CN103613827B - Composite TDE flame-proof polyethylene of carbon nanotube bridging phenyl-phosphonic acid rare-earth salts and preparation method thereof - Google Patents

Composite TDE flame-proof polyethylene of carbon nanotube bridging phenyl-phosphonic acid rare-earth salts and preparation method thereof Download PDF

Info

Publication number
CN103613827B
CN103613827B CN201310594207.1A CN201310594207A CN103613827B CN 103613827 B CN103613827 B CN 103613827B CN 201310594207 A CN201310594207 A CN 201310594207A CN 103613827 B CN103613827 B CN 103613827B
Authority
CN
China
Prior art keywords
carbon nanotube
phosphonic acid
earth salts
phenyl
acid rare
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201310594207.1A
Other languages
Chinese (zh)
Other versions
CN103613827A (en
Inventor
冉诗雅
郭正虹
方征平
赵黎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningbo Institute of Technology of ZJU
Original Assignee
Ningbo Institute of Technology of ZJU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningbo Institute of Technology of ZJU filed Critical Ningbo Institute of Technology of ZJU
Priority to CN201310594207.1A priority Critical patent/CN103613827B/en
Publication of CN103613827A publication Critical patent/CN103613827A/en
Application granted granted Critical
Publication of CN103613827B publication Critical patent/CN103613827B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • 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
    • C08K5/02—Halogenated hydrocarbons
    • C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses composite TDE flame-proof polyethylene of a kind of carbon nanotube bridging phenyl-phosphonic acid rare-earth salts and preparation method thereof, it is characterized in that: prepared by each component of 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.The carbon nanotube bridging phenyl-phosphonic acid rare-earth salts hybrid that the present invention prepares has lamella and tubular structure simultaneously, and carbon nanotube plays the effect connecting phenyl-phosphonic acid rare-earth salts lamella, and the two dispersion is comparatively even, does not have obvious Cluster Phenomenon; Only add the flame retardant properties that a small amount of bridging hybrid just can significantly improve material, form complete layer of charcoal of compacting, suppress poly melting drip phenomenon; This hybrid has tubulose and laminate structure simultaneously, and bromide fire retardant is composite has good flame retardant effect to polyethylene afterwards.

Description

Composite TDE flame-proof polyethylene of carbon nanotube bridging phenyl-phosphonic acid rare-earth salts and preparation method thereof
Technical field
The present invention relates to synthesis modification, the preparation of 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 excellent 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 generally uses due to good gas phase flame retardant effect in polyethylene.
Carbon nanotube to have after high length-to-diameter ratio, large specific surface area and polarity process character such as the avidity of polymkeric substance, is introduced in material and will the mechanical property of matrix material, thermal characteristics etc. is greatly enhanced.Carbon nanotube obviously can 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 and the material of polyethylene anti-flaming performance can be improved, become the technical problem that the industry is urgently to be resolved hurrily.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, provide one with conventional flame retardant as bromide fire retardant is composite, flame-proof polyethylene can 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:
Polyethylene 87 parts
Bromide fire retardant 10 parts
Carbon nanotube bridging phenyl-phosphonic acid rare-earth salts 3 parts.
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) (space high-tech new material technology company limited is won in Beijing).
Carbon nanotube bridging phenyl-phosphonic acid rare-earth salts (organic inorganic hybridization thing) of the present invention is obtained by Co deposited synthesis, 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 DEG C being more than or equal to 250W;
(2) getting 1 ~ 2mmol rare earth nitrate is dissolved in 50ml water, is slowly added drop-wise to by this solution in the solution of step (1) gained, and at 60 ~ 80 DEG C, continues ultrasonic 0.1-1h obtain suspension;
(3) be transferred in hydrothermal reaction kettle by step (2) gained suspension, after then reactor being placed in the baking oven 20-26h of 90-110 DEG C, hydro-thermal reaction stops obtaining suspension;
(4) by step (3) gained suspension suction filtration, after deionized water wash, filtration, be dried to constant weight at 80 DEG C 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 DEG C of baking ovens;
(2) join in Thermal-Haake torque rheometer (HAAKE torque rheometer) by after dried carbon nanotube bridging phenyl-phosphonic acid rare-earth salts, TDE and antimonous oxide and polyethylene premix again, at 180 ~ 200 DEG C, melt blending 8 ~ 12min under 60 ~ 80r/min condition, the carbon nanotube bridging phenyl-phosphonic acid rare-earth salts be 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 prepared has lamella and tubular structure simultaneously, and carbon nanotube plays the effect connecting phenyl-phosphonic acid rare-earth salts lamella, and the two dispersion is comparatively even, does not have obvious Cluster Phenomenon.
(2) by above-mentioned hybrid and TDE composite usage in polyethylene, only add the flame retardant properties that a small amount of bridging hybrid just can significantly improve material, form complete layer of charcoal of compacting, suppress poly melting drip phenomenon; This hybrid has tubulose and laminate structure simultaneously, and bromide fire retardant is composite has good flame retardant effect to polyethylene afterwards.
(3) synthesis of the present invention, working method are simple, and successful, be 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 (carbon-free nanoscale pipe) of Fig. 3 fire-retardant polyethylene material.
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.Some nonessential improvement that the person skilled in the art in this field makes the present invention according to content of 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 namely 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 DEG C being more than or equal to 250W;
(2) getting 1mmol cerous nitrate is dissolved in 50ml water, is slowly added drop-wise to by this solution in the solution of step (1) gained, and continues ultrasonic 0.5h at 60 DEG C.
(3) be transferred in hydrothermal reaction kettle by gained suspension, after then reactor being placed in 100 DEG C of baking oven 24h, hydro-thermal reaction stops.
(4) by gained suspension suction filtration, then after deionized water wash, filtration, be dried to constant weight at 80 DEG C 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 above-mentioned steps synthesis comparison phenyl-phosphonic acid cerium (CeHPP), only need not introduce carbon nanotube in step (1).
Hybrid and comparison transmission electron microscope photo are see accompanying drawing 1-4.Phenyl-phosphonic acid cerium presents laminated structure, and carbon nanotube can play as " bridge " effect of lamella of connecting, and then hybrid is formed entirety that one has lamella and hard skeleton simultaneously.
The carbon nanotube (MWNTs) that the present embodiment adopts 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 by carbon nanotube bridging phenyl-phosphonic acid cerium hybrid, phenyl-phosphonic acid cerium, TDE and antimonous oxide in 80 DEG C of baking ovens dry 6 hours;
(2) will join in Thermal-Haake torque rheometer after dried hybrid (carbon nanotube bridging phenyl-phosphonic acid cerium), TDE and antimonous oxide and polyethylene premix again, at 180 DEG C, melt blending 10min under 60r/min condition, obtains flame-proof composite material and carbon nanotube bridging phenyl-phosphonic acid cerium organic inorganic hybridization thing and TDE compositional flame-retardant polythene material.
Concrete formula is 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 is prepared burden by the weight percent (wt%) in above table, after melt blending, prepared matrix material after preheating 5min, is boosted to 15MPa and is incubated 10min, for performance test after pressurize naturally cooling is shaping in 180 DEG C of vulcanizing presses.
The qualitative energy of the steady oxidation of embodiment heat:
Sample thief 5 ~ 10mg, in air atmosphere, adopt TGA209F1 thermogravimetric analyzer (NETZSCH, Germany) to measure the thermo-oxidative stability of material, temperature rise rate is 20 DEG C/min, and temperature range is 300 ~ 700 DEG C.After average is got in parallel three experiments, obtained experimental data arranges as shown in table 2.
Table 2 materials Example thermal stability of the present invention
T 5%, T 50%temperature respectively when representative sample thermal weight loss 5wt%, 50wt%.T maxrepresent temperature during maximum heat weight loss rate.
As can be seen from Table 2, the introducing of independent CeHPP does not improve the thermo-oxidative stability of material, and MWNTs add the thermostability that can significantly improve material, this is mainly because carbon nanotube forms reticulated structure in the material, the motion of the restriction superpolymer section of company.In addition, the heat decomposition temperature of PE/BFR/Ce-MWNTs is also improved, but due to the content of carbon nanotubes in hybrid 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 according to GB/T2408-1996 standard and is carried out on CZF-3 type horizontal vertical burning determinator, and test sample is of a size of 130 × 13 × 3mm 3, each sample test 5 battens, 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 GovmarkMCC-2 micro combustions calorimeter according to ASTMD7309-07 standard.This instrument is a pyrolytic decomposition-combustion flow calorimeter.In experiment; by the powdered sample of 4-6 milligram inert atmosphere (80ml/min) protection under with the speed of 1 DEG C/s from room temperature to 650 DEG C; then the volatile matter decomposed will be mixed into the roasting kiln of 900 DEG C with oxygen (20ml/min), be calculated the enthalpy of combustion of degradation production by record oxygen depletion amount.Test result is as shown in table 3.
(3) carbon residue morphology characterization (SEM): sample processes and obtains carbon residue in five minutes in retort furnace, under 400 DEG C of conditions.S-4800 surface sweeping Electronic Speculum is observed the stereoscan photograph obtaining carbon residue, as shown in Figure 2.
Table 3 materials Example combustionproperty of the present invention
PHRR: heat release rate peak value; THR: total thermal discharge; TPHRR: the temperature that heat release rate peak value is corresponding; HRC: Thermal release hold, the ratio of sample heat release rate and temperature rise rate, reaction material easily light degree; t 1, t 2: represent that first and second time of sample removes burning things which may cause a fire disaster, the sustained combustion time after lighting respectively.
Adding of bromide fire retardant can make polyethylene reach V-2 level in UL-94 test.Continue to add CeHPP, although combustion time shortens, due to the existence of molten drop phenomenon, PE/BFR/CeHPP remains V-2 level.MWNTs adds the flame retardant properties sharply worsening material on the contrary, makes PE/BFR/MWNTs not have rank.And carbon nanotube bridging phenyl-phosphonic acid cerium hybrid can melting drip phenomenon in Inhibition test process, makes PE/BFR/Ce-MWNTs material by V-0 level, obviously improves the flame retardant properties of material.
Compare with vertical combustion experiment, miniature calorimetric test has similar result.After same amount hybrid adds, the flame retardant properties of material is than adding separately carbon nanotube or phenyl-phosphonic acid cerium excellence.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 explain flame retardant effect well.Only there is the sample of bromide fire retardant substantially to burn completely, only have the carbon residue of a small amount of porosity and looseness to remain.The more complete densification of the layer of charcoal that sample is formed after adding hybrid.Even carbon nanotube forms network skeleton, and phenyl-phosphonic acid cerium tablet layer covers the space of skeleton, and then heat insulation matter.

Claims (6)

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 of 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;
The preparation process 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 under 60 ~ 80 ° of C being more than or equal to 250W;
(2) getting 1 ~ 2mmol rare earth nitrate is dissolved in 50ml water, is slowly added drop-wise to by this solution in the solution of step (1) gained, and under 60 ~ 80 ° of C, continues ultrasonic 0.1-1h obtain suspension;
(3) be transferred in hydrothermal reaction kettle by step (2) gained suspension, after then reactor being placed in the baking oven 20-26h of 90-110 ° of C, hydro-thermal reaction stops obtaining suspension;
(4) by step (3) gained suspension suction filtration, then after deionized water wash, filtration, be dried to constant weight under 80 ° of C and obtain carbon nanotube bridging phenyl-phosphonic acid rare-earth salts.
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 of following weight part:
Polyethylene 87 parts
Bromide fire retardant 10 parts
Carbon nanotube bridging phenyl-phosphonic acid rare-earth salts 3 parts.
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: described bromide fire retardant is the TDE of mass ratio 4:1 and the mixture of antimonous oxide.
6. 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 C baking ovens;
(2) will join in Thermal-Haake torque rheometer after dried carbon nanotube bridging phenyl-phosphonic acid rare-earth salts, TDE and antimonous oxide and polyethylene premix again, at 180 ~ 200 ° of C, melt blending 8 ~ 12min under 60 ~ 80r/min condition, the carbon nanotube bridging phenyl-phosphonic acid rare-earth salts be uniformly mixed and TDE compositional flame-retardant polythene material;
The preparation process 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 under 60 ~ 80 ° of C being more than or equal to 250W;
(2) getting 1 ~ 2mmol rare earth nitrate is dissolved in 50ml water, is slowly added drop-wise to by this solution in the solution of step (1) gained, and under 60 ~ 80 ° of C, continues ultrasonic 0.1-1h obtain suspension;
(3) be transferred in hydrothermal reaction kettle by step (2) gained suspension, after then reactor being placed in the baking oven 20-26h of 90-110 ° of C, hydro-thermal reaction stops obtaining suspension;
(4) by step (3) gained suspension suction filtration, then after deionized water wash, filtration, be dried to constant weight under 80 ° of C and obtain carbon nanotube bridging phenyl-phosphonic acid rare-earth salts.
CN201310594207.1A 2013-11-21 2013-11-21 Composite TDE flame-proof polyethylene of carbon nanotube bridging phenyl-phosphonic acid rare-earth salts and preparation method thereof Active CN103613827B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310594207.1A CN103613827B (en) 2013-11-21 2013-11-21 Composite TDE flame-proof polyethylene of carbon nanotube bridging phenyl-phosphonic acid rare-earth salts and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310594207.1A CN103613827B (en) 2013-11-21 2013-11-21 Composite TDE flame-proof polyethylene of carbon nanotube bridging phenyl-phosphonic acid rare-earth salts and preparation method thereof

Publications (2)

Publication Number Publication Date
CN103613827A CN103613827A (en) 2014-03-05
CN103613827B true CN103613827B (en) 2015-12-02

Family

ID=50164549

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310594207.1A Active CN103613827B (en) 2013-11-21 2013-11-21 Composite TDE flame-proof polyethylene of carbon nanotube bridging phenyl-phosphonic acid rare-earth salts and preparation method thereof

Country Status (1)

Country Link
CN (1) CN103613827B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
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
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
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

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101429302A (en) * 2008-12-01 2009-05-13 上海金发科技发展有限公司 Halogen free flame-proof composite material of polythene and preparation method thereof
CN102241850A (en) * 2011-06-22 2011-11-16 青岛润兴塑料新材料有限公司 Polyethylene modified plastic with high performance and double resistance and manufacture method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9085678B2 (en) * 2010-01-08 2015-07-21 King Abdulaziz City For Science And Technology Clean flame retardant compositions with carbon nano tube for enhancing mechanical properties for insulation of wire and cable

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101429302A (en) * 2008-12-01 2009-05-13 上海金发科技发展有限公司 Halogen free flame-proof composite material of polythene and preparation method thereof
CN102241850A (en) * 2011-06-22 2011-11-16 青岛润兴塑料新材料有限公司 Polyethylene modified plastic with high performance and double resistance and manufacture method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Effects of carbon nanotubes on the thermal stbility and flame retardancy of intumescent flame-retarded polypropylene;Baoxian Du,et al.;《Polymer Degradation and Stability》;20110810;第96卷(第10期);1725-1731 *
Synthesis of cerium phenylphosphonate and its synergistic flame retardant effect with decabromodiphenyl oxide in glass-fiber reinforced poly(ethylene terephthalate);Chao Chen,et al.;《Polymer Composites》;20131011;第35卷(第3期);539-547 *

Also Published As

Publication number Publication date
CN103613827A (en) 2014-03-05

Similar Documents

Publication Publication Date Title
CN103613827B (en) Composite TDE flame-proof polyethylene of carbon nanotube bridging phenyl-phosphonic acid rare-earth salts and preparation method thereof
Zhang et al. Design of h-BN@ boronate polymer core-shell nanoplates to simultaneously enhance the flame retardancy and mechanical properties of epoxy resin through the interficial regulation
Wang et al. Synthesis of N-methyl triazine-ethylenediamine copolymer charring foaming agent and its enhancement on flame retardancy and water resistance for polypropylene composites
Xu et al. Component ratio effects of hyperbranched triazine compound and ammonium polyphosphate in flame‐retardant polypropylene composites
Kong et al. Effect on thermal and combustion behaviors of montmorillonite intercalation nickel compounds in polypropylene/IFR system
CN108503895B (en) Preparation method of lanthanum-loaded organic phosphorus-modified nitrogen-doped graphene and flame-retardant modified ABS thereof
Li et al. Synergistic flame retardant effects of ammonium polyphosphate in ethylene‐vinyl acetate/layered double hydroxides composites
Qin et al. Synergistic effect of modified expanded graphite and zinc borate on the flammability, thermal stability and crystallization behavior of LLDPE/EVA composites with Mg (OH) 2/Al (OH) 3
Feng et al. Synergistic effect of ammonium polyphosphate and triazine-based charring agent on the flame retardancy and combustion behavior of ethylene-vinyl acetate copolymer
Qian et al. Flammability and thermal degradation behavior of ethylene‐vinyl acetate/layered double hydroxides/zinc borate composites
Wang et al. Synergistic effect between zeolitic imidazolate framework‐8 and expandable graphite to improve the flame retardancy and smoke suppression of polyurethane elastomer
Jia et al. Flame retardant ethylene‐vinyl acetate composites based on layered double hydroxides with zinc hydroxystannate
Li et al. Preparation and properties of polybutylene‐terephthalate/graphene oxide in situ flame‐retardant material
CN111690202A (en) High-flame-retardance high-crust-forming low-smoke halogen-free flame-retardant oxygen-insulating layer cable material
Shi et al. Flammability of polystyrene/aluminim phosphinate composites containing modified ammonium polyphosphate
CN110079012A (en) Compound synergistic halogen-free flame retardant polypropylene composite material of graphene/POSS and preparation method thereof
Lv et al. Flame retardancy and mechanical properties of EVA nanocomposites based on magnesium hydroxide nanoparticles/microcapsulated red phosphorus
Zhang et al. Synergistic flame retardant effect of cerium‐based DOPO derivative and intumescent flame retardants in polypropylene
Liu et al. Synthesis of C o3 (HPO 4) 2 (OH) 2 nanosheets and its synergistic effect with intumescent flame retardants in ethylene‐vinyl acetate copolymer
Zhou et al. Enhancement of wollastonite on flame retardancy and mechanical properties of PP/IFR composite
Jiao et al. Properties of fire agent integrated with molecular sieve and tetrafluoroborate ionic liquid in thermoplastic polyurethane elastomer
Cao et al. Self-assembled biobased chitosan hybrid carrying N/P/B elements for polylactide with enhanced fire safety and mechanical properties
Zhao et al. Mechanical performance and flame retardancy of polypropylene composites containing zeolite and multiwalled carbon nanotubes
Yang et al. Synergistic effect of expandable graphite and aluminum hypophosphite in flame‐retardant ethylene vinyl acetate composites
Jiao et al. Synergistic effects of titanium dioxide with layered double hydroxides in EVA/LDH composites

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant