powder added in the ethanol solution B is 1.8.
And (5) heating, stirring and reacting at the temperature of 50-60 ℃ and at the stirring speed of 350rpm.
The centrifugal speed of the step (5) is 8000rpm, and the time is 5-10min.
The invention has the beneficial effects that:
the 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide (DOPO) derivative DPP prepared by the invention can generate strong dehydrating agents such as metaphosphoric acid and polymetaphosphoric acid in the pyrolysis process, can play an excellent role in catalyzing the dehydration of carbon-containing compounds to form stable carbon layers, forms active free radicals such as PO, PO2, HPO and the like at high temperature, and reacts with HO, H and alkane free radicals in gas phase, thereby terminating the chain reaction of the base material, playing a gas phase flame retardant role, and enhancing the catalytic char formation effect due to the introduction of silicon element; the phosphorus flame retardant combines the physical barrier effect and the catalytic carbonization effect of MXene, and has good fireproof safety.
Drawings
FIG. 1 is a physical diagram of a flame retardant DPP-MXene prepared in example 1;
FIG. 2 is an infrared chart of DPP prepared in step (1) of example 1, raw material DOPO and silane coupling agent SCA;
FIG. 3 is an infrared image of the flame retardant DPP-MXene and the starting material MXene prepared in example 1;
FIG. 4 is a graph of the thermogravimetry of the flame retardants DPP-MXene and DPP prepared in example 1.
Detailed Description
The present invention is further illustrated by the following specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
A preparation method of a high-efficiency phosphorus flame retardant comprises the following steps:
(1) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and silane coupling agent gamma-glycidoxypropyltrimethoxysilane (SCA) are added into a three-neck bottle with a condenser tube and mechanical stirring according to the molar ratio of 1:1, the temperature is increased to 180 ℃ under the atmosphere of nitrogen, the mixture is vigorously stirred and reacted for 6 hours at the rotating speed of 300r/min, the mixture is cooled to 50 ℃, and an ethanol solution A (obtained by mixing ethanol and ultrapure water according to the mass ratio of 1:2) with the volume being 2 times of the volume of reactants is added into the three-neck bottle and stirred and reacted for 30 minutes; then, carrying out reduced pressure distillation at 60 ℃ under the condition of 0.07Mpa until the quality is not changed any more, and drying the residue at normal temperature for 24h to obtain a DOPO coupling silane coupling agent intermediate compound DPP;
(2) Dispersing 1g of MXene in 35mL of dimethyl sulfoxide by ultrasonic for 30min, magnetically stirring at the rotating speed of 15r/min for 48h, centrifuging at the rotating speed of 15000rpm for 120min, collecting sediments, and drying in a vacuum drying oven at 60 ℃ for 72h to obtain pretreated MXene powder;
(3) Mixing 20mL of ultrapure water and 180mL of absolute ethanol to prepare an ethanol solution B, adding 1.8g of DPP into a three-neck flask containing 50mL of the ethanol solution B, and stirring at the temperature of 60 ℃ at the speed of 300rpm for 1h to obtain a solution A;
(4) Putting 1g of pretreated MXene powder into a glass bottle containing 50mL of ethanol solution B, performing ultrasonic treatment for 15min, then putting the pretreated MXene powder into a 250mL three-neck flask, adding 50mL of ethanol solution B, stirring at the rotating speed of 200rpm under the condition of nitrogen bubbling and the temperature of 30 ℃, and dropwise adding the solution A into the three-neck flask by using a peristaltic pump (the dropping speed of the peristaltic pump is about 1.2 mL/min); after the dropwise addition is finished, reacting for 3 hours at the rotation speed of 350rpm and the temperature of 55 ℃ to obtain a solution B; and (3) centrifuging the solution B at 8000rpm for 5min, finally washing the solution B with an ethanol solution for 3 times, and freeze-drying the solution B for 48 hours to obtain the product DPP-Mxene, wherein the substance is a black powdery product as shown in figure 1.
Example 2
A preparation method of a high-efficiency phosphorus flame retardant comprises the following steps:
(1) Adding 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and silane coupling agent Aminopropyltrimethoxysilane (APS) into a three-neck bottle with a condenser tube and mechanical stirring according to the molar ratio of 1.3, heating to 210 ℃ under nitrogen atmosphere, violently stirring at the rotating speed of 300r/min for reaction for 7h, and cooling to 55 ℃; adding an ethanol solution A (the ethanol solution A is obtained by mixing ethanol and ultrapure water according to the mass ratio of 1:2) with the volume of 1.5 times of the volume of the reactant into the three-neck flask, and stirring for reaction for 30min; carrying out reduced pressure distillation at 70 ℃ under the pressure of 0.07Mpa until the quality is not changed any more, and drying the residue at normal temperature for 24h to obtain a DOPO coupling silane coupling agent intermediate compound DPP;
(2) Dispersing 2g MXene into 80mL dimethyl sulfoxide by ultrasonic for 60min, magnetically stirring for 48h at the rotating speed of 15r/min, centrifuging for 120min at the rotating speed of 15000rpm, collecting sediments, and drying for 96h in a vacuum drying oven at 40 ℃ to obtain pretreated MXene powder;
(3) Mixing 80mL of ultrapure water with 720mL of absolute ethanol to prepare an ethanol solution B, adding 4g of DPP into a three-neck flask containing 100mL of ethanol solution B, and stirring at the temperature of 50 ℃ for 1h at the speed of 300rpm to obtain a solution A;
(4) Placing 2g of pretreated MXene powder in a glass bottle containing 100mL of ethanol solution B, performing ultrasonic treatment for 10min, then placing the pretreated MXene powder in a 500mL three-neck flask, adding 100mL of ethanol solution B, stirring at the rotating speed of 200rpm under the condition of nitrogen bubbling and the temperature of 35 ℃, and dropwise adding the solution A into the three-neck flask by using a peristaltic pump (the dropping speed of the peristaltic pump is about 1.2 mL/min); after the dropwise addition is finished, reacting for 2 hours at the rotation speed of 350rpm and the temperature of 50 ℃ to obtain a solution B; and (3) centrifuging the solution B at 8000rpm for 10min, finally washing the solution B with ethanol solution B for 3 times, and freeze-drying the solution B for 48 hours to obtain the product DPP-MXene.
Example 3
A preparation method of a high-efficiency phosphorus flame retardant comprises the following steps:
(1) Adding 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and a silane coupling agent gamma-aminopropyltriethoxysilane (KH 550) into a three-neck bottle with a condenser pipe and mechanical stirring according to the molar ratio of 1.5, heating to 220 ℃ under the nitrogen atmosphere, violently stirring at the rotation speed of 300r/min for reacting for 8h, and cooling to 60 ℃; adding an ethanol solution (the ethanol solution is obtained by mixing ethanol and ultrapure water according to the mass ratio of 1:2) with the volume of 1.6 times of the reactant volume into the three-neck flask, and violently stirring at the rotating speed of 300r/min for reaction for 30min; distilling under reduced pressure under 65,0.07Mpa until the mass is not changed any more, and drying the residue at normal temperature for 24h to obtain DOPO coupling silane coupling agent intermediate compound DPP;
(2) Dispersing 1.3g MXene into 50mL dimethyl sulfoxide by ultrasonic for 40min, magnetically stirring at the rotating speed of 15r/min for 48h, centrifuging at the rotating speed of 15000rpm for 120min, collecting sediments, and drying in a vacuum drying oven at 50 ℃ for 84h to obtain pretreated MXene powder;
(3) Mixing 20mL of ultrapure water and 180mL of absolute ethanol to prepare an ethanol solution B, adding 2.47g of DPP into a three-neck flask containing 74.1mL of the ethanol solution B, and stirring at the temperature of 70 ℃ for 1h at the speed of 300rpm to obtain a solution A;
(4) Putting 1.3g of pretreated MXene powder into a glass bottle containing 50mL of ethanol solution B, performing ultrasonic treatment for 30min, then putting the pretreated MXene powder into a 250mL three-neck flask, adding 50mL of ethanol solution, stirring at the rotation speed of 200rpm under the condition of nitrogen bubbling and the temperature of 25 ℃, and then dropwise adding A into the three-neck flask by using a peristaltic pump (the dropping speed of the peristaltic pump is about 1.2 mL/min); after the dropwise addition is finished, reacting for 4 hours at the rotating speed of 350rpm and the temperature of 60 ℃ to obtain a solution B; and (3) centrifuging the solution B at 8000rpm for 6min, finally washing the solution B with ethanol solution 3 times, and freeze-drying the solution for 48h to obtain the product DPP-MXene.
FIG. 2 is an infrared chart of DPP prepared in step (1) of example 1, raw material DOPO and silane coupling agent SCA, and it can be seen from the chart that P-H in epoxy group and DOPO disappeared after high temperature reaction and became 1100cm in length -1 C-O stretching vibration of the aliphatic secondary alcohol appears, which shows that the addition reaction of DOPO and SCA occurs to obtain a product DPP, and the success of DPP preparation is shown.
FIG. 3 Infrared ray picture of DPP-MXene as flame retardant and MXene as raw material prepared in example 1, as seen in spectrum of DPP-MXene, 563cm -1 A Ti-O characteristic peak is shown nearby, and 3460cm is obtained after the reaction -1 The characteristic peak of nearby hydroxyl groups is reduced and is 741cm -1 A stretching vibration peak of 1086cm of Si-O-Ti appears nearby -1 A stretching vibration peak of Si-O-Si appears nearby, and the DPP and MXene are shown to react to generate DPP-MXene.
FIG. 4 graph of thermal weight loss of flame retardants DPP-MXene and MXene prepared in example 1 and DOPO coupling with silane coupling agent intermediate compound DPP; the graph shows that the maximum degradation temperature (Tmax) of the modified high-molecular flame retardant DPP-MXene is obviously improved compared with that of MXene, and the introduction of MXene optimizes the carbon residue condition of DPP, which shows that the flame retardant DPP-MXene obtained in example 1 has a remarkable catalytic carbon formation effect and flame retardant effect on flame retardance.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes in the embodiments and modifications thereof may be made, and equivalents may be substituted for elements thereof; and the modifications or the substitutions do not make the essence of the corresponding technical solutions deviate from the technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the efficient phosphorus flame retardant is characterized by comprising the following steps of:
(1) Mixing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with silane coupling agent, heating to 180-220 ℃ under the protection of nitrogen, and reacting for 6-8h under the condition of vigorous stirring;
(2) Cooling the reactant in the step (1) to 50-60 ℃, adding an ethanol solution A, stirring for reacting for 30 minutes, carrying out reduced pressure distillation, and drying at normal temperature to obtain a DOPO-linked silane coupling agent intermediate compound;
(3) MXene is ultrasonically dispersed in dimethyl sulfoxide, magnetically stirred for 48 hours, and centrifuged to collect sediment, and the sediment is dried in vacuum to obtain pretreated MXene powder;
(4) Adding DOPO linked silane coupling agent intermediate compound into ethanol solution B, and stirring at 50-70 deg.C at 300rpm for 1h to obtain solution A;
(5) And (2) placing the pretreated MXene powder in an ethanol solution B, performing ultrasonic treatment for 10-30min, adding the ethanol solution B, stirring under nitrogen bubbling, dropwise adding the solution A, heating after dropwise adding, stirring, reacting for 2-4h to obtain a solution B, centrifuging the solution B, washing for 3 times by using the ethanol solution B, and performing freeze drying to obtain the efficient phosphorus flame retardant.
2. The method for preparing a high efficiency phosphorus based flame retardant according to claim 1, wherein the silane coupling agent in step (1) is one or more of gamma-glycidoxypropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, and aminopropyltrimethoxysilane.
3. The preparation method of the efficient phosphorus flame retardant according to claim 1, wherein the molar ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the silane coupling agent in the step (1) is 1:1-1.5; the rotation speed under the condition of vigorous stirring is 300r/min.
4. The method for preparing the efficient phosphorus flame retardant according to claim 1, wherein the ethanol solution A in the step (2) is obtained by mixing ethanol and ultrapure water in a mass ratio of 1:2, and the addition amount of the ethanol solution A is 1.5-2 times of the volume of the reactant; the reduced pressure distillation temperature is 60-70 deg.C, and the pressure is 0.07Mpa.
5. The preparation method of the efficient phosphorus flame retardant according to claim 1, wherein in the step (3), the mass volume ratio g: mL of MXene to dimethyl sulfoxide is 1; the magnetic stirring speed is 15rpm; the centrifugal speed is 15000rpm, and the centrifugal time is 120min; vacuum drying at 40-60 deg.C for 72-96 hr.
6. The method for preparing the efficient phosphorus flame retardant according to claim 1, wherein the ethanol solution B in the step (4) is obtained by mixing absolute ethanol and ultrapure water in a volume ratio of 9:1; the mass volume ratio g: mL of the DOPO coupling silane coupling agent intermediate compound to the ethanol solution B is 1.
7. The preparation method of the efficient phosphorus flame retardant according to claim 1, wherein the mass-to-volume ratio g: mL of the pretreated MXene powder to the ethanol solution B in the step (5) is 1; the stirring speed was 200rpm and the temperature was 25-35 ℃.
8. The method for preparing the efficient phosphorus-based flame retardant according to claim 1, wherein the mass ratio of the DOPO coupling silane coupling agent intermediate compound to the pretreated MXene powder in the step (5) is 1.8-2:1.
9. The method for preparing the efficient phosphorus flame retardant according to claim 1, wherein the temperature of the step (5) is raised, the stirring reaction temperature is 50-60 ℃, and the stirring rotation speed is 350rpm.
10. The method for preparing the efficient phosphorus flame retardant according to claim 1, wherein the centrifugal rotation speed in the step (5) is 8000rpm, and the time is 5-10min.
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| CN112063200A (en) * | 2020-09-06 | 2020-12-11 | 西北工业大学 | MXene-based solvent-free nano fluid and preparation method thereof |
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