CN110066443A - A kind of halogen-free fire-retardant polyethylene material and its preparation method and application - Google Patents
A kind of halogen-free fire-retardant polyethylene material and its preparation method and application 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
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- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
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- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
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- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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Abstract
The invention discloses a kind of halogen-free fire-retardant polyethylene materials and its preparation method and application.This halogen-free fire-retardant polyethylene material includes the raw material of following mass parts: LDPE80~95 part；5~15 parts of non-halogen phosphoric acid ester based flame retardant；1~5 part of nitrogenated flame retardant；0.2~0.8 part of antioxidant；0.1~0.5 part of diffusing oil；0.3~0.7 part of lubricant.It also discloses the preparation method of this halogen-free fire-retardant polyethylene material simultaneously, also discloses the application of this halogen-free fire-retardant polyethylene material.Halogen-free fire-retardant polyethylene material of the invention is fire-retardant and excellent in mechanical performance, the flexibility of product is good, and feel touch is not pricked the hand, and resilience is good, it is repeatable to recycle, environment-protecting and non-poisonous, flame retardant property reaches UL94 V-2, and self-extinguishment is good, preparation method is simple, production cost is low, is easy to carry out industrialization large-scale production, suitable for preparing simulated decorative product and plug inner membrance.
Description
Technical field
The invention belongs to fire proofing technical fields, more particularly to a kind of halogen-free fire-retardant polyethylene material and its preparation side
Method and application.
Background technique
Polyethylene (PE) is with odorless, nontoxic, resistance to low temperature is excellent, chemical stability is good, resistance to most of soda acids, water suction
Property it is small, electrical insulating property is excellent the advantages that, be widely used in fields such as chemical industry, agricultural, building and packagings, especially emulation PE dress
The demand of jewellery trade, polyethylene is increasing, it is desirable that increasingly tighter, many products are all elevated to from the indoor requirement of satisfaction
Meet outdoor requirement.Good weatherability, colour-fast, flame retardant property is stable, the polythene material of halogen-free environmental is following
Development trend.However, conventional Zero halogen flame resistance polyethylene is typically all to use ammonium polyphosphate and pentaerythrite as fire retardant, it is fire-retardant
Agent additive amount is 20~30%, and flame retardant effect is preferable, but mechanical properties decrease is serious, and mobility is also magnanimous decline, processing
It is difficult.
For simulated decorative conduct industry, main includes emulation greening lawn, and simulated Christmas tree emulates branch etc., and inserts
Head inner membrance, these product itself flame-retardancy requirements are not high, but need self-extinguishment, cannot ignite on a large scale, to fire retardant, especially
The environmental requirement of bromine antimony is higher, and service performance requires also very clear, it is necessary to resistant to bending, it is not easy to be broken, hardness is low, does not prick the hand.
But it is directed to halogen-free fire-retardant polyethylene material used in simulated decorative conduct industry and plug inner membrance, it at present still can be unreal
The polyethylene product of existing above-mentioned performance meets the requirement in market.
Summary of the invention
Of the existing technology in order to overcome the problems, such as, one of the objects of the present invention is to provide a kind of Zero halogen flame resistance polyethylenes
Material, the second object of the present invention are to provide the preparation method of this halogen-free fire-retardant polyethylene material, the purpose of the present invention it
Three are to provide this halogen-free fire-retardant polyethylene material in the application of simulated decorative product and plug inner membrance.
In order to achieve the above purpose, the technical solution used in the present invention is:
The present invention provides a kind of halogen-free fire-retardant polyethylene material, this halogen-free fire-retardant polyethylene material includes following quality
The raw material of part:
LDPE (low density polyethylene (LDPE)): 80~95 parts；
Non-halogen phosphoric acid ester based flame retardant: 5~15 parts；
Nitrogenated flame retardant: 1~5 part；
Antioxidant: 0.2~0.8 part；
Diffusing oil: 0.1~0.5 part；
Lubricant: 0.3~0.7 part.
In this halogen-free fire-retardant polyethylene material, the preferred mass parts of LDPE are 83~87 parts；Non-halogen phosphoric acid ester class is fire-retardant
The preferred mass parts of agent are 9~12 parts；The preferred dosage of nitrogenated flame retardant is 2~4 parts；The preferred dosage of antioxidant be 0.3~
0.5 part；The preferred dosage of diffusing oil is 0.2~0.4 part；The preferred dosage of lubricant is 0.4~0.6 part.
Preferably, in this halogen-free fire-retardant polyethylene material, the bending modulus of LDPE is 90MPa~120MPa, and fracture is stretched
Long rate > 150%, the melt index at 190 DEG C of test condition, 2.16kg are 20g/10min~50g/10min.
Preferably, in this halogen-free fire-retardant polyethylene material, non-halogen phosphoric acid ester based flame retardant is selected from the bis- (diphenyl of bisphenol-A-
Phosphate) (BDP), phosphate toluene diphenyl ester (CDP), resorcinol bis- (diphenyl phosphoesters) (RDP), tricresyl phosphate
(TCP), at least one of tricresyl phosphate (dimethylbenzene) ester (TXP), poly aryl phosphate ester (PX-200)；It is further preferred that
Non-halogen phosphoric acid ester based flame retardant is selected from bisphenol-A-bis- (diphenyl phosphoesters), phosphate toluene diphenyl ester, the bis- (diphenyl of resorcinol
Phosphate), at least one of tricresyl phosphate；Still further preferably, non-halogen phosphoric acid ester based flame retardant is selected from bisphenol-A-
One of bis- (diphenyl phosphoesters), resorcinol bis- (diphenyl phosphoesters) or combinations thereof object.
Preferably, in this halogen-free fire-retardant polyethylene material, nitrogenated flame retardant is selected from melamine, cyanuric acid melamine
At least one of amine, two melamine of pyrophosphoric acid, boric acid melamine, orthophosphoric acid melamine, polyphosphoric acid melamine；Into
One step is preferred, and nitrogenated flame retardant is selected from melamine, melamine cyanurate, boric acid melamine, polyphosphoric acid melamine
At least one of；Still further preferably, nitrogenated flame retardant is selected from boric acid melamine.
Preferably, in this halogen-free fire-retardant polyethylene material, 4,4 '-butylidenebis of antioxidant (6- tert-butyl -3- methyl
Phenol) (No. CAS: 85-60-9) and distearyl pentaerythritol diphosphite (No. CAS: 3806-34-6) be with mass ratio 1:
(2~6) antioxidant compounded；It is further preferred that antioxidant be 4,4 '-butylidenebis (6- tert-butyl -3- methylphenol) and
Distearyl pentaerythritol diphosphite is with mass ratio 1:(3~5) compounding antioxidant；Still further preferably, antioxygen
Agent is 4,4 '-butylidenebis (6- tert-butyl -3- methylphenol) and distearyl pentaerythritol diphosphite with mass ratio
The antioxidant of 1:4 compounding.
Preferably, in this halogen-free fire-retardant polyethylene material, diffusing oil is octamethylcy-clotetrasiloxane；Further preferably
, diffusing oil is the octamethylcy-clotetrasiloxane that viscosity is 500mPas~700mPas at 25 DEG C.
Preferably, in this halogen-free fire-retardant polyethylene material, lubricant is selected from stearic acid, stearate, stearate, second
Support at least one of bis-stearamides (EBS), polyethylene wax；It is further preferred that lubricant is selected from stearic acid, stearic acid
At least one of calcium, zinc stearate, butyl stearate, ethylene bis stearamide, polyethylene wax；Still further preferably, moisten
Lubrication prescription is selected from ethylene bis stearamide.
The present invention provides the preparation method of above-mentioned halogen-free fire-retardant polyethylene material, this halogen-free fire-retardant polyethylene material
Preparation method, comprising the following steps:
1) by LDPE and diffusing oil in stirrer for mixing；
2) nitrogenated flame retardant, antioxidant, lubricant are added in blender again, mixing obtains mixture；
3) it adds mixture into the main spout of double screw extruder, non-halogen phosphoric acid ester based flame retardant is hindered by liquid
Combustion agent adding set is added to the 4th~5 section of double-screw extruder screw；
4) it is kneaded, is squeezed out by double screw extruder, be granulated, obtain halogen-free fire-retardant polyethylene material.
Preferably, in the preparation method step 1) of this halogen-free fire-retardant polyethylene material, mixed temperature is 40 DEG C~60
℃；It is further preferred that mixed temperature is 50 DEG C.
Preferably, in the preparation method step 3) of this halogen-free fire-retardant polyethylene material, liquid flame retardant adding set packet
Include sequentially connected non-halogen phosphoric acid ester based flame retardant head tank, air pump oil filling pipe, pans, metering device, output channel and mist
Change air gun.
Preferably, in preparation method step 3) the liquid flame retardant adding set of this halogen-free fire-retardant polyethylene material, nothing
Halophosphate based flame retardant head tank is externally provided with heating bag, and temperature is set as 110 DEG C~130 DEG C, can make non-halogen phosphoric acid ester class
Fire retardant viscosity reduces, convenient for conveying；It is further preferred that heating bag set temperature is 120 DEG C.
Preferably, in preparation method step 3) the liquid flame retardant adding set of this halogen-free fire-retardant polyethylene material, in
Between tank be equipped with infrared detecting set, graticule is equipped in pans, is more than graticule, suspends oil transportation；Temperature-controlling system, temperature are equipped in pans
Degree is set as 110 DEG C~130 DEG C；It is further preferred that pans set temperature is 120 DEG C.
Preferably, in preparation method step 3) the liquid flame retardant adding set of this halogen-free fire-retardant polyethylene material, meter
Amount device is made of measuring tank, weighing balance, control valve and PLC control system；Liquid flame-proof is set by PLC control system
Agent additive amount, weighing balance accurate measurement, control valve carry out residual quantity adjustment.
Preferably, in the preparation method of this halogen-free fire-retardant polyethylene material, double screw extruder squeezes for parallel dual-screw
Machine out, design parameter are as follows: screw diameter is 70mm~95mm, and screw slenderness ratio is (42~46): 1.
Preferably, in the preparation method step 4) of this halogen-free fire-retardant polyethylene material, each area's temperature of double screw extruder
It is as follows to spend parameter: 100 DEG C~115 DEG C of paragraph 1, the 2nd section to the 4th section 160 DEG C~170 DEG C, the 5th section to the 11st section 165~160
DEG C, 160 DEG C of head.
The present invention also provides above-mentioned this halogen-free fire-retardant polyethylene materials to prepare simulated decorative product and/or plug inner membrance
In application.
Preferably, in, simulated decorative product include but are not limited to emulation greening lawn, simulated Christmas tree, artificial tree
The seasonal artificial product such as branch.
The beneficial effects of the present invention are:
Halogen-free fire-retardant polyethylene material of the invention is fire-retardant and excellent in mechanical performance, and the flexibility of product is good, and feel touches
It does not prick the hand, resilience is good, repeats and recycles, environment-protecting and non-poisonous, flame retardant property reaches UL94V-2, and self-extinguishment is good, preparation side
Method is simple, and production cost is low, is easy to carry out industrialization large-scale production, suitable for preparing simulated decorative product and plug inner membrance.
Specifically, advantages of the present invention is as follows:
1) LDPE of high fluidity is because present invention is mainly applied to emulate dress as matrix resin in present invention selection
Jewellery trade and plug inner membrance, mainly emulation greening lawn, simulated Christmas tree, emulation branch etc., these products are to matrix tree
The requirement of rouge is that hardness is low, at low cost, and resilience is good, it is not easy to it is broken, ageing-resistant, simulated effect is good, and it is easily worked molding, in
The LDPE of high fluidity can satisfy these requirements.Although and flame-proof elastomer used in the prior art can expire in toughness
Foot, but appearance is compared with dumb light, it is at high cost, it is not suitable for, the hardness of Flame Retardant HDPE or PP are higher, and pliability is inadequate.
2) phosphate ester flame retardants and the combination of boric acid melamine are used as fire retardant by the present invention, and phosphate ester flame retardants exist
Phosphorus compound first generates the non-ignitibility liquid film of phosphoric acid when burning, and and then phosphoric acid is further dehydrated production metaphosphoric acid, inclined phosphorus
Acid aggregates into ammonium metaphosphate in turn, and in this process, not only the liquid film of phosphoric acid production plays covering, but also ammonium metaphosphate
It is strong acid and strong dewaterer, polythene material can be made to be dehydrated and carbonize, this charing film has completely cut off air, has played fire-retardant work
With, boric acid melamine as the gas source in flame-retardant system, and the presence of boron, boron-containing glass platform protective layer can be formed, is risen
To it is heat-insulated and isolation air effect, so that polythene material is reached flame retardant effect, in addition, liquid based flame retardant viscosity itself compared with
It is low, it also can be further improved the mobility of material.
3) present invention uses antioxidant 4,4 '-butylidenebis (6- tert-butyl -3- methylphenol) and double octadecyl seasons penta
Antioxidant made of tetrol bis-phosphite compounding, distearyl pentaerythritol diphosphite have preferable process
Heat-resisting protective and the protection of the color inhibition in later period；The volatility of 4,4 '-butylidenebis (6- tert-butyl -3- methylphenol) is low, and heat is steady
Qualitative height, high temperature process are not decomposed.Compounding antioxidant system can make the preservation for protecting fire-retardant polyethylene material in processing and later period.
4) present invention selects diffusing oil, is that can make relative components is less to help because diffusing oil has certain viscosity
Agent is uniformly adhered to and is distributed in polyethylene particles, and diffusing oil has inside and outside lubricity, reduces coefficient of friction, improves product
Demolding performace, to the dispersibility of pigment better than other low molecules oil, product can configure various chromatic colours.
5) present invention selects canned phosphate ester flame retardants, air pump oil filling pipe, pans, metering device, output channel, mist
Change the liquid appending apparatus of air gun composition, liquid is held at 100 DEG C or more in overall process, and viscosity reduces, be conducive to convey,
PLC system control, weighing balance accurate measurement, it is ensured that liquid flame retardant adds as desired, in 4~5 sections of feeding screw rods of screw rod
Machine, existing enough length are sufficiently kneaded with other materials, and are unlikely to that time length is added and causes phosphate ester flame retardants point
Solution, this device is easy to use, and metering is accurate, is suitable for quantization production.
Detailed description of the invention
Fig. 1 is the schematic diagram of halogen-free fire-retardant polyethylene material preparation method of the present invention.
Specific embodiment
The contents of the present invention are described in further detail below by way of specific embodiment.Original used in embodiment
Material unless otherwise specified, can be obtained from routine business approach.
The raw material composition (mass parts) of the fire-retardant polyethylene material of Examples 1 to 3 and comparative example 1~5 is as shown in table 1 below.
In table 1, LDPE G812, place of production Singapore polyolefin, MI 25g/10min；LDPE 868-000, place of production China Maoming Petrochemical,
MI is 50g/10min.Antioxidant used is 4,4 '-butylidenebis (6- tert-butyl -3- methylphenol) and double octadecyl seasons
The antioxidant that penta tetrol bis-phosphite is compounded with mass ratio 1:4.Diffusing oil is octamethylcy-clotetrasiloxane.
The material quality part of the flame-proof polyethylene of 1 Examples 1 to 3 of table and comparative example 1~5 forms
Attached drawing 1 is the schematic diagram of halogen-free fire-retardant polyethylene material preparation method of the present invention.Referring to Fig.1, illustrate embodiment 1~
3 and comparative example 3~4 fire-retardant polyethylene material preparation method the following steps are included:
1) LDPE is covered into bung, unlatching is stirred according in mass parts ratio investment high-speed mixer (500r/min) of table 1
Mix, from above bung in oil filler additional proportion diffusing oil, stir 1min, set temperature be 50 DEG C；
2) nitrogenated flame retardant, antioxidant, lubricant are added step 1) and obtained in mixture according still further to ratio, stirred
2min, material after mixing are added in double screw extruder from main feeding；
3) non-halogen phosphoric acid ester based flame retardant is passed through into liquid flame retardant adding set from the oiling between 4~5 sections of screw rod
Mouth is added in double screw extruder.
4) the above material is in parallel dual-screw extruding machine, carries out mixing extrusion, it is cooling after tie rod, pelletizing, screening, obtain
The uniform halogen-free fire-retardant polyethylene material of grain.
Liquid flame retardant adding set described in step 3) includes non-halogen phosphoric acid ester based flame retardant head tank, air pump oiling
Pipe, pans, metering device, output channel, atomization air gun composition.
Non-halogen phosphoric acid ester based flame retardant head tank described in step 3), outer tank have heating bag, and temperature is set as 120 DEG C, makes
Its viscosity reduces, convenient for conveying.
Pans described in step 3) have the function of infrared acquisition, are equipped with graticule in tank, are more than graticule, suspend oil transportation, tank
Interior to have temperature-controlling system, temperature is set as 120 DEG C.
Metering device described in step 3) is made of measuring tank, weighing balance, control valve and PLC control system, is controlled in PLC
Liquid flame retardant additive amount, weighing balance accurate measurement are set in system processed, control valve carries out residual quantity adjustment.
The screw diameter of parallel dual-screw extruding machine described in step 4) is 75mm, screw slenderness ratio 44:1, each area's temperature
Degree are as follows: 100~115 DEG C of first segment, second segment is to the 4th section 160~170 DEG C, the 5th 11 sections 165~160 DEG C of Duan Zhi, machine
First 160 DEG C.
Different material additive amounts is according to corresponding embodiment or comparative example unlike Examples 1 to 3 and comparative example 3~4
Mass parts be added.
The preparation method of the fire-retardant polyethylene material of comparative example 1 the following steps are included:
1) LDPE is covered bung, stirring is opened, from bung according in the mass parts ratio investment high-speed mixer of table 1
Above in oil filler additional proportion diffusing oil, stir 1min, set temperature be 50 DEG C；
2) bromide fire retardant, antioxidant, lubricant are added in 1) according still further to ratio, stir 2min, after mixing object
Material is added in double screw extruder from main feeding；
3) the above material is in parallel dual-screw extruding machine, carries out mixing extrusion, it is cooling after tie rod, pelletizing, screening, obtain
The uniform halogen-free fire-retardant polyethylene material of grain.
The screw diameter of the parallel dual-screw extruding machine of step 3) is 75mm, screw slenderness ratio 44:1, each area's temperature are as follows:
100~115 DEG C of first segment, second segment is to the 4th section 160~170 DEG C, the 5th 11 sections 165~160 DEG C of Duan Zhi, head 160
℃。
The preparation method of the fire-retardant polyethylene material of comparative example 2 the following steps are included:
1) LDPE is covered bung, stirring is opened, from bung according in the mass parts ratio investment high-speed mixer of table 1
Above in oil filler additional proportion diffusing oil, stir 1min, set temperature be 50 DEG C；
2) ammonium polyphosphate compound flame retardant, antioxidant, lubricant are added in 1) according still further to ratio, stir 2min, mixing
Material is added in double screw extruder from main feeding after uniformly；
3) the above material is in parallel dual-screw extruding machine, carries out mixing extrusion, it is cooling after tie rod, pelletizing, screening, obtain
The uniform halogen-free fire-retardant polyethylene material of grain.
The screw diameter of the parallel dual-screw extruding machine of step 3) is 75mm, screw slenderness ratio 44:1, each area's temperature are as follows:
100~115 DEG C of first segment, second segment is to the 4th section 180~190 DEG C, the 5th 11 sections 195~190 DEG C of Duan Zhi, head 190
℃。
The preparation method of the fire-retardant polyethylene material of comparative example 5 the following steps are included:
1) LDPE and non-halogen phosphoric acid ester based flame retardant are proportionally put into high-speed mixer, covers bung, unlatching is stirred
Mix, from above bung in oil filler additional proportion diffusing oil, stir 1min, set temperature be 50 DEG C；
2) antioxidant, lubricant are added in 1) according still further to ratio, stir 2min, material adds from main feeding after mixing
Enter into double screw extruder；
3) the above material is in parallel dual-screw extruding machine, carries out mixing extrusion, it is cooling after tie rod, pelletizing, screening, obtain
The uniform halogen-free fire-retardant polyethylene material of grain.
The screw diameter of the parallel dual-screw extruding machine of step 3) is 75mm, screw slenderness ratio 44:1, each area's temperature are as follows:
100~115 DEG C of first segment, second segment is to the 4th section 160~170 DEG C, the 5th section 165~160 DEG C, 160 DEG C of head.
The fire-retardant polyethylene material test result of Examples 1 to 3 and comparative example 1~5 is as shown in table 2.
The test result of the flame-proof polyethylene of 2 Examples 1 to 3 of table and comparative example 1~5
Indication test method in table 2 is as follows:
Melt index (MI): it is carried out according to ASTM D-1238 standard；
Density: it is carried out according to ASTM D-792 standard；
Elongation at break: it is carried out according to ASTM D-638 standard；
Cantilever beam impact strength: it is carried out according to ASTM D-256 standard；
Anti-flammability: vertical combustion performance is tested by UL94 vertical combustion standard, batten with a thickness of 1.6mm and
3.2mm；
Color difference meter: Central Asia NH310, light source D65.
As shown in Table 2: phosphate ester flame retardants and nitrogenated flame retardant tool in halogen-free fire-retardant polyethylene material of the invention
There is synergistic effect, additive amount is few, and it is little to Effect on Mechanical Properties, and mobility can also be improved.The poly- second of halogen-free flameproof of the present invention
The good fluidity of alkene, excellent in mechanical performance, flame retardant property meet UL94V-2, and it is not high to can be applied to flame-retardancy requirements, environmental requirement
Higher simulated decorative conduct industry such as emulates greening lawn, simulated Christmas tree, emulation branch and plug inner membrance industry.It is made
At product flexibility it is good, feel touch do not prick the hand, resilience is good, repeat recycle, it is environment-protecting and non-poisonous.
The present invention uses distinctive liquid flame retardant adding set, and it is convenient that liquid flame retardant is added, and is easy to measure and be arranged
Quantization production may be implemented in adjustment, mature technology, and work efficiency is high, at low cost.If from comparative example 5 as can be seen that phosphorus
Esters of gallic acid liquid flame retardant does not feed double screw extruder from special liquid flame retardant adding set, and directly adds from main feeding
Enter, fire retardant can be caused to generate degradation, flame retarding efficiency degradation, degraded toughness.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of halogen-free fire-retardant polyethylene material, it is characterised in that: the raw material including following mass parts:
LDPE:80~95 part；
Non-halogen phosphoric acid ester based flame retardant: 5~15 parts；
Nitrogenated flame retardant: 1~5 part；
Antioxidant: 0.2~0.8 part；
Diffusing oil: 0.1~0.5 part；
Lubricant: 0.3~0.7 part.
2. a kind of halogen-free fire-retardant polyethylene material according to claim 1, it is characterised in that: the bending modulus of the LDPE
For 90MPa~120MPa, elongation at break > 150%, the melt index at 190 DEG C of test condition, 2.16kg is 20g/
10min~50g/10min.
3. a kind of halogen-free fire-retardant polyethylene material according to claim 1, it is characterised in that: the non-halogen phosphoric acid ester class resistance
It fires agent and is selected from bisphenol-A-bis- (diphenyl phosphoesters), phosphate toluene diphenyl ester, resorcinol bis- (diphenyl phosphoesters), tricresyl phosphate
At least one of toluene ester, tricresyl phosphate (dimethylbenzene) ester, poly aryl phosphate ester.
4. a kind of halogen-free fire-retardant polyethylene material according to claim 1, it is characterised in that: the nitrogenated flame retardant is selected from
Melamine, melamine cyanurate, two melamine of pyrophosphoric acid, boric acid melamine, orthophosphoric acid melamine, polyphosphoric acid three
At least one of poly cyanamid.
5. a kind of halogen-free fire-retardant polyethylene material according to claim 1, it is characterised in that: the antioxidant is 4,4 '-
Butylidenebis (6- tert-butyl -3- methylphenol) and distearyl pentaerythritol diphosphite are with mass ratio 1:(2~6) it is multiple
The antioxidant matched.
6. a kind of halogen-free fire-retardant polyethylene material according to claim 1, it is characterised in that: the diffusing oil is prestox
Cyclotetrasiloxane.
7. a kind of halogen-free fire-retardant polyethylene material according to claim 1, it is characterised in that: the lubricant is selected from tristearin
At least one of acid, stearate, stearate, ethylene bis stearamide, polyethylene wax.
8. a kind of preparation method of the halogen-free fire-retardant polyethylene material as described in any one of claim 1~7, it is characterised in that: packet
Include following steps:
1) by LDPE and diffusing oil in stirrer for mixing；
2) nitrogenated flame retardant, antioxidant, lubricant are added in blender again, mixing obtains mixture；
3) it adds mixture into the main spout of double screw extruder, non-halogen phosphoric acid ester based flame retardant is passed through into liquid flame retardant
Adding set is added to the 4th~5 section of double-screw extruder screw；
4) it is kneaded, is squeezed out by double screw extruder, be granulated, obtain halogen-free fire-retardant polyethylene material.
9. a kind of preparation method of halogen-free fire-retardant polyethylene material according to claim 8, it is characterised in that: in step 3),
Liquid flame retardant adding set includes sequentially connected non-halogen phosphoric acid ester based flame retardant head tank, air pump oil filling pipe, pans, meter
Measure device, output channel and atomization air gun.
10. a kind of any one of claim 1~7 halogen-free fire-retardant polyethylene material is preparing simulated decorative product and/or plug
Application in inner membrance.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110724326A (en) * | 2019-09-12 | 2020-01-24 | 广东聚石化学股份有限公司 | Halogen-free flame-retardant high-density polyethylene material and preparation method and application thereof |
| CN110734596A (en) * | 2019-09-12 | 2020-01-31 | 广东聚石化学股份有限公司 | halogen-free flame-retardant low-density polyethylene material, and preparation method and application thereof |
| CN116693964A (en) * | 2023-06-12 | 2023-09-05 | 惠州森叶工艺品有限公司 | Precipitation type polyethylene material, preparation method and simulation pine branch |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265752A (en) * | 2013-06-04 | 2013-08-28 | 广东聚石化学股份有限公司 | Halogen-free flame retardant thermoplastic polyolefin cable material |
| CN104592635A (en) * | 2015-01-30 | 2015-05-06 | 上海日之升新技术发展有限公司 | Special material for copper pollution resistant sockets and preparation method thereof |
| CN104610641A (en) * | 2015-01-30 | 2015-05-13 | 上海日之升新技术发展有限公司 | Metal-passivated high-strength PE material and preparation method thereof |
| CN106751867A (en) * | 2017-01-04 | 2017-05-31 | 中国工程物理研究院化工材料研究所 | The method that microcellular rubber foamed material is prepared based on overcritical injection molding technology |
-
2019
- 2019-04-11 CN CN201910290749.7A patent/CN110066443B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265752A (en) * | 2013-06-04 | 2013-08-28 | 广东聚石化学股份有限公司 | Halogen-free flame retardant thermoplastic polyolefin cable material |
| CN104592635A (en) * | 2015-01-30 | 2015-05-06 | 上海日之升新技术发展有限公司 | Special material for copper pollution resistant sockets and preparation method thereof |
| CN104610641A (en) * | 2015-01-30 | 2015-05-13 | 上海日之升新技术发展有限公司 | Metal-passivated high-strength PE material and preparation method thereof |
| CN106751867A (en) * | 2017-01-04 | 2017-05-31 | 中国工程物理研究院化工材料研究所 | The method that microcellular rubber foamed material is prepared based on overcritical injection molding technology |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110724326A (en) * | 2019-09-12 | 2020-01-24 | 广东聚石化学股份有限公司 | Halogen-free flame-retardant high-density polyethylene material and preparation method and application thereof |
| CN110734596A (en) * | 2019-09-12 | 2020-01-31 | 广东聚石化学股份有限公司 | halogen-free flame-retardant low-density polyethylene material, and preparation method and application thereof |
| CN116693964A (en) * | 2023-06-12 | 2023-09-05 | 惠州森叶工艺品有限公司 | Precipitation type polyethylene material, preparation method and simulation pine branch |
| CN116693964B (en) * | 2023-06-12 | 2023-12-26 | 惠州森叶工艺品有限公司 | Precipitation type polyethylene material, preparation method and simulation pine branch |
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