CN104262751B - The flexible Polyethylene Pipe Resin of permanence antistatic - Google Patents

The flexible Polyethylene Pipe Resin of permanence antistatic Download PDF

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CN104262751B
CN104262751B CN201410536498.3A CN201410536498A CN104262751B CN 104262751 B CN104262751 B CN 104262751B CN 201410536498 A CN201410536498 A CN 201410536498A CN 104262751 B CN104262751 B CN 104262751B
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polyethylene pipe
pipe resin
tpe
base material
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CN104262751A (en
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张明
于金平
曹振东
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Yangzhou University
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Yangzhou University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer

Abstract

A kind of flexible Polyethylene Pipe Resin of permanence antistatic, by weight, by 100 parts of PE RT resins, 20 35 parts of conductive agglomerates, 28 parts of thermoplastic elastomer (TPE)s, 15 parts of dispersants, 0 0.5 parts of antioxidant, 0 0.5 parts of releasing agents, 0 0.5 parts of fluid lubricant mix homogeneously in homogenizer, then through twin-screw extrusion water-cooled pelletize, processing temperature is at 180 195 DEG C.Extruding pipe material after special material for tube drying, cooling, traction, finished product.Compared with prior art, it is good that the present invention has antistatic property, reaches the effect of permanent anti-static, hot strength, bending strength, impact strength is suitable with pure PE RT, and bending modulus is lower, maintains the flexible advantage of PE tubing, convenient transport and construction and installation, and resistance to environment capacity is good, low cost, the specific insulation of the flexible Polyethylene Pipe Resin of this permanent anti-static can be stablized 106Ω·cm。

Description

The flexible Polyethylene Pipe Resin of permanence antistatic
Technical field
The present invention relates to a kind of flexible Polyethylene Pipe Resin of permanence antistatic, belong to composite technology neck Territory.
Background technology
Under " to mould Dai Gang " calls, the application of plastics is more and more extensive, but plastics have high resistance, is using During, run into contact, rub, the situation such as collision can accumulate electrostatic charge on the surface of plastic, and the electrostatic charge produced is difficult With transfer, when running up to a certain degree, can bring about potential safety hazard.
PE-RT i.e. heat-proof polythene, it uses ethylene and the method for octene copolymer, by controlling quantity and the distribution of side chain Obtain the molecular structure of uniqueness, improve thermostability and the toughness of PE.PE-RT tubing good stability, ageing-resistant, service life Long, creep-resistant property is excellent, and tubing is readily bent, easy construction, but PE-RT tubing has high resistance, limits it Application in fields such as colliery conveyings.
Use polymer-based conductive black composite prepared by general technology, need to add the conduction charcoal of relatively high filler loading capacity Black, the mechanical properties decrease causing composite is obvious, and loses the flexible feature of PE-RT.Add antistatic additive to reach The antistatic effect arrived, runs into the situations such as washing, friction during the use of goods, often loses antistatic effect, resistance to ring Border ability is poor.
Carbon powder dust has electric conductivity, and density is little, easily flies away aloft, carries to machine and operator Carry out certain potential safety hazard, and due to white carbon black and PE-RT grain diameter over-widened gap, no matter in homogenizer or In double-screw feeding device, all it is difficult to reach preferable mixed effect.
PE-RT pipeline is readily bent, convenient construction, and resistance to low temperature is good, can transport at low ambient temperatures, construct；Resist The ability of external force collision is much higher than other tubing.But after interpolation conductive black, composite often becomes fragile, it is difficult to bending, Work progress is more easily damaged.
Summary of the invention
It is an object of the invention to provide a kind of flexible Polyethylene Pipe Resin of permanence antistatic, solve existing typically Polymer-matrix electric conduction white carbon black compound system prepared by technique, its electric conductivity drastically declines along with the rising of temperature, more than 70 DEG C The problem losing antistatic effect, by invention while keeping the mechanical property of PE-RT tubing excellence, i.e. hot strength is 14.0MPa, bending strength is 12.3MPa, bending modulus 325.5MPa, and cantilever beam impact strength is that constantly composite has Lower bending modulus, tubing is flexible rolling in certain radius, also has permanence antistatic performance, has good ring Border adapts to ability, acid-alkali-corrosive-resisting, has good heat creep resistance energy, can keep anti-quiet in the range of room temperature to 125 DEG C Electrical property.
It is an object of the invention to be achieved through the following technical solutions, a kind of flexible polyvinyl piping materials of permanence antistatic PP Pipe Compound, is characterized in that, with medium density polyethylene PE-RT as base material, adds black masterbatch, thermoplastic elastomer (TPE), dispersant, resists Oxygen agent, releasing agent and fluid lubricant；Weight portion shared by each component is respectively medium density polyethylene PE-RT base material 100 parts, charcoal Black masterbatch 20-35 part, thermoplastic elastomer (TPE) 2-8 part, dispersant 1-5 part, antioxidant 0-0.5 part, releasing agent 0-0.5 part, liquid Lubricant 0-0.5 part.
Described medium density polyethylene PE-RT base material uses melt index MFR=0.6-0.8g/10min, test pressure to bear Lotus 2.16 kilograms, temperature 195 DEG C.
Described black masterbatch, the content of carbon black one 50%, during wherein carrier uses LLDPE, EVA, PP.
Described thermoplastic elastomer (TPE) uses the one of POE, POE-g-MAH, the wherein melted finger of POE and POE-g-MAH Number MFR=0.5-5g/10min, tests pressure load 2.16 kilograms, test temperature 195 DEG C.
Described dispersant uses Tissuemat E, EBS, the one of butyl titanate class.
Described antioxidant use the one of the double lauryl of antioxidant 1010, irgasfos 168, thio-2 acid or one with On mixture.
Described releasing agent uses zinc stearate, the one of Tissuemat E.
Described fluid lubricant uses liquid paraffin and one or more mixture of methyl-silicone oil.
A kind of permanence antistatic flexible Polyethylene Pipe Resin preparation method, is characterized in that, described method includes Following steps:
1) by medium density polyethylene PE-RT base material, black masterbatch, thermoplastic elastomer (TPE) is respectively dried；
2) black masterbatch after drying is placed in homogenizer by component, adds respective components fluid lubricant, low Speed stirring added respective components dispersant high-speed stirred 2-3 minute after 1-2 minute；
3) then to step 2) homogenizer in insert medium density polyethylene PE-RT base material and the thermoplastic of respective components Property elastomer, add respective components fluid lubricant, high-speed stirred 2-3 minute；
4) in the homogenizer of step 3), add antioxidant and the releasing agent of respective components, high-speed stirred 4-5 minute, Discharging.
5) by above-mentioned steps 4) mixture of gained adds in double screw extruder hopper and carries out extruding pelletization, extruder temperature Degree is for 180-195 DEG C.Rotating speed 200-400r/min.
The invention has the beneficial effects as follows: the viscoelasticity difference of conductive agglomerate carrier and matrix can affect carrier in the base Pattern and the dispersion of white carbon black, affect mechanical property and the electric conductivity of composite then.By thermoplastic elastomer (TPE) and carrier Synergism so that conductive agglomerate carrier forms continuous print conductive network structure in the base, and conducting medium is optionally led In electric network, conducting medium matrix mutually in constitute conductive network structure, significantly reduce the percolation threshold of system, and bullet The addition of gonosome, significantly reduces the modulus of composite, maintains the flexible feature of PE tubing, owing to conductive agglomerate carries Body and matrix have the preferable compatibility, and the mechanical property of composite is close to pure PE-RT tube material, and hot strength exceedes 14.0MPa, bending strength is less than 360.0MPa more than 12.3MPa, bending modulus, and cantilever beam impact strength is continuous.
Polymer-matrix electric conduction white carbon black compound system prepared by general technology, its electric conductivity is along with under the rising drastically of temperature Fall, often loses antistatic effect more than 70 DEG C.Compared to the polymer-matrix electric conduction white carbon black compound system of general technology, this The permanent anti-static flexible PE-RT tubing of bright preparation has good adaptive capacity to environment, acid-alkali-corrosive-resisting, has good Heat creep resistance energy, can keep antistatic property in the range of room temperature to 125 DEG C, and specific insulation can be stablized 106 Ω·cm。
The present invention uses the thermoplastic elastomer (TPE) that bending modulus is relatively low, and composite carries out plasticization and modification, reduces compound The modulus of material, compared to plasticizers such as conventional aliphatic dibasic acid ester, Phthalates, the many esters of gallic acid of benzene, has The advantages such as plasticising is lasting, nontoxic.
Accompanying drawing explanation
Fig. 1 is the embodiment of the present invention 1 morphology analysis metallograph when amplifying 3000 times；
Fig. 2 is the embodiment of the present invention 1 morphology analysis metallograph when amplifying 20000 times；
Fig. 3 is the embodiment of the present invention 2 morphology analysis metallograph when amplifying 3000 times；
Fig. 4 is the embodiment of the present invention 2 morphology analysis metallograph when amplifying 20000 times；
Fig. 5 is the embodiment of the present invention 3 morphology analysis metallograph when amplifying 3000 times；
Fig. 6 is the embodiment of the present invention 3 morphology analysis metallograph when amplifying 20000 times.
Detailed description of the invention
Further illustrate the present invention in conjunction with the embodiments:
Embodiment 1, a kind of flexible Polyethylene Pipe Resin of permanence antistatic, weight portion shared by each component is respectively For: medium density polyethylene PE-RT 100 parts, EVA carrier conductive black master batch 25 parts, thermoplastic elastomer (TPE) POE 5.5 parts, dispersion Agent EBS 1.5 parts, antioxidant 1010 0.2 part, irgasfos 168 0.2 part, 0.2 part of stearic acid release agent zinc, liquid paraffin 0.2 Part.
Medium density polyethylene PE-RT base material uses melt index MFR=0.6-0.8g/10min, tests pressure load 2.16 Kilogram, temperature 195 DEG C.
Melt index is to weigh the parameter of high polymer mobility quality, is denoted as MFR, is defined as thermoplastic resin in regulation temperature Under degree, pressure load, by the polymer weight in standard aperture in 10 minutes, unit is g/10min.
Preparation method comprises the following steps:
1) by 1.5Kg medium density polyethylene PE-RT base material, 0.375Kg EVA carrier conductive black master batch, 82.5g POE Thermoplastic elastomer (TPE) is respectively dried；
2) the 0.375Kg EVA carrier conductive black master batch after drying is placed in homogenizer, adds 1.5g liquid Paraffin, adds 22.5g EBS dispersant high-speed stirred 2-3 minute after stirring at low speed 1-2 minute；
3) to step 2) homogenizer in insert 1.5Kg medium density polyethylene PE-RT base material and 82.5g POE heat Thermoplastic elastic, adds 1.5g liquid paraffin, high-speed stirred 2-3 minute；
4) adding stearic acid release agent zinc 3g in the homogenizer of step 3), antioxidant 1010, irgasfos 168 are 3g, high-speed stirred 4-5 minute discharging；
5) by above-mentioned steps 4) mixture of gained adds in double screw extruder hopper and carries out extruding pelletization, extruder temperature Degree is for 180-195 DEG C.Rotating speed 200-400r/min.
The morphology analysis metallograph of embodiment 1 is as shown in Figure 1, 2.
Embodiment 2, a kind of flexible Polyethylene Pipe Resin of permanence antistatic, weight portion shared by each component is respectively For: medium density polyethylene PE-RT 100 parts, EVA carrier conductive black master batch 30 parts, thermoplastic elastomer (TPE) POE-g-MAH 3 parts, Dispersant EBS 1.5 parts, antioxidant 1010 0.2 part, irgasfos 168 0.2 part, 0.2 part of stearic acid release agent zinc, methyl-silicone oil 0.2 part.
Medium density polyethylene PE-RT base material uses melt index MFR=0.6-0.8g/10min, tests pressure load 2.16 Kilogram, temperature 195 DEG C.
Melt index is to weigh the parameter of high polymer mobility quality, is denoted as MFR, is defined as thermoplastic resin in regulation temperature Under degree, pressure load, by the polymer weight in standard aperture in 10 minutes, unit is g/10min.
Preparation method comprises the following steps:
1) by 1.5Kg medium density polyethylene PE-RT base material, 0.45Kg EVA carrier conductive black master batch, 45g POE- G-MAH thermoplastic elastomer (TPE) is respectively dried；
2) the 0.45Kg EVA carrier conductive black master batch after drying is placed in homogenizer, adds 1.5g methyl Silicone oil, adds 22.5g EBS dispersant high-speed stirred 2-3 minute after stirring at low speed 1-2 minute；
3) then to step 2) homogenizer in insert 1.5Kg medium density polyethylene PE-RT base material and 45g POE- G-MAH thermoplastic elastomer (TPE), adds 1.5g methyl-silicone oil, high-speed stirred 2-3 minute；
4) adding stearic acid release agent zinc 3g in the homogenizer of step 3), antioxidant 1010, irgasfos 168 are 3g, high-speed stirred 4-5 minute discharging；
5) by above-mentioned steps 4) mixture of gained adds in double screw extruder hopper and carries out extruding pelletization, extruder temperature Degree is for 180-195 DEG C.Rotating speed 200-400r/min.
The morphology analysis metallograph of embodiment 2 is as shown in Figure 3,4.
Embodiment 3, a kind of flexible Polyethylene Pipe Resin of permanence antistatic, weight portion shared by each component is respectively For: medium density polyethylene PE-RT 100 parts, LLDPE carrier conductive black master batch 30 parts, thermoplastic elastomer (TPE) POE 4 parts, dispersion Agent EBS 1.5 parts, antioxidant 1010 0.2 part, irgasfos 168 0.2 part, 0.2 part of stearic acid release agent zinc, liquid paraffin 0.2 Part.
Medium density polyethylene PE-RT base material uses melt index MFR=0.6-0.8g/10min, tests pressure load 2.16 Kilogram, temperature 195 DEG C.
Melt index is to weigh the parameter of high polymer mobility quality, is denoted as MFR, is defined as thermoplastic resin in regulation temperature Under degree, pressure load, by the polymer weight in standard aperture in 10 minutes, unit is g/10min.
Preparation method comprises the following steps:
1) by 1.5Kg medium density polyethylene PE-RT base material, 0.45Kg LLDPE carrier conductive black master batch, 60g POE Thermoplastic elastomer (TPE) is respectively dried；
2) the 0.45Kg EVA carrier conductive black master batch after drying is placed in homogenizer, adds 1.5g liquid Paraffin, adds 22.5g EBS dispersant high-speed stirred 2-3 minute after stirring at low speed 1-2 minute；
3) to step 2) homogenizer in insert 1.5Kg medium density polyethylene PE-RT base material and 60g POE heat Thermoplastic elastic, adds 1.5g liquid paraffin, high-speed stirred 2-3 minute；
4) adding stearic acid release agent zinc 3g in the homogenizer of step 3), antioxidant 1010, irgasfos 168 are 3g, high-speed stirred 4-5 minute discharging；
5) by above-mentioned steps 4) mixture of gained adds in double screw extruder hopper and carries out extruding pelletization, extruder temperature Degree is for 180-195 DEG C.Rotating speed 200-400r/min.
The morphology analysis metallograph of embodiment 3 is as shown in Figure 5,6.
Relevant detailed results such as table 1:
Table 1 embodiment performance test
As Figure 1-3, embodiment all occurs in that contiguous network in compound system matrix to embodiment 1,2,3 morphology analysis Structure, and conductive black is enriched at master batch carrier phase or continuous phase and carrier boundary, is so formed in compound system Conductive network structure, is effectively increased the electric conductivity of compound system.

Claims (6)

1. the flexible Polyethylene Pipe Resin of permanence antistatic, is characterized in that, with medium density polyethylene PE-RT as base Material, adds black masterbatch, thermoplastic elastomer (TPE), dispersant, antioxidant, releasing agent and fluid lubricant；Weight shared by each component Amount part is respectively medium density polyethylene PE-RT base material 100 parts, black masterbatch 20-35 part, thermoplastic elastomer (TPE) 2-8 part, dispersant 1-5 part, antioxidant 0.4-0.5 part, releasing agent 0.2-0.5 part, fluid lubricant 0.2-0.5 part；Described medium density polyethylene PE-RT base material uses melt index MFR=0.6-0.8g/10min, tests pressure load 2.16 kilograms, temperature 195 DEG C；Described Black masterbatch, the content of carbon black one 50%, during wherein carrier uses LLDPE, EVA, PP；Described thermoplastic elastomer (TPE) is adopted By the one of POE, POE-g-MAH, wherein melt index MFR=0.5-5g/10min of POE and POE-g-MAH, test pressure is born Lotus 2.16 kilograms, test temperature 195 DEG C.
The flexible Polyethylene Pipe Resin of permanence antistatic the most according to claim 1, is characterized in that, described divides Powder uses EBS, the one of butyl titanate class.
The flexible Polyethylene Pipe Resin of permanence antistatic the most according to claim 1, is characterized in that, described is anti- Oxygen agent uses one or more mixture of the double lauryl of antioxidant 1010, irgasfos 168, thio-2 acid.
The flexible Polyethylene Pipe Resin of permanence antistatic the most according to claim 1, is characterized in that, described is de- Mould agent uses zinc stearate, the one of Tissuemat E.
The flexible Polyethylene Pipe Resin of permanence antistatic the most according to claim 1, is characterized in that, described liquid Body lubricant uses liquid paraffin and one or more mixture of methyl-silicone oil.
6. the preparation method of the flexible Polyethylene Pipe Resin of permanence antistatic as claimed in claim 1, is characterized in that, Said method comprising the steps of:
1) by medium density polyethylene PE-RT base material, black masterbatch, thermoplastic elastomer (TPE) is respectively dried；
2) black masterbatch after drying is placed in homogenizer by component, adds respective components fluid lubricant, and low speed stirs Respective components dispersant high-speed stirred 2-3 minute is added after mixing 1-2 minute；
3) then to step 2) homogenizer in insert medium density polyethylene PE-RT base material and the thermoplastic elastomehc of respective components Gonosome, adds the fluid lubricant of respective components, high-speed stirred 2-3 minute；
4) in the homogenizer of step 3), add antioxidant and the releasing agent of respective components, high-speed stirred 4-5 minute, go out Material；
5) by above-mentioned steps 4) mixture of gained adds in double screw extruder hopper and carries out extruding pelletization, and extruder temperature is 180-195 DEG C, rotating speed 200-400r/min.
CN201410536498.3A 2014-10-13 2014-10-13 The flexible Polyethylene Pipe Resin of permanence antistatic Active CN104262751B (en)

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CN104788986A (en) * 2015-04-30 2015-07-22 安徽省潜山县创先实业有限公司 Antistatic thermoplastic rubber band and preparation method thereof
CN105254989B (en) * 2015-09-23 2017-07-18 浙江瑞堂塑料科技有限公司 A kind of anti-electrical breakdown permanent anti-static type rotation molding composite polyethylene material
WO2019099131A1 (en) 2017-11-17 2019-05-23 Exxonmobil Chemical Patents Inc. Pe-rt pipes and processes for making the same
CN111675846A (en) * 2020-06-13 2020-09-18 厦门毅兴行塑胶原料有限公司 Toughened PE (polyethylene) granules and preparation method and application thereof
CN112210161B (en) * 2020-10-28 2022-12-27 上海凯波电缆特材股份有限公司 Halogen-free oxygen-barrier layer cable material and preparation method and application thereof
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