CN1058033C - Anti-electrostatic fire retardant low-density polyethylene hose - Google Patents
Anti-electrostatic fire retardant low-density polyethylene hose Download PDFInfo
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- CN1058033C CN1058033C CN94116662A CN94116662A CN1058033C CN 1058033 C CN1058033 C CN 1058033C CN 94116662 A CN94116662 A CN 94116662A CN 94116662 A CN94116662 A CN 94116662A CN 1058033 C CN1058033 C CN 1058033C
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Abstract
The present invention relates to an antistatic fire retardant low-density polyethylene hose which is formed by the method that low-density polyethylene, combustion-supporting modifying agents CPE, DBDPO and Sb2O3, zinc borate containing water, organic antistatic agents, antistatic auxiliary agents and coupling agents are proportionally mixed, coupled, coated, prilled, squeezed in a tubular mode, formed, cooled, dragged successively, and then the mixtures are coiled. The hose has favorable antistatic performance, fire retardant performance, pressure resistant performance and shock resistant performance, the surface resistivity reaches a magnitude order of 10<5> omega. The hose is free from external factors, such as temperature, water washing, wiping, etc., and can be widely used for water supply pipes, water drainage pipes, spraying pipes and air pipes of underground coal mines.
Description
The present invention relates to a kind of chemical composition, the macromolecular material of the modification of a kind of industrial application specifically, what used a kind of more precisely down-hole has antistatic and new LDPE (film grade) (LDPE) flexible pipe flame-retarding characteristic.
For a long time, the [underground persons attempt partly or entirely to replace the steel pipe of use at present with plastic pipe.The plastic pipe quality is light, corrosion-resistant, the life-span is long, cost is low, but relatively with steel, except shortcomings such as withstand voltage low, shock resistance difference, its maximum weakness is inflammable and very easily produces static and be difficult to and leak, thus desire the down-hole use must fire-retardant and antistatic aspect carry out modification.
The flame-retardant modified fire retardant that normally adds in resin can select one or more mixing in the fire retardants such as phosphorus system, halogen system, antimony system to use.
Antistatic modified method has two kinds, and a kind of is powder such as carbon black, graphite or the metal-powder etc. of evenly sneaking into electro-conductive material in resin.The down-hole with give, its surface resistivity of water shoot must reduce to 10
7The Ω order of magnitude, airduct and whitewashing must reduce to 10 with pipe
8The Ω order of magnitude, for the surface resistivity that reduces LDPE significantly must add a large amount of conducting material powder, to add 25～30% such as carbon black, so a large amount of inorganicss is sneaked among the LDPE and must be reduced its physical strength, thereby make withstand voltage and the resistance to impact shock poor performance, this method is unsuitable for processing the down-hole plastic pipe.Second method is to add organic antistatic agents, because the wetting ability of static inhibitor forms " moisture film " to leak static at frosting, organic antistatic agents is very little to the physical strength influence, but its surface resistivity can only reduce to 10
8The Ω order of magnitude, this method modified resins only are fit to the above water pipe of processing 12 inch and are used for the down-hole, are not suitable for processing caliber and are used for the down-hole less than 12 inch and airduct, shotcrete pipe etc.
CN1085920A 93109001.6 disclosed a kind of linear low density polyethylene fire retardant sleeves and method for making be in new LDPE (film grade), add clorafin, Sb2O3, Sb2O5, coupling agent, Ca (HCO3) 2, AL (OH) 3 through compound, kneading, granulation, plastify, extrude to coil and form, be used for building, the transfer lime of telecommunication, decoration conductor insulation sleeve pipe and inflammable gas, liquid etc.Chinese patent 90106274.X discloses polyethylene hose and manufacture method is to be base-material with the polyethylene, adding bromide fire retardant carries out flame-retardant modified, it is antistatic modified to adopt graphitized carbon black or static inhibitor to carry out, blending and modifying and activation treatment under stablizer, linking agent, action of coupling agents.This invention has fire-retardant, antistatic, good toughness, quality softness, physical strength advantages of higher than general polyvinyl piping materials.
Carry out antistatic, fire-retardant and withstand voltage simultaneously to LDPE and three of shock resistances aspect during modification, have complement each other, the one side of synergistic positive-effect, also exist phase out-phase simultaneously from, the one side of the negative effect of anti-effect mutually, select materials and fill a prescription when proper, positive-effect is greater than negative effect, make the performance of three aspects obtain abundant modification, select materials and fill a prescription not at that time, negative effect is greater than positive-effect, although a certain performance is able to abundant modification, other performances are then very poor, cause overall performance to fail to improve.
The object of the present invention is to provide a kind of polyvinyl piping materials, especially antistatic property antistatic, fire-retardant and that the physical strength synergistic effect is good not to be subjected to the influence of ambient conditions and long-term existence, to guarantee downhole safety production.
The present invention is achieved in that
The method that antistatic modified employing organic antistatic agents and inorganic salt (antistatic auxiliary agent) combine, the mechanism of its modification is to form the very thin electrolyte solution liquid of one deck at frosting to approach, belong to second class conductor positive and negative ion conduction, this impurity that just is different from surface formation " moisture film " when only using organic antistatic agents holds the liquid conduction, the electronic conduction that also is different from the tunnel effect of graphitized carbon black, this law can greatly reduce the surface resistivity of plastics.
The flame-retardant modified chlorinatedpolyethylene (CPE) that selects is a main flame retardant, and auxilliary bromine system (decabromodiphynly oxide, DBDPO), antimony system (antimonous oxide Sb2O3), (contain hydrate zinc borate, 2ZnO3B2O33.5H2O) fire retardant forms composite flame-retardant agent in boron system.This composite fire retardant is effective, can discharge hydrogenchloride (HCL) when being heated because of CPE, and HCL produces series reaction with antimonous oxide, finally generates water (H2O) and volatile butter of antimony (SbCL3) absorbing and cooling temperature; Contain hydrate zinc borate when contacting burning things which may cause a fire disaster with the coexistence of brominated (or chlorine) fire retardant; can generate boron bromide (BBr3); zinc bromide (ZnBr2) or boron chloride (BCL3); zinc chloride (ZnCL2) also discharges crystal water; when running into HBr or HCL, zinc borate also can give birth to halogenation boron or zinc halide; halogenation boron under the high temperature or zinc halide can form the protective layer of glass densification in the burning telogenesis; not only heat insulation but also secluding air; play fire retardation; simultaneously halogenation boron is the same with the same butter of antimony of zinc halide (SbCL3) catches extremely strong OH and the H free radical of reactive behavior in the gas phase, disturbs and the chain reaction of interruption incendiary.
CPE is not only good fire retardant, itself when chlorinity be exactly an elastomerics 30～40% the time, also be a kind of good plastic toughening properties-correcting agent, thus after adding CPE, good flame retardation effect not only, and the withstand voltage and shock resistance of tubing also is improved.
More than various properties-correcting agent with base-material new LDPE (film grade) (LDPE) and coupling agent in following ratio (weight ratio, down with) batching
New LDPE (film grade) 100
Chlorinatedpolyethylene 30～35
Decabromodiphynly oxide 7～10
Antimonous oxide 6～12
Contain hydrate zinc borate 12～24
Organic antistatic agents 5～8
Antistatic auxiliary agent 15～20
Coupling agent 1～3
Described organic antistatic agents can be HKD-520, HKD-508, HKD-500 etc., is used alone or two or more composite use, and ratio is any, 5～8 parts of control total amounts.
Described antistatic auxiliary agent can be the inorganic salt of sodium or solubilities such as potassium or calcium or magnesium, is used alone or two or more composite use, and ratio is any, 15～20 parts of control total amounts.
Described coupling agent can be titanate ester such as TC-F, NZD-311 etc. or silane series class such as KH-550, KH-560 etc., is used alone or two or more composite use, and ratio is any, 1～3 part of control total amount.
Above various materials are just obtained white, softish anti-electrostatic fire retardant LDPE flexible pipe after by following processes.
At first in high mixer, mix, dry, coupling and surface coat and handle granulation then, last moulding.Concrete operations are as follows:
1, earlier DBDPO, the Sb2O3 that measures being contained hydrate zinc borate, antistatic auxiliary agent, to drop into high-speed mixer and mixing even, and dry in this process.
2, will spray into by the coupling agent of acetone diluted in the material that is stirring in the high mixer, and above several materials be carried out surperficial coupling handle.
3, throwing the CPE and the organic antistatic agents that measure again makes above various material thorough mixing in high mixer even.
4, drop into the LDPE pellet at last, thorough mixing in high mixer makes various modified additives be coated on the surface of pellet gradually, till the intact all auxiliary agents of even coating.
5, the material that comes out in high mixer is through the granulation of mixed milling type twin screw extruder.
6, pellet squeezes pipe after promptly be the anti-electrostatic fire retardant LDPE flexible pipe of requirement up to specification after finalizing the design, cooling off, draw, coil by single screw extrusion machine, appearance white.
The present invention be applicable to the processing down-hole with give, water shoot, shotcrete pipe and airduct, especially be fit to coal mine and use.Because the present invention has adopted the composite flame-retardant agent based on chlorinatedpolyethylene, soft, the good toughness of not only good flame retardation effect, and quality can tolerate the pressure of the interior mobile material of pipe to tube wall, can tolerate the bump of extraneous spoil or coal cinder again.
Excellent antistatic of the present invention can show not only that frosting is the positive and negative ion conduction of second class conductor, makes its surperficial resistivity reach 10
5The order of magnitude of Ω, and show that its static resistance is affected by environment less, such as the order of magnitude that only descends half of its surface resistivity through washing or after wiping examination, winter and summer its surface resistivity differ less than an order of magnitude.This is that other antistatic modifiers are beyond one's reach, such as the simple organic antistatic agents that uses, after washing and wiping examination, its surface resistivity 3～4 orders of magnitude that will descend, must could recover through several hrs or after several days, (easily have between decubation static cause accident), sometimes even can not recover automatically.Also can differ 3～4 orders of magnitude in winter and summer.
Embodiment:
1, with 7 parts of DBDPO, 6 parts of Sb2O3,12 parts contain hydrate zinc borate, 15 parts of NaCL drop in the high mixers and stirred 5～8 minutes under 80 ℃ of conditions, to spray in the material that is stirring through 1 part of TC-F of acetone diluted then, continue to stir 25～30 minutes, make it and the abundant coupling of above-mentioned material.Then drop into 30 parts of CPE and 5 parts of HKD-520 and stirred 5～10 minutes, drop into 100 parts of LDPE pellets at last, fully stir and heat up 100 ℃, up to the LDPE particle various properties-correcting agent glue and by even coating till.
The material that comes out in high mixer is through the twin screw extruder granulation, and the temperature of each section is controlled to be 90 ℃, 100 ℃, 120 ℃, 110 ℃, 80 ℃ successively respectively, and screw speed is 35 rev/mins.
To squeeze pipe in the single screw rod tube extruding machine of pellet input, control length-to-diameter ratio 20～25, compression ratio 3～4, each zone temperatures of fuselage is controlled to be 100 ℃, 120 ℃, 150 ℃, 140 ℃ and 90 ℃ successively.Motor speed is 20 rev/mins, 15～20 meters/hour of pulling speeds.The tubing of extruding is rolled into satisfactory anti-electrostatic fire retardant LDPE flexible pipe through mould shape, cooling traction hub disk.
2, get 10 parts of DBDPO, 12 parts of Sb2O3 contain 24 parts of hydrate zinc borates, KCL20 part, 3 parts of NZD-311,35 parts of CPE, 8 parts of HKD-508, LDPE100 part.Processing is with embodiment 1.
3, get 7 parts of DBDPO, 6 parts of Sb2O3 contain 12 parts of hydrate zinc borates, NaCL10 part, 5 parts of CaCL2,2 parts of TC-F, 1 part of NZD-311,35 parts of CPE, 8 parts of HKD-500, LDPE100 part.Processing is with embodiment 1.
4, get 10 parts of DBDPO, 12 parts of Sb2O3 contain 24 parts of hydrate zinc borates, K2SO410 part, 5 parts of MgCL2,1 part of KH-550,30 parts of CPE, HKD-5205 part, LDPE100 part.Processing is with embodiment 1.
5, get 10 parts of DBDPO, 6 parts of Sb2O3 contain 24 parts of hydrate zinc borates, CaCL28 part, 7 parts of MgCL2,3 parts of KH-560,30 parts of CPE, HKD-5208 part, LDPE100 part.Processing is with embodiment 1.
6, get 7 parts of DBDPO, 12 parts of Sb2O3 contain 12 parts of hydrate zinc borates, each 10 parts of Na2SO4, KNO3, TC-F1 part, CPE35 part, 3 parts of HKD-520,2 parts of HKD-500, LDPE100 part.Processing is with embodiment 1.
7, get 9 parts of DBDPO, 9 parts of Sb2O3 contain 18 parts of hydrate zinc borates, MgCL210 part, 7 parts of CaCL2, each 1 part of TC-F, KH-560, CPE32 part, HKD-5203 part, 4 parts of HKD-508, LDPE100 part.Processing is with embodiment 1.
8, get 8 parts of DBDPO, 10 parts of Sb2O3 contain respectively 6 parts of 20 parts of hydrate zinc borates, NaNO3, K2SO4, CaCL2, each 1 part of KH-550, KH-560, CPE34 part, each 2 parts of HKD-520, HKD-508, HKD-500, LDPE100 part.Processing is with embodiment 1.
9, get 9 parts of DBDPO, 7 parts of Sb2O3 contain 14 parts of hydrate zinc borates, 10 parts of KCL, 9 parts of CaCL2,2 parts of TC-F, 31 parts of CPE, 8 parts of HKD-520, LDPE100 part.Processing is with embodiment 1.
10, get 8 parts of DBDPO, 8 parts of Sb2O3 contain 15 parts of hydrate zinc borates, each 8 parts of MgCL2, Na2SO4,2 parts of NZD-311,33 parts of CPE, 7 parts of HKD-520, LDPE100 part.Processing is with embodiment 1.
Organic antistatic agents HKD-520, HKD-508 and HKD-500 used in above embodiment are that the Chemical Engineering Institute, HangZhou City produces.Used coupling agent TC-F raised the chemical plant in the Tian Changxian of Anhui Province days to produce, and NZD-311, KH-550 and KH-560 all are that Nanjing, Jiangsu Province dawn chemical industry one factory produces.The each component measure unit is gram or kilogram.
Batching and the anti-electrostatic fire retardant low-density polyethylene hose that obtains of processes according to the above ratio, (Ministry of Coal Industry specifies and detects unit) tests through national coal winning machinery quality examination center, and 1 meter long surface resistivity of tubing is less than 3 * 10
5, (standard value 1 * 10
8/ rice).Fire-retardant index, flaming combustion time average are 2.17 seconds, (prescribed value 3 seconds), the longest 4.75 seconds of flaming combustion time wherein, (prescribed value is 10 seconds); The flameless combustion time average is 2.22 seconds, (prescribed value is≤20 seconds), and what wherein the flameless combustion time was the longest is 4.30 seconds, (prescribed value is 60 seconds).Antistatic in a word and fire-retardant index all is significantly less than the specified standards value.
Claims (3)
1, a kind of anti-electrostatic fire retardant low-density polyethylene hose, by base-material new LDPE (film grade) and modified additive through mixing, coupling, coating, granulation, squeeze the pipe aftershaping, it is characterized in that:
New LDPE (film grade) 100 weight parts
Chlorinatedpolyethylene 30～35 weight parts
Decabromodiphynly oxide 7～10 weight parts
Antimonous oxide 6～12 weight parts
Contain hydrate zinc borate 12～24 weight parts
Organic antistatic agents 5～8 weight parts
Soluble inorganic salt 15～20 weight parts of sodium or potassium or calcium or magnesium
1～3 part of weight part of titanate ester or silane coupling agent
2, a kind of anti-electrostatic fire retardant low-density polyethylene hose according to claim 1 is characterized in that: described organic antistatic agents is HKD-520 or HKD-508 or HKD-500.
3, a kind of anti-electrostatic fire retardant low-density polyethylene hose according to claim 1 and 2, described coupling agent are TC-F or NZD-311 or KH-550 or KH-560.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94116662A CN1058033C (en) | 1994-10-07 | 1994-10-07 | Anti-electrostatic fire retardant low-density polyethylene hose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94116662A CN1058033C (en) | 1994-10-07 | 1994-10-07 | Anti-electrostatic fire retardant low-density polyethylene hose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1124746A CN1124746A (en) | 1996-06-19 |
| CN1058033C true CN1058033C (en) | 2000-11-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94116662A Expired - Fee Related CN1058033C (en) | 1994-10-07 | 1994-10-07 | Anti-electrostatic fire retardant low-density polyethylene hose |
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| CN (1) | CN1058033C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6843274B1 (en) * | 2003-06-25 | 2005-01-18 | Air Systems International, Inc. | Electrically conductive confined space ventilator conduit formed of conductive polymer, electrical grounding circuit for ventilation system using same, and methods of using and forming same |
| CN101311211B (en) * | 2007-05-25 | 2011-01-26 | 上海上塑控股（集团）有限公司 | Polyethylene pipes for underground mine use |
| CN101402753B (en) * | 2008-10-31 | 2011-03-16 | 浙江七色鹿色母粒有限公司 | Begin-color flame-proof antistatic polyolefin master batch |
| CN103509263B (en) * | 2013-10-11 | 2015-11-04 | 广东聚石化学股份有限公司 | A kind of environmental protection addition type polyethylene anti-flaming master batch and preparation method thereof |
| CN104558746B (en) * | 2013-10-23 | 2017-02-01 | 中国石油化工股份有限公司 | Flame-retardant and antistatic polyethylene composition and preparation method thereof |
| CN110078997B (en) * | 2019-04-30 | 2022-03-29 | 金旸（厦门）新材料科技有限公司 | Double-resistance special material for mining thin-wall polyethylene pipeline and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0215444A2 (en) * | 1985-09-13 | 1987-03-25 | Idemitsu Petrochemical Co. Ltd. | Polyethylene resin composition |
| CN1051542A (en) * | 1990-12-14 | 1991-05-22 | 张淑杰 | Manufacture method of polymerized composite materials and products thereof |
| CN1070061A (en) * | 1991-08-23 | 1993-03-17 | 日立电线株式会社 | Non-halogenated fire-proof resin composition and bag are with the electric wire and cable of this thing |
-
1994
- 1994-10-07 CN CN94116662A patent/CN1058033C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0215444A2 (en) * | 1985-09-13 | 1987-03-25 | Idemitsu Petrochemical Co. Ltd. | Polyethylene resin composition |
| CN1051542A (en) * | 1990-12-14 | 1991-05-22 | 张淑杰 | Manufacture method of polymerized composite materials and products thereof |
| CN1070061A (en) * | 1991-08-23 | 1993-03-17 | 日立电线株式会社 | Non-halogenated fire-proof resin composition and bag are with the electric wire and cable of this thing |
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| Publication number | Publication date |
|---|---|
| CN1124746A (en) | 1996-06-19 |
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