CN114231011A - Preparation method of phenyl phosphine oxide and graphene-POSS flame-retardant polycarbonate material - Google Patents
Preparation method of phenyl phosphine oxide and graphene-POSS flame-retardant polycarbonate material Download PDFInfo
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000003063 flame retardant Substances 0.000 title claims abstract description 73
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 64
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 64
- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical compound O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 40
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 8
- JNTPTNNCGDAGEJ-UHFFFAOYSA-N 6-chlorohexan-1-ol Chemical compound OCCCCCCCl JNTPTNNCGDAGEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 23
- OTBHHUPVCYLGQO-UHFFFAOYSA-N bis(3-aminopropyl)amine Chemical compound NCCCNCCCN OTBHHUPVCYLGQO-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000010992 reflux Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 238000001746 injection moulding Methods 0.000 claims description 16
- 230000002195 synergetic effect Effects 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 239000008187 granular material Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- -1 imino graphene Chemical compound 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 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 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 239000004593 Epoxy Substances 0.000 abstract description 4
- 125000001309 chloro group Chemical group Cl* 0.000 abstract description 4
- 125000001841 imino group Chemical group [H]N=* 0.000 abstract description 4
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 abstract description 3
- 230000001476 alcoholic effect Effects 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 125000000879 imine group Chemical group 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000007142 ring opening reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- AZAQDXJWNHXLOG-UHFFFAOYSA-N phenylphosphanium;chloride Chemical compound [Cl-].[PH3+]C1=CC=CC=C1 AZAQDXJWNHXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention relates to the technical field of polycarbonate flame retardance, and discloses a preparation method of a phenyl phosphine oxide and graphene-POSS flame-retardant polycarbonate material, which comprises the following steps of firstly carrying out amino-terminated imino modification on graphene; then, carrying out an epoxy ring-opening reaction on a single epoxy group on POSS and an amino-terminated group on graphene to generate an imino graphene-POSS; then, reacting alcoholic hydroxyl on 6-chloro-1-hexanol with a chlorine functional group of diphenylphosphine chloride to generate chlorine-terminated diphenyl phosphine oxide; and finally, grafting of phenyl phosphine oxide and graphene-POSS is realized through a chlorine functional group on the chlorine-terminated diphenyl phosphine oxide and an imine group on the imidized graphene-POSS, so that the phenyl phosphine oxide and graphene-POSS flame retardant is prepared, and the phenyl phosphine oxide and graphene-POSS flame retardant is applied to flame-retardant polycarbonate, so that the effective technical effect of remarkably improving the flame retardant performance is achieved.
Description
Technical Field
The invention relates to the technical field of polycarbonate flame retardance, in particular to a preparation method of a phenyl phosphine oxide and graphene-POSS flame-retardant polycarbonate material.
Background
Although the main chain of the polycarbonate contains benzene rings, the polycarbonate can be condensed into aromatic carbon substances during combustion reaction, the relative carbon forming rate is high, the polycarbonate can be self-extinguished, and the flame retardant grade can reach the standard of UL94V-2, the flame retardant effect is still not ideal when the polycarbonate is applied to various high and new technical fields.
The research on the flame retardance of the silicon-containing flame retardant POSS on polycarbonate is disclosed in the literature at present, and the application of graphene and organic phosphorus compounds to flame-retardant organic polymer materials is also disclosed in the literature.
The following references are cited for the present invention: the research and performance research of epoxy POSS modified epoxy resin in volume 71 and phase 5 of 2020 of the chemical industry journal discloses the structure and preparation method of epoxy POSS;
the invention tries to synthesize a phenyl phosphine oxide and graphene-POSS flame-retardant polycarbonate material, provides a new method for preparing the phenyl phosphine oxide and graphene-POSS flame-retardant polycarbonate material, and adopts a cone calorimeter to simulate the combustion behavior of the material in an actual fire, thereby comprehensively evaluating various properties of the material in the heating combustion process.
Disclosure of Invention
Technical problem to be solved
The invention aims to provide a phenyl phosphine oxide and graphene-POSS flame retardant and a preparation method of the phenyl phosphine oxide and graphene-POSS flame retardant.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a phenyl phosphine oxide-graphene-POSS flame-retardant polycarbonate material comprises the following steps:
step S1, preparing amino-terminated imino graphene:
placing 5-12 parts of graphene in H2SO4And HNO3The mixed solvent is subjected to ultrasonic treatment at room temperature, diluted and filtered, washed to be neutral by distilled water, and dried in vacuum to obtain carboxylated graphene;
placing the carboxylated graphene into a flask containing 100-500 parts of 3, 3 '-diaminodipropylamine, performing ultrasonic treatment at room temperature, adding N, N' -dicyclohexylcarbodiimide, uniformly mixing, refluxing in an oil bath, and drying to obtain amino-terminated imidized graphene;
step S2, preparation of imidized graphene-POSS:
adding 7-20 parts of epoxy group POSS and acetone into a four-neck flask provided with a stirrer, a condenser pipe, a constant pressure funnel and a thermometer, stirring and preheating, adding 1.3-3 parts of amino-terminated imidized graphene, and carrying out heat preservation reaction to obtain imidized graphene-POSS;
step S3, preparing the phenyl phosphine oxide and graphene-POSS flame retardant:
sequentially adding 8-20 parts of 6-chloro-1-hexanol, tetrahydrofuran and triethylamine into a four-neck flask provided with a stirrer, a constant-pressure dropping funnel and a reflux condenser tube, stirring at room temperature, adding 17-25 parts of diphenylphosphinic chloride into a reaction system, and performing reflux reaction after the dropwise addition is finished to obtain chloro-terminated diphenylphosphine oxide;
adding 8-20 parts of chlorine-terminated diphenyl phosphine oxide, N-Dimethylformamide (DMF) and 30-80 parts of imidized graphene-POSS into a single-neck flask, and reacting to obtain phenyl phosphine oxide and graphene-POSS flame retardant;
step S4, preparing a flame-retardant polycarbonate material with phenyl phosphine oxide and graphene-POSS:
weighing 1-12 parts of phenylphosphine oxide synergistic graphene-POSS flame retardant and 100 parts of polycarbonate, mixing, tabletting and cooling after blending, drying granules, and performing injection molding on an injection molding machine to obtain a standard sample of the phenylphosphine oxide synergistic graphene-POSS flame retardant polycarbonate material.
Preferably, the step S1: refluxing for 36-48h at the temperature of 110-150 ℃ in an oil bath, and drying to obtain the terminal amino-imino graphene.
Preferably, the step S2: stirring and preheating for 30-60min at 40-60 ℃, and reacting for 4-6h under the condition of heat preservation to obtain the imidized graphene-POSS.
Preferably, the step S3: after the dropwise addition, the temperature is raised to 40-60 ℃, and reflux reaction is carried out for 18-25h, so as to obtain the chloro-terminated diphenyl phosphine oxide.
Preferably, the step S3: reacting for 12-24h at 60-90 ℃ to obtain the phenylphosphine oxide synergistic graphene-POSS flame retardant.
Preferably, the step S4: mixing at 140-230 deg.C for 2-15min, and drying at 90-150 deg.C.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
according to the preparation method, firstly, the graphene is subjected to carboxylation treatment, and the amino group on 3, 3' -diamino dipropylamine reacts with the carboxyl group to realize the amino-terminated imino modification of the graphene;
then, carrying out an epoxy ring-opening reaction on a single epoxy group on POSS and an amino-terminated group on graphene to generate an imino graphene-POSS, so that the graphene is grafted on one end of 3, 3 '-diamino dipropylamine, and the POSS is grafted on the other end of 3, 3' -diamino dipropylamine;
then, reacting alcoholic hydroxyl on 6-chloro-1-hexanol with a chlorine functional group of diphenylphosphine chloride to generate chlorine-terminated diphenyl phosphine oxide;
finally, grafting of the phenyl phosphine oxide and the graphene-POSS is realized through a chlorine functional group on the chlorine-terminated diphenyl phosphine oxide and an imine group on the imidized graphene-POSS, so that the phenyl phosphine oxide and graphene-POSS flame retardant is prepared;
the phenyl phosphine oxide and graphene-POSS flame retardant is applied to flame-retardant polycarbonate, the LOI value of the phenyl phosphine oxide and graphene-POSS flame-retardant polycarbonate material reaches 29.0-39.1%, and the phenyl phosphine oxide and graphene-POSS flame-retardant polycarbonate material is obviously superior to that of the prior art in a series of flame-retardant index parameters such as total released heat THR, heat release rate peak PHRR, effective combustion heat peak PEHC and the like;
the main flame retardant mechanism is as follows: phosphorus element in the phenylphosphine oxide can promote the polycarbonate matrix to rapidly generate a carbon layer during combustion, graphene can further promote the generation of the carbon layer by blocking the exchange of substances and energy between flame and the polycarbonate matrix, and silicon element in the POSS can effectively promote the stability of the carbon layer, so that the beneficial technical effect of synergistic flame retardance is realized.
Detailed Description
Example 1:
a preparation method of a phenyl phosphine oxide-graphene-POSS flame-retardant polycarbonate material comprises the following steps:
step S1, preparing amino-terminated imino graphene:
0.1g of graphene was placed in 120mL of H2SO4And HNO3Performing ultrasonic treatment for 4 hours at room temperature in a volume ratio of 3: 1, diluting, filtering, washing with distilled water to be neutral, and performing vacuum drying to obtain carboxylated graphene;
placing the carboxylated graphene into a flask containing 3g of 3, 3 '-diaminodipropylamine, performing ultrasonic treatment at room temperature for 30min, adding 0.1g of N, N' -dicyclohexylcarbodiimide, uniformly mixing, refluxing for 48h at 110 ℃ in an oil bath, performing ultrasonic treatment on the product with absolute ethyl alcohol to remove the residual N, N '-dicyclohexylcarbodiimide and 3, 3' -diaminodipropylamine, repeatedly washing the final product with distilled water for several times, and drying to obtain the aminoiminomethylated graphene;
step S2, preparation of imidized graphene-POSS:
adding 10g of epoxy group POSS and 50mL of acetone into a four-neck flask provided with a stirrer, a condenser pipe, a constant-pressure funnel and a thermometer, stirring and preheating at 60 ℃ for 30min, adding 1.3g of amino-terminated imidized graphene, and carrying out heat preservation reaction for 4h to obtain imidized graphene-POSS;
step S3, preparing the phenyl phosphine oxide and graphene-POSS flame retardant:
sequentially adding 1.3g of 6-chloro-1-hexanol, 15mL of tetrahydrofuran and 3.5g of triethylamine into a 50mL four-neck flask provided with a stirrer, a constant-pressure dropping funnel and a reflux condenser, stirring at room temperature, adding 2.3g of diphenylphosphinic chloride into a reaction system within 1h, heating to 60 ℃ after the dropwise addition is finished, and carrying out reflux reaction for 25 h;
after the reaction is finished, filtering triethylamine hydrochloride, concentrating the filtrate by a rotary evaporator to remove part of solvent, pouring the filtrate into deionized water, precipitating solid, sequentially washing the obtained product with cold tetrahydrofuran and distilled water for 3 times after suction filtration, and drying the product in vacuum at 50 ℃ for 48 hours to obtain chlorine-terminated diphenyl phosphine oxide;
adding 2g of chlorine-terminated diphenyl phosphine oxide, 30mL of N, N-Dimethylformamide (DMF) and 8g of imidized graphene-POSS into a 50mL single-neck flask, reacting at 90 ℃ for 12h, precipitating in deionized water to separate out a solid, and drying in vacuum to obtain the phenyl phosphine oxide synergistic graphene-POSS flame retardant;
step S4, preparing a flame-retardant polycarbonate material with phenyl phosphine oxide and graphene-POSS:
firstly, drying the polycarbonate for 12 hours at 120 ℃; then weighing 8g of phenyl phosphine oxide synergistic graphene-POSS flame retardant and 100g of polycarbonate, mixing for 15min at 180 ℃, tabletting and cooling after blending, drying granules at 110 ℃, performing injection molding on an injection molding machine to obtain a standard sample of the phenyl phosphine oxide synergistic graphene-POSS flame retardant polycarbonate material, and testing the correlation performance.
Example 2:
a preparation method of a phenyl phosphine oxide-graphene-POSS flame-retardant polycarbonate material comprises the following steps:
step S1, preparing amino-terminated imino graphene:
0.12g of graphene was placed in 120mL of H2SO4And HNO3Performing ultrasonic treatment for 5 hours at room temperature in a volume ratio of 3: 1, diluting, filtering, washing with distilled water to be neutral, and performing vacuum drying to obtain carboxylated graphene;
placing the carboxylated graphene into a flask containing 5g of 3, 3 '-diaminodipropylamine, performing ultrasonic treatment at room temperature for 60min, adding 0.12g of N, N' -dicyclohexylcarbodiimide, uniformly mixing, refluxing for 36h at 150 ℃ in an oil bath, performing ultrasonic treatment on the product with absolute ethyl alcohol to remove the residual N, N '-dicyclohexylcarbodiimide and 3, 3' -diaminodipropylamine, repeatedly washing the final product with distilled water for several times, and drying to obtain the aminoiminomethylated graphene;
step S2, preparation of imidized graphene-POSS:
adding 7g of epoxy group POSS and 50mL of acetone into a four-neck flask provided with a stirrer, a condenser pipe, a constant-pressure funnel and a thermometer, stirring and preheating at 40 ℃ for 60min, adding 1.5g of amino-terminated imidized graphene, and carrying out heat preservation reaction for 6h to obtain imidized graphene-POSS;
step S3, preparing the phenyl phosphine oxide and graphene-POSS flame retardant:
sequentially adding 0.8g of 6-chloro-1-hexanol, 15mL of tetrahydrofuran and 3.5g of triethylamine into a 50mL four-neck flask provided with a stirrer, a constant-pressure dropping funnel and a reflux condenser, stirring at room temperature, adding 2.5g of diphenylphosphinic chloride into a reaction system within 1h, heating to 40 ℃ after the dropwise addition is finished, and carrying out reflux reaction for 24 h;
after the reaction is finished, filtering triethylamine hydrochloride, concentrating the filtrate by a rotary evaporator to remove part of solvent, pouring the filtrate into deionized water, precipitating solid, sequentially washing the obtained product with cold tetrahydrofuran and distilled water for 3 times after suction filtration, and drying the product in vacuum at 50 ℃ for 48 hours to obtain chlorine-terminated diphenyl phosphine oxide;
adding 1.2g of chlorine-terminated diphenyl phosphine oxide, 30mL of N, N-Dimethylformamide (DMF) and 5g of imidized graphene-POSS into a 50mL single-neck flask, reacting at 60 ℃ for 24 hours, precipitating and separating out solids in deionized water, and drying in vacuum to obtain the phenyl phosphine oxide synergistic graphene-POSS flame retardant;
step S4, preparing a flame-retardant polycarbonate material with phenyl phosphine oxide and graphene-POSS:
firstly, drying the polycarbonate for 12 hours at 120 ℃; then weighing 1g of phenyl phosphine oxide synergistic graphene-POSS flame retardant and 100g of polycarbonate, mixing for 5min at 230 ℃, tabletting and cooling after blending, drying granules at 90 ℃, performing injection molding on a standard sample of the phenyl phosphine oxide synergistic graphene-POSS flame retardant polycarbonate material on an injection molding machine, and testing the correlation performance.
Example 3:
a preparation method of a phenyl phosphine oxide-graphene-POSS flame-retardant polycarbonate material comprises the following steps:
step S1, preparing amino-terminated imino graphene:
0.05g of graphene was placed in 120mL of H2SO4And HNO3Ultrasonic treating at room temperature for 2 hr at a volume ratio of 3: 1, diluting, filtering, washing with distilled water to neutrality, and vacuum filteringDrying to obtain carboxylated graphene;
placing the carboxylated graphene in a flask containing 1g of 3, 3 '-diaminodipropylamine, performing ultrasonic treatment at room temperature for 20min, adding 0.05g of N, N' -dicyclohexylcarbodiimide, uniformly mixing, refluxing at 130 ℃ in an oil bath for 40h, performing ultrasonic treatment on the product with absolute ethyl alcohol to remove the residual N, N '-dicyclohexylcarbodiimide and 3, 3' -diaminodipropylamine, repeatedly washing the final product with distilled water for several times, and drying to obtain the aminoiminomethylated graphene;
step S2, preparation of imidized graphene-POSS:
adding 20g of epoxy group POSS and 50mL of acetone into a four-neck flask provided with a stirrer, a condenser pipe, a constant-pressure funnel and a thermometer, stirring and preheating at 50 ℃ for 30min, adding 3g of amino-terminated imidized graphene, and carrying out heat preservation reaction for 5h to obtain imidized graphene-POSS;
step S3, preparing the phenyl phosphine oxide and graphene-POSS flame retardant:
sequentially adding 2g of 6-chloro-1-hexanol, 15mL of tetrahydrofuran and 3.5g of triethylamine into a 50mL four-neck flask provided with a stirrer, a constant-pressure dropping funnel and a reflux condenser tube, stirring at room temperature, adding 1.7g of diphenylphosphinic chloride into a reaction system within 1h, heating to 60 ℃ after the dropwise addition is finished, and carrying out reflux reaction for 18 h;
after the reaction is finished, filtering triethylamine hydrochloride, concentrating the filtrate by a rotary evaporator to remove part of solvent, pouring the filtrate into deionized water, precipitating solid, sequentially washing the obtained product with cold tetrahydrofuran and distilled water for 3 times after suction filtration, and drying the product in vacuum at 50 ℃ for 48 hours to obtain chlorine-terminated diphenyl phosphine oxide;
adding 0.8g of chlorine-terminated diphenyl phosphine oxide, 30mL of N, N-Dimethylformamide (DMF) and 3g of imidized graphene-POSS into a 50mL single-neck flask, reacting for 15h at 80 ℃, precipitating and separating out solids in deionized water, and drying in vacuum to obtain the phenyl phosphine oxide synergistic graphene-POSS flame retardant;
step S4, preparing a flame-retardant polycarbonate material with phenyl phosphine oxide and graphene-POSS:
firstly, drying the polycarbonate for 12 hours at 120 ℃; then weighing 12g of phenyl phosphine oxide synergistic graphene-POSS flame retardant and 100g of polycarbonate, mixing for 10min at 140 ℃, tabletting and cooling after blending, drying granules at 150 ℃, performing injection molding on an injection molding machine to obtain a standard sample of the phenyl phosphine oxide synergistic graphene-POSS flame retardant polycarbonate material, and performing a correlation performance test.
Comparative example 1:
a preparation method of a graphene flame-retardant polycarbonate material comprises the following steps:
firstly, drying the polycarbonate for 12 hours at 120 ℃; then weighing 0.1g of graphene and 100g of polycarbonate, mixing for 15min at 180 ℃, tabletting and cooling after blending, drying granules at 110 ℃, performing injection molding on a standard sample of the graphene flame-retardant polycarbonate material on an injection molding machine, and testing the correlation performance.
Comparative example 2:
a preparation method of a POSS flame-retardant polycarbonate material comprises the following steps:
firstly, drying the polycarbonate for 12 hours at 120 ℃; then weighing 7g of epoxy group POSS and 100g of polycarbonate, mixing for 5min at 230 ℃, tabletting and cooling after blending, drying granules at 90 ℃, injection molding into a standard sample of POSS flame-retardant polycarbonate material on an injection molding machine, and testing the correlation performance.
Comparative example 3:
a preparation method of a phenylphosphine chloride flame-retardant polycarbonate material comprises the following steps:
firstly, drying the polycarbonate for 12 hours at 120 ℃; then weighing 1.7g of diphenylphosphine chloride and 100g of polycarbonate, mixing for 10min at 140 ℃, tabletting and cooling after blending, drying granules at 150 ℃, performing injection molding on an injection molding machine to obtain a standard sample of the phenylphosphine chloride flame-retardant polycarbonate material, and performing correlation performance test.
And (3) performance measurement:
firstly, testing the flame-retardant polycarbonate materials prepared in the examples and the comparative examples by adopting an oxygen index instrument according to the GB/T2406-93 standard, wherein the test results are shown in the following table 1;
secondly, adopting a cone calorimeter to perform reaction at 50kW/m according to ISO5660-1 standard2The test is carried out under the heat radiation power, the sample size is 100mm multiplied by 6mm, and the test result is shown in the following table 2;
TABLE 1
| Sample (I) | Limiting oxygen index (LOI value,%) |
| Example 1 | 39.1 |
| Example 2 | 29.0 |
| Example 3 | 31.4 |
| Comparative example 1 | 24.8 |
| Comparative example 2 | 23.0 |
| Comparative example 3 | 20.5 |
As can be seen from Table 1, the LOI value of the phenyl phosphine oxide and graphene-POSS flame-retardant polycarbonate material is significantly higher than that of the flame-retardant polycarbonate material of the comparative example;
TABLE 2
As can be seen from Table 2, the phenyl phosphine oxide is remarkably superior to the flame-retardant polycarbonate material of the comparative example in a series of flame-retardant index parameters such as total heat release THR, heat release rate peak PHRR, effective combustion heat peak PEHC and the like;
in combination with the limiting oxygen index mentioned above, it can be concluded that: the phenyl phosphine oxide is cooperated with the graphene-POSS flame retardant to remarkably improve the flame retardant capability of the polycarbonate.
Claims (6)
1. A preparation method of a phenyl phosphine oxide-graphene-POSS flame-retardant polycarbonate material is characterized by comprising the following steps:
step S1, preparing amino-terminated imino graphene:
placing 5-12 parts of graphene in H2SO4And HNO3The mixed solvent is subjected to ultrasonic treatment at room temperature, diluted and filtered, washed to be neutral by distilled water, and dried in vacuum to obtain carboxylated graphene;
placing the carboxylated graphene into a flask containing 100-500 parts of 3, 3 '-diaminodipropylamine, performing ultrasonic treatment at room temperature, adding N, N' -dicyclohexylcarbodiimide, uniformly mixing, refluxing in an oil bath, and drying to obtain amino-terminated imidized graphene;
step S2, preparation of imidized graphene-POSS:
adding 7-20 parts of epoxy group POSS and acetone into a four-neck flask provided with a stirrer, a condenser pipe, a constant pressure funnel and a thermometer, stirring and preheating, adding 1.3-3 parts of amino-terminated imidized graphene, and carrying out heat preservation reaction to obtain imidized graphene-POSS;
step S3, preparing the phenyl phosphine oxide and graphene-POSS flame retardant:
sequentially adding 8-20 parts of 6-chloro-1-hexanol, tetrahydrofuran and triethylamine into a four-neck flask provided with a stirrer, a constant-pressure dropping funnel and a reflux condenser tube, stirring at room temperature, adding 17-25 parts of diphenylphosphinic chloride into a reaction system, and performing reflux reaction after the dropwise addition is finished to obtain chloro-terminated diphenylphosphine oxide;
adding 8-20 parts of chlorine-terminated diphenyl phosphine oxide, N-Dimethylformamide (DMF) and 30-80 parts of imidized graphene-POSS into a single-neck flask, and reacting to obtain phenyl phosphine oxide and graphene-POSS flame retardant;
step S4, preparing a flame-retardant polycarbonate material with phenyl phosphine oxide and graphene-POSS:
weighing 1-12 parts of phenylphosphine oxide synergistic graphene-POSS flame retardant and 100 parts of polycarbonate, mixing, tabletting and cooling after blending, drying granules, and performing injection molding on an injection molding machine to obtain a standard sample of the phenylphosphine oxide synergistic graphene-POSS flame retardant polycarbonate material.
2. The method for preparing the phenylphosphine oxide-graphene-POSS flame-retardant polycarbonate material according to claim 1, wherein the step S1: refluxing for 36-48h at the temperature of 110-150 ℃ in an oil bath, and drying to obtain the terminal amino-imino graphene.
3. The method for preparing the phenylphosphine oxide-graphene-POSS flame-retardant polycarbonate material according to claim 1, wherein the step S2: stirring and preheating for 30-60min at 40-60 ℃, and reacting for 4-6h under the condition of heat preservation to obtain the imidized graphene-POSS.
4. The method for preparing the phenylphosphine oxide-graphene-POSS flame-retardant polycarbonate material according to claim 1, wherein the step S3: after the dropwise addition, the temperature is raised to 40-60 ℃, and reflux reaction is carried out for 18-25h, so as to obtain the chloro-terminated diphenyl phosphine oxide.
5. The method for preparing the phenylphosphine oxide-graphene-POSS flame-retardant polycarbonate material according to claim 1, wherein the step S3: reacting for 12-24h at 60-90 ℃ to obtain the phenylphosphine oxide synergistic graphene-POSS flame retardant.
6. The method for preparing the phenylphosphine oxide-graphene-POSS flame-retardant polycarbonate material according to claim 1, wherein the step S4: mixing at 140-230 deg.C for 2-15min, and drying at 90-150 deg.C.
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| WO2017128960A1 (en) * | 2016-01-27 | 2017-08-03 | 厦门大学 | Phosphorus-containing fluorine-containing synergistic flame-retardant compound and preparation method therefor |
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| WO2017128960A1 (en) * | 2016-01-27 | 2017-08-03 | 厦门大学 | Phosphorus-containing fluorine-containing synergistic flame-retardant compound and preparation method therefor |
| CN106632958A (en) * | 2016-09-29 | 2017-05-10 | 四川大学 | Method for preparing a flame-retardant water-based polyurethane based on reactive graphene flame retardant |
| US20190276599A1 (en) * | 2016-11-23 | 2019-09-12 | Xiamen University | Phosphorus-nitrogen-silicon-containing polymeric flame retardant and preparation method and application thereof |
| CN107815116A (en) * | 2017-11-03 | 2018-03-20 | 台州学院 | A kind of graphene hybrid particle fire retardant and its preparation method and application |
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