CN1220725C - Anti-electrostatic flame-retardant polyvinyl material - Google Patents
Anti-electrostatic flame-retardant polyvinyl material Download PDFInfo
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- CN1220725C CN1220725C CN 02135428 CN02135428A CN1220725C CN 1220725 C CN1220725 C CN 1220725C CN 02135428 CN02135428 CN 02135428 CN 02135428 A CN02135428 A CN 02135428A CN 1220725 C CN1220725 C CN 1220725C
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Abstract
The present invention relates to an antistatic flame retardant polyethylene material. The components comprise: 100 portions by weight of high density polyethylene, 5 to 24 portions by weight of compound fire retardant and 3 to 7 portions by weight of compound antistatic agent. The antistatic flame retardant polyethylene material has good antistatic and fire retardant synergistic effect, and has the advantages of excellent antistatic performance, excellent fire retardant performance, soft texture, good toughness, good impact resistance, no rupture of pipe via heavy press, high intensity, large supporting pressure, good corrosion resistance, capability of resisting erosion of various chemical media, no electrochemical corrosion, no rust, no scale formation, simple component and easy preparation. The pipe material can completely replace steel tubes, can be widely used for mines and engineering of water supply, drainage and draining of construction, and has the advantages of smooth inner wall, small pipe resistance, no poison, sanitation, light weight and convenient construction.
Description
Technical field
The present invention relates to a kind of improved polythene material, belong to the organic plastics technical field.
Background technology
Plastics replace metal to obtain promoting in a lot of fields.According to the requirement of five ministries and commissions, the cast iron pipe pipeline will progressively be eliminated after 2000, replace by plastics tubing, plastic pipe has good corrosion resistance, cost is low, in light weight, life-span is long, advantage easy for installation, but, plastics tubing has simultaneously and very easily produces static, inflammable, withstand voltage low and poor impact resistance, it is complicated to make prescription, shortcomings such as operation inconvenience, therefore, polythene material is awaited further adjustment, improve, improve its performance,, need to adapt to harsh environmental conditions especially for the mining plastics in down-hole, more need to improve its static resistance, flame retardant resistance improves intensity, toughness etc.
Summary of the invention
Technical problem to be solved by this invention is: provide that a kind of antistatic and flame retardant synergistic effect is good, good toughness, quality softness, intensity height, and batching is simple, preparation is easy to anti-electrostatic flame-retardant polyvinyl material.
Anti-electrostatic flame-retardant polyvinyl material of the present invention, its batching contain following weight to be formed:
100 parts of high density polyethylene(HDPE)s
5～24 parts of composite flame-retardant agents
3～7 parts of composite antistatic agents.
Containing following weight during batching is formed preferably forms:
100 parts of high density polyethylene(HDPE)s
3～15 parts of new LDPE (film grade)s
5～24 parts of composite flame-retardant agents
3～7 parts of composite antistatic agents.
Containing following weight during preferred batching is formed forms:
100 parts of high density polyethylene(HDPE)s
8～12 parts of new LDPE (film grade)s
10～20 parts of composite flame-retardant agents
4～6 parts of composite antistatic agents.
Wherein composite antistatic agent is the JH-plastic anti-static agent, and composite flame-retardant agent is micro encapsulation red phosphorus FR-200S.Composite antistatic agent and composite flame-retardant agent are the product of compound composition, and there is sale in market.Single product, adapted when the preparation polythene material is simplified the batching operation, simplifies making processes, makes things convenient for industrializing implementation, reduces cost in many ways, increases the benefit.
Composite flame-retardant agent, composite antistatic agent also have following characteristics: few additive, high density, polymolecularity, highly versatile, tinctorial strength are about 25%, and water content is less than 0,05%, thawing rate 99,99%.
Composite flame-retardant agent mainly comprises: one or more of halogen containing organic compound, antimonous oxide, hydrated aluminum oxide, decabromodiphynly oxide, hydration lead borate, chlorinatedpolyethylene and phosphorus system, antimony system, bromine system, boron system etc.The reaction of the halogen atom that halogen-containing organic compound decomposites and polyethylene generates HX{X and represent halogen atom }, HX can make OH, the minimizing of H concentration with the great OH of activity, H free radical reaction, combustionvelocity is slowed down, fray-out of flame; The HX reaction that antimonous oxide and halogen containing organic compound decomposite generates the higher antimony trihalide of boiling point, attached to frosting oxygen is cut off, and reaches fire-retardant purpose; The hydrated aluminum oxide decomposes can absorb a large amount of heat and reduce the temperature of superpolymer, reaches the purpose of fire extinguishing.Can discharge hydrogenchloride when CPE is heated, hydrogenchloride produces a series of reflections with antimonous oxide, finally generates water and volatile butter of antimony absorbing and cooling temperature; Contain hydrate zinc borate when contacting burning things which may cause a fire disaster with brominated or the coexistence of chlorine fire retardant; can generate boron bromide, zinc bromide or boron chloride, zinc chloride and discharge crystal water; when running into hydrogenchloride or hydrogen bromide, zinc borate also can generate halogenation boron or zinc halide; halogenation boron under the high temperature or zinc halide can form the protective layer of the densification of vitreous state at burning surface; it is heat insulation secluding air again; play fire retardation; simultaneously halogenation boron and zinc halide are caught extremely strong H and the OH free radical of reactive behavior in the gas-phase reaction with butter of antimony is the same, disturb and interrupt the incendiary chain reaction.
Composite antistatic agent can be the special-purpose static inhibitor of polyolefine.Its mechanism of modification is to form the very thin electrolyte solution liquid of one deck at frosting to approach, and can greatly reduce the surface resistivity of plastics.Its main component can be the inorganic salt of sodium or solubilities such as potassium or magnesium, is used alone or two or more composite use; Can be HKD-520, HKD508, HKD-500 also, be used alone or several above composite use.
Polyethylene is nonpolar crystalline polymer, thereby has an excellent chemical stability, the aqueous solution of energy acid-and base-resisting and salt under the room temperature, even under comparatively high temps, polyethylene is not had obvious effect yet, so good corrosion resistance, polyethylene itself is nontoxic simultaneously, so have good sanitation performance, is a kind of green product.
Poly melt viscosity is to the shearing rate sensitivity, increase with shearing rate reduces, when shearing rate surpasses threshold value, be prone to mobile defects such as melt fracture, consider the factor such as intensity, impact strength, elongation at break of finished product simultaneously, we have individual scope when selecting materials, promptly melt the body flow rate between 0.9～13, tensile strength is between 25～40, and resisting environmental stress and cracking is between 250～400.Melt flow ratio between 25～40, yield strength between 6～10, shock strength about 30, elongation at break is between 400～500, modulus in flexure is between 800～1000.
The polyvinyl resin Intermolecular Forces is little, and the molecular chain flexibility is good, and basic structure is simple, regular, crystallizing power with certain degree, but its crystallization is subjected to the influence of the molecular chain degree of branching, with the increase of the degree of branching, reduced the regularity and the symmetry of macromolecular chain, crystallizing power also decreases.High density polyethylene(HDPE) is the long linear structure that a small amount of side chain is only arranged, and molecular energy more closely flocks together and forms higher density and degree of crystallinity.New LDPE (film grade) degree of crystallinity is low, and molecular stuffing is not tight, and density is less.Because the difference of degree of crystallinity makes the mechanical property difference bigger.In general, the degree of crystallinity height all increases density, tensile strength, hardness, softening temperature, heat-drawn wire, and elongation at break descends.The characterization of molecules of linear low density polyethylene is the linear structure with some amount side chain, and side chain has guaranteed its toughness, and linear portion has been given its enough intensity, density, degree of crystallinity, fusing point.The sub polyethylene subchain is submissive, and second-order transition temperature is lower, but because its crystallinity makes it have certain intensity in wide temperature range, the height of degree of crystallinity and molecular weight has determined the quality of its mechanical property.The linear low density polyethylene performance is pliable and tough, shock-resistant, high density polyethylene(HDPE) tensile strength, rigidity, hardness are better than linear low density polyethylene, help the thin-walled property and the lightweight of goods, but to the environmental stress cracking sensitivity, be easy to brittle cracking under surrounding medium, promptly environmental stress crack resistance is not as new LDPE (film grade).
The linear low density polyethylene molecular chain is a short-chain branch, molecular structure is between the low high density polyethylene(HDPE) of linearity and have between the new LDPE (film grade) of long-chain branch, its weight-average molecular weight is bigger, molecular weight distribution is narrower, side chain is more on the macromolecular chain, almost there is not long-chain branch, thereby degree of crystallinity is higher, so its physical and mechanical properties is better than common new LDPE (film grade), aspect mechanical property, the linear low density polyethylene tensile strength is than the high 50%-70% of common new LDPE (film grade), elongation is high more than 50%, impact strength, puncture intensity and low-temperature impact resistance is all better, and fusing point is than new LDPE (film grade) height, the use temperature wide ranges.Therefore, we mix use with high density polyethylene(HDPE) according to a certain ratio with linear low density polyethylene, the finished product of making had so both kept the advantage that the intensity of high density polyethylene(HDPE) is big, bear pressure height, thermal distortion difference, had kept the shock-resistance of linear low density polyethylene good again, the advantage of good toughness.Simultaneously, the environmental stress resistance performance increases, and does not have considerable change under heat, oxygen and mechanical shearing effect.
During the present invention forms, can also add the additive of other performance, as the Masterbatch toner etc.
The present invention's preparation gets final product according to the conventional preparation technology's preparation of engineering plastics.By prepare burden requirement batching of the present invention, can prepare different section bars, as tubing, sheet material etc., the down-hole is mining mostly is tubing.Tubing uses the production of SJ series screw rod plastic forcing machine to get final product, and the screw rod plastic forcing machine is the major equipment of plastics continuous extrusion.Use different screw rods and be equipped with different die head, subsidiary engine, but various thermoplastic plastic pipes, profiled material, bar, sheet material, plastic hollow goods such as production soft or hard polyethylene, polyethylene, polypropylene.This series forcing machine mainly contains extrusion system, temperature controlling system, transmission system, electric control cabinet, drive-motor, frame six parts composition.
1, the screw rod in the extrusion system, machine barrel are the key parts of entire machine, adopt high-quality alloy steel, and via nitride is handled and strict retrofit forms, thereby higher wear-resisting, solidity to corrosion and high hardness have been guaranteed, prolonged work-ing life of screw rod, machine barrel, connected body and reinforced cover adopt special construction, have improved the transmitting capacity of material at screw rod, machine barrel.
2, the screw rod in the extrusion system links by two keys and speed reducer output shaft, material enters the feeding section of screw rod from funnel, rotation with screw rod is fed forward, and progressively be heated, shearing, mixing, fusion, entering has behind the screw compression district 80% material to become viscous state by vitreous state, the viscous state material enters the laggard single stage plastication of note amount section, and by evenly, extrusion die quantitatively.
3, the temperature controlling system of this serial forcing machine adopts cast aluminum heaters heating and blower fan cooling, and the cooling trench design is reasonable on the well heater, and the heating radiating surface is big, good cooling results, and temperature control adopts temperature sensor to control automatically.
4, transmission system is made up of band transmission and reduction box transmission two portions, and wherein reduction box adopts the transmission of two-stage involute urve, and the flank of tooth has enough contacts and crooked supporting capacity through Overheating Treatment and precision work, has characteristics such as running is steadily reliable, efficient height.
5, drive-motor adopts YCT series electromagnetic speed-adjusting asynchronous machine or Y series three-phase asynchronous motor, and the selection of screw speed is as long as twisting electric machine control speed setting knob cashier's office in a shop can obtain needed rotating speed.
6, frame adopts high-quality structural steel, and steel plate is welded, rational in infrastructure, more stable and stronger.
This screw rod plastic forcing machine has become general conventional equipment, uses operation to tire out no longer in detail and states.
Technical process is as follows:
Prepare burden → stir → material loading (oven dry) → extrude → cooling and shaping → traction → cutting discharging → warehouse-in.
Tubing of the present invention detects through Shandong Province's quality supervision and test institute, Shandong Province's plastics inspection center, and detected result and mineral polyethylene piping materials national standard (MT558.2-1996) contrast are as follows:
Interventions Requested unit's technical requirements assay
Surface resistivity Ω≤1 * 10
91.6 * 10
6
Vertical relaxation shrinkage %≤3 1
Oxidation induction time min 〉=20 54
Elongation at break % 〉=200 1060
Tensile yield strength Mpa 〉=8.34 9.81
(2m, 1kg) leakless, nothing are destroyed and are passed through in falling weight impact test
Hydro-test ne-leakage, nothing are destroyed and are passed through
Wall thickness deviation mm 0～+ 0.8+0.7
Flat (internal diameter coincidence) flawless, nothing are destroyed and are passed through
Flaming combustion≤10/≤18 2/10
Flameless combustion≤60/≤120 24/94
Anti-electrostatic flame-retardant polyvinyl material of the present invention is antistatic and flame retardant synergistic effect is good, has excellent antistatic property and flame retardant properties, the quality softness, good toughness, shock-resistance is good, and weight is pressed piping, can not cause breaking, the intensity height, it is big to bear pressure, good corrosion resistance, erosion that can anti-various chemical mediators, no galvanic corrosion, non-corrosive, non-scaling, and batching is simple, preparation is easy.Tubing of the present invention can replace steel pipe fully and be widely used in that mine, building are given, draining, plasma discharge engineering, inner wall smooth, the resistance of ducting is little, non-toxic sanitary is in light weight, easy construction.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
Anti-electrostatic flame-retardant polyvinyl material of the present invention, its ingredients by weight consists of:
High density polyethylene(HDPE) 100kg
New LDPE (film grade) 10kg
Micro encapsulation red phosphorus FR-200S fire retardant 15kg
JH-plastic anti-static agent 5kg
Masterbatch 1kg
The JH-plastic anti-static agent is mainly used in the antistatic treatment of plastics such as polyethylene, polypropylene, soft PVC, polystyrene, ABS, technical target of the product: white is to little yellow sheet or meal, fusing point is 40～50 ℃, hydroxyl value is 6.6～7.5%, and pH value (1% aqueous solution) is 6.8～7.2.The product performance characteristics are as follows:
(1) with the intermiscibility appropriateness of polyethylene, polypropylene, soft PVC, polystyrene, ABS etc., antistatic property excellence, lasting is used this static inhibitor, can make product surface resistance reach 10
7～10
10Ω.
(2) this product belongs to the non-ionic type product, and good heat resistance can stand the plastic working temperature, and the processing characteristics and the physical and mechanical properties of plastics had no adverse effects.
(3) easy to use, static inhibitor and cold the mixing of plastic raw materials are got final product.Unit with good conditionsi carries out heat again and mixes (about 60 ℃) after cold mixing, and its dispersion effect is better.
The JH-plastic anti-static agent that we test use is raised sub-novel plastic institute by Changzhou and is produced.
Micro encapsulation red phosphorus FR-200S fire retardant adopts double-coated, compare with common red phosphorus have difficult moisture absorption, in air, be difficult for oxidized, be difficult for causing and do not produce characteristics such as toxic gas in dust explosion, shock resistance degree height, the processing.Its dispersiveness, physical-mechanical property, thermostability and flame retardant resistance all are significantly increased and improve.
The product main performance index:
Outward appearance: mulberry powder;
Red phosphorus content 85%;
Spontaneous ignition temperature: 300-350;
Water regain (100) 1.2;
Discharge phosphuret-(t)ed hydrogen amount (106) 2 after the carbonization.
Be used for thermoplastic resins such as PE, PP, EVA, PC, PA, PBT, EEA, PET, thermosetting resins such as epoxy, phenolic aldehyde, unsaturated polyester reach class synthetic rubber such as divinyl rubber, ethylene-propylene rubber(EPR).Be specially adapted to the place that a small amount of fire retardant can meet the demands.
We test the micro encapsulation red phosphorus FR-200S fire retardant of use and are produced by Lianyungang seawater chemical industry one factory.
The preparation method:
The material for preparing is dropped in the screw extrusion press, draw plastic pipe, the forcing machine length-to-diameter ratio is 25～35, and compression ratio is 4～8.Process control parameter is:
80～120 ℃ of hopper drying temperatures
80～120 ℃ in head one district, 80～120 ℃ in head two districts, 80～120 ℃ in head three districts;
80～120 ℃ in fuselage one district, 80～120 ℃ in fuselage two districts, 80～120 ℃ in fuselage three districts,
80～120 ℃ in fuselage four districts, 80～120 ℃ in fuselage five districts;
Main frame speed governing 18～22hz;
Tractor lock 50～70hz;
Vacuum meter control 0.03～0.07Mpa.
Embodiment 2
Anti-electrostatic flame-retardant polyvinyl material of the present invention, its ingredients by weight consists of:
High density polyethylene(HDPE) 100kg
New LDPE (film grade) 12kg
Micro encapsulation red phosphorus FR-200S fire retardant 20kg
JH-plastic anti-static agent 6kg
Masterbatch 1.2kg.
The preparation method is basic identical with embodiment 1.
Embodiment 3
Anti-electrostatic flame-retardant polyvinyl material of the present invention, its ingredients by weight consists of:
High density polyethylene(HDPE) 100kg
Micro encapsulation red phosphorus FR-200S fire retardant 18kg
JH-plastic anti-static agent 6kg
Masterbatch 1.2kg.
The preparation method is basic identical with embodiment 1.
Embodiment 4
Anti-electrostatic flame-retardant polyvinyl material of the present invention, its ingredients by weight consists of:
High density polyethylene(HDPE) 100kg
New LDPE (film grade) 12kg
Micro encapsulation red phosphorus FR-200S fire retardant 8kg
JH-plastic anti-static agent 5kg
Masterbatch 0.8kg.
The preparation method is basic identical with embodiment 1.
Embodiment 5
Anti-electrostatic flame-retardant polyvinyl material of the present invention, its ingredients by weight consists of:
High density polyethylene(HDPE) 100kg
New LDPE (film grade) 12kg
Micro encapsulation red phosphorus FR-200S fire retardant 16kg
JH-plastic anti-static agent 6kg
Masterbatch 1.1kg.
The preparation method is basic identical with embodiment 1.
Embodiment 6
Anti-electrostatic flame-retardant polyvinyl material of the present invention, its ingredients by weight consists of:
High density polyethylene(HDPE) 100kg
Micro encapsulation red phosphorus FR-200S fire retardant 21kg
JH-plastic anti-static agent 5kg
Masterbatch 1.3kg.
The preparation method is basic identical with embodiment 1.
Claims (3)
1, a kind of anti-electrostatic flame-retardant polyvinyl material is characterized in that its batching contains following weight and forms:
100 parts of high density polyethylene(HDPE)s
5～24 parts of micro encapsulation red phosphorus FR-200S composite flame-retardant agents
3～7 parts of JH-plastic anti-static agents.
2, anti-electrostatic flame-retardant polyvinyl material according to claim 1 is characterized in that its batching contains following weight and forms:
100 parts of high density polyethylene(HDPE)s
3～15 parts of new LDPE (film grade)s
5～24 parts of micro encapsulation red phosphorus FR-200S composite flame-retardant agents
3～7 parts of JH-plastic anti-static agents.
3, anti-electrostatic flame-retardant polyvinyl material according to claim 2 is characterized in that its batching contains following weight and forms:
100 parts of high density polyethylene(HDPE)s
8～12 parts of new LDPE (film grade)s
10～20 parts of micro encapsulation red phosphorus FR-200S composite flame-retardant agents
4～6 parts of JH-plastic anti-static agents.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02135428 CN1220725C (en) | 2002-08-16 | 2002-08-16 | Anti-electrostatic flame-retardant polyvinyl material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02135428 CN1220725C (en) | 2002-08-16 | 2002-08-16 | Anti-electrostatic flame-retardant polyvinyl material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1418907A CN1418907A (en) | 2003-05-21 |
| CN1220725C true CN1220725C (en) | 2005-09-28 |
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|---|---|---|---|
| CN 02135428 Expired - Fee Related CN1220725C (en) | 2002-08-16 | 2002-08-16 | Anti-electrostatic flame-retardant polyvinyl material |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731888B (en) * | 2012-05-22 | 2014-06-18 | 宁波一舟塑胶有限公司 | Multilayer coated red phosphorus low-smoke halogen-free flame-retardant polyolefin cable sheath material and preparation method thereof |
| CN104419076A (en) * | 2013-08-26 | 2015-03-18 | 首安工业消防有限公司 | Thermosensitive temperature-sensing composite high molecular material and preparation method thereof |
| CN103554606A (en) * | 2013-10-30 | 2014-02-05 | 安徽国通高新管业股份有限公司 | Pipe material for non-scaling pipelines |
| CN103992553A (en) * | 2014-04-30 | 2014-08-20 | 安徽省宁国市明浩包装材料有限公司 | Antistatic gas discharge tube and production method thereof |
| CN104497397A (en) * | 2014-12-17 | 2015-04-08 | 常熟市先锋乐器有限公司 | Musical instrument string not easy to rust |
| CN105020488A (en) * | 2015-07-06 | 2015-11-04 | 江苏圣通环境工程有限公司 | PE water supply pipe and processing method thereof |
| CN106905654A (en) * | 2015-12-23 | 2017-06-30 | 上海邦中新材料有限公司 | A kind of flame-retardant and anti-static composite and its preparation method and application |
| CN107759884A (en) * | 2017-11-08 | 2018-03-06 | 宝鸡盛鼎管业有限责任公司 | Flame-retardant and anti-static high density polyethylene (HDPE) electric power protecting pipe formula and preparation method |
| CN107936341A (en) * | 2017-11-30 | 2018-04-20 | 明光市裕阳新材料有限公司 | A kind of flame retarded polymeric material and preparation method thereof |
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2002
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