CN1858098A - Anti-static flame-retarding polyethylene composition and its preparing method - Google Patents
Anti-static flame-retarding polyethylene composition and its preparing method Download PDFInfo
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- CN1858098A CN1858098A CN 200610040792 CN200610040792A CN1858098A CN 1858098 A CN1858098 A CN 1858098A CN 200610040792 CN200610040792 CN 200610040792 CN 200610040792 A CN200610040792 A CN 200610040792A CN 1858098 A CN1858098 A CN 1858098A
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Abstract
The antistatic flame-retarding polyethylene composition consists of HDPE 36.5-50 weight portions, and antistatic flame-retarding master batch 50-63.5 weight portions, which contains LLDPE 10-31 weight portions, carbon black 20-30 weight portions, fire retardant 20-50 weight portions, smoke suppressor 6-24 weight portions, coupling agent 0.1-8 weight portions, dispersant 6-16 weight portions and antioxidant in proper amount. The great amount components of the master batch may be added after being pelletized to facilitate continuous addition and reduce dust pollution. The product has surface resistivity below 105 and oxygen index over 26 and other technological indexes reaching the use requirement.
Description
Technical field
The invention belongs to plastics processing and application technology, be specifically related to a kind of anti-static flame-retardant plastic composition.
Background technology
Because polyethylene has light weight, is easy to moulding, chemical proofing, outward appearance better waits good characteristic, is widely used in the shell, automobile inner decorative piece material of household electrical appliances, business automation equipment, TV and game machine etc.
But because poly insulativity is good, the volume specific resistance of polyolefin articles is up to 10
16Ω cm can not leak away the static that is produced with charged other objects frictions or when peeling off, and easily causes accumulation of static electricity, and the dust in the absorbed air causes dangerous accidents such as thunderbolt.The blown film processing difficulties can take place aborning, printing and application printing ink adhere to inequality, static can cause the flase operation of unicircuit (IC), destroy reservoir, cause various static obstacles, in addition presence of fire, harm such as powder blast, for this reason, prevent that the polyethylene static hazard from becoming the problem of people's common concern.
What patent CN200310105635.X related to is a kind of anti-electrostatic fire retardant composition, and composition comprises 20～45 parts of high density polyethylene(HDPE)s, 40～30 parts of polyethylene antistatic master batchs, 40～25 parts of polyethylene anti-flaming masterbatch.Polyethylene antistatic master batch in the composition consists of: 100 parts of polyethylene support resins, specific surface area is greater than 800g/m
2High electric conductivity carbon black A be 25～40 parts, specific surface area is less than 500g/m
2Common graphitized carbon black B be 5～10 parts, 2.0～4.0 parts of carbon black treatment agents, 0.4～1.0 part in oxidation inhibitor, 2.0～5.0 parts of polyethylene waxs.Consisting of of polyethylene anti-flaming masterbatch: 100 parts of polyethylene support resins, 100～150 parts of fire retardants, 25～40 parts of smoke suppressors, 2.0～3.0 parts in oxidation inhibitor.Above composition is to prepare the antistatic and fire-retardant two kinds of master batches of high addition in advance, and then these two kinds of master batches are mixed the back anti-electrostatic fire retardant PP Pipe Compound that is extruded in twin screw with the HDPE of required modification; The interpolation of the carbon black of higher deal and fire retardant etc. in the process of producing master batch, stirrer for mixing (mixing is an intermittent type), the twin screw extrusion equipment is all used in the production of two kinds of master batches.Problems such as bridge formation and shearing resistance can take place in higher non-resin addition aborning, make the continuous production difficulty, and working strength is big, the prefabricated production cost of products that also increased greatly of twice master batch.
Summary of the invention
Purpose of the present invention is exactly disposable preparation antistatic antiflaming master batches, adds preparation anti-electrostatic fire retardant PP Pipe Compound in the polyethylene to, makes the PP Pipe Compound surface resistivity reduce to 10
9Below the Ω, satisfy normal production and application requiring.The electrostatic energy of generation is promptly leaked away,
The prescription of composition among the present invention only with the auxiliary agent of low amount, can keep original performance of resin, can make the surface resistivity of flame-retardant and anti-static polyethylene PP Pipe Compound reach 10 again
5Below the Ω.
For make auxiliary agent such as antistatic and fire retardant can and full and uniform the working of polyvinyl resin, we have adopted powder granulation technology, continuous production high-content master batch smoothly, and only need produce a kind of preparation master batch.With after high density polyethylene(HDPE) mixes, granulation on the double-screw extruding pelletizing machine makes the anti-electrostatic flame-retardant polyvinyl PP Pipe Compound with ready master batch.
A kind of anti-static flame-retarding polyethylene composition: polyethylene is 36.5～50 parts in the composition, 50～63.5 parts of anti-electrostatic fire retardant masterbatch;
Polyethylene is 10～31 parts in the masterbatch, 20～30 parts of carbon blacks, 20～50 parts of fire retardants, 6～24 parts of smoke suppressors, 0.1～8 part of coupling agent, 6～16 parts of dispersion agents, 0.05～2.0 part in oxidation inhibitor.
A kind of method for preparing anti-static flame-retarding polyethylene composition comprises following steps:
1, with 20～30 parts of carbon blacks, 20～50 parts of thorough mixing of fire retardant, adds coupling agent, smoke suppressor, dispersion agent, oxidation inhibitor in batches successively, after the mixing fully, add 10～31 parts of mixing of linear low density polyethylene powder.
2, with the material granulation that mixes, preparation flame-retardant and anti-static master batch.
3, with 50～63.5 parts of antistatic antiflaming master batches, 36.5～50 parts of thorough mixing of high density polyethylene(HDPE).
4, with the material extruding pelletization that mixes, make anti-static flame-retarding polyethylene composition.
Under certain condition, the sooty surface-area is big more, and its electroconductibility is strong more.So adopt specific surface area among the present invention greater than 800g/cm
2Carbon black.
Fire retardant adopts high bromine-containing compound, as pentabromo-biphenyl ether, octa-BDE, decabromodiphenyl oxide, tetrabromo-bisphenol.Better consumption 15～30% (weight percent).
Smoke suppressor can be used boride, stannic oxide, zinc oxide, zinc borate, aluminum oxide, aluminium hydroxide and silicic acid antimony, particularly antimonous oxide (Sb
2O
3) halogen containing flame-retardant there is good synergism, the favorable dispersity of antimonous oxide in high density polyethylene(HDPE), addition 3～10% preferably.
Micro encapsulation red phosphorus has flame-retardant modified preferably effect, and carbon black not only can improve antistatic property, but also the flame retardant effect of micro encapsulation red phosphorus is had good synergy, can eliminate drippage and be fuming phenomenon.After carbon black and the modification of micro encapsulation red phosphorus, flame retardant properties improves, volume specific resistance and surface resistivity reduce, and excellent in impact resistance own is maintained substantially, and heat-drawn wire and flexural strength have been improved greatly, every performance all can satisfy the general needs of using, and common add-on is 6～12% (weight percents).
Coupling agent can be divided into silicane, titanate ester, aluminium esters of gallic acid, zirconium class, organic chromium class and complex class etc. by its chemical structure.Above-mentioned several big class coupling agent is domestic all production at present basically, wherein before two classes and complex class be widely used.
The silane coupling agent consumption is generally needs 0.25～0.5% of processing treatment weight.
Titanate coupling agent is to be applicable to carbon black coupling agent preferably, and it is broadly divided into four classes: monoalkoxy type, monoalkoxy pyrophosphate type, sting mould assembly (comprising 100 types, 200 types) and ligand.Wherein chelating titanate is applicable to the sooty surface treatment, is preferable coupling agent.Better consumption 2～4%.
The structural formula of chelating type,
-OX-is the atomic group that is connected with titanium atom or claims bonding group that this group will determine the feature of titanic acid ester.Group has alkoxyl group, acyloxy, carboxyl, sulphur acyloxy, phosphorus oxygen base, pyrophosphoryl oxygen base etc.
-R-is the short-chain alkyl of facile hydrolysis or water is had the chelate group of certain stability that titanic acid ester forms the unimolecular layer of coupling agent by the surface hydroxyl reaction of functional group and carbon black or fire retardant, thereby plays the chemical coupling effect.
-Y-is that titanic acid ester is carried out crosslinked functional group, and promptly titanic acid ester is commonly hydrogen atom most than the long-chain end, also can be unsaturated group, amino, epoxy group(ing), carboxyl, hydroxyl or sulfenyl, forms chemical coupling by them and polymer macromolecule reaction.
Aluminium zirconate class coupling agent consumption is few, and general consumption is that 0.02～0.5% of inorganics weight can reach stable effect, and such coupling agent excellent performance, of many uses is easy to synthesize.It can significantly reduce the viscosity of Inorganic Fillers Filled system, improves its flowability.
Be applicable to the coupling agent that carbon black and fire retardant use simultaneously, secondly our first-selected aluminium zirconate class coupling agent is titanate coupling agent and silane coupling agent.
Oxidation inhibitor is used hindered amines and phosphoric acid ester usually, selects plastic working industry used various components usually, as β-(3,5-di-t-butyl-4-hydroxy phenyl) octadecanol ester: three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester etc.
Because the adding of carbon black etc., the processing fluidity of reduction resin that can be in various degree, and low-molecular-weight wax adds as dispersion agent not only promotes the dispersion of carbon black etc. and gives material better mobile in the polymkeric substance.Therefore the suitable proportioning of carbon black and low-molecular-weight wax is the key that Masterbatch processing and quality realize.The low-molecular-weight wax fusing point is low, and melting range is wide, if low-molecular-weight wax adds too much, the master batch melt fluidity is big, can play outer lubrication by work in-process, has weakened shearing action, but can make the sooty maldistribution; Moreover, influence product size stability and cause performance to reduce because add-on too much can make the machine-shaping difficulty.The oligopolymer add-on is more suitable between 0.2～8% (weight percent).
The preparation method of low-molecular-weight wax mainly contains two kinds: cracking process and polymerization.The molecular weight product that cracking process is produced is not easy control, molecular weight distribution broad; Adopt polymerization, the polyethylene wax molecular weight of this method preparation is controlled easily, and narrow distribution.The result shows that polyethylene wax number average relative molecular mass has dispersion effect preferably when 1000～4000 scopes, and the polyethylene wax relative molecular mass is high more, dispersive ability is strong more, and the consumption of polyethylene wax changes to some extent with the difference of polyethylene wax relative molecular mass, processed and applied condition.The optimum amount of this research is about 6%; Molecular weight distribution has certain influence to the performance of polyethylene wax.The low-molecular-weight wax that preferably adopts polymerization to produce among the present invention requires 300 ℃ not decompose or seldom decompose: number average relative molecular weight 3000～4000; Molecular weight distribution is narrower, is preferably in below 5.
Low-molecular-weight wax generally is irregular laminar, and when high-speed mixing, easily sticking dirt takes place the inwall at mixing tank, the present invention preferably adopts median size at 4～40 microns, the outward appearance Powdered micronization PE wax that is white in color can improve the blended effect, reduces the sticking dirty phenomenon of wax.
Mineral wax has montanin wax, paraffin, purification ceresine, mineral tallow etc. natively.It is cured that montanin wax also is called the illiteracy dawn, and the employing main component is C
24～C
32Lipid acid and C
26～C
32The ester that Fatty Alcohol(C12-C14 and C12-C18) constituted.
Paraffin be oil after fractionation, be included in the mixture of the various polymer saturated hydrocarbons in the lubricating oil distillate.Paraffin is crystalline mineral wax, mainly is made up of solid-state normal paraffin.
The present invention preferably adopts crystalline wax, helps disperseing and reduces sticking dirty phenomenon in the mixing process.Can select for use and cover cured or paraffin of dawn, consumption 2～4% (weight percent).
Powder granulation technology is adopted in the masterbatch granulation, and along with the raising of environmental protection demand and Automation of Manufacturing Process degree, the present invention adopts extrusion process to carry out the master batch granulation.Extruder granulation equipment according to principle of work and structure can be divided into vacuum depression bar tablets press, list (two) screw extruder pelletizer, model stamping machine, plunger pushing machine, roller extrusion machine, to the roller gear tablets press etc.What we adopted is plunger pushing machine.
Compared with the prior art, in effective component proportioning of the present invention and the addition, reduced the addition of main component, change original twice master batch granulation into a granulation, shortened Production Flow Chart, make the PP Pipe Compound performance keep original performance substantially, the more suitable processing of product, can realize serialization production, the products production cost descends, and the surface resistivity of product is 10
8Below the Ω, oxygen index is more than 26, and the technical indicator of PP Pipe Compound satisfies service requirements.Various auxiliary agents in the master batch can adopt the extruder grain technology of powder when high addition, to overcome high continuous processing difficulties of adding component, and problem such as dust is big.
Embodiment
Embodiment 1
Composite formula: high density polyethylene(HDPE): 50 parts
Flame-proof antistatic master material: 50 parts
Wherein:
The flame-proof antistatic master material prescription is:
Linear low density polyethylene (powder): 31 parts
Graphitized carbon black: 20 parts
Fire retardant (decabromodiphenyl oxide): 30 parts
Smoke suppressor (Sb
2O
3): 6 parts
Coupling agent (aluminium zirconate class): 0.6 part
Oxidation inhibitor (1076) β-(3,5-di-t-butyl-4-hydroxy phenyl) octadecanol ester: 0.2 part
Oxidation inhibitor (168) three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester: 0.2 part
Dispersion agent (low-molecular-weight wax): 12 parts
Embodiment 2
Composite formula, the proportioning of high density polyethylene(HDPE) and flame-proof antistatic master material is with embodiment 1.
Wherein:
The flame-proof antistatic master material prescription is:
Linear low density polyethylene (powder): 29 parts
Graphitized carbon black: 22 parts
Fire retardant (decabromodiphenyl oxide): 30 parts
Smoke suppressor (Sb
2O
3): 6 parts
Coupling agent (aluminium zirconate class): 0.6 part
Oxidation inhibitor (1076): 0.2 part
Oxidation inhibitor (168): 0.2 part
Dispersion agent (low-molecular-weight wax): 12 parts
Embodiment 3
Composite formula, the proportioning of high density polyethylene(HDPE) and flame-proof antistatic master material is with embodiment 1.
Wherein:
The flame-proof antistatic master material prescription is:
Linear low density polyethylene (powder): 27 parts
Graphitized carbon black: 24 parts
Fire retardant (decabromodiphenyl oxide): 30 parts
Smoke suppressor (Sb
2O
3): 6 parts
Coupling agent (aluminium zirconate class): 0.6 part
Oxidation inhibitor (1076): 0.2 part
Oxidation inhibitor (168): 0.2 part
Dispersion agent (low-molecular-weight wax): 6 parts
Embodiment 4
Composite formula, the proportioning of high density polyethylene(HDPE) and flame-proof antistatic master material is with embodiment 1.
Wherein:
The flame-proof antistatic master material prescription is:
Linear low density polyethylene (powder): 25 parts
Graphitized carbon black: 26 parts
Fire retardant (decabromodiphenyl oxide): 30 parts
Smoke suppressor (Sb
2O
3): 6 parts
Coupling agent (aluminium zirconate class): 0.6 part
Oxidation inhibitor (1076): 0.2 part
Oxidation inhibitor (168): 0.2 part
Dispersion agent (low-molecular-weight wax): 12 parts
Embodiment 5
Composite formula, the proportioning of high density polyethylene(HDPE) and flame-proof antistatic master material is with embodiment 1.
Wherein:
The flame-proof antistatic master material prescription is:
Linear low density polyethylene (powder): 23 parts
Graphitized carbon black: 28 parts
Fire retardant (decabromodiphenyl oxide): 30 parts
Smoke suppressor (Sb
2O
3): 6 parts
Coupling agent (aluminium zirconate class): 0.6 part
Oxidation inhibitor (1076): 0.2 part
Oxidation inhibitor (168): 0.2 part
Dispersion agent (low-molecular-weight wax): 12 parts
Embodiment 6
Composite formula, the proportioning of high density polyethylene(HDPE) and flame-proof antistatic master material is with embodiment 1.
Wherein:
The flame-proof antistatic master material prescription is:
Linear low density polyethylene (powder): 21 parts
Graphitized carbon black: 30 parts
Fire retardant (decabromodiphenyl oxide): 30 parts
Smoke suppressor (Sb
2O
3): 6 parts
Coupling agent (aluminium zirconate class): 0.6 part
Oxidation inhibitor (1076): 0.2 part
Oxidation inhibitor (168): 0.2 part
Dispersion agent (low-molecular-weight wax): 12 parts
The performance index of composition are as follows:
Oxygen index: 26.5
Volume specific resistance: 4.1 * 10
5Ω m
Surface resistivity: 3.2 * 10
4Ω
Melt flow rate (MFR) (5KG): 0.1g/10min
Tensile yield strength: 27.28MPa
Shock strength: 8.45KJm
-2
Embodiment 7
Composite formula, the proportioning of high density polyethylene(HDPE) and flame-proof antistatic master material is with embodiment 1.
Wherein:
The flame-proof antistatic master material prescription is:
Linear low density polyethylene (powder): 30.4 parts
Graphitized carbon black: 30 parts
Fire retardant (octa-BDE): 20 parts
Smoke suppressor (Sb
2O
3): 6.6 parts
Coupling agent (aluminium zirconate class): 0.6 part
Oxidation inhibitor (1076): 0.2 part
Oxidation inhibitor (168): 0.2 part
Dispersion agent (low-molecular-weight wax): 12 parts
Embodiment 8
Composite formula, the proportioning of high density polyethylene(HDPE) and flame-proof antistatic master material is with embodiment 1.
Wherein:
The flame-proof antistatic master material prescription is:
Linear low density polyethylene (powder): 27.6 parts
Graphitized carbon black: 30 parts
Fire retardant (octa-BDE): 22 parts
Smoke suppressor (Sb
2O
3): 7.4 parts
Coupling agent (aluminium zirconate class): 0.6 part
Oxidation inhibitor (1076): 0.2 part
Oxidation inhibitor (168): 0.2 part
Dispersion agent (low-molecular-weight wax): 12 parts
Embodiment 9
Composite formula, the proportioning of high density polyethylene(HDPE) and flame-proof antistatic master material is with embodiment 1.
Wherein:
The flame-proof antistatic master material prescription is:
Linear low density polyethylene (powder): 27 parts
Graphitized carbon black: 30 parts
Fire retardant (octa-BDE): 24 parts
Smoke suppressor (Sb
2O
3): 6 parts
Coupling agent (aluminium zirconate class): 0.6 part
Oxidation inhibitor (1076): 0.2 part
Oxidation inhibitor (168): 0.2 part
Dispersion agent (low-molecular-weight wax): 12 parts
Embodiment 10
Composite formula:
Composite formula, the proportioning of high density polyethylene(HDPE) and flame-proof antistatic master material is with embodiment 1.
Wherein:
The flame-proof antistatic master material prescription is:
Linear low density polyethylene (powder): 24.4 parts
Graphitized carbon black: 30 parts
Fire retardant (octa-BDE): 26 parts
Smoke suppressor (Sb
2O
3): 6.6 parts
Coupling agent (aluminium zirconate class): 0.6 part
Oxidation inhibitor (1076): 0.2 part
Oxidation inhibitor (168): 0.2 part
Dispersion agent (low-molecular-weight wax): 12 parts
Embodiment 11
Composite formula:
Composite formula, the proportioning of high density polyethylene(HDPE) and flame-proof antistatic master material is with embodiment 1.
Wherein:
The flame-proof antistatic master material prescription is:
Linear low density polyethylene (powder): 23.4 parts
Graphitized carbon black: 30 parts
Fire retardant (octa-BDE): 28 parts
Smoke suppressor (Sb
2O
3): 5.6 parts
Coupling agent (aluminium zirconate class): 0.6 part
Oxidation inhibitor (1076): 0.2 part
Oxidation inhibitor (168): 0.2 part
Dispersion agent (low-molecular-weight wax): 12 parts
Embodiment 12
Composite formula:
Composite formula, the proportioning of high density polyethylene(HDPE) and flame-proof antistatic master material is with embodiment 1.
Wherein:
The flame-proof antistatic master material prescription is:
Linear low density polyethylene (powder): 21 parts
Graphitized carbon black: 30 parts
Fire retardant (octa-BDE): 30 parts
Smoke suppressor (Sb2O3): 6 parts
Coupling agent (aluminium zirconate class): 0.6 part
Oxidation inhibitor (1076): 0.2 part
Oxidation inhibitor (168): 0.2 part
Dispersion agent (low-molecular-weight wax): 12 parts
Embodiment 13
Composite formula, the proportioning of high density polyethylene(HDPE) and flame-proof antistatic master material is with embodiment 1.
Wherein:
The flame-proof antistatic master material prescription is:
Linear low density polyethylene (powder): 21 parts
Graphitized carbon black: 30 parts
Fire retardant (pentabromo-biphenyl ether): 30 parts
Smoke suppressor (Sb2O3): 6 parts
Coupling agent (aluminium zirconate class): 0.6 part
Oxidation inhibitor (1076): 0.2 part
Oxidation inhibitor (168): 0.2 part
Dispersion agent (low-molecular-weight wax): 12 parts
Embodiment 14
Composite formula:
High density polyethylene(HDPE): 43.5 parts
Flame-proof antistatic master material: 56.5 parts
Wherein:
The flame-proof antistatic master material prescription is:
Linear low density polyethylene (powder): 10 parts
Graphitized carbon black: 30 parts
Fire retardant (pentabromo-biphenyl ether): 50 parts
Smoke suppressor (Sb2O3): 10 parts
Coupling agent (aluminium zirconate class): 0.6 part
Oxidation inhibitor (1076): 0.2 part
Oxidation inhibitor (168): 0.2 part
Dispersion agent (low-molecular-weight wax): 12 parts
Embodiment 15
Composite formula, the proportioning of high density polyethylene(HDPE) and flame-proof antistatic master material is with embodiment 1.
Wherein:
The flame-proof antistatic master material prescription is:
Linear low density polyethylene (powder): 21 parts
Graphitized carbon black: 30 parts
Fire retardant (tetrabromo-bisphenol): 30 parts
Smoke suppressor (Sb
2O
3): 6 parts
Coupling agent (aluminium zirconate class): 0.6 part
Oxidation inhibitor (1076): 0.2 part
Oxidation inhibitor (168): 0.2 part
Dispersion agent (low-molecular-weight wax): 12 parts
Embodiment 16
Composite formula:
High density polyethylene(HDPE): 43.5 parts
Flame-proof antistatic master material: 56.5 parts
Wherein:
The flame-proof antistatic master material prescription is:
Linear low density polyethylene (powder): 10 parts
Graphitized carbon black: 30 parts
Fire retardant (tetrabromo-bisphenol): 50 parts
Smoke suppressor (Sb2O3): 10 parts
Coupling agent (aluminium zirconate class): 0.6 part
Oxidation inhibitor (1076): 0.2 part
Oxidation inhibitor (168): 0.2 part
Dispersion agent (low-molecular-weight wax): 12 parts
Embodiment 17
Composite formula is identical with embodiment 6, and the aluminium zirconate class coupling agent consumption in the anti-electrostatic fire retardant masterbatch among the embodiment 6 is changed into: 0.1 part, the LLDPE powder is 21.5 parts
Embodiment 18
Composite formula is identical with embodiment 6, and the aluminium zirconate class coupling agent consumption in the anti-electrostatic fire retardant masterbatch among the embodiment 6 is changed into: 0.2 part, the LLDPE powder is 21.4 parts
Embodiment 19
Composite formula is identical with embodiment 6, and the aluminium zirconate class coupling agent consumption in the anti-electrostatic fire retardant masterbatch among the embodiment 6 is changed into: 0.4 part, the LLDPE powder is 21.2 parts
Embodiment 20
Composite formula is identical with embodiment 6, and the aluminium zirconate class coupling agent consumption in the anti-electrostatic fire retardant masterbatch among the embodiment 6 is changed into: 0.8 part, the LLDPE powder is 20.8 parts
Embodiment 21
Composite formula is identical with embodiment 6, and the aluminium zirconate class coupling agent consumption in the anti-electrostatic fire retardant masterbatch among the embodiment 6 is changed into: 1.0 parts, the LLDPE powder is 20.6 parts
Embodiment 22
Composite formula is identical with embodiment 6, and titante coupling agent (the stinging mould assembly) consumption in the anti-electrostatic fire retardant masterbatch among the embodiment 6 is changed into: 4 parts, the LLDPE powder is 17.6 parts
Titanate ester chelating type coupling agent. can select KR-138S, the KR-212 in dawn chemical plant, Nanjing, following examples are identical.
Embodiment 23
Composite formula is identical with embodiment 6, and metatitanic acid esters of gallic acid coupling agent (the stinging mould assembly) consumption in the anti-electrostatic fire retardant masterbatch among the embodiment 6 is changed into: 6 parts, the LLDPE powder is 15.6 parts
Embodiment 24
Composite formula is identical with embodiment 6, and metatitanic acid esters of gallic acid coupling agent (the stinging mould assembly) consumption in the anti-electrostatic fire retardant masterbatch among the embodiment 6 is changed into: 8 parts, the LLDPE powder is 13.6 parts
Embodiment 25
Composite formula is identical with embodiment 6, and the dispersion agent low-molecular-weight wax consumption in the anti-electrostatic fire retardant masterbatch among the embodiment 6 is changed into: 6 parts, the LLDPE powder is 27 parts
Embodiment 26
Composite formula is identical with embodiment 6, and the dispersion agent low-molecular-weight wax consumption in the anti-electrostatic fire retardant masterbatch among the embodiment 6 is changed into: 8 parts, the LLDPE powder is 25 parts
Embodiment 27
Composite formula is identical with embodiment 6, and the dispersion agent low-molecular-weight wax consumption in the anti-electrostatic fire retardant masterbatch among the embodiment 6 is changed into: 10 parts, the LLDPE powder is 23 parts
Embodiment 28
Composite formula is identical with embodiment 6, and the dispersion agent low-molecular-weight wax consumption in the anti-electrostatic fire retardant masterbatch among the embodiment 6 is changed into: 16 parts, the LLDPE powder is 17 parts
Embodiment 29
Composite formula is identical with embodiment 6, and the crystalline paraffin consumption of the dispersion agent in the anti-electrostatic fire retardant masterbatch among the embodiment 6 is changed into: 4 parts, the LLDPE powder is 29 parts
Embodiment 30
Composite formula is identical with embodiment 6, and the crystalline paraffin consumption of the dispersion agent in the anti-electrostatic fire retardant masterbatch among the embodiment 6 is changed into: 6 parts, the LLDPE powder is 27 parts
Embodiment 31
Composite formula is identical with embodiment 6, and the crystalline paraffin consumption of the dispersion agent in the anti-electrostatic fire retardant masterbatch among the embodiment 6 is changed into: 8 parts, the LLDPE powder is 25 parts
Embodiment 32
Composite formula is identical with embodiment 6, and the dispersion agent montanin wax consumption in the anti-electrostatic fire retardant masterbatch among the embodiment 6 is changed into: 4 parts, the LLDPE powder is 29 parts
Embodiment 33
Composite formula is identical with embodiment 6, and the dispersion agent montanin wax consumption in the anti-electrostatic fire retardant masterbatch among the embodiment 6 is changed into: 6 parts, the LLDPE powder is 27 parts
Embodiment 34
Composite formula is identical with embodiment 6, and the dispersion agent montanin wax consumption in the anti-electrostatic fire retardant masterbatch among the embodiment 6 is changed into: 8 parts, the LLDPE powder is 25 parts
Embodiment 35
Composite formula:
Composite formula, the proportioning of high density polyethylene(HDPE) and flame-proof antistatic master material is with embodiment 1.
Wherein:
The flame-proof antistatic master material prescription is:
Linear low density polyethylene (powder): 15 parts
Graphitized carbon black: 30 parts
Fire retardant (tetrabromo-bisphenol): 30 parts
Smoke suppressor (red phosphorus): 12 parts
(micro encapsulation red phosphorus: can adopt Tianjin flame-retarded technology institute to produce, below identical) coupling agent (aluminium zirconate class): 0.6 part
Oxidation inhibitor (1076): 0.2 part
Oxidation inhibitor (168): 0.2 part
Dispersion agent (low-molecular-weight wax): 12 parts
Embodiment 36
Composite formula:
High density polyethylene(HDPE): 36.5 parts
Flame-proof antistatic master material: 63.5 parts
Wherein:
The flame-proof antistatic master material prescription is:
Linear low density polyethylene (powder): 10 parts
Graphitized carbon black: 30 parts
Fire retardant (tetrabromo-bisphenol): 50 parts
Smoke suppressor (red phosphorus): 24 parts
Coupling agent (aluminium zirconate class): 0.6 part
Oxidation inhibitor (1076): 0.2 part
Oxidation inhibitor (168): 0.2 part
Dispersion agent (low-molecular-weight wax): 12 parts
The performance index of composition are as follows:
Oxygen index: 28.5%
Volume specific resistance: 3.5 * 105 Ω m
Surface resistivity: 2.4 * 104 Ω
Melt flow rate (MFR) (5KG): 0.1g/10min
Tensile yield strength: 28.16MPa
Shock strength: 7.22KJm-2
Embodiment 37
Composite formula:
High density polyethylene(HDPE): 40.5 parts
Flame-proof antistatic master material: 59.5 parts
Wherein:
The flame-proof antistatic master material prescription is:
Linear low density polyethylene (powder): 10 parts
Graphitized carbon black: 30 parts
Fire retardant (tetrabromo-bisphenol): 50 parts
Smoke suppressor (red phosphorus): 16 parts
Coupling agent (aluminium zirconate class): 0.6 part
Oxidation inhibitor (1076): 0.2 part
Oxidation inhibitor (168): 0.2 part
Dispersion agent (low-molecular-weight wax): 12 parts
Embodiment 38:
20 parts of graphitized carbon blacks, fire retardant (decabromodiphenyl oxide) are used the high-speed mixer thorough mixing for 30 parts, add 0.6 part of coupling agent (aluminium zirconate class), smoke suppressor (Sb successively
2O
3) 6 parts, 12 parts of dispersion agents (low-molecular-weight wax), oxidation inhibitor (1076) β-(3,5-di-t-butyl-one 4-hydroxy phenyl) the octadecanol ester is 0.2 part, oxidation inhibitor (168) three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester is 0.2 part, behind the thorough mixing, add 31 parts of linear low density polyethylene powders with plunger pushing machine extruding pelletization, 160 ℃ of prilling temperatures make the anti-electrostatic fire retardant masterbatch; 50 parts of 50 parts of flame-proof antistatic master materials, high density polyethylene(HDPE) are mixed the back granulation with the high-speed mixing agent, and 200 ℃ of prilling temperatures make anti-static flame-retarding polyethylene composition.
In the above example, graphitized carbon black can adopt the BlackPear of U.S. Cabot Corporation, or the Ensaco350G of Belgian Te Migao company; The decabromodiphynly oxide that the fire retardant decabromodiphenyl oxide selects emerging chemical plant, Laizhou City, Shandong to produce; Smoke suppressor (Sb
2O
3) antimonous oxide that can select Taojiang County, Hunan Tiger Mountain antimony products factory to produce; Coupling agent (aluminium zirconate class) can be selected (MANCHEM) series of French Rhone-Poulenc company; Dispersion agent (low-molecular-weight wax) can be selected Kingsoft, Shanghai Venus plastic molding and processing plant, Fine Chemical Factory of Beijing University of Chemical Technology, second auxiliary factory, Beijing, joint operation chemical plant, Beijing University of Chemical Technology Rushan etc., U.S. Yi Shi Man, Hong Kong BASF AG, LG Corp of South Korea, Samsung etc., LLDPE index and low density polyethylene.
Claims (7)
1, a kind of anti-static flame-retarding polyethylene composition, polyethylene is 36.5～50 parts in the composition, 50～63.5 parts of anti-electrostatic fire retardant masterbatch, polyethylene is 10～31 parts in the anti-electrostatic fire retardant masterbatch, 20～30 parts of carbon blacks, 20～50 parts of fire retardants, 6～24 parts of smoke suppressors, 0.1～8 part of coupling agent, 6～16 parts of dispersion agents, 0.05～2.0 part in oxidation inhibitor.
2, composition according to claim 1 is characterized in that: carbon black adopts specific surface area greater than 800g/cm
2Carbon black.
3, composition according to claim 1 is characterized in that: fire retardant adopts pentabromo-biphenyl ether, octa-BDE, decabromodiphenyl oxide, tetrabromo-bisphenol.
4, composition according to claim 1, it is characterized in that: smoke suppressor is selected boride for use, stannic oxide, zinc oxide, zinc borate, aluminum oxide, aluminium hydroxide, silicic acid antimony.
5, composition according to claim 1 is characterized in that: coupling agent is aluminium zirconate class coupling agent, titanate coupling agent, silane coupling agent.
6, a kind of method for preparing anti-static flame-retarding polyethylene composition comprises following steps:
1), with 20～30 parts of carbon blacks, 20～50 parts of thorough mixing of fire retardant, add coupling agent, smoke suppressor, dispersion agent, oxidation inhibitor in batches successively, mix fully after, add 10～31 parts of mixing of linear low density polyethylene powder.
2), with the material granulation that mixes, preparation flame-retardant and anti-static master batch.
3), with 50～63.5 parts of antistatic antiflaming master batches, high density polyethylene(HDPE) 36.5～50 thorough mixing.
4), with the material extruding pelletization that mixes, make anti-static flame-retarding polyethylene composition.
7, preparation method according to claim 6 is characterized in that: powder granulation technology is adopted in the granulation of step 2.
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| CN105670081A (en) * | 2016-03-07 | 2016-06-15 | 太仓市晨洲塑业有限公司 | Novel polyethylene |
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