CN1221604C - Antistatic fireproof composite polyethylene pipe and its production process - Google Patents
Antistatic fireproof composite polyethylene pipe and its production process Download PDFInfo
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- CN1221604C CN1221604C CN 03138807 CN03138807A CN1221604C CN 1221604 C CN1221604 C CN 1221604C CN 03138807 CN03138807 CN 03138807 CN 03138807 A CN03138807 A CN 03138807A CN 1221604 C CN1221604 C CN 1221604C
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Abstract
The present invention relates to an antistatic fire retardant composite polyethylene pipe, wherein the weight composition of which comprises 5 to 15% of fire retardant which comprises bromine, 3 to 10% of compounds which contain antimony, 5 to 8% of conductive carbon black, 1 to 3% of polyethylene wax, 0.5 to 3% of antioxidant and the rest components are balance of polyethylene, wherein the conductive carbon black preferably uses modified conductive carbon black; the modified conditions comprise that the conductive carbon black is heated for more than 10 minutes at the temperature of 100 to 300 DEG C under the condition of 30 to 1000 Pa of vacuum; the polyethylene preferably uses the mixture of polyethylene with high density and polyethylene with low-density; the polyethylene with low-density is 15 to 30% of the total amount of a pipe composition; and the polyethylene with high density is 30 to 70% of the total amount of the pipe composition. The antistatic fire retardant composite polyethylene pipe has the advantages of good antistatic and fire retardant synergistic effect of the pipe, excellent physical and mechanical performance and permanent antistatic performance of the pipe, the antistatic performance of the pipe can not disappear with time traction, and the safety coefficients of coal mine operation can be greatly improved.
Description
Technical field
The present invention relates to anti-electrostatic flame-retardant polyvinyl composite pipe and preparation technology, this composite pipe colliery preferably uses.
Background technology
In the mining pipes of down-hole, replace metal tube more and more to come into one's own with plastic pipe.Plastic pipe is subjected to people's favor, is that not only cost is low because of it, and is in light weight, easy for installation, and corrosion resistance and good, the down-hole long service life, but also exist inflammable simultaneously, easily produce shortcomings such as static, therefore, the domestic improvement that has a lot of people to be devoted to plastic pipe.
Aspect flame-retardant modified, mainly be by in resin, adding additive flame retardant.The fire retardant kind is a lot, can be used alone type, also several fire retardants can be mixed and use.Normal use brominated flame-retardant and antimony containing compounds arranged.Antistatic modified aspect mainly contains two kinds of methods: the one, adopt modes such as plating, coating, stickup at product surface, and this method cost height pollutes big.The 2nd, additive process is added static inhibitor or electroconductive stuffing in non-polar resin, but improper because of some measure, its electrostatic efficiency often can not be permanent, causes promoting the use of of this tubing to be subjected to certain restriction.As polyvinyl piping materials, base-material generally adopts high density polyethylene(HDPE) or new LDPE (film grade).
Summary of the invention
Technical problem to be solved by this invention provides a kind of antistatic property lasting, excellent anti-electrostatic flame-retardant polyvinyl composite pipe and preparation technology thereof, and purpose of the present invention can also be in the physical and mechanical properties that keeps improving on the basis of antistatic, flame retardant properties tubing.
Anti-electrostatic flame-retardant polyvinyl composite pipe of the present invention is characterized in that its weight consists of:
The polyethylene of brominated flame-retardant 5～15%, antimony containing compounds 3～10%, electrical conductivity Carbon black 5～8%, polyethylene wax 1～3%, oxidation inhibitor 0.5～3%, surplus.
Electrical conductivity Carbon black is a kind of permanent antistatic agent, add the back plastic material and can in life-time service, not lose antistatic property because of reasons such as washing, wearing and tearing, electrical conductivity Carbon black C as the light carbon black plant production of Shandong China, it is to gather to generate from Qilu Petrochemical company petroleum cracking thing, has a kind of special hollow shell structure, critical addition is less, and is less to other Effect on Performance of material.Its particulate has maximum surface area under the identical situation of unit mass, therefore big with the contact area of polyethylene matrix, is easy to form comparatively perfect, uniform conductive network.Because there are numerous not sharing electrons in the carbon black particle surface, the particle size carbon black size is near nano level, intergranular easily forms the dendritic three-dimensional structure aggregate of firm chain with chemisorption, conduct electricity very well, but be difficult for disperseing, only under bigger shear-mixed power effect, could in matrix, disperse well, and the height of carbon black conductive modified effect depends on his dispersing morphology.Therefore in order to increase the wetting ability of conductive carbon black and matrix resin, improve interfacial adhesion strength, do not cause it to cause the reduction of conductive capability because of long shear-mixed again, the present invention preferably carries out modification to conductive carbon black and handles, and preferably adopts the modification electrical conductivity Carbon black in promptly forming:
Modified condition is: electrical conductivity Carbon black heats more than 10 minutes general 10～60 minutes through 100～300 ℃ under 30～1000Pa vacuum condition.The modification electrical conductivity Carbon black adds in the polyvinyl resin, further increased the specific surface area of carbon black, promote greying, eliminate the active group of black carbon surface effectively, improved the electric conductivity of carbon black self, be convenient to its appropriateness again and disperse, the contradiction of dispersiveness and electroconductibility when having solved processing preferably.Graft reaction takes place in electrical conductivity Carbon black and polyvinyl resin in the banburying process, cause the electroconductibility that has not only guaranteed material behind the master batch again with the compounded tubing of other material well, and greatly improved the stability of conducting electricity, the antistatic property of tubing is forever existed.
Fire retardant of the present invention adopts brominated flame-retardant and antimony containing compounds and usefulness, good flame retardation effect, and the thermostability height is brought into play fire-retardant effect best.Brominated flame-retardant has many commercially available prod, as brominated Polystyrene, brominated epoxy resin, bromination phenoxy resin, bromination imines, decabromodiphynly oxide etc., and preferred decabromodiphynly oxide; Antimony containing compounds also adopts the commercially available prod, as antimonous oxide, four oxidations, three antimony, sodium antimonate, antimony tartrate etc., and preferred antimonous oxide.Antimonous oxide and decabromodiphynly oxide are used, can generate the big antimony peroxide of fire retardation, isolated effect is strong, can dilute the concentration of inflammable gas and promote the resin surface charing simultaneously, have the good flame synergy, bring into play good flame-retardant effect jointly.
Polyethylene is a resin matrix of the present invention, it both can adopt high density polyethylene(HDPE) as prior art, also can adopt new LDPE (film grade), the present invention preferably adopts the mixing of high density polyethylene(HDPE) and new LDPE (film grade) to form, new LDPE (film grade) be tubing form total amount 15～30%, high density polyethylene(HDPE) be tubing form total amount 30～70%.High density polyethylene(HDPE) and new LDPE (film grade) are used according to a certain ratio, guarantee that the tubing of extruding has good physical and mechanical property, can satisfy the requirement of down-hole life-time service fully.
Described oxidation inhibitor adopts commercially available various products, as antioxidant 1010 or oxidation inhibitor 168.
The manufacturing process of tubing of the present invention comprises the steps:
(1) preparation fire retardant masterbatch: brominated flame-retardant, antimony containing compounds, oxidation inhibitor, new LDPE (film grade) are mixed extruding pelletization, and wherein new LDPE (film grade) is 5～10% of a tubing composition total amount;
(2) preparation antistatic master batch: electrical conductivity Carbon black, polyethylene wax, oxidation inhibitor, new LDPE (film grade) are mixed banburying, granulation, and wherein new LDPE (film grade) is 10～20% of a tubing composition total amount;
(3) preparation special material for tube: fire retardant masterbatch, antistatic master batch, high density polyethylene(HDPE) are mixed extruding pelletization, and high density polyethylene(HDPE) is for forming 30～70% of total amount for tubing;
(4) special material for tube extruding pipe material obtains finished product through typing, cooling, traction.
In above-mentioned preparation technology, preparation fire retardant masterbatch and the used separately oxidation inhibitor of preparation antistatic master batch be respectively the oxidation inhibitor total amount half get final product.When the matrix polyethylene all adopts high density polyethylene(HDPE) or new LDPE (film grade), the used poly amount of preparation fire retardant masterbatch is 5～10% of a tubing composition total amount, the used poly amount of preparation antistatic master batch is 10～20% of a tubing composition total amount, and surplus is the used poly amount of preparation special material for tube.
In above-mentioned preparation technology, electrical conductivity Carbon black still preferably adopts the electrical conductivity Carbon black of modification, it not only has the effect that common carbon black can effectively reduce the plastics volume specific resistance electrical conductivity Carbon black of modification, and because of its production technique special, carry out high-temperature heat treatment again under given conditions, add in the polyethylene then, through the Banbury mixer banburying, improve the dispersiveness of carbon black, extrude with other raw materials mixing again after making master batch, in tubing, form the relative uniform conductive network that distributes, greatly improve the antistatic property of tubing.
Advantage of the present invention:
Antistatic and the flame retardant synergistic effect of tubing is good, and has an excellent physical and mechanical properties, the antistatic property of tubing is nonvolatil, passing that can be not in time and disappearing, can improve the safety coefficient of colliery operation greatly, be applicable to plumbing under the coal mine, blow or pump the tubing of gases such as gas.
Below be tubing correlated performance index test result:
1, alcohol blast burner combustionproperty:
The maximum monodromes of 6 summations (S) (S)
Combustion time standard value measured value standard value measured value
Flaming combustion≤18.00 4.8≤10.00 1.2
Flameless combustion≤120.00 6.7≤60.00 1.6
2, conductivity:
The standard value measured value
Internal surface resistance mean value ()≤1.0 * 10
93.2 * 10
4
Outside surface resistance mean value ()≤1.0 * 10
97.6 * 10
4
3, physical and mechanical properties:
The standard value measured value
Flattening test leakless leakless
Tensile strength, Mpa 〉=7.8 13.62
Tension fracture elongation rate, % 〉=200 527.13
More than standard value is according to standard MT558.1-1996 test in the test, and measured value is 5 times a mean value, and the specification of tubing is φ 110.
Embodiment
Following examples but do not limit the present invention in order to explanation the present invention.
Embodiment one: weight consists of:
Decabromodiphynly oxide 10%, antimonous oxide 7%, electrical conductivity Carbon black 6%, polyethylene wax 2%, antioxidant 1010 2%, new LDPE (film grade) 25%, high density polyethylene(HDPE) 48%.
Electrical conductivity Carbon black is handled through following modification: electrical conductivity Carbon black is under the 300Pa vacuum condition, through 300 ℃ of heating 10 minutes.
Manufacturing process is according to manufacturing process of the present invention.
Embodiment two: weight consists of:
Decabromodiphynly oxide 15%, antimonous oxide 3%, electrical conductivity Carbon black 8%, polyethylene wax 3%, antioxidant 1010 3%, new LDPE (film grade) 15%, high density polyethylene(HDPE) 53%.
The modification of electrical conductivity Carbon black is treated to: electrical conductivity Carbon black is under the 500Pa vacuum condition, through 200 ℃ of heating 30 minutes.
Embodiment three: weight consists of:
Decabromodiphynly oxide 5%, antimonous oxide 10%, electrical conductivity Carbon black 5%, polyethylene wax 1%, oxidation inhibitor 168 1%, new LDPE (film grade) 30%, high density polyethylene(HDPE) 48%.
The modification of electrical conductivity Carbon black is handled: electrical conductivity Carbon black is under the 30Pa vacuum condition, through 100 ℃ of heating 60 minutes.
Embodiment four: weight consists of:
Decabromodiphynly oxide 5%, antimonous oxide 3%, electrical conductivity Carbon black 5%, polyethylene wax 1%, oxidation inhibitor 168 1%, new LDPE (film grade) 15%, high density polyethylene(HDPE) 70%.
Embodiment five: weight consists of:
Decabromodiphynly oxide 5%, antimonous oxide 10%, electrical conductivity Carbon black 5%, polyethylene wax 1%, oxidation inhibitor 168 1%, high density polyethylene(HDPE) 78%.
The modification of electrical conductivity Carbon black is handled: electrical conductivity Carbon black is under the 100Pa vacuum condition, through 300 ℃ of heating 40 minutes.
Embodiment six: weight consists of:
Brominated Polystyrene 12%, four oxidations, three antimony 5%, electrical conductivity Carbon black 7%, polyethylene wax 2%, oxidation inhibitor 1682%, new LDPE (film grade) 72%.
The modification of electrical conductivity Carbon black is handled: electrical conductivity Carbon black is under the 1000Pa vacuum condition, through 100 ℃ of heating 10 minutes.
Claims (7)
1, a kind of anti-electrostatic flame-retardant polyvinyl composite pipe is characterized in that its weight consists of:
The polyethylene of brominated flame-retardant 5～15%, antimony containing compounds 3～10%, electrical conductivity Carbon black 5～8%, polyethylene wax 1～3%, oxidation inhibitor 0.5～3%, surplus.
2, composite pipe according to claim 1, it is characterized in that described electrical conductivity Carbon black is the electrical conductivity Carbon black through following condition modification: electrical conductivity Carbon black heats more than 10 minutes through 100～300 ℃ under 30～1000Pa vacuum condition.
3, composite pipe according to claim 1, it is characterized in that described polyethylene is made up of high density polyethylene(HDPE) and new LDPE (film grade), new LDPE (film grade) be tubing form total amount 15～30%, high density polyethylene(HDPE) be tubing form total amount 30～70%.
4, composite pipe according to claim 1 is characterized in that described brominated flame-retardant is a decabromodiphynly oxide, and antimony containing compounds is an antimonous oxide.
5, composite pipe according to claim 1 is characterized in that described oxidation inhibitor adopts antioxidant 1010 or oxidation inhibitor 168.
6, a kind of technology of making the described composite pipe of claim 1 is characterized in that comprising the steps:
(1) preparation fire retardant masterbatch: brominated flame-retardant, antimony containing compounds, oxidation inhibitor, new LDPE (film grade) are mixed extruding pelletization, and wherein new LDPE (film grade) is 5～10% of a tubing composition total amount;
(2) preparation antistatic master batch: electrical conductivity Carbon black, polyethylene wax, oxidation inhibitor, new LDPE (film grade) are mixed banburying, granulation, and wherein new LDPE (film grade) is 10～20% of a tubing composition total amount;
(3) preparation special material for tube: fire retardant masterbatch, antistatic master batch, high density polyethylene(HDPE) are mixed extruding pelletization, and high density polyethylene(HDPE) is 30～70% of a tubing composition total amount;
(4) special material for tube extruding pipe material obtains finished product through typing, cooling, traction.
7, technology according to claim 6, it is characterized in that described electrical conductivity Carbon black is the electrical conductivity Carbon black through following condition modification: electrical conductivity Carbon black heats more than 10 minutes through 100～300 ℃ under 30～1000Pa vacuum condition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03138807 CN1221604C (en) | 2003-07-12 | 2003-07-12 | Antistatic fireproof composite polyethylene pipe and its production process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03138807 CN1221604C (en) | 2003-07-12 | 2003-07-12 | Antistatic fireproof composite polyethylene pipe and its production process |
Publications (2)
| Publication Number | Publication Date |
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| CN1487014A CN1487014A (en) | 2004-04-07 |
| CN1221604C true CN1221604C (en) | 2005-10-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 03138807 Expired - Fee Related CN1221604C (en) | 2003-07-12 | 2003-07-12 | Antistatic fireproof composite polyethylene pipe and its production process |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348694C (en) * | 2004-05-21 | 2007-11-14 | 中国石油天然气股份有限公司 | Flame-retardant resin composition having positive temperature coefficient of resistance |
| CN1831412B (en) * | 2006-04-07 | 2010-09-01 | 李寿山 | Ventilation/gas exhaust tube with fire resistance antistatic performance hollow structure wall |
| CN100417685C (en) * | 2006-06-01 | 2008-09-10 | 中国石化扬子石油化工有限公司 | Anti-static flame-retarding polyethylene composition and its preparing method |
| 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 |
| CN101125941B (en) * | 2007-08-03 | 2010-09-08 | 安徽国通高新管业股份有限公司 | Polyethylene pipe for non-excavation traction method construction |
| CN101845168A (en) * | 2010-04-30 | 2010-09-29 | 三斯达(福建)塑胶有限公司 | Environment-friendly, antiflaming and antistatic foaming material and preparation method thereof |
| CN101907206B (en) * | 2010-06-13 | 2011-10-19 | 河北拓安管业有限公司 | Steel-belt occlusion welding plastic-coated composite pipe and preparation method thereof |
| CN101921424B (en) * | 2010-08-23 | 2011-12-07 | 河北颐通管业有限公司 | Raw material for manufacturing pipe for transporting combustible gases |
| CN103012934A (en) * | 2012-12-28 | 2013-04-03 | 山东金德新型管业有限公司 | Polyethylene tube for mining and preparation method thereof |
| CN103090123B (en) * | 2013-01-23 | 2015-01-14 | 浙江飞龙管业有限公司 | High impact polyvinyl chloride (PVC) pipe capable of noise reduction and static elimination |
| CN103992553A (en) * | 2014-04-30 | 2014-08-20 | 安徽省宁国市明浩包装材料有限公司 | Antistatic gas discharge tube and production 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 |
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2003
- 2003-07-12 CN CN 03138807 patent/CN1221604C/en not_active Expired - Fee Related
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