CN104829903A - Low temperature resistance HDPE micro-crosslinking system explosion suppression material and preparation method thereof - Google Patents
Low temperature resistance HDPE micro-crosslinking system explosion suppression material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to the technical field of explosion suppression materials of flammable and explosive liquids (gases) during processes such as production, transportation, storage and use, particularly to a low temperature resistance HDPE micro-crosslinking system explosion suppression material and a preparation method thereof. The method comprises: carrying out high speed and uniform mixing on HDPE, an initiator, a fire retardation masterbatch, ultralong silver nano-wires, a melting and dropping resistance agent, an antioxidant, and a modified low temperature resistance rubber in a high speed mixer, carrying out co-mixing extrusion through a twin-screw extruder, and carrying out pelletizing and drying so as to be used for spare. According to the present invention, the performance of the explosion suppression material is effectively improved under the low temperature (-50 to -60 DEG C) condition, the service life is prolonged, the safety is increased, and the generations of safety risk and other problems in the use environment are avoided.
Description
Technical field
The present invention relates to the explosion-suppressing material technical field of inflammable and explosive liquid (gas) bodies such as gasoline, diesel oil, kerosene, aero oil, liquefied gas, Sweet natural gas, propane in production, transport, storage and use procedure, particularly relate to micro-cross-linking system explosion-suppressing material of a kind of low temperature resistant HDPE and preparation method thereof.
Background technology
As everyone knows, inflammable and explosive liquid (gas) bodies such as gasoline, diesel oil, kerosene, aero oil, liquefied gas, Sweet natural gas, propane are in production, transport, storage and use procedure, because security measures is improper or surprisingly cause burning and explosion hazard, often cause great property damage and loss of life and personal injury.Therefore various countries research and develop explosion-suppressing material and product in succession, improve the safety issue of inflammable and explosive liquid (gas) body in production, use and storage and transport process, prevent the fire explosion of danger chemical.
The U.S. uses polyurethane foam explosion-suppressing material at the beginning in the safety of military oil product and accumulating, in use finds its poor chemical stability afterwards, soon replace by aluminum alloy explosion suppression material.Fuel tank inner chamber is divided into several " loculuses " by cellular barrier material, and these " loculuses " effectively can suppress flame transmission, and pressure of explosion ripple is sharply declined; Meanwhile this cellular material has very high surperficial usefulness, absorbs the heat of burning release, the temperature after combustion reactions is reduced, the degrees of expansion of reactant gases reduces, force value in container increases not quite, makes combustionvelocity not reach the tripping speed of blast, thus reaches datonation-inhibition object.
Be applied to the body material preparing block blast-proof materials at present and be mainly divided into metal alloy class and non-metallic material, but metal block explosion suppression sphere for the datonation-inhibition pressure range of decrease, to the rejection of flame propagation velocity be difficult to improve; For filling and the use of oil storage tank or oil pipeline, oxidation with aging after will become fragile, form fragment, can drop when being subject to vibrating chip, pollutes or result in blockage to pipeline road to oil product; The transport of metal block explosion suppression sphere and use procedure need supporting structure, stack and are highly restricted; Fill explosion-suppressing material and need manual operation, and need auxiliary support frame; Difficulty is cleaned after the fouling of use procedure wire netting or blocking mesh; Aluminium alloy and the netted explosion-suppressing material of aluminum magnesium alloy yielding under flame pressure, affect datonation-inhibition function.Nonmetal explosion-suppressing material mainly polyurethane foamed material, has lighter weight and less occupation rate, but its moisture-resistant degree is poor, easily hydrolysis and affect whole quality product, cause the accident.
Disclosed nonmetal explosion-suppressing material base nylon 6 at present, the processing temperature of nylon66 fiber and polyphenylene sulfide is too high, and the resistance to low temperature of PA6 is generally at-20 DEG C ~-30 DEG C, and the low temperature resistant embrittlement temperature of nylon66 fiber is near-30 DEG C.PP is selected the base material into explosion-proof ball by developer in addition at present simultaneously, but we find that the resistance to petrol and diesel oil performance of PP base material is good not, and PP, under-10 DEG C of envrionment conditionss, low temperature brittleness occurs.
Summary of the invention
For the shortcoming that current explosion-proof lamp is in use existing, such as processing temperature is higher, difficult processing, cannot be low temperature resistant etc. shortcoming.Patent of the present invention essentially disclose a kind of low temperature resistant, processing temperature is lower, easy-formation HDPE explosion-suppressing material and preparation method thereof, disclosed formula effectively can improve explosion-suppressing material under low temperature environment (-50 DEG C ~-60 DEG C) condition, extend its work-ing life, increase its security, avoid its in environment for use problem, the problem includes: the generation of 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, calculates according to weight fraction:
Wherein, the base material HDPE trade mark is 8008,8920,8007,1600J, 5218EA etc., and melting index is at 10 ~ 20g/10min;
Initiator is 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane, UN-125F, TAIC, TGIC, BTPB, ERJL etc.,
Fire-retardant master granule, adopt compound flame retardant blended with HDPE according to a certain percentage, preparation hyperconcentration master batch, wherein the ratio of fire retardant 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, and triazine halogen-free flame retardants is mainly PDM, PDD, PEPA, pentaerythrite diphosphate two hydrogen ester trimeric cyanamide, ring-type kind phosphate ester melamine salt fire retardant, XPM-1000; Metal fire retardant is mainly metal oxide, is mainly antimonous oxide, diethyl hypo-aluminum orthophosphate, aluminium hydroxide, magnesium hydroxide etc.;
Described overlength nano-silver thread is conductive filler material, and addition is 1 ~ 5 part, and wherein nano-silver thread is self-control, by each composition weight number
Wherein said inhibitor is chloride metallic compound, as NaCl, FeCl
2, CuCl
2deng; Tensio-active agent is PVP (polyvinylpyrrolidone), PEG etc.; Solvent is polyalcohols, as propylene glycol, glycerol, butantetraol etc.,
Adopt the method for multistep manufacture nano silver wire: Silver Nitrate and part surface promoting agent (40% ~ 50% of tensio-active agent total mass mark) are dissolved in a solvent, ultrasonic disperse 10 ~ 20min, microwave heating reaction 5 ~ 10min, the silver-colored line that pre-synthesis length is shorter, then add inhibitor and remaining tensio-active agent successively, continue reaction 15 ~ 30min, centrifuge washing, obtain overlength silver line, the length of silver-colored line is up to 400 ~ 500um, and diameter can reach about 150nm.
Above-mentioned anti-dropping agent is kaolin, clay or polytetrafluorethylepowder powder etc., and particle diameter is at about 10um;
Above-mentioned oxidation inhibitor is antioxidant 1010,168 etc.;
Cold resistant rubber is terpolymer EP rubber, paracril, organo-silicone rubber (terpolymer EP rubber can use the injection grade trade mark 4045,4770R, 3722P, 3745P, 4570,4640 etc., paracril available powders 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: according to above-mentioned formula, by HDPE, initiator, fire-retardant master granule, overlength nano-silver thread, anti-dropping agent, oxidation inhibitor, modification cold resistant rubber, high-speed mixing is carried out in high-speed mixer, blended speed is at 100r/min, after it mixes, extrude through twin screw extruder melt blending, the temperature of twin screw extruder is at about 190 DEG C.Pelletizing, dries, for subsequent use.
Beneficial effect of the present invention is:
(1) select HDPE as the matrix resin of explosion-proof ball, there is processing temperature lower, the feature of easy-formation, the explosion-proof ball of variform can be prepared;
(2) modification is passed through, add cold resistant rubber, effectively improve explosion-proof ball under low temperature environment (-50 DEG C ~-60 DEG C) condition, extend its work-ing life, increase its security, its problem in environment for use is avoided, the problem includes: the generation of the problems such as potential safety hazard, simultaneously by induction HDPE and the micro-crosslinked formation that also can promote conductive network to a certain extent of rubber, also to improve a lot for whole system mechanical property;
(3) this base material of HDPE due to its intramolecule structure too regular, and be unfavorable for fire retardant, the effective dispersion wherein of anti-electrostatic nano silver line, the present invention have selected specific modified resin terpolymer EP rubber, paracril, organo-silicone rubber, while improving low-temperature performance, also the dispersiveness of fire retardant and the static inhibitor of filling in matrix resin can be improved, its fire-retardant and anlistatig performance of effective raising, simultaneously in patent of the present invention, the fire retardant added is halogen-free flame-retardant, in the process used, avoid the pollution to environment, by adding of homemade overlength nano-silver thread, be conducive to forming space three-dimensional conductive network structure, improve the connectivity between conductive filler material, reduce the add-on of conductive filler material, and silver-colored line stable in properties, there is good electrostatic retentivity.
Embodiment
Embodiment 1
The preparation of overlength nano-silver thread:
Now Silver Nitrate and part surface promoting agent PVP (1 part) are dissolved in solvent glycerol, ultrasonic disperse 20min, microwave heating (120 DEG C) reaction 5min, the silver-colored line that pre-synthesis length is shorter, then add inhibitor NaCl and remaining tensio-active agent PVP (1 part) successively, continue microwave heating reaction 15min, centrifuge washing, obtain overlength silver line, the length of silver-colored line is up to about 400um, and diameter can reach about 150nm.
The preparation of fire-retardant master granule:
Adopt compound flame retardant blended with HDPE according to a certain percentage, preparation hyperconcentration master batch, wherein the mass ratio of fire retardant accounts 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 is 1:1:1, triazine halogen-free flame retardants PDM; Metal fire retardant antimonous oxide.
The preparation of low temperature resistant HDPE explosion-proof ball material:
According to above-mentioned formula by HDPE 8008,2,5-dimethyl-2,5-bis(t-butylperoxy) hexane, fire-retardant master granule, overlength nano-silver thread, kaolin, irgasfos 168, organo-silicone rubber, high-speed mixing is carried out in high-speed mixer, blended speed is at 100r/min, after it mixes, extrude through twin screw extruder melt blending, the temperature of twin screw extruder 190 DEG C.Pelletizing, dries, obtains a kind of raw material of low temperature resistant HDPE explosion-proof ball.
Embodiment 2
The preparation of overlength nano-silver thread:
Now Silver Nitrate and part surface promoting agent PVP (0.5 part) are dissolved in solvent ethylene glycol, ultrasonic disperse 20min, microwave heating (120 DEG C) reaction 5min, the silver-colored line that pre-synthesis length is shorter, then add inhibitor FeCl successively
2with remaining tensio-active agent PVP (0.5 part), continue microwave heating reaction 15min, centrifuge washing, obtain overlength silver line, the length of silver-colored line is up to about 400um, and diameter can reach about 150nm.
The preparation of fire-retardant master granule:
Adopt compound flame retardant blended with HDPE according to a certain percentage, preparation hyperconcentration master batch, wherein the mass ratio of fire retardant accounts 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 is 1:1:1, triazine halogen-free flame retardants PDD; Metal fire retardant diethyl hypo-aluminum orthophosphate.
The preparation of low temperature resistant HDPE explosion-proof ball material:
According to above-mentioned formula HDPE 8920, TAIC, fire-retardant master granule, overlength nano-silver thread, PTFE, antioxidant 1010, terpolymer EP rubber, high-speed mixing is carried out in high-speed mixer, blended speed is at 100r/min, after it mixes, extrude through twin screw extruder melt blending, the temperature of twin screw extruder 190 DEG C.Pelletizing, dries, obtains a kind of raw material of low temperature resistant HDPE explosion-proof ball.
Embodiment 3
The preparation of overlength nano-silver thread:
Now Silver Nitrate and part surface promoting agent PEG (0.5 part) are dissolved in solvent ethylene glycol, ultrasonic disperse 20min, microwave heating (120 DEG C) reaction 5min, the silver-colored line that pre-synthesis length is shorter, then add inhibitor C uCl successively
2with remaining Surfactant PEG (0.5 part), continue microwave heating reaction 15min, centrifuge washing, obtain overlength silver line, the length of silver-colored line is up to about 400um, and diameter can reach about 150nm.
The preparation of fire-retardant master granule:
Adopt compound flame retardant blended with HDPE according to a certain percentage, preparation hyperconcentration master batch, wherein the mass ratio of fire retardant accounts 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 is 1:1:1, triazine halogen-free flame retardants pentaerythrite diphosphate two hydrogen ester trimeric cyanamide; Metal fire retardant magnesium hydroxide.
The preparation of low temperature resistant HDPE explosion-proof ball material:
According to above-mentioned formula HDPE 1600J, UN-125F, fire-retardant master granule, overlength nano-silver thread, clay, antioxidant 1010, paracril, high-speed mixing is carried out in high-speed mixer, blended speed is at 100r/min, after it mixes, extrude through twin screw extruder melt blending, the temperature of twin screw extruder 190 DEG C.Pelletizing, dries, obtains a kind of raw material of low temperature resistant HDPE explosion-proof ball.
Embodiment 4
The preparation of overlength nano-silver thread:
Now Silver Nitrate and part surface promoting agent PVP (0.5 part) are dissolved in solvent ethylene glycol, ultrasonic disperse 20min, microwave heating reaction 5min, the silver-colored line that pre-synthesis length is shorter, then add inhibitor FeCl successively
2with remaining tensio-active agent PVP (0.5 part), continue microwave heating reaction 15min, centrifuge washing, obtain overlength silver line, the length of silver-colored line is up to about 400um, and diameter can reach about 150nm.
The preparation of fire-retardant master granule:
Adopt compound flame retardant blended with HDPE according to a certain percentage, preparation hyperconcentration master batch, wherein the mass ratio of fire retardant accounts 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 is 1:1:1, triazine halogen-free flame retardants PDD; Metal fire retardant diethyl hypo-aluminum orthophosphate.
The preparation of low temperature resistant HDPE explosion-proof ball material:
According to above-mentioned formula HDPE 8920, TAIC, fire-retardant master granule, overlength nano-silver thread, PTFE, antioxidant 1010, POE, high-speed mixing is carried out in high-speed mixer, blended speed is at 100r/min, after it mixes, extrude through twin screw extruder melt blending, the temperature of twin screw extruder 190 DEG C.Pelletizing, dries, obtains a kind of raw material of low temperature resistant HDPE explosion-proof ball.
Embodiment 5
The preparation of fire-retardant master granule:
Adopt compound flame retardant blended with HDPE according to a certain percentage, preparation hyperconcentration master batch, wherein the mass ratio of fire retardant accounts 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 is 1:1:1, triazine halogen-free flame retardants PDM; Metal fire retardant antimonous oxide.
The preparation of low temperature resistant HDPE explosion-proof ball material:
According to above-mentioned formula by HDPE 8008,2,5-dimethyl-2,5-bis(t-butylperoxy) hexane, fire-retardant master granule, graphite 250G, kaolin, irgasfos 168, terpolymer EP rubber, high-speed mixing is carried out in high-speed mixer, blended speed is at 100r/min, after it mixes, extrude through twin screw extruder melt blending, the temperature of twin screw extruder 190 DEG C.Pelletizing, dries, obtains a kind of raw material of low temperature resistant HDPE explosion-proof ball.
Table 1 correlated performance is tested
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Tensile strength/Mpa | 30 | 32 | 31 | 20 | 26 |
| Shock strength/J.m -1 | 165 | 160 | 150 | 100 | 130 |
| Volume specific resistance/Ω .cm -1 | 1.05×10 5 | 1.16×10 5 | 1.19×10 5 | 2.0×10 7 | 3.0×10 7 |
| UL 94 vertical combustion | V 0 | V 0 | V 0 | V 2 | V1 |
| Brittle temperature/DEG C | -80 | -85 | -90 | -30 | -80 |
Claims (10)
1. a high density polyethylene(HDPE) explosion-suppressing material, is characterized in that: described high density polyethylene(HDPE) explosion-suppressing material each component of filling a prescription is calculated as according to weight fraction,
2. high density polyethylene(HDPE) explosion-suppressing material as claimed in claim 1, is characterized in that: described HDPE is the base material of described high density polyethylene(HDPE) explosion-suppressing material, melting index at 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, is characterized in that: described initiator is 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane, UN-125F, TAIC, TGIC, BTPB or ERJL.
4. high density polyethylene(HDPE) explosion-suppressing material as claimed in claim 1, is characterized in that: described fire-retardant master granule is that employing compound flame retardant and HDPE are blended, the hyperconcentration master batch prepared,
Wherein, the mass ratio of described compound flame retardant accounts for 70% ~ 80%, described compound flame retardant system triazine halogen-free flame retardants, metal fire retardant and the convex soil of organic illiteracy, and wherein the mass ratio of three is 1:1:1,
Described triazine halogen-free flame retardants is PDM, PDD, PEPA, pentaerythrite diphosphate two hydrogen ester trimeric cyanamide, ring-type kind phosphate ester melamine salt fire retardant or XPM-1000,
Described metal fire retardant is metal oxide, is mainly antimonous oxide, diethyl hypo-aluminum orthophosphate, aluminium hydroxide or magnesium hydroxide.
5. high density polyethylene(HDPE) explosion-suppressing material as claimed in claim 1, is characterized in that: the preparation technology of described overlength nano-silver thread is, by each composition weight number
Silver Nitrate and part surface promoting agent are dissolved in described solvent, ultrasonic disperse 10 ~ 20min, microwave heating reaction 5 ~ 10min, the silver-colored line that pre-synthesis length is shorter, add inhibitor and remaining tensio-active agent more successively, continue reaction 15 ~ 30min, centrifuge washing, obtains overlength nano-silver thread.
6. high density polyethylene(HDPE) explosion-suppressing material as claimed in claim 5, is characterized in that: described inhibitor is NaCl, FeCl
2, CuCl
2.
7. high density polyethylene(HDPE) explosion-suppressing material as claimed in claim 5, is characterized in that: described solvent is propylene glycol, glycerol or butantetraol.
8. high density polyethylene(HDPE) explosion-suppressing material as claimed in claim 1, is characterized in that: described anti-dropping agent is kaolin, clay or polytetrafluorethylepowder powder.
9. high density polyethylene(HDPE) explosion-suppressing material as claimed in claim 1, is characterized in that: described oxidation inhibitor is antioxidant 1010 or 168.
10. the preparation method of the high density polyethylene(HDPE) explosion-suppressing material as described in any one of claim 1 to 9, it is characterized in that: described preparation method is, according to described formula, by HDPE, initiator, fire-retardant master granule, overlength nano-silver thread, anti-dropping agent, oxidation inhibitor, modification cold resistant rubber, high-speed mixing is carried out in high-speed mixer, blended speed is at 100r/min, after it mixes, extrude through twin screw extruder melt blending, the temperature of twin screw extruder 190 DEG C, pelletizing, dries, for subsequent use.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108192270A (en) * | 2017-12-29 | 2018-06-22 | 中国人民解放军62025部队 | It is a kind of suitable for flame-proof ABS resin base block blast-proof materials of the coat of metal and preparation method thereof |
| 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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| 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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| CN104829903B (en) | 2017-09-08 |
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