CN101759900B - Halogen-free flame-retardant and anti-static polyethylene material, pipe and preparing method thereof - Google Patents
Halogen-free flame-retardant and anti-static polyethylene material, pipe and preparing method thereof Download PDFInfo
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Abstract
A halogen-free flame-retardant and anti-static polyethylene material, a pipe and a preparing method thereof belong to the processing field of plastic pipes. The present invention aims to provide a halogen-free flame-retardant and anti-static polyethylene material and a pipe prepared from the material. The halogen-free flame-retardant and anti-static polyethylene material is prepared from 70 to 99 shares of polyethylene, 1 to 30 shares of expanded graphite (EG)/ polyethylene (PE) superfine composite powder, 1 to 30 shares of synergistic flame retardant and 1 to 5 shares of conductive black by the steps of melting and blending at a temperature of 160 DEG C to 200 DEG C, extruding, granulating and drying. The EG/ PE superfine composite powder is made by simultaneously grinding PE and EG with a millstone type mechanochemical reactor, and the granularity of the powder is 1000 meshes. The halogen-free flame-retardant and anti-static polyethylene pipe made from the halogen-free flame-retardant and anti-static polyethylene material prepared according to the present invention has the characteristics of halogen-free flame retardation, high flame-retardant efficiency and excellent comprehensive mechanical properties. Besides, the raw material cost of the halogen-free flame-retardant and anti-static polyethylene pipe can be largely reduced, and the pipe is simply processed and conveniently made.
Description
Technical field
The present invention relates to a kind of halogen-free flame-retardant and anti-static polyethylene material and use the halogen-free flame-retardant and anti-static polyethylene pipe of this material prepn and their preparation method, belong to the plastic conduit manufacture field.
Background technology
Polyethylene tube uses more and more widely in mine because of characteristics such as light weight, corrosion-resistant, ageing-resistant, easy installations, in mine, is mainly used in and presses wind, draining, ventilates, takes out slurry, firedamp drainage etc.Accumulative static is bigger to mine harm on the plastic pipe, is example with the pipe that draws out methane, in the extraction process; The mobile material mainly is the gas main body in the pipeline, but is mingled with the dust of some amount, and these have the air-flow of solid dust; When in plastic conduit, flowing with certain speed, frequent friction and collision will take place with tube wall in gas and solid dust, thus generation intensive static; With the spark discharge phenomenon; The energy of its discharge spark is enough to light gas, causes fire or gas explosion easily, causes mine accident; Do not reach industry requirement but general Vilaterm (PE) tubing is antistatic with flame retardant properties, therefore need special mine to use the flame-retardant and anti-static polyethylene pipe special.
Because fire-retardant can antistaticly be two independently processes, therefore preparing the polythene material that has flame retardant resistance and static resistance concurrently needs respectively to its modification.Both at home and abroad PE fire-retardant and antistatic modified carried out big quantity research.
Polyethylene anti-flaming mainly contains following several kinds of approach:
(1) halogenated flame retardant is Organohalogen compounds (is representative with ten bromines, hexabromo) and Sb
2O
3Composite use is carried out fire-retardant to PE.When combustion decomposition, can catch the radical that the PE DeR generates, delay or stops the incendiary chain reaction, discharge big, the difficult gas that fires of density.After adding a spot of red phosphorus and zinc borate, its oxygen index is greatly improved.This flame-retardant system flame retardant effect is better, but when burning the amount of being fuming big, produce corrosion and toxic gas, the feature of environmental protection is poor, is limited gradually to use at present.
When (2) fire retardant mechanism of phosphorus flame retardant was polymer combustion, red phosphorus formed the verivate of phosphoric acid, played the effect that absorbs heat, hindered the generation of incendivity product; The PO radical that generates is mended and is caught H and the OH radical in the flame, plays fire-retardant effect.Red phosphorus content 8% can make the fire-retardant rank of HDPE reach UL94 V0 level, and the characteristics of this flame-retardant system are that the amount of being fuming is little, low toxicity, consumption are few, and flame retardant effect still can.But poor with resin compatible, instability, easy firing, need coat.
(3) the nitrogen flame retardant is subject to heat release CO when presence of fire
2, N
2, NH
3, NO
2And H
2Non-flammable gases such as O, the concentration of the inflammable gas that produces when oxygen in the diluent air and superpolymer decomposes is taken away a part of heat simultaneously.Nitrogen ability Mulberry Extract suppresses the chain reaction of superpolymer, thereby has reached fire-retardant purpose.The nitrogen flame retardant has flame retardant properties preferably in urethane, polymeric amide.At present, using the fire-retardant PE poor effect of nitrogen flame retardant separately, mainly is because become due to the charcoal poor effect.This flame-retardant system addition is bigger, and processing characteristics is relatively poor, and material mechanical performance is relatively poor, and palpus and phosphorus flame retardant, carbon forming agent are joined use mutually, and cost is higher.
(4) organic expander type fire retardant, IFR (Intumescent Flame Ratardant) has high flame retardant, and the behavior of no molten drop drippage has fabulous resistivity to long-time or repeated exposure in flame; Halogen, non-oxidation antimony; Advantages such as low cigarette, nontoxic, non-corrosiveness gas generation.Expansion type flame retardant is made up of three parts, i.e. carbon source, acid source, foaming source.Acid source refers generally to mineral acid or can when the burning heating, original position generate sour salt, like materials such as phosphoric acid, sulfuric acid and SULPHOSUCCINIC ACID ESTERs.Carbon source refers generally to the polyol compound of many carbon, like tetramethylolmethane, terepthaloyl moietie etc.The foaming source refers to nitrogenous many carbon cpds, like urea, dicyandiamide, polymeric amide, trichlorine cyanogen ammonia etc.The shortcoming of expansibility flame-proof system is that addition is big, and processing characteristics is relatively poor, and cost is higher.
(5) inorganic combustion inhibitor is a kind of halogen-free flame retardants, have Heat stability is good, fire-retardant nontoxic, non-volatile, do not produce corrosive gases, the amount of being fuming little, do not produce secondary pollution etc., low cost and other advantages has critical role in poly fire-retardantization.Mainly contain white lake, Marinco H, zinc borate etc., its mechanism of action is to absorb the heat that thermolysis produces, and reduces system temperature, promotes charing and the generation that presses down cigarette, thus the performance fire retardation.But the inorganic combustion inhibitor addition is big, poor processability, products machinery poor performance.The development trend of inorganic combustion inhibitor is super-refinement, ultra-fine dispersion and synergistic effect, improves processing characteristics and goods mechanical property thereby reduce loading level with this.
PE antistatic modified mainly contains three kinds of technology:
(1) in PE, adds static inhibitor; (2) obtain antistatic property at PE tube-surface coating electrically conductive coating; (3) in PE, add electro-conductive material.Because performance reliability is poor, it is less to be difficult to durable applications for preceding two kinds of technology.Commonplace way is in resin, to add electro-conductive material.These electro-conductive materials have metallic substance (like metal-powder, steel fiber, metal fragment etc.), gold-plated inorganic fibre (like coated metal spun glass, coated metal mica etc.) and carbon class electro-conductive material (like carbon black, graphite, thomel etc.).Metallic substance is owing to, difficulties in dispersion poor with resin compatible, and the mechanical property of electro-conductive material is not good enough; The electrical efficiency of gold-plated inorganic fibre is low, and the conductivity persistence is poor; For carbon class electro-conductive material, the consistency of itself and resin relatively better, addition is low, electrical efficiency is higher, and material property is better, uses comparatively widely at present.
Now, use comparatively ripe and industrialized mine is that employing bromide fire retardant and graphitized carbon black carry out fire-retardant and antistatic modified [Chen Long, Wang Lianchao respectively with flame-retardant and anti-static (two anti-) polythene material; Ding Liangyu, Kou Guanxiang, Ding Yunsheng; Plastics are made [J], 2008,8:94].But still there are some problems:
1. adopting bromine is flame-retardant system (PBDE), and this system amount of being fuming when burning is big, produces macro-corrosion property gas and toxic gas, and the feature of environmental protection is poor.In recent years, along with the environmental protection cry increases day by day, this flame-retardant system is limited gradually and replaces, like the use that has been under an embargo in Europe;
2. this system modification cost is totally higher, and with 10,000 yuan of/ton calculating of HDPE price, the raw materials cost of this system is 1.25 ten thousand yuan/ton, apparently higher than conventional H DPE tubing;
3. the toughness of system is relatively poor.
Therefore, need exploitation high-performance, low-cost halogen-free flame-retardant and anti-static polyethylene material and pipeline.
Expansible black lead (EG) is a kind of novel halogen-free flame-retardant agent that occurs in recent years, and it is to utilize graphite can form the characteristic of intercalation compound, through chemical treatment, makes it form certain special intercalation compound by natural flake graphite.EG is inflatable hundreds of times of volume at high temperature, and expanded product has splendid oxidation-resistance and high thermal resistance, thereby can be used as expanding fire retardant and use.In addition, EG is a kind of carbon class electro-conductive material, in flame-retardant polymer, can increase the electroconductibility of material.Utilize the EG modified PE, have following advantage:
1. belong to inorganic combustion inhibitor (Halogen), highly effective flame-retardant (being superior to the chemically expansible flame-retardant system under many situation), nontoxic, nothing is dripped, is hanged down cigarette, do not have migration;
2. belong to the graphite-like filler, help the improvement of antistatic property;
3. cheap, price per ton is than the low 3000-5000 of PE unit;
4. initial expansion temperature is higher than the processing temperature of PE tubing greater than 200 ℃;
5. better heat-resisting property and lower thermal conductivity.
Yan Aihua etc. add the PE/APP system with EG as synergistic flame retardant, have studied its flame retardant properties [Yan Aihua, Zhou Zhiqiang, Wu Ze, chemical engineer [J], 2006,3:48], and when APP/EG content is 35%, the oxygen index of system can reach 29.Yang Yongfang etc. have studied the influence [Yang Yongfang, Liu Minjiang, Tian Libin, plastics [J], 2003,32:16] of EG to PE flame retardant properties and conductivity, and the result shows that when EG content was 30%, the oxygen index of system can reach 27, and surface resistivity is less than 10
5Ω cm.Because the EG raw materials for production are the Vermiculithina China ink, its granularity is all bigger.In above report, the minimum grain size of EG is 300um, and the mechanical property that adds material after the Vilaterm system is deterioration significantly.With the high density polyethylene(HDPE) is example, and behind the EG of adding 30%, the elongation at break of system is merely 12%, can not satisfy the requirement of pipe performance far away.The flame retardant properties of material is difficult to further effectively improve simultaneously.Therefore, need the development new technology to prepare high performance PE/EG flame-retardant and anti-static material.
Summary of the invention
The objective of the invention is to adopt bromide fire retardant and graphitized carbon black to carry out the deficiency of fire-retardant and antistatic modified polythene material respectively to having now; And the deficiency of expansible black lead (EG) modified poly ethylene, a kind of halogen-free flame-retardant and anti-static polyethylene material is provided and utilizes the halogen-free flame-retardant and anti-static polyethylene pipeline of this material prepn.
For realizing above-mentioned purpose, technical scheme of the present invention:
Halogen-free flame-retardant and anti-static polyethylene material is characterized in that it is to be prepared from subordinate's materials of weight proportions: 70～99 parts of Vilaterm, 1～30 part of EG/PE ultrathin composite powder, 1～30 part of synergistic flame retardant, 1～5 part of graphitized carbon black; Wherein said EG/PE ultrathin composite powder is that weight proportion is the composite granule of 50～1 parts of PE, 99～50 parts of EG, and its granularity is-1000 orders
Particularly, the preparation method of expansible black lead (EG)/Vilaterm (PE) ultrathin composite powder is: PE and EG are milled to-1000 purpose ultrathin composite powders in force chemical reactor, the weight proportion of PE and EG is:
50～1 parts of Vilaterm
99～50 parts of expansible black leads
Preferred scheme is 10～1 parts of PE, 99～90 parts of EG.
Said expansible black lead (EG) is that natural flake graphite is obtained through chemical oxidation or electrochemical process processing.Granularity is the 10-200 order, and initial expansion temperature is greater than 200 ℃, and ratio of expansion is greater than 100 times industrial goods.
The present invention preferably adopts the millstone type force chemical reactor like ZL 95111258.9, EG and PE is milled jointly preparation EG/PE ultrathin composite powder.This reactor drum can provide powerful extruding, shearing action, makes PE and EG receive the effect of multiple stress such as vertical, hoop, shearing and fragmentation is sheared, pulverizes, disperses, produced and pulverize and force-chemical reaction (power activated grafting).Through mill 10-30 all over after, the granularity of EG/PE ultrathin composite powder can be crossed 1000 mesh sieves.Not only can effectively reduce the granularity of EG, also can make the EG surface active, increase consistency with PE.
Further, described halogen-free flame-retardant and anti-static polyethylene material is to be prepared from subordinate's materials of weight proportions: 75～95 parts of Vilaterm, 5～25 parts of EG/PE ultrathin composite powders, 5～20 parts of synergistic flame retardants, 3～5 parts of graphitized carbon blacks.
Said Vilaterm (PE) is with～CH
2～be the unitary new LDPE (film grade) of repeating structure, medium-density polyethylene or high density polyethylene(HDPE).
Said graphitized carbon black is that form is that any one or multiple graphitized carbon black such as granular, fibrous, sheet cooperate.
Said synergistic flame retardant is to assist the EG fire retardant to improve the fire retardant of flame retardant effect, can adopt APP (comprising I type and II type), red phosphorus, Mg (OH)
2, Al (OH)
3, one or more the cooperation among the PER etc.
The present invention provides the preparation method of above-mentioned halogen-free flame-retardant and anti-static polyethylene material; It is characterized in that:, extrude, granulation, be drying to obtain in 160～200 ℃ of following melt blendings with 70～99 parts of Vilaterm, 1～30 part of EG/PE ultrathin composite powder, 1～30 part of synergistic flame retardant, 1～5 part of mixing of graphitized carbon black; Wherein said EG/PE ultrathin composite powder is that weight proportion is the composite granule of 99～50 parts of PE50～1 part, EG, and its granularity is-1000 orders.
Preferred scheme is 75～95 parts of Vilaterm, 5～25 parts of EG/PE ultrathin composite powders, 5～20 parts of synergistic flame retardants, 3～5 parts of graphitized carbon blacks.
More excellent scheme is that halogen-free flame-retardant and anti-static polyethylene material is prepared from subordinate's materials of weight proportions:
4 parts of 90 parts of Vilaterm, 10 parts, 10 parts red phosphorus of the ultra-fine composite powder of EG/PE, graphitized carbon black; Wherein said EG/PE ultrathin composite powder is that weight proportion is 50 parts of new LDPE (film grade)s of PE, with 50 parts of granularities be that 200 order expansible black lead compound mean particle sizes are 1500 purpose EG/PE ultrathin composite powders; Or
2 parts of 80 parts of Vilaterm, 20 parts, 5 parts APP of the ultra-fine composite powder of EG/PE, graphitized carbon black; Wherein said EG/PE ultrathin composite powder is that weight proportion is 20 parts of new LDPE (film grade)s, with 80 parts of granularities be that 100 order expansible black lead compound mean particle sizes are 1500 purpose EG/PE ultrathin composite powders.
The present invention also provides a kind of halogen-free flame-retardant and anti-static polyethylene pipe, and the preparation process is following: the halogen-free flame-retardant and anti-static polyethylene material by above-mentioned preparation obtains 160～200 ℃ of following extrusion mouldings in pipe extruder.
The halogen-free flame-retardant and anti-static polyethylene material and the pipeline of the present invention's preparation have following advantage:
Halogen-free flameproof belongs to the environment-friendly and green material;
Flame retarding efficiency is high, hour just can effective fire-retardant PE at fire retardant and synergistic flame retardant addition;
Comprehensive mechanical performance is good.Because EG handles through force chemical reactor and PE jointly in the present invention, not only reduced the granularity of EG, also increased itself and the consistency of PE, so the flame-retardant and anti-static material for preparing and the excellent property of pipeline;
Can reduce the usage quantity of expensive conductive carbon black, be the requirement that just can reach the antistatic property of MT 181-88 " underground mine use plastics tubing safety performance detects standard " at 3% o'clock at conductive carbon black content;
EG is cheap than halogen system or other organic fire-retardants, can reduce the raw materials cost of flame-retardant and anti-static tubing by a relatively large margin.
Through embodiment the present invention is specifically described below; It is important to point out that embodiment only is used for the present invention is further specified; Can not be interpreted as the restriction to protection domain of the present invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of foregoing invention.
Description of drawings
Fig. 1 is the influence (EG granularity 80 orders) of EG content to the PE80 mechanical property
Fig. 1-a X-coordinate is an EG content, and ordinate zou is a ys;
Fig. 1-b X-coordinate is an EG content, and ordinate zou is an elongation at break;
Fig. 1-c X-coordinate is an EG content, and ordinate zou is a notched Izod impact strength.
Fig. 2 EG content is to the influence of PE80 oxygen index, and X-coordinate is an EG content, and ordinate zou is an oxygen index.
Fig. 3 EG content is to the influence of PE80 conductivity, and X-coordinate is an EG content, and ordinate zou is the logarithm of surface resistivity.
Fig. 4 conductive carbon black content is to the influence of PE80/EG-T (90/10) surface resistivity, and X-coordinate is a conductive carbon black content, and ordinate zou is the logarithm of surface resistivity.
Embodiment
To surpass EG/PE ultrathin composite powder and Vilaterm, synergistic flame retardant and graphitized carbon black by a certain percentage after stirrer for mixing; Through screw extrusion press in 170～200 ℃ of melt blendings extrude, granulation, drying, make halogen-free flame-retardant and anti-static polyethylene material.The weight proportion of EG/PE ultrathin composite powder, Vilaterm, synergistic flame retardant, graphitized carbon black is:
70～99 parts of PE
1～30 part of EG/PE ultrathin composite powder
1～30 part of synergistic flame retardant
1～5 part of graphitized carbon black
Preferably: 75～95 parts of Vilaterm, 5～25 parts of EG/PE ultrathin composite powders, 5～20 parts of synergistic flame retardants, 3～5 parts of graphitized carbon blacks.
Said EG/PE ultrathin composite powder is that PE and EG are adopted the millstone type force chemical reactor like ZL 95111258.9, EG and PE is milled jointly preparation EG/PE ultrathin composite powder.This reactor drum can provide powerful extruding, shearing action, makes PE and EG receive the effect of multiple stress such as vertical, hoop, shearing and fragmentation is sheared, pulverizes, disperses, produced and pulverize and force-chemical reaction (power activated grafting).Through mill 10-30 all over after, the granularity of EG/PE ultrathin composite powder can be crossed 1000 mesh sieves.Not only can effectively reduce the granularity of EG, also can make the EG surface active, increase consistency with PE.Wherein, the weight proportion of PE and EG is:
50～1 parts of PE
99～50 parts of EG
Preferred scheme is 10～1 parts of PE, 99～90 parts of EG.
Said PE is with～CH
2～be the unitary new LDPE (film grade) of repeating structure, medium-density polyethylene or high density polyethylene(HDPE).
Said EG handles natural flake graphite through chemical oxidation or electrochemical process, granularity is the 10-200 order, and initial expansion temperature is greater than 200 ℃, and ratio of expansion is greater than 100 times industrial goods.
Said synergistic flame retardant is APP (comprising I type and II type), red phosphorus, Mg (OH)
2, Al (OH)
3, one or more cooperation wherein such as PER.
Said graphitized carbon black is that form is that any one or multiple graphitized carbon black such as granular, fibrous, sheet cooperate.
The preparation process of halogen-free flame-retardant and anti-static polyethylene pipe is following: above-mentioned preparation halogen-free flame-retardant and anti-static polyethylene material is extruded the halogen-free flame-retardant and anti-static polyethylene pipe under 160～200 ℃ in pipe extruder.The halogen-free flame-retardant and anti-static polyethylene pipe flame retarding efficiency for preparing is high, hour just can effective fire-retardant PE at fire retardant and synergistic flame retardant addition; Simultaneously, can reduce the usage quantity of expensive conductive carbon black, be the requirement that just can reach the antistatic property of MT 181-88 " underground mine use plastics tubing safety performance detects standard " at 3% o'clock at conductive carbon black content; Comprehensive mechanical performance is good.
Though the EG modification can improve the flame retardant properties and the antistatic property of material simultaneously, after EG added PE, the mechanical property of material is deterioration greatly, did not reach the performance requriements (like Fig. 1) that tubing uses.Its major cause is that the granularity of EG is bigger on the one hand, has produced the filler effect.The consistency that is EG and PE on the other hand is relatively poor.Below compared mechanical property and the flame retardant properties with modified PE before and after the force chemical reactor processing,, the proportioning raw materials of following table 1 please be provided like table 1 with EG:
(1) comparative sample (EG is untreated):
92 parts of PE, 8 parts of EG
(2) test sample is handled EG with force chemical reactor and is obtained EG/PE ultrathin composite powder, EG/PE=95/5.
92 parts of PE
8 parts of EG/PE ultrathin composite powders
Can see from table 1; With being untreated EG and handle the PE of EG modification with force chemical reactor; Its ys and oxygen index change little, but significantly increase with its elongation at break of PE and the notched Izod impact strength of force chemical reactor processing EG modification, can reach the requirement that tubing uses fully.
Table 1 EG handles front and back to the PE Effect on Performance
| EG granularity (μ m) | Ys (MPa) | Elongation at break (%) | Notched Izod impact strength (kJ/m 2) | Oxygen index (%) | ||
| PE80/EG(92/8) | EG is untreated | 400-500 | 20.1 | 35 | 14.8 | 20 |
| PE80/EG-T(92/8) | EG handles through force chemical reactor | 10-20 | 20.5 | 328 | 20.5 | 18 |
Annotate: the EG that EG handles through force chemical reactor is called for short EG-T
Because MT 181-88 " underground mine use plastics tubing safety performance detects standard " requires regulation, the oxygen index of the flame-retardant and anti-static material of use must be greater than 27, and surface resistivity must be less than 10
8Ω cm, and use the EG modified PE merely, flame retardant properties and antistatic property do not reach the safety standard request for utilization.As shown in Figures 2 and 3.Therefore need in system, add synergistic flame retardant and graphitized carbon black.
Fig. 4 is the influence of graphitized carbon black content to PE/EG (90/10) co-mixing system surface resistivity.Can see that the graphitized carbon black weight content is just can reach " underground mine use plastics tubing safety performance detects standard " at 3% o'clock to anlistatig requirement regulation, and adds the comparatively expensive graphitized carbon black of price merely, then addition must be greater than 6%.
Table 2 is synergistic flame retardant influences to PE80/EG-T (90/10) system flame retardant properties and mechanical property.Can know that by table 2 behind the adding synergistic flame retardant, the mechanical property of system and flame retardant properties can reach mechanical properties of tubular goods and " underground mine use plastics tubing safety performance the detects standard " requirement to flame retardant properties fully.
Table 2 synergistic flame retardant is to PE80/EG (90/10) Effect on Performance
| Ys (MPa) | Elongation at break (%) | Oxygen index (%) | Testing vertical flammability | |
| PE/EG-T(90/10) | 20.1 | 300 | 20 | F |
| PE/EG-T/APP(90/10/8) | 19.8 | 233 | 27 | V1 |
| PE/EG-T/ red phosphorus (90/10/8) | 20.0 | 210 | 29 | V1 |
| PE/EG-T/ red phosphorus/PER (90/10/8/8) | 18 | 180 | 30 | V0 |
Through embodiment the present invention is specifically described below; It is important to point out that embodiment only is used for the present invention is further specified; Can not be interpreted as the restriction to protection domain of the present invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of foregoing invention.
The preparation of embodiment 1 the present invention unit halogen fire retardant, antistatic polyethylene pipe
With 1 part of high density polyethylene(HDPE) in 80 ℃ of baking ovens of temperature after dry 4 hours; With 99 parts of granularities be 10 order expansible black leads; Mix in the adding impeller, in force chemical reactor, mill 10 times, obtaining mean particle size is 1000 purpose EG/PE ultrathin composite powders.
80 parts of PE100 level high-density polyethylenes in 80 ℃ of baking ovens of temperature after dry 2 hours, are added in the impellers with 20 parts of ultrathin composite powders, 1 part of APP, 3 parts of graphitized carbon blacks and to mix, in 190 ℃ of following melt blendings of temperature extrude, granulation, drying; Obtain halogen-free flame-retardant and anti-static polyethylene material, the tensile strength of material is 22MPa, and notched Izod impact strength is 20kJ/m2; Elongation at break is 350%; Oxygen index is 30, and UL-94 reaches the V0 level, and surface resistivity is 5 * 10
6Ω cm.
Above-mentioned preparation gained halogen-free flame-retardant and anti-static polyethylene material is extruded dn40, the antistatic flame-retardant polyethylene tubing of SDR11 in pipe extruder under 190 ℃.Pipe performance satisfies the requirement of MT558.1-2005 to MPE100.
The preparation of embodiment 2 halogen-free flame-retardant and anti-static polyethylene pipes of the present invention
With 50 parts of new LDPE (film grade)s in 80 ℃ of baking ovens of temperature after dry 4 hours; With 50 parts of granularities be 200 order expansible black leads; Mix in the adding impeller, in force chemical reactor, mill 30 times, obtaining mean particle size is 3000 purpose EG/PE ultrathin composite powders.
90 portions of PE80 level medium-density polyethylenes in 80 ℃ of baking ovens of temperature after dry 2 hours, are added in the impellers with 10 parts of ultrathin composite powders, 10 parts of red phosphorus, 10 parts of PER, 4 parts of graphitized carbon blacks and to mix, in 180 ℃ of following melt blendings of temperature extrude, granulation, drying; Obtain halogen-free flame-retardant and anti-static polyethylene material, the tensile strength of material is 18MPa, and notched Izod impact strength is 18kJ/m2; Elongation at break is 400%; Oxygen index is 32, and UL-94 reaches the V0 level, and surface resistivity is 3.5 * 10
5Ω cm.
Above-mentioned preparation gained halogen-free flame-retardant and anti-static polyethylene material is extruded dn1200, the antistatic flame-retardant polyethylene tubing of SDR17 in pipe extruder under 190 ℃.Pipe performance satisfies the requirement of MT558.1-2005 to MPE80.
The preparation of embodiment 3 halogen-free flame-retardant and anti-static polyethylene pipes of the present invention
With 20 parts of high density polyethylene(HDPE)s in 80 ℃ of baking ovens of temperature after dry 4 hours; With 80 parts of granularities be 80 order expansible black leads; Mix in the adding impeller, in force chemical reactor, mill 20 times, obtaining mean particle size is 1500 purpose EG/PE ultrathin composite powders.
70 parts of PE100 level high-density polyethylenes in 80 ℃ of baking ovens of temperature after dry 2 hours, are added in the impeller with 30 parts of ultrathin composite powders, 1 part of APP, 1 part of graphitized carbon black and to mix, in 200 ℃ of following melt blendings of temperature extrude, granulation, drying; Obtain halogen-free flame-retardant and anti-static polyethylene material, the tensile strength of material is 20MPa, and notched Izod impact strength is 20kJ/m2; Elongation at break is 340%; Oxygen index is 29, and UL-94 reaches the V1 level, and surface resistivity is 7 * 10
5Ω cm.
Above-mentioned preparation gained halogen-free flame-retardant and anti-static polyethylene material is extruded dn800, the antistatic flame-retardant polyethylene tubing of SDR17 in pipe extruder under 200 ℃.Pipe performance satisfies the requirement of MT558.1-2005 to MPE100.
The preparation of embodiment 4 halogen-free flame-retardant and anti-static polyethylene pipes of the present invention
With 20 parts of new LDPE (film grade)s in 80 ℃ of baking ovens of temperature after dry 4 hours; With 80 parts of granularities be 100 order expansible black leads; Mix in the adding impeller, in force chemical reactor, mill 20 times, obtaining mean particle size is 1500 purpose EG/PE ultrathin composite powders.
80 portions of PE80 level medium-density polyethylenes in 80 ℃ of baking ovens of temperature after dry 4 hours, are added in the impellers with 20 parts of ultrathin composite powders, 5 parts of APP, 2 parts of graphitized carbon blacks and to mix, in 180 ℃ of following melt blendings of temperature extrude, granulation, drying; Obtain halogen-free flame-retardant and anti-static polyethylene material, the tensile strength of material is 17MPa, and notched Izod impact strength is 23kJ/m2; Elongation at break is 450%; Oxygen index is 28, and UL-94 reaches the V1 level, and surface resistivity is 8 * 10
5Ω cm.
Above-mentioned preparation gained halogen-free flame-retardant and anti-static polyethylene material is extruded dn125, the antistatic flame-retardant polyethylene tubing of SDR13.6 in pipe extruder under 180 ℃.Pipe performance satisfies the requirement of MT558.1-2005 to MPE80.
Claims (9)
1. halogen-free flame-retardant and anti-static polyethylene material is characterized in that it is to be prepared from the following weight proportion raw material: 70～99 parts of Vilaterm, 1～30 part of EG/PE ultrathin composite powder, 1～30 part of synergistic flame retardant, 1～5 part of graphitized carbon black; Wherein said EG/PE ultrathin composite powder is that weight proportion is that 50～1 parts of PE, EG adopt the millstone type force chemical reactor to be milled to the composite granule that obtains below 1000 orders jointly for 99～50 parts; Said EG is an expansible black lead.
2. halogen-free flame-retardant and anti-static polyethylene material according to claim 1 is characterized in that: the weight proportion of PE and EG is 10～1 parts of PE, 90～99 parts of EG in the said EG/PE ultrathin composite powder.
3. halogen-free flame-retardant and anti-static polyethylene material according to claim 1 and 2 is characterized in that: described halogen-free flame-retardant and anti-static polyethylene material is to be prepared from the following weight proportion raw material: 75～95 parts of Vilaterm, 5～25 parts of EG/PE ultrathin composite powders, 5～20 parts of synergistic flame retardants, 3～5 parts of graphitized carbon blacks.
4. halogen-free flame-retardant and anti-static polyethylene material according to claim 1 and 2 is characterized in that: said Vilaterm is with～CH
2～be the unitary new LDPE (film grade) of repeating structure, medium-density polyethylene or high density polyethylene(HDPE); Described synergistic flame retardant is APP I type, APP II type, red phosphorus, Mg (OH)
2, Al (OH)
3, at least a among the PER.
5. halogen-free flame-retardant and anti-static polyethylene material according to claim 3 is characterized in that: said Vilaterm is with～CH
2～be the unitary new LDPE (film grade) of repeating structure, medium-density polyethylene or high density polyethylene(HDPE); Described synergistic flame retardant is APP I type, APP II type, red phosphorus, Mg (OH)
2, Al (OH)
3, at least a among the PER.
6. halogen-free flame-retardant and anti-static polyethylene material according to claim 1 and 2 is characterized in that: said EG granularity is 10～200 orders, and initial expansion temperature is greater than 200 ℃, and ratio of expansion is greater than 100 times.
7. halogen-free flame-retardant and anti-static polyethylene material according to claim 6 is characterized in that: halogen-free flame-retardant and anti-static polyethylene material is prepared from the following weight proportion raw material:
4 parts of 90 parts of Vilaterm, 10 parts, 10 parts red phosphorus of the ultra-fine composite powder of EG/PE, graphitized carbon black; Wherein said EG/PE ultrathin composite powder is that weight proportion is 50 parts of new LDPE (film grade)s of PE, with 50 parts of granularities be that 200 order expansible black lead compound mean particle sizes are 1500 purpose EG/PE ultrathin composite powders; Or
2 parts of 80 parts of Vilaterm, 20 parts, 5 parts APP of the ultra-fine composite powder of EG/PE, graphitized carbon black; Wherein said EG/PE ultrathin composite powder is that weight proportion is 20 parts of new LDPE (film grade)s, with 80 parts of granularities be that 100 order expansible black lead compound mean particle sizes are 1500 purpose EG/PE ultrathin composite powders.
8. the method for preparing halogen-free flame-retardant and anti-static polyethylene material; It is characterized in that:, extrude, granulation, be drying to obtain in 160～200 ℃ of following melt blendings with 70～99 parts of Vilaterm, 1～30 part of EG/PE ultrathin composite powder, 1～30 part of synergistic flame retardant, 1～5 part of mixing of graphitized carbon black; Wherein said EG/PE ultrathin composite powder is that weight proportion is 50～1 parts of PE, 99～50 parts of EG, adopts the millstone type force chemical reactor to be milled to the composite granule that obtains below 1000 orders jointly.
9. halogen-free flame-retardant and anti-static polyethylene pipe, it is characterized in that: it is to be obtained 160～200 ℃ of following extrusion mouldings by the halogen-free flame-retardant and anti-static polyethylene material that each described halogen-free flame-retardant and anti-static polyethylene material of claim 1-7 or the said preparation method of claim 8 prepare.
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| CN102888047B (en) * | 2012-09-25 | 2014-09-03 | 长沙前元塑料技术开发有限公司 | Composition for preparing highly-conductive flame retardant plastic, highly-conductive flame retardant plastic prepared thereby and preparation method thereof |
| CN103073775B (en) * | 2013-02-03 | 2015-07-08 | 义乌市满旺机械设备有限公司 | Preparation method for environment-friendly anti-flaming anti-static polyethylene pipeline |
| CN103059388A (en) * | 2013-02-03 | 2013-04-24 | 王达 | Halogen-free flame retardant polythene (PE) pipe |
| CN103059390B (en) * | 2013-02-03 | 2015-10-28 | 福建省感创精密机械有限公司 | A kind of preparation method of halogen-free flameproof PE pipe |
| CN103804757A (en) * | 2014-01-20 | 2014-05-21 | 苏州新区华士达工程塑胶有限公司 | Flame-retardant ultraviolet-proof polyethylene plastic |
| CN104262751B (en) * | 2014-10-13 | 2016-08-24 | 扬州大学 | The flexible Polyethylene Pipe Resin of permanence antistatic |
| CN108752695A (en) * | 2018-06-05 | 2018-11-06 | 芜湖市艾德森自动化设备有限公司 | A kind of preparation method of flame-retardant and anti-static polyethylene resin |
| CN111925582A (en) * | 2020-08-18 | 2020-11-13 | 宿迁市洁宝宝新型材料有限公司 | Halogen-free flame-retardant antistatic polyethylene pipe and preparation method thereof |
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