CN104829903B - A kind of micro- cross-linking system explosion-suppressing materials of low temperature resistant HDPE and preparation method - Google Patents
A kind of micro- cross-linking system explosion-suppressing materials of low temperature resistant HDPE and preparation method Download PDFInfo
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- 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
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08L2201/02—Flame or fire retardant/resistant
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- 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
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- C08L2205/00—Polymer mixtures characterised by other features
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- 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
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- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Abstract
The present invention relates to explosion-suppressing material technical field of inflammable and explosive liquid (gas) body during production, transport, storage and use, more particularly to micro- cross-linking system explosion-suppressing materials of a kind of low temperature resistant HDPE and preparation method thereof.By HDPE, initiator, fire-retardant master granule, overlength nano-silver thread, anti-dropping agent, antioxidant, modified cold resistant rubber, after progress mixed at high speed is uniform in high-speed mixer, extruded through double screw extruder melt blending, pelletizing, drying is standby.Explosion-suppressing material is effectively increased under the conditions of low temperature environment (50 DEG C~60 DEG C), extends its service life, increases its security, it is to avoid its generation present in use environment the problems such as potential safety hazard.
Description
Technical field
The present invention relates to the inflammable and explosive liquid such as gasoline, diesel oil, kerosene, aero oil, liquefied gas, natural gas, propane (gas) body
Explosion-suppressing material technical field during production, transport, storage and use, more particularly to a kind of micro- crosslinkeds of low temperature resistant HDPE
It is explosion-suppressing material and preparation method thereof.
Background technology
It is well known that the inflammable and explosive liquid such as gasoline, diesel oil, kerosene, aero oil, liquefied gas, natural gas, propane (gas) body exists
During production, transport, storage and use, because safety measure is improper or surprisingly causes burning and explosion accident, often make
Into great property loss and casualties.Therefore various countries research and develop explosion-suppressing material and product in succession, improve inflammable and explosive liquid (gas)
Body production, using and storage and transport process in safety issue, prevent endanger chemicals fire explosion.
The U.S. uses polyurethane foam explosion-suppressing material in the safety of military oil product and accumulating at the beginning, is using later
Its poor chemical stability is found in journey, is replaced soon by aluminum alloy explosion suppression material.Cellular barrier material is by fuel tank
Inner chamber is divided into several " small chambers ", and these " small chambers " can effectively suppress flame transmission, blast pressure ripple is drastically declined；With
This cellular material is with very high surface efficiency simultaneously for this, and the temperature after combustion reaction drops in the heat of absorption burning release
Low, the degrees of expansion of reacting gas reduces, and the pressure value in container increases less, burning velocity is not reached the limit speed of blast
Degree, so as to reach datonation-inhibition purpose.
The matrix material for being applied to prepare block blast-proof materials at present is broadly divided into metal alloy class and nonmetallic materials, but
It is that metal block explosion suppression sphere is difficult to improve for the datonation-inhibition pressure range of decrease, the rejection to flame propagation velocity；For oil storage tank or
The filling of oil pipeline and use, oxidation after aging with that will become fragile, formation fragment, and can drop chip when vibrated, to oil
Product pollute or pipeline road are resulted in blockage；Metal block explosion suppression sphere is transported and needs supporting construction using process, stacks height
It is restricted；Filling explosion-suppressing material needs artificial operation, and needs auxiliary support frame；Use the fouling of process wire netting or blocking
Cleaned after mesh difficult；Aluminium alloy and the netted explosion-suppressing material of almag are yielding under flame pressure, influence datonation-inhibition function.It is non-
Metal explosion-suppressing material is mainly polyurethane foamed material, with lighter weight and smaller occupation rate, but its moisture-resistant degree
Property it is poor, easily hydrolysis and influence whole product quality, cause the accident.
The processing temperature of presently disclosed nonmetallic explosion-suppressing material base nylon 6, nylon66 fiber and polyphenylene sulfide is too high,
PA6 resistance to low temperature is general at -20 DEG C~-30 DEG C, and the low temperature resistant brittle temperature of nylon66 fiber is near -30 DEG C.While mesh
It is preceding to also have developer that PP is selected to the base material for explosion-proof ball, but it have been found that the resistance to petrol and diesel oil performance of PP base materials is not good enough, PP
Under -10 DEG C of environmental conditions, occurs low temperature brittleness.
The content of the invention
For current explosion-proof lamp existing shortcoming in use, such as processing temperature is higher, hardly possible processing, it is impossible to
Low temperature resistant the shortcomings of.It is relatively low that patent of the present invention essentially discloses a kind of low temperature resistant, processing temperature, easy-formation HDPE explosion-suppressing materials and
Its preparation method, disclosed matching somebody with somebody can effectively improve explosion-suppressing material under the conditions of low temperature environment (- 50 DEG C~-60 DEG C), prolong
Its long service life, increases its security, it is to avoid its generation present in use environment the problems such as potential safety hazard.
High density polyethylene (HDPE) explosion-suppressing material described in the technical solution adopted for the present invention to solve the technical problems, according to
Weight fraction is calculated：
Wherein, the base material HDPE trades mark are 8008,8920,8007,1600J, 5218EA etc., and melt index is in 10~20g/
10min；
Initiator be 2,5- dimethyl -2,5- bis(t-butylperoxy)s hexane, UN-125F, TAIC, TGIC, BTPB,
ERJL etc.,
Fire-retardant master granule, is blended with HDPE, hyperconcetration master batch is prepared, wherein fire-retardant according to a certain percentage using compound flame retardant
The ratio of agent probably accounts for 70%~80%, fire retardant system triazine halogen-free flame retardants and metal fire retardant and the convex soil of organic illiteracy,
Mass ratio wherein shared by three is 1：1：1, triazine halogen-free flame retardants is mainly PDM, PDD, PEPA, pentaerythrite diphosphate two
Hydrogen ester melamine, ring-type kind phosphate ester melamine salt fire retardant, XPM-1000；Metal fire retardant is mainly metal oxide, main
To be antimony oxide, diethyl hypo-aluminum orthophosphate, aluminium hydroxide, magnesium hydroxide etc.；
The overlength nano-silver thread is conductive filler, and addition is 1~5 part, and wherein nano-silver thread is self-control, by each component
Parts by weight
Wherein described inhibitor is chloride metallic compound, such as NaCl, FeCl2、CuCl2Deng；Surfactant is
PVP (polyvinylpyrrolidone), PEG etc.；Solvent is polyalcohols, such as propane diols, glycerine, erythrol,
The method that nano silver wire is prepared using multistep：By silver nitrate and part surface activating agent (surfactant gross mass
In a solvent, 10~20min of ultrasonic disperse, microwave heating response 5~10min are pre-synthesis for the dissolving of the 40% of fraction~50%)
The shorter silver wire of length, sequentially adds inhibitor and remaining surfactant, continues to react 15~30min, centrifuge washing,
Overlength silver wire is obtained, the length of silver wire is up to 400~500um, and diameter can reach 150nm or so.
Above-mentioned anti-dropping agent is kaolin, clay or polytetrafluorethylepowder powder etc., and particle diameter is in 10um or so；
Above-mentioned antioxidant is antioxidant 1010,168 etc.；
Cold resistant rubber is ethylene propylene diene rubber, nitrile rubber, (ethylene propylene diene rubber can use injection grade board to organic silicon rubber
Numbers 4045,4770R, 3722P, 3745P, 4570,4640 etc., nitrile rubber can with powder level trade mark N41,3345,1052,26A,
33A etc.).
Present invention also offers a kind of preparation method of above-specified high density polyethylene explosion-suppressing material：, will according to above-mentioned formula
HDPE, initiator, fire-retardant master granule, overlength nano-silver thread, anti-dropping agent, antioxidant, modified cold resistant rubber, in high-speed mixer
Middle carry out mixed at high speed, blending speed is in 100r/min, after it is well mixed, is extruded through double screw extruder melt blending,
The temperature of double screw extruder is at 190 DEG C or so.Pelletizing, drying is standby.
The beneficial effects of the present invention are：
(1) it is relatively low with processing temperature from matrix resins of the HDPE as explosion-proof ball, the characteristics of easy-formation, it can make
The explosion-proof ball of standby variform；
(2) by modification, cold resistant rubber is added, explosion-proof ball is effectively improved in low temperature environment (- 50 DEG C~-60 DEG C) bar
Under part, extend its service life, increase its security, it is to avoid its hair present in use environment the problems such as potential safety hazard
It is raw, while by inducing HDPE and the micro- crosslinking of rubber also to promote the formation of conductive network to a certain extent, for whole body
It is that mechanical property is greatly enhanced；
(3) this base materials of HDPE due to its intramolecule structure it is excessively regular, and be unfavorable for fire retardant, anti-electrostatic nano silver
Line wherein effectively scattered, the present invention have selected specific modified resin ethylene propylene diene rubber, nitrile rubber, organosilicon rubber
Glue, while cryogenic property is improved, can also improve the dispersiveness of the fire retardant filled in matrix resin and antistatic additive, effectively
Raising its fire-retardant and anlistatig performance, while in patent of the present invention, the fire retardant of addition is halogen-free flame-retardant, is made
During, it is to avoid the pollution to environment, by the addition of homemade overlength nano-silver thread, advantageously form space three-dimensional and lead
Electric network structure, improves the connectivity between conductive filler, reduces the addition of conductive filler, and silver wire property is steady
It is fixed, with good electrostatic retentivity.
Embodiment
Embodiment 1
The preparation of overlength nano-silver thread：
Now silver nitrate and part surface activating agent PVP (1 part) are dissolved in solvent glycerine, ultrasonic disperse 20min is micro-
(120 DEG C) reaction 5min of Wave heating, the shorter silver wire of pre-synthesis length sequentially adds inhibitor NaCl and remaining surface
Activating agent PVP (1 part), continues microwave heating response 15min, and centrifuge washing obtains overlength silver wire, and the length of silver wire is up to
400um or so, diameter can reach 150nm or so.
The preparation of fire-retardant master granule：
It is blended according to a certain percentage with HDPE using compound flame retardant, prepares the quality of hyperconcetration master batch, wherein fire retardant
Than accounting for 70%, fire retardant system triazine halogen-free flame retardants, metal fire retardant and the convex soil of organic illiteracy, wherein three's mass ratio are 1：
1：1, triazine halogen-free flame retardants PDM；Metal fire retardant antimony oxide.
The preparation of the low temperature resistant explosion-proof ball materials of HDPE：
According to above-mentioned formula by HDPE 8008,2,5- dimethyl -2,5- bis(t-butylperoxy)s hexane, fire-retardant master granule,
Overlength nano-silver thread, kaolin, irgasfos 168, organic silicon rubber, carry out mixed at high speed in high-speed mixer, and speed is blended
In 100r/min, after it is well mixed, extruded through double screw extruder melt blending, 190 DEG C of the temperature of double screw extruder.
Pelletizing, drying, obtains a kind of raw material of low temperature resistant HDPE explosion-proof balls.
Embodiment 2
The preparation of overlength nano-silver thread：
Now silver nitrate and part surface activating agent PVP (0.5 part) are dissolved in solvent ethylene glycol, ultrasonic disperse 20min,
Microwave heats (120 DEG C) reaction 5min, and the shorter silver wire of pre-synthesis length sequentially adds inhibitor FeCl2With it is remaining
Surfactant PVP (0.5 part), continues microwave heating response 15min, and centrifuge washing obtains overlength silver wire, and the length of silver wire is high
Up to 400um or so, diameter can reach 150nm or so.
The preparation of fire-retardant master granule：
It is blended according to a certain percentage with HDPE using compound flame retardant, prepares the quality of hyperconcetration master batch, wherein fire retardant
Than accounting for 70%.Fire retardant system triazine halogen-free flame retardants, metal fire retardant and the convex soil of organic illiteracy, wherein three's mass ratio are 1：
1：1, triazine halogen-free flame retardants PDD；Metal fire retardant diethyl hypo-aluminum orthophosphate.
The preparation of the low temperature resistant explosion-proof ball materials of HDPE：
According to above-mentioned formula HDPE 8920, TAIC, fire-retardant master granule, overlength nano-silver thread, PTFE, antioxidant 1010, ternary
EP rubbers, carries out mixed at high speed, blending speed is in 100r/min, after it is well mixed, through double spiral shells in high-speed mixer
Bar extruder melt blending is extruded, 190 DEG C of the temperature of double screw extruder.Pelletizing, drying, obtains a kind of low temperature resistant HDPE explosion-proof
The raw material of ball.
Embodiment 3
The preparation of overlength nano-silver thread：
Now silver nitrate and part surface activating agent PEG (0.5 part) are dissolved in solvent ethylene glycol, ultrasonic disperse 20min,
Microwave heats (120 DEG C) reaction 5min, and the shorter silver wire of pre-synthesis length sequentially adds inhibitor C uCl2With it is remaining
Surfactant PEG (0.5 part), continues microwave heating response 15min, and centrifuge washing obtains overlength silver wire, and the length of silver wire is high
Up to 400um or so, diameter can reach 150nm or so.
The preparation of fire-retardant master granule：
It is blended according to a certain percentage with HDPE using compound flame retardant, prepares the quality of hyperconcetration master batch, wherein fire retardant
Than accounting for 70%.Fire retardant system triazine halogen-free flame retardants, metal fire retardant and the convex soil of organic illiteracy, wherein three's mass ratio are 1：
1：1, the hydrogen ester melamine of triazine halogen-free flame retardants pentaerythrite diphosphate two；Metal fire retardant magnesium hydroxide.
The preparation of the low temperature resistant explosion-proof ball materials of HDPE：
According to above-mentioned formula HDPE 1600J, UN-125F, fire-retardant master granule, overlength nano-silver thread, clay, antioxidant 1010,
Nitrile rubber, carries out mixed at high speed, blending speed is in 100r/min, after it is well mixed, through double spiral shells in high-speed mixer
Bar extruder melt blending is extruded, 190 DEG C of the temperature of double screw extruder.Pelletizing, drying, obtains a kind of low temperature resistant HDPE explosion-proof
The raw material of ball.
Embodiment 4
The preparation of overlength nano-silver thread：
Now silver nitrate and part surface activating agent PVP (0.5 part) are dissolved in solvent ethylene glycol, ultrasonic disperse 20min,
Microwave heating response 5min, the shorter silver wire of pre-synthesis length, sequentially adds inhibitor FeCl2With remaining surface-active
Agent PVP (0.5 part), continues microwave heating response 15min, and centrifuge washing obtains overlength silver wire, and the length of silver wire is up to 400um
Left and right, diameter can reach 150nm or so.
The preparation of fire-retardant master granule：
It is blended according to a certain percentage with HDPE using compound flame retardant, prepares the quality of hyperconcetration master batch, wherein fire retardant
Than accounting for 70%.Fire retardant system triazine halogen-free flame retardants, metal fire retardant and the convex soil of organic illiteracy, wherein three's mass ratio are 1：
1：1, triazine halogen-free flame retardants PDD；Metal fire retardant diethyl hypo-aluminum orthophosphate.
The preparation of the low temperature resistant explosion-proof ball materials of HDPE：
According to above-mentioned formula HDPE 8920, TAIC, fire-retardant master granule, overlength nano-silver thread, PTFE, antioxidant 1010, POE,
Mixed at high speed is carried out in high-speed mixer, blending speed is in 100r/min, after it is well mixed, molten through double screw extruder
Melt blending extrusion, 190 DEG C of the temperature of double screw extruder.Pelletizing, drying, obtains a kind of raw material of low temperature resistant HDPE explosion-proof balls.
Embodiment 5
The preparation of fire-retardant master granule：
It is blended according to a certain percentage with HDPE using compound flame retardant, prepares the quality of hyperconcetration master batch, wherein fire retardant
Than accounting for 70%, fire retardant system triazine halogen-free flame retardants, metal fire retardant and the convex soil of organic illiteracy, wherein three's mass ratio are 1：
1：1, triazine halogen-free flame retardants PDM；Metal fire retardant antimony oxide.
The preparation of the low temperature resistant explosion-proof ball materials of HDPE：
According to above-mentioned formula by HDPE 8008,2,5- dimethyl -2,5- bis(t-butylperoxy)s hexane, fire-retardant master granule,
Graphite 250G, kaolin, irgasfos 168, ethylene propylene diene rubber, carry out mixed at high speed in high-speed mixer, and blending speed exists
100r/min, after it is well mixed, is extruded, 190 DEG C of the temperature of double screw extruder through double screw extruder melt blending.Cut
Grain, drying, obtains a kind of raw material of low temperature resistant HDPE explosion-proof balls.
The correlated performance of table 1 is tested
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Tensile strength/Mpa | 30 | 32 | 31 | 20 | 26 |
| Impact strength/J.m-1 | 165 | 160 | 150 | 100 | 130 |
| Specific insulation/Ω .cm-1 | 1.05×105 | 1.16×105 | 1.19×105 | 2.0×107 | 3.0×107 |
| The vertical combustions of UL 94 | V 0 | V 0 | V 0 | V 2 | V1 |
| Brittle temperature/DEG C | -80 | -85 | -90 | -30 | -80 |
Claims (8)
1. a kind of high density polyethylene (HDPE) explosion-suppressing material, it is characterised in that：Described high density polyethylene (HDPE) explosion-suppressing material formula each group
Divide and be calculated as according to weight fraction,
Described overlength nano-silver thread length is 400~500um,
The preparation technology of described overlength nano-silver thread is, by each component parts by weight
Silver nitrate and part surface activating agent are dissolved in the solvent, 10~20min of ultrasonic disperse, microwave heating response 5
~10min, the shorter silver wire of pre-synthesis length sequentially adds inhibitor and remaining surfactant, continues to react 15
~30min, centrifuge washing obtains overlength nano-silver thread,
Described inhibitor is NaCl, FeCl2Or CuCl2。
2. high density polyethylene (HDPE) explosion-suppressing material as claimed in claim 1, it is characterised in that：Described HDPE is the high density
The base material of polyethylene explosion-suppressing material, melt index in 10~20g/10min, the trade mark is 8008,8920,8007,1600J or
5218EA。
3. high density polyethylene (HDPE) explosion-suppressing material as claimed in claim 1, it is characterised in that：Described initiator is 2,5- diformazans
Base -2,5- bis(t-butylperoxy) hexane, UN-125F, TAIC, TGIC or ERJL.
4. high density polyethylene (HDPE) explosion-suppressing material as claimed in claim 1, it is characterised in that：Described fire-retardant master granule is using multiple
It is blended with fire retardant and HDPE, the hyperconcetration master batch prepared,
Wherein, the mass ratio of the compound flame retardant accounts for 70%~80%, the compound flame retardant system triazine halogen-free flame retardants,
The mass ratio of metal fire retardant and organo montmorillonite, wherein three is 1：1：1,
The triazine halogen-free flame retardants is PDM, the hydrogen ester melamine of pentaerythrite diphosphate two or ring-type kind phosphate ester melamine salt
Fire retardant,
The metal fire retardant is antimony oxide, diethyl hypo-aluminum orthophosphate, aluminium hydroxide or magnesium hydroxide.
5. high density polyethylene (HDPE) explosion-suppressing material as claimed in claim 1, it is characterised in that：Described solvent is propane diols, third
Triol or erythrol.
6. high density polyethylene (HDPE) explosion-suppressing material as claimed in claim 1, it is characterised in that：Described anti-dropping agent is kaolinite
Soil, clay or polytetrafluorethylepowder powder.
7. high density polyethylene (HDPE) explosion-suppressing material as claimed in claim 1, it is characterised in that：Described antioxidant is antioxidant
1010 or 168.
8. a kind of preparation method of high density polyethylene (HDPE) explosion-suppressing material as described in any one of claim 1 to 7, its feature exists
In：The preparation method is, according to the formula, by HDPE, initiator, fire-retardant master granule, overlength nano-silver thread, anti-dropping agent,
Antioxidant, modified cold resistant rubber, carry out mixed at high speed in high-speed mixer, and blending speed treats that it is mixed in 100r/min
After uniform, extruded through double screw extruder melt blending, 190 DEG C of the temperature of double screw extruder, pelletizing, drying is standby.
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| CN114702745A (en) * | 2022-04-22 | 2022-07-05 | 宁海宏德新材料科技有限公司 | HDPE (high-density polyethylene) enhanced master batch and chemical barrel applying same |
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