CN103613827A - CNT(carbon nano tube)-bridged rare-earth phenylphosphonate compounded decabromodiphenylethane flame-retardant polyethylene and preparation method thereof - Google Patents
CNT(carbon nano tube)-bridged rare-earth phenylphosphonate compounded decabromodiphenylethane flame-retardant polyethylene and preparation method thereof Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/2279—Oxides; Hydroxides of metals of antimony
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- C08K5/00—Use of organic ingredients
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- C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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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
- C08K9/02—Ingredients treated with inorganic substances
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- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention discloses a kind of CNT(carbon nano tube)-bridged rare-earth phenylphosphonate compounded decabromodiphenylethane flame-retardant polyethylene and a preparation method thereof. The CNT-bridged rare-earth phenylphosphonate compounded decabromodiphenylethane flame-retardant polyethylene is characterized by being prepared from the following components in parts by weight: 60-100 parts of polyethylene, 5-15 parts of a bromine-series flame retardant, and 1-5 parts of CNT-bridged rare-earth phenylphosphonate. A CNT-bridged rare-earth phenylphosphonate hybrid prepared according to the invention simultaneously has lamellar and tubular structures, a CNT achieves an effect of connecting a rare-earth phenylphosphonate lamella, and the CNT and the rare-earth phenylphosphonate lamella are dispersed relatively uniformly and have no obvious clustering phenomenon; the flame retardant property of the material can be obviously improved just through adding a small amount of a bridging hybrid, and a complete and compact carbon layer is formed so as to inhibit a melt dripping phenomenon of polyethylene; the hybrid simultaneously has lamellar and tubular structures, and has a good flame retardant effect on polyethylene after being compounded with the bromine-series flame retardant.
Description
Technical field
The present invention relates to the preparation of synthesis modification, polymer composite or the technological process of batching, relate to organic inorganic hybrid compositional flame-retardant polyethylene and preparation thereof, be specially composite TDE flame-proof polyethylene of carbon nanotube bridging phenyl-phosphonic acid rare-earth salts and preparation method thereof.
Technical background
Polyethylene has good mechanical property, chemical resistance and workability, and purposes is very extensive.But poly inflammableness limits its application in some aspects to a great extent.Bromide fire retardant is because good gas phase flame retardant effect is generally used in polyethylene.
Carbon nanotube has high length-to-diameter ratio, large specific surface area and polarity process after character such as avidity to polymkeric substance, be introduced in material the mechanical property that makes matrix material, thermal characteristics etc. be greatly enhanced.Carbon nanotube can obviously reduce the heat release rate of polymkeric substance, but carbon nanotube can worsen the performance of polymkeric substance in traditional flame retardant test (as UL-94) on the contrary under many circumstances.And how to provide a kind of carbon nanotube to combine with polyethylene, also can improve the material of polyethylene anti-flaming performance, become industry technical problem urgently to be resolved hurrily.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, provide a kind of can be as composite in bromide fire retardant with conventional flame retardant, on flame-proof polyethylene, have the composite TDE flame-proof polyethylene of good synergistic carbon nanotube bridging phenyl-phosphonic acid rare-earth salts.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme: the composite TDE flame-proof polyethylene of a kind of carbon nanotube bridging phenyl-phosphonic acid rare-earth salts, and this material is prepared by each component of following weight part:
Polyethylene (PE) 60-100 part
Bromide fire retardant 5-15 part
Carbon nanotube bridging phenyl-phosphonic acid rare-earth salts 1-5 part.
As preferably, the described composite TDE flame-proof polyethylene of carbon nanotube bridging phenyl-phosphonic acid rare-earth salts, this material is prepared by each component of following weight part:
87 parts of polyethylene
10 parts of bromide fire retardants
3 parts of carbon nanotube bridging phenyl-phosphonic acid rare-earth saltss.
Polyethylene of the present invention is high density polyethylene(HDPE).
Carbon nanotube of the present invention is amination multi-walled carbon nano-tubes, (NH
2, 0.45wt%; Purity, >95%; Length ,～50mm; Outer diameter, 8-15nm) (Beijing rich space high-tech new material technology company limited).
Carbon nanotube bridging phenyl-phosphonic acid rare-earth salts of the present invention (organic inorganic hybridization thing) is synthesized into by coprecipitation method, and its step is as follows:
(1) get 2～4mmol phenyl-phosphonic acid and 0.5～1g carbon nanotube dispersed in 50ml water, this suspension is put into ultrasonic apparatus, with the power ultrasonic 0.1-1h at 60～80 ℃ that is more than or equal to 250W;
(2) get 1～2mmol rare earth nitrate and be dissolved in 50ml water, this solution is slowly added drop-wise in the solution of step (1) gained, and at 60～80 ℃, continue ultrasonic 0.1-1h and obtain suspension;
(3) step (2) gained suspension is transferred in hydrothermal reaction kettle, then reactor is placed in after the baking oven 20-26h of 90-110 ℃, hydro-thermal reaction stops obtaining suspension;
(4) by step (3) gained suspension suction filtration, through deionized water wash, filter after, be dried to constant weight at 80 ℃ and obtain carbon nanotube bridging phenyl-phosphonic acid rare-earth salts.
Bromide fire retardant of the present invention is the TDE of mass ratio 4:1 and the mixture of antimonous oxide.
Another technical problem that the present invention will solve is to provide a kind of preparation method of the above-mentioned composite TDE flame-proof polyethylene of carbon nanotube bridging phenyl-phosphonic acid rare-earth salts, and preparation process comprises:
(1) first by carbon nanotube bridging phenyl-phosphonic acid rare-earth salts, TDE and antimonous oxide dry 6～12h in 60～80 ℃ of baking ovens;
(2) will after dried carbon nanotube bridging phenyl-phosphonic acid rare-earth salts, TDE and antimonous oxide and polyethylene premix, join in Thermal-Haake torque rheometer (HAAKE torque rheometer) again, at 180～200 ℃, melt blending 8～12min under 60～80r/min condition, the carbon nanotube bridging phenyl-phosphonic acid rare-earth salts being uniformly mixed and TDE compositional flame-retardant polythene material.
Due to the enforcement of above technical scheme, the present invention compared with prior art has the following advantages:
(1) the carbon nanotube bridging phenyl-phosphonic acid rare-earth salts hybrid preparing has lamella and tubular structure simultaneously, and carbon nanotube plays the effect that connects phenyl-phosphonic acid rare-earth salts lamella, and the two dispersion is comparatively even, there is no obvious Cluster Phenomenon.
(2) by above-mentioned hybrid and TDE composite usage in polyethylene, only add a small amount of bridging hybrid just can obviously improve the flame retardant properties of material, form the complete charcoal layer compacting, suppress poly melting drip phenomenon; This hybrid has tubulose and laminate structure simultaneously, and bromide fire retardant is composite rear polyethylene is had to good flame retardant effect.
(3) of the present invention synthetic, working method is simple, and successful, is applicable to actual application.
Accompanying drawing explanation
Fig. 1 phenyl-phosphonic acid cerium hybrid transmission electron microscope picture a(carbon-free nanoscale pipe).
Fig. 2 carbon nanotube bridging phenyl-phosphonic acid cerium hybrid transmission electron microscope picture b(has carbon nanotube).
The carbon residue scanning electron microscope (SEM) photograph of Fig. 3 fire-retardant polyethylene material (carbon-free nanoscale pipe).
The carbon residue scanning electron microscope (SEM) photograph (having carbon nanotube) of Fig. 4 fire-retardant polyethylene material.
Embodiment
Below by specific embodiment, the present invention is described in further detail, but the present invention is not only confined to following examples.The person skilled in the art in this field some nonessential improvement that content is made the present invention according to the present invention and adjustment still belong to protection scope of the present invention.
Example formulations is as follows:
The present embodiment is tested with carbon nanotube bridging phenyl-phosphonic acid cerium hybrid (Ce-MWNTs), and hybrid preparation method adopts the preparation method of above-mentioned carbon nanotube bridging phenyl-phosphonic acid rare-earth salts hybrid, is specially:
(1) get 2mmol phenyl-phosphonic acid and 0.5g amination multi-walled carbon nano-tubes is scattered in 50ml water, this suspension is put into ultrasonic apparatus, with the power ultrasonic 0.5h at 60 ℃ that is more than or equal to 250W;
(2) get 1mmol cerous nitrate and be dissolved in 50ml water, this solution is slowly added drop-wise in the solution of step (1) gained, and at 60 ℃, continue ultrasonic 0.5h.
(3) gained suspension is transferred in hydrothermal reaction kettle, then reactor is placed in after 100 ℃ of baking oven 24h, hydro-thermal reaction stops.
(4) by gained suspension suction filtration, then through deionized water wash, filter after, be dried to constant weight at 80 ℃ and obtain carbon nanotube bridging phenyl-phosphonic acid cerium hybrid.Consider the Tiny Mass loss in experimentation, in hybrid, the mass ratio of carbon nanotube and phenyl-phosphonic acid cerium is 1:4.
(5) adopt the synthetic comparison phenyl-phosphonic acid cerium (CeHPP) of above-mentioned steps, only need in step (1), not introduce carbon nanotube.
Hybrid and comparison transmission electron microscope photo are referring to accompanying drawing 1-4.Phenyl-phosphonic acid cerium presents laminated structure, and carbon nanotube can play the effect that connects lamella as " bridge ", and then makes hybrid form an integral body simultaneously with lamella and hard skeleton.
The carbon nanotube that the present embodiment adopts (MWNTs) is amination multi-walled carbon nano-tubes (NH
2, 0.45wt%; Purity, >95%; Length ,～50mm; Outer diameter, 8-15nm).
Then by carbon nanotube bridging phenyl-phosphonic acid cerium hybrid and other mixed raw materials for carbon nanotube bridging phenyl-phosphonic acid cerium hybrid of the present invention and TDE compositional flame-retardant high density polyethylene material, concrete preparation method:
(1) first carbon nanotube bridging phenyl-phosphonic acid cerium hybrid, phenyl-phosphonic acid cerium, TDE and antimonous oxide are dried to 6 hours in 80 ℃ of baking ovens;
(2) will after dried hybrid (carbon nanotube bridging phenyl-phosphonic acid cerium), TDE and antimonous oxide and polyethylene premix, join in Thermal-Haake torque rheometer again, at 180 ℃, melt blending 10min under 60r/min condition, obtaining flame-proof composite material is carbon nanotube bridging phenyl-phosphonic acid cerium organic inorganic hybridization thing and TDE compositional flame-retardant polythene material.
Specifically fill a prescription in Table 1:
Table 1 embodiment of the present invention formula and sample number into spectrum
The polyethylene that the present embodiment adopts is high density polyethylene(HDPE), raises sub-petrochemical industry, trade mark 5000s, and melting index is 0.9g/10min; Bromide fire retardant (BFR) adopts TDE and antimonous oxide, and the two mass ratio is 4:1.
Different numbered samples are prepared burden by the weight percent in above table (wt%), after melt blending, prepared matrix material in 180 ℃ of vulcanizing presses after preheating 5min, is boosted to 15MPa insulation 10min, after the moulding of pressurize naturally cooling for performance test.
The qualitative energy of the steady oxidation of embodiment heat:
Sample thief 5～10mg adopts TGA209F1 thermogravimetric analyzer (NETZSCH, Germany) to measure the thermo-oxidative stability of material in air atmosphere, and temperature rise rate is 20 ℃/min, and temperature range is 300～700 ℃.Parallel three experiments are got after average, and obtained experimental data arranges as shown in table 2.
Table 2 material embodiment of the present invention thermal stability
T
5%, T
50%temperature when difference representative sample thermal weight loss 5wt%, 50wt%.T
maxtemperature while representing maximum heat weight loss rate.
As can be seen from Table 2, the introducing of CeHPP does not improve the thermo-oxidative stability of material separately, and MWNTs add the thermostability that can obviously improve material, this is mainly in material, to form reticulated structure due to carbon nanotube, restriction superpolymer connects the motion of section.In addition, the heat decomposition temperature of PE/BFR/Ce-MWNTs is also improved, but because the content of carbon nanotubes in hybrid is lower, so increase rate does not have PE/BFR/MWNTs obvious.
Embodiment flame retardant properties
The test of the present embodiment flame retardant properties is divided into three part of detecting: vertical combustion, miniature taper calorimetric and carbon residue morphology characterization, and specific implementation process is as follows:
(1) vertical combustion test (UL94) is tested and is carried out on CZF-3 type horizontal vertical burning determinator according to GB/T2408-1996 standard, and test sample is of a size of 130 * 13 * 3mm
3, 5 battens of each sample test, get average, then according to the regulation in GB, with reference to the incendivity of experimental result evaluation material.Test result is as shown in table 3.
(2) miniature calorimetric test (MCC): combustionproperty is carried out on the miniature burning calorimeter of GovmarkMCC-2 according to ASTMD7309-07 standard.This instrument is pyrolytic decomposition-combustion flow calorimeter.In experiment; the powdered sample of 4-6 milligram speed with 1 ℃/s under inert atmosphere (80ml/min) protection is warming up to 650 ℃ from room temperature; then the volatile matter decomposing will be mixed into the roasting kiln of 900 ℃ with oxygen (20ml/min), by recording oxygen depletion amount, calculate the enthalpy of combustion of degradation production.Test result is as shown in table 3.
(3) carbon residue morphology characterization (SEM): sample is processed and obtained carbon residue for five minutes in retort furnace, under 400 ℃ of conditions.In S-4800 surface sweeping Electronic Speculum, observe the stereoscan photograph that obtains carbon residue, as shown in Figure 2.
Table 3 material embodiment of the present invention combustionproperty
PHRR: heat release rate peak value; THR: total thermal discharge; TPHRR: the temperature that heat release rate peak value is corresponding; HRC: heat discharges to be held, the ratio of sample heat release rate and temperature rise rate, the degree of easily lighting of reaction material; t
1, t
2: represent respectively after first and second time of sample lighted, to remove burning things which may cause a fire disaster, the sustained combustion time.
Adding of bromide fire retardant can make polyethylene reach V-2 level in UL-94 test.Continue to add CeHPP, although shorten combustion time, due to the existence of molten drop phenomenon, PE/BFR/CeHPP remains V-2 level.MWNTs adds the flame retardant properties that sharply worsens on the contrary material, makes PE/BFR/MWNTs there is no rank.And carbon nanotube bridging phenyl-phosphonic acid cerium hybrid can suppress the melting drip phenomenon in experimentation, make PE/BFR/Ce-MWNTs material by V-0 level, obviously improve the flame retardant properties of material.
Experiment is compared with vertical combustion, and miniature calorimetric test has similar result.After same amount hybrid adds, the flame retardant properties of material is more excellent than adding separately carbon nanotube or phenyl-phosphonic acid cerium.In the sample of all the present embodiment, PE/BFR/Ce-MWNTs demonstrates minimum PHRR, THR and HRC.
The stereoscan photograph of carbon residue can be explained flame retardant effect well.Only there is the sample of bromide fire retardant substantially to burn completely, only have the carbon residue residue of a small amount of porosity and looseness.Sample adds the more complete densification of formed charcoal layer after hybrid.Even carbon nanotube forms network skeleton, and phenyl-phosphonic acid cerium lamella covers the space of skeleton, and then heat insulation matter.
Claims (7)
1. the composite TDE flame-proof polyethylene of carbon nanotube bridging phenyl-phosphonic acid rare-earth salts, is characterized in that: prepared by each component by following weight part:
Polyethylene 60-100 part
Bromide fire retardant 5-15 part
Carbon nanotube bridging phenyl-phosphonic acid rare-earth salts 1-5 part.
2. the composite TDE flame-proof polyethylene of carbon nanotube bridging phenyl-phosphonic acid rare-earth salts according to claim 1, is characterized in that: prepared by each component by following weight part:
87 parts of polyethylene
10 parts of bromide fire retardants
3 parts of carbon nanotube bridging phenyl-phosphonic acid rare-earth saltss.
3. the composite TDE flame-proof polyethylene of carbon nanotube bridging phenyl-phosphonic acid rare-earth salts according to claim 1 and 2, is characterized in that: described polyethylene is high density polyethylene(HDPE).
4. the composite TDE flame-proof polyethylene of carbon nanotube bridging phenyl-phosphonic acid rare-earth salts according to claim 1 and 2, is characterized in that: described carbon nanotube is amination multi-walled carbon nano-tubes.
5. the composite TDE flame-proof polyethylene of carbon nanotube bridging phenyl-phosphonic acid rare-earth salts according to claim 1 and 2, is characterized in that: the step of described carbon nanotube bridging phenyl-phosphonic acid rare-earth salts is as follows:
(1) get 2～4mmol phenyl-phosphonic acid and 0.5～1g carbon nanotube dispersed in 50ml water, this suspension is put into ultrasonic apparatus, with the power ultrasonic 0.1-1h at 60～80 ℃ that is more than or equal to 250W;
(2) get 1～2mmol rare earth nitrate and be dissolved in 50ml water, this solution is slowly added drop-wise in the solution of step (1) gained, and at 60～80 ℃, continue ultrasonic 0.1-1h and obtain suspension;
(3) step (2) gained suspension is transferred in hydrothermal reaction kettle, then reactor is placed in after the baking oven 20-26h of 90-110 ℃, hydro-thermal reaction stops obtaining suspension;
(4) by step (3) gained suspension suction filtration, then through deionized water wash, filter after, be dried to constant weight at 80 ℃ and obtain carbon nanotube bridging phenyl-phosphonic acid rare-earth salts.
6. the composite TDE flame-proof polyethylene of carbon nanotube bridging phenyl-phosphonic acid rare-earth salts according to claim 1 and 2, is characterized in that: described bromide fire retardant is the TDE of mass ratio 4:1 and the mixture of antimonous oxide.
7. a preparation method for the composite TDE flame-proof polyethylene of carbon nanotube bridging phenyl-phosphonic acid rare-earth salts, is characterized in that: preparation process comprises:
(1) first by carbon nanotube bridging phenyl-phosphonic acid rare-earth salts, TDE and antimonous oxide dry 6～12h in 60～80 ℃ of baking ovens;
(2) will after dried carbon nanotube bridging phenyl-phosphonic acid rare-earth salts, TDE and antimonous oxide and polyethylene premix, join in Thermal-Haake torque rheometer again, at 180～200 ℃, melt blending 8～12min under 60～80r/min condition, the carbon nanotube bridging phenyl-phosphonic acid rare-earth salts being uniformly mixed and TDE compositional flame-retardant polythene material.
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| CN103992612A (en) * | 2014-05-19 | 2014-08-20 | 宁波泛塑新材料科技有限公司 | High-polymer bromine flame retardant/nano clay compound flame-retardant ABS (acrylonitrile-butadiene-styrene) resin and preparation method thereof |
| CN107216485A (en) * | 2017-06-02 | 2017-09-29 | 浙江大学宁波理工学院 | Fullerene modification phenyl-phosphonic acid rare earth hetero compound, polycarbonate composite material containing it and preparation method thereof |
| CN107266764A (en) * | 2017-06-07 | 2017-10-20 | 常州市绿意管道有限公司 | A kind of fire-retardant polyethylene material and preparation method thereof |
| CN110294886A (en) * | 2019-07-01 | 2019-10-01 | 金陵科技学院 | Used in electronic industry flame-resistant high-temperature-resistant polyethylene and preparation method thereof |
| CN112679916A (en) * | 2020-12-09 | 2021-04-20 | 金发科技股份有限公司 | PBT composition and preparation method and application thereof |
| CN115287824A (en) * | 2022-06-29 | 2022-11-04 | 惠州市普林摩斯无纺布有限公司 | Antibacterial anti-mite non-woven fabric for mattress lining and preparation process thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103992612A (en) * | 2014-05-19 | 2014-08-20 | 宁波泛塑新材料科技有限公司 | High-polymer bromine flame retardant/nano clay compound flame-retardant ABS (acrylonitrile-butadiene-styrene) resin and preparation method thereof |
| CN107216485A (en) * | 2017-06-02 | 2017-09-29 | 浙江大学宁波理工学院 | Fullerene modification phenyl-phosphonic acid rare earth hetero compound, polycarbonate composite material containing it and preparation method thereof |
| CN107216485B (en) * | 2017-06-02 | 2019-06-11 | 浙江大学宁波理工学院 | Fullerene modification phenyl-phosphonic acid rare earth hetero compound contains its polycarbonate composite material and preparation method thereof |
| CN107266764A (en) * | 2017-06-07 | 2017-10-20 | 常州市绿意管道有限公司 | A kind of fire-retardant polyethylene material and preparation method thereof |
| CN110294886A (en) * | 2019-07-01 | 2019-10-01 | 金陵科技学院 | Used in electronic industry flame-resistant high-temperature-resistant polyethylene and preparation method thereof |
| CN112679916A (en) * | 2020-12-09 | 2021-04-20 | 金发科技股份有限公司 | PBT composition and preparation method and application thereof |
| CN112679916B (en) * | 2020-12-09 | 2022-04-19 | 金发科技股份有限公司 | PBT composition and preparation method and application thereof |
| CN115287824A (en) * | 2022-06-29 | 2022-11-04 | 惠州市普林摩斯无纺布有限公司 | Antibacterial anti-mite non-woven fabric for mattress lining and preparation process thereof |
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