CN107629288A - Polyethylene/metal hydroxides/Ketjen black fire proofing and preparation method thereof - Google Patents
Polyethylene/metal hydroxides/Ketjen black fire proofing and preparation method thereof Download PDFInfo
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- CN107629288A CN107629288A CN201710799263.7A CN201710799263A CN107629288A CN 107629288 A CN107629288 A CN 107629288A CN 201710799263 A CN201710799263 A CN 201710799263A CN 107629288 A CN107629288 A CN 107629288A
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- Prior art keywords
- ketjen black
- polyethylene
- metal hydroxides
- fire proofing
- ketjen
- 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.)
- Granted
Links
- 239000003273 ketjen black Substances 0.000 title claims abstract description 61
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 44
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 43
- -1 Polyethylene Polymers 0.000 title claims abstract description 42
- 229910000000 metal hydroxide Inorganic materials 0.000 title claims abstract description 36
- 150000004692 metal hydroxides Chemical class 0.000 title claims abstract description 36
- 238000004079 fireproofing Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 14
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 12
- 229920001903 high density polyethylene Polymers 0.000 claims description 5
- 239000004700 high-density polyethylene Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 241000872198 Serjania polyphylla Species 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 239000000155 melt Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 18
- 238000002485 combustion reaction Methods 0.000 abstract description 11
- 239000003063 flame retardant Substances 0.000 abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 230000004888 barrier function Effects 0.000 abstract description 4
- 239000000779 smoke Substances 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 24
- 238000000034 method Methods 0.000 description 4
- 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 class 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 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A kind of polyethylene/metal hydroxides/Ketjen black fire proofing and preparation method thereof, the material is prepared by each component by following portion rate (phr):Polyethylene 100phr, the 140phr of metal hydroxides 125, the 5phr of Ketjen black 1.It is branched form to the Ketjen black that the present invention has, and specific surface area is big, and network structure is easily formed in polymer matrix;Ketjen black is added in polyethylene/metal hydroxide material, the network structure that Ketjen black is formed stops the transmission of heat and quality in combustion process as Physical barriers, so as to retarded combustion process;In the case where fire retardant adds equal parts, the vertical combustion grade and limited oxygen index value of polyethylene/metal hydroxides/Ketjen black composite are improved, peak value HRR and total smoke delivery decrease, and metal hydroxides and Ketjen black are used to that in flame-proof polyethylene synergy can be played.
Description
Technical field
The present invention relates to the technical process of the preparation of high molecular fire retardant material, processing or dispensing, and in particular to a kind of poly- second
Alkene/metal hydroxides/Ketjen black fire proofing and preparation method thereof.
Technical background
Polyethylene is widely used in daily life due to its excellent mechanical property, chemical stability and workability etc.
Various aspects.But due to polyethylene, easily combustion, caloric value are big in itself, burning velocity is fast and during burning along with drippage, from
And limit its application in higher field is required to fire-retardant rank.As skilful the gradual of safety and environmental protection consciousness of global range adds
By force, traditional halogenated flame retardant has become increasingly limited, Halogen, low cigarette, low toxic and environment-friendly type flame retarded polymeric material oneself into
The target pursued for people.Metal hydroxides is one of earliest environmentally friendly flame-retardant system of development, but relatively low resistance
Fuel efficiency rate drastically influence the extension of its application always.
Ketjen black is made by great original special producing technique, and purity is high, performance is high.Ketjen black has branched
Form, and reference area is larger, is easily fully contacted between active material.Filled Ketjen black as filler to macromolecule
In matrix, network structure is easily formed due to its side chain form.Based on this advantage, Ketjen black is introduced to polyethylene/metallic hydrogen
In oxide system, Ketjen black formed network structure can be formed in combustion Physical barriers so that hinder heat and
The transmission of quality, improve the flame retarding efficiency of metal hydroxides.
The content of the invention
The present invention is directed to the above-mentioned deficiency of prior art, and Ketjen black is incorporated into polyethylene/metal hydroxides system,
Polyethylene/metal hydroxides/Ketjen black composite wood of a kind of fire resistance, heat endurance and good mechanical performance is prepared
Material.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows:A kind of polyethylene/metal hydroxide
Thing/Ketjen black fire proofing, the material are prepared by each component by following portion rate (phr):
Polyethylene 100phr
Metal hydroxides 125-140phr
Ketjen black 1-5phr.
Polyethylene of the present invention is high density polyethylene (HDPE).
Metal hydroxides of the present invention is aluminium hydroxide or magnesium hydroxide;Metal hydroxides, environmental protection is cheap, holds
Easily obtain.
The purity of Ketjen black of the present invention>99%, there is branched form, pattern is shown in accompanying drawing 1.Ketjen black and carbon black
Different, Ketjen black is branched form, and compared to the spherical-like morphology of carbon black, the mechanism of Ketjen black is that branched forms network;
The mechanism of nano carbon black is to catch free radical, and grain diameter influence is larger, and the efficiency of the smaller seizure of size may be higher.
The present invention also provides a kind of preparation method of polyethylene/metal hydroxides/Ketjen black fire proofing, detailed process
Including:By metal hydroxides and Ketjen black in 70-90 DEG C of baking oven dry 4-8h, then according to formula rate by polyethylene,
After metal hydroxides and Ketjen black stirring, add into torque rheometer and carry out melt blending:Reaction temperature is 170-190
DEG C, rotating speed 50-70r/min, reaction time 8-12min;Can obtain black have the block flame-proof polyethylene of metallic luster/
Metal hydroxides/Ketjen black composite.
Compared with prior art, the present invention has the advantage that as follows with beneficial effect:
(1) Ketjen black that has of the present invention its be branched form, specific surface area is big, is easily formed in polymer matrix
Network structure;Ketjen black is added in polyethylene/metal hydroxide material, the network structure that Ketjen black is formed is as physics
Barrier layer stops the transmission of heat and quality in combustion process, so as to retarded combustion process;Equal parts are added in fire retardant
In the case of, the vertical combustion grade and limited oxygen index value of polyethylene/metal hydroxides/Ketjen black composite are carried
Height, peak value HRR and total smoke delivery decrease, and metal hydroxides and Ketjen black are used for flame-proof polyethylene
In can play synergy.
(2) metal hydroxides and Ketjen black compounding use are added into polyethylene, is made fire-retardant by melt blending
Polythene material.Compared with adding metal hydroxides merely, in the case where reaching same vertical burning grade, metal hydrogen-oxygen
The addition for being used in conjunction with reducing fire retardant of compound and Ketjen black, so as to improve the heat endurance of fire proofing and power
Learn performance.
(3) Ketjen black and polyethylene and metal hydroxide material are used in mixed way by the present invention first, and proportioning is simple, without
Other materials, the side chain morphosis for making full use of Ketjen black to have are added, so that the network structure formed is in combustion
Physical barriers can be formed and then hinder the transmission of heat and quality, improve the flame retarding efficiency of metal hydroxides.
Brief description of the drawings
The transmission electron microscope photo of Fig. 1 Ketjen blacks.
The thermogravimetric curve of Fig. 2 polyethylene/aluminium hydroxide/Ketjen black material.
The taper calorimetric curve of Fig. 3 polyethylene/aluminium hydroxide/Ketjen black material.
Embodiment
The present invention is described in further detail below by specific embodiment, but the present invention is not limited solely to following reality
Apply example.The person skilled in the art in the field according to present invention to some nonessential modifications and adaptations for making of the present invention still
Belong to protection scope of the present invention.
Embodiment
Aluminium hydroxide (ATH) and Ketjen black (KB) are dried 5h by the embodiment of the present invention in 85 DEG C of baking ovens, then will be highly dense
After spending polyethylene (HDPE), aluminium hydroxide and Ketjen black stirring, add into torque rheometer and carry out melt blending, reaction temperature
For 180 DEG C, rotating speed 60r/min, reaction time 8min, obtain well mixed composite i.e. polyethylene/aluminium hydroxide/
Ketjen black fire proofing, specific formula are as shown in table 1.
After flame-proof composite material melt blending, preparation-obtained sample is preheated into 5min in 180 DEG C of vulcanizing presses
Afterwards, 15MPa insulation 7min are boosted to, being used for properties after the shaping of pressurize natural cooling tests.
The formula of the embodiment of the present invention of table 1., heat endurance and fire resistance
aT20%It is expressed as temperature during sample thermal weight loss 20wt%;
TmaxIt is expressed as temperature during maximum heat weight loss rate, Tmax1、Tmax2First, second maximum thermal decomposition speed is corresponded to respectively
Rate.
The present embodiment heat stability testing:Powder sample 5-10mg is taken, is determined in nitrogen atmosphere using thermogravimetric analyzer,
Heating rate is 20 DEG C/min, and temperature range is 50-700 DEG C.Test result is as shown in table 1, and specific curve is shown in accompanying drawing 3.In phase
In the case of fire retardant addition, the addition of Ketjen black can improve polyethylene/aluminum hydroxide material heat decomposition temperature and
Carbon left, and heat endurance improves with the increase of Ketjen black content.As heat endurance is improved, the application of material
Also will be enlarged by.
The test of the present embodiment fire resistance is divided into three parts:Limited oxygen index test, vertical burn test and taper amount
Thermal test, specific implementation process are as follows:
(1) limited oxygen index test (LOI) is tested, sample according to GB/T2406-1993 standards on HC-2 type oxygen index instruments
Bar size is 130 × 6 × 3mm3, each 15 battens of sample test, then according to revised law specified in national standard, calculate material
Oxygen index (OI).Test result is as shown in table 1.
(2) vertical burn test (UL-94) is burnt in CZF-3 types horizontal vertical according to GB/T2408-1996 standards and determined
Test and carry out on instrument, test specimen size is 130 × 13 × 3mm3, each 5 battens of sample test, average is taken, then basis
Regulation in national standard, with reference to the flammability of experimental result evaluation material.Test result is as shown in table 1.
(3) taper calorimetric test (Cone) is according to the canonical measures of ASTM E1354/ISO 5660, sample size 100*100*
3mm3, hot-fluid 35kW/m2.Test result is as shown in table 2, and specific curve is shown in accompanying drawing 2.
The taper calorimetric test result of the embodiment of the present invention of table 2.
aPHRR is expressed as peak value HRR;
THR is expressed as total heat release;
TignIt is expressed as ignitor firing time;
TSP is expressed as total smoke delivery
The addition of aluminium hydroxide can be reduced by adding Ketjen black, while keep the vertical combustion grade of UL-94V0 ranks,
It can be seen that Ketjen black can lift the vertical combustion grade of polyethylene/aluminium hydroxide system.Meanwhile in different content aluminium hydroxide body
The Ketjen black content added in system is higher, and the limited oxygen index value of fire proofing is higher.Taper calorimetric test is as can be seen that in phase
In the case of fire retardant addition, the addition of Ketjen black can reduce the peak heat release speed of polyethylene/aluminum hydroxide material
Rate and total smoke delivery.Test result shows that Ketjen black and aluminium hydroxide have cooperative flame retardant effect in polyethylene system.
The present embodiment Mechanics Performance Testing:Carried out according to GB/T1040 on cupping machine, draw speed 50mm/min,
Test environment temperature is 25 ± 2 DEG C, and test specimen number >=5, data are averaged, and test result is as shown in table 3.By Ketjen black
It is added in polyethylene/aluminium hydroxide system, tensile strength, stretch modulus and the elongation at break of material increase.It is comprehensive
Upper fire resistance, heat endurance and the tensile property that can be seen that sample P E/ATH136/KB4 is superior to sample P E/ATH160.
Ketjen black does not deteriorate its tensile property while polyethylene anti-flaming performance is improved, and this application to polyethylene has actual anticipate
Justice.
The extension test result of the embodiment of the present invention of table 3.
Claims (5)
- A kind of 1. polyethylene/metal hydroxides/Ketjen black fire proofing, it is characterised in that:By each group for pressing portion rate below Divide and prepare:Polyethylene 100phrMetal hydroxides 125-140phrKetjen black 1-5phr.
- A kind of 2. polyethylene/metal hydroxides/Ketjen black fire proofing according to claim 1, it is characterised in that:Institute The polyethylene stated is high density polyethylene (HDPE).
- A kind of 3. polyethylene/metal hydroxides/Ketjen black fire proofing according to claim 1, it is characterised in that:Institute The metal hydroxides stated is aluminium hydroxide or magnesium hydroxide.
- A kind of 4. polyethylene/metal hydroxides/Ketjen black fire proofing according to claim 1, it is characterised in that:Institute The Ketjen black purity stated>99%, there is branched form.
- A kind of 5. polyethylene/metal hydroxides/Ketjen black fire proofing according to claim 1, it is characterised in that:System Standby step includes:(1) first metal hydroxides and Ketjen black are placed in 70-90 DEG C of baking oven and dry 4-8h;(2) again by dried metal hydroxides and Ketjen black with being added to Thermal-Haake torques after polyethylene premix In rheometer, the melt blending 8-12min under the conditions of 170~190 DEG C, 60-80r/min, the polyethylene/gold being uniformly mixed Belong to hydroxide/Ketjen black fire proofing.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109810404A (en) * | 2018-12-24 | 2019-05-28 | 浙江大学宁波理工学院 | A kind of polypropylene/metal hydroxides/rare earth compound fire proofing |
-
2017
- 2017-09-07 CN CN201710799263.7A patent/CN107629288B/en not_active Expired - Fee Related
Non-Patent Citations (3)
Title |
---|
韩黎刚: "纳米碳材料复配氢氧化铝阻燃HDPE的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
韩黎刚等: "金属氢氧化物协效阻燃聚烯烃的研究进展", 《材料科学与工程学报》 * |
黄瑞鑫等: "《世界精细化学产品质量标准汇编》", 31 December 1989 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109810404A (en) * | 2018-12-24 | 2019-05-28 | 浙江大学宁波理工学院 | A kind of polypropylene/metal hydroxides/rare earth compound fire proofing |
CN109810404B (en) * | 2018-12-24 | 2021-11-23 | 浙江大学宁波理工学院 | Polypropylene/metal hydroxide/rare earth compound flame-retardant material |
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