CN1289591C - Antistatic flame-retardant polyethylene composition - Google Patents
Antistatic flame-retardant polyethylene composition Download PDFInfo
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- CN1289591C CN1289591C CN 200310105635 CN200310105635A CN1289591C CN 1289591 C CN1289591 C CN 1289591C CN 200310105635 CN200310105635 CN 200310105635 CN 200310105635 A CN200310105635 A CN 200310105635A CN 1289591 C CN1289591 C CN 1289591C
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Abstract
The present invention relates to a plastic composition of antistatic fire-retardant polyethylene. The composition has the components according to the proportion by weight: 20 to 45 portions of high-density polyethylene, 40 to 30 portions of antistatic master batches of polyethylene and 40 to 25 portions of fire-retardant master batches of polyethylene, wherein the antistatic master batches of polyethylene use two graphitized carbon black with different specific surface areas, the graphitized carbon black is processed by treating agents, the antistatic and fire retardant synergistic effect is good, and the processing performance and the mechanical performance are excellent. The fire retardant master batches of polyethylene use a compound fire retardant, bromobenzene ether which is an organic compound and contains halogen is used as a main fire retardant, antimonous oxide is used as a synergistic agent and a smoke suppressing agent; the synergistic action of the master batches and antistatic agents is good; therefore, the composition has stable performance and is processed easily. The composition has excellent antistatic performance, flame retardant performance, processing performance and mechanical performance, and is used for preparing pipe materials with various purposes in underground coal mines. The pipe materials have excellent comprehensive performance, and satisfy the requirements of trade standard MT558.1 of coal departments.
Description
Technical field
The invention belongs to plastics processing and application technology, relate to a kind of anti-static flame-retardant plastic composition.
Background technology
In recent years,, add the promotion of national policy, be widely used in every field because polyvinyl piping materials has advantages such as inexpensive light weight, easy for installation, environmental protection.Wherein, mineral polyethylene piping materials is except the physical and mechanical properties that should possess general plastic pipe, and the particular requirement that also should satisfy the colliery promptly must have static resistance, and self-extinguishing and products of combustion also must not have toxicity.Polyethylene is a kind of organic polymer material, and its volume specific resistance is very high, is 10
16-20Ω/cm will produce static through friction, and accumulates in frosting, but therefore fire hazard and gas explosion must be carried out antistatic modified with the polyvinyl resin of pipe to operating mine.Method of modifying commonly used at present comprises interpolation static inhibitor or materials such as conductive carbon black and metal-powder in resin.Static inhibitor is a kind of surfactant, and its anlistatig mechanism is that the water-wet side of static inhibitor absorbs airborne moisture content, forms a kind of conduction moisture film at material surface, thereby reduces surface resistivity, makes the static charge that has produced thank rapidly.If the static inhibitor on surface falls behind because of washing or wiping, inner static inhibitor molecule can also be shifted to the surface, thereby recovers its antistatic property.Anti-electrostatic fire retardant material that CN1418907A and CN1114607A relate to or tubing all are to have adopted static inhibitor to carry out antistatic modified to polyvinyl resin.The quality of the polyethylene products antistatic property of use static inhibitor will rely on the humidity of surrounding environment greatly, and the antistatic effect in dry environment is relatively poor, and this causes danger because of static often.And static inhibitor itself is generally some ionized materials in water, As time goes on, static inhibitor will go out because of the outside gradually chromatography of the dissolving of surface portion, form textural defect at material internal, when influencing the mechanical property of material, antistatic property is decayed gradually.
In polyethylene, add graphitized carbon black, reach surface chemical property preferably because carbon structureization has bigger specific surface area, so can obtain good antistatic effect.Because the problem of the performance of carbon black own, the sooty consumption reached more than 20 parts, just can make polyethylene have good antistatic performance in the past, but at this moment Drawing abillity, mechanical property variation are restricted its application in tubing.ZL90106274 discloses a kind of manufacture method of polyethylene hose, and its sooty add-on surpasses 20 parts, and this patent utilization crosslinking technological has remedied and added the mechanical property loss of energy that a large amount of carbon blacks cause.Continuous development along with black carbon technology, the carbon black that adds less umber in recent years in matrix material just can obtain good antistatic effect, but because the specific surface area of graphitized carbon black is very big, add the melt viscosity that will have a strong impact on matrix material in the resin, it is excessive moment of torsion to occur in extrusion, extrudes phenomenons such as instability.The technology that the present invention relates to comprise with two kinds of carbon blacks and with and it is carried out necessary processing, interpolation part properties-correcting agent in matrix material to improve above-mentioned situation, has been obtained good effect simultaneously.
Summary of the invention
Technical problem to be solved by this invention provides the polyethylene anti-static flame-retardant plastic composition of a kind of electrical property, processing characteristics, good mechanical performance, is mainly used in the colliery pipeline of making various uses.
The anti-electrostatic flame-retardant polyvinyl plastics composite is characterized in that its weight consists of: high density polyethylene(HDPE) 20-45 part, and polyethylene antistatic master batch 40-30 part, polyethylene anti-flaming masterbatch 40-25 part, wherein:
The weight of polyethylene antistatic master batch consists of: 100 parts of polyethylene support resins, specific surface area is greater than 800g/m
2High electric conductivity carbon black A 25-40 part, specific surface area is less than 500g/m
2Common graphitized carbon black B 5-10 part, carbon black treatment agent 2.0-4.0 part, oxidation inhibitor 0.4-1.0 part, polyethylene wax 2.0-5.0 part,
The weight of polyethylene anti-flaming masterbatch consists of: 100 parts of polyethylene support resins, fire retardant 100-150 part, smoke suppressor 25-40 part, oxidation inhibitor 2.0-3.0 part.
The preparation method of polyethylene antistatic master batch comprises the steps:
A. graphitized carbon black adds treatment agent in the 200-1000rpm stirrer, and normal temperature stirred 5-10 minute down;
B. with various auxiliary agents with vector resin blend in stirrer, stir and emit material after 5 minutes;
C. with mixed material through length-to-diameter ratio greater than 30 twin screw extruder group granulation, the preparation antistatic master batch.Extrusion temperature is controlled between 160-220 ℃.
Carbon black treatment agent in the polyethylene antistatic master batch can be selected titanate coupling agent, silane coupling agent, and aluminate coupling agent, optimal selection is a titanate coupling agent.The effect of coupling agent is to make carbon black and these two kinds of different properties materials of vector resin can be compatible more fully, selected titanate coupling agent, silane coupling agent, aluminate coupling agent are the common component utilized of plastic working industry, as titanate coupling agent: general formula:
(RO) R in is an alkyl, wherein 1≤m≤4;
-OX-can be carboxyl, sulfonic group, sulfuryl etc.;
-R-is long-chain carbon atom such as alkyl, aromatic base etc.;
-Y-be can with the group of thermosetting polymer reaction, as two keys, amino etc.
M+n in the formula≤6.
Silane coupling agent: general structure: RSiX
3, R is the active group that avidity or response capacity are arranged with polymer molecule, as amino, sulfydryl, vinyl, epoxy group(ing), cyano group, methacryloxy etc.X be can hydrolysis alkoxyl group (as methoxyl group, oxyethyl group etc.) or chlorine.For example: vinyltriethoxysilane etc.
Oxidation inhibitor is preferably phosphoric acid ester and suffocated amine antioxidant mixes use, and the two preferably mixes by weight ratio of 1: 1.Phosphoric acid ester and suffocated amine antioxidant are selected plastic working industry used various components usually.
Vector resin is a new LDPE (film grade).
It is good that antistatic master batch of the present invention and the antistatic master batch that uses other static inhibitor productions are compared antistatic effect.Handle by two kinds of carbon blacks mixing uses and to these two kinds of carbon blacks, solved a difficult problem that is difficult for processing when the carbon black add-on is big, use common twin screw extruder just can process granulation, and the mechanical property of composition is influenced not quite.The two anti-tubing that uses said composition to produce can satisfy the needs of the various water delivery gas transmissions in down-hole fully.
The preparation method of polyethylene anti-flaming masterbatch comprises the steps:
A. vector resin and various auxiliary agent are added in the stirrer of 200-1000rpm, stir and emit material after 5 minutes.
B. with mixed material through the granulation of twin screw extruder group, the preparation flame-retardant master batch.Extrusion temperature is controlled between 165-220 ℃, and speed is decided according to extruding electric current.
Polyethylene anti-flaming masterbatch used carrier resin is the new LDPE (film grade) powder.Oxidation inhibitor is preferably phosphoric acid ester and suffocated amine antioxidant mixes use, and the two preferably mixes by weight ratio of 1: 1.
Phosphoric acid ester and suffocated amine antioxidant are selected plastic working industry used various components usually.
Fire retardant and smoke suppressor are still selected used various components usually for use, and fire retardant is as ten bromobenzenes connection ether, smoke suppressor such as antimonous oxide.
The method for preparing anti-electrostatic flame-retardant polyvinyl plastics composite of the present invention, as follows:
A. with polyethylene antistatic master batch 40-30 part, polyethylene anti-flaming masterbatch 40-25 part is emitted material with thorough mixing in the homogenizer of high density polyethylene(HDPE) 20-45 part input 200-1000rpm after 5 minutes.
B. with mixed material through the twin screw extruder granulation, make plastics composite of the present invention, prilling temperature is controlled between 160-250 ℃.
What the present invention used is composite flame-retardant agent, is main flame retardant with halogen-containing organic compound ten bromobenzenes connection ether etc., and antimonous oxide etc. are synergistic agent and smoke suppressor.The synergy of this composite flame-retardant agent and static inhibitor makes the stable performance of goods and is easy to processing well.
Adopt the graphitized carbon black of two kinds of different specific surface areas, graphitized carbon black is handled with treatment agent, two kinds of graphitized carbon blacks and usefulness, antistatic and flame retardant synergistic effect is good, processing and good mechanical performance.
The polyethylene composition of the present invention's development is antistatic modifier with the graphitized carbon black, and adopts flame-retarded technology to make this plastics composite have excellent antistatic, flame retardant resistance, processing characteristics and mechanical property, is used to prepare underground mine use various uses tubing.This tubing has excellent comprehensive performances, and satisfies the requirement of the industry standard MT558.1 of Ministry of Coal Industry.
Anti-static flame-retarding polyethylene composition of the present invention can reach following physical index, surface resistivity≤1.0 * 10
6Ω, tensile strength 〉=18.0MPa, elongation at break 〉=350%, melt flow rate (MFR) is between 0.10-0.30.
The present invention compares with the prior art technology, has tangible advantage and positively effect.
1, technology is reasonable, has improved its processing characteristics in the electrical property that guarantees material, mechanical property, has solved the difficult problem of carbon black filled post-treatment poor performance, has obtained a kind of anti-static flame-retardant plastic of high comprehensive performance.
2, the present invention for improving the China's coal-mine working environment at coal mines, prolongs the life cycle of down-hole with pipe in the application implementation in antistatic flame-resistant pipe field, reduces operation intensity, and it is of far-reaching significance to reduce coal mining enterprise's investment.
Embodiment
Embodiment 1
Composite formula:
High density polyethylene(HDPE): 40 parts
Antistatic master batch: 35 parts
Flame-retardant master batch: 25 parts
Wherein:
The prescription of antistatic master batch is:
Linear low density polyethylene: 100 parts
High electric conductivity carbon black (specific surface area 828m
2/ g): commercially available 30 parts
Common graphitized carbon black (specific surface area 164m
2/ g): 8 parts of U.S. Cabot Co.,Ltd
Antioxidant 1010: 0.4 part of oxidation inhibitor 168:0.4 part
Titanate coupling agent (monoalkyl class): 3.5 parts
Polyethylene wax: 4 parts
The flame-retardant master batch prescription:
Linear low density polyethylene: 100 parts
Decabromodiphenyl oxide: 125 parts
Antimonous oxide: 25 parts
Oxidation inhibitor: 1010:1.5 part 168:1.5 part
As follows through twin screw extruder granulation resulting composition performance index:
Melt flow rate (MFR): 0.1g/10min (190 ℃ of 2.16kg)
Stretching yield stress: 17.67MPa
Elongation at break: 700
Surface resistivity: 1.2 * 10
3Ω
Flaming combustion: 2.0s
Flameless combustion: 5.2s
The two anti-tubing of producing with said composition detects the requirement that reaches Ministry of Coal Industry of People's Republic of China (PRC) industry standard (MT558.1-1996) fully through national authority department.
Embodiment 2
Composite formula:
High density polyethylene(HDPE): 40 parts
Antistatic master batch: 30 parts
Flame-retardant master batch: 30 parts
Wherein:
The prescription of antistatic master batch and flame-retardant master batch prescription are identical with embodiment 1
As follows through twin screw extruder granulation resulting composition performance index:
Melt flow rate (MFR): 0.4g/10min (190 ℃ of 2.16kg)
Stretching yield stress: 18.52MPa
Elongation at break: 685
Surface resistivity: 2.4 * 10
3Ω
Flaming combustion: 1.54s
Flameless combustion: 3.68s
The two anti-tubing of producing with said composition detects the requirement that reaches Ministry of Coal Industry of People's Republic of China (PRC) industry standard (MT558.1-1996) fully through national authority department.
Embodiment 3
The prescription of antistatic master batch and flame-retardant master batch is with embodiment 1:
The prescription of composition is:
High density polyethylene(HDPE): 22 parts
Polyethylene antistatic master batch: 38 parts
Polyethylene anti-flaming masterbatch: 40 parts
Embodiment 4
The prescription of antistatic master batch and flame-retardant master batch is with embodiment 1:
The prescription of composition is:
High density polyethylene(HDPE): 43 parts
Polyethylene antistatic master batch: 33 parts
Polyethylene anti-flaming masterbatch: 25 parts
Embodiment 5
The prescription of antistatic master batch and flame-retardant master batch is with embodiment 1:
The prescription of composition is:
High density polyethylene(HDPE): 30 parts
Polyethylene antistatic master batch: 30 parts
Polyethylene anti-flaming masterbatch: 40 parts
Embodiment 6
Press the composite formula of embodiment 2, the flame-retardant master batch prescription is constant, changes the prescription of antistatic master batch:
Linear low density polyethylene: 100 parts
High electric conductivity carbon black (specific surface area 828m
2/ g): commercially available 35 parts
Common graphitized carbon black (specific surface area 164m
2/ g): 5 parts of U.S. Cabot Co.,Ltd
Antioxidant 1010: 0.4 part of 168:0.4 part
Titanate coupling agent (monoalkyl class): 4 parts
Polyethylene wax: 5 parts
As follows through twin screw extruder granulation resulting composition performance index:
Melt flow rate (MFR): 0.1g/10min (190 ℃ of 2.16kg)
Stretching yield stress: 15.52MPa
Elongation at break: 572
Surface resistivity: 0.8 * 10
3Ω
Flaming combustion: 2.5s
Flameless combustion: 5.1s
The two anti-tubing of producing with said composition detects the requirement that reaches Ministry of Coal Industry of People's Republic of China (PRC) industry standard (MT558.1-1996) fully through national authority department.
Embodiment 7
Press the composite formula of embodiment 2, the flame-retardant master batch prescription is constant, changes the prescription of antistatic master batch:
New LDPE (film grade): 100 parts
The high electric conductivity carbon black specific surface is: 828m
228 parts of/g
Common graphitized carbon black specific surface area is: 164m
27 parts of/g
The composition of oxidation inhibitor, titanate coupling agent, polyethylene wax is constant.
Embodiment 8
Press the composite formula of embodiment 2, the flame-retardant master batch prescription is constant, changes the prescription of antistatic master batch:
New LDPE (film grade): 100 parts
High electric conductivity carbon black specific surface＞800m
225 parts of/g
Common graphitized carbon black specific surface area is 500m
25 parts of/g
2 parts of titanate coupling agent monoalkyl classes
2 parts of polyethylene waxs
Oxidation inhibitor is formed constant.
Embodiment 9
Press the composite formula of embodiment 2, the flame-retardant master batch prescription is constant, changes the prescription of antistatic master batch:
New LDPE (film grade): 100 parts
High electric conductivity carbon black specific surface＞800m
238 parts of/g
Common graphitized carbon black specific surface area is 100-400m
26 parts of/g
4 parts of titanate coupling agent monoalkyl classes
The composition of oxidation inhibitor, polyethylene wax is constant.
Embodiment 10
Press the composite formula of embodiment 2,
The prescription of antistatic master batch:
New LDPE (film grade): 100 parts
High electric conductivity carbon black specific surface＞800m
230 parts of/g
Common graphitized carbon black specific surface area is 100-400m
28 parts of/g
3.5 parts of titanate coupling agent monoalkyl classes
The composition of oxidation inhibitor, polyethylene wax is constant.
The flame-retardant master batch prescription:
New LDPE (film grade): 100 parts
Decabromodiphenyl oxide: 100 parts
Antimonous oxide: 40 parts
Oxidation inhibitor is formed constant.
Claims (3)
1, a kind of anti-electrostatic flame-retardant polyvinyl plastics composite is characterized in that its weight consists of: high density polyethylene(HDPE) 20-45 part, and polyethylene antistatic master batch 40-30 part, polyethylene anti-flaming masterbatch 40-25 part, wherein:
The weight of polyethylene antistatic master batch consists of: 100 parts of polyethylene support resins, specific surface area is greater than 800g/m
2High electric conductivity carbon black A 25-40 part, specific surface area is less than 500g/m
2Common graphitized carbon black B 5-10 part, carbon black treatment agent 2.0-4.0 part, oxidation inhibitor 0.4-1.0 part, polyethylene wax 2.0-5.0 part, described carbon black treatment agent is titanate coupling agent, silane coupling agent or aluminate coupling agent, and oxidation inhibitor is the mixture of phosphoric acid ester and suffocated amine antioxidant
The weight of polyethylene anti-flaming masterbatch consists of: 100 parts of polyethylene support resins, fire retardant 100-150 part, smoke suppressor 25-40 part, oxidation inhibitor 2.0-3.0 part, described fire retardant is a decabromodiphenyl oxide, and smoke suppressor is an antimonous oxide, and oxidation inhibitor is the mixture of phosphoric acid ester and suffocated amine antioxidant.
2, composition according to claim 1 is characterized in that the polyethylene support resin that polyethylene antistatic master batch and polyethylene anti-flaming masterbatch are adopted is a new LDPE (film grade).
3, composition according to claim 1 is characterized in that described carbon black treatment agent is a titanate coupling agent.
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Cited By (1)
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| CN104558746A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Flame-retardant and antistatic polyethylene composition and preparation method thereof |
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| 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 |
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| US8829102B2 (en) * | 2010-10-27 | 2014-09-09 | Cabot Corporation | High loading carbon black masterbatch for pressure pipe applications |
| CN102093618A (en) * | 2010-12-30 | 2011-06-15 | 曲阜市东宏实业有限公司 | Conductive master batch for mining polyethylene pipe and production method thereof |
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| CN102432939B (en) * | 2011-11-07 | 2013-07-17 | 中国蓝星（集团）股份有限公司 | Antistatic flame-retardant ultra high molecular weight polyethylene composition and preparation method thereof |
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| CN103059374B (en) * | 2012-12-07 | 2014-09-10 | 江苏德威新材料股份有限公司 | High-temperature-resistant silane-crosslinked flame-retardation insulating material for automobile wires and preparation method thereof |
| CN103554950B (en) * | 2013-10-25 | 2017-01-11 | 东北林业大学 | Flame-retardant antistatic wood powder/polypropylene wood-plastic composite material with silane modified conductive carbon black, and preparation method of composite material |
| CN105086076A (en) * | 2015-08-20 | 2015-11-25 | 晶锋集团股份有限公司 | Waste-plastic-added environment-friendly cable sheath material and preparation method thereof |
| CN106633344A (en) * | 2016-11-30 | 2017-05-10 | 山东东方新材料有限公司 | Antistatic functional masterbatch, production process thereof, and production process of polyethylene pipes |
| CN112011113A (en) * | 2020-03-23 | 2020-12-01 | 桐城市东风塑胶有限责任公司 | Plastic flame-retardant film |
| CN113480793A (en) * | 2021-07-21 | 2021-10-08 | 山东建安实业有限公司 | Polyethylene gas pipeline processing technology |
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2003
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558746A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Flame-retardant and antistatic polyethylene composition 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 |
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